Laboratory pilot scale evaluation of heat reallocation ...
Transcript of Laboratory pilot scale evaluation of heat reallocation ...
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Laboratory pilot scale evaluation of heat reallocation properties of a bio-sourced
water stable Aluminum dicarboxylate Metal Organic Framework
Anastasia Permyakova, Alexandre Skrylnyk, Maame Affram, Emilie Courbon, Sujing Wang, Farid Nouar, Georges Mouchaham, U-Hwang Lee, Anil H. Valekar,
Jong-San Chang, Thomas Devic, Guy de Weireld, Nathalie Steunou,* Marc Frère,* Christian Serre*
Institut Lavoisier, UMR CNRS 8180, Université de Versailles St-Quentin en Yvelines, 45 Avenue des Etats-Unis, 78035 Versailles Cedex, France
Faculté Polytechnique de UMONS, Service de Thermodynamique et de Physique mathématique, 31, boulevard Dolez, 7000 Mons, Belgium
European Community Programme (FP7), SOTHERCO Project
I • Energy reallocation: principles, promising materials
II • Metal Organic Frameworks for energy reallocation
III • New bio-sourced MOF MIL-160(Al): structure, synthesis,
water sorption properties, hydrothermal stability
IV • MIL-160(Al) for energy storage application
V • MIL-160(Al) for heat-pump application
VI • Conclusions
Table of content
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I • Energy reallocation: principles, promising materials
II • Metal Organic Frameworks for energy reallocation
III • New bio-sourced MOF MIL-160(Al): structure, synthesis,
water sorption properties, hydrothermal stability
IV • MIL-160(Al) for energy storage application
V • MIL-160(Al) for heat-pump application
VI • Conclusions
Table of content
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Foundation: reversible reaction A + B ↔ C + heat
solar heat as driving energy
High T heat (80-100°C)
water vapor
Medium T heat (30-45°C)
Low T heat (5-15°C)
desorption condenser
water vapor
Medium T heat (25-45°C)
adsorption evaporation
Principles of Thermochemical Energy Storage and transformation
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H2O Open storage systems
Materials for heat reallocation
Chemical sorption
(H2O + inorganic salt) Energy output:
160-630 kWh/m3
Kinetics: slow
Physical sorption (H2O+Inorganic and
Hybrid Porous Solids) Energy output:
90 kWh/m3
Kinetics: fast
Working pairs
Energy storage application Inter-seasonal storage Cycle time: several months Large quantity of material
Heat-pump application Cycle time: several minutes Small quantity of material
Working fluid
Hydrothermal stability
Suitable hydrophilicities (steep uptake at p/p0<0.3-0.4)
High sorption capacity
Easy regeneration (Td=80-100°C of solar collectors)
Stability under numerous cycles
Scalability
Adsorption at too high relative
pressure
Very expensive due to
templated syntheses
Energy demanded regeneration (up
to T=140°C)
Physical sorption materials
Water sorption capacity, g H2O/g dry material
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+ Stable, cheap - Limited in adsorption capacity
I • Energy reallocation: principles, promising materials
II • Metal Organic Frameworks for energy reallocation
III • New bio-sourced MOF MIL-160(Al): structure, synthesis,
water sorption properties, hydrothermal stability
IV • MIL-160(Al) for energy storage application
V • MIL-160(Al) for heat-pump application
VI • Conclusions
Table of content
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Metal Organic Frameworks (MOFs)
• Organic-inorganic hybrids • Crystalline • Porous
Structure of CAU-10(Al)
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AlO4(OH)2
AlO4(OH)2 1,3 BDC
6 Å
1D square-shaped channels ~ 6 Å
CAU: Christian-Albrechts-University
cis chains of AlO4(OH)2 corner-sharing octahdera
A robust rigid hydrophilic Al-MOF
Versatile chemistry • modification of SBU • Choice of organic ligand
Structural versatility • micro-, mesoporous • topology • rigid or flexible
Tunable properties
• Amphiphilic character Easy regeneration
Metal Organic Frameworks (MOFs)
hydrophobic
hydrophilic
P/P0
Wat
er u
ptak
e Amphiphilic caracter
Functionalization
O-O
-O O
NH2
O-O
-O O
OH
HO
O-O
-O O
SO3H
polar functional groups
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MIL-125(Ti)-NH2
0,5 0,3 0,1
0,2 0,4 0,6 0,8 1
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MIL-127(Fe)
Correlation between structural and adsorption properties
m i c r o p o r o u s m e s o p o r o u s
Hydrophilic Amphiphilic Hydrophobic
0
0,5
1
1,5
2
0 0,2 0,4 0,6 0,8 1
p/p°
MIL-101(Cr)
CAU-10(Al) MIL-125(Ti)-NH2 UiO-66(Zr)-NH2 MIL-100(Fe) MIL-101(Cr) MIL-100(Fe)
Water adsorption isotherms: adsorption capacity (g/g)
0
0,5
1
0 0,2 0,4 0,6 0,8 1
p/p°
MIL-100(Fe)
Amphiphilic character → position of adsorption step (p/p0)
MIL-125(Ti)-NH2
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Correlation between structure and adsorption properties Dehumidification,
Open cycle air-conditioning
Heat-pump and thermochemical energy storage
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0,3
0,6
0,9
1,2
1,5 p/p0 = 0-0.3 p/p0 = 0.3-0.5
Adsorption capacity, g/g
Hydrophilic Amphiphilic Hydrophobic
Hydrothermal stability
Suitable hydrophilicities (steep uptake at p/p0<0.3)
High sorption capacity
CAU-10: advantages and limitations Water sorption isotherms at 25°C Excellent cycling stability
Suitable hydrophilicity Why CAU-10?
But…
↑ hydrophilic character of MOF → good for heat-pump ↑ polarity of linker → solubility in water↑, → possible synthesis in water Green biocompatible synthesis?
Petrol-based linker Synthesis in toxic solvent (DMF)
more hydrophilic bio-sourced Industrial producation by Avantium
0,4 0,3 0,2 0,1 0,0
0,2 0,4 0,6 0,8
adsorption capacity (g/g)
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MIL-160(Al): an alternative approach for hydrophilic MOFs
MIL-160(Al) isostructural with CAU-10
CAU-10 MIL-160(Al)
Computational
Design
DFT optimized structure
Alternative strategy
Standard approach to enhance the hydrophilicity of MOF: grafting polar functional groups O-O
-O O
NH2
O-O
-O O
OH
HO
O-O
-O O
SO3H
• higher affinity for water • decrease of the Vpore and thus, total uptake
UiO-66(Zr)-NH2 and MIL-125(Ti)-NH2
G. Maurin,D. Damasceno-Borges, A. Cadiau 13
I • Energy reallocation: principles, promising materials
II • Metal Organic Frameworks for energy reallocation
III • New bio-sourced MOF MIL-160(Al): structure, synthesis,
water sorption properties, hydrothermal stability
IV • MIL-160(Al) for energy storage application
V • MIL-160(Al) for heat-pump application
VI • Conclusions
Table of content
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A new hydrophilic Al dicarboxylate MOF: structure and synthesis
Structure solved from XRPD, Modelling and Solid State NMR
and DFT modelling
Isostructural with CAU-10
A. Cadiau et al., Adv. Mater, 2015
6 Å
Green scalable synthesis: solvent (H2O, reflux) cheap Al salts as metal precursor 2,5 Furane dicarboxylic linker produced from biomass (Avantium)
1D channels ~ 6 Å
Cis chains of AlO4(OH)2
Al(OH)[O2C-C4H2O-CO2].nH2O
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MIL-160(Al): optimization of synthesis
High throughput synthesis methodology
Screening of synthesis parameters New conditions:
AlCl3 precursor NaOH A. Cadiau et al., Adv. Mater, 2015
High yield (93% based on Al)
+ Al(OH)(CH3COO)2
H2O
reflux (24h)
MIL-160 13.82 g
93 % (dry)
eco-compatible and friendly less corrosive
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Initially reported conditions:
CAU-10(Al)
MIL-160(Al)
Water sorption properties of MIL-160(Al) and CAU-10
Origin of the increased hydrophilicity?
MIL-160(Al) more hydrophilic adsorbent:
water uptake at lower p/p0 Larger uptake at saturation: 0.37 g/g vs 0.32 g/g
A. Cadiau et al., Adv. Mater, 2015
- Adsorption site: μ2-OH (more accessible compared to CAU-10)
- Additional interactions between H(H2O) & O(furan)
MIL-160
Water sorption isotherms at 298K
G. Maurin
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5 10 15 20 25 30
MIL-160(Al): hydrothermal stability and cycling stability
No loss after more than 10 cycles
A. Cadiau et al., Adv. Mater, 2015
Hydrothermal treatment: boiling water for 1 day
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Wight, %
Time, h
Temperature, °C
T adsorption at 30°C (RH 80%)
T desorption at 100°C (RH 0.03%)
250
100
0 0,2 0,4 0,6 0,8 1
p/p0
ml/g
N2 sorption porosimetry Porosity maintained
X-ray powder diffraction Preservation of structure
2 Theta – scale (°)
I • Energy reallocation: principles, promising materials
II • Metal Organic Frameworks for energy reallocation
III • New bio-sourced MOF MIL-160(Al): structure, synthesis,
water sorption properties, hydrothermal stability
IV • MIL-160(Al) for energy storage application
V • MIL-160(Al) for heat-pump application
VI • Conclusions
Table of content
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Energy storage application: operating conditions
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Working fluid: water Closed energy storage system T condenser =T evaporator=10°C
P=1,25 kPa
Δm, mg
Time, h
Temperature, °C
T desorption at 80°C (solar collectors)
T adsorption at 30°C T min for space-heating
in winter
Gravimetric lift: Δm = m adsorbed – m desorbed
MIL-160 : the best choice from physical sorption materials
0,06
0,12
0,20
0,32 0,34
0,36 0,37
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87
144
244
284 300 308
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50
100
150
200
250
300
0
0,1
0,2
0,3
0,4
0,5Cycling loading lift
Energy storage capacity
Hydrophilic character of MOFs
Highest cycling loading lift Highest energy storage capacity Excellent cycling stability Green bio sourced synthesis
Condition of lift: ads. at 30°C, 1.25 kPa des. at 80°C, 1.25 kPa
Cycling lift, g/g Energy storage capacity, Wh/kg
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Scale-up and shaping of MIL-160(Al) Scale-up:
Multiplying all amounts by ca. 10 times Larger scale glass reactor (2L) 400 g of MIL-160
Granulation method MIL-160(Al)+ silica sol solution Granulation using the rotating fan Drying
KRICT, Korea, J-S Chang Granules of MIL-160(Al): 0.5-1.8 mm 22
Characterization of MIL-160(Al) before and after shaping PXRD Nitrogen sorption porosimetry IR TGA
0
120
240
360
0 0,5 1
p/p0
MIL-160 shaped_adsMIL-160 shaped_desMIL-160 powder_adsMIL-160 powder_des
Powder: SBET=1150 m2.g-1
Shaped: SBET=1010 m2.g-1
MIL-160(Al) powder
MIL-160(Al) shaped
4 10 20 30 40 50 60
2 Theta – scale (°)
Va/cm3(STP) g-1
N2 sorption porosimetry X-ray powder diffraction
Preservation of structure Porosity maintained 23
Water sorption and energy storage properties of MIL-160(Al)
Gravimetric loading lift of powder and shaped MIL-160(Al)
Lift conditions: Adsorption: 30°C / p=1.25 kPa Desorption: 80°C/p=1.25 kPa
300 Wh/kg 292 Wh/kg
MIL-160(Al) powder 0.36 g/g
MIL-160(Al) shaped 0.32 g/g
High energy storage capacity:
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Water sorption properties of MIL-160(Al)
Critical data for modelling of different operating conditions (T, P)
Water sorption isotherms at different temperatures (30-80°C, step of 10°C)
0
0,1
0,2
0,3
0,4
0 1000 2000 3000 4000 5000 6000 7000 8000
p, Pa
60°C 40°C 50°C
30°C
70°C
80°C
Adsorption capacity, g/g
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Pilot test open-system prototype
I. Dry air generator II. Controlled air humidification system III. Adsorption column
Adsorption process: T=30°C, p=1.32 kPa Air flow rate: 215 l/min
The measurement of input and output air temperatures → the thermal power curve
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H= A*Cp*ΔT H: thermal power (W) A: air mass flow rate (kg/s) Cp: air heat capacity (J/kg*K) ΔT: temperature difference between input and output air
Pilot test open-system prototype
Input and output air temperatures
The thermal power curve
0
30
60
90
0:00 0:30 1:00 1:30 2:00 2:31time
343 Wh/kg (141 kWh/m3)
Thermal heat power, W
Energy storage capacity Energy storage density
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0
100
200
300
400
T ads=30°C/ p=1.25 kPa T des=80°C/ p=1.25 kPa This work
Literature T ads = 40°C/ p=1.20 kPa
T des=90°C
Comparison with other materials
Energy storage capacity, Wh/kg
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I • Energy reallocation: principles, promising materials
II • Metal Organic Frameworks for energy reallocation: which?
III • New bio-sourced MOF MIL-160(Al): structure, synthesis,
water sorption properties, hydrothermal stability
IV • MIL-160(Al) for energy storage application
V • MIL-160(Al) for heat-pump application
VI • Conclusions
Table of content
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MIL-160(Al): heat-pump applications
MIL-160: one of the best MOF so far at lift 1, close to SAPO-34
Gravimetric water loading lift (g/kg)
A. Cadiau
T ads=40°C/ p=1.2 kPa T des=95°C/ p=5.6 kPa
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I • Energy reallocation: principles, promising materials
II • Metal Organic Frameworks for energy reallocation: which?
III • New bio-sourced MOF MIL-160(Al): structure, synthesis,
water sorption properties, hydrothermal stability
IV • MIL-160(Al) for energy storage application
V • MIL-160(Al) for heat-pump application
VI • Conclusions
Table of content
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Conclusions:
I. New hydrothermally stable hydrophilic MOF: MIL-160(Al) • Alternative strategy of hydrophilic MOF synthesis • Green bio-sourced synthesis with high yield (93%) II. Excellent properties of MIL-160(Al) for heat pump application • Enhanced hydrophilicity • Excellent stability under numerous cycles • Performance comparable and even higher than SAPO-34
III. A series of MOFs towards space heating application • MIL-160(Al): best candidate (highest cycling loading lift, stability, green and
cheap synthesis) • Energy capacity: 300 Wh/kg • Scape-up (400 g) and Shaping • Pilot test with an open reactor (348 Wh/kg or 144 kWh/m3) • Higher performance compared to zeolites, SAPO-34 and AlPO-18
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Acknowledgements: • Porous Solid team, UVSQ, France C. Serre, N. Steunou, T. Devic, F. Nouar, S. Wang, C. Martineau, A. Cadiau, M. Affram
• Service thermodynamique, UMONS, Belgium M. Frère, A. Srylnyk, E. Courbon, G. De Weireld
• University of Montpellier: D. Damasceno-Borges, G. Maurin (DFT, GCMC, MD)
• TU Delft, ND: J. Gascon, F. Kaptjeen, M. De Lange (Heat transfer calculations)
• KRICT, Korea: J-S Chang, Y-K Hwang (Heat transfer) • European Community Programme (FP7), SoTherCo and SoTherCo partners
Thank you for attention! 33