a novel reactive separation method for carbon dioxide
TRANSCRIPT
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Fatemeh Sadat Zebarjad, Jingwen Gong,
Kristian Jessen and Theodore T. Tsotsis
Mork Family Department of Chemical Engineering and Materials Science,
University of Southern California, Los Angeles, CA 90089-1211
UCFER Annual Review Meeting, October 5-6, 2021
A Novel Reactive Separation Method for
Carbon Dioxide Capture From Flue Gas
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Talk Outline
• Introduction
• Experimental Approach
• Preliminary Results
• Conclusions and Future Work
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Motivation and Project Goals
Methanol
Synthesis
Overcome
thermodynamic
limitations
Membrane Contactor Reactor (MCR)
High conversion
Fossil Fuel Extinction Excessive CO2
Emissions
CO2 separation
RWGSSyngas
Fuels
(Methanol)
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Overcoming MeS Equilibrium Limitations
Use a Membrane Contactor Reactor (MCR)
Conversion per
pass=<25%
P=30-100 bar
T=220 °Cz
CO + 2H2 ⇌ CH3OH
CO2 + 3H2 ⇌ CH3OH + H2O
CO2 + H2 ⇌ CO+H2O
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Lab-Scale MCR System
H2/CO/CO2
Sweep Liquid
H2/CO/CO2 + Methanol
Sweep Liquid+ Methanol
Liquid
Flow
Gas
Flow
Membrane
Liquid
Phase
Gas
Phase
MeOH
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MeS-MCR Advantages
▪ Higher Process Synergy - From combining reaction and
separation in the same unit
▪ Overcoming Equilibrium Limitations - Through in-situ
product removal
▪ Higher Energy Efficiency - The liquid sweep also serves
as an effective coolant
▪ A More Compact and Flexible Design
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Project Objectives
• Investigate the performance of novel integrated process combining a
RWGS reactor (RWGSR) and a MCR for efficient methanol synthesis
from waste CO2. Study its performance for a broad range of pressure
and temperature conditions.
• Use an experimentally-validated model to assess the full range of
attainable conversions, aiming to obtain >90% carbon capture and
utilization.
• Carry out a techno-economic analysis (TEA) of the proposed
RWGSR/MCR process to compare performance with that of the
conventional, absorption-based carbon separation and capture (CSC)
technologies.
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Project Tasks and Timeline
Q1 Q2 Q3 Q4 Q5 Q6 Q7 Q8
Task 1.0 - Design and Construction of the RWGS-MCR MeS System
Milestones
a) RWGSR component constructed ♦
b) WGSR and MCR-MeS components combined ♦
Task 2.0 - Testing of the Individual RWGSR and MCR Sub-Systems
Milestones
c) Performance of the RWGSR determined ♦
d) Performance of the MCR -MeS subsystem studied ♦
Task 3.0 - Testing of the Proposed CO2 Separation/Capture Process in the
RWGS-MCR MeS System
Milestones
e) Testing of the RWGSR-MCR system processing flue gas completed ♦
f) Analysis of the experimental data completed ♦
Task 4.0 - Mathematical Modeling and Process Optimization
Milestones
g) RWGSR-MCR model validated by experimental data ♦
h) Design of scaled-up system completed ♦
i)Optimization of scaled-up system completed ♦
Task 5.0 - Preliminary Process TEA
Milestones
j) Preliminary system TEA completed ♦
k) Final report prepared and submitted ♦
Quarters
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Membrane Modification
Layer Material
Thicknes
s
(µm)
Average
Pore Size
(Å)
Support α-Alumina 1100 2000-4000
First Layer α-Alumina 10-20 500
Second
Layer𝛾-Alumina 2-3 100
Length (cm) 9
Outer Diameter (mm) 5.9
Inner Diameter (mm) 4.7
Properties of the ceramic membrane • Modified Ceramic Membrane
– Hydrophobic Instead of Hydrophilic (OH-)
– Avoid Complete Wetting of the Membrane
– Fluoroalkylsilane (FAS) Agents
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Sweep Liquid
❑ Highly polar compounds; MeOH has considerably higher solubility than CO and H2
in them
❑ Typical IL’s have extremely low vapor pressures (<10-9 bar), which is advantageous
when compared to other low boiling point (B.P.) organic solvents
❑ Significantly simplified downstream separation of the MeOH from the solvent
❑ Very high decomposition temperatures
❑ High thermal capacity (thermal energy storage)
Tetraethylene glycol dimethyl ether (TGDE)
Ionic liquid advantages Ionic liquid advantages
Ethyl-3-methylimidazolium tetrafluoroborate
Ionic Liquid (IL) Organic Solvent
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CO2 Solubility in the IL
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0 0.5 1 1.5 2 2.5 3 3.5 4
Solu
bil
ity o
f C
O2
in I
L
Equilibrium Pressure (MPa)
25°C 40°C
60°C 70°C
220°C
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MeOH Solubility in the IL and TGDE
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
0 0.5 1 1.5 2 2.5 3 3.5 4
Met
han
ol
Solu
bil
ity
Equilibrium Pressure (Mpa)
TGDE-150°C
TGDE-170°C
TGDE-190°C
TGDE-210°C
TGDE-230°C
IL-200°C
IL-220°C
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MeS-MCR Performance
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IL Stability Under Reaction Conditions
HDO
HDO
1 2,3
4
5
6
1
23
4 56
Before experiment
After experiment andMeOH/H2O stripping
400 MHz 1H Nuclear Magnetic Resonance (NMR) Results of the [EMIM][BF4] IL
NMR studies show that the IL structure is stable and no irreversible bonds
with methanol and water are created.
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Task 1.0 – Design and Construction of
the RWGSR/MCR MeS System
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Schematic of Experimental Set-up
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Lab-Scale Experimental Set-Up
The combined RWGSR and MCR-MeS system.
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Task 2.0 – Testing of the Individual RWGSR
and MCR MeS Subsystems
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MeS Kinetic Studies
▪ Packed-Bed Reactor Model
2 2 2 2 23
2 2 2 2 2 22 2
2 2 2 2
2 2 2 2 2 22 2
' ' * 3
5 2 3 4 1
3
3 4
'
1 3
3 4
*
10 1
[1 (1/ )( / )]
(1 ( / )( / ) )
[1 ( )( / )]
(1 ( / )( / ) )
3066log 10
CH OH
H O H O
H O H O
a CO H H O H CO
MeOH
H H H H H O H O
CO CO H O H CO
RWGS
H H H H H O H O
k K K K P P K P P P Pr
K K K K P P K P K P
k P K P P P Pr
K K K K P P K P K P
KT
−=
+ + +
−=
+ + +
= −
*
10 3
.592
2073log 1/ 2.029K
T
−= +
2 2 22
' ' '
1 5 2 3 4 2 3 4 3 4 5 1/H Oa H H H Ok k K K K k K K K K k K k K k k= = = = =
Van den Bussche et al. (1996)
▪ Rate Expressions
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Rate Parameter Estimation
Temperature-Dependent Rate Constants
A(i) B(i)
k51.459928 31575.31
k418766.2 -0.00451
k3 7.79461E-7 91306.78
k2 4.64815E-11 126110.78
k1 153463133.88 -73698.32
K = A(i)exp(-B(i)/RT)
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RWGSR Performance at Equilibrium
CO2 equilibrium conversion in the RWGSR CF of gas mixture at the exit of the RWGSR at equilibrium.
0
10
20
30
40
50
60
70
80
0 1 2 3 4 5
CO
2E
qu
ilib
rium
Conver
sion %
RWGSR Feed, H2:CO2 Ratio
T=673K
T=773K
T=873K
T=973K
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0 1 2 3 4 5C
arb
on
Fac
tor
of
the
RW
GS
R O
utl
et
RWGSR Feed, H2:CO2 Ratio
T=673K
T=773K
T=873K
T=973K
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MeS-PBR Conversion at Various T and CF
(a) P= 20 bar, (b) P=25 bar, (c) P=30 bar; dots are the experimental points and surfaces are model calculations
a)b)
c)
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MeS-PBR Conversion at Various P and CF
(a) T= 200 oC, (b) T=220 oC, (c) T=240 oC; dots are the experimental points and surfaces are model calculations
a)b)
c)
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PBR and MCR Conversion vs. W/F, Varying T
SN=2, P=30 bar, CF=0.37 (Left Side Plot), CF=0.502 (Right Side Plot)
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PBR and MCR Conversion vs. W/F, Varying P
SN=2, T=220 oC, CF=0.37 (Left Side Plot), CF=0.502 (Right Side Plot)
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SN=2, P=30 bar, CF=0.37, W/F=20 Kg*s/mol
10
15
20
25
30
35
40
45
0 1 2 3 4 5 6 7
Co
nv
ersi
on%
Liquid Flow Rate (cc/min)
Equilibrium=200℃
PBR=200℃
MR=200℃
Equilibrium=220℃
PBR=220℃
MR=220℃
Equilibrium=240℃
PBR=240℃
MR=240℃
PBR and MCR Conversion vs. LF, Varying T
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PBR and MCR Conversion vs. LF, Varying P
SN=2, T=220 oC CF=0.37, W/F=20 Kg*s/mol
15
20
25
30
35
40
45
50
0 1 2 3 4 5 6 7
Co
nv
ersi
on%
Liquid Flow rare (cc/min)
Equilibrium=20bar
PBR=20bar
MR=20bar
Equilibrium=25bar
PBR=25bar
MR=25bar
Equilibrium=30bar
PBR=30bar
MR=30bar
Equilibrium=35bar
PBR=35bar
MR=35bar
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Progress To Date
• RWGSR/MeS-MCR lab-scale system designed and constructed.
• Performance of the MeS-MCR subsystem studied and its ability to
functions as a 2nd stage following the RWGSR validated.
• In-house MeS kinetic model validated with the additional MeS-PBR
data generated under conditions relevant to the proposed application.
• RWGS catalyst prepared and characterized. Testing to evaluate its
catalytic performance under relevant experimental conditions
currently ongoing.
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Future Work
• Continue and complete the performance evaluation of the RWGSR
subsystem. Initiate and complete the study of the integrated
RWGSR/MeS-MCR system to evaluate its performance for a broad
range of pressure and temperature conditions.
• Use the experimentally-validated model for process design and scale-
up to assess the attainable region of conversions, aiming to obtain
>90% carbon capture and utilization.
• Carry out a techno-economic analysis (TEA) of the proposed
RWGSR/MeS-MCR process to compare performance with that of
the conventional, absorption-based carbon separation and capture
(CSC) technologies.
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Potential Areas of Collaborative Work with NETL
• Preparation and characterization of novel RWGS catalysts
(ongoing).
• Optimizing engineering design and reaction conditions for the novel
CSC process and evaluating their impact on the balance of plant.
• Evaluating the economics and environmental aspects of the CSC
process, and comparing them with those of the absorption-based
processes.
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Acknowledgements
The financial support of the US Department of Energy (through the UCFER
cooperative agreement), and the technical guidance and assistance of Krista
Hill (NETL Task Monitor) and Doug Kaufmann (NETL Technical Point of
Contact) are gratefully acknowledged.