US011396452B2

( 12) United States Patent ( 10) Patent No .: US 11,396,452 B2

Riabtsev et al . (45 ) Date of Patent : Jul . 26 , 2022
( 54 ) METHOD FOR PREPARING LITHIUM ( 30 ) Foreign Application Priority Data
CONCENTRATE FROM LITHIUM-BEARING
NATURAL BRINES AND PROCESSING Apr. 14 , 2017 ( RU ) RU2017113039
THEREOF INTO LITHIUM CHLORIDE OR
LITHIUM CARBONATE (51 ) Int. Ci .
B01J 47/02 (2017.01 )
( 71 ) Applicant: Ecostar-Nautech Co. , Ltd. , COID 15/04 (2006.01 )
Novosibirskaia oblast ( RU) COID 15/08 ( 2006.01 )
(52) U.S. CI.
( 72 ) Inventors: Aleksandr Dmitriyevich Riabtsev, CPC COID 15/04 (2013.01 ) ; B01J 47/02
Novosibirsk (RU ); Natalya Pavlovna (2013.01 ) ; COID 15/08 ( 2013.01 ) ; COIP
Kotcupalo , Novosibirsk ( RU ) ; Valeriy 2006/80 ( 2013.01 )
Ivanovich Titarenko , Novosibirsk ( 58 ) Field of Classification Search
(RU ); Larisa Timofeyevna Menzheres, CPC . C01D 15/04 ; C01D 15/08 ; C01F 5/24 ; C01F
Novosibirsk (RU ); Elena Viktorovna 11/181 ; CO1F 5/14 ; BO1J 45/00 ;
Mamylova , Novosibirsk (RU );
Aleksandr Aleksandrovich Kurakov, ( Continued )
Novosibirsk (RU ); Nikolay (56) References Cited
Mikhaylovich Nemkov, Novosibirsk
( RU) ; Andrey Aleksandrovich U.S. PATENT DOCUMENTS
Kurakov , Novosibirsk (RU ); Sergei
Aleksandrovich Antonov , Novosibirsk 4,159,311 A 6/1979 Lee et al .
(RU ) ; Elizaveta Petrovna Gushchina , 4,221,767 A 9/1980 Lee et al .
Novosibirsk (RU ) (Continued )
( 73 ) Assignee : ECOSTAR - NAUTECH CO . , LTD ., FOREIGN PATENT DOCUMENTS
Novosibirsk (RU )
CL 44210 6/2004
( * ) Notice: Subject to any disclaimer, the term of this CL 53829 6/2013
patent is extended or adjusted under 35 ( Continued )
U.S.C. 154 ( b ) by 423 days .
( 21 ) Appl . No .: OTHER PUBLICATIONS
16 /605,127
Apr. 13 , 2018 Y. I. Ostroushko , T. V. Degtyareva Hydromineral raw material is a
(22 ) PCT Filed : sustainable lithium source . Analytical review . TSNIATOMINFORM ,
1999, 64 p.
( 86) PCT No .: PCT/RU2018/ 050041
( Continued )
$ 371 (c ) ( 1 ) , Primary Examiner Timothy C Vanoy
( 2) Date : Oct. 14 , 2019
(74 ) Attorney, Agent, or Firm -Calfee Halter &
( 87 ) PCT Pub . No .: WO2018 /190754 Griswold LLP
PCT Pub . Date : Oct. 18 , 2018 (57) ABSTRACT
(65 ) Prior Publication Data A method for preparing lithium concentrate from natural
lithium -bearing brines was developed . The brine is first
US 2021/0139339 A1 May 13 , 2021 ( Continued )
WL - I
Odginal natural bom
Pulp

Filio DGAL- With WL - 1 Sadimentation

vembilan
waspletno
w.th
C: ( clarified
Sainted DGAI- CI Jaru??l trlm .
with L - 1
Prodiputo
of mechanical
umpturstice Pine Silirion
Displace WL- ) Filter generation
to the be
Core CDUAL dre parifled isom
Satprised DCAT.C1 with Ebatical impuries
Midual brine
WL - 3 WTU - I

Heated brinc to
Dispiac en DEWL - 2 sorpulon at Lici
fron sheets 1.2 , 19
Completion FOGALAT
will Lici
WL.Z Saturated VLDCAL-3 - CI WELCH
WL - 4 Sarotido cf lici
first step
DGA_C1stwution with :C :
Dispiace Of WL - 3 GAL - Cl saturated with
LiCi with bride Natural brine partialis
WL - 9 open with respect
Satursed DGALIC' with toLiC
W2-4 Banc draining ! Criginal DGAL - C
VL? Princ TEISIMI
sxcond stop
Dissement of HL - 4 (HO ) DGAI.ch DGAL -Cl partial
Pod wpliquol'L ' TITI turned the LILI | amrated atLIU
the saturated sodbeni
DGAL - C Fit WL - 5 Satu I couplechy
Perius, ensukur
sexy momsbxt43
spenuh per TO
Lel
Displacement of WL-S
? cuputih
LICE
Primary lilura Elexrption of Lia
tirst step Pilation
SOULMIK I Shex : 2
Patty Small fraction of DGAL - Cl to Bnining will
megnezted produbon of amate proca hanc
kete ,condensate
of secondary seanu DGAL -CI LICI DGALI sheets 1.2.1
froskets 1.2.1.3 ???
Reyxation heating
ILO DCBOTPRIOD OF LIGI Aual htte parl with
second step TEPL to Licland cooled
olurilor processT UTLO
purpoginto sale or into
statuen
Completely record DGAL -CU
 US 11,396,452 B2
Page 2

subjected to purification from the suspended solids , then 4,477,367 A 10/1984 Burba , III
filtered through a static layer of a granulated sorbent based 5,219,550 A 6/1993 Brown et al.
5,389,349 A 2/1995 Bauman et al .
on LiCl.2Al (OH ) 3.mH20 , where m=3-5 , to obtain a primary 5,599,516 A 2/1997 Bauman et al .
lithium concentrate . The process is carried out in sorption 6,207,126 B1 3/2001 Boryta et al.
desorption units consisting of 4 columns, two of which are 7,157,065 B2 1/2007 Boryta et al.
in the process of sorption of lithium chloride from the brine, 2012/0141342 A1 6/2012 Alurralde et al .
one column is in the process of washing the sorbent satu 2018/0245180 A1 * 8/2018 Cheng B01J 20/28004
rated with lithium chloride from the brine, and one column FOREIGN PATENT DOCUMENTS
is in the process of lithium chloride desorption. The primary
lithium concentrate is converted to a secondary lithium CL 58136 6/2013
concentrate by concentration in evaporative pools or reverse CL 201502830 9/2016
osmotic concentration - desalination . The secondary lithium CN
RU
1 558 871 A * 12/2004
1531388 C 11/1994
BO1J 49/53
concentrate is used for further production of lithium chloride RU 2223142 C2 2/2004
or lithium carbonate . RU 2455063 C2 7/2012
RU 2516538 C2 8/2013
19 Claims , 11 Drawing Sheets RU 2543214 C2 2/2015
SU 1588712 A1 8/1990
WO 03037794 A1 5/2003
WO 03041857 A1 5/2003
( 58 ) Field of Classification Search WO WO 2012 163 791 A1 * 12/2012 CO1D 15/04
CPC B01J 47/02 ; B01J 39/07 ; CO1P 2006/80 ;
CO1P 2006/82 ; C22B 3/20 ; C22B 3/24 ; OTHER PUBLICATIONS
C22B 3/44 ; C22B 7/006 ; C22B 26/12
See application file for complete search history. N. P. Kotsupalo , A A. D. Ryabtsev. Chemistry and technology of
obtaining lithium compounds from lithium -bearing hydromineral
( 56 ) References Cited raw material, publ . by Geo , Novosibirsk, 2008 , 291 p .
U.S. PATENT DOCUMENTS Office action from Chile Application No. 2018-000938 dated May
26 , 2020 with machine translation .
4,243,392 A 1/1981 Brown et al . Office action from Chile Application No. 2018-000938 dated Nov.
4,271,131 A 6/1981 Brown et al . 16 , 2020 with machine translation .
4,274,834 A 6/1981 Brown et al .
4,347,327 A 8/1982 Lee et al . * cited by examiner
U.S. Patent Jul . 26 , 2022 Sheet 1 of 11 US 11,396,452 B2

Original natural brine

WL - 1 Pulp

Filling DGAL - Cl with WL - 1 Sedimentation

centrifugation
Complete saturation of DGAL -CI
with Lici
Centrate ( clarified
Saturated DGAI - CI natural brine )
WL - 2 with WL - 1 Precipitate
of mechanical
impurities Fine filtration
Displacement of WL - 1 Filter regeneration
to the brine
Complete saturation of DGAL -CT
with LiC1 Brine purified from
Saturated DGAL - C1 with
mechanical impurities
residual brine
WL - 3 WL - 1

Heated brine to
Displacement of WL - 2 sorption of LiCi
from sheets 1.2 , 1.3
Complete saturation of DGAL -CI
with Lici
WL - 2 Saturated WL
DGAL
-3
-CIwith
WL - 4 Sorption of Lici
first step
DGAL - Cl saturation with LiCi
Displacement of WL - 3 DGAL - Cl saturated with
Licl with brine Natural brine partially
WL - 3 spent with respect
Saturated DGAL - C1 with to Lici
WL - 4 Brine draining Original DGAL-CI
WL - 5 Brine LiClsorption
Displacement of WL - 4 (H2O ) second step
WL - 5 DGAL - CI DGAL - Cl partially
Partial desorption of LiCl fron saturated with LiCi saturated with Lic1
the saturated sorbent
WL - 4
DGAL - Cl with WL - 5 Natural brine completely
Permeate , condensate of spent with respect to
secondary steam from sheet 4.2 Lici
Displacement ofWL-5
with LiCl solution
Primary lithium Desorption of Lici Filtration
concentrate to sheet 1.2 first step
Partially Small fraction of DGAL - CI to Brine to heating with
Permeate , condensate regenerated production of granulated process heat to
DGAL -CI sheets 1.2 , 1.3
of secondary steam DGAL - C1 Lici
from sheets 1.2, 1.3 solution
Recuperation heating
H2O Desorption of Li?i Natural brine spent with
second step respect to LiCl and cooled
to further processingorto
pumping into salar or into
stratum
mpletely regenerated DGAL -CI
Fig . 1 ( 1.1 )
U.S. Patent Jul . 26 , 2022 Sheet 2 of 11 US 11,396,452 B2

NazCO3 solution BaCl2

from sheet 1.3 Ba (OH ) 2
Precipitation of sulfate ions
Filtration Carbonization
Small fraction of DGAL -CI to
BaSO4 LiCi solution LiHCO3 production of granulated
precipitate purified from S04 solution DGAL -CI
Primary lithium
Precipitation of Ca and concentrate from sheet 1.1
Mg at pH = 10.5-11.0
Filtration
Filtration
Precipitate of Waste
CaCO3 200 kg/m2 regenerate
Mg( OH )23MgCO33H20 purified Liçi CaCl2, MgCl2, Concentration
solution LiCl , HC1 desalination by
from sheets 1.3 , reverse osmosis
to sheet 1.4 Lithium concentrate Permeate
obtained by reverse (deminera
osmosis lized
Precipitation of Li2CO3 with admixed water)
magnesium and
Separation from the LizÇO calcium
mother liquor
washing of Li2CO3
Repulping
Carbonization

Lithium concentrate
obtained by reverse
osmosis comprising
LiHCO3
Furnace gas
Heating t = 85 ° C , P = 0.5 atm + CO2 from sheet 1.3
Decarbonization CO2
Mother liquor
(NaCl) Precipitation of Ca and Mg
Phase separation Brine
Mixing 3N HCI solution Acidifying to heating
from sheet 1.3 from sheet 1.1
Heated Acidifying Evaporation
brine Licl concentration by
to sheet 1.1 evaporation Heated brine to
Salting out NaCl and KC1 sheet 1.1 Condensate
NaCl +KCI 485-490 kg /m3 Precipitate of of secondary
Condensate of crystals Secondary lithium CaCO3 steam
secondary with admixture ofLiCl solution concentrate Mg ( OH ) 2-3MgCO3-3H20
steam LiCi H2O

Washing Mixing
Washing
200 kg /m3 LiCl solution Waste
Washing compr. K , Na, SO4, Ca , Mg Precipitate of washing
NaC1 + KCI CaCO3 solution
lithium crystals Mg(OH ) 2-3MgCO3-3H20
containing
solution
Dissolving Permeate, condensate of
secondary steam
NaCl + KCI solution to sheets 1.1 , 1.3
to sheet 1.3
Fig . 1 ( 1.2 )
U.S. Patent Jul . 26 , 2022 Sheet 3 of 11 US 11,396,452 B2

NaCI+ KCI
solution
from sheet 1.2
Lewatit208 - TP -Na
Waste
regenerate
CaCl2, MgCl2, Ion exchange purification
LiCl, HCI from Ca and Mg 3N HCI solution
to sheet 1.2 to sheets 1.2, 1.4
Regeneration of resin
Conversion into Na - form

Natural gas
Purificd
NaCH+ KC1
H2 solution
Introduction of H2 Ejecting C12
Electromembrane process Cl2 absorption
Catholyte 3N HCI ( NH2)2CO
solution CO2
NaOH + KOH
solution
Dissolving
Mixture of natural Atmosphere air ( NH2 ) 2CO
gas and H2 solution

Burning
Obtaining heating
steam Permeate,
condensate of
Furnace Heating steam secondary steam
gas P = 6 atm from sheets 1.1 , 1.2
t = 280 ° C t= 160 °C
CO2 - 10 vol %
to evaporation

Carbonization Condensate
Evaporation of secondary
steam
Condensate of
Furnace gas Saturated Na2CO3 secondary
t = 70 ° C solution to sheet 1.2 steam
100 % humidity to sheet 1.2

Heated brine to Gas cooling

sheet 1.1 Brine
Brine heating to hcating
H2O vapour condensation from sheet 1.1
Furnace gas Furnace gas
t = 25 ° C , 100 % humidity t=25°C, 100% humidity + CO2
to sheets 1.1 , 1.2

Fig . 1 ( 1.3 )
U.S. Patent Jul . 26 , 2022 Sheet 4 of 11 US 11,396,452 B2

Purified 200 kg/m3

LiCl solution from
sheet 1.2 Lewatit 208TP in the Li- form
Waste 3N HC1 H20
regenerate Ion exchange purification solution
to sheet 1.2 Regeneration of resin from sheet 1.3
Dissolving
Conversion into Li- form Air t = 90 ° C
LiOH H20 moisture content Atmosphere
Saturated 75-80 % air
Secondary lithium NaCl and KCI
concentrate purified from solution
Ca and Mg NaCl and KCI Drying t = 90 ° C
crystals withadmixture
of LiC1.H20
Evaporation Lic1 crystals,
Salting out NaCl and KCI moisture content
10-12 wt %
Washing
Suspension: Na?i and KCI Air t - 110 ° C
crystals with admixture of Lici moisture content Atmosphere
H2O in 485-490 kg /m3 LiCl brine
Lithium - containing Washed 5,80% air
waste NaCl and KCI
washing liquid crystals
Cooling Drying t = 110 ° C
Filtration

NaCl and KC1 Crystals of commercial

crystals to obtaining LiCl with residual
Chloride brine alkaline solution moisture content of
LiCi 485-490 kg/m3 < 4 wt%
NaCl + KCI 2-4 kg/m3
Permeate , condensate
of secondary steam from
Evaportion LiOH · H2O sheets 1.2 , 1.3
Crystallization of LiCl. H2O
Centrifugation Dissolving
Centrate LiC1 ?. HO Chloride -alkaline
washing liquid
crystals

Washing
waste chloride - alkaline
washing Washed
3N HCI liquid LICI . H2O
solution crystals
from sheet 1.3
Acidifying
Waste chloride
washing liquid

Fig. 1 ( 1.4)
U.S. Patent Jul . 26 , 2022 Sheet 5 of 11 US 11,396,452 B2

Sorption of
1) Original brine 1 LiCI
2 Waste
brine
Primary
lithium
3 4 concentrate

)
2
H2O
Displacemnt ofbrine Desorption of
Lici
Original brine

Displacement 1 2
of brine
HO SoforptionLici
Desorption of 3 4
LiC1
Primary
lithium
concentrate Waste
H2O
brine
3)
Desorption of Displacement
Primary Lici of brine
lithium
concentrate
1 2

Waste
3
Sorption of 4 Original brine
brine Lici

Waste Primary
brine lithium
concentrate
1 2
Desorption of
Lici
ofSorptionLici H20

3 4
Displacement
of brine

Original brine

Fig . 2
U.S. Patent Jul . 26 , 2022 Sheet 6 of 11 US 11,396,452 B2

Original natural brine

WL - 1 Pulp

Filling DGAL - Cl with WL - 1 Sedimentation

centrifugation
Complete saturation of DGAL -CI
with Lici
Centrate ( clarified
Saturated DGAL -CI natural brine)
WL - 2 with WL - 1
Precipitate
of mechanical
admixtures Fine filtration
Displacement of WL - 1 Filter regeneration
to brine
Complete saturation of DGAL -C1 Brine purified from
With Lici
Saturated DGAL -CI with mechanical impurities
residual brine
WL - 3 WL - 1

Heated brine to
Displacement of WL -2 sorption of Lici
from sheets 3.2 , 3.3
Complete saturation of DGAL -CI
with Lici
WL - 2 Saturated DGAL - CI with
WL - 3
WL - 4 Sorption of Lici
first step
Saturation of DGAL-Cl with Lich
Displacement of WL - 3 DGAL- Cl saturated with
LiCl with brine Waste natural brine partially with
WL - 3 respect to Lici
Saturated DGAL- C1 Brine draining
with WL - 4 Original DGAL - C1
WL - 5 Brine Sorption ofLici
Displacement of WL -4 ( H2O) second step
WL - 5 DGAL -C1 saturated DGAL - Cl partially
Partial desorption of Lici with LiCI saturated with Lici
from saturated sorbent
WL - 4
DGAL - Cl with WL - 5 Natural brine completely
Permeate , condensate of spent with respect
secondary steam from sheet 3.2 to Lici
Displacement of WL -5
with LiCl solution
Primary lithium Desorption of Lici Filtering
concentrate to sheet 3.2 first step
Brine to heating
Small fraction of DGAL - CI to with
Partially production of granulated process heat to
Permeate,
condensate of
regenerated DGAL - C1 sheets 3.2 , 3.3
secondary steam DGAL -C1 Lici
from sheets 3.2, 3.3 solution
Recuperation heating
H2O Desoprtion of Waste Natural brine with
LiCl second step respect to LiCl and cooled
to further processing or to
pumping into salar or into
stratum
Com tely regenerated DGAL - C1
Fig. 3 ( 3.1 )
U.S. Patent Jul . 26 , 2022 Sheet 7 of 11 US 11,396,452 B2

Na2CO3 solution Ba(OH) 2

froin sheet 3.3
Precipitation of sulfate ions
Filtering Carbonization
BaSO4 Small fraction of DGAL - Cl for
precipitate LiCi solution LiHCO3 producing granulated
purified from SO4 solution DGAL - CI
Primary lithium
Precipitation of Caand concentrate from sheet 3.1
Mg at pH= 10,5-11,0
Filtration
Precip
Precipitate of
CaCO3
Waste
regenerate
Filtration

200 kg / m
Mg(OH ) 2-3MgCO : 3H20purified CaCl2, MgCl2, Concentration
Lici LiCl, HC1 desalination
solution from sheet 3.3 by reverse osmosis
Lithium concentrate Permeate
þbtained by reverse (deminera
osmosis lized
Precipitation of Li2CO3 with admixed water)
magnesium and
Separation from the LiCO3 calcium
mother solution
Washing of LizCO .
Repulping
wet
Carbonization
Li2CO3

Lithium
Microwave drying concentrate
obtained by reverse
osmosis comprising
Commercial Li , CO3 of LiHCO3
99.5 % purity
Heating t = 85 ° C , P=0.5 atm CO2 from sheet 3.3
Decarbonization CO2
Mother liquor
(NaCl) Precipitation of Ca and Mg
Phase separation Brine
Mixing 3N HCI solution Acidifying to heating
from sheet 3.3 from sheet 3.1
Heated Acidifying Evaporation
brine LiCl concentration by
to sheet 3.1 evaporation Heated brine to
Salting out NaCl and KCI sheet 3.1 Condensate of
Precipitate of secondary
Condensate NaCl + KCI
crystals 485-490 kg/mº Secondary lithium CaCO3 stcam
pf secondary
steam
with admixture oLiCi soltuion concentrate Mg (OH )2: 3MgCO33H2O
LiCl • H2O
Washing Mixing
Washing
200 kg/m3 Lici solution Waste
comprising K, Na, SO4, Precipitate of washing
Washing NaCI+ KCI Ca, Mg CaCO3 solution
lithium crystals Mg(OH ) 2-3MgCO33H20
containing
solution
Dissolving Permeate , condensate of
secondary steam to
NaCl+ KCI solution sheets 3.1 , 3.3
to sheet 3.3
Fig . 3 (3.2)
U.S. Patent Jul . 26 , 2022 Sheet 8 of 11 US 11,396,452 B2

NaCI + KC1
solution
from sheet 3.2
Lewatit208 - TP - Na
Waste
regenerate
CaCl2, MgCl2, Ion exchange purification
LiCl, HCI from Ca and Mg 3N HCI solution
to sheet 3.2 to sheet 3.2
Regeneration of resin
Conversion into Na - form

Natural gas
Purified
NaCI + KCI
Hz solution
Introduction of H2 Ejecting Cl2
Electromembrane process Cl2 absorption
Catholyte 3N HCI (NH2).CO
NaOH + KOH solution
solution
Dissolving
Mixture of natural Atmosphere air (NH2)2CO
gas and H2 solution

Burning
Obtaining heating
steam
Permeate ,
condensate of
Furnace Heating steam secondary
gas P=6 atm stcam from
t = 280 ° C t= 160 ° C sheets 3.1, 3.2
CO2 - 10 % by vol . to evaporation

Carbonization Condensate
Evaporation of secondary
steam
Condensate of
Furnace Saturated Na2CO3 secondary
gas soluton to sheet 3.2 steam
t = 70 ° C to sheet 3.2
100% humidity

Heated brine to Gas cooling

sheet 3.1 Brine
Brine heating to heating
H20 vapour condensation from sheet 3.1
Furnace gas Furnace gas
t= 25 ° C , 100 % humidity t=25 °C , 100 % humidity + CO2
to sheets 3.1 , 3.2

Fig . 3 ( 3.3 )
U.S. Patent Jul . 26 , 2022 Sheet 9 of 11 US 11,396,452 B2

Original natural brine

WL - 1 Pulp

Filling DGAL-Cl with WL - 1 Sedimentation

centrifugation
Complete saturation of DGAL -CI
with Licl
Centrate ( clarified
Saturated DGA1 -C1 Precipitate natural brine)
WL - 2 with WL - 1 of mechanical
admixtures
Fine filtration
Displacement of WL - 1 Filter regeneration
to the brine
Complete saturation of DGAL -CI Brine purified from
with Lici
Saturated DGAL -Cl with mechanical impurities
residual brine
WL - 3 WL - 1

Heated brine to
Displacement of WL - 2 sorption of LiCi
from sheets 4.2 , 4.3
Complete saturation of DGAL - C1
with Lici
WL - 2 Saturated DGAL -Cl with
WL - 3
WL - 4 Sorption of Lici
first step
DGAL - CI saturation with LiCl
Displacement of WL - 3 DGAL -C1 saturated with
LiCl with brine Waste natural brine partially
WL - 3 with respect to
Saturated DGAL - Cl with Lici
WL - 4 Brine draining Original DGAL- C1

WL - 5 Brinc LiCl sorption

Displacement of WL - 4 (H20 ) second step
WL -5 DGAL -C1 DGAL - Cl partially
Partial desorption of LiCl from saturated with Lici saturated with Lici
the saturated sorbent
WL - 4
DGAL -CI with WL - 5 Natural brine completely
Permeate , condensate of spent with respect to
secondary steam from sheet 4.2 Lici
Displacement of WL -5
with LiCl solution
Primary lithium Desorption of LiCI Filtration
concentrate to sheet 4.2 first step
Brine to heating with
Partially Small fraction of DGAL - CI to process heat to
Permeate , regenerated production of granulated sheets 4.2 , 4.3
condensate of DGAL - CI
DGAL -C1 Lici
secondary steam solution
from sheet 4.2
Recuperation heating
H2O Desorption of Lici Waste natural brine with
second step respect to LiCl and cooled
to further processing or to
pumping into salar or into
stratum
Completely regenerated DGAL - C1
Fig . 4 ( 4.1)
U.S. Patent Jul . 26 , 2022 Sheet 10 of 11 US 11,396,452 B2

BaOH2

Precipitation of sulfate ions

Filtration
Small fraction of DGAL - Cl to
BaSO4
precipitate LiCl solution production of granulated
(NH4 )2CO3 solution purified from SO4 DGAL - CI
from sheet 4,3
Primary lithium
Precipitation of Ca and concentrate from sheet 4.1
Mg at pH = 10.5-11.0
Filtration
Filtration
Precipitate of Lewatit 208TP (Li)
CaCO3
Mg (OH )23MgCO : 3H20 Reagent purified Concentration
to sheet 4.31 LiCl solution desalination
by reverse osmosis
485-490 kg /m2 Permeate
Licl solution Lithium concentrate (deminera
from sheet 4.3 obtained by reverse lized
osmosis
with admixed water)
Mixing magnesium and T
calcium
Spent Tegnrate Ion exchange purification
from Ca and Mg
Acid regeneration of HCl
Repulping
resin Carbonization
Conversion into Li- form Mixing
Saturated
Lizco Lithium concentrate
COZ solution obtained by reVCISC
to sheet 4.3 osmosis comprising
Dissolving LiHCO3
(NH4)2CO3 Finely purified CO2 from sheet 4.3
solution Heating t = 85 ° C , P = 0.5 atm
from sheet 4.3 200 kg /m3 Lici CO2
solution Decarbonization

Spentswoalutiong
Precipitation of Li2CO3
Li2CO3 Li2CO3 Precipitation of Ca and Mg
Phase separation
??? Acidifying
Separation fromthe Brine to heating ,
mother solution Evaporation from sheet 4.1
Washing
Heated
NH4C1 solution Wet brine, Condensate of
comprising Li2CO3 to sheet 4.1 Precipitate of secondary
CaCO3
NaCl + KCI crystals Secondary lithium Mg (OH ) 2.3MgCO3-3H20 steam
concentrate :
to sheet 4.3 170-190 kg /m LiCl solution
Microwave drying comprising K , Na, SO4 , Ca, Mg
Washing
Commercial Li2CO3 Waste
of 99.9% purity
Precipitate of washing
CaCO3 solution
Mg(OH )2-3MgCO3-3H20
Condensate of secodary
steamfrom sheet 4.3 to sheet 4.3
Permeate , condensate of
secondary steam to sheets 4.1 , 4.3
Fig . 4 ( 4.2)
U.S. Patent Jul . 26 , 2022 Sheet 11 of 11 US 11,396,452 B2

Precipitate of
CaCO3
Mg(OH )23MgCO33HO from sheet 4.2

CO2 from sheet 4.2

Heating t = 850 ° C
CO2 Decarbonization

washing solution CaO + MgO

Repulping
Pulp

Decomposition of NH4C1
NH 3,
Pulp:
MgO in solution of Absorption of NH3 and CO2
CaCl2 + NaCl + KC1
Cooling
Centrifugation Obtaining
(NH4)2CO3 solution
Washing
CaCl2 solution (NH4 )2CO3
solution
NaCl + KC1 Mgo to sheet 4.2

Permeate , condensate of
Washing secondary steam from sheet 4.2
Salts:
NH4C1 Solution of NH4Cl solution comprising
compr. Lic1 Condensate
NH4C1 NaC1 + KCI from sheet 4.2
NaC1 of secondary
??? steam

HC1 Brine to heating, to sheet 4.2

Acidifying from sheet 4.1
Heated brine , Evaporation
to sheet 4.1
Salting out NH4C1
Salts: 485-490 kg/m3
NH4C1 Licl solution
NaCl
??? to sheet 4.2
LiCl•H2O

Fig . 4 (4.3 )
 US 11,396,452 B2
1 2
METHOD FOR PREPARING LITHIUM insoluble NaCl , KCI , CaCl2 , MgCl2 ( U.S. Pat. No. 4,271 ,
CONCENTRATE FROM LITHIUM -BEARING 131 ) [ 4 ] , or by carbonizing lithium carbonate until it is
NATURAL BRINES AND PROCESSING completely converted into soluble and free from the main
THEREOF INTO LITHIUM CHLORIDE OR admixtures lithium bicarbonate, followed by decarboniza
LITHIUM CARBONATE 5 tion and precipitation of higher purity lithium carbonate
(U.S. Pat . No. 6,207,126 ) [ 6 ] .
CROSS - REFERENCE TO RELATED Thus, preparation of lithium concentrate from conven
APPLICATIONS tional lithium -bearing hydromineral raw material does not
imply deep purification thereof from admixtures due to such
This application is a 371 of PCT Application No. PCT/ 10 purification being quite challenging. Purity of lithium prod
RU2018 /050041 filed on Apr. 13 , 2018 , which claim priority ucts prepared from such concentrate is increased by repu
to Russian Application No.RU 2017113039 filed on Apr. 14 , rification of the products obtained .
2017 , the contents of which are hereby incorporated by It is impossible to prepare lithium concentrates with high
reference as if recited in their entirety. 15
lithium concentration from nonconventional lithium -bearing
hydromineral raw material ( natural brines of magnesium
TECHNICAL FIELD chloride, calcium chloride and mixed types) by conventional
halurgic methods, because formation and salting out of such
The present invention relates to the field of lithium binary salts as LiCl.MgCl2.6H2O and LiCl.CaC12.5H2O ,
hydrometallurgy and may be used for preparing lithium together with salted off CaCl2.6H20 and MgCl2.6H2O crys
concentrates by enrichment of natural lithium -bearing brines 20 talline hydrates is inevitable upon its evaporation. Thus, it is
and producing commercial lithium products from these only possible to prepare lithium concentrates from noncon
concentrates. ventional lithium -bearing hydromineral raw material by
BACKGROUND
selective lithium recovery followed by concentration to
25
obtain the content of lithium that allows producing lithium
carbonate or chloride . There are US patents describing the
In the world practice lithium products are prepared both use of sorbents for selective recovery of lithium from
from lithium -bearing hard mineral ( spodumene, lepidolite , lithium - bearing brines , the sorbents being microcrystalline
petalite ) and hydromineral (lake brines, salars brines, deep lithium aluminates formed in the pores of ion exchange resin
groundwater brines , mineralized waters ) raw material (U.S. Pat . Nos . 4,159,311 , 4,221,767 , 4,347,327 , 4,477,367 ,
sources . 30
While in the past century the manufacturers of lithium sorbents 5,389,349 ) [ 7-11 ] . However, during real -time use of such
it was found that, first, macropores of the resin
products primarily used hard mineral raw material sources , become clogged by mechanical admixtures contained in the
in the XXI century preference is given to lithium -bearing brines, thereby hindering the access of lithium to the crystals
hydromineral raw material, since employment of this type of of the selective sorbent, and second , crystals of the selective
raw material sources allows not only to build lithium plants 35 sorbent are washed from the support very quickly.
with higher economic and ecological performance, but also Later a method for recovering lithium from lithium
to construct manufacturing units for advanced processing of bearing brines was proposed , which used a sorbent based on
this type of raw material due to its multicomponency and macro - crystalline form ofLiX / Al(OH )3 compound, wherein
affordability of recovery of other valuable components (Os X_OH " , C1- , NO3- , SO42- , capable of introducing lithium
troushko Y. I. , Degtyareva T. V. Hydromineral raw material 40 without structure disturbance (U.S. Pat . No. 5,599,516 ) [ 12 ] .
is a sustainable lithium source . Analytical review . TSNI- The main deficiencies of this method, however, are large
ATOMINFORM , 1999 , 64 p . ) [ 1 ] .
All modern technologies for preparing lithium salts from crystalsofcaused
losses sorbent due to destruction (decrepitation ) of its
by inevitable local overstrain in the crystals
lithium -bearing hydromineral raw material are based on its formed and the necessity to heat the desorbing liquid to 90 °
enrichmentlithium
ventional with -lithium
bearing. Enrichment
hydromineralwith
rawlithium
materialof(natu
con- 45 C. during recovery of lithium from the saturated sorbent.
ral brines of sodium chloride type with low magnesium and natural A method for preparing lithium concentrate by enriching
calcium content) is generally carried out by successive developedlithium -bearing brines with granulated sorbent was
, which is based on composite -amorphous form of
salting out macro - components upon evaporation (NaCl , the compound composed of LiCl.2Al ( OH ) 3.mH , O ' ,
KCI , KC1.MgCl2.6H20 , MgCl2.6H20) and simultaneous 50 wherein m=3-5 , having a defect in its structure, which upon
concentration of the original brine with respect to lithium to corresponding pretreatment of the sorbent ( aqueous treat
contents that allow producing lithium chloride and / or car ment) allows creating the deficiency of lithium in the
bonate from the obtained lithium concentrates of 98-99 % compound and carrying out a reversible process of interca
purity (U.S. Pat. Nos . 4,243,392 , 274,834 ) [ 2 , 3 ] . Removal lation of lithium chloride in the brine medium and deinter
of admixtures ( SO2- 4 , Ca2 + , Mg² + ) from thereby prepared 55 calation thereof in the fresh water medium ( Chemistry and
lithium concentrates is carried out by converting the admix technology of preparing lithium compounds from lithium
tures into poorly soluble CaSO4 , CaCO3 , Mg ( OH ) 2 salts bearing hydromineral raw material) [ 13 ] .
using CaCl2 , CaO , Na2CO3 as reagents (U.S. Pat . No. 1
Hereinafter DGAL - Cl - chlorine- containing form of double aluminum
4,271,131 ) [ 4 ] . After reagent purification and before obtain- lithium hydroxide
ing lithium products from lithium concentrates, boron is 60 A method for preparing granulated sorbent selective for
typically recovered in the form of boric acid by extraction lithium is described in the following sources : PCT applica
with high molecular weight alcohols (U.S. Pat . No. 5,219 , tion PCT/DE 01.04062 , Germany [ 14 ] , pat . RU 2223142 ,
550 ) [ 5 ] RU 2455063 [ 15 , 16 ] . Based on this sorbent, a method for
To prepare lithium products of higher grade from lithium selective recovery of lithium chloride from lithium -bearing
concentrates, lithium salts LiCl and Li2CO3 are processed 65 natural brines was developed , which comprises recovery of
into salts of greater purity either by using isopropyl alcohol primary lithium concentrate affording further concentration
in which lithium chloride is highly soluble , as opposed to with respect to lithium using any of the known methods,
 US 11,396,452 B2
3 4
including evaporation . Use of the granulated sorbent based of 190-210 kg /m ", subjected to reagent purification from
on amorphous form of LiCl.2Al ( OH ) 2.mH2O compound calcium and magnesium and is used as producing lithium
instead of crystalline granules, from the hydrated compound concentrate for obtaining lithium compounds: lithium car
LiCl/ Al(OH ), allows carrying out all process stages of the bonate , lithium hydroxide monohydrate, lithium chloride ,
enrichment process at room temperature, to give primary 5 etc. Proposed method allows lowering the degree of abra
lithium concentrate comprising, depending on lithium con- sion of the sorbent to 7-10% and bringing the purity of
centration of the brine , from 4.0 to 6.0 g /l of lithium chloride lithium carbonate obtained by said method up to 99.5 % .
with residual content of macrocomponent base of the brine By its technical essence and the achieved result this
of no more than 6.0 g / 1. To minimize the weight of one - time method for preparing lithium concentrate from lithium
load of the granulated sorbent, this invention used sorption- 10 bearing natural brines and processing thereof is the closest
desorption enrichment unit with moving sorbent layer. The analogue of the claimed method, and it is chosen by the
method for obtaining lithium chloride from lithium -bearing authors as the prototype . Along with the above -mentioned
brines based on the use of granulated selective sorbent and advantages the prototype has the following deficiencies.
the plant for implementation thereof are described ( PCT One of the deficiencies is unability to achieve high lithium
application PCT/DE 01/04061, Germany) [ 17 ] . 15 recovery ratio from the brines under conditions of achieving
However, along with the apparent above mentioned - high degree of saturation of the granulated sorbent. In order
advantages this method has deficiencies, one of which is to bring the dynamic capacity with respect to lithium chlo
high degree of abrasion of the sorbent (more than 37 % a ride close to the predicted value under the conditions which
year ) during its movement in the equipment. Lithium chlo- provide the maximum driving force to the process of lithium
ride prepared in accordance with this method has a purity of 20 intercalation, i . e . during filtration of the original brine
no more than 98 % . This method does not envisage prepa- through the sorbent layer “ continuously ” , lithium chloride
ration of the most sought after lithium compound, lithium recovery ratio from the brine is 50-55 % . During the stepwise
carbonate. Furthermore, implementation of the alternative of mode of contacting the brine with the sorbent lithium
the method with moving sorbent requires development of chloride recovery ratio may be increased up to 75-80% , but
complex nonstandard equipment leading to increased 25 simultaneously the total volume of the brine filtered through
expenses of practical implementation of this method . the sorbent during the same time period increases by several
In order to eliminate the deficiencies of this production times . This especially adversely impacts processing of brine
process a method for preparing lithium concentrate from with low LiCl content ( less than 1 kg / m ), when total flow
natural brines and processing thereof into lithium products is rate of the brine filtered through the sorbent goes beyond the
proposed ( pat. RU 2516538 ) [ 18 ] . 30 actual flow capacity of the equipment .
The above -mentioned deficiencies are eliminated in the The second significant deficiency of this method is
proposed method for preparing lithium concentrate from arranging the brine displacement process from the sorbent
lithium -bearing brines by carrying out the process of lithium layer by the displacement liquid in the direction downwards
enrichment of the brine in the sorption -desorption unit from the top and using sodium chloride solution or primary
consisting of two columns filled with the granulated selec- 35 lithium concentrate as the displacement liquid . The move
tive sorbent. One of the columns is in the mode of constant ment of displacement liquid downwards from the top leads
lithium saturation ( intercalation ), while the other column is to significant compaction of the sorbent layer and to an
in the mode of brine removal and recovery (deintercalation ) increase in the hydraulic resistance . Due to high content of
of lithium from the saturated granulated sorbent. The mode CaCl2 and MgCl , of the brine during the contact of the brine
of brine flow through the column at the stage of saturation 40 with sodium chloride solution , upon displacement sodium
can either be continuous or portion -wise ( portions of the chloride is salted out from the solution and its solid phase is
brine of predetermined volume with various content of Lici , deposited within the sorbent layer. Use of primary lithium
increasing with each portion ). During the portion -wise mode concentrate as the salting - out liquid leads to lower yield of
the first portion of the brine that was subjected to the stage commercial primary lithium concentrate .
of contact with the granulated sorbent is considered waste 45 Furthermore , purification of primary lithium concentrate
with respect to the content of lithium . Removal of the brine in the prototype method is associated either with high
from the saturated granulated sorbent is carried out by investment costs in case of using the alternative with ion
stepwise displacement with portions of sodium chloride exchange purification on the KU - 2 cation - exchange resin in
solution or portions of lithium concentrate . Desorption of the Li-form , or with low efficiency of the purification
lithium chloride from the brine- free granulated sorbent is 50 process in case of the alternative of calcium and magnesium
also carried out stepwise using portions of water with removal in the form of poorly soluble compounds upon
various content of LiCl , until complete removal of interca- contacting the heated primary lithium concentrate with the
lated lithium chloride from the granulated sorbent. The solid lithium carbonate phase , which is a significant defi
primary lithium concentrate obtained , which is an aqueous ciency of this method . The following should also be listed
LiCl solution with concentration of 5.0 to 5.5 kg/m com- 55 among the deficiencies of the prototype method : the absence
prising CaCl2 , MgCl2 , NaCl , KCI , sulfate ions as admix- of technological solutions with respect to purification of the
tures, is purified from calcium and magnesium using ion natural lithium - bearing brine from mechanical admixtures,
exchange method on the KU - 2 cation - exchange resin in the the absence of measures for recycling solid waste product
Li - form or by conversion into insoluble compounds CaCO3 represented by sodium chloride prepared upon evaporation
and Mg (OH)2.3MgCO3.3H,0 by bringing the primary 60 of the mother liquor from the stage of lithium carbonate
lithium concentrate into contact with the solid phase of precipitation with soda ash ; unability to obtain battery -grade
lithium carbonate at a temperature of 60-90 ° C. The primary lithium carbonate ( purity qualification of 99.9 % ) due to
lithium concentrate is then subjected to concentration in the higher concentration of admixtures, which are alkali metals ,
evaporating basins to LiCl content of 220-350 kg/m or by calcium and magnesium . Besides , the method does not
reverse osmosis method with subsequent evaporation to 65 envisage preparation of anhydrous lithium chloride from the
LiCl content of 350-400 kg/ m ”, whereby NaCl and KCl are secondary lithium concentrate , which along with lithium
salted out, is diluted with demineralized water to the content carbonate is a sought after commercial lithium product.
 US 11,396,452 B2
5 6
Proposed method for preparing lithium concentrate from portion of the washing liquid is used to fill the column and
lithium -bearing natural brines and processing thereof into then is displaced from the column with the second portion of
lithium chloride and /or lithium carbonate preserves all the the washing liquid , directing the displaced volume to mixing
advantages of the prototype and eliminates its main defi- with the natural lithium -bearing brine purified from sus
ciencies . 5 pended solids , the second portion of the washing liquid is
displaced from the column with the third portion of the
SUMMARY OF THE INVENTION washing liquid and is used in the next washing cycle as the
first portion of the washing liquid, the third portion of the
Technical result of the proposed method which allows washing liquid is displaced from the column with the fourth
eliminating said deficiencies is achieved by preliminary 10 portion of the washing liquid and is used in the next cycle
treatment of the natural brine to remove suspended solids by as the second portion of the washing liquid , the fourth
sedimentation centrifugation of the brine with removal of portion of the washing liquid is displaced with the fifth
the formed precipitate, followed by filtering the centrate portion of the washing liquid ( fresh water) and is used in the
with fine filters regenerated by back washing with the stream next cycle as the third portion of the washing liquid , the fifth
of filtered brine followed by feeding the stream of the waste 15 portion of the washing liquid is displaced from the column
regenerating brine to the stage of sedimentation centrifuga- with the corresponding portion of the desorbing liquid and
tion together with the original lithium -bearing natural brine , is used in the next cycle as the fourth portion of the washing
if the content of suspended solids in the original lithium- liquid , in the next cycle fresh portion of fresh water is used
bearing natural brine is 1.0 kg /m² and higher, or by filtering as the fifth portion of the washing liquid, desorption of
the original natural lithium -bearing brine with fine filters 20 lithium chloride from the sorbent washed from the brine is
regenerated by back washing with the stream of filtered carried out by successive stepwise filtering of predetermined
brine followed by sedimentation centrifugation of the stream volumes of the desorbing liquids, on the assumption that
of waste regenerating solution with removal of the precipi- after bringing the first volume of the desorbing liquid, which
tate and feeding the centrate to the stage of filtering together is a diluted aqueous lithium chloride solution with admixed
with the original natural lithium -bearing brine, if the content 25 residual brine components ( first step desorbing liquid ), into
of suspended solids in the original natural brine is less than contact with the sorbent, it is removed from the process as
1.0 kg/m3. the primary lithium concentrate , after bringing the second
Technical result is achieved by preparation of the primary volume of the desorbing liquid, which is fresh water ( second
lithium concentrate by its sorption enrichment with lithium step desorbing liquid ), into contact with the sorbent, it is
using granulated sorbent based on the compound LiCl.2A1 30 used as the first step desorbing liquid of the desorption stage
( OH ) 3.H20 , wherein m=3-5 ; primary lithium concentrate is in the next cycle together with the volume of the desorbing
prepared in sorption -desorption units, each consisting of liquid displaced from the column by the corresponding
four columns filled with the granulated sorbent, two of volume of lithium -bearing brine at the sorption stage of the
which are in the process of lithium chloride sorption from next cycle ;
the brine , one is in the process of washing the sorbent 35 Technical result is achieved by converting the primary
saturated with lithium chloride from the brine, and one is in lithium concentrate obtained from lithium -bearing natural
the process of lithium chloride desorption from the sorbent brine into secondary lithium concentrate using one of the
washed from the brine , the stream of the brine separated following alternatives:
from suspended solids is always first passed through the according to the first alternative, primary lithium concen
column with the sorbent partially saturated with lithium 40 trate is subjected to solar concentration with respect to
chloride ( first sorption step ), then through the column with lithium chloride in the evaporating basin with simultaneous
the sorbent that was subjected to the stage of lithium purification from calcium and magnesium by preliminary
chloride desorption from the sorbent ( second sorption step ) , separating the primary lithium concentrate into two streams,
wherein after the sorbent is completely saturated with in one of which the predetermined amount of lithium
lithium chloride in the first column in the direction of the 45 carbonate by weight is repulped, the pulp is carbonized with
movement of the brine stream , this column is changed over carbon dioxide or CO2 comprising gaseous mixture in the
to the stage of washing the sorbent from the brine , the mode of pulp circulation until all lithium carbonate is
column that was in the process of washing the sorbent from dissolved, then this stream is mixed with the other stream of
the brine is changed over to the stage of lithium chloride primary lithium concentrate, mixed solution is directed into
desorption from the saturated sorbent, the column that was 50 the evaporating basin for concentration of the liquid phase
in the process of lithium chloride desorption from the with respect to LiCl to 220 kg / m ”, decarbonization and
2

saturated sorbent is changed over to the stage of sorption as gradual conversion of soluble calcium and magnesium chlo
the second step column, using the column with partially rides into poorly soluble compounds CaCO3 and
saturated sorbent as the first sorption step, which on the Mg (OH ) 2.3Mg2 ( OH ) 2.3H20 , which are separated from the
previous sorption stage was used as the second step column, 55 KCl
then the cycle is repeated following the experimentally
concentrated lithium chloride solution comprising NaCl and
as main admixtures, to obtain LiCl content of 190-200
established cyclogram ; the linear velocity of liquid phases in kg / m ”, which is the used to obtain lithium chloride or
the columns on all stages of producing primary lithium lithium carbonate ;
concentrate is maintained at the level of 5-7 m / h , wherein according to the second alternative, the predetermined
the sorbent is washed from brine by preliminary draining the 60 amount of Li, CO3 by weight is repulped in the primary
brine from the column, then stepwise washing of the sorbent lithium concentrate obtained by concentration - desalination
successively with five portions of washing liquid in the by reverse osmosis , the pulp is carbonized with carbon
upward direction, each having 1/3 of the volume of the dioxide or CO2 comprising gaseous mixture in the mode of
sorbent in the column, wherein four portions out of five are pulp circulation until all lithium carbonate is dissolved , the
the washing liquids with various content of brine compo- 65 solution is heated to a temperature of 80-85 ° C. under
nents which decreases with each step of washing , and the vacuum treatment up to 0.5 atm , decarbonized , directing the
fifth portion is the volume of fresh water, wherein the first released carbon dioxide to the stage of carbonization of the
 US 11,396,452 B2
7 8
pulp prepared from lithium carbonate and lithium concen- lithium concentrate or with the stream of lithium concentrate
trate obtained by reverse osmosis , and simultaneously con- obtained by reverse osmosis , the mother liquor from the
verting CaCl2 and MgCl2 into insoluble CaCO3 and lithium carbonate precipitating stage is acidified with hydro
Mg (OH ) 2.3MgCO3.3H20 precipitates, which are separated chloric acid to a pH = 6.0-6.5 , evaporated to obtain LiCl
from the liquid phase, the liquid phase of an aqueous LiCl 5 concentration in the liquid phase of 485-490 kg / m °, liquid
solution with admixed NaCl and KC1 , is concentrated with phase is separated from the salted out NaCl crystals with
respect to lithium chloride using electrodialysis or heating admixed KCl crystals and is mixed with the stream of
process , or a combination thereof, whereupon the Lici secondary lithium concentrate used for obtaining lithium
solution is brought to a concentration of 190-200 kg /m3 (of chloride, NaCl crystals with admixed KCl crystals are
the secondary lithium concentrate ), which is then used to 10 washed from the residual mother liquor, mixed with the
obtain lithium chloride or lithium carbonate; washed NaCl and KCl crystals that were salted out during
Technical result is achieved by first subjecting the lithium evaporation of the stream of the secondary lithium concen
chloride obtained from the secondary lithium concentrate to trate during production of LiCl , dissolved in the calculated
reagent purification from magnesium , calcium , sulfate and volume of demineralized water to obtain aa solution of alkali
borate ions using barium hydroxide or oxide and carbon 15 metal chlorides with NaCl concentration of 250-260 kg / m ”,
dioxide as reagents, then to fine ion exchange purification on obtained solution is subjected to electromembrane process ,
the Lewatit 208 - TP polyampholyte in the Li- form or ana- generating NaOH solution and hydrogen at the cathode and
logues thereof, concentration by evaporation to LiCl content chlorine at the anode , generated hydrogen is mixed with the
of 485-490 kg /m² ( lithium chloride brine ) , whereby the stream of natural gas , the gaseous mixture is burned to give
crystals of NaCl and KCl are salted out, the obtained lithium 20 heat energy for obtaining heating steam , which in turn is
chloride brine is cooled to room temperature , precipitated used as heating medium in evaporating lithium concentrates
NaCl and KCl crystals with admixed LiC1.H2O crystals are and mother chloride solution from the Li_C03 precipitating
separated from the liquid phase , the crystals are washed stage , the furnace gas comprising CO2 is used for carbon
stepwisely in the mode of repulping and squeezing with izing the Na2CO3 solution , converting it into Na2CO3 solu
three portions of washing chloride brine , each having two 25 tion ( carbonate solution ) and using it as the precipitating
times the volume of the portion of the crystals being washed , reagent at the lithium carbonate precipitating stage , anodic
two of which portions are mixed chloride solutions (NaCl + chlorine is introduced with the stream of aqueous carbamide
KC1 + LiCl ) with content of LiCl decreasing with each por- solution , thereby producing hydrochloric acid solution used
tion, and the third portion is aa mixed solution of alkali metal for acidifying carbonate - containing solutions before evapo
chlorides which is free of LiCl , the first portion of the 30 ration thereof and for regeneration of the waste Lewatit
washing chloride solution (waste washing liquid ) is directed 280 - TP polyampholyte ;
to the stage of evaporation , preliminarily mixing it with the Technical result is achieved by obtaining technical -grade
secondary lithium concentrate purified from the admixtures, lithium carbonate from the secondary lithium concentrate
the other two portions of washing chloride solution are used subjected to reagent purification from calcium , magnesium ,
for successive stepwise washing of the next portion of 35 sulfate and borate ions by precipitating lithium carbonate
crystals, fresh (the third ) portion of chloride washing solu- from the whole stream of the secondary lithium concentrate
tion is prepared by dissolving sodium chloride or sodium by bringing it into contact under stirring at a temperature of
chloride with admixed potassium chloride in demineralized 90-95 ° C. , with the sodium carbonate solution comprising
water, wherein the cooled and separated from the crystals of potassium carbonate , whereby after separation from the
precipitated salts lithium chloride brine with residual NaCl + 40 mother liquor one part of lithium carbonate is precipitated
KCl content of no more than 2 kg /m² is evaporated until and used for obtaining lithium bicarbonate solution which is
LiCl is converted into solid lithium chloride monohydrate then used to purify the primary lithium concentrate or the
phase , the residual mother liquor from the stage of lithium lithium concentrate obtained by reverse osmosis from cal
chloride brine evaporation and crystallization of LiCl H , O is cium and magnesium , the other (producing) part of lithium
separated from the lithium chloride monohydrate crystals 45 carbonate is washed stepwisely in the mode of repulping and
and mixed with the purified secondary lithium concentrate centrifugation with three portions of washing solution hav
being transported for evaporation , lithium chloride mono- ing three times the volume of the portion of lithium carbon
hydrate crystals are washed from the residual mother liquor ate being washed at a temperature of 90-95 ° C. , first with
with aa washing liquid composed of, in wt % : Lic1— (98.5- two portions of saturated lithium carbonate solution with the
99.0 ) , LiOH— ( 1.0-1.5 ) , waste liquid is acidified with hydro- 50 content of sodium and chloride ion decreasing with each
chloric acid to a pH = 6-7 and mixed with the purified portion , and then with a portion of demineralized water,
secondary lithium concentrate being transported for evapo- wherein after bringing the first portion of the washing
ration , washed LiCl H2O crystals are processed from the solution into contact with lithium carbonate it is directed to
residual alkalinity by bringing them into contact with the the stage of Li_CO3 pulp production used for carbonization,
calculated amount of hydrochloric acid and dried until 55 converting the solid Li_CO3 phase into LiHCO3 solution and
anhydrous lithium chloride is obtained by two - step air using it for purification of the primary lithium concentrate or
flow -drying, maintaining the temperature of the drying zone the lithium concentrate obtained by reverse osmosis from
at 85-90 ° C. during the first step , 108-110 ° C. during the calcium and magnesium , the other two portions of the
second step , the moisture content of the air flow at the outlet washing solution are used for successive stepwise washing
of the drying zones being 75-80 % , the other stream of 60 of the next portion of lithium carbonate, washed lithium
secondary lithium concentrate is used for precipitating carbonate crystals are subjected to microwave drying to a
lithium carbonate therefrom upon bringing it into contact residual moisture content of 0.4 % by weight;
with the solution of sodium carbonate or the solution of Technical result is achieved by obtaining battery - grade
sodium carbonate comprising potassium carbonate, precipi- lithium carbonate from the secondary lithium concentrate
tated lithium carbonate is separated from the mother liquor 65 subjected to reagent purification from calcium , magnesium ,
from the Li2CO3 precipitating stage by centrifugation and is sulfate and borate ions and fine ion exchange purification
directed to repulping with the part of the stream of primary from calcium and magnesium on the Lewatit 208 - TP
 US 11,396,452 B2
9 10
polyampholyte in the Li - form by carrying out precipitation 2. Increasing the degree of lithium chloride selective
with saturated aqueous ammonium carbonate solution at recovery in sorption enrichment of lithium -bearing natural
room temperature, the lithium carbonate precipitate is sepa- brines with lithium chloride using the DGAL - C1 granulated
rated from the mother ammonium chloride solution , one part sorbent, to obtain primary lithium concentrate ;
of the lithium carbonate precipitate is used for obtaining 5 3. Lowering the losses of lithium chloride and reducing
lithium bicarbonate solution which is then used to purify of energy consumption in production of lithium concentrate by
the primary lithium concentrate or lithium concentrate developing an advantageous procedure for brine removal
obtained by reverse osmosis from calcium and magnesium , from the columns of the sorption - desorption units prior to
the other ( producing) part of the lithium carbonate precipi
tate is washed stepwisely in the mode of repulping and 10 4.desorption
the stage;
More cost efficient method for purification of the
centrifugation with three portions of the washing solution , primary lithium concentrate or the lithium concentrate
each having three times the volume of the portion being obtained by reverse osmosis from calcium and magnesium ;
washed, at a temperature of 90-95 ° C. , first with two 5. Obtaining anhydrous lithium chloride of a grade cor
portions of saturated lithium carbonate solution with the
content of ammonium and chloride ions decreasing with is responding to a technical specification TU 95.1926-89 and
suitable for obtaining battery - grade lithium metal;
each portion, and then with a portion of demineralized water, 6. Avoiding using imported soda ash in production of
wherein after bringing the first portion of the washing
solution into contact with lithium carbonate it is directed to technical-grade Li_CO2 by substituting is with the soda ash
the stage of Li_CO3 pulp production used for carbonization , solution prepared from the mother liquor from the Li2CO3
converting the solid Li2CO3 phase into LiHCO3 solution and 20 precipitation stage and effluent furnace gas ;
using it for purification of the primary lithium concentrate or 7. Possibility of producing battery - grade lithium carbon
the lithium concentrate obtained by reverse osmosis from ate from the primary lithium concentrate, substituting the
calcium and magnesium , the other two portions of the expensive imported soda ash reagent with the cheaper local
washing solution are used for successive washing of the next limestone or dolomite .
portion of lithium carbonate , washed lithium carbonate 25 The data supporting possibility of realization of the
crystals are subjected to microwave drying to a residual claimed invention are presented on FIGS . 1-4 and in the
moisture content of 0.2 % by weight, ammonium chloride is Examples
salted out from the mother liquor from the lithium carbonate
precipitating stage by evaporation, after separation from the DESCRIPTION OF THE DRAWINGS
mother liquor from the evaporation stage ammonium chlo- 30
ride is washed from the residual mother liquor, waste FIG . 1. ( sheets 1.1 , 1.2 , 1.3 , 1.4 ) Flow chart of obtaining
washing solution is directed to evaporation by mixing it with primary lithium concentrate from lithium -bearing natural
the mother liquor from the lithium precipitating stage , the brines and processing thereof into anhydrous lithium chlo
mother liquor from the stage of evaporation and salting out ride
ammonium chloride crystals, which is 480-490 kg /m3 LiCl 35 FIG . 2. Operational scheme for sorption -desorption unit
solution with admixed NH4C1 , is in turn mixed with the of four columns with granulated selective DGAL - C1 sorbent
secondary lithium concentrate before its ion exchange puri- FIG . 3. ( sheets 3.1 , 3.2 , 3.3 ) . Flow chart of obtaining
fication on the Lewatit 208 - TP polyampholyte in the Li- primary lithium concentrate from lithium -bearing natural
form , ammonium chloride washed from the mother liquor is brines and processing thereof into technical - grade lithium
decomposed by treating it with water pulp comprising CaO 40 carbonate using the scheme with soda ash .
or CaO as the solid phase with admixed MgO , SiO2 and FIG . 4. ( sheets 4.1 , 4.2 , 4.3 ) Flow chart of obtaining
Fe , O3 , removing the released ammonia , mixing it with primary lithium concentrate from lithium -bearing natural
carbon dioxide at the ratio of 2 : 1 and absorbing the gaseous brines and processing thereof into battery -grade lithium
mixture by water upon cooling the liquid and gaseous phases carbonate using the scheme with limestone .
in the stepwise countercurrent mode , removing the waste 45 Remark : the following abbreviations are used on flow
absorbent as saturated ammonium carbonate solution used charts 1 , 3 , 4 : DGAL -C1 - granulated sorbent based on the
for precipitating lithium carbonate, the pulp formed after the chlorine-containing form of double aluminum lithium
removal of ammonia is separated by filtration or centrifu- hydroxide; WL - washing liquid.
gation, the liquid phase of calcium chloride solution with The description of implementation of the proposed
admixed NaCl and KCl is removed from the process and 50 method is given below .
used in municipal services as a reagent for consolidation of In accordance with the flow chart ( FIG . 1 ) , obtaining of
earth roads ( summer season ) and as a deicing reagent primary lithium concentrate from the lithium bearing natural
( winter season) , solid phase of Mgo with admixed SiO2 and brine and processing thereof into anhydrous lithium chloride
Fe ,O2 is used for the production of magnesium products, are performed as follows. Original natural brine passes the
calcium oxide and carbon dioxide necessary for decompo- 55 stage of purification from mechanical admixtures. If the
sition of ammonium chloride and production of (NH4)2CO3 content of mechanical admixtures is 1.0 kg/m3 and higher,
solution are obtained by thermal decomposition of the the brine is first subjected to sedimentation centrifugation,
precipitate of CaCO3 and Mg (OH ) 2.3MgCO3.3H , O salts then to fine filtering. Waste filtering elements are regener
formed at the stage of purifying the primary lithium con- ated with the stream of filtered brine countercurrent to the
centrate from calcium and magnesium , mixed with commi- 60 direction of brine stream during filtration purification . Waste
nuted natural limestone or dolomite . brine from the filtering elements regeneration stage is mixed
Advantages of the proposed solutions in comparison to with the original natural brine being transported for cen
prototype method consist in : trifugation .
1. Expanding the range of lithium -bearing hydromineral The brine purified from the mechanical admixtures if first
raw material sources suitable for producing lithium com- 65 directed to recuperation heating with the stream of brine
pounds by using lithium -bearing natural brines comprising waste with respect to lithium which passed the limit of
suspended solids ; sorption concentration, then to heating by recycling the
 US 11,396,452 B2
11 12
process heat released during the stages of evaporation and and on the other hand - permeate ( demineralized water with
cooling , wherein the natural brine is used as a coolant. the total salt content of no more than 30 g /dmº), used in the
Heated brine comes into sorption -desorption unit for process as washing , displacement and desorbing liquid ,
selective two - step lithium chloride sorption by the DGAL- thereby lowering the consumption of fresh water . In turn , in
C1 granulated sorbent. At the first sorption step brine stream 5 the lithium concentrate obtained by reverse osmosis which
comes into contact with partially saturated sorbent thereby is preliminarily mixed with the waste regenerate of ion
completely saturating the latter over the time period allowed exchange purification of the secondary lithium concentrate
for the sorption stage . At the same time at the second and washing carbonate solution from the stage of lithium
sorption step brine stream separated from lithium chloride carbonate precipitation, the calculated amount of lithium
by 45-55 % comes into contact with the original ( fresh ) 10 carbonate is repulped, the pulp is carbonized with carbon
sorbent, wherein it is separated from lithium chloride by dioxide until all lithium carbonate is dissolved and con
45-55 % more, partially saturating the sorbent. The brine that verted into lithium bicarbonate solution according to the
was subjected to the sorption stage (mother brine ) is sub- reaction :
jected to filtration in order to capture the small sorbent Li2CO3 + CO2 + H20-2LiHCO3 (1 ) .
fraction carried out from the columns. First step sorbent 15
saturated with lithium chloride is separated from the brine The obtained bicarbonate -chloride lithium - containing
by first draining it from the column and directing the drained solution is concentrated to LiCl content of 190-200 kg/m² by
volume back to sorption, and then by stepwise successive evaporation with simultaneous purification from calcium
washing with five volumes of washing liquid , four of which and magnesium , producing secondary lithium concentrate .
comprise the washing liquid with various content of brine 20 At that in case natural solar concentration in the basins is
components which decreases with each step of washing , and used for evaporating the solution , the process of its natural
the fifth portion is fresh water. The first portion of washing evaporation
lithium
is accompanied by gradual decomposition of
bicarbonate and conversion of calcium and magne
liquid (WL - 1 ) is used to fill the column separated from the
brine and is displaced from the column with the second sium ions into insoluble compounds with CO32- and OH
portion of the washing liquid (WL - 2 ). Directing the dis- 25 anions formed upon decomposition of LiHCO3 .
placed volume to mixing with the natural lithium -bearing The process may be described by the following chemical
brine heated and purified from suspended solids , the second reactions:
portion of the washing liquid is displaced from the column 2LiHCO3 ?Li2CO3+ H2O + CO2 (2 ) ,
with the third portion of the washing liquid (WL - 3 ) and is
used in the next cycle as WL - 1 , the third portion of the 30 Li2CO3 +H20 -- LIHCO3+ LiOH (3 ) ,
washing liquid is displaced from the column with the fourth
washing liquid ( WL - 4 ) and is used in the next cycle as Ca2++C032- ? CaCO3 ( 4 ),
WL - 2 , the fourth portion of the washing liquid is displaced
from the column with the fifth portion of the washing liquid 4Mg2 ++3C032- + 20H- + 3H20
( fresh water ) and is used in the next cycle as WL - 3 , the fifth 35 Mg ( OH )2.3MgCO3.3H20 ( 5 ).
portion of the washing liquid is displaced from the column If it is not possible to use natural solar concentration, the
with the corresponding portion of the desorbing liquid chloride - bicarbonate lithium -containing solution is first
(aqueous LiCl solution) and is used in the next cycle as heated under intense stirring and at an underpressure of 0.5
WL - 4 . In the next cycle fresh portion of fresh water is used atm to a temperature of 85 ° C. , carrying out decarbonization
as the fifth portion of the washing liquid , this arrangement 40 and precipitating calcium and magnesium into insoluble
of brine removal from the column is optimal , because it compounds CaCO3 and Mg (OH )22.3MgCO3.3H20 . Com
provides sufficiently complete brine removal ( above 98 % ) at plete decarbonization process takes 45-60 minutes . After
the minimal amount of the washing steps equal to five. The decarbonization is complete and the admixtures are precipi
predetermined amount of lithium chloride is desorbed from tated , the solution after being acidified is evaporated to
the sorbent that is washed from the brine and saturated with 45 obtain secondary lithium concentrate and condensate of
lithium chloride by filtering portions of desorbing liquids of secondary steam .
predetermined volumes through the sorbent layer on the After mixing the obtained secondary lithium concentrate
assumption that the first portion of the desorbing liquid, with the concentrated LiCl solution obtained upon process
which is a diluted aqueous lithium chloride solution with ing the mother liquor from the lithium carbonate precipita
admixed residual brine components, is removed from the 50 tion stage , it is directed to reagent purification from calcium ,
process as the primary lithium concentrate after being magnesium and sulfate ions due to increased admixtures
brought into contact with the sorbent. After bringing the content upon evaporation of the secondary lithium concen
second portion of the desorbing liquid , which is fresh water, trate . Reagent purification is performed on the basis of two
into contact with the sorbent, it is used as the first step possible alternatives . According to the first alternative BaCl2
desorbing liquid in the next cycle together with the volume 55 is used as a reagent for precipitating barium , and the
of desorbing liquid displaced from the sorbent by the calculated amount of Na2CO3 is used as a reagent for
corresponding volume of lithium -bearing brine at the sorp- purification from calcium and magnesium .
tion stage of the next cycle . The scheme of the operating The purification process may be described by the follow
cycle of the sorption - desorption unit of four columns is ing chemical equations :
shown in more detail on FIG . 2. The obtained primary 60 Ba2++ SO42- ? BaSO4V (6 ) ,
lithium concentrate is filtered in order to capture the small
sorbent fraction carried out from the sorption -desorption CaCl2+ Na2CO3 ? CaCO3\ + 2NaCl (7 ) ,
columns during desorption .
After filtration the primary lithium concentrate is sub Na2CO3 + H20 -- NaOH + NaHCO3 (8 ) ,
jected to concentration -desalination by reverse osmosis , 65
producing on one hand lithium concentrate obtained by 4MgCl2 + 3Na2CO3 + 2NaOH + 3H20 ?
reverse osmosis with the total salt content of up to 60 kg /mº, Mg ( OH )2.3MgCO3.3H2O + 8NaCl .
)
9
(
 US 11,396,452 B2
13 14
According to the second alternative Ba (OH ) 2 is used as a Conversion of the resin into the Li - form may also be
reagent for purification of the secondary lithium concentrate performed using the LiHCO3 solution instead of LiOH
from sulfate ions , and the solution of LiHCO3 , obtained by solution , according to the reaction :
carbonizing the pulp , prepared from the calculated amounts
of lithium carbonate and washing carbonate solution , with 5
carbon dioxide, is used as a reagent for purification from ( 19 )
calcium and magnesium . This alternative of the purification
process may be described by the following chemical equa H Li
tions :
2 [L] . + 4LiHCO3 2 [ L] + 4H20 + 2CO2
Ba (OH ) 2 ? Ba2++ 2OH ( 10) , 10
H Li
Ba2++ SO 2- BaSO4 + ( 11 ) ,
HCO3- + OH ? C032- +H2O ( 12) , Waste regenerating solution is directed to mixing with the
Ca2 + + CO32- + CaCO3 ( 13 ) , lithium concentrate obtained by reverse osmosis for the
4Mg2 ++3C032- + 20H + 3H20 ? 15 preparation of the Li2CO3 pulp , carbonization and using for
Mg ( OH )2.3MgCO3.31201 ( 14) . purifying the lithium concentrate obtained by reverse osmo
sis or the primary lithium concentrate from calcium and
The viability of a particular alternative of purification is magnesium
determined as the stage of plant engineering. .
After filtering and separation from the solid precipitates 20 The stream of secondary lithium concentrate passed
phase the reagent purified secondary lithium concentrate , through fine purification from calcium and magnesium is
which is the lithium chloride solution, is divided into two evaporated to LiCl content of 485-490 kg / m °, cooled to the
predetermined streams, one of which is directed to Li2CO3 room temperature, whereby NaCl and KCl are salted out
precipitation by getting into contact with the saturated from the solution to their residual total content of no more
Na2CO3 solution . The obtained Li ,C03 is used for purifying 25 than 4 kg / m .
the primary lithium concentrate or purifying the lithium After separation of NaCl and KCl crystals from the LiCl
concentrate obtained by reverse osmosis from calcium and solution the latter is evaporated, whereby lithium chloride
magnesium . The other stream of lithium chloride is directed monohydrate ( LiC1.H2O ) is crystallized, the crystals formed
to fine ion exchange purification from the residual content of are separated from the residual liquid phase by centrifuga
calcium and magnesium on the Lewatit 208 - TP ampholyte 30 tion . Centrate is directed back to evaporation , Lici H2O
in the Li- form or analogues thereof. crystals are washed from the residual mother liquor with
The process of ion exchange purification is described by chloride - alkaline solution ( 1.0-1.5 % by weight of LiOH in
the following equations: the saturated LiCl solution) . Addition of LiOH into the LiCl
1 ) Sorption solution allows conversion of the residual sodium and
35 potassium admixtures contained in the solid phase of
( 15 ) LiC1.H20 crystalline hydrate into the washing solution .
Li After being acidified , the waste washing solution containing
sodium and potassium is directed to mixing with the sec
Ca2+ + [L ] [ L ] = Ca + 2Lit, ondary lithium concentrate finely purified from calcium and
Li 40 magnesium and to evaporation . The Lici.H2O crystals
( 16 ) washed from the mother liquor are directed to two - stage
Li drying. The drying is performed in the air flow . At the first
Mg2 + + [ L ] = Mg + 2Lit. stage the crystals of lithium chloride monohydrate are dried
to a residual moisture content of 10-12 % by weight at the
Li 45 drying zone temperature of 90 ° C. At the second stage the
temperature of the drying zone is increased to 110 ° C. , to
2 ) Regeneration obtain anhydrous LiCl with a residual moisture content of
less than 4 % by weight, that corresponds to the requirements
of technical specification TU 95.1926-89 . To avoid concen
( 17) 50 tration of water vapors , the relative humidity of air at the
[L ] =Ca +
[ L ] = Mg + 4HCI outlet of the drying zones at both stages is maintained within
H 75-80 ° C. The NaCl and KCl crystals salted out during
evaporation of the secondary lithium concentrate purified
2 [ L] + CaCl2 +
MgCl2 from the admixtures comprising the LiCl.H2O crystals as an
H 55 admixture , are washed with saturated chloride solution pre
pared from the mixture of NaCl and KCl crystals. Washed
3 ) Conversion into the Li - Form
NaCl and KCl crystals are used as raw material for obtaining
alkaline solution (NaOH and KOH ) , which in turn is used
for obtaining carbonate solution (Na2CO3 and K2CO3 ) .
( 18 )
60 Lithium - containing waste washing solution formed upon
washing the NaCl and KCl crystals is directed to mixing
H Li with the purified secondary lithium concentrate and to
K
2 [L] .
H
+ 4LiOH 2 [L] + 4H20 .
evaporation. The mother liquor from the stage of lithium
carbonate precipitation, which is the NaCl solution with
3
65 concentration of 220-230 kg/m² with admixed KCl (the
content is 2 kg/ m ”) and Li2CO3 (the content is 11-12 kg/m ) ,
is in turn acidified, decarbonized and evaporated, salting out
 US 11,396,452 B2
15 16
the NaCl and KCl crystals to obtain LiCl concentration in NaCl and KCl after acidifying, is evaporated, salting out
the evaporated solution of 485-490 kg /m3. NH4Cl , to the level of LiCl content of 485-490 kg /m3. After
After separation from the NaCl and KCl crystals the separation of the crystals the liquid phase is directed to
lithium -containing liquid phase is directed to mixing with mixing with the secondary lithium concentrate before ion
the secondary lithium concentrate being transported to 5 exchange purification thereof, and the NH4Cl crystals with
reagent purification from the admixtures. The NaCl and KC1 admixtures are reacted with the CaO or CaO pulp with
crystals are washed from the mother liquor with the con- admixed MgO prepared by decomposition of the CaCO ,
densate of secondary steam , mixed with the NaCl and KC1 precipitate with admixed 3MgCO3.Mg ( OH ) 2.3H20 or lime
crystals recovered upon evaporation of the stream of the stone and dolomite according to the reaction :
secondary lithium concentrate finely purified from calcium 10
and magnesium , which is directed to obtaining commercial
lithium chloride, the mixture of crystals is dissolved in the ( 23 )
condensate of secondary steam , forming aqueous NaCl CaCO3
t = 850 ° C.
Cao CO21 , +
solution with admixed KCl with the total salt content of ( 24 )
260-270 kg /mº. The solution is finely purified from the 15
calcium and magnesium admixture by ion exchange method CaCO3 MgCO3 +
t = 850 ° C.=

CaO + MgO + 20021 .

on the Lewatit 208 - TP resin in the Na - form and is directed
to electromembrane process to obtain NaOH solution
( catholyte) and anodic chlorine gas . Catholyte is carbonized The reaction between NH4Cl and CaO in the presence of
with the effluent furnace gas , producing the
Na2CO3 solution, in accordance with the reaction :
saturated 20 water proceeds with release of heat (Q) and is accompanied
by intense distillation of ammonia in accordance with the
CO2 + 2NaOH - Na2CO3 + H2O ( 20 ) . exothermic reaction :
Soda ash solution is used as the precipitating reagent for 2NH4Cl + CaO ™ 2NH3q31 + CaCl2 + H2O + Q ( 25 ) .
obtaining the predetermined amount of Li2CO3 . Furnace gas 25 Gaseous mixture of ammonia and carbon dioxide pre
is a waste product of the process of producing heating steam pared upon preparation of CaO is , in turn , absorbed by water
in a waste - heat boiler upon burning the gaseous mixture
consisting of the natural gas and hydrogen. Gaseous mixture upon cooling in the countercurrent mode, to obtain concen
is obtained by entraining cathodic hydrogen from the gas trated (NH4) 2CO3 solution according to the reaction :
separator of the catholyte circuit of the electromembrane 30 (26) .
device with the stream of the original natural gas . Anodic 2NH3+ CO2+H20264/2CO3
Thus obtained ( NH4 ) 2CO3 solution
chlorine is converted into 3.0N - 3.5N hydrochloric acid ing Li_C0z from the secondary lithium concentrate finely is used for precipitat
solution by entraining anodic chlorine from gas separator of
the anolyte circuit of the electromembrane device with the purified Mother
from the admixtures (reaction 22 ) .
suspension formed at the stage of NH4Cl decom
stream of aqueous carbamide solution followed by absorp- 35
tion , accompanied by the following chemical reaction : position with limestone and distillation of NH3 is centri
fuged , separating the solid MgO phase with admixed SiO2
3C12 + (NH2) 2CO + H20-6HCl+N2r + CO21 ( 21 ) . and Fe_03 from the liquid phase . Liquid phase which is a
Hydrochloric acid solution is used for regeneration of ion CaCl , solution of 250-270 kg/m with little 2-4 kg/m3
exchange resin , acidifying and decarbonizing the solutions 40 admixture of NaCl and KCl is used either in municipal
services as an anti- dust reagent and deicing reagent, or as a
before evaporation , and for other purposes of the production reagent for lowering the sulfate ions content of the original
process.
The technical process of preparing the primary lithium natural brine , if the brine is characterized by a higher content
concentrate and processing thereof into technical - grade of sulfate ions .
lithium carbonate ( FIG . 3 ) differs from the technical process 45 Because the content of sodium and potassium chlorides in
of preparing the primary lithium concentrate and processing the secondary lithium concentrate finely purified from cal
thereof into anhydrous lithium chloride only in that the cium and magnesium is within 2-4 kg /m3, after the precipi
whole stream of prepared and purified from the calcium and tated lithium carbonate is washed from the mother liquor, the
total concentration of sodium and potassium in the finished
magnesium admixtures secondary lithium concentrate is 50 product is less than 0.002 % by weight. The main admixture
processed into Li2CO3 following the same scheme .
The technical process of preparing the primary lithium in the washed Li C0z is NH_C1 . However, during the
concentrate and processing thereof into battery - grade process of drying of the wet lithium carbonate NH C1 is
lithium carbonate is presented on FIG . 4. The main differ hydrolyzed to ultimately form volatile products NHz and
ences between this technical process and the technical HCl in accordance with the chemical equation:
process of preparing technical - grade lithium carbonate ( FIG . 55
3 ) consist in that the stream of the secondary lithium ( 27 )
concentrate , reagent-purified from the calcium and magne
sium admixtures, is subjected to fine ion exchange purifi t = 80-90 ° C.
cation on the Lewatit 208 - TP ampholyte in the Li - form or NH4Cl + H2O NH4OH + HCIT .
analogues thereof, and precipitation of lithium carbonate 60 ( 28 )
from the secondary lithium concentrate finely purified from NH4OH
ts20 ° C.
NH31 + H20 .
the admixtures is performed by using ammonium carbonate
according to the reaction:
2LiCl + (NH4) 2CO3 - Li2CO3 + 2NH4Cl Thus the proposed production process (FIG . 4 ) allows ,
( 22 ) . 65 given that the limestone or dolomite deposit is available, to
At that the mother liquor from the precipitation stage , produce battery - grade lithium carbonate from multicompo
which is an aqueous NH4Cl solution with little admixed nent lithium -bearing natural brines , simultaneously lower
 US 11,396,452 B2
17 18
ing the cost of production by replacing the expensive soda stages of brine removal and regeneration ) in the proposed
ash with cheaper limestone or dolomite reagents . unit is 10% higher than in the prototype.
Proposed invention will now be illustrated by the specific
examples . TABLE 2
5
Example 1 Mean Lici
content
Volume Volume Licl in the
Natural seepage lithium -bearing brine with a density of Structure
of
of the of the recovery sorbent
1215 g /dm3, pH = 6.2 , material composition ( g /dmº): LiCl
9
10 sorption-
brine
passed
sorbent
in the
ratio
from the
of the
frontal
1.16 ; NaCl —53.5 ; KC1—21.3 ; CaCl2—182.3 ; MgCl2 desorption through , column , brine , column,
47.2 ; Br 4.0 ; Fetotal_0.01 ; suspended solids 4.3 ; total unit dm3 dm3 % g /dm3
salt content of 305.4 g /dm , was subjected to centrifugation Prototype 28.2 3.7 56.1 1.76
on the laboratory sedimentation centrifuge, centrate was Proposed 28.2 3.7 93.0 1.95
separated from the solid precipitate phase . Centrate was 15
analyzed for the residual content of suspended solids and
filtered through fine textile filter. Filtrate was analyzed for Example 3
the content of suspended solids . Suspended solids captured
on the filter were washed with the countercurrent stream of Comparative tests were conducted on the pilot unit con
a mixture of filtrate and air (regenerate).Waste regenerate 20 sisting of two identical sorption -desorption columns pre
was analyzed for the content of suspended solids . Obtained pared for the stage of brine removal, loaded with 3.7 dm of
results are presented in Table 1 . the granulated DGAL -C1 sorbent each , using the following
It follows from the contents of the table that the combined procedure.
purification of the natural brine from the suspended solids 10 dm of the displacement liquid ( aqueous LiCl solution
( centrifugation + filtration ) provides the degree of purifica- 25 with concentration of 6 g /dmº) was pumped into column No.
tion at the level of 99.9 % . At that no more than 5 % of the 1 in the direction of the movement of the displacement liquid
volume of the filtered brine is required for regeneration of stream through the column section downwards from the top .
the filter, providing the concentration of suspended solids in Displacement liquid of the same volume was pumped into
the stream of waste regenerate that is close to the content of column No. 2 with similar pump in the upward direction .
suspended solids in the original brine . 30 Initial flow rate of the displacement liquid through both
columns was set at the level of 0.2 dm3/min . By the end of
TABLE 1 the experiment the flow rate through the column No. 1
Content Volume Residual Residual Volume Concen
lowered to 0.08 dm3/min , while the flow rate through the
of of the content of content of the tration column No. 2 remained constant during the whole experi
suspended original the of the filtrate of 35 ment. At that 10 dm3 of the displacement liquid passed
solids in brine suspended suspended used for suspended through the column No. 1 within 77 minutes , while the same
the subjected solids in solids in
original to centrifu the
filter solids
the centrate regen the waste
in volume of the displacement liquid passed through the col
brine , gation , centrate , filtrate , eration , regenerate, umn No. 2 within 50 minutes . Obtained results unambigu
g /dm3 dm g /dm3 g /dm3 dm? g /dm3 ously indicate that displacing brine from the sorbent layer in
- 40 the direction downwards from the top leads to compaction of
4.36 2.17 0.24 Less than
0.005
0.13 3.95
the granular layer and significant increase in its resistance to
the displacement stream , which ultimately leads to increased
pressure in the column at the same flow rate of the washing
liquid . Then comparative tests were continued in the direc
Example 2 45 tion of finding out the impact of the direction of movement
of the displacement liquid on the degree of washing from the
Comparative tests using natural stratal lithium -bearing brine . For this purpose desorption of LiCl from the sorbent
brine of the Znamenskoye deposit in the Irkutsk region separated from the brine in the columns No. 1 and No. 2 was
purified from suspended solids and iron , were conducted on performed. Upon desorption the following primary lithium
the laboratory bench represented by sorption -decorption 50 concentrates were obtained . Concentrate from the column
units of two columns (prototype) and four columns (pro- No. 1 ( composition, g /dmº): Lic1—5.3 ; residual brine—6.4 .
posed unit , FIG . 4 ) . Brine composition ( g /dmº): LiCl— 2.5 ; Concentrate from the column No. 2 ( composition , g / dmº):
NaC1—6.1 ; KC1—8.2 ; CaCl2-330; MgCl2—115 ; Br - LiCl —5.1 ; residual brine 6.2. The experiment has shown
10.1 ; total salt content of 472 g / dmº, pH value of 4.2 . 28.2 that the degree of washing the sorbent from the brine
dm of the original brine was passed through each of the 55 virtually does not depend on the direction of movement of
units : through one column with the sorbent that was sub- the displacement liquid through the sorbent layer. Thus by a
jected to regeneration stage in the prototype, successively set of two factors displacement of the brine in the upward
through two columns in the proposed unit ( the first column direction is more preferred.
in the direction of the movement of the brine stream had
partially saturated sorbent, the second column had the sor- 60 Example 4
bent that was subjected to regeneration stage ) . Comparative
tests results are presented in Table The influence of the amount of steps of washing the
It unambiguously follows from the contents of Table 2 sorbent from the brine in the column that was subjected to
that the recovery ratio in the proposed sorption -desorption the sorption stage on the residual brine content in the
unit is more than 11.6 times higher than in the prototype unit. 65 obtained primary lithium concentrate was studied on a pilot
Furthermore, the degree of sorbent saturation with lithium bench including a sorption -desorption unit of four columns .
chloride in the frontal column ( the column changing over to The study was performed in a set mode , strictly following
 US 11,396,452 B2
19 20
the sequence of the process stages presented on FIG . 1 . TABLE 4 - continued
Natural brine of the Znamenskoye deposit in the Irkutsk
region (the composition is provided in Example 2 ) was used Substance
( element, ion )
Content, % by
weight
as the lithium -bearing brine . Load volume of the granulated
sorbent in the columns of sorption -desorption unit was 3.7 5 Si
OH
Less than 0.002
0.01
dm . The volume of washing liquid on each of the washing SO4 0.04
steps was 1.1 dm ”. Obtained results are presented in Table Pb Less than 0.003
3. SO4 Less than 0.005
The studies have shown that the optimal amount of steps HO 0.2
10
in stepwise -countercurrent washing of the sorbent from the
brine is five washing steps, because further increasing the Furthermore, during the preparation of Licl from the
amount of washing steps does not lead to significant increase primary lithium concentrate, the following was produced as
in the purity of the obtained primary lithium concentrate , byproducts: NaCl -644.9 g ( 641.1 g from the mother liquor
while the operational costs attributed to increase in the from the lithium carbonate precipitation stage , 3.8 g from
amount of washing steps do increase significantly. At the 15
the secondary lithium concentrate deeply purified from
same time reducing the amount of washing steps leads to calcium and magnesium ); KC1-10.6 g , comprising LiCl as
content of the brine components in the primary lithium an admixture in the amount of 0.02 % by weight, i . e . 0.13
concentrate increased by more than three times . g.

TABLE 3
20 Example 6
Load Composition of the Crystals of NaCl + KC1 with admixed LiCl were dissolved
volume Volume Original brine primary lithium in the demineralized water bringing the total salt content of
of the of composition , concentrate
the solution to 262 g /dm3 ( solution volume being 11 dmº).
sorbent the g /dm ? produced
25 The solution was subjected to electromembrane process on
Amount into washing the rest of the rest of the laboratory electrolysis cell ( CTIEM - 1 membrane, cur
of SDU liquid on
washing columns, each step, components
the brine the brine rent density 2 kA /m²) in the circulation -withdrawal mode of
steps dm3 dm3 Licl in total Lici components
in total catholyte movement and circulation - supplying mode of
anolyte movement (alkali metal chlorides solution ). Upon
3.7 1.1 2.5 469.5 6.0 77.2 30 processing 2.73 dm of alkaline solution was obtained,
auw
4
5
6
3.7
3.7
3.7
1.1
1.1
1.1
2.5
2.5
2.5
469.5
469.5
469.5
5.9
6.1
6.0
23.7
6.9
comprising ( g /dm3): NaOH— 160.57 ; KOH—2.92 ; LiOH
0.03 . The solution was brought into contact with effluent
6.4
furnace gases of the gas burner in which the propane -butane
mixture was burned . Carbonization was stopped when the
Example 5 35 alkaline value of the carbonized solution changed over to a
pH value of 10. After carbonization the volume of the
3 solution decreased to 1.98 dm3. The content of alkali metal
200 dm of the natural lithium -bearing brine of the Zna carbonates was as follows ( g /dm ” ): Na2CO3 -293.23 ;
menskoye deposit m the Irkutsk region ( the composition is K2CO3_4.93 ; Li , C030.05 . Obtained solution having the
provided in Example 2 ) was processed on the experimental 40 temperature of 75.4° C. was brought into contact with the
bench . The processing was performed following the flow LiCl solution having the concentration of 196 g/dm and the
charts presented on FIG . 1 and FIG . 2 , producing anhydrous volume of 2.41 dm ». The yield of Li_C03 in the solid phase
lithium chloride. At that the alternative of concentrating the was
primary lithium concentrate by reverse osmosis with puri g /dm 365.3 at the Li_CO , content in the mother liquor of 11.2
”. It unambiguously follows from the obtained results
fication of the lithium concentrate obtained by reverse 45 that chloride crystals recovered from the mother chloride
osmosis from calcium and magnesium by thermal decom solution formed after precipitating Li CO23 from the second
position of lithium bicarbonate produced in the lithium ary lithium concentrate may be processed into carbonate
concentrate obtained by reverse osmosis by carbonization of
the lithium carbonate solid phase , preliminarily included Na C0 , solution comprising K2CO3 and Li CO3 , which is
also an effective agent for precipitating Li , CO2 from the
into the lithium concentrate obtained by reverse osmosis , 50 LiCl solution .
with carbon dioxide . To obtain lithium carbonate necessary
for purification of the lithium concentrate obtained by Example 7
reverse osmosis in this experiment, soda ash solution with a
concentration of 300 g /dmº was used, obtained by dissolving 700 dm3 of the natural lithium -bearing brine of magne
commercial Na2CO3 in the demineralized water. Conse- 55 sium chloride type from the Qinghai provence (Gaermu,
quently 464.8 g of anhydrous lithium chloride was obtained , China) was processed on the experimental bench, the brine
chemical composition thereof is presented in Table 4 . having the following composition , g /dmº: Licl — 2.75 ;
NaCl — 23.1; KC1—19.1 ; MgCl2—349.2 ; B40 ,–1.2 ;
TABLE 4 SO4-2.3 ; Fe 0.003 ; density — 1280 g /dmº, pH value 6 ; 2

Substance Content, % by 60 total salt content of 401 g / dm ", strictly following the flow
(element, ion ) weight chart presented on FIG . 3 .
Licl
The brine was processed in batches of 50 dm² each . Mean
( Na + K)
99.52
0.03
lithium recovery ratio from the brine was 90% . 14 samples
Ca Less than 0.005 of lithium carbonate were obtained , a total of 1507.9 g .
Fe Less than 0.001 65 Chemical analysis has shown that the composition of the
Al Less than 0.005 obtained product was stable . Analysis results are presented
in Table 6 .
 US 11,396,452 B2
21 22
TABLE 6 It follows from the contents of the table that the purity of
lithium carbonate obtained from natural lithium -bearing
Content of the component,
% by weight
brine using the proposed technology ( the scheme on FIG . 4 )
is higher than 99.8 % , and the prepared product corresponds
Component typical best 5 to the requirements of the global market for battery - grade
analyzed product product Li_C03
Li2CO3 99.6 99.7 CITED LITERATURE
Na 0.0250 0.0230
C1 0.0080 0.0040
Ca 0.0290 0.0040 10 1. Y. I. Ostroushko, T. V. Degtyareva Hydromineral raw
Mg 0.0040 0.0024 material is a sustainable lithium source. Analytical review .
SO4 0.0100 0.007 Moscow, publ . by TSNIATOMINFORM , 1999 , 64 p .
K 0.0030 0.0021 2.U.S. Pat . No. 4,243,392 Process for solar concentration of
loss of ignition 0.0960 0.0622 lithium chloride brines/ P. M. Brown, et. al . Filed on 23
( 200 ° C. ) Jul . 1981 .
insoluble 0.1550 0.0950
precipitate ( HCI ) 15 3. U.S. Pat.No.4,274,834 Process for purification of lithium
Fe 0.0004 0.0003 chloride / P . M. Brown , et . al . Filed on 23 Jul . 1984 .
4.U.S. Pat . No. 4,271,131 Production ofhighly pure lithium
chloride / P . M. Brown et . Al . Filed on 2 Jun . 1981 .
It follows from the obtained results that the purity of the 5. U.S. Pat . No. 5,219,550 Production of low boron lithium
lithium carbonate obtained from the natural lithium -bearing 20 carbonate from lithium containing brine / P . M. Brown , D.
brine using the proposed process ( the scheme on FIG . 3 ) is A. Boryta . Publ. on 1993 .
significantly higher than 99 % , and the prepared product 6. from U.S. Pat . No. 6,207,126 Recovery of lithium compounds
brines / D . A. Boryta , T. F. Kullberg, A. M. Nhurston.
corresponds to the requirements of the global market with Filed on 2001 .
respect to technical - grade Li2CO3 . 25 7. U.S. Pat . No. 4,159,311 Recovery of lithium from brines /
J. M. Lee , W. C Bauman . Appl. 26 Jun . 1979 .
Example 8 8. U.S. Pat . No. 4,221,767 Recovery of lithium from brines /
J. M. Lee , W. C. Bauman . Appl. 9 Sep. 1980 .
600 dm of the natural lithium -bearing brine of the Zna 9. U.S. Pat . No. 4,347,327 Recovery of lithium from brines /
menskoye deposit in the Irkutsk region (the composition is 30 31 Aug.Lee1982
J. M. , W. C. Bauman . Appl. 19 Nov. 1979. Publ. on
.
provided in Example 2 ) was processed on the experimental 10. U.S. Pat . No. 4,477,367 Recovery of lithium from
bench following the flow chart presented on FIG . 4. The brines /J . L. Burba . October 1984 .
brine was processed in batches of 50 dm3 each . Mean Lici 11. U.S. Pat . No. 5,389,349 Recovery of lithium values from
recovery ratio from the brine was 93 % . Slaked lime from 35 brines / W.C . Bauman , J. L. Burba. Filed on 24 May 1990 .
Publ . on 14 Feb. 1995 .
PAO “ Krasnoyarskiy khimiko -metallurgicheskiy zavod ” 12. U.S. Pat . No. 5,599,516 Recovery of lithium values from
was used for decomposition of NH_C1 salt . Balloon carbon brines / W . C. Bauman, J. L. Burba . Filed on 13 Feb. 1995 .
dioxide was used to obtain the absorbed mixture of NHz : Publ . on 4 Feb. 1997 .
Cl2 =2 : 1 . Mean value of the recovery ratio of the ammonium 40 13. N. P. Kotsupalo , A A. D. Ryabtsev Chemistry and
salt was 99.2 % . Limestone decomposition was not carried technology of obtaining lithium compounds from lithium
out because practical implementation of this process is bearing hydromineral raw material, publ. by Geo , Novo
sibirsk , 2008 , 291 p .
obvious . 12 samples of lithium carbonate were obtained . A 14. PCT/DE 01/04062 Method for obtaining granulated
quarter of weight was taken from each sample and thor- 45
sorbent for lithium recovery from the brines and a plant
oughly mixed . Representative samples were taken from the for implementation thereof / A . D. Ryabtsev, N. P. Kotsu
obtained mixture and analyzed for the content of the main palo , L. T. Menzheres et . al . Filed on 25 Oct. 2001 .
substance and admixtures , the content of which is limited by 15. Pat. RU2223142 Method for obtaining sorbent for
recovery of lithium from the brine/ L . T. Menzheres, A. D.
the requirements for battery - grade lithium carbonate . Ryabtsev, E. V. Mamylova et. al . Publ. on 10 Feb. 2004 .
Obtained results are shown in Table 7 . Bull . No 23 .
TABLE 7

Li2CO3
content,
%
by Admixture content, % by weight.

weight Na Mg ??. K Fe Zn Cu Pb Si Al Mn Ni SO42 Cl

more less less less less less less less less less less less 0.0005 less 0.001
than than than than than than than than than than than than than
99.8 0.001 0.002 0.002 0.001 0.0005 0.0003 0.0003 0.001 0.0003 0.001 0.001 0.01
 US 11,396,452 B2
23 24
16. Pat. RU2455063 Method for producing granulated sor- 5. The method of claim 1 , wherein the granulated sorbent
bent for lithium recovery from the brine / A . D. Ryabtsev, is LiCl.2Al ( OH ) 3.mH2O based sorbent with deficiency of
V. I. Titarenko , N. P. Kotsupalo et. al . A decision on patent LiC ) , wherein m= 3-5 .
grant of 27 Feb. 2012 . 6. The method of claim 1 , wherein the washing at step 2 )
17. PCT/DE 01/04061 Method for obtaining lithium chlo- 5 is carried out by stepwise displacement of the brine from the
ride from solutions and a plant for implementation layer of granulated sorbent with portions of displacement
thereof/ A . D. Ryabtsev, L. T. Menzheres, V. I. Titarenko liquid of predetermined volume.
et . al . Filed on 25 Oct. 2001. 7. The method of claim 1 , wherein the desorption step
18. Pat. RU2516538 Method for obtaining lithium concen- 3 ) is carried out by stepwise filtering through the layer of
trate from lithium -bearing natural brines and processing 10 granulated sorbent of portions of desorbing liquids, remov
thereof ( prototype ). ing the portions of filtrate from the process as the primary
What is claimed is : lithium concentrate , which is a lithium chloride solution
1. A method for preparing a lithium concentrate from with admixture of components of the brine .
lithium - bearing brine, comprising: 8. The method of claim 7 , wherein the admixture of
1 ) sorption of lithium chloride from lithium -bearing brine 15 components of the brine is selected from calcium , magne
using a sorption -desorption unit, the unit comprising sium , sodium , potassium , boron , sulfate ions .
granulated sorbent, 9. The method of claim 1 , further comprising a step of
2 ) washing the sorbent saturated with lithium chloride purification of the primary lithium concentrate from calcium
from the brine, and magnesium admixtures by precipitating them in the
3 ) desorption of the lithium chloride from the sorbent to 20 form of insoluble CaCO3 and Mg(OH)2.3MgCO3.3H2O
obtain primary lithium concentrate, wherein : salts .
the sorption -desorption unit consists of four columns each 10. The method of claim 1 , wherein the linear velocity of
filled with the granulated sorbent, wherein two columns the liquid phases in the columns on all stages of producing
are at the stage of lithium chloride sorption from the the primary lithium concentrate is maintained at the level of
brine, one column is at the stage of washing the lithium 25 5-7 m /h , the sorbent is washed from the brine by preliminary
chloride saturated sorbent from the brine, and one draining the brine from the column, then stepwise washing
column is at the stage of lithium chloride desorption the sorbent successively with five portions of washing liquid
from the sorbent washed from the brine, in the upward direction, each having 1/3 of the volume of the
wherein a stream of the brine is always first passed sorbent in the column, wherein four portions out of five are
through the column with the sorbent partially saturated 30 the washing liquids with various content of brine compo
with lithium chloride the first sorption step , nents which decreases with each step of washing , and the
then the stream of the brine is passed through the column fifth portion is the volume of fresh water, wherein the first
with the sorbent, which column has passed the stage of portion of the washing liquid is used to fill the column and
lithium chloride desorption from the sorbent, the sec- then it is displaced from the column with the second portion
ond sorption step, 35 of the washing liquid , directing the displaced volume to
wherein after the sorbent is completely saturated with mixing with the lithium -bearing brine purified from sus
lithium chloride in the first column (in the direction of pended solids , the second portion of the washing liquid is
the brine stream ), this column is changed over to the displaced from the column with the third portion of the
stage of washing the sorbent from the brine, washing liquid and is used in the next washing cycle as the
the column that was at the stage of washing the sorbent 40 first portion of the washing liquid, the third portion of the
from the brine is changed over to the stage of lithium washing liquid is displaced from the column with the fourth
chloride desorption from the saturated sorbent, portion of the washing liquid and is used in the next cycle
the column that was at the stage of lithium chloride as the second portion of the washing liquid , the fourth
desorption from the saturated sorbent is changed over portion of the washing liquid is displaced with the fifth
to the stage of sorption as a column of the sorption 45 portion of the washing liquid and is used in the next cycle
second step , and as the third portion of the washing liquid, the fifth portion of
the column that was at the stage of sorption as a column the washing liquid is displaced from the column with the
of the second sorption step is changed over to the stage corresponding portion of the desorbing liquid and is used in
of sorption as a column of the first sorption step , the next cycle as the fourth portion of the washing liquid , in
then the cycle is repeated. 50 the next cycle fresh portion of fresh water is used as the fifth
2. The method of claim 1 , wherein the lithium -bearing portion of the washing liquid, desorption of lithium chloride
brine prior to step 1 ) is subjected to : from the sorbent washed from the brine is carried out by
sedimentation centrifugation of the brine to obtain a successive stepwise filtering of predetermined volumes of
centrate and the centrate is then filtered by filters, or the desorbing liquids through the sorbent layer in the col
filtration by filters to obtain lithium -bearing brine purified 55 umn, on the assumption that after bringing the first volume
from suspended solids . of the desorbing liquid, which is a diluted aqueous lithium
3. The method of claim 2 , wherein the filters are regen- chloride solution with admixed residual brine components
erated by back washing with the stream of filtered brine ( first step desorbing liquid ), into contact with the sorbent, it
followed by sedimentation centrifugation of the stream of is removed from the process as the primary lithium concen
waste regenerating brine with removal of the precipitate and 60 trate , after bringing the second volume of the desorbing
feeding the centrate to the stage of filtering of the original liquid, which is fresh water (second step desorbing liquid ),
lithium -bearing brine , if the suspended solids in the original into contact with the sorbent, it is used as the first step
brine are in the amount of less than 1.0 kg/m3. desorbing liquid of the desorption stage in the next cycle
4. The method of claim 1 , wherein the lithium -bearing together with the volume of the desorbing liquid displaced
brine at step 1 ) is filtered (passed ) through the layer of 65 from the column filled with sorbent by the corresponding
granulated sorbent in the upward direction to obtain granu- volume of lithium -bearing brine at the sorption stage of the
lated sorbent saturated with lithium chloride. next cycle .
 US 11,396,452 B2
25 26
11. The method of claim 10 , wherein the desorbing liquids from the liquid phase , the crystals are washed stepwisely in
are water with various content of lithium chloride . the regime of repulping and squeezing with three portions of
12. The method of claim 1 , further comprising steps : washing chloride brine, each having two times the volume
concentration of the purified lithium concentrate or con- of the portion of the crystals being washed, two of which
centration - desalination of the purified lithium concen- 5 portions are mixed chloride solutions (NaCl + KCI + LiCl )
trate by reverse osmosis followed by thermal evapora- with content of LiCl decreasing with each portion , and the
tion to salt out NaCl and KCl crystals ; third portion is a mixed solution of alkali metal chlorides
separation of NaCl and KCl crystals; free of LiCl , after bringing the first portion of the washing
dilution of the filtrate to LiCl content of 190-200 kg /mº; chloride solution (waste washing liquid ) into contact with
purification from calcium and magnesium admixtures to 10 the crystals it is directed to the stage of evaporation, pre
obtain secondary lithium concentrate . liminarily mixing it with the lithium concentrate purified
13. The method of claim 1 , further comprising: from the admixtures, the other two portions of the washing
solar concentration of the primary lithium concentrate chloride solution are used for successive stepwise washing
with respect to lithium chloride in a evaporating basin of the next portion of crystals, fresh (the third ) portion of
with simultaneous purification from calcium and mag- 15 chloride washing solution is prepared by dissolving sodium
nesium by preliminary splitting the primary lithium chloride or sodium chloride with admixed potassium chlo
concentrate into two streams, in one of which a prede- ride in demineralized water, the cooled and separated from
termined amount of lithium carbonate is repulped , the crystals lithium chloride brine with residual NaCl + KC1
carbonization of the pulp with carbon dioxide or CO2 content of no more than 2 kg/m² is evaporated until LiCl is
comprising gaseous mixture in the regime of pulp 20 converted into solid phase of lithium chloride monohydrate
circulation until all lithium carbonate is dissolved, then crystalline hydrate, the residual mother liquor from the stage
mixing this stream with the other stream of primary of lithium chloride brine evaporation and crystallization of
lithium concentrate, directing the mixed solution into Lici.H , O is separated from LiCl.H , O crystalline hydrate
the evaporating basin for concentrating the liquid phase and mixed with the purified lithium concentrate being trans
with respect to LiCl , decarbonization and gradual con- 25 ported for evaporation, lithium chloride monohydrate crys
version of the soluble calcium and magnesium chlo- talline hydrate is washed from the residual mother liquor
rides into insoluble compounds CaCO3 and with a washing liquid comprising, in wt % : LiCl — 99.0
Mg (OH ) 2.3MgCO3.3H20 , which are separated from 98.5 ; LiOH— 1.0-1.5 , waste washing liquid is acidified with
the concentrated LiCl solution comprising NaCl and hydrochloric acid to a pH = 6-7 and mixed with the purified
KCl as main admixtures to obtain secondary lithium 30 lithium concentrate being transported for evaporation,
concentrate ; washed crystals are processed from the residual alkalinity by
repulping the predetermined amount of Li2CO3 in the bringing them into contact with the calculated amount of
stream of primary lithium concentrate obtained by hydrochloric acid and dried until anhydrous lithium chloride
concentration -desalination by reverse osmosis , carbon- is obtained by two - step air flow -drying, maintaining the
izing the pulp with carbon dioxide or CO2 comprising 35 temperature of the drying zone at 85-90 ° C. during the first
gaseous mixture in the regime of pulp circulation until step , 108-110 ° C. during the second step , the moisture
all lithium carbonate is dissolved , heating the solution content of the air flow at the outlet of the drying zone being
to a temperature of 80-85 ° C. under vacuum treatment 75-80% , the other stream of lithium concentrate is used for
up to 0.5 atm , decarbonizing, directing the released precipitating lithium carbonate therefrom upon bringing it
carbon dioxide to the stage of carbonization of the pulp 40 into contact with the solution of sodium carbonate or the
prepared from lithium carbonate and lithium concen- solution of sodium carbonate comprising potassium carbon
trate obtained by reverse osmosis , and simultaneously ate , precipitated lithium carbonate is separated from the
converting CaCl , and MgCl , into insoluble CaCO3 and mother liquor by centrifugation and is directed to repulping
Mg (OH ) 2.3MgCO3.3H2O precipitates, which are sepa-
2 with the part of the stream of primary lithium concentrate or
rated from the liquid phase , concentrating the liquid 45 with the stream of lithium concentrate obtained by reverse
phase, which is an aqueous LiCl solution with admixed osmosis , for subsequent carbonization, the mother liquor
NaCl and KCl with respect to lithium chloride using from the lithium carbonate precipitating stage is acidified to
electrodialysis or heating process, or a combination a pH = 6.0-6.5 , evaporated to obtain LiCl concentration in the
thereof, until LiCl solution with the concentration of liquid phase of 485-490 kg/ m , liquid phase is separated
2

190-200 kg/m3 to obtain secondary lithium concen- 50 from the salted out NaCl crystals with admixed KCl crystals
trate . and is mixed with the stream of lithium concentrate used for
14. A method for preparation a lithium chloride, compris- obtaining lithium chloride, NaCl crystals with admixed KC1
ing : crystals are washed from the mother liquor, mixed with the
a) providing a lithium concentrate by the method accord- washed NaCl and KCl crystals that were salted out during
ing to claim 1 ; 55 evaporation of the stream of the lithium concentrate upon
b ) dehydration of the lithium concentrate . producing LiCl , dissolved in the calculated volume of
15. The method of claim 14 , wherein the lithium concen- demineralized water to obtain a solution of alkali metal
trate is split into two streams, one stream of the lithium chlorides with NaCl concentration of 250-260 kg / m ”, the 9

concentrate is first subjected to reagent purification from solution is subjected to electromembrane process generating
magnesium , calcium , sulfate and borate ions using barium 60 NaOH solution and hydrogen at the cathode and chlorine at
hydroxide or oxide and carbon dioxide as reagents, then it is the anode , generated hydrogen is mixed with the stream of
2

subjected to fine ion exchange purification from calcium and natural gas , the gaseous mixture is burned to give heat
magnesium on a polyampholyte in the Li- form , concentra- energy for obtaining heating steam , which in turn is used as
tion by evaporation to LiCl content of 485-490 kg/m3 heating medium in evaporating lithium concentrates and
( lithium chloride brine) , the obtained lithium chloride brine 65 mother chloride liquor from the Li , CO3 precipitating stage ,
is cooled to room temperature, separate the precipitated the furnace gas comprising CO2 is used for carbonizing the
NaCl and KCl crystals with admixed LiC1.H2O crystals NaOH solution , converting it into Na2CO3 solution (carbon
 US 11,396,452 B2
27 28
ate solution) and using it as the precipitating reagent at the water pulp comprising CaO with admixed Mgo , SiO2 and
lithium carbonate precipitating stage , anodic chlorine is Fe2O3 , removing the released ammonia , mixing it with
induced and absorbed by the stream of aqueous carbamide carbon dioxide at the ratio of 2 : 1 and absorbing the gaseous
solution, thereby producing hydrochloric acid solution used mixture by water upon cooling the liquid and gaseous phases
for acidifying carbonate - containing solutions before evap0 5 in the stepwise countercurrent mode , removing the waste
ration thereof and for regeneration of the waste polyampho absorbent as saturated ammonium carbonate solution used
lyte . for precipitating lithium carbonate, the pulp formed after the
removal of ammonia is separated by filtration or centrifu
16. A method for preparation lithium carbonate, compris gation
ing : , the liquid phase of calcium chloride solution with
a) providing a lithium concentrate by the method accord- 10 used
admixed NaCl and KCl is removed from the process and
in municipal services during summer season as a
ing to claim 1 ; reagent for consolidation of earth roads and as a deicing
b ) precipitation of the lithium carbonate. reagent during winter season , solid phase of Mgo with
17. The method of claim wherein the lithium concen
admixed SiO2 and Fe2O3 is used for the production of
trate is further subjected to ion exchange purification from magnesium
calcium and magnesium using a polyampholyte in the 15 necessary forproducts , calcium oxide and carbon dioxide
decomposition of ammonium chloride and
Li- form .
18. The method of claim 16 , wherein precipitation is production
decomposition
of (NH4) 2CO3 solution are obtained by thermal
of the precipitate of CaCO3 and
carried out by using saturated aqueous ammonium carbonate Mg (OH ) 2.3MgCO3.3H2O salts formed at the stage of puri
solution at room temperature, the lithium carbonate precipi
tate is separated from the ammonium chloride mother liquor, 20 fying the primary lithium concentrate or the lithium con
centrate obtained by reverse osmosis from calcium and
one part of the lithium carbonate precipitate is used to obtain magnesium , mixed with comminuted natural limestone or
lithium bicarbonate solution which is used for purification of
the lithium concentrate obtained by reverse osmosis from dolomite .
19. The method of claim 16 , wherein precipitation is
iscalcium
washedandstepwisely
magnesium , the other part of lithium carbonate 2

in the regime of repulping and cen- 25 carried out from

it intothecontact
whole ,stream
under ofstirring
the lithium
, with concentrate
trifugation with three portions of the washing solution , each by bringing
carbonate solution comprising potassium carbonate at a
the sodium
having three times the volume of the portion of lithium temperature of 90-95 ° C. , whereby after separation from the
carbonate being washed , at a temperature of 90-95 ° C. , first
with two portions of saturated lithium carbonate solution mother liquor one part of lithium carbonate is precipitated
with the content of ammonium and chloride ions decreasing 30 and used to obtainthelithium
lithiumbicarbonate
concentratesolution
obtainedwhich is then
with each portion, and then with a portion of demineralized used to purify
osmosis or the primary lithium concentrate from calcium
by reverse
water, after bringing the first portion of the washing solution and magnesium , the other ( producing ) part of lithium car
into contact with lithium carbonate it is directed to the stage bonate is washed stepwisely in the mode of repulping and
of Li , CO3 pulp production and using it to purify of the
primary lithium concentrate or the lithium concentrate 35 centrifugation
having three
with three portions of washing solution each
times the volume of the portion of lithium
obtained by reverse osmosis from calcium and magnesium, carbonate being washed at a temperature of 90-95 ° C. , first
the other two portions of the washing solution are used for with two portions of saturated lithium carbonate solution
successive washing of the next portion of lithium carbonate , with the content of sodium and chloride ion decreasing with
washed lithium carbonate crystals are subjected to micro
wave drying to obtain a residual moisture content of 0.2 wt 40 each
after portion
bringing, and
thethen
firstwith a portion
portion of theofwashing
demineralized
solutionwater
into,
% , ammonium chloride is salted out from the mother liquor contact with lithium carbonate it is directed to the stage of
from the lithium carbonate precipitating stage by evapora Li , CO , pulp production used for carbonization , converting
tion, after separation from the mother liquor from the the solid Li CO3 phase into LiHCO3 solution and using it for
evaporation stage ammonium chloride is washed from the
residual mother liquor, waste washing solution is directed to 45 purification of the primary lithium concentrate or the lithium
concentrate obtained by reverse osmosis from calcium and
evaporation by mixing it with the mother liquor from the magnesium , the other two portions of the washing solution
lithium precipitating stage , the mother liquor from the
evaporation stage , which is 485-490 kg/m3 LiCl solution are used for successive stepwise washing of the next portion
with admixed NH_C1 , is in turn mixed with the lithium 50 of lithium carbonate, washed lithium carbonate crystals are
subjected to microwave drying to obtain aa residual moisture
concentrate before its ion exchange purification using a content of 0.4 wt . % .
polyampholyte in the Li- form , ammonium chloride washed
from the mother liquor is decomposed by treating it with