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(19)

(11) EP 2 591 130 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.:

of the grant of the patent: C22B 3/38 (2006.01) C22B 26/12 (2006.01)
03.05.2017 Bulletin 2017/18 C22B 7/00 (2006.01) C01B 25/30 (2006.01)

(21) Application number: 11803831.4 (86) International application number:

PCT/KR2011/005026
(22) Date of filing: 08.07.2011
(87) International publication number:
WO 2012/005545 (12.01.2012 Gazette 2012/02)

(54) METHOD FOR ECONOMICAL EXTRACTION OF LITHIUM FROM SOLUTION INCLUDING LITHIUM
VERFAHREN ZUR WIRTSCHAFTLICHEN EXTRAKTION VON LITHIUM AUS EINER LÖSUNG MIT
LITHIUM
PROCÉDÉ POUR L’EXTRACTION ÉCONOMIQUE DE LITHIUM À PARTIR D’UNE SOLUTION
COMPRENANT DU LITHIUM

(84) Designated Contracting States: • KIM, Ki Young

AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Yongin-si
GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO Gyeonggi-do 446-916 (KR)
PL PT RO RS SE SI SK SM TR
(74) Representative: Potter Clarkson LLP
(30) Priority: 07.12.2010 KR 20100124089 The Belgrave Centre
09.07.2010 KR 20100066391 Talbot Street
Nottingham NG1 5GG (GB)
(43) Date of publication of application:
15.05.2013 Bulletin 2013/20 (56) References cited:
JP-A- 2006 057 142 JP-A- 2008 066 019
(73) Proprietor: Research Institute Of US-A1- 2003 228 251 US-B1- 6 207 126
Industrial Science & Technology
Kyungsangbuk-do 790-330 (KR) • STEVEN TANDY ET AL: "LITHIUM PRODUCTION
FROM HIGHLY SALINE DEAD SEA BRINES",
(72) Inventors: REVIEWS IN CHEMICAL ENGINEERING, REIDEL,
• CHON, Uong DORDRECHT, NL, vol. 9, no. 3-4, 1 December 1993
Pohang-si (1993-12-01), pages 293-318, XP008176938, ISSN:
Gyeongsangbuk-do 790-751 (KR) 0167-8299, DOI: 10.1515/REVCE.1993.9.3-4.293
• KWON, Oh Joon [retrieved on 2011-05-18]
Pohang-si • J.A. EPSTEIN ET AL: "Extraction of lithium from
Gyeongsangbuk-do 790-751 (KR) the dead sea", HYDROMETALLURGY, vol. 6, no.
• KIM, Ki Hong 3-4, 1 January 1981 (1981-01-01), pages 269-275,
Pohang-si XP055184426, ISSN: 0304-386X, DOI:
Gyeongsangbuk-do 790-390 (KR) 10.1016/0304-386X(81)90044-X
• SONG, Chang Ho
Incheon 406-130 (KR) Remarks:
• HAN, Gi Chun The file contains technical information submitted after
Cheongju-si
EP 2 591 130 B1

the application was filed and not included in this

Chungbuk 361-775 (KR) specification

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR)

 1 EP 2 591 130 B1
Description
Technical Field
[0001] The present invention relates to a method of
extracting lithium from a lithium bearing solution.
Background Art
[0002] The application of lithium currently extends to
diverse industries,including the rechargeable battery,
glass, ceramic, alloy, lubricant, and pharmaceutical in-
dustries. The lithium rechargeable battery has recently
been receiving attention as a main power source for hy-
brid and electric cars, and the market for lithium recharge-
able batteries for cars is expected to continue growing
to approximately one-hundred times the conventional
compact battery markets for cell phones and notebooks.
[0003] In addition, a global movement towards more
stringent environmental regulations is likely to expand
the application of lithium to not only the hybrid and electric
car industries, but to the electrical, chemical and energy
fields as well. Thus, a dramatic increase of both domestic
and foreign demand for lithium is expected.
[0004] The main sources for the lithium could be min-
erals, brine and seawater. Although minerals such as
spodumene, petalite and lepidolite contain relatively
large amountsof lithium, ranging from approximately 1 to
1.5%, the extraction involves complicated processes
such as floatation, calcining at a high temperature, grind-
ing, acid mixing, extraction, purification, concentration
and precipitation. These processes, require high energy
consumption, are considered to be cost-ineffective, and
the use of acids during the lithium extraction also causes
environmental pollution.
[0005] It has been reported that approximately
2.531011 tons of lithium is dissolved in seawater. Al-
though the majority of technologies involve inserting an
extraction device containing an absorbent into the sea-
water in order to extract lithium by treating with acids after
selectively absorbing the lithium, it is extremely inefficient
and uneconomical to directly extract the lithium from sea-
water because the concentration of lithium contained in
the seawater is limited to 0.17ppm.
[0006] Due to the aforementioned disadvantages, lith-
ium is currently extracted from brine produced from nat-
ural salt lakes, but salts such as Mg, Ca, B, Na, K, SO4
are also dissolved in the brine.
[0007] Further, the concentration of lithium contained
in the brine ranges from approximately 0.3 to 1.5g/L, and
lithium contained in the brine is usually extracted in the
form of lithium carbonate having a solubility of about
13g/L. Even assumingthat lithium contained in the brine
is completely converted to lithium carbonate, the concen-
tration of lithium carbonate in the brine is limited to 1.59
to 7.95g/L (the molecular weight of Li2CO3 is 74, and the
atomic weight of Li is 7. If the concentration of lithium is
multiplied by 5.3 (74414 6.3), the concentration of lith-
2
ium carbonate can be estimated). Since most of the lith-
ium carbonate concentration is lower than the solubility
of lithium carbonate, the extracted lithium carbonate re-
dissolves,and thus there is a problem of the lithium ex-
5 traction yield being extremely low.
[0008] Traditionally, in order to extract lithium carbon-
ate from lithium contained in brine, the brine pumped
from the natural salt lake was stored in evaporation ponds
and subsequently naturally evaporated outdoors over a
10 long period of time, for instance about one year, to con-
centrate the lithium by several tenfold. Then, the impuri-
ties such as magnesium, calcium, boron were precipitat-
ed in order to be removed, and the method required an
amount greater than the solubility of lithium carbonate to
15 precipitate.
[0009] For instance, Chinese Patent Pub. No.
1,626,443 describes a method of extracting lithium,
wherein brine is evaporated and concentrated under so-
lar heat, and the concentrate is subject to repeated elec-
20 tro-dialysis in order to obtain brine containing concen-
trated lithium with a low amount of magnesium.
[0010] ’Lithium Production From Highly Saline Dead
Sea Brines’ Tandy et al. Reviews in Chemical Engineer-
ing, vol. 9, no. 3-4, 1993 describes a method of lithium
25 extraction from Dead Sea brines through the addition of
a sodium phosphate solution.
[0011] Such conventional methods require the evapo-
ration and concentration of the brine, which are time-
consuming and unproductive, especially during rainy
30 seasons. Further, the loss of lithium is unavoidable when
lithium is precipitated along with other impurities in the
form of a salt.
Disclosure of Invention
35
Technical Problem
[0012] In accordance with an embodiment of the
present invention, a method of economical extraction of
40 high purity lithium phosphate with high extraction yield
from brine, which does not require the processes of evap-
oration and concentration of the brine for a long period
of time, by using lithium phosphate having low solubility
may be provided.
45
Solution to Problem
[0013] In accordance with an embodiment of the
present invention, a method of economical extraction of
50 lithium from a lithium bearing solution by adding a phos-
phorous supplying material to the solution to precipitate
lithium phosphate from the dissolved lithium is provided,
wherein the lithium bearing solution is brine and the con-
centration of lithium in the brine is 0.1g/L or more.
55 [0014] In one embodiment of the present invention, the
phosphorous supplying material may be one selected
from the group consisting of phosphorous, phosphoric
acid, phosphate and a mixture thereof.
2
 3 EP 2 591 130 B1
[0015] In one embodiment of the present invention, the
concentration of the lithium phosphate may be 0.39g/L
or more.
[0016] In the present invention, the concentration of
lithium in the lithium bearing solution may be 0.1g/L or
more. More specifically, the concentration may be 0.2g/L
or more, or 0.5g/L or more. The concentration of 60g/L
or more, however, may not be economical because a
great amount of time is required for the high-enrichment
of lithium.
[0017] In one embodiment of the present invention, the
method may further comprise a step of extracting lithium
phosphate by filtering the precipitated lithium phosphate
from the lithium bearing solution.
[0018] In one embodiment of the present invention, the
lithium bearing solution may be brine.
[0019] In one embodiment of the present invention, the
brine may contain impurities including magnesium, bo-
ron, calcium, or a mixture thereof.
[0020] In one embodiment of the present invention, pri-
or to precipitating lithium phosphate from dissolved lith-
ium by adding a phosphorous supplying material in the
brine, the method may further comprise a step of precip-
itating and removing impurities in the brine, including
magnesium, boron, calcium, or a mixture thereof by add-
ing a hydroxyl ion in the brine.
[0021] In one embodiment of the present invention, the
step ofprecipitating lithium phosphate from dissolved lith-
ium by adding a phosphorous supplying material may be
performed at room temperature or higher.
[0022] In one embodiment of the present invention, the
hydroxyl ion may be a negative ion of sodium hydroxide.
[0023] In one embodiment of the present invention, the
step of precipitating and removing impurities in the brine,
including magnesium, boron, calcium, or a mixture there-
of by adding a hydroxyl ion in the brine may be a step of
precipitating and removing impurities in the brine, includ-
ing magnesium, boron and calcium, by adding a hydroxyl
ion in the brine.
[0024] In one embodiment of the present invention, the
step of precipitating and removing impurities in the brine,
including magnesium, boron and calcium, by adding a
hydroxyl ion in the brine may further comprise the steps
of:(a) producing magnesium hydroxide from the magne-
sium by adding a hydroxyl ion in the brine; (b) absorbing
boron inthe magnesium hydroxide to extract magnesium
and boron by co-precipitating magnesium and boron; and
(c) precipitating calcium by adjusting the pH of the filtrate
from which magnesium and boron are removed to be at
least 12.
[0025] In one embodiment of the present invention, the
step of producing magnesium hydroxide from the mag-
nesium by adding a hydroxyl ion in the brine may be a
step of producing magnesium hydroxide from the mag-
nesium by adding a hydroxyl ion while maintaining the
pH of the brine to be in the range of 8.5 to 10.5. The step
of absorbing boron in the magnesium hydroxide to extract
magnesium and boron by co-precipitatingmagnesium
4
and boron may be performed by absorbing the boron in
the brine including the magnesium hydroxide having a
pH ranging from 8.5 to 10.5 inthe magnesium hydroxide
to extract magnesium and boron by co-precipitating mag-
5 nesium and boron. The step of producing magnesium
hydroxide from the magnesium by adding a hydroxyl ion
in the brine, while maintaining the pH of the brine to be
in the range of 8.5 to 10.5 by adding a hydroxyl ion in the
brine, and the step of absorbing the boron in the brine
10 including the magnesium hydroxide having apH ranging
from 8.5 to 10.5 in the magnesium hydroxide to extract
magnesium and boron by co-precipitatingmagnesium
and boron may be performed simultaneously.
[0026] In another embodiment of the present invention,
15 the step of precipitating lithium phosphate from dissolved
lithium by adding a phosphorous supplying material may
be followed by a step of filtering the precipitated lithium
phosphate and extracting it in the form of a high purity
powder.
20 [0027] In yet another embodiment of the present in-
vention, thestep of precipitating calcium by adjusting the
pH of the filtrate from which magnesium and boron are
removed to be at least 12 may be a step of precipitating
calcium hydroxide or calcium carbonate from calcium by
25 adding hydroxyl ion, carbonate ion, or a mixture thereof.
Advantageous Effects of Invention
[0028] In accordance with an embodiment of the
30 present invention, without the processes of evaporation
and concentration of brine for a long period of time, lithium
dissolved in the brine may be economically extracted as
lithium with high extraction yield by precipitation using
lithium phosphate having low solubility.
35
Brief Description of Drawings
[0029]
40 FIG. 1 is a graph depicting the surface charge
change of magnesium hydroxide according to the
pH of the brine.
FIG. 2 is a graph depicting the concentration change
45 of magnesium ions in the filtrate relative to the NaOH
addition amount.
FIG. 3 is a graph depicting the concentration change
of boron ions in the filtrate relative to the NaOH ad-
50 dition amount.
FIG. 4 is a graph depicting the concentration change
of lithium ions in the filtrate relative to the NaOH ad-
dition amount.
55
FIG. 5 is a graph depicting the concentration change
of calcium ions in the filtrate relative to the NaOH
addition amount.
3
 5 EP 2 591 130 B1
FIG. 6 is a graph depicting the concentration of lith-
ium relative to the reaction time when lithium phos-
phate is precipitated from lithium.
FIG. 7 is a graph depicting the concentration of lith-
ium relative to the reaction time and temperature
when lithium phosphate is precipitated from lithium.
FIG. 8 is a graph depicting the concentration of lith-
ium phosphate in the filtrate relative to the reaction
time when lithium carbonate is precipitated from lith-
ium.
Mode for the Invention
[0030] The features of one embodiment of the present
invention will be described in more detail with reference
to the figures as follows.
[0031] In accordance with an embodiment of the
present invention, a method of economical and efficient
extraction of lithium from a lithium bearing solution by
adding a phosphorous supplying material to the solution
to precipitate lithium phosphate instead of lithium car-
bonate from the dissolved lithium is provided, wherein
the lithium bearing solution is brine and the concentration
of lithium in the brine is 0.1g/L or more.
[0032] Due to its solubility being approximately 13g/L,
a relatively large amount of lithium carbonate (Li2CO3)
may be dissolved in the water. It is difficult to extract
lithium from a lithium bearing solution, such as brine, be-
cause an extremely small concentration of lithium of
0.5g/L to 1.5g/L is dissolved. Even if lithium carbonate is
produced by adding sodium carbonate to the lithium
bearing solution, most of it redissolves.
[0033] The solubility of lithium phosphate (Li3PO4),
however, is approximately 0.39g/L, which is relatively
lower than that of lithium carbonate. Accordingly, it is
possible to extract even a small concentration of 0.5g/L
or 1.5g/L of lithium dissolved in the lithium bearing solu-
tion, such as brine, which can be precipitated and sepa-
rated into lithium phosphate in a solid state by adding a
phosphorous supplying material in the lithium bearing
solution.
[0034] In the present invention, the concentration of
lithium in the lithium bearing solution is 0.1g/L or more.
More specifically, the concentration may be 0.2g/L or
more, or 0.5g/L or more. The concentration of 60g/L or
more, however, may not be economical because a great
amount of time is required for the high-enrichment of lith-
ium.
[0035] The phosphorous supplying material selected
from the group consisting of phosphorous, phosphoric
acid, phosphate, and a mixture thereof is added to the
lithium bearing solution to produce lithium phosphate. In
addition, in order for the lithium phosphate to be precip-
itated in a solid state without being re-dissolved, the con-
centration (i.e., the dissolved concentration in the lithium
bearing solution) should be 0.39g/L or greater.
6
[0036] In the case the phosphorous supplying material
is a compound capable of altering the pH of the lithium
bearing solution (e.g., phosphoric acid), hydroxide ions
can be concurrently used to prevent the precipitated lith-
5 ium phosphate from re-dissolving once the pH of the so-
lution decreases.
[0037] The phosphate may be, for example, but is not
limited thereto, potassium phosphate, sodium phos-
phate, and ammonium phosphate. Specifically, the am-
10 monium may be (NR4)3PO4, wherein R is independently
a hydrogen, a heavy hydrogen, a substituted or unsub-
stituted C1-C10 alkyl group, but not limited thereto.
[0038] More specifically, the phosphate may be, for ex-
ample, but is not limited thereto, mono-potassium phos-
15 phate, di-potassium phosphate, tri-potassium phos-
phate, monosodium phosphate, di-sodium phosphate,
tri-sodium phosphate, aluminum phosphate, zinc phos-
phate, poly-ammonium phosphate, sodium-hexa-meta-
phosphate, monocalcium phosphate, di-calcium phos-
20 phate, and tri-calcium-phosphate.
[0039] The phosphorous supplying material may be
water-soluble. In the case the phosphorous supplying
material is water-soluble, the reaction with lithium con-
tained in the lithium bearing solution may easily occur.
25 [0040] The precipitated lithium phosphate may be ex-
tracted by filtering the lithium bearing solution.
[0041] Further, the method of economical extraction of
lithium from a lithium bearing solution by adding a phos-
phorous supplying material to the solution to precipitate
30 lithium phosphate from the dissolved lithium may be per-
formed at room temperature. More specifically, the tem-
perature may be more than 20°C, 30°C, 50°Cor 90°C.
[0042] In the present invention, the term "room tem-
perature"is not limited to a definite temperature, and it is
35 construed to mean a temperature without the application
of external energy. Accordingly, the room temperature
may vary depending on time and place.
[Step of Removing Impurities Precipitates]
40
[0043] In accordance with an embodiment of the
present invention, a step of removing impurities in the
brine, including magnesium, boron or calcium, by adding
a hydroxyl ion in a lithium bearing solution (e.g., brine)
45 followed by precipitating may be included.
[0044] The hydroxyl ion may be, for example, but is
not limited thereto, sodium hydroxide, potassium hydrox-
ide, an ammonium hydroxide. Specifically, the ammoni-
um may be NR4OH, wherein R is independently a hydro-
50 gen, a heavy hydrogen, a substituted or unsubstituted
C1-C10 alkyl group, but is not limited thereto. More spe-
cifically, the hydroxide may be an anion of sodium hy-
droxide.
[0045] More specifically, the hydroxyl ion may be an
55 anion of hydroxide salt produced as a byproduct during
the extraction of lithium, because the cation of hydroxide
salt has high solubility.
[0046] In one embodiment of the present invention, the
4
 7 EP 2 591 130 B1
step of precipitating and removing impurities in the brine,
including magnesium, boron or calcium, by adding a hy-
droxyl ion in the lithium bearing solution (e.g., brine, and
hereinafter the solution is assumed to be brine) may be
a step of precipitating and removing impurities in the
brine, including magnesium, boron and calcium, by add-
ing a hydroxyl ion in the brine.
[0047] In one embodiment of the present invention, the
step of precipitating and removing impurities in the brine,
including magnesium, boron or calcium, by adding a hy-
droxyl ion in the brine may further comprise the steps of:
(a) producing magnesium hydroxide from the magnesi-
um by adding a hydroxyl ion in the brine; (b) absorbing
boron in the magnesium hydroxide to extract magnesium
and boron by co-precipitating magnesium and boron; and
(c) precipitating calcium by adjusting the pH of the filtrate
from which magnesium and boron are removed to be at
least 12.
[0048] Depending on the amount of magnesium, the
step of (a) producing magnesium hydroxide from the
magnesium by adding a hydroxyl ion in the brine and the
step of (b) absorbing boron in the magnesium hydroxide
to extract magnesium and boron by co-precipitating mag-
nesium and boron may be performed individually or con-
currently.
[0049] In other words, if a sufficient amount of magne-
sium hydroxide is produced and the produced magnesi-
um hydroxide is capable of absorbing most of the boron,
steps (a) and (b) may be performed simultaneously,
whereas the steps may be performed separately if the
amount of magnesium produced is insufficient.
[0050] In one embodiment of the present invention, for
example, the magnesium may be produced as magne-
sium hydroxide by adding a hydroxyl ion (e.g., NaOH) to
a lithium bearing brine including magnesium, boron, and
calcium.
[0051] The pH of the brine with the added hydroxyl ion
(e.g., NaOH) may be adjusted to be between 8.5 and
10.5 and subsequently, the co-precipitation of magnesi-
um and boron may be possible by absorbing boron in the
magnesium hydroxide.
[0052] The steps may be performed concurrently.
[0053] In order to elevate the pH of the brine to the
range from 8.5 to 10.5, magnesium dissolved in the brine
may be precipitated as magnesium hydroxide by adding
a hydroxyl ion (e.g., NaOH). Magnesium hydroxide is
characterized in having a low solubility of 0.009g/L, and
has a tendency to easily precipitate in a basic solution
having a pH of 8 or higher.
[0054] In addition, by maintaining the pH of the brine
to be between 8.5 and 10.5, boron (e.g.,boron ions) may
be absorbed on the surface of the produced magnesium
hydroxide to co-precipitate magnesium and boron.
[0055] In this regard, the surface charge of the mag-
nesium hydroxide can be utilized.
[0056] In general, the surface charge of the magnesi-
um hydroxide is greatly influenced by the pH of the so-
lution. When the surface charge of the magnesium hy-
8
droxide is positive, the boron ions existing in the form of
a negative ion, such as H2BO3- or HBO3 2-, are absorbed
in the magnesium hydroxide, and the magnesium and
boron dissolved in the lithium bearing solution canbe re-
5 moved by simultaneous extraction. When the surface
charge of the magnesium hydroxide is negative, howev-
er, the negatively charged boron ions are not absorbed
in the magnesium hydroxide.
[0057] If the pH of the brine is below 8.5, the removal
10 efficiency of magnesium will decline because a relatively
low pH results in an insufficient amount of precipitated
magnesium hydroxide from magnesium ions dissolved
in the brine. On the other hand, if the pH exceeds 10.5,
as seen in FIG. 1, the surface charge of magnesium hy-
15 droxide would be negatively charged, and the boron ions
cannot be absorbed thereon. Consequently, the absorb-
ance of positively charged lithium ions present in the brine
will lead to a substantial loss of lithium.
[0058] In order to simultaneously extract both magne-
20 sium and boron by precipitation, a hydroxyl ion (e.g.,
NaOH) may be added to the brine in phases, which allows
the pH maintenance of the brine to be between 8.5 to
10.5.
[0059] An adequate amount of a hydroxyl ion
25 (e.g.,NaOH) is added to the brine having nearly a neutral
pH to adjust the pH in the range between 8.5 and 10.5.
This allows the absorbance of boron (e.g.,boron ions) on
the surface charge of the magnesium hydroxide to co-
precipitate most of the magnesium and boron dissolved
30 in the brine.
[0060] In order to additionally co-precipitate the re-
maining magnesium and boron existing in the filtrate after
most of the magnesium and boron are precipitated, an
additional hydroxyl ion(e.g., NaOH) may be added to the
35 filtrate to adjust the pH to be between 8.5 and 10.5 and
subsequently precipitate the remaining magnesium and
boron.
[0061] It is preferable to add the hydroxyl ion (e.g.,
NaOH) in phases because if a large amount of the hy-
40 droxyl ion is added at onceto precipitate magnesium and
boron dissolved in the brine, the pH of the brine is not
likely to be maintained at between 8.5 and 10.5, and thus
the co-precipitation efficiency of magnesium and boron
is likely to drop as well, resulting in the loss of lithium.
45 [0062] In order to separate the precipitated magnesi-
um hydroxide absorbed with the boron from the brine, a
filtration is performed to extract magnesium and boron
simultaneously and to obtain the resulting filtrate.
[0063] Calcium may be precipitated by adding a hy-
50 droxyl ion or carbonate ion (e.g., NaOH, carbonate, or a
mixture thereof) to the filtrate from which magnesium and
boron are extracted to adjust the pH to be 12 or higher.
[0064] Depending on the types of hydroxyl ion or car-
bonate ion used, calcium hydroxide or carbonate hydrox-
55 ide may be precipitated.
[0065] If the filtration step to separate the precipitated
magnesium hydroxide absorbed with the boron from the
brine is omitted, and the pH is adjusted to be 12 or higher
5
 9 EP 2 591 130 B1
to eliminate calcium, the surface charge of magnesium
hydroxide would be converted to negative,because the
pH of the brine deviates from the range of 8.5 and 10.5.
In this case, the boron absorbed inthe magnesium hy-
droxide will be desorbed, and instead, positive lithium
ions will be absorbed, causing both the loss of lithium
and a decrease in the boron extraction yield.
[0066] The calcium hydroxide and the calcium carbon-
ate, having very lowsolubility, are easily precipitated
when the pH is 12 or higher. Thus, it is preferable to
maintain the pH of the filtrate to be 12 or higher.
[0067] In one embodiment of the present invention, for
example, a mixture of an alkali and carbonate can be
added.
[0068] The alkali is selected from the group consisting
of NaOH, KOH, Ca(OH)2, NH4OH, R4NOH·5H20 and a
mixture thereof, wherein R is independently a C1-C10
alkyl group, such as, miethyl, ethyl, propyl or butyl.
[0069] Since OH-supplied from the addition of the alkali
(e.g., NaOH) is used up in the production of calcium hy-
droxide, a significant amount of alkali (e.g., NaOH) is
added in order to maintain the pH level of the lithium
bearing solution to be at least 12. When the calcium car-
bonate is added alone or in combination with the alkali
(e.g., NaOH), the pH could be economically maintained
to be at least 12 even if the amount of alkali could be
relatively reduced.
[0070] The carbonate is selected from the group hav-
ing high solubility consisting of Na2CO3 , K2CO3, and a
mixture thereof, and sodium and potassium included in
the carbonate are dissolved in the filtrate. The precipitat-
ed calcium hydroxide or calcium carbonate is separated
from the remaining filtrate, and subsequently calcium is
extracted.
[Step of Precipitating Lithium Phosphate]
[0071] A phosphate supplying material may be added
to the remaining filtrate from which the impurities are re-
moved to precipitate lithium phosphate from lithium con-
tained in the brine.
[0072] The step of precipitating lithium phosphate from
the lithium bearing brine may be performed at room tem-
perature or above, or at 40°Cor above. More specifically,
the step may be performed at 50°Cor above, 60°Cor
above, 70°Cor above, 80°Cor above, or 90°Cor above.
[0073] The phosphorous supplying material may be
selected from the group consisting of phosphorous,
phosphoric acid, phosphate, and a mixture thereof.
[0074] In order for the lithium phosphate to be precip-
itated in a solid state without being re-dissolved, the con-
centration (i.e., the dissolved concentration in the lithium
bearing solution) should be 0.39g/L or greater.
[0075] The phosphate may be, for example, but is not
limited thereto, potassium phosphate, sodium phos-
phate, and ammonium phosphate. Specifically, the am-
monium may be (NR4)3PO 4, wherein R is independently
a hydrogen, a heavy hydrogen, a substituted or unsub-
10
stituted C1-C10 alkyl group, but not limited thereto.
[0076] More specifically, the phosphate may be, for ex-
ample, but is not limited thereto, mono-potassium phos-
phate, di-potassium phosphate, tri-potassium phos-
5 phate, monosodium phosphate, di-sodium phosphate,
tri-sodium phosphate, aluminum phosphate, zinc phos-
phate, poly-ammonium phosphate, sodium-hexa-meta-
phosphate, mono-calcium, phosphate, di-calcium phos-
phate, and tri-calcium-phosphate.
10 [0077] The phosphorous supplying material may be
water-soluble. In the case the phosphorous supplying
material is water-soluble, the reaction with lithium con-
tained in the lithium bearing solution may easily occur.
[0078] Further, after the phosphorous supplying mate-
15 rial is added, the filtrate is calcinatedfor 10 to 15 minutes
at room temperature, or at a temperature range of
40-200°C, 50-200°C, 60-200°C, 70-200°C, 80-200°C, or
90-200°C.
[0079] Although it is advantageous to extend the cal-
20 cining time and raise the temperature for the purpose of
producing lithium phosphate, if the calcining time ex-
ceeds 15 minutes or if the calcining temperature exceeds
200°C the production yield of lithium phosphate may be
saturated.
25
[Step of Extracting Lithium Phosphate]
[0080] After precipitating lithium phosphate from lithi-
um dissolved in the brine, the step of extracting the pre-
30 cipitated lithium phosphate filtered from the filtrate may
be performed.
[0081] Upon such filtration, the extracted lithium phos-
phate may be washed to obtain high purity lithium phos-
phate powder.
35 [0082] The present invention is further illustrated by
the following examples, although the following examples
relate to preferred embodiments and are not to be con-
strued as limiting on the scope of the invention.
40 [Example 1]
[0083] NaOH was added to brine containing magnesi-
um ions 20,000ppm, boron ions 900ppm, calcium
ions350ppm, and lithium ions 900ppm to precipitate mag-
45 nesium hydroxide. While adjusting the pH of the brine,
the surface charge of the precipitated magnesium hy-
droxide was measured. The results are shown in FIG. 1.
[0084] As shown in FIG. 1, the surface charge of the
magnesium hydroxide was maintained with a positive
50 charge when the pH range of the NaOH added brine was
between 8.5 and 10.5. Accordingly, the boron ions with
a negative charge were easily absorbed on the magne-
sium hyrdroxide, and the positively charged lithium ions
were prevented from being absorbed. This minimized the
55 loss of lithium, and efficiently extracted both magnesium
and boron from the brine at the same time.
6
 11 EP 2 591 130 B1
[Example 2]
[0085] While altering the pH, magnesium hydroxide
was precipitated from the brine containing magnesium
ions20,000ppm, boron ions 900ppm, calcium ions
350ppm, and lithium ions900ppm. Subsequently, a filtra-
tion was performed to separate the precipitated magne-
sium hydroxide from the brine. The filtrate was collected
to measure the amount of magnesium, boron and lithium.
The results are shown in FIGs.2, 3, and 4, respectively.
[0086] As shown in FIG. 2, an increase in the amount
of NaOH added had no significant impact on the pH of
the brine in the beginning, because OH- ion was used for
the production of magnesium hydroxide. However, a con-
tinuous increase in the amount of NaOH gradually de-
creased the magnesium amount in the filtrate, and as the
OH- ion increased, the amount of magnesium decreased-
to 4ppm once the pH of the brine reached 9.8. This indi-
catedthat 99.8% of the magnesium ions dissolved in the
brine wereextracted.
[0087] Inaddition, as shown in FIG. 3, the amount of
boron ions dissolved in the brine initially decreased as
the amount of NaOH added increased. This may be ex-
plained by the fact that the pH change could be insignif-
icantly affected by the addition of NaOH in the beginning,
and the surface charge of the magnesium hydroxide pre-
cipitated from the brine having a pH value of 10.5 or lower
had a positive charge. Thus, the negatively charged bo-
ron ions present in the filtrate were precipitated while
adsorbed on the surface of the magnesium hydroxide.
[0088] As seen in FIG. 4, the amount of lithum ions
present in the filtrate were initially not influenced by the
addedamount of NaOH. This could be explained by the
fact that the positively charged lithium ionsexisting in the
lithium bearing solution were not absorbed inthe magne-
sium hydroxide because the surface charge of magne-
sium hydroxide had a positive charge in the beginning.
If an excessive amount of NaOH was added, however,
the pH of the brine surpassed 10.5. Then,the surface
charge of the magnesium hydroxide was converted to a
negative charge and the negatively charged boron ions
werenot absorbed to the surface. Consequently, the con-
centration of boron ionsexisting in the filtrate dramatically
increased. On the contrary, the concentration of positive-
ly charged lithium ions existing in the filtrate rapidly de-
creased as the lithium ions were absorbed to the surface
of the magnesium hydroxide.
[0089] Accordingly, these results indicate that the add-
ed amount of NaOHmust be controlled to maintain the
pH of the brine to be between 8.5 and 10.5 in order to
extract magnesium and boron simultaneously, while min-
imizing the loss of lithium from the brine.
[Example 3]
[0090] NaOH wasadded to the brine containing mag-
nesium ions 20,000ppm, boron ions900ppm, calcium
ions 350ppm, and lithium ions 900ppm to precipitate cal-
12
cium hydroxide from the solution containing calcium ions.
Subsequently, a filtration was performed to separate the
precipitated calcium hydroxide from the brine. The re-
sulting filtrate was collectedto measure the amount of
5 calcium. The result is shown in FIG. 5.
[0091] As shown in FIG. 5, as the added amount of
NaOH increased, the amount of calcium in the filtrate
gradually decreased. When the pH of the brine reached
12, the amount of calcium was reduced to be 6.5ppm,
10 and 98% of the calcium ions dissolved in the brine was
extracted. Accordingly, it is preferable to increase the pH
of the lithium bearing solution to be at least 12 in order
to enhance the extract yield of the calcium ions from the
brine.
15 [0092] However, when the pH of the brine was prema-
turely adjusted to be at least 12 in the beginning, the
surface charge of the precipitated magnesium hydroxide
had a negative charge. This prevented the absorbance
of the boron ions and caused the loss of lithium due to
20 the absorbance of positively charged lithium ions. Prior
to extracting calcium by adding NaOH, the pH of the brine
was adjusted to be between 8.5 and 10.5 so that the
magnesium hydroxide having a positive charge was pre-
cipitated to prevent the absorbance of the lithium ions.
25 Once the boron ions were absorbed, the simultaneous
extraction of magnesium and boron was performed.
Then, the pH of the remaining filtrate from which mag-
nesium and boron were extracted wasadjusted to be at
least 12 to precipitate the calcium hydroxide from calci-
30 um.
[Example 4]
[0093] The impurities, including magnesium, calcium
35 and boron, were removed from the brine, and 7.217g/L
of sodium phosphate was added to the remaining filtrate
dissolved with the concentration of lithium ions being
0.917g/L. The filtrate was maintained to be reacted for
15 to 60 minutes, while elevating the temperature to
40 90°C.
[0094] Once the reaction was completed, the precipi-
tated lithium phosphate was separated by filtering, and
the remaining filtrate was collected to measure the con-
centration of lithium. The result is shown in FIG. 6.
45 [0095] As shown in FIG. 6, the concentration of lithium
in the filtrate initially decreased dramatically when sodi-
um phosphate was added to the brine. After the reaction
time passed 15 minutes, the concentration of lithium in
the filtrate came to be below 50 mg/ L. This indicated that
50 more than 95% of lithium dissolved in the brine was pre-
cipitated and separated as lithium phosphate.
[0096] Since the solubility of lithium phosphate is ap-
proximately 0.39g/L, which is much lower than the solu-
bility of lithium carbonate, adding a material including
55 phosphorous, such as sodium phosphate, in the brine
precipitated lithium phosphate in the form of solid from a
small amount of lithium dissolved in the brine. In addition,
as can be seen in FIG. 7, if the calcining temperature
7
 13 EP 2 591 130 B1
exceeded 90°C the lithium extraction yield was more than
90% after the reaction time of 10 minutes, and the yield
was more than 95% after 15 minutes.
[Comparative Example 1]
[0097] The impurities, including magnesium, calcium
and boron, were removed from the brine, and 7g/L of
sodium carbonatewas added to the remaining filtrate dis-
solved with the concentration of lithium ions being
0.917g/L. The filtrate was maintained to be reacted for
15 to 60 minutes, while elevating the temperature to 90°C
[0098] Once the reaction was completed, the precipi-
tated lithium carbonate was separated by filtering, and
the remaining filtrate was collected to measure the con-
centration of lithium. The result is shown in FIG. 8.
[0099] As shown in FIG. 8, even if sodium carbonate
was added to the lithium bearing solution, and reacted
for 15 to 60 minutes, the concentration of lithium in the
filtrate was almost identical to the concentration of lithium
in the brine prior to the reaction.
[0100] In other words, due to its high solubility of ap-
proximately 13g/L, a large amount of lithium carbonate
can be dissolved in the water. Therefore, it would be ex-
tremely difficult to extract a small amount of lithium dis-
solved in the brine in the form of lithium carbonate, unless
the precipitation amount of lithium carbonate is increased
by evaporation and concentration of the brine.
[0101] By precipitating lithium dissolved in the brine by
using lithium phosphate having a low solubility, the proc-
esses of evaporation as well as concentration of brine
are not required, and the economical extraction of lithium
with high extraction yield, while minimizing the loss of
lithium, may be possible.
[0102] In the foregoing specification, specific embodi-
ments of the present invention have been described.
[0103] Accordingly, the specification and figures are to
be regarded in an illustrative rather than a restrictive
sense, and all such modifications are intended to be in-
cluded within the scope of present invention. The bene-
fits, advantages, solutions to problems, and any ele-
ment(s) that may cause any benefit, advantage, or solu-
tion to occur or become more pronounced are not to be
construed as a critical, required, or essential features or
elements as described herein.
Claims
1. A method of economical extraction of lithium from a
lithium bearing solution by adding a phosphorous
supplying material to the solution to precipitate lith-
ium phosphate from the dissolved lithium, and
wherein the lithium bearing solution is brine, and the
concentration of lithium in the brine is 0.1 g/L or more.
2. The method according to claim 1, wherein the phos-
phorous supplying material is one selected from the
14
group consisting of phosphorous, phosphoric acid,
phosphate, and a mixture thereof.
3. The method according to claim 1, wherein the total
5 concentration of the lithium phosphate in brine is
0.39g/L or more.
4. The method according to claim 1, wherein the con-
centration of lithium in the lithium bearing solution is
10 0.1g/L to 1.5g/L.
5. The method according to claim 1, wherein the meth-
od further comprises a step of precipitating and re-
moving impurities in the brine, including magnesium,
15 boron, calcium or a mixture thereof by adding a hy-
droxyl ion in the brine prior to precipitating lithium
phosphate from dissolved lithium by adding a phos-
phorous supplying material in the brine.
20 6. The method according to claim 1, wherein the step
of precipitating lithium phosphate from dissolved lith-
ium by adding a phosphorous supplying material is
performed at room temperature or higher.
25 7. The method according to claim 1, wherein the step
of precipitating lithium phosphate from dissolved lith-
ium by adding a phosphorous supplying material is
performed at 90°C or higher.
30 8. The method according to claim 5, wherein the hy-
droxyl ion is a negative ion of sodium hydroxide.
9. The method according to claim 5, wherein the step
of precipitating and removing impurities in the brine,
35 including magnesium, boron, calcium, or a mixture
thereof by adding a hydroxyl ion in the brine is a step
of precipitating and removing impurities in the brine,
including magnesium, boron and calcium, by adding
a hydroxyl ion in the brine.
40
10. The method according to claim 9, wherein the step
of precipitating and removing impurities in the brine,
including magnesium, boron and calcium, by adding
a hydroxyl ion in the brine further comprises the steps
45 of:
(a) producing magnesium hydroxide from the
magnesium by adding a hydroxyl ion in the brine;
(b) absorbing boron in the magnesium hydrox-
50 ide to extract magnesium and boron by co-pre-
cipitating magnesium and boron; and
(c) precipitating calcium by adjusting the pH of
the filtrate from which magnesium and boron are
removed to be at least 12.
55
11. The method according to claim 10, wherein the step
of producing magnesium hydroxide from the mag-
nesium by adding a hydroxyl ion in the brine is a step
8
 15 EP 2 591 130 B1
of producing magnesium hydroxide from the mag-
nesium by adding a hydroxyl ion while maintaining
the pH of the brine to be in the range of 8.5 to 10.5
the step of absorbing boron in the magnesium hy-
droxide to extract magnesium and boron by co-pre-
cipitating magnesium and boron is a step of absorb-
ing the boron in the brine including the magnesium
hydroxide having a pH ranging from 8.5 to 10.5 in
the magnesium hydroxide to extract magnesium and
boron by co-precipitating magnesium and boron and
the step of producing magnesium hydroxide from the
magnesium by adding a hydroxyl ion in the brine,
while maintaining the pH of the brine to be in the
range of 8.5 to 10.5 by adding a hydroxyl ion in the
brine, and the step of absorbing the boron in the brine
including the magnesium hydroxide having a pH
ranging from 8.5 to 10.5 in the magnesium hydroxide
to extract magnesium and boron by co-precipitating
magnesium and boron is performed simultaneously.
12. The method according to claim 5, wherein the step
of precipitating lithium phosphate from dissolved lith-
ium by adding a phosphorous supplying material is
followed by a step of filtering the precipitated lithium
phosphate and extracting it in the form of a high purity
powder.
13. The method according to claim 10, wherein the step
of precipitating calcium by adjusting the pH of the
filtrate from which magnesium and boron are re-
moved to be at least 12 is a step of precipitating
calcium hydroxide or calcium carbonate from calci-
um by adding hydroxyl ion, carbonate ion, or a mix-
ture thereof.
Revendications
1. Procédé d’extraction économique de lithium à partir
d’une solution renfermant du lithium par ajout d’un
matériau d’alimentation phosphoreux à la solution
pour précipiter le phosphate de lithium à partir du
lithium dissous, et
dans lequel la solution renfermant du lithium est une
saumure, et la concentration en lithium dans la sau-
mure est de 0,1 g/l ou plus.
2. Procédé selon la revendication 1, dans lequel le ma-
tériau d’alimentation en phosphore est un élément
choisi dans le groupe constitué du phosphore, de
l’acide phosphorique, du phosphate et d’un mélange
de ceux-ci.
3. Procédé selon la revendication 1, dans lequel la con-
centration totale en phosphate de lithium dans la
saumure est de 0,39 g/l ou plus.
4. Procédé selon la revendication 1, dans lequel la con-
16
centration en lithium dans la solution renfermant du
lithium est de 0,1 g/l à 1,5 g/l.
5. Procédé selon la revendication 1, dans lequel le pro-
5 cédé comprend en outre une étape de précipitation
et d’élimination d’impuretés dans la saumure, in-
cluant le magnésium, le bore, le calcium ou un mé-
lange de ceux-ci par ajout d’un ion hydroxyle dans
la saumure avant de précipiter le phosphate de li-
10 thium à partir de lithium dissous par ajout d’un ma-
tériau d’alimentation phosphoreux dans la saumure.
6. Procédé selon la revendication 1, dans lequel l’étape
de précipitation de phosphate de lithium à partir de
15 lithium dissous par ajout d’un matériau d’alimenta-
tion phosphoreux est réalisée à température am-
biante ou plus.
7. Procédé selon la revendication 1, dans lequel l’étape
20 de précipitation de phosphate de lithium à partir de
lithium dissous par ajout d’un matériau d’alimenta-
tion phosphoreux est réalisée à 90 °C ou plus.
8. Procédé selon la revendication 5, dans lequel l’ion
25 hydroxyle est un ion négatif d’hydroxyde de sodium.
9. Procédé selon la revendication 5, dans lequel l’étape
de précipitation et d’élimination d’impuretés dans la
saumure, incluant le magnésium, le bore, le calcium
30 ou un mélange de ceux-ci par ajout d’un ion hydroxy-
le dans la saumure, est une étape de précipitation
et d’élimination d’impuretés dans la saumure, in-
cluant le magnésium, le bore et le calcium, par ajout
d’un ion hydroxyle dans la saumure.
35
10. Procédé selon la revendication 9, dans lequel l’étape
de précipitation et d’élimination d’impuretés dans la
saumure, incluant le magnésium, le bore et le cal-
cium, par ajout d’un ion hydroxyle dans la saumure
40 comprend en outre les étapes de :
(a) production d’hydroxyde de magnésium à
partir du magnésium par ajout d’un ion hydroxyle
dans la saumure ;
45 (b) absorption de bore dans l’hydroxyde de ma-
gnésium pour extraire le magnésium et le bore
par coprécipitation de magnésium et de bore ; et
(c) précipitation de calcium par ajustement du
pH du filtrat duquel le magnésium et le bore sont
50 éliminés pour qu’il soit d’au moins 12.
11. Procédé selon la revendication 10, dans lequel l’éta-
pe de production d’hydroxyde de magnésium à partir
du magnésium par ajout d’un ion hydroxyle dans la
55 saumure est une étape de production d’hydroxyde
de magnésium à partir du magnésium par ajout d’un
ion hydroxyle tout en conservant le pH de la saumure
dans la plage de 8,5 à 10,5
9
 17 EP 2 591 130 B1
l’étape d’absorption de bore dans l’hydroxyde de ma-
gnésium pour extraire le magnésium et le bore par
coprécipitation de magnésium et de bore est une
étape d’absorption du bore dans la saumure incluant
l’hydroxyde de magnésium ayant un pH allant de 8,5
à 10,5 dans l’hydroxyde de magnésium pour extraire
le magnésium et le bore par coprécipitation de ma-
gnésium et de bore et
l’étape de production d’hydroxyde de magnésium à
partir du magnésium par ajout d’un ion hydroxyle
dans la saumure, tout en conservant le pH de la sau-
mure dans la plage de 8,5 à 10,5 par ajout d’un ion
hydroxyle dans la saumure, et l’étape d’absorption
du bore dans la saumure incluant l’hydroxyde de ma-
gnésium ayant un pH allant de 8,5 à 10,5 dans l’hy-
droxyde de magnésium pour extraire le magnésium
et le bore par coprécipitation de magnésium et de
bore sont réalisées simultanément.
12. Procédé selon la revendication 5, dans lequel l’étape
de précipitation de phosphate de lithium à partir de
lithium dissous par ajout d’un matériau d’alimenta-
tion phosphoreux est suivie d’une étape de filtration
du phosphate de lithium précipité et de son extrac-
tion sous forme d’une poudre de grande pureté.
13. Procédé selon la revendication 10, dans lequel l’éta-
pe de précipitation de calcium par ajustement du pH
du filtrat duquel le magnésium et le bore sont élimi-
nés pour qu’il soit d’au moins 12 est une étape de
précipitation d’hydroxyde de calcium ou de carbo-
nate de calcium à partir de calcium par ajout d’un
ion hydroxyle, d’un ion carbonate ou d’un mélange
de ceux-ci.
Patentansprüche
1. Verfahren zum wirtschaftlichen Extrahieren von Li-
thium aus einer Lithium enthaltenden Lösung durch
Hinzufügen eines Phosphor beitragenden Materials
zu der Lösung, um Lithiumphosphat aus dem gelös-
ten Lithium auszufällen, und
wobei die Lithium enthaltende Lösung Salzlösung
ist und die Konzentration von Lithium in der Salzlö-
sung wenigstens 0,1 g/l beträgt.
2. Verfahren nach Anspruch 1, wobei das Phosphor
beitragende Material eines ist, das ausgewählt ist
aus der Gruppe bestehend aus Phosphor, Phos-
phorsäure, Phosphat und einem Gemisch daraus.
3. Verfahren nach Anspruch 1, wobei eine Gesamtkon-
zentration des Lithiumphosphats in Salzlösung we-
nigstens 0,39 g/l beträgt.
4. Verfahren nach Anspruch 1, wobei die Konzentrati-
on von Lithium in der Lithium enthaltenden Lösung
18
0,1 g/l bis 1,5 g/l beträgt.
5. Verfahren nach Anspruch 1, wobei das Verfahren
ferner einen Schritt des Ausfällens und des Entfer-
5 nens von Verunreinigungen, einschließlich Magne-
sium, Bor, Calcium oder einer Mischung daraus, aus
der Salzlösung durch Hinzufügen eines Hydroxyli-
ons in die Salzlösung vor dem Ausfällen von Lithi-
umphosphat aus gelöstem Lithium durch Hinzufü-
10 gen eines Phosphor bereitstellenden Materials zu
der Salzlösung umfasst.
6. Verfahren nach Anspruch 1, wobei der Schritt des
Ausfällens von Lithiumphosphat aus gelöstem Lithi-
15 um durch Hinzufügen eines Phosphor bereitstellen-
den Materials bei Raumtemperatur oder einer höhe-
ren Temperatur durchgeführt wird.
7. Verfahren nach Anspruch 1, wobei der Schritt des
20 Ausfällens von Lithiumphosphat aus gelöstem Lithi-
um durch Hinzufügen eines Phosphor bereitstellen-
den Materials bei 90 °C oder einer höheren Tempe-
ratur durchgeführt wird.
25 8. Verfahren nach Anspruch 5, wobei das Hydroxylion
ein negatives Natriumhydroxidion ist.
9. Verfahren nach Anspruch 5, wobei der Schritt des
Ausfällens und des Entfernens von Verunreinigun-
30 gen, einschließlich Magnesium, Bor, Calcium oder
einer Mischung daraus, aus der Salzlösung durch
Hinzufügen eines Hydroxylions in die Salzlösung ein
Schritt des Ausfällens und des Entfernens von Ver-
unreinigungen, einschließlich Magnesium, Bor und
35 Calcium, aus der Salzlösung durch Hinzufügen ei-
nes Hydroxylions in die Salzlösung ist.
10. Verfahren nach Anspruch 9, wobei der Schritt des
Ausfällens und des Entfernens von Verunreinigun-
40 gen, einschließlich Magnesium, Bor und Calcium, in
der Salzlösung durch Hinzufügen eines Hydroxyli-
ons in die Salzlösung ferner die folgenden Schritte
umfasst:
45 (a) Erzeugen von Magnesiumhydroxid aus dem
Magnesium durch Hinzufügen eines Hydroxyli-
ons in die Salzlösung;
(b) Absorbieren von Bor in dem Magnesiumhy-
droxid, um Magnesium und Bor durch gleichzei-
50 tiges Ausfällen von Magnesium und Bor zu er-
halten; und
(c) Ausfällen von Calcium durch Einstellen des
pH-Werts des Filtrats, aus dem Magnesium und
Bor entnommen werden, auf wenigstens 12.
55
11. Verfahren nach Anspruch 10, wobei der Schritt des
Erzeugens von Magnesiumhydroxid aus dem Mag-
nesium durch Hinzufügen eines Hydroxylions in die
10
 19 EP 2 591 130 B1 20

Salzlösung ein Schritt zum Erzeugen von Magnesi-

umhydroxid aus dem Magnesium durch Hinzufügen
eines Hydroxylions ist, bei dem der pH-Wert der
Salzlösung im Bereich 8,5 bis 10,5 gehalten wird,
der Schritt des Absorbierens von Bor in dem Mag- 5
nesiumhydroxid zum Extrahieren von Magnesium
und Bor durch gemeinsames Ausfällen von Magne-
sium und Bor ein Schritt des Absorbierens von Bor
in der Salzlösung, bei dem das Magnesiumhydroxid
einen pH-Wert von 8,5 bis 10,5 aufweist, in dem Ma- 10
gnesiumhydroxid zum Extrahieren von Magnesium
und Bor durch gemeinsames Ausfällen von Magne-
sium und Bor ist, und
der Schritt des Erzeugens von Magnesiumhydroxid
aus dem Magnesium durch Hinzufügen eines Hy- 15
droxylions zu der Salzlösung, bei dem der pH-Wert
der Salzlösung im Bereich 8,5 bis 10,5 gehalten wird,
indem ein Hydroxylion in die Salzlösung gegeben
wird, und der Schritt des Absorbierens von Bor in
der Salzlösung, bei dem das Magnesiumhydroxid ei- 20
nen pH-Wert von 8,5 bis 10,5 aufweist, in dem Ma-
gnesiumhydroxid zum Extrahieren von Magnesium
und Bor durch gemeinsames Ausfällen von Magne-
sium und Bor, gleichzeitig ausgeführt werden.
25
12. Verfahren nach Anspruch 5, wobei der Schritt des
Ausfällens von Lithiumphosphat aus gelöstem Lithi-
um durch Hinzufügen eines Phosphor bereitstellen-
den Materials gefolgt wird von einem Schritt des Fil-
terns des ausgefällten Lithiumphosphats und des 30
Extrahierens desselben in der Form eines hochrei-
nen Pulvers.

13. Verfahren nach Anspruch 10, wobei der Schritt des

Ausfällens von Calcium durch Einstellen des pH- 35
Werts des Filtrats, aus dem Magnesium und Bor ent-
fernt werden, auf wenigstens 12 ein Schritt des Aus-
fällens von Calciumhydroxid oder Calciumcarbonat
aus Calcium durch Hinzufügen eines Hydroxylions,
eines Carbonations oder einer Mischung aus diesen 40
ist.

45

50

55

11
EP 2 591 130 B1

12
EP 2 591 130 B1

13
EP 2 591 130 B1

14
EP 2 591 130 B1

15
 EP 2 591 130 B1

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• CN 1626443 [0009]

Non-patent literature cited in the description

• TANDY et al. Lithium Production From Highly Saline

Dead Sea Brines. Reviews in Chemical Engineering,
1993, vol. 9 (3-4 [0010]

16