thermodynamics of phase change solvents · ccs conference 2013: 28‐29 may, 2013 antwerp, belgium...
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Thermodynamics of Phase Change Solvents
Waseem Arshad, Muhammad; Thomsen, Kaj; von Solms, Nicolas; Svendsen, Hallvard Fjøsne
Publication date:2013
Document VersionPublisher's PDF, also known as Version of record
Link back to DTU Orbit
Citation (APA):Waseem Arshad, M. (Author), Thomsen, K. (Author), von Solms, N. (Author), & Svendsen, H. F. (Author).(2013). Thermodynamics of Phase Change Solvents. Sound/Visual production (digital)
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CCS Conference 2013: 28‐29 May, 2013Antwerp, Belgium
Muhammad Waseem Arshad
Supervisors: Assoc. Prof. Kaj Thomsen (DTU) Assoc. Prof. Nicolas von Solms (DTU)Prof. Hallvard Fjøsne Svendsen (NTNU)
Thermodynamics of Phase Change Solvents
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Outline
2
• Introduction• Experimental Work Freezing Point Depression Heat of Absorption Vapor liquid equillibrium
• Thermodynamic Modeling DEEA‐CO2‐H2O
• Main Conclusions• Future work
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Introduction
2‐(diethylamino)ethanol (DEEA)
• Low heat of reaction (bicarbonate)• Low heat requirement for reversion • High loading capacity• Low reaction rate
3‐(methylamino)propylamine (MAPA)
• Fast reaction rate• High heat of reaction (carbamate)• High heat requirement for reversion
3
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Introduction
CO2 lean phase
4
CO2 rich phase
Phase change solventDEEA‐MAPA‐CO2‐H2O system give liquid‐liquid split with lower phase rich in CO2 and upper phase lean in CO2
‐ Phase change solvents has potetial for:• Low ciculation rate in the desorber
• Smaller size of desorber (low capital cost)
• Improved energy efficiency
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Introduction
5
Lean Phase
Rich Phase
Decanter
Mixer
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6
Freezing Point Depression
• Measurement of freezing point is considered the most accurate method to determine water activity
– Water activity is a key parameter for the amount of water evaporated in the desorber
– Low water activity means less evaporation of water in the desorber and low energy consumption during solvent regeneration
– Water activity is only a weak function of temperature– Water activity measured at low temperature is not very different from water activity at absorber and stripper temperatures
– Water activity is very useful for thermodynamic modelling
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Experimental: Freezing Point Depression
7
A, Thermostatic bath with ethanol B, Cooling jacket C, Sample glass with magnetic
stirrer D, Rubber stopper with sample
glass lid E, Device for manual stirring F, Controlled temperature ethanolbath with magnetic stirrer
G, Pt100 Thermometer H, Data acquisition unit
Fosbøl, P. L.; Pedersen, M. G.; Thomsen, K. J. Chem. Eng. Data 2011, 56, 995‐1000.
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Experimental: Freezing Point Depression
8
Measured Freezing Point
Heat of Crystallisation
Crystallisation
Fosbøl, P. L.; Pedersen, M. G.; Thomsen, K. J. Chem. Eng. Data 2011, 56, 995‐1000.
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9
DEEA‐MAPA‐H2ODEEA‐H2O and MAPA‐H2O
Results: Freezing Point Depression
Arshad, M. W.; Fosbøl, P. L.; von Solms, N.; Thomsen, K. J. Chem. Eng. Data 2013, published online.
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10
DEEA‐CO2‐H2O MAPA‐CO2‐H2O
Results: Freezing Point Depression
Arshad, M. W.; Fosbøl, P. L.; von Solms, N.; Thomsen, K. J. Chem. Eng. Data 2013, published online.
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1, 2L jacketed reactor2a & 2b, CO2 storage cylinders3, CO2 mass flow controller4, Amine solution feed bottle5, Vaccuum pump
Calorimeter Model CPA‐122Chemisens AB, Sweden
11Kim, I.; Svendsen. H. F. Ind. Eng. Chem. Res. 2007, 46, 5803‐5809
4
2b
1
CO2
2a
Control DeviceVRC200
FCO2
PP
P
P
P
5
T
Control Device
Thermostat
WP TN
T TP
n
3
To air
Vacuum
Experimental: Heat of Absorption and VLE of CO2
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• Moles of CO2 (Peng‐Robinson EOS)• Power curve (Integration)• Amine concentration (known)
12
Experimental: Heat of Absorption and VLE of CO2
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Tested Concentrations
• 5M DEEA
• 2M MAPA
• 1M MAPA
• 5M DEEA + 2M MAPA (phase split)
• 5M DEEA + 1M MAPA (phase split)
Temperature = 40 oC (absorption), 80 oC and 120 oC (desorption)Total Pressure = ~6 bar
13
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Sample Results: Heat of Absorption
Overall comparison of all systems at Absorption & Desorption conditions
14
0
20
40
60
80
100
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8
∆H
abs
(kJ/
mol
CO
2)
Loading (mol CO2/ mol amine)
40oC
5M DEEA2M MAPA1M MAPA5M DEEA + 2M MAPA5M DEEA + 1M MAPA30% MEA (0.5 CO2 Loading)
0
50
100
150
200
250
0 0.2 0.4 0.6 0.8 1 1.2 1.4
Loading (mol CO2/ mol amine)
120oC5M DEEA2M MAPA1M MAPA5M DEEA + 2M MAPA5M DEEA + 1M MAPA30% MEA (0.5 CO2 Loading)
Arshad, M. W.; Fosbøl, P. L.; von Solms, N.; Svendsen, H. F.; Thomsen, K. Submitted to J. Chem. Eng. Data.
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VLE of CO2 in 5M DEEA
15
0
200
400
600
800
1000
1200
0 0.2 0.4 0.6 0.8 1 1.2
Ptot
al(k
Pa)
CO2 Loading (mol CO2/ mol DEEA)
5M DEEA 40 oC - This work
80 oC - This work
120 oC - This work
80 oC - iCap D1.3.2
100 oC - iCap D1.3.2
120 oC - iCap D1.3.2
Blue Data from Calorimeter ‐ This workRed Data from Equilibrium Cell – iCap D1.3.2
Sample Results: Vapor‐Liquid Equilibrium of CO2
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Thermodynamic Modeling
16
• Amine‐CO2‐H2O systems are electrolyte systems
• Extended UNIQUAC, an electrolyte thermodynamic model will be used to model the phase change solvents system
• The systems to be modeled are: DEEA‐CO2‐H2O MAPA‐CO2‐H2O DEEA‐MAPA‐CO2‐H2O (phase split)
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Extended UNIQUAC
17
• Extended UNIQUAC = Original UNIQUAC + Extended Debye‐Hückle
• Liquid phase activity coefficients are calculated with the UNIQAC equation
• Vapor phase fugacity coefficients are calculated with SRK EoS
Combinatorail Residual Extended Debye-Hückle
E E E EG G G G
RT RT RT RT
UNIQUAC entropic termr = volume parameterq = surface area parameter
Electrostatic interaction
UNIQUAC enthalpic termBinary interaction energy parameter
0 298.15Tij ij iju u u T
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Modeling: DEEA‐CO2‐H2O
18
Physical equilibria:
Chemical equilibria:
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Vapor Pressure of DEEA
19
0
0.5
1
1.5
2
2.5
0 50 100 150 200 250
Vapo
r Pressure/ bar
T/ oC
Extended UNIQUAC
Kapteina et al., 2005
iCap D1.3.2, 2011
Klepacova et al., 2011
Steele et al., 2002
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20
‐30
‐25
‐20
‐15
‐10
‐5
0
0 2 4 6 8 10 12
Freezing
Point/ o C
DEEA/ mol per kg water
Extended UNIQUAC
This work
Freezing Point Depression of DEEA
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21
Excess Molar Enthalpy of DEEA
‐3000
‐2500
‐2000
‐1500
‐1000
‐500
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
HE(J/ mol)
XDEEA (mol fraction)
Mathonat et al., 1997
Extended UNIQUAC
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22
VLE of CO2 in 5M DEEA
0
1
2
3
4
5
6
7
8
0 2 4 6 8 10 12 14 16
PCO2/ ba
r
CO2 / mol per kg water
Extended UNIQUAC
5M DEEA ‐ 40oC, This work
5M DEEA ‐ 120oC, This work
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23
Heat of Absorption of CO2 in 5M DEEA
‐70
‐60
‐50
‐40
‐30
‐20
‐10
00 2 4 6 8 10 12 14 16
∆Hab
s(kJ/ m
ol CO
2)
CO2 / mol per kg water
Extended UNIQUAC
5M DEEA ‐ 40oC, This Work
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Main Conclusions• Freezing point depressions were measured in CO2 loaded and unloaded systems Unloaded systems: DEEA‐H2O, MAPA‐H2O and DEEA‐MAPA‐H2O Loaded systems: DEEA‐CO2‐H2O and MAPA‐CO2‐H2O
• Heat of absorption and VLE of CO2 data were measured at 40, 80 and 120oC for the systems: 5M DEEA and 2M & 1M MAPA 5M DEEA + 2M MAPA (phase split) 5M DEEA + 1M MAPA (phase split)
• Model parameters were determined for the DEEA‐CO2‐H2Osystem
24
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Future Work
• Improving the model parameters for DEEA‐CO2‐H2Osystem
• Modeling the MAPA‐CO2‐H2O and DEEA‐MAPA‐CO2‐H2O systems
25
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Acknowledgement
• This project is fully funded by European Commissionunder the 7th Framework Program (Grant no.241393) through iCap project
26
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Thank You!