energy 2 capture applying separation process 2 methyl 1 ...€¦ · 2 capture system applying phase...
TRANSCRIPT
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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)
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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]
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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
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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
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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 )
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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
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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
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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)
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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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