Europäisches Patentamt

(19) European Patent Office *EP000796222B1*

Office européen des brevets (11) EP 0 796 222 B1
(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.7: C01D 5/08, C01D 5/18
of the grant of the patent:
26.01.2000 Bulletin 2000/04 (86) International application number:
PCT/US95/14960
(21) Application number: 95940022.7
(87) International publication number:
(22) Date of filing: 13.11.1995 WO 96/16899 (06.06.1996 Gazette 1996/26)

(54) CO-PRODUCTION OF POTASSIUM SULFATE AND SODIUM SULFATE

COPRODUKTION VON KALIUMSULFAT UND NATRIUMSULFAT
PRODUCTION SIMULTANEE DE SULFATE DE POTASSIUM ET DE SULFATE DE SODIUM

(84) Designated Contracting States: • HOLDENGRABER, Curt

BE DE ES 36000 Qiryat Tivon (IL)

(30) Priority: 28.11.1994 US 348115 (74) Representative: Lee, Nicholas John et al

Haseltine Lake & Co.,
(43) Date of publication of application: Imperial House,
24.09.1997 Bulletin 1997/39 15-19 Kingsway
London WC2B 6UD (GB)
(73) Proprietor: DEAD SEA WORKS LTD
84100 Beer Sheva (IL) (56) References cited:
DD-A- 244 540 DE-A- 1 467 244
(72) Inventors: DE-C- 4 340 105 DE-C- 4 340 806
• LAMPERT, Shalom FR-A- 2 210 571 US-A- 4 215 100
24952 Maalot (IL)
EP 0 796 222 B1

Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give
notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in
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99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR)

 1 EP 0 796 222 B1 2

Description at high and low temperatures. The effluent from Stage

1, of composition 'a' (at 25°C) (see Figure 1b), is cooled
FIELD AND BACKGROUND OF THE INVENTION to about 0°C (Figure 1a), precipitating Glauber's salt for
reuse and possibly some sodium chloride, depending
[0001] The present invention relates to processes for 5 on the water balance in the system. The potassium val-
producing potassium and sodium sulfate, and, more ues are concentrated in the aqueous phase. After sep-
particularly, to processes for producing potassium sul- aration, the solution is evaporated at high temperature,
fate and sodium sulfate from potash and hydrated sodi- yielding sodium chloride and further concentrating the
um sulfate. potassium ions in solution. The sodium chloride is re-
10 moved as the process by-product, and the hot liquor is
Sodium Sulfate Production: cooled, precipitating potassium as KCl and/or glaserite,
which is subsequently returned to the reaction stages.
[0002] Various processes are known for producing Alternatively, the hot brine is reacted with Glauber's salt
sodium sulfate from hydrated sources of sodium sulfate. recovered from the cooling crystallization stage to pro-
High-quality commercial grades of sodium sulfate are 15 duce a glaserite suspension, which is returned to Stage
usually produced from Glauber's salt (Na2SO4∗10H2O). 1.
Natural Glauber's salt deposits ("mirabilite") exist in cold [0007] Other cyclic processes ("Type II") utilize the dif-
climates. Glauber's salt can also be obtained by cooling ferent solubility behaviors of potassium chloride and so-
a natural brine, a solution obtained by solution-mining, dium chloride at high temperatures. The quantity of wa-
or a process stream. The cooling is effected in ponds or 20 ter added to the reaction stages is set such that glaserite
in crystallizers (surface-cooled or vacuum-cooled). and solution 'b' (at 25°C) are produced in Stage 1 (Fig-
[0003] Anhydrous sodium sulfate is typically pro- ure 1b). The glaserite is then reacted with potash and
duced from Glauber's salt by evaporative crystallization water to produce the potassium sulfate product and a
in a multiple-effect or mechanical vapor recompression liquor of composition 'c'. The liquor is returned to Stage
(MVR) evaporator, by dehydration in a rotary dryer, or 25 1. The effluent liquor from Stage 1 is evaporated at high
by melting followed by salting out with sodium chloride. temperatures (75-110°C), producing pure NaCl, and the
Glauber's salt often contains insoluble matter which is end liquor is returned to Stage 1.
unacceptable in high-grade anhydrous sodium sulfate, [0008] It must be emphasized that the production of
hence, dissolution, filtration (and auxiliary separation potassium sulfate from potash and sodium sulfate is a
methods such as desliming), and evaporative crystalli- 30 low value-added process, even when the sodium chlo-
zation operations are necessary to obtain such material. ride by-product can be marketed. The multi-stage proc-
Alternatively, the Glauber's salt can be melted to pro- esses described above are capital-intensive and ener-
duce low quality "salt cake" grade sodium sulfate. The gy-intensive.
saturated mother liquor is then filtered and evaporated [0009] The Type I processes are particularly complex,
to produce high-grade sodium sulfate. 35 requiring a large number of unit operations. These in-
clude 4 to 6 filtration steps, not including filtration of the
Potassium Sulfate Production: washed potassium sulfate product. Moreover, cooling
crystallization is used to bring the temperature of the
[0004] In the production of potassium sulfate from pot- Stage 1 effluent to 0°C. The heat of crystallization of
ash and sodium sulfate, thermodynamic and economic 40 Glauber's salt, which is substantial (18.4 kcal/M), must
constraints dictate that the potassium sulfate be pro- also be removed at low temperatures. The cooling and
duced in two stages. In conventional processes, these heating costs associated with this stage coupled with
stages consist of: expensive equipment (crystallizers, heat exchangers,
coolant system, etc.) are a serious disadvantage.
1) Production of glaserite (K3Na(SO4)2) from sodi- 45 [0010] The Type II processes have no cooling stage
um sulfate, potash, and Stage 2 liquor; below ambient conditions. However, the process has an
2) Production of potassium sulfate from potash, wa- inordinately-large recycle stream (, 10 tons/ton K2SO4
ter, and glaserite from Stage 1. produced), which increases energy consumption. The
low ratio of water evaporated to throughput in the evap-
[0005] The mother liquor produced in Stage 1 con- 50 orative crystallization stage drastically reduces the nat-
tains substantial quantities of dissolved potassium and ural slurry density, requiring large crystallizers and/or
sulfate, which generally warrants a recovery operation. more sophisticated crystallization technology.
The currently-known processes differ primarily in the [0011] Although Glauber's salt is a relatively inexpen-
scheme used to retrieve these potassium and sulfate sive source of sodium sulfate, the additional water from
values. 55 the Glauber's salt decreases the conversion in the re-
[0006] Several processes ("Type I") take advantage action stages and increases the sulfate composition of
of the different solubility behaviors of potassium chlo- the Stage 1 effluent. Some cyclic processes cannot be
ride, sodium chloride, and sodium sulfate/Glauber's salt operated using Glauber's salt while others require addi-

2
 3 EP 0 796 222 B1 4

tional unit operations (e.g., evaporation). To date, no dissolved. This decreases the solubility of sodium sul-
process using Glauber's salt has been realized commer- fate, whereby anhydrous sodium sulfate is precipitated
cially. out of solution as the only stable solid phase. Thus, the
[0012] Another inexpensive source of sodium sulfate raw material is converted to anhydrous sodium sulfate,
is aqueous sodium sulfate. However, the water-to-sodi- 5 and the sodium sulfate from the evaporation stage is re-
um sulfate ratio in aqueous sodium sulfate is higher than covered. The sodium sulfate can be used to produce
that of Glauber's salt, such that the problem of excess potassium sulfate, and any excess material is a valuable
water worsens considerably. No cyclic processes using co-product.
aqueous sodium sulfate as the raw material have been
devised heretofore. 10 BRIEF DESCRIPTION OF THE DRAWINGS
[0013] There is thus a widely recognized need for, and
it would be highly advantageous to have, a process for [0018] The invention is herein described, by way of
producing potassium sulfate from sodium sulfate which example only, with reference to the accompanying
would be more efficient and more economical than here- drawings, wherein:
tofore known. 15
FIGs. 1a, 1b and 1c are solution phase diagrams
SUMMARY OF THE INVENTION for Na2SO4/2NaCl/K2SO4/2KCl/H2O system at 0°,
25° and 100°C, respectively;
[0014] According to the present invention there is pro- FIG. 2 is a block diagram schematically depicting
vided a process for producing potassium sulfate or po- 20 processes according to the present invention.
tassium sulfate and sodium sulfate from potash and a
sodium sulfate/water source, comprising the steps of: DESCRIPTION OF THE PREFERRED
(a) subjecting a sodium sulfate source to conversion EMBODIMENTS
with potash in an aqueous medium to yield glaserite pre-
cipitate and a first mother liquor; (b) converting the gla- 25 [0019] The present invention is of processes for the
serite precipitate with potash and water to produce a po- co-production of potassium sulfate and sodium sulfate.
tassium sulfate precipitate and a second mother liquor; The principles and operation of processes according to
(c) returning the second mother liquor to step (a); (d) the present invention may be better understood with ref-
evaporating the first mother liquor such that a sodium erence to the drawings and the accompanying descrip-
chloride and anhydrous sodium sulfate solids mixture is 30 tion.
precipitated in a third mother liquor; (e) subjecting the [0020] Referring now to the drawings, Figure 2 illus-
solids from step (d) to a sodium sulfate/water source to trates several embodiments of the present invention.
produce anhydrous sodium sulfate; and (f) returning the [0021] The proposed process is realized as follows:
third mother liquor for conversion to potassium salts. The conversion of potash 10 and sodium sulfate 46 and/
[0015] According to further features in preferred em- 35 or 76 to potassium sulfate 42 is carried out in two reac-
bodiments of the invention described below, the source tion stages. In the first stage, or glaserite production
of sodium sulfate is Glauber's salt, semi-anhydrous so- stage, 14, the reaction can be effected at 15-100°C. But,
dium sulfate, i.e., a mixture of sodium sulfate and Glau- while reaction kinetics and crystal growth rate improve
ber's salt or partially hydrated sodium sulfate, or any so- with increasing temperature, equilibrium data show a
dium sulfate solution which can yield sodium sulfate in 40 decrease in conversion with increasing temperature,
the presence of sodium chloride, such as vanthoffite so- and energy costs increase. As a result, operating at
lution. near-ambient conditions (20-40°C) is optimal.
[0016] The present invention allows the use of inex- [0022] Potash 10, sodium sulfate 46 and/or 76,
pensive and available sources of sodium sulfate. The stream 28 from the recovery stage (described below),
invention takes advantage of the fact that the solubility 45 and brine 40 from the glaserite decomposition stage
behavior of potassium chloride differs greatly with the (described below) are introduced. The sodium sulfate
solubility behaviors of sodium chloride and sodium sul- source is primarily or exclusively anhydrous sodium sul-
fate with changing temperature. With increasing tem- fate, but some Glauber's salt and/or aqueous sodium
perature, the solubility of potassium chloride is greatly sulfate can be added (not shown). The term 'potash' is
increased, whereas the solubility of sodium chloride ris- 50 meant to indicate any potassium chloride containing
es only slightly, and that of sodium sulfate decreases or material including, for example, sylvinite.
remains constant. [0023] In the first stage 14 the sodium sulfate and pot-
[0017] The present invention also makes use of the ash dissolve, generating a supersaturation with respect
fact that the solubility of sodium sulfate decreases with to glaserite, such that glaserite is precipitated. The sys-
increasing concentration of sodium chloride. Thus, so- 55 tem can also be supersaturated with respect to sodium
dium chloride/sodium sulfate solid mixture produced at chloride, such that some sodium chloride is co-precipi-
high temperature can be added to the sodium sulfate tated. The slurry is dewatered and delivered 20 to the
feed source, such that the sodium chloride is completely glaserite decomposition stage 16. The mother liquor 26

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 5 EP 0 796 222 B1 6

has the following composition in weight%: potassium: of such impurities and can be added directly 33 to vessel
2.5-6; sodium: 7.5-10; chloride: 10-17; sulfate: 1.3-8; 72. Alternatively, a Glauber's salt containing impurities
water: the balance. The mother liquor composition cor- 35 can first be melted in a suitable melter 34, with the
responds to the points on and above the NaCl/glaserite aqueous phase 74 being filtered before being intro-
equilibrium line or to the points on and/or to the right of 5 duced to the stream 30, and the concentrated solids 76
the Na2SO4/glaserite equilibrium line. The mother liq- being used to produce glaserite in the first reaction stage
uor, which contains substantial quantities of potassium 14. Another alternative is to feed all or a portion of solid
and sulfate, is processed in the recovery stage which is phase 76 directly into filtering and washing vessel 82.
described below. [0028] The solid sodium chloride from stream 30 is not
[0024] The glaserite decomposition stage 16 is per- 10 in equilibrium in the sulfate-rich medium 72, and dis-
formed at 15-60°C, with the preferred temperature solves. The dissolved sodium chloride reduces the sol-
range being 20-40°C, due to the same considerations ubility of sodium sulfate, such that sodium sulfate is pre-
delineated in the first stage. Potash 10 and water 18 are cipitated. The sodium sulfate slurry 44 is filtered and
introduced along with the stream 20 obtained from the washed 82 thoroughly with water or clear sodium sulfate
first stage 14. The potash and glaserite solids dissolve, 15 solution 56 in counter-current fashion to obtain a low-
generating a supersaturation solely with respect to po- chloride sodium sulfate product 84, which is then dried.
tassium sulfate, such that potassium sulfate is selective- The spent wash 86 is fed into vessel 72. The effluent
ly precipitated. The maximum conversion is obtained liquor 80 from vessel 72, containing under 20 mole%
when the mother liquor approaches the KCl/K2SO4/gla- sulfate, is discharged, utilized in another process, or
serite/H2O invariant point. The potassium sulfate slurry 20 processed to produce high grade sodium chloride and
52 is dewatered and washed 22. The wet product 42 is sodium sulfate.
then dried. The mother liquor 40 removed from the re- [0029] While the invention has been described with
actor of the glaserite decomposition stage 16 is returned respect to a limited number of embodiments, it will be
to the glaserite production stage 14; the spent washwa- appreciated that many variations, modifications and oth-
ter 50, however, can be used in the glaserite decompo- 25 er applications of the invention may be made.
sition stage 16. Some or all of stages 14, 16 and 22 may
be effected in a single countercurrent differential con-
tactor. Claims
[0025] The brine 26 produced in the production of gla-
serite 14 is evaporated 60 at 70-130°C, with the pre- 30 1. A process for producing potassium sulfate or potas-
ferred range being 95-110°C, to remove water 62. If nec- sium sulfate and sodium sulfate from potash and a
essary, the brine can be filtered (not shown) prior to sodium sulfate/water source, comprising the steps
evaporation to remove any insoluble matter. The evap- of:
oration of water produces a supersaturation of sodium
salts (sodium sulfate, sodium chloride, or both, depend- 35 (a) subjecting a sodium sulfate source to con-
ing on the operating temperature, feed brine composi- version with potash in an aqueous medium to
tion, and the amount of water evaporated per unit feed). yield glaserite precipitate and a first mother liq-
Care must be taken not to over-evaporate. When over- uor;
evaporation occurs, the additional precipitation of sodi- (b) converting said glaserite precipitate with
um salts drives the mother liquor composition to the Na- 40 potash and water to produce a potassium sul-
Cl/Na2SO4/glaserite/H2O invariant point, at which point fate precipitate and a second mother liquor;
the undesirable co-precipitation of glaserite occurs. (c) returning said second mother liquor to step
[0026] After a solid/liquid separation, the potassium- (a);
enriched brine 28 is cooled 70 and returned to the gla- (d) evaporating said first mother liquor such
serite decomposition stage 14. The sodium salts 30 pro- 45 that a sodium chloride and anhydrous sodium
duced during the evaporative crystallization are subject- sulfate solids mixture is precipitated in a third
ed, in a suitable vessel 72, to a low-quality and/or water- mother liquor;
containing source of sodium sulfate 12 such as aqueous (e) subjecting said solids from step (d) to a so-
sodium sulfate, Glauber's salt, vanthoffite, or similar, dium sulfate/water source to produce anhy-
with the addition of water as necessary. Each of the 50 drous sodium sulfate; and
above-referenced, alone or in combination is referred to (f) returning said third mother liquor for conver-
hereinafter singly or collectively as "sodium sulfate/wa- sion to potassium salts.
ter source". The vanthoffite can readily be obtained by
reacting sodium chloride with astrakanite. 2. A process according to claim 1, further comprising:
[0027] In order to obtain a high quality anhydrous so- 55
dium sulfate product, the aqueous source of sodium sul- (g) returning the requisite amount of said anhy-
fate can be filtered to remove insoluble impurities. Glau- drous sodium sulfate to step (a) as raw materi-
ber's salt crystallized from clear brines is generally free al, with any excess material being removed as

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 7 EP 0 796 222 B1 8

a co-product. Kaliumsulfat und Natriumsulfat aus Pottasche und

einer Natriumsulfat-Wasserquelle, umfassend die
3. A process according to claim 1, wherein said sodi- Schritte:
um sulfate/water source includes aqueous sodium
sulfate. 5 (a) Umsetzen einer Natriumsulfatquelle mit
Pottasche in einem wässrigen Medium, so
4. A process according to claim 1, wherein said sodi- dass ein Glaserit-Niederschlag und eine erste
um sulfate/water source includes Glauber's salt. Mutterlauge erhalten werden;

5. A process according to claim 1, wherein said sodi- 10 (b) Umsetzen des Glaserit-Niederschlages mit
um sulfate/water source includes semi-anhydrous Pottasche und Wasser, so dass ein Kaliumsul-
sodium sulfate. fat-Niederschlag und eine zweite Mutterlauge
erhalten werden;
6. A process according to claim 1, wherein said sodi-
um sulfate/water source includes vanthoffite. 15 (c) Rückführen der zweiten Mutterlauge zu
Schritt (a);
7. A process according to claim 1, wherein the aque-
ous sodium sulfate is obtained by melting Glauber's (d) Eindampfen der ersten Mutterlauge, so
salt or semi-anhydrous sodium sulfate, with the sol- dass ein Feststoffgemisch aus Natriumchlorid
id sodium sulfate produced in the melter being used 20 und wasserfreiem Natriumsulfat in einer dritten
as a raw material for step (a). Mutterlauge ausgefällt wird;

8. A process according to claim 1, wherein the aque- (e) Unterwerfen der Feststoffe aus Schritt (d)
ous sodium sulfate is obtained by melting Glauber's einer Natriumsulfat-Wasserquelle, so dass
salt with the solids produced being removed as by- 25 wasserfreies Natriumsulfat erzeugt wird; und
product, and the solid sodium sulfate produced from
the aqueous sodium sulfate being used as raw ma- (f) Rückführen der dritten Mutterlauge zur Um-
terial for step (a). wandlung in Kaliumsalze.

9. A process according to claim 1, wherein at least one 30 2. Verfahren nach Anspruch 1, zudem umfassend:
of the sources of sodium sulfate source used in step
(a) is low-quality salt-cake, such that at least part of (g) Rückführen der erforderlichen Menge was-
the high-grade sodium sulfate produced can be re- serfreien Natriumsulfates zu Schritt (a) als Roh-
moved as co-product. material, wobei überschüssiges Material als
35 Coprodukt entfernt wird.
10. A process according to claim 1, wherein said third
mother liquor is subjected to conversion with Glau- 3. Verfahren nach Anspruch 1, wobei die Natriumsul-
ber's salt, wherein the reaction mixture is substan- fat-Wasserquelle wässriges Natriumsulfat enthält.
tially cooled, and wherein glaserite is precipitated
in a fourth mother liquor and recovered to step (a) 40 4. Verfahren nach Anspruch 1, wobei die Natriumsul-
and wherein the fourth mother liquor is subsequent- fat-Wasserquelle Glaubersalz enthält.
ly evaporated according to step (d).
5. Verfahren nach Anspruch 1, wobei die Natriumsul-
11. The process according to claim 1, wherein the con- fat-Wasserquelle semiwasserfreies Natriumsulfat
version of said third mother liquor is effected in-situ 45 enthält.
in step (a) with the addition of Glauber's salt, such
that glaserite is precipitated in said first mother liq- 6. Verfahren nach Anspruch 1, wobei die Natriumsul-
uor, and recovered to step (b) and wherein the first fat-Wasserquelle Vanthoffit enthält.
mother liquor is subsequently evaporated accord-
ing to step (d). 50 7. Verfahren nach Anspruch 1, wobei das wässrige
Natriumsulfat durch Schmelzen von Glaubersalz
12. The process according to claim 1, wherein said oder semiwasserfreiem Natriumsulfat erhalten
evporating includes evaporative crystallization. wird, wobei das in der Schmelzvorrichtung herge-
stellte feste Natriumsulfat als Rohmaterial für
55 Schritt (a) verwendet wird.
Patentansprüche
8. Verfahren nach Anspruch 1, wobei das wässrige
1. Verfahren zur Herstellung von Kaliumsulfat oder Natriumsulfat durch Schmelzen von Glaubersalz

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 9 EP 0 796 222 B1 10

mit den erzeugten Feststoffen erhalten wird, die als outre :

Nebenprodukte entfernt werden, und das aus dem
wässrigen Natriumsulfat hergestellte feste Natrium- (g) le retour de la quantité requise dudit sulfate
sulfat als Rohmaterial für Schritt (a) verwendet wird. de sodium anhydre à l'étape (a) comme matiè-
5 re première, toute matière en excès étant éli-
9. Verfahren nach Anspruch 1, wobei mindestens eine minée comme produit simultané.
der in Schritt (a) verwendeten Natriumsulfatquellen
ein minderwertiger Salzkuchen ist, so dass zumin- 3. Procédé selon la revendication 1, dans lequel ladite
dest ein Teil des entstandenen hochwertigen Natri- source de sulfate de sodium/eau inclut du sulfate
umsulfats als Coprodukt entfernt werden kann. 10 de sodium aqueux.

10. Verfahren nach Anspruch 1, wobei die dritte Mutter- 4. Procédé selon la revendication 1, dans lequel ladite
lauge einer Umsetzung mit Glaubersalz unterwor- source de sulfate de sodium/eau inclut du sel de
fen wird, das Reaktionsgemisch im Wesentlichen Glauber.
gekühlt wird, Glaserit in einer vierten Mutterlauge 15
ausgefällt und zu Schritt (a) rückgeführt wird, und 5. Procédé selon la revendication 1, dans lequel ladite
die vierte Mutterlauge anschließend gemäß Schritt source de sulfate de sodium/eau inclut du sulfate
(d) eingedampft wird. de sodium semi-anhydre.

11. Verfahren nach Anspruch 1, wobei in Schritt (a) die 20 6. Procédé selon la revendication 1, dans lequel ladite
Umwandlung der dritten Mutterlauge in situ unter source de sulfate de sodium/eau inclut de la van-
Zugabe von Glaubersalz erfolgt, so dass Glaserit in thoffite.
der ersten Mutterlauge ausgefällt und zu Schritt (b)
rückgeführt wird und die erste Mutterlauge an- 7. Procédé selon la revendication 1, dans lequel le sul-
schließend gemäß Schritt (d) eingedampft wird. 25 fate de sodium aqueux est obtenu en faisant fondre
du sel de Glauber ou du sulfate de sodium semi-
12. Verfahren nach Anspruch 1, wobei das Verdampfen anhydre, le sulfate de sodium solide produit dans le
Verdampfungskristallisation umfasst. four à fusion étant utilisé comme matière première
pour l'étape (a).
30
Revendications 8. Procédé selon la revendication 1, dans lequel le sul-
fate de sodium aqueux est obtenu en faisant fondre
1. Procédé de production de sulfate de potassium ou du sel de Glauber, les solides produits étant élimi-
de sulfate de potassium et de sulfate de sodium à nés comme produits secondaires, et le sulfate de
partir de potasse et d'une source de sulfate de so- 35 sodium solide produit à partir du sulfate de sodium
dium/eau, comprenant les étapes de : aqueux étant utilisé comme matière première pour
l'étape (a).
(a) la soumission d'une source de sulfate de so-
dium à la conversion avec de la potasse dans 9. Procédé selon la revendication 1, dans lequel au
un milieu aqueux pour donner un précipité de 40 moins une des sources des sources de sulfate de
glasérite et une première liqueur mère ; sodium utilisée dans l'étape (a) est un salignon de
(b) la conversion dudit précipité de glasérite faible qualité, de sorte qu'au moins une partie du
avec de la potasse et de l'eau pour produire un sulfate de sodium de qualité élevée produit peut
précipité de sulfate de potassium et une secon- être retirée comme produit simultané.
de liqueur mère ; 45
(c) le retour de ladite seconde liqueur à l'étape 10. Procédé selon la revendication 1, dans lequel ladite
(a) ; troisième liqueur mère est soumise à la conversion
(d) l'évaporation de ladite première liqueur mè- avec du sel de Glauber, dans lequel le mélange de
re de sorte qu'un mélange de solides de chlo- réaction est substantiellement refroidi, et dans le-
rure de sodium et de sulfate de sodium anhydre 50 quel la glasérite est précipitée dans une quatrième
est précipité dans une troisième liqueur mère ; liqueur mère et récupérée à l'étape (a) et dans le-
(e) la soumission desdits solides de l'étape (d) quel la quatrième liqueur mère est ultérieurement
à une source de sulfate de sodium/eau pour évaporée suivant l'étape (d).
produire du sulfate de sodium anhydre ; et (f)
le retour de la troisième liqueur mère pour la 55 11. Procédé selon la revendication 1, dans lequel la
conversion en sels de potassium. conversion de ladite troisième liqueur mère est ef-
fectuée in-situ dans l'étape (a) avec l'addition de sel
2. Procédé selon la revendication 1 comprenant en de Glauber, de sorte que la glasérite est précipitée

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 11 EP 0 796 222 B1 12

dans ladite première liqueur mère et récupérée

dans l'étape (b) et dans lequel la première liqueur
mère est ultérieurement évaporée selon l'étape (d).

12. Procédé selon la revendication 1, dans lequel ladite 5

évaporation inclut la cristallisation par évaporation.

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