8th Sep.,2015Regina CanadaRegina,Canada

ExperimentalMeasurementofRegenerationEnergyinCO2 CaptureSystemApplyingPhaseSeparationProcessusinghighconcentration2Amino2methyl1propanolg g y p p

TakaoNakagaki*a,ShunsukeSatoag ,HiroshiSatob andYasuro Yamanakab

a WasedaUniversity,Japanb IHICorporationy, p p

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RequirementsforPCCSandhowtoapproach(Operating condition)(Operatingcondition)

SensibleheatHeatofvaporization

Absorption fluxFlow rate AbsorptionfluxFlowrate

Concentration&CO2 loadingMulti pressure stripping3)

Temperatureswing

H+ acceptor

(pKa)

RNH+RNH+Fast:RNCOO H+

MultipressurestrippingRateofreactions

Condensationprecipitateseparation

Heat of reaction (depend on substance)

pHHCO3(Lowtemp.stripping)

4)

Hr

Nonidealmixing2)DissolutionofgasintoliquidChemicalreaction

Heatofreaction (dependonsubstance)MEA1)

NovelamineBlendamines

TechnologiesQuantumchemistryOrganic synthesis

Exploringsolvent

0 1 2 3 4Regeneration energy (GJ/t)

Target

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Organicsynthesis1)RITE,COURSE50NEDOProjectreport(2006),2)Kim,I.et.al.,Chem.Eng.Sci.64(2009)20272038,3)Jassim,M.,Rochelle,G.Ind.andEng.Chem.Res.48(8)(2006)24652472,4)Oexmann,J.,Kather,A.,Int.J.ofGHGCtrl.4(2010)3643

2

Regenerationenergy(GJ/t)

2Amino2methyl1propanol(AMP) Moderately sterically hindered primary amineM.W. 89.14 g/mol Moderately,stericallyhinderedprimaryamine Lowerregenerationenergy Lowercorrosiveness Lower reaction rate (promoter: PZ etc )2) 3) Unstable

M.W.89.14g/molB.P. 165.5CM.P. 25.5C

Lowerreactionrate(promoter:PZetc.)2)3)

CH3OH

H3CO OH

H3C

NHCO

CH3Unstable

carbamate1)

H

:N HC

O

O

CH3OHH2N

: +NHC

O + CH3OHH3N

ProtonatedAMP

O OHH3C2 OH

H3C

H3CCH3

H C CH3 BicarbonateAMP

pKa=8.8(40C)

OHHN

C

:H

OH :C

O

H

OHH3C

H2N

CH3

+ Carbamatehydrolysis

Bicarbonate

Kc=[AMPCOO]/[AMP][HCO3]

Experimental:PrecipitationofAMPChemical structureAMP 50wt% (5 6M) at 40C Chemical structureby Raman spectroscopyCation: Protonated AMPAnion: Carbonate (1068 cm1)

AMP 50wt% (5.6M) at 40 C getting whitely turbid by precipitation of salt

(AMPH)2(CO3)

CO32 +2AMPH+ (AMPH)2(CO3)

AMPH+ + H2O AMP +H3O+

2H O H O+ + OH

Reaction model in AMPREA (ASPEN PLUS)*

( Equilibrium)2H2O H3O+ + OHHCO3 + H2O H3O+ + CO32

CO2 + OH HCO3

( Equilibrium)

2 3

HCO3 CO2 + OH

AMP + CO2 + H2O AMPCOO + H3O+

COO O+ CO O

( Kinetic)

/134Barzagli,F., ChemSusChem,5,(2012)17241731

AMPCOO + H3O+ AMP + CO2 + H2O*Jamal, A., et al., Chem. Eng. Sci. 61 (2006) 65716603

VLEandabsorptionrate:AMPandMEAVapor Liquid Equilibrium CO absorption rate

200

250

ol/m

2 /s) 10

7

AMP50wt%+PZ5wt%1000

)VaporLiquidEquilibrium

40 C 1atm

CO2 absorptionrate

(wt%)

100

150

nrate(kmo

Precipitation100

ssure(kPa) 40 C,1atm

10%CO2 /N2Bal.

0

50

100

absorptio

n

MEAAMP30wt%

AMP50wt%10

partialpres

10kPa,40 C1.5kPa120C 0

0 0.2 0.4 0.6CO2 loading (molCO2/molamine)

CO2

0 1

1

CO2p

CyclecapacityAMP >MEA

0 4

1) Tong D et al Int J GHG Ctrl 6 (2012)37 47

0.10 0.2 0.4 0.6 0.8 1CO2 loading (molCO2/molamine) 0.3

0.4

ding

olamine)

HCO3,CO3AMPorAMPH+ carbonateAMPorAMPH+ carbamate

K < 0.01

13CNMR

1)Tong,D.et.al.,Int.J.GHGCtrl,6(2012)37472)Jou,F.Y.et.al.,CanadianJ.Chem.Eng.73(1995)1401473)Kundu,M.et.al.,J.Chem.Eng.Data48(2003)7897964)Roberts,B.E.et.al.,Chem.Eng.Comm.64(1988)105111 0.1

0.2CO

2load

molCO2/mo Kc

ConceptualPFDandoperatingline(AMP50%)Flue gasoutlet

Liquid phaseSolid phase

g

Waterwash

Topinlet

Middle inlet

120

CO rich

milean

d

Flue gasinlet

Middleinlet

40C

80

100

C)

RichHEX

CO2richliquid

Absorber

CO2se

liquidinlet

CO2 recoveryCooler

C d

QV

60C60

80

perature(

50wt%

Richoutlet

HEX

CondenserSolidliquidseparator

40 C

40Tem

p

Topinlet

Middle inlet(Semilean)

Phase

10kPaEquil.(40wt%)

Stripper

CO2 richslurry40C

50 C

20inlet(Lean)

CO2 richslurry

separation

=Cycle capacityHypothetical

+

( )

HEX CO2richliquidReboiler

90C

50C 00.1 0.2 0.3 0.4 0.5 0.6CO2 loading (molCO2/molamine)

=Cyclecapacity

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CO2lean liquidQF 110C2 g ( 2 )

CO2 recoverybybatch operationFlue gasoutlet

Weight

Batchoperationresult

0 20 40 60 80 100 120

Liquid phaseSolid phase

g

Waterwash

Topinlet

Middle inlet

AMP H2O

AMP=50wt%100gg

milean

d

Flue gasinlet

Middleinlet

Freshsolution 2

CO

11.3g=0.46*

Equilibriumliquid:T=60C,pCO2=10kPaCO2se

liquidinlet

Cooler

(From Stripper

solution

After CO2

49%

LiquidSolidseparation:T=40oC,p=0.8atm

Solidliquidseparator

AMPcarbonatesalt

(FromStripperviaHEX)

Afterabsorption

Liquid Solid49%

61%

51%

39%Suctionfiltration

(CO2 richslurry) Aftercooling

(35%)(54%)=0.49*=0.43*Vacuumpump

Buchner funnel &filterSolid

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*AnalyzedbyTOCLiquid

7

140

MeasurementofheatoffusionH t f CO b ti b DRC

80100120

(kJ/mol)HeatofCO2 absorptionbyDRC Precipitation

MassFlowControllers

Gas

+25~30kJ/mol40C

204060 AMP25wt%(Kim,2011)

AMP30wt%AMP50wt%Syringe

GasCollectionBufferTank

00 0.1 0.2 0.3 0.4 0.5 0.6

CO2 loading (molCO2/molamine)000023.4

CO2 N2

TC HeaterDummyHeater

BallFilter

DCPower

80

100

0.5

0.0

%/g)

Stirrer PC

Thermostat

R1R2 40

60

1.5

1.0

tiveweight

tflow(W/ TGDSC

=0.00=0.51

ThermostatTemperatureMeasurement

0

20

2.5

2.0 Relat

Heat

6mgsampleonopenAlpan

Meltingpoint

peak=224J/g

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0 20 40 60 80 100 120TemperatureC(5C/min.)

1000

Operatingconditionofstripper(CO i h li ) CO

100

e(kPa)

(CO2 richliq.) CO2 recovery

CondenserQ

10

ialpressure

Stripper60C

1

CO2part

Plots:VLEexperimental HEX

CO lean liquid

CO2richliquid

0.10 0.2 0.4 0.6 0.8 1

CO2 loading (molCO2/molamine)

CO2lean liquidReboiler

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BenchscaleCO2 separationapparatusl d T 90 4 C

Backpressurevalve

Insulated andheated tubing

TIC1110C 0 54

PT 200kPa

Experimentalprocedure:1.Startupwithfilledwater

2 P h t d AMP

T3 90.4C

Packing(Inside)

EF

p

(Returnto top ofabsorber) Gas meter3.1L/min

(Chilled brine)=0.542.PumpupheatedAMP

carbonateslurrytotopofstripperatconstantrate of 30 ml/min

SamplingforTOCanalysis=0.09

RecoveredCOventilation

rateof30ml/min.3.Controlleanliquidpump&electricheater to keep water

0.000 g

Weight scaleforcondensedwater 1.36g/min

Slurry / liquidpump(30ml/min)

heatertokeepwaterlevel&T2 constant

El t i h t

(Datalogger)AMPcarbonateslurryreservoir tank

(3 Liter) Electric heater

Leanliquidpump

000023.4

Power meter

(3Liter)

Thermostatic

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p p PowermeterThermostaticwater bath(70C)

TIC2120C

10

Regenerationenergyestimation30% MEA 30% AMP 50% AMP 50% AMP (E)

2

30%MEA 30%AMP 50%AMP 50%AMP(E)M 4.91 3.37 6.62* 6.62*

PT kPa 200 200 300 200T1 C 90 90 90 110

GJ/tCO

T1 C 90 90 90 110T2 C 120 120 110 120T3 C 120 120 110 90.4PH2O_2 kPa 198.5 198.5 143.3 198.5

PCO2_2 kPa 1.5 1.5 156.7 1.5m1 molCO2/molamine 0.52 0.6 0.5 0.54m2 0.2 0.18 0.15 0.09

H kJ/ l CO 85 80 80 80

HR kJ/molCO2 85 80 80 80

Hv kJ/kg 2202 2202 2230 2202Cp kJ/kgK 3.60 3.75 3.50 3.50 kg/L 1.08 1.08 1.06 1.06

CO2 kg/L 1.08 1.08 1.06 1.06WCO2/Wsol kgCO2/kgamine 64.0 81.8 96.2 123.7

Wv/WCO2 kgH2O/kgCO2 0.22 0.22 0.12 0.23QR 1.93 1.82 1.82 1.82

GJ/tCO2QH 1.69 1.90 0.73 0.28QV 0.49 0.49 0.28 0.50QF (0.00) (0.00) (0.57) (0.57)Q 4 10 4 20 2 82 2 59

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Qtotal 4.10 4.20 2.82 2.59

4 5

Experimentalresult:regenerationenergy

4.0

4.5CO2

QV Liquid phaseSolid phase

Flue gasoutlet

Water Topinlet

3.0

3.5

yG

J/t

Est. Exp.QF

Solid phase

milean

Flue gas

Waterwash

Middleinlet

40C

2.0

2.5

nen

ergy QH

CO2sem

liquid

ginlet

CO2 recoveryCooler

d

Qv

60C

1.0

1.5

eneratio

St i

CondenserSolidliquidseparator

40C

0 0

0.5Reg

QRStripper

HEX CO rich liquid

CO2 richslurry

50C0.0

MEA AMP AMP 50%

300 kPa90/110 C

200 kPa110/120 C

200 kPa90/120 C

HEX

CO2lean liquid

CO2richliquidReboiler

QF90C

110C

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MEA30%

AMP30%

AMP 50%(Phase separation)

Conclusions

We proposed a precipitating 2Amino2methyl1propanol (AMP) carbonatesolvent process for CO2 capture and estimated regeneration energy by theequilibriumbased method using properties obtained by VLE and calorimetry.Also, a regeneration test using a benchscale CO2 separation apparatus was

conducted to empirically confirm the estimated regeneration energy of the stripper.

In order to avoid precipitating in absorber, the absorbing solution should bekept at temperatures of higher than 60 C while CO loading capacity decreaseskept at temperatures of higher than 60 C, while CO2 loading capacity decreasescompared to 40 C.

The precipitated solid obtained by simple suction filtration contained 35%p p y pmoisture and 61% of total absorbed CO2, which was equivalent to 0.49 of CO2loading.

The regeneration energy using the precipitating AMP carbonate solvent processwas estimated at 2.82 GJ/tCO2 by equilibriumbased calculation methodvalidated experimentally by a benchscale test.

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