Advanced Membrane Reactors in Energy Systems Development of novel membranes for membrane reactors.
Wim Haije Joop Schoonman Cor PetersWim Haije, Joop Schoonman, Cor Peters
www.ecn.nl
Advanced Membrane Reactors in Energy SystemsAdvanced Membrane Reactors in Energy Systems Development of novel membranes for membrane reactors.
Objective:
The purpose of this project is to develop H2 and CO2 membranes to allow combinations of natural gas reforming or WGS with H2 or CO2 separation in separation enhanced reactors, i.e. membrane reactors, for carbon-freeseparation enhanced reactors, i.e. membrane reactors, for carbon free hydrogen production or electricity generation.
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The ECN TUD GCEP project layoutoverall efficiencies
economics
The ECN-TUD GCEP project layout
systemstudies
b
experimentalresults
reactorrequirements
reactordesign
membrane & catalyst
development
desired specificationsfundamental knowledgecharacterization
reactor testspatentsIP
materialsresearch
IPpublications
newdevelopments
T k 1 S t l i d th d i l ti E t d b ECNTask 1. System analysis and thermodynamic evaluations Task 2. Hydrogen membrane research & development Task 3. CO2 membranes research & development Task 4. Catalyst screening Task 5. Reactor modelling and design
Executed by ECNExecuted by TUD Executed by ECN+TUD Executed by ECN Executed by ECN
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Task 5. Reactor modelling and design Executed by ECN
A li ti th l hN2, H2O
Application: the general scheme
Air
O 79% Npowerpowerplantplant
CH
O2, 79% N2
H2
HTS
Natural gasCH4, LTS
Reforming Shift H2/CO2separationseparation CO2
H2-MR: SR + WGS
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CO2-MR: WGS only
A li ti th l hApplication: the general scheme
Hi h idH2O Catalyst particles
Membrane
or natural gasSyngas (CO,H2,CO2) Retentate
High-pressure sideH2O
CH4+H2O CO+3H2 CO+H2O H2+CO2 H2, H2O,(CO2,CH4, CO)
y p
MembranePermeate CO2
Low-pressure side
In steam sweep flowSteam sweep flow CO2 CO2 CO2 CO2
Low pressure side
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Membrane developmentCO3-ions
• ECN: CO2 selective membranes (hydrotalcite): H2O
• TU Delft: Nano-structured ceramic membrane for perm selective H2 separation:
• TU Delft: Ionic liquids for CO2 separation:
NN CH3CH2
CH2
CH2
CH3 SO
OC
F
FF
C
F
F
F
SO
O
N+
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Membrane development
Mechanisms of separation:
• Thermal assisted hopping ECNpp gof carbonate through the bulk lattice:
TUD• Molecular sieving:
• Affinity based
U
TUD- Dissolution-diffusion - Preferred adsorption
and exclusion: ECN
TUD
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Characterisation and development of CO2 selective ceramic dense or porous membranes
Materials Science-HTC membranes
or porous membranes CO3-ions
Brucite layer
Mg6Al2(OH)16CO3·4H2O (lit.) H2O
CO2 transport channel??
Rhombohedral system:
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a=b≈3Å c≈23Å mR3−
Materials Science-HTC membranes
• Membrane material issues:- Thermal stability- Mechanical stability- Synthesis- Compositional windowCompositional window- (Micro)structure- Morphology
• Key question:- Porous or dense??
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700
20oC
450oC
Materials Science-HTC membranes
500
600
700 450oC
400oC
Lin
(Cps
)
300
400350oC
300oCInterlayer water out: ≈1.5 Å
10
100
200
300 C
100oC
01 089 0460 (C) H d t l it (M 0 667Al0 333)(OH)2(CO3)0 167(H2O)0 5 Rh b H 3 04600 b 3 04600 22 77200 l h 90 000 b t 90 000 120 000 P i iti R 3 (166)File: MG 50 pellet RT N2 after heattreatments.raw - Start : 5.000 ° - End: 80.000 ° - Step: 0.050 ° - Step time: 4. sFile: MG 50 pellet 450 N2 H2O.raw - Start: 5.000 ° - End: 80.000 ° - Step: 0.050 ° - Step time: 2. sFile: MG 50 pellet 400 N2 H2O.raw - Start: 5.000 ° - End: 80.000 ° - Step: 0.050 ° - Step time: 2. sFile: MG 50 pellet 350 N2 H2O.raw - Start: 5.000 ° - End: 80.000 ° - Step: 0.050 ° - Step time: 2. sFile: MG 50 pellet 300 N2 H2O.raw - Start: 5.000 ° - End: 80.000 ° - Step: 0.050 ° - Step time: 38. sFile: MG 50 pellet 100 N2 CO2.raw - Start: 5.000 ° - End: 80.000 ° - Step: 0.050 ° - Step time: 2. s
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2-Theta - Scale8 10 20 30 40 50 60 70
In-Situ XRD:
HTC under
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01-089-0460 (C) - Hydrotalcite, syn - (Mg0.667Al0.333)(OH)2(CO3)0.167(H2O)0.5 - Rhombo.H.axes - a 3.04600 - b 3.04600 - c 22.77200 - alpha 90.000 - beta 90.000 - gamma 120.000 - Primitive - R-3m (166) N2/CO2/H2O
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230°C
Materials Science-HTC membranes
6
8
10
12
eigh
t (m
g)
Sample weight
CO2
Water
150°C 230°C
320°C440°C
Porous!!
0
2
4
6
0 1000 2000 3000 4000 5000 6000
We Porous!!
Time (s)
( )( ) ( )( ) OyHOxHOHCOAlMgOyHOxHOHCOAlMg Cads 2212324
1502212324 ... +⎯⎯ →⎯ ° (1)
Decomposition pathway from in-situ XRD + DRIFT, TGA/MS:
( )( ) ( )( ) OxHOHCOAlMgOxHOHCOAlMg C212324
230212324 . +⎯⎯ →⎯ ° (2)
( )( ) ( ) OHOAlOHMgMgCOOHCOAlMg C23223
32012324 3.3. +⎯⎯ →⎯ ° (3)
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( ) OHCOOMgAlMgOOAlOHMgMgCO C2242
4403223 3.3.3. ++⎯⎯ →⎯ ° (4)
Neutron Diffraction on GEM, ISIS
Materials Science-HTC membranes
Mg25,
Mg50
Mg90
Composition: Mg/Al=1.8 ⇒
Mg0 64Al0 36(OH)2(CO3)0 18·1.0 H2O
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Mg0.64Al0.36(OH)2(CO3)0.18 1.0 H2O
Materials Science-Porous HTC membranes
Mechanical instability of these claylike materialsMechanical instability of these claylike materials automatically leads to supported membranes.
Two main routes:
•Applying a coating of HTC on a support•Applying a coating of HTC on a support
•Modifying the surface of the outer support layer to obtain CO affinity (basicity) providedlayer to obtain CO2 affinity (basicity) provided the pore size is small enough.
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Materials Science-Porous HTC membranes
Prerequisite in the coating case is to be able to make small, nano sized, particles. Options:
C i it ti f M t l lt•Co-precipitation from Metal-salt precursors
•Exfoliation of HTC with formamide
•Sol-gel synthesis
•Emulsions (to be done)
Prerequisite for surface layer modification is finding the right, reactive, surface, the right
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modifier and the right reaction conditions.
Materials Science-Porous HTC membranes
Co-precipitation:p p
Small particles 10-30 nm found in aggregates that are hard to disintegrate
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Materials Science-Porous HTC membranes
Exfoliation:Exfoliation:
Mentioned in literature as aliterature as a method to peel off the brucite layers of HTCHTC.
Could not be reproduced: large aggregates
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Materials Science-Porous HTC membranes
Sol-gel synthesis:Sol gel synthesis:
A large number of recipes have been tested with variations in precursors, solvent, pH, ratios, temperature etctemperature, etc.
All variants resulted in HTC plus impurity (reagents)plus impurity (reagents), some also yielded small, isometric, particles partly in
pH=8, particle diameter10-40 nm
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aggregates.
Materials Science-Porous HTC membranes
Modification of the surface/walls of poresModification of the surface/walls of pores of a micro-porous support system
First experiments on green Boehmite
A bi t No HTC formed•Ambient pressure
•T 25 or 80 oC
Mg salts added
No HTC formed
Mg salts added.
Hydrothermal reaction @ 180oC HTC formedHighly crystalline
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Materials Science-Porous HTC membranes
Conclusions:
Two ways to ‘affinity tuned’ porous membranes have to be further explored:
1.Nano particle based15
Size Distribution by Intensity
2.Modified surface based0
5
10
0.1 1 10 100 1000 10000
Inte
nsity
(%)
Size (d.nm)
To be done:
1.Prevent aggregation, formulate coating recipe, drying/calcination
2 U l t d f l i ti t
Record 301: SG1.4 2-butanol gel in its sol f iltered Record 302: SG1.4 2-butanol gel in its sol f ilteredRecord 303: SG1.4 2-butanol gel in its sol f iltered Record 304: SG1.4 2-butanol gel in its sol f ilteredRecord 305: SG1.4 2-butanol gel in its sol f iltered
2.Use real support, degree of precalcination etc.
Make small membranes via both routes and determine performance
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Molecular sieving
A
Molecular sieving
AAtomic layer deposition:
BdInitial pore
C dH2Initial pore diameter
D
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Molecular sievingMolecular sievingPrerequisites:
Monodisperse pore size•Monodisperse pore size distribution of the support
•MCM•MCM
•Hydrothermally stable membranemembrane
•Hybrid Al/Si oxide microporous films p(poster)
•ALD with stable oxideMCM:
mesoporous ceramic
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pmembrane
Molecular sievingMolecular sieving
5 00E 02
6,00E-02
7,00E-02
N physisorptionSiO2
1 00E-02
2,00E-02
3,00E-02
4,00E-02
5,00E-02
Dv(
d)
[cc/
A/g
\]
40
50
60
70
80
90
t (cp
s)
N2 physisorption
0,00E+00
1,00E-02
0 10 20 30 40 50 60 70
Pore width (A)
0
10
20
30
40
10 15 20 25 30 35 40 45 50 55 60
2-Theta
Int
MCM LR order, d=3 nm
200
250
300
TEM
0
50
100
150
Int (
cps)
Proceed with ALD!
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0 1 2 3 4 5 6 7 8 92-Theta
with ALD!
Dissolution Diffusion: Ionic LiquidsDissolution-Diffusion: Ionic Liquids
Abbreviation: [emim][Tf2N]
1-ethyl-3-methyl-imidazolium-bis-(trifluoromethylsulphonyl) imide
Abbreviation: [bmim][Tf2N]
1 b t l 3 meth l imida oli m bis(trifluoromethylsulphonyl) imide 1-butyl-3-methyl-imidazolium-bis-(trifluoromethylsulphonyl) imide
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Dissolution Diffusion: Ionic Liquids
Cailletet Tube
Dissolution-Diffusion: Ionic Liquids
S lSample mixture
The number of phases can be observedThe number of phases can be observed visually
Adjustable Pressure and/or Temperature
Measuring Range 0.3-15 MPa, 250-450 K
Accuracy 0.03 MPa, 0.02 K
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Dissolution Diffusion: Ionic LiquidsDissolution-Diffusion: Ionic Liquids
•The curvature in the CO2comparison of CO2, CO, H2, and CH4 solubilities in [bmim][Tf2N] 2solubilities & the linear solubilities of H2 and CH4suggest an optimal mid-range
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14
16
H2 CO2
pressure for maximum separation efficiency.
• The opposite trends of 8
10
12
P, M
Pa
CH4
CO
ppsolubilities of CO2 and H2with temperature suggest operation at lowest possible
4
6
P
333.15 K353.15 K373 15 K
temperature for best separation.
•Absorption selectivity
0
2
0 0.1 0.2 0.3 0.4 0.5 0.6
mole fraction CO2/CH4/CO/H2
373.15 K393.15 K413.15 K433.15 K453.15 K
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Absorption selectivity 5<CO2/H2<15
Dissolution Diffusion: Ionic LiquidsDissolution-Diffusion: Ionic Liquids
2μm
Architecture of an asymmetricasymmetric membrane support
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Dissolution Diffusion: Ionic LiquidsDissolution-Diffusion: Ionic Liquids
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Dissolution Diffusion: Ionic LiquidsDissolution-Diffusion: Ionic Liquids
P θγ cos4Δ50
14 P (1
dP γ=Δ
40
30P (b
ar)
12
10
8
10-9 m
ol m-2
80
bar)
γ = 30 mN/m γ = 50 mN/mγ = 70 mN/m
20
10
6
4
2Pa-1s
-1)
60
40
ce p
ress
ure
(b
γ
Target
10080604020t (min)
Bmim triflate: 37 5 mN/m !!20
0
Lapl
a Target
Thanks to ECN-EEI-MST:
Bmim triflate: 37,5 mN/m !!
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806040200Laplace pore diameter (nm) Jaap Vente, Luci Correia, Johan Overbeek
Dissolution Diffusion: Ionic LiquidsDissolution-Diffusion: Ionic Liquids
Transport through IL membrane ≈ Solubility x p g yDiffusivity
To be done:
•Measure transport and derive diffusivity
•Determine absorption kineticsDetermine absorption kinetics
Furthermore:
•Measure multi gas absorption•Measure multi gas absorption
•Determine effect of steam (WGS)
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•Determine IL vapor pressure @ 250-400oC
Thank you co-workers:
Virginie Feuillade
Yen Tran
Kostas Stoitsas Posters outside on:
Sona Raeissi Hybrid alumina-silica support
MCM materialsMCM materials
Ionic Liquids
WGS t l tWGS catalysts
Precursors coating materials/surface modification
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materials/surface modification