h ( µ v w } i / v v } À ] } v v e Á } l Æ µ ] À p v Ç ~/e€¦ · 0rohfxodu 0rghov 7udqvsruw...
TRANSCRIPT
![Page 1: h ( µ v W } i / v v } À ] } v v E Á } l Æ µ ] À P v Ç ~/E€¦ · 0rohfxodu 0rghov 7udqvsruw surshuwlhv ([solflw lrqlf vshflhv 3ro\phu fkdlq frqirupdwlrq 6$)7 (txdwlrq ri 6wdwh](https://reader035.vdocuments.site/reader035/viewer/2022071003/5fbff224bd391418ec6a9aef/html5/thumbnails/1.jpg)
EU funded Project
Innovation and Networks Executive Agency(INEA)
Grant Agreement Number: 727734
![Page 2: h ( µ v W } i / v v } À ] } v v E Á } l Æ µ ] À P v Ç ~/E€¦ · 0rohfxodu 0rghov 7udqvsruw surshuwlhv ([solflw lrqlf vshflhv 3ro\phu fkdlq frqirupdwlrq 6$)7 (txdwlrq ri 6wdwh](https://reader035.vdocuments.site/reader035/viewer/2022071003/5fbff224bd391418ec6a9aef/html5/thumbnails/2.jpg)
Molecular Models Transport properties Explicit ionic species Polymer chain
conformation
SAFT Equation of State Water absorption “Reaction” equilibrium Speciation
Hard Chains Dispersion Association
Reference Fluid Molecular Interactions Ion-Ion
+ -
+ +
Empirical Models Diffusivity correlation Hydration/Permeabilit
y relationship Macroscopic behavior
Kim, T. J., Li, B., & Hägg, M. B., J. Pol. Sci. B: Pol. Phys., 42 (23), 4326-4336, 2004
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Facilitated Transport for Gas Separation
Fixed CarrierMobile Carrier
Transport Mechanism
Dense
Solution Diffusion
i = 1…,nc
Sol-Diff Flux
FacilitatedSolution Diffusion
Chemical Reaction&
Facilitated Flux
Improved Performance
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Highest Density of Amino Group on Chain
POLYBASE PROPERTIES Suitable for CO2 separation
Poly-(vinylamine)
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L. Deng and M. B. Hägg, J. Mem. Sci. 363, 295-301 (2010)
R. H. vs. Permeance+ CO2 absorption+ Reaction products+ Permeant mobility
Swelling Regimes
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0.1gH2OgPVAm
Water clusters as effective free volume Pore limiting diameter Pore size distribution Percolation degree
What is the effect of (poly) electrolytes?
0.5gH2OgPVAm
0.9gH2OgPVAm
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Black: Neutral PVAmRed: 20% Protonated PVAmBlue: 50% Protonated PVAm
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Simulated displacement as function of time
Diffusive dynamics dominated by H2O Pore limiting diameter Pore size distribution Percolation degree
Charged particles strongly couple to polymer motion
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Black: Neutral PVAmRed: 20% Protonated PVAmBlue: 50% Protonated PVAm
Upper shaded area: maximum pore volumeLower shaded area: limiting pore diameter
a
Ac-
Slow-moving ionic species obstruct water channel formation
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Black: Neutral PVAmRed: 20% Protonated PVAmBlue: 50% Protonated PVAmGreen: Bulk water
Similar activation energies, different volume effects
For highly hydrated systems, diffusion follows Arrhenius power law behavior. Tortuosity-controlled environment as function of protonation.
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Numerous polymer + solvent theories, e.g. Mackie-Meares equation
D : diffusion coefficientD0 : bulk solvent diffusion coefficientΦ : effective free volume
H2O + gas solutes
J.S. Mackie, P. Meares, Proc. R. Soc. London A232, 1955
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Black: Neutral PVAmRed: 20% Protonated PVAmBlue: 50% Protonated PVAm
For high T M-M model reasonable=Free volume effect
For low T, M-M model fails=Solvent-polymer coupling > kT
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Ac-
Protonation-dependent Percolation threshold Charge groups acting
as gatekeepers H2O and gas transport
modulated by H2O channels
Free-volume effects dominate for high-T Decoupling of solvent-
polymer interactions H2O and gas diffusion
modulated by H2O
Effective Free Volume Ions strongly couple to
amine groups
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Molecular Models Transport properties Explicit ionic species Polymer chain
conformation
SAFT Equation of State Water absorption “Reaction” equilibrium Speciation
Hard Chains Dispersion Association
Reference Fluid Molecular Interactions Ion-Ion
+ -
+ +
Empirical Models Diffusivity correlation Hydration/Permeabilit
y relationship Macroscopic behavior
Kim, T. J., Li, B., & Hägg, M. B., J. Pol. Sci. B: Pol. Phys., 42 (23), 4326-4336, 2004
![Page 16: h ( µ v W } i / v v } À ] } v v E Á } l Æ µ ] À P v Ç ~/E€¦ · 0rohfxodu 0rghov 7udqvsruw surshuwlhv ([solflw lrqlf vshflhv 3ro\phu fkdlq frqirupdwlrq 6$)7 (txdwlrq ri 6wdwh](https://reader035.vdocuments.site/reader035/viewer/2022071003/5fbff224bd391418ec6a9aef/html5/thumbnails/16.jpg)
H2O + -[RNH2]- + CO2 HCO3- + -[RNH3
+]-
Reacting Water Swollen Polymer System
PVAm
Adsorbed Water Molecules Enhance the Reaction
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Reacting Water Swollen Polymer System
PVAm
Adsorbed Water Molecules Swell the Polymer Matrix
Adsorbed Water Molecules Open New ‘Windows’
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-12
-11
-10
-9
-8
-7
-6
-5
-4
-3
-2
0.000 0.100 0.200 0.300 0.400 0.500
log
D [c
m2 /
s]
Water Content [g/g]
Water Diffusion in PVAm (35°C)H2O in PVAm Water Self DiffusionFirst Regime Second Regime
Two Regimes Identified:
- Water Sorption Around Amino Groups- Water Sorption in a Water Medium Environment
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0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0.000 0.100 0.200 0.300 0.400 0.500
Poro
sity
Water Content [g/g]
Matrix Porosity
Two Regimes Identified:
- Water Sorption Around Amino Group- Water Sorption in a Water Medium Environment
S. Prager, J. Chem. Phys., 1960Choi P. et al., J. Electrochem Soc., 2005
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0
0.5
1
1.5
2
2.5
0.000 0.100 0.200 0.300 0.400 0.500
Tort
uosi
ty
Water Content [g/g]
Marix Tortuosity
Two Regimes Identified:
- Water Sorption Around Amino Group- Water Sorption in a Water Medium Environment
S. Prager, J. Chem. Phys., 1960Choi P. et al., J. Electrochem Soc., 2005
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PC-SAFT EoSPerturbed Chain Statistical Associating Fluid Theory Equation of State
(charged) Hard Chains Dispersive Interactions Associative Interactions
Reference Fluid Molecular Interactions
ares = aref + adisp+ ahb + aion
Ion interactions
+ -
+ +
Gross, Sadowski, Ind. Eng. Chem. Res., 2001Naeem, Sadowski, Fluid Phase Equilib, 2010
Huang, Radosz, Ind. Eng. Chem. Res., 1990
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Water 2B: 2sites for H Bond (+/-)PVAm 2B: 2sites for H Bond (+/-)
PVAm / Water
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CO2 / Water
Water 2B: 2sites for H Bond (+/-)CO2 2B: 2sites for H Bond (+/-)
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0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0.000001 0.00001 0.0001 0.001 0.01 0.1 1 10 100 1000 10000
RH
P CO2 kPa
0.01 g CO2 /g PVAm_308.15K 0.05 g CO2 / g PVAm_308.15K0.1 g CO2 / g PVAm_308.15K 0.15 g CO2 / g PVAm_308.15K0.2 g CO2 / g PVAm_308.15K 0.3 g CO2 / g PVAm_308.15K0.01 g CO2 /g PVAm_358.15K 0.05 g CO2 / g PVAm_358.15K0.1 g CO2 / g PVAm_358.15K 0.15 g CO2 / g PVAm_358.15K0.2 g CO2 / g PVAm_358.15K 0.3 g CO2 / g PVAm_358.15K
PVAm / CO2 / Water
Water 2B: 2sites for H Bond (+/-) CO2 2B: 2sites for H Bond (+/-)PVAm 2B: 2sites for H Bond (+/-)
T
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Understanding Diffusivity
The increase in water content open new windows in the internal structure
At higher water content the species flow towards the water channels
This causes the higher mobility / diffusivity values
Understanding Solubility
The PC-SAFT it is able to describe the water uptake in PVAm
The chemical reaction used can explain the water role in the ion formation
The pePC-SAFT can predict the total CO2
uptake as function of process parameters: Temperature Relative Humidity Partial
Pressure
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