PERFORMANCE ANALYSIS OF BENCHMARK PLANT FOR

SELECTIVE LITHIUM RECOVERY FROM SEAWATER

PERFORMANCE ANALYSPERFORMANCE ANALYSISIS OF OF BENCHMARK PLANT FOR BENCHMARK PLANT FOR

SELECTIVE LITHIUM RECOVERY SELECTIVE LITHIUM RECOVERY FROM SEAWATERFROM SEAWATER

Kazuharu YOSHIZUKAFaculty of Environmental Engineering, The University of Kitakyushu

Marek HOLBA, Takeshi YASUNAGA, Yasuyuki IKEGAMIInstitute of Ocean Energy, Saga University

yoshizuka@env.kitakyu-u.ac.jp

Kazuharu YOSHIZUKAFaculty of Environmental Engineering, The University of Kitakyushu

Marek HOLBA, Takeshi YASUNAGA, Yasuyuki IKEGAMIInstitute of Ocean Energy, Saga University

yoshizuka@env.kitakyu-u.ac.jp

Application Fields of LithiumApplication Fields of Lithium

Electric vehicle Electric vehicle without emissionwithout emission

EnergyEnergy66LiLi

44HeHe

TT

nn

Next energy fuel for Next energy fuel for nuclear fusionnuclear fusion

Light alloy mixed Light alloy mixed with Al for aircraftwith Al for aircraft

Rechargeable battery Rechargeable battery of mobile IT devicesof mobile IT devices

Recovery of Lithium from SeawaterRecovery of Lithium from Seawater

Since the concentration of lithium ion in seawater is Since the concentration of lithium ion in seawater is quite low (quite low (0.10.1--0.2ppm0.2ppm) as well as that of sodium ion ) as well as that of sodium ion is extremely high (is extremely high (10,800ppm10,800ppm), selective recovery ), selective recovery method of lithium ion should be developed.method of lithium ion should be developed.

Ion exchange recovery method using MnOIon exchange recovery method using MnO2 2 type type adsorbent having spinel structure (adsorbent having spinel structure (--MnOMnO22))

This adsorbent can be synthesized from lithium manganese oxide This adsorbent can be synthesized from lithium manganese oxide (Li(LixxMnMnyyOO44) using ion exchange of Li) using ion exchange of Li++by Hby H++..

Mines and Salt Lakes Mines and Salt Lakes 14,000,000 tons14,000,000 tons

Seawater Seawater 230,000,000,000 tons230,000,000,000 tons

Economical Potential of Lithium Recovery Economical Potential of Lithium Recovery from Seawaterfrom Seawater

10-6 10-5 10-4 10-3 10-2 10-1 100 101 102 103 104 105 106 107101

102

103

104

105

106

107

Mg

BrSr

Rb

I MoU

V

NiZn

Cs

CrCu

Fe

GeAg

Co

Ga

Pt

Pd

Au

In

10-6 10-5 10-4 10-3 10-2 10-1 100 101 102 103 104 105 106 107101

102

103

104

105

106

107

I

Concentration in seawater [ppb (=Concentration in seawater [ppb (=g/kg]g/kg]

Mar

ket P

rice

[JP

Y/k

g]M

arke

t Pric

e [J

PY

/kg]

Economically Economically possiblepossible

Economically difficultEconomically difficult

Li

Angstrom pore Having Li+ sizeAngstrom pore Angstrom pore Having LiHaving Li++ sizesize

Li+0.78

LiLi++0.780.78

K+1.33

KK++1.331.33

Na+0.98

NaNa++0.980.98

Ca2+1.06

CaCa2+2+1.061.06

Ion Size Memorized AdsorbentIon Size Memorized Adsorbent

Adsorbent Having High SelectivityAdsorbent Having High Selectivity for Lithium Ionfor Lithium IonSpinel Type LiSpinel Type LixxMnMn22OO44

Synthesis of LiSynthesis of LixxMnMnyyOO4 4 and and --MnOMnO22Mn3O4MnMn33OO44 LiOHH2OLiOHLiOHHH22OO++

Molar ratio Li : Mn =Molar ratio Li : Mn = 1:2 or 1.5:21:2 or 1.5:2

Mixing & Grinding (15min)Mixing & Grinding (15min)

Pre-sinteringPrePre--sinteringsintering 425425ooC, 5hC, 5h

Mixing & Grinding (15min)Mixing & Grinding (15min)

Main-sinteringMainMain--sinteringsintering

SlowSlow--cooling in electric oven for 12hcooling in electric oven for 12h

LixMn2O4LiLixxMnMn22OO44

500500ooC, 5hC, 5h

Acid treatment by 1M HClAcid treatment by 1M HClAcid treatment by 1M HCl

-MnO2--MnOMnO22

To keep the crystal structure,To keep the crystal structure,stirring in acid solution of stirring in acid solution of molar ratiomolar ratio [Li[Li++] : [H] : [H++] = 1 : 40] = 1 : 40for overnight (Several times for overnight (Several times repeating)repeating)

IonIon--recognizable recognizable adsorbent of Liadsorbent of Li++

SlowSlow--cooling at room temp. for 1.5hcooling at room temp. for 1.5h

pH Dependency of Lithium AdsorptionpH Dependency of Lithium Adsorption

Batchwise Adsorption ExperimentBatchwise Adsorption Experiment

qq LiLi/ m

mol

g/ m

mol

g-- 11

pH of pH of SeawaterSeawater

33 44 55 66 77 88 9900

0.50.5

1.01.0

1.51.5

2.02.0

2.52.5

LiLi1.51.5MnMn22OO44LiLi11MnMn22OO44

pHpH

Metal conc.: Li (5mM) + Na (5mM)Metal conc.: Li (5mM) + Na (5mM)

Adsorbent wt.: 0.02gAdsorbent wt.: 0.02g

Aq. Soln.: 0.1MAq. Soln.: 0.1M--NHNH44OHOH--NHNH44Cl buffer, 10mLCl buffer, 10mL

Initial pH: 6.0 Initial pH: 6.0 -- 9.09.0

Time: 5hTime: 5h

Temp.: 303KTemp.: 303K

Measurement: AASMeasurement: AAS

High adsorption ability of High adsorption ability of LiLi++ at pH of seawaterat pH of seawater

Influence of Metal Ions on Lithium AdsorptionInfluence of Metal Ions on Lithium Adsorption

[M] / [Li][M] / [Li]00 200200 400400 600600 800800

0.00.0

0.50.5

1.01.0

1.51.5

2.02.0

2.52.5

qq LiLi/ m

mol

g/ m

mol

g-- 11

NaNa++MgMg2+2+CaCa2+2+KK++

Metal conc.: Li (5mM) + M (5mM~4M) Metal conc.: Li (5mM) + M (5mM~4M)

Adsorbent wt.: 0.02gAdsorbent wt.: 0.02gAq. soln.: pH 8.1 Aq. soln.: pH 8.1

(0.1M(0.1M--NHNH44OHOH--NHNH44Cl buffer, 10mL)Cl buffer, 10mL)

Time; 5hTime; 5h

Temp.; 303KTemp.; 303K

Measurement: AASMeasurement: AAS

No Influence on lithium No Influence on lithium adsorption more than adsorption more than [M] / [Li] = 800[M] / [Li] = 800

Batchwise Adsorption ExperimentBatchwise Adsorption Experiment

Granulation of Adsorbent for Column PackingGranulation of Adsorbent for Column PackingLiCl 0.25g + Chitin 0.05gLiCl 0.25g + Chitin 0.05g

in Nin N--methyl 2methyl 2--pyrrolidinone 5mlpyrrolidinone 5ml

++--MnOMnO2 2 5g under stirring5g under stirring

+ 2+ 2--propanol propanol

PrecipitationPrecipitation

vacuum filtration, rinse with vacuum filtration, rinse with deionized water, dry at 60deionized water, dry at 60ooCC

1wt.%Chitin1wt.%Chitin--granulated adsorbentgranulated adsorbent

SEM image of SEM image of granulated granulated adsorbentadsorbent

(x60)(x60)

Photograph of Photograph of granulated and granulated and

powder powder adsorbents adsorbents

Column Apparatus for Lab Scale ExperimentColumn Apparatus for Lab Scale Experiment

Bed volume (B.V.)Flow rate [cm3/min]

Adsorbent volume [cm3]Supplying time [min]

Micro tube pumpMicro tube pump

Feed solutionFeed solution Adsorption ColumnAdsorption Column

Fraction collectorFraction collector CottonCotton

AdsorbentAdsorbent

Micro tube pumpMicro tube pump

Feed solutionFeed solution Adsorption ColumnAdsorption Column

Fraction collectorFraction collector Cotton

AdsorbentGlass beads

Column Separation of Lithium from SeawaterColumn Separation of Lithium from Seawater

Aq. Soln.: Artificial seawater (pH=8.1), Adsorbent wt.: 3Aq. Soln.: Artificial seawater (pH=8.1), Adsorbent wt.: 3..0g, 0g, Flow rate: 0.Flow rate: 0.3333cmcm33/min, Elutant: 1.0 mol/L HCl/min, Elutant: 1.0 mol/L HCl

0

1000

2000

3000

4000

Li Li Na Na Mn Mn

ElutionElution

B.V. [ B.V. [ -- ]]0 5 10 15 20 25 300 100 200 300 400 500

0

5

10BreakthroughBreakthrough

B.V. [ B.V. [ -- ]]

Met

al Io

n C

once

ntra

tion

[ppm

]M

etal

Ion

Con

cent

ratio

n [p

pm]

Benchmark Plant of Lithium Recovery from Benchmark Plant of Lithium Recovery from Seawater in IOESSeawater in IOES

SeawaterSeawater

Desalination Desalination pplantlant

Evaporation Evaporation CrystallizerCrystallizer

Precipitated Solid Precipitated Solid Containing LithiumContaining Lithium

Pre filterPre filter

PP

HCl HCl solutionsolution

Adsorption columns for Adsorption columns for Li recovery with Li recovery with --MnOMnO22

PP

LiCl solution eluted by HClLiCl solution eluted by HClPerformance of EquipmentPerformance of Equipment

Adsorbent weight: 60 kg Adsorbent weight: 60 kg

Adsorbent volume: 0.6 mAdsorbent volume: 0.6 m3 3

Eluting aq. soln.Eluting aq. soln. 0.8 M HCl0.8 M HCl

Flow rate of seawater supplyFlow rate of seawater supply 200 L/h200 L/h

Benchmark Plant of Lithium Recovery from Benchmark Plant of Lithium Recovery from Seawater in IOESSeawater in IOES

Performance of EquipmentPerformance of Equipment

Adsorbent weight: 60kg x 2 columnsAdsorbent weight: 60kg x 2 columns

Adsorbent volume: 0.6mAdsorbent volume: 0.6m3 3 x 2 columnsx 2 columns

Eluting aq. soln.Eluting aq. soln. 11--0.2M HCl0.2M HCl

Flow rate of seawater supplyFlow rate of seawater supply 200L/h200L/h

Adsorption ColumnAdsorption Column Evaporation CrystallizerEvaporation Crystallizer

Benchmark Plant of Lithium Recovery from Benchmark Plant of Lithium Recovery from Seawater in IOESSeawater in IOES

Breakthrough Curve of Lithium Using Benchmark Plant Breakthrough Curve of Lithium Using Benchmark Plant for for 150 Days150 Days Operation (Operation (20020044/12/21/12/212005/7/13)2005/7/13)

Flow Volume of Seawater [mFlow Volume of Seawater [m33]]00 100100 200200 300300 400400 500500 600600 700700 800800

00

0.020.02

0.040.04

0.060.06

0.080.08

0.100.10

0.120.12

0.140.14

0.160.16Li

thiu

m C

once

ntra

tion

[ppm

]Li

thiu

m C

once

ntra

tion

[ppm

]

Evaporated Salt Obtained from Evaporated Salt Obtained from 150 Days150 Days OperationOperation

Dried Dried precipitateprecipitate791g791g

0.040.0450.050.02.02.0SrClSrCl22

n.qn.q. . 19.419.4MnClMnCl22

3.263.264.114.1113.413.4CaClCaCl22

14.314.30.570.578.28.2MgClMgCl22

3.53.50.940.943.33.3KClKCl78.178.10.260.2620.420.4NaClNaCl

0.0030.00311,00011,00033.333.3LiClLiCl

Content in Content in seawater seawater [wt%][wt%]

Concentration Concentration ratio ratio [%][%]

ContentContent[wt%][wt%]ElementElement

TheThe Components of the Precipitate Salt Components of the Precipitate Salt Obtained fromObtained from 150 Days150 Days OperationOperation

Performance of Lithium Recovery from SeawaterPerformance of Lithium Recovery from Seawater

Flow Volume of Seawater [mFlow Volume of Seawater [m33]]00 100100 200200 300300 400400 500500 600600 700700 800800

00

0.020.02

0.040.04

0.060.06

0.080.08

0.100.10

0.120.12

0.140.14

0.160.16

Lith

ium

Con

cent

ratio

n [p

pm]

Lith

ium

Con

cent

ratio

n [p

pm]

Flow Volume of Seawater [mFlow Volume of Seawater [m33]]00 100100 200200 300300 400400 500500 600600 700700 800800

00

0.020.02

0.040.04

0.060.06

0.080.08

0.100.10

0.120.12

0.140.14

0.160.16

Lith

ium

Con

cent

ratio

n [p

pm]

Lith

ium

Con

cent

ratio

n [p

pm]

1 cycle of adsorption stage would be required to 10 % of 1 cycle of adsorption stage would be required to 10 % of breakthrough of Libreakthrough of Li++ concentration:concentration:

LiLi++ Adsorption stage : 80 mAdsorption stage : 80 m3 3 (400 h)(400 h)washing stage : 1 mwashing stage : 1 m33 (5 h)(5 h)Elution stage : 0.6 mElution stage : 0.6 m33 (3 h)(3 h)Adsorbent washing stage : 1 mAdsorbent washing stage : 1 m33 (5 h)(5 h)

1 cycle of full operation = 413 h 1 cycle of full operation = 413 h (18 days) (18 days) 20 cycles of full operation / year20 cycles of full operation / year5 kg of LiCl5 kg of LiCl

8080385385kWh/gkWh/g--LiLiEnergyEnergyrequirementsrequirements

34,10013,300mm33Water consumedWater consumed34,100165,400kWhkWhEnergy consumedEnergy consumed5,300450450g/yearg/yearAdsorbed LiAdsorbed Li

Proposed Proposed casecase

PresentPresentcasecase

UnitUnit

Economical Analysis of Lithium RecoveryEconomical Analysis of Lithium Recovery

Analysis software: PowersimAnalysis software: Powersim

Energy requirement can be reduced to 1/5.

Multiple Utilization of Ocean Energy and ResourcesMultiple Utilization of Ocean Energy and Resources

Deep Ocean Water(DOW)Deep Ocean Water(DOW)

Surface WaterSurface Water

HydrogenHydrogen

LithiumLithium

DOWDOW IceIce

FoodsFoods

Mineral WaterMineral Water

Cool GreenCool GreenHouse PlantHouse Plant

Local AreaLocal AreaChilling SystemChilling System

AquacultureAquaculture

Potable WaterPotable Water

Power SupplyPower Supply

Surface W.Surface W.

DesalinationDesalination

Deep Ocean WaterDeep Ocean Water

DOWDOW

ElectricityElectricity

Fresh WaterFresh Water Reuse of DOWReuse of DOW

Ocean Thermal Energy Conversion (OTEC)Ocean Thermal Energy Conversion (OTEC)

Multiple Utilization of Ocean Energy and ResourcesMultiple Utilization of Ocean Energy and Resources