Download - WP4 Annual Meeting 2012
WP7. Gas-phase separation pilot plant TOTAL-PF
Task 4.1: MOF screening CNRS-LCP & CNRS-ILV
T4.2: Propane/propylene
separation
CNRS-ILV
FEUP
T4.3: Acid gas separation & recovery: H2S/CO2
CO2 CNRS-LCP
CO2 & H2S FPMS
T4.5: N2 recovery from light hydrocarbons
Lab scale CNRS-LCP
Lab-pilot scale FPMS
T4.6: C6/aliphatics separation
Lab scale CNRS-IGCM
Upscaling FEUP
T4.4. CO2 and H2 purification
Lab scale CNRS-LCP
Lab-pilot scale FPMS
WP4: Application of MOF materials in gas or vapor recovery & separation
Deliverables – 2011 WP4.4
D4.4 Process operation of PSA and SMB propane/propylene-lab scale units (first generation MOFs)
Faculdade de Engenharia da Universidade do Porto July 2011 29/07/2011
WP4.13 D4.13 CO2/CO separation using 5 different MOF phases in powder form Laboratoire Chimie Provence July 2011 20/12/2011
WP4.17 D4.17 Comparison of N2/C3H6 separation using five different MOF phases in powder form
Laboratoire Chimie Provence December 2011 19/03/2012
WP4.5
D4.5 Development of propane/propylene gas phase separations (PSA and SMB) with first generation MOFs shaped
Faculdade de Engenharia da Universidade do Porto January 2012 30/12/2011
WP4.9 CO2/H2S separation using 5 different MOF phases in powder form Faculté Polytechnique de Mons July 2012
Deliverables – 2009 / 2010 D4.1 (CNRS-ILV/LCP), D 4.3 (FEUP), D4.12 (CNRS-LCP), D4.8 (FPMS), D4.16 (CNRS_LCP), D4.19 (CNRS-IGCM)
Deliverables – 2012
WP4.6 D4.6 Process operation of PSA and SMB propane/propylene-lab scale units (2nd generation MOFs)
Faculdade de Engenharia da Universidade do Porto July 2012
WP4.14 D4.14 Comparison of CO2/CO separation using 5 different MOF phases in powder and shaped form Laboratoire Chimie Provence July 2012
WP4.20 Comparison of benzene/light olefins adsorption using 5 different MOF phases in powder and shaped form Institut Charles Gerhardt July 2012
WP4.21 Comparison of alkylbenzenes separation using 5 different MOF phases in powder and shaped form Institut Charles Gerhardt July 2012
WP4.10 Comparison of CO2/ H2S separation using 5 different MOF phases in powder and shaped form
Faculté Polytechnique de Mons November 2012
WP4.18 Lab pilot scale separation of N2/C3H6 using second generation MOFs Laboratoire Chimie Provence November 2012
WP4.2 Final analysis of high throughput experiments carried out on new MOF phases Laboratoire Chimie Provence January 2013
WP4.2 Final analysis of high throughput experiments carried out on new MOF phases Institut Lavoisier January 2013
inlet outlet
Case T (ºC)
P (barg)
Composition (%wt) Impurities P
(barg) Composition
(%wt) Case 1 C3 splitter: debottlenecking taken out from the top of the column
36, 34-38 20 (liquid) 14 (flash)
C3-: 85 – 95 C3+: 5-15 - 20 C3-: 96-97%
Case 2 C3 splitter: debottlenecking taken out from the reactor
20 22 C3-: 82 C3+: 18
tracks of TriEthylAluminium* and
oligomers 20 C3-: 96
Business cases: Polyolefins:
T4.2 Propane/ Propylene
* From polymerization catalyst
inlet outlet
Case T (ºC)
P (barg)
Composition (%wt) Impurities P
(barg) Composition
(%wt) Case 1 C3 splitter: debottlenecking taken out from the bottom of the column
58 22 C3-: 30 C3+: 70
tracks of TriEthylAluminium*, oligomers, sylanes
>12 n.a.**
Case 2 C3 splitter: debottlenecking taken out from the bottom of the column
31 12.6 C3-: 10 C3+: 90***
tracks of TriEthylAluminium* and
oligomers any n.a.**
Case 3 C3 splitter: quality improvement taken out from the reactor
23 12 C3-: 92 C3+: 8 - any n.a.**
Reference material: 13X zeolite (SMB), 4A zeolite (PSA)
Business cases: Basechemicals:
* From polymerization catalyst ** No outlet composition specifications were provided. Study different possibilities. *** Not sure about the composition. To be confirmed.
T4.3 Acid gas separation H2S/CO2 Reference material: none
inlet outlet
Case T (ºC)
P (bar)
Composition (%wt) Impurities P
(bar) Composition
(%wt) Case 1 Low contaminant 50 80
CO2: 5 CH4: 94 H2S: 1 H2O: 0
Mercaptan, hydrocarbons, BTX <80
CO2<1 CH4>99 H2S: 1 ppm
Case 2 High contaminant 50 80
CO2: 40 CH4: 50 H2S: 10 H2O: 0
Mercaptan, hydrocarbons, BTX <80
CO2: 2 CH4: 95 H2S: 1 ppm
T4.4 Syngas purification Reference material: Activated carbon (Norit R2030)
inlet Outlet
Case T (ºC)
P (bar)
Composition (%mol) Impurities P
(bar) Composition
(%mol) Case 1 Methanol 50 65
H2: 57 CO2: 39 CO: 3 H2S: 0.7
CH4, N2, COS, H2O 60 H2>90%, Rec> 95% H2S<1ppm
Case 2 Fisher-Tropsch 50 33
H2: 47 CO2: 30 CO: 22 H2S: 0.7
CH4, N2, COS, H2O 26 CO2<5 H2S<1ppm
T4.5 N2 recovery from light hydrocarbons Reference material: none
inlet Outlet
Case T (ºC)
P (bar)
Composition (%wt) Impurities P
(bar) Composition
(%mol) Polypropylene 70 1 N2: 70
C3H6: 30 C6 1 N2: >95
Polyethylene 70 1
N2: 70 C4: 24 C6: 6
1 N2: >95
T4.6 C6/aliphatics separation Reference material: 5A zeolite, BEA (linear/branched hexane isomers)
inlet outlet
Case T (ºC)
P (bar)
Composition (%mol) Impurities P
(bar) Composition
(%mol) Linear/ branched hexane isomers 50-150 1 n-paraffins from fuel 50-150 1 Aromatics/olefins 50-150 1 Normal and branched alkylbenzene 50-150 1
Group Leader Type of Sample and Amount Sample Name Date
P. Llewelyn (Marseille, France)
FA395 27.03.2012
P. Llewelyn (Marseille, France)
CLH54 13.03.2012
P. Llewelyn (Marseille, France)
G. De Weirield
(Mons, Belgium)
1g
20g
CLH11 09.01.2011
PRODUCTS DELIVERED FROM ILV (WP4)
MIL-88B(Fe)(CH3)4 1g
UiO-66(Zr) (CO2)H 1g
June 2011 - Today
UiO-66(Zr) (CO2H)2
Departamento de Engenharia Química Rua Dr. Roberto Frias, S/N | 4200-465 Porto| Portugal [email protected]
http://lsre.fe.up.pt
Propane/propylene gas phase separation
Alírio E. Rodrigues, José M. Loureiro, João C. Santos, Alexandre F. P. Ferreira,
Marta Campo, Ana Mafalda Ribeiro
MACADEMIA Project – 2nd Annual Meeting - Porto, June 2011
MACADEMIA Samples
2nd generation shapped MOFs KRICT Cu-BTC pellets (received 07.2010)
KRICT Cu-BTC spheres (received 11.2010)
KRICT UiO-66(Zr) (received 11.2010)
Equilibrium of adsorption
Absolute adsorbed amount:
10
Adsorption isotherms (D4.5)
Cu-BTC Tablets (KRICT)
Cu-BTC Spheres (KRICT)
UIO-66 Tablets (KRICT)
UIO-66 Powder (KRICT)
MIL-125(Ti)_NH2 Spheres (KRICT)
Propane 323 K 348 K 373 K
323 K 348 K 373 K
373 K (act 423 K) 373 K (act 553 K)
373 K (act 423 K)
373 K (act 423 K)
Propylene 323 K 348 K 373 K
323 K 348 K 373 K
373 K (act 423 K) 373 K (act 553 K)
373 K (act 423 K)
373 K (act 423 K)
Isobutane 323 K 348 K 373 K
323 K 348 K 373 K
Butane 323 K 348 K 373 K
323 K 348 K 373 K
Adsorption isotherms: KRICT Cu-BTC tablets (D4.5)
A. Wagener, M. Schindler, F. Rudolphi, S. Ernst, Chem. Ing. Tech. 79 (2007) 851-855. M. Hartmann, S. Kunz, D. Himsl, O. Tangermann, S. Ernst, A. Wagener, Langmuir 24 (2008) 8634-8642. N. Klein, A. Henschel, S. Kaskel, Microporous Mesoporous Mater. 129 (2010) 238-242.
0
10
20
30
40
50
60
70
0 1 2 3 4
Isost
eric
hea
t of a
dsor
ptio
n (k
J mol
-1)
Loading (mol kg-1)
Propylene
ExperimentalWagener et al.
0
10
20
30
40
50
60
70
0 1 2 3 4
Isost
eric
hea
t of a
dsor
ptio
n (k
J mol
-1)
Loading (mol kg-1)
Isobutane
ExperimentalHartmann et al.
0
10
20
30
40
50
60
70
0 1 2 3 4
Isost
eric
hea
t of a
dsor
ptio
n (k
J mol
-1)
Loading(mol kg-1)
Propane
ExperimentalWagener et al.
0
10
20
30
40
50
60
70
0 1 2 3 4
Isost
eric
hea
t of a
dsor
ptio
n (k
J mol
-1)
Loading (mol kg-1)
Butane
ExperimentalKlein et al.
0
1
2
3
4
5
0 100 200 300 400 500
Amou
nt a
dsor
bed
(mol
kg-1
)
Pressure (kPa)
Propane
323 K (adsorption)323 K (desorption)348 K (adsorption)348 K (desorption)373 K (adsorption)373 K (desorption)
0
1
2
3
4
5
0 100 200 300 400 500
Amou
nt a
dsor
bed
(mol
kg-1
)
Pressure (kPa)
Propylene
323 K (adsorption)323 K (desorption)348 K (adsorption)348 K (desorption)373 K (adsorption)373 K (desorption)
0
1
2
3
4
5
0 100 200 300 400 500
Amou
nt a
dsor
bed
(mol
kg-
1)
Pressure (kPa)
Isobutane
323 K (adsorption)323 K (desorption)348 K (adsorption)348K (desorption373 K (adsorption)373 K (desorption) 0
1
2
3
4
5
0 100 200 300 400 500
Amou
nt a
dsor
bed
(mol
kg-
1)
Pressure (kPa)
Butane
323 K (adsorption)323 K (desorption)348 K (adsorption)348 K (desorption)373 K (adsorption)373 K (desorption)
Adsorption isotherms: Cu-BTC spheres KRICT (D4.5)
A. Wagener, M. Schindler, F. Rudolphi, S. Ernst, Chem. Ing. Tech. 79 (2007) 851-855. N. Klein, A. Henschel, S. Kaskel, Microporous Mesoporous Mater. 129 (2010) 238-242. M. Hartmann, S. Kunz, D. Himsl, O. Tangermann, S. Ernst, A. Wagener, Langmuir 24 (2008) 8634-8642.
0
10
20
30
40
50
60
70
0 1 2 3 4 5 6 7 8
Isost
eric
hea
t of a
dsor
ptio
n (k
J mol
-1)
Loading (mol kg-1)
Propane
ExperimentalWagener et al
0
10
20
30
40
50
60
70
0 1 2 3 4 5 6
Isost
eric
hea
t of a
dsor
ptio
n (k
J mol
-1)
Loading (mol kg-1)
Isobutane
ExperimentalHartmann et al.
0
10
20
30
40
50
60
70
0 1 2 3 4 5 6
Isost
eric
hea
t of a
dsor
ptio
n (k
J mol
-1)
Loading (mol kg-1)
Butane
Experimental
Klein et al0
10
20
30
40
50
60
70
0 1 2 3 4 5 6 7 8
Isost
eric
hea
t of a
dsor
ptio
n (k
J mol
-1)
Loading (mol kg-1)
Propylene
ExperimentalWagener et al.
0
1
2
3
4
5
6
7
8
9
0 100 200 300 400 500
Adso
rbed
amou
nt (m
ol k
g-1)
Pressure (kPa)
Propane
323 K (desorption)323 K (adsorption)348 K (adsorption)348 K (desorption)373K (adsorption)373 K (desorption)
0
1
2
3
4
5
6
7
8
9
0 100 200 300 400 500
Adso
rbed
amou
nt (m
ol k
g-1)
Pressure (kPa)
Isobutane
323 K (adsorption)323 K (desorption)348 K (adsorption)348 K (desorption)373 K (adsorption)373 K (desorption) 0
1
2
3
4
5
6
7
8
9
0 100 200 300 400 500
Adso
rbed
amou
nt (
mol
kg-1
)
Pressure (kPa)
Butane
323 K (adsorption)323 K (desorption)348 K (adsorption)348 K (desorption)373 K (adsorption)373 K (desorption)
0
1
2
3
4
5
6
7
8
9
0 100 200 300 400 500
Adso
rbed
amou
nt (m
ol k
g-1)
Pressure (kPa)
Propylene
323 K (adsorption)323 K (desorption)348 K (adsorption)348 K (desorption)373 K (adsorption)373 K (desorption)
Adsorption isotherms: UiO-66 (Zr) KRICT (D4.5)
Shaping reduces the adsorption capacity in near 15 %
UiO-66 (Zr) is not selective
0.0
0.5
1.0
1.5
2.0
2.5
3.0
0 100 200 300 400
Adso
rbed
amou
nt (m
ol k
g-1)
Pressure (kPa)
UiO-66(Zr) tabletsPropylene adsorption at 373 K
Activation at 423 KActivation at 553 K
0.0
0.5
1.0
1.5
2.0
2.5
3.0
0 100 200 300 400
Adso
rbed
amou
nt (m
ol k
g-1)
Pressure (kPa)
UiO-66 (Zr) tabletsPropane adsorption at 373 K
Activation at 423 KActivation at 553 K
Higher activation temperatures do not increase adsorption capacity
0.00.20.40.60.81.01.21.41.61.82.0
0 20 40 60 80 100 120 140 160
Adso
rbed
amou
nt (m
ol k
g-1)
Pressure (kPa)
UiO-66 (Zr) activated at 423 K
Propane (powder)Propylene (powder)Propane (tablets)Propylene (tablets)
Effect of activation:
Effect of shaping:
Adsorption isotherms: MIL-125(Ti)_NH2 KRICT (D4.5)
0
1
2
3
4
5
0 100 200 300 400 500 600
Adso
rbed
am
ount
(mol
kg-1
)
Pressure (kPa)
Propane
Propylene
MIL-125(Ti)-NH2 at 373 K
MIL-125(Ti)_NH2 spheres from KRICT
Adsorption equilibrium measurements of propane, propylene at 100 ºC and different pressures (from 0 to 5 bar) in:
Fixed bed unit
16
Oven
N2
C3H
6
C3H
8
FMFC3
FMFC2
FMFC1
KT3
KT2
KT1
SV2 - In
SV1 - In
Diapragm Vacuum Pump
SV3 - Out
SV4 - Out
SV5
RV
SP
SV6 C2H
6
F
MFC4
CV3
CV1
CV2
MR3
MR2
MR1
MR4
Filter
Filter
iC4H
10
MR5
I-29
V-24
He
MR6
H2
MR7
CombustibleFID
Air
MR8
Carrier gas
Back Pressure Regulator
GCChompack
CP9001
Exhaustion system
Vacuum pump
Make-up
SV7
Comburent
Carrier gas
Breakthrough curves (D4.5)
Cu-BTC spheres KRICT
Single component
Propane Propylene Isobutane Butane
Binary C3 Propane / Propylene
Pseudobinary C3/C4
Propane / Isobutane Isobutane / Propane Propylene / Isobutane Isobutane /Propylene
Pseudoternary C3/C4
Propane + Propylene / Isobutane Isobutane / Propane + Propylene Propane + Propylene / Butane
Oven
N2
C3H
6
C3H
8
FMFC3
FMFC2
FMFC1
KT3
KT2
KT1
SV2 - In
SV1 - In
Diapragm Vacuum Pump
SV3 - Out
SV4 - Out
SV5
RV
SP
SV6 C2H
6
F
MFC4
CV3
CV1
CV2
MR3
MR2
MR1
MR4
Filter
Filter
iC4H
10
MR5
I-29
V-24
He
MR6
H2
MR7
CombustibleFID
Air
MR8
Carrier gas
Back Pressure Regulator
GCChompack
CP9001
Exhaustion system
Vacuum pump
Make-up
SV7
Comburent
Carrier gas
Cu-BTC spheres from KRICT (D4.5)
0.00.10.20.30.40.50.60.70.80.91.0
0 500 1000 1500 2000 2500 3000
Mol
ar fl
owra
te (m
mol
/s)
Time (s)
Isobutane adsorption373 K & 150 kPa
Q = 1SLPM
0.00.10.20.30.40.50.60.70.80.91.0
0 500 1000 1500 2000 2500 3000M
olar
flow
rate
(mm
ol/s
)Time (s)
Propylene adsorption373K & 150 kPa
Q = 1SLPM0.00.10.20.30.40.50.60.70.80.91.0
0 500 1000 1500 2000 2500 3000
Mol
ar fl
owra
te (m
mol
/s)
Time (s)
Propane adsorption373 K & 150 kPa
Q = 1SLPM
370
380
390
400
410
420
430
440
0 500 1000 1500 2000 2500 3000
Tem
pera
ture
(K)
Time (s)
Bottom
Middle
Top (wall)
370
380
390
400
410
420
430
440
0 500 1000 1500 2000 2500 3000
Tem
pera
ture
(K)
Time (s)
Bottom
Middle
Top (wall)
370
380
390
400
410
420
430
440
0 500 1000 1500 2000 2500 3000
Tem
pera
ture
(K)
Time (s)
BottomMiddleTop (wall)
Mass of adsorbent: 0.122 kg
Highlights – lab-scale 1C-PSA
Highlights – lab-scale 1C-PSA
MACADEMIA annual meeting : Work Package 3 : FPMs
Université de Mons
PhD student : Sébastien Vaesen (12 months)
PhD student : Nicolas Heymans (3 months)
Non permanent Staff
22
Publications WP4 implication A complete procedure for acidic gas separation by adsorption on MIL-53 (Al),
Micropor. Mesopor. Mat. , 154, 2012, 93-09
Université de Mons
D4.9: CO2/H2S separation using 5 different MOF phases in powder form (month 30)
Co-adsorption isotherms are being measured. The delay come from the non-possibility of measuring pure and mixture isotherms at the same time. We will start the measurement in July
D4.10: Comparison of CO2/H2S separation using 5 different MOF phases in powder and shaped form (month 40)
We received MIL-125(Ti)_NH2 and UiO-66(Zr)_NH2 in the 2 forms from KRICT Request to change the mixture H2S/CH4 in stead of CO2/H2S for D4.9, D4.10 and D4.11 (industrial interest)
Deliverables
23
Université de Mons 24
Results : UiO-66(Zr) BTEC
Outgassing : 100°C Isotherms : 30°C H2S: regenerable
Université de Mons
Results : MIL-125(Ti)_NH2
25
Comparison between the 3 samples :
• VG761 from IL (SBET : 1244 m²/g) • Powder from KRICT (SBET : 1472 m²/g) • Pellets from KRICT (SBET : 1187 m²/g)
Same outgassing conditions (200°C/8h under vacuum). Properties of MOF from KRICT are close to the sample from Versailles.
Université de Mons
• UiO-66(Zr) BTEC : stable to H2S. • Synthesis from KRICT give close results compared to the
original sample for the MIL-125(Ti)_NH2. To do list : • Study a last new MOF (UiO-66(Zr)(NH2)) in pure compound
adsorption ; • Mixture adsorption on MOF (Powder and shaped) More
samples in the two forms from Krick ?
Conclusions and Perspectives
26
Estelle Lenoir
Andrew Wiersum
Supervision : • Christelle Vagner • Sandrine Bourrelly • Philip Llewellyn
Estelle Soubeyrand-Lenoir, Christelle Vagner, Philip Llewellyn Laboratoire MADIREL, Université Aix-Marseille / CNRS UMR 7246
WP4 Progress London
June 2012
Experiments summary
Target : Evaluation of the impact of water vapour on MOFs
Experiments summary of the progress since the last meeting in Marseille
Effect of water vapour on CO2 adsorption
Results of dynamic adsorption: CO2 breakthrough under dry or humid flow
Water sorption study on MIL-127(Fe) and of their regenerative capacity
In progress : Dynamic study on Takeda 5A
Gravimetric adsorption of H2O on CPO-27
CO2 ? H2O
H2O
Estelle Soubeyrand-Lenoir, Christelle Vagner, Philip Llewellyn Laboratoire MADIREL, Université Aix-Marseille / CNRS UMR 7246
WP4 Progress London
June 2012
Estelle Lenoir
NaX
HKUST-1(Cu)
UiO-66(Zr)
MIL-100(Fe)
MIL-101(Cr)
MIL-127(Fe)
CO2 Sorption with Humidity
CO2
H2O
High uptake &
Low Energetic price
Estelle Soubeyrand-Lenoir, Christelle Vagner, Philip Llewellyn Laboratoire MADIREL, Université Aix-Marseille / CNRS UMR 7246
WP4 Progress London
June 2012
JACS in press (ID: ja-2012-02787x) "How water fosters a remarkable 5-fold increase in low pressure
CO2 uptake within the mesoporous MIL-100(Fe)“
Recent work of A. Wiersum
• Pure component adsorption isotherms on shaped samples (KRICT) – UiO-66, UiO-66-NH2, MIL-100(Fe),
MIL-125(Ti)-NH2, MIL-127(Fe) • Mixture predictions/comparison with experiments
– UiO-66-NH2(shaped): CO2/CH4 and CO2/N2
• Evaluation of shaped MOFs for C3=/N2 separation
– UiO-66-NH2
– MIL-127(Fe) – High throughput evaluation of MOFs – CAU-10 with different functionalized ligands (Kiel) – UiO-66-BTeC activated at different temperatures (ILV)
Deliverable D4.17
Andrew Wiersum
Andrew Wiersum, Sandrine Bourrelly, Philip Llewellyn Laboratoire MADIREL, Université Aix-Marseille / CNRS UMR 7246
WP4 Progress London
June 2012
SCREENING
EVALUATION
TESTS
Discovery and research for new samples of interest
Optimisation of the adsorbents
Number of samples
Precision of information
MOF Batch Origin powder/shaped ATG
BET
He N2
CO2
CH4
C2H6
C3H6
C3H8
He N2
CO CO2
CH4
C2H6
C3H6
C3H8
C4H1
0
He N2
CO CO2
CH4
C2H6
C3H4
C3H6
C3H8
C4H1
0
CO2
/ CO
CO2
/ CH4
CO2
/ N2
CO /
CH4
CO /
N2
C3=
/ C3
C3=
/ N2
N2
C3H6
10C
20C
40C
50C
70C
NaX 1 1 1 1 1NaY 1Takeda 5A shaped 1 1 1 1 1 1 1 1 1 1MIL-47(V) powder 1 1 1 1 1Zr-BDC VG 982 ILV powder 1 - 1 1 1 1 1 1 1 1 1UiO-66(Zr) VG 862 ILV powder 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0.5 0.5 0.5 0UiO-66(Zr) (hydrox) VG 862 ILV powder 1 1 1 1 1UiO-66(Zr) FR 49 ILV powder 1 1 1 1 1 1 1 1 1 1 1 1 1 1UiO-66(Zr) KRICT shaped 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1UiO-66(Zr)-NH2 EC 146 ILV powder 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0.5 0.5 0.5 0.5 0 0UiO-66(Zr)-NH2 (hydrox) EC 146 ILV powder 1 1 1 1 1 1 1 1 1 1 1UiO-66(Zr)-NH2 KRICT shaped 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0.5 1 1UiO-66(Zr)-Br FR 121 ILV powder 1 1 1UiO-66(Zr)-Br (hydrox) FR 121 ILV powder 1 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5Cu-BTC RO 53 ILV powder 1 - 1 1 1Cu-BTC KRICT powder 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1CAU-1 Kiel powder 1 - 1 1 1 1 1 1 1 1Basolite F300 BASF powder 1 - 1 1 1 1 1 1 1 1MIL-53(Al) Kiel powder 1 - 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1MIL-100(Al) Kiel powder 1 1 1 1 1 1 1 1 1 1 1MIL-100(Fe)-HF (150C) KRICT powder 1 1 1 1 1 1 1 1 1 1 1 1MIL-100(Fe)-HF (250C) KRICT powder 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0.5MIL-100(Fe)-HF KRICT shaped 1 1 1 1 1 1 1MIL-101(Cr) KRICT powder 1 1 1 1 1 1 1 1 1 1 1 1 1 1MIL-125(Ti) MDH 465 A ILV powder 1 1 1 1 1 1 1 1 1 1 1MIL-125(Ti) KRICT powder 1 1 1 1 1 1 1 1 1 1MIL-125(Ti)-NH2 FR 72 ILV powder 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1MIL-125(Ti)-NH2 KRICT shaped 1 1 1 1 1 1 1 1 1 1 0.5MIL-127(Fe) CH 52 ILV powder 1 1 1 1 1 1 1 1 1 1 1 -MIL-127(Fe) KRICT shaped 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1MIL-100(Al) KRICT powder 1 1 1 1 1 1 1 1MIL-100(Cr) KRICT powder 1 1 1 1 1 1 1 1MIL-100(V)-HQ KRICT powder 1 1 1 1 1 1 1 1MIL-100(V)-LQ KRICT powder 1 - 1 1 1 1 1 1 1MIL-100(Fe)-F KRICT powder 1 1 1 1 1 1 1 1MIL-53(Al)-Cl Kiel powder 1 1 1 1 1MIL-53(Al)-Br Kiel powder 1 1 1 1 1MIL-53(Al)-NH2 Kiel powder 1 1 1 1 1MIL-53(Al)-Me Kiel powder 1 1 1 1 1MIL-53(Al)-COOH Kiel powder 1 1 1 1 1MIL-53(Al)-(OH)2 Kiel powder 1 1 1 1 1CAU-10-H Kiel powder 1 1 1CAU-10-OH Kiel powder 1 1 1CAU-10-NH2 Kiel powder 1 1 1CAU-10-NO2 Kiel powder 1 1 1CAU-10-CH3 Kiel powder 1 1 1CAU-10-OCH3 Kiel powder 1 1 1MIL-100(Fe) no F KRICT powder 1 1 1 1 1MIL-100(Fe) no F KRICT shaped 1UiO-66(Zr)-BTeC CLH 11 ILV powder 1 1 1 1MIL88B-(CH3)4 FA395 ILV powder 1 1UiO-66(Zr) new KRICT powderUiO-66(Zr)-NH2 new KRICT powderCu-BTC new KRICT powder
CO2Sample 70CMixturesCalorimetryGravimetryChar. High-throughput
Andrew Wiersum, Sandrine Bourrelly, Philip Llewellyn Laboratoire MADIREL, Université Aix-Marseille / CNRS UMR 7246
WP4 Progress London
June 2012
– Same shape of isotherm for CH4, amount adsorbed reduced by 25% – Slightly different shaped isotherm for CO2
– Different adsorption mechanism for C3s – BET surface: 1070 m2/g (powder)
? m2/g (shaped)
Adsorption measurements on shaped MOFs: UiO-66-NH2
0
1
2
3
4
5
6
7
8
9
0 10 20 30 40 50 60 70
n ads
/ m
mol
.g-1
Pressure / bar
UiO66-NH2(powder) / UiO66-NH2(shaped) comparison: CO2 at 303K
UiO66-NH2(powder): CO2
UiO66-NH2(shaped): CO2
0
1
2
3
4
5
6
0 10 20 30 40 50 60 70
n ads
/ m
mol
.g-1
Pressure / bar
UiO66-NH2(powder) / UiO66-NH2(shaped) comparison: CH4 at 303K
UiO66-NH2(powder): CH4
UiO66-NH2(shaped): CH4
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
0 2 4 6 8 10
n ads
/ m
mol
.g-1
Pressure / bar
UiO66-NH2(powder) / UiO66-NH2(shaped) comparison: C3s at 303K
UiO66-NH2(powder): C3H6
UiO66-NH2(powder): C3H8
Andrew Wiersum, Sandrine Bourrelly, Philip Llewellyn Laboratoire MADIREL, Université Aix-Marseille / CNRS UMR 7246
WP4 Progress London
June 2012
– Similar enthalpies for CO2 and CH4
– Different enthalpies, especially at high coverage, for C3s
Adsorption measurements on shaped MOFs: UiO-66-NH2
0
5
10
15
20
25
30
35
40
0.0 2.0 4.0 6.0 8.0
-Qad
s/ k
J.mol
-1
n ads / mmol.g-1
Calo Vert: UiO66-NH2 (-) / Carbon Dioxide / 30°C
UiO66-NH2 (powder)
UiO66-NH2 (shaped)
UiO66-NH2 (shaped)0
5
10
15
20
25
30
0.0 1.0 2.0 3.0 4.0
-Qad
s/ k
J.mol
-1
n ads / mmol.g-1
Calo Vert: UiO66-NH2 (-) / Methane / 30°C
UiO66-NH2 (powder)
UiO66-NH2 (shaped)
UiO66-NH2 (shaped)0
10
20
30
40
50
60
0.0 1.0 2.0 3.0 4.0 5.0 6.0
-Qad
s/ k
J.mol
-1
n ads / mmol.g-1
Calo Vert: UiO66-NH2 (-) / Propane / 30°C
UiO66-NH2 (powder)
UiO66-NH2 (shaped)
UiO66-NH2 (shaped)
Andrew Wiersum, Sandrine Bourrelly, Philip Llewellyn Laboratoire MADIREL, Université Aix-Marseille / CNRS UMR 7246
WP4 Progress London
June 2012
Deliverables CNRS-Marseille D4.13: CO2/CO separation using 5 different MOF phases in powder form
D4.17: Comparison of N2/C3H6 separation using 5 different MOF phases in powder
and shaped form
D4.14: Comparison of CO2/CO separation using 5 different MOF phases in powder
and shaped form month 36 D4.18: Lab pilot scale separation of N2/C3H6 using second generation MOF’s month 40
D4.2: Final analysis of high throughput experiments carried out on new MOF phases month 42
D4.15: Lab pilot scale-scale separation of CO2/CO separation using second generation MOF month 48
Delivered December 2011 (on time)
Delivered March 2012 (3 months late) due to extra experiments on shaped samples at 70°C
UM
R 52
53 -
Inst
itut d
e Ch
imie
Mol
écul
aire
et
des
Mat
éria
ux d
e M
ontp
ellie
r Adsorption and separation of light hydrocarbons from the vapour phase using different MOFs
D4.19 – D4.21
Thuy Khuong Trung, Philippe Gonzales, Naseem Ramsahye François Fajula, Philippe Trens
Laboratoire des Matériaux Avancés pour la Catalyse et la Santé
7th Framework Programme
D-4.19. Monocomponents adsorption of light hydrocarbons using 5 MOFs Comparison Benzene / n-hexane
0
100
200
300
400
500
600
700
800
900
1000
0 0.2 0.4 0.6 0.8 1
Ads
orbe
d am
ount
/ m
g.g-
1
Relative pressure, p/p°
MIL-101(Cr)HKUST-1MIL-47(V) - 303KUIO-66(Zr)MIL-53(Al)
0
100
200
300
400
500
600
700
800
0 0.2 0.4 0.6 0.8 1A
dsor
bed
amou
nt /
mg.
g-1
Relative pressure, p/p°
MIL-101(Cr)
HKUST-1
MIL-53(Al)
UIO-66(Zr)
MIL-47(V)
MIL-125(Ti)-NH2
n-Hexane adsorption at 313 K Benzene adsorption at 313 K
0
10
20
30
40
50
60
70
80
0
20
40
60
80
100
120
140
160
0 50 100 150 200 250
Enth
alpy o
f ads
orpt
ion / -
kJ.m
ol-1
Adso
rbed
amou
nt / c
m3 .g-1
Pressure / Torr
Results : Co adsorption of n-hexane/Benzene (66%) on MIL-101(Cr)
D-4.19: Coadsorption of Benzene / n-hexane using 5 MOFs
0
50
100
150
200
250
300
350
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Adso
rbed
amou
nt / m
g.g-1
Relative pressure, p/p°
n-hexane1-hexeneTolueneMethylcyclohexaneCyclohexaneBenzene
D4.20 Comparison of benzene/light olefins adsorption using 5 different MOF phases in powder and shaped form.
Adsorption isotherms obtained at 313 K on UIO-66(Zr) Powder form
Cyclohexene and methyl-1 cyclohexene still to come..
Vapour adsorption of xylenes at 313 K
Deliverable D4.21: Comparison of alkylbenzenes separation using 5 different MOF phases in powder and shaped form
0
50
100
150
200
250
300
350
0 0.2 0.4 0.6 0.8 1
Adso
rbed
amou
nt / m
g.g-1
Relative pressure, p/p°
o-xylene
m-xylene
p-xylene
0
200
400
600
800
1000
1200
1400
0 0.2 0.4 0.6 0.8 1
Adso
rbed
amou
nt / m
g.g-1
Relative pressure, p/p°
p-Xylene
o-Xylene
m-Xylene
MIL-101(Cr) Powder form UIO-66(Zr) Powder form
MIL-125(Ti) to be done soon
Hydrocarbon Retention time SP (Mins)
Hexene 2,338 Benzene 4,005 Cyclohexene 10,243 Toluene 7,243 Methylcyclohexane 23,643 1methyl1cyclohexene 13,52 M-Xylene 6,452 P-Xylene 5,420 O-Xylene 17,976
Deliverable D4.21: Comparison of alkylbenzenes separation using 5 different MOF phases in powder and shaped form
Separation of unsaturated hydrocarbons using MIL-101(Cr) (Powder form)
Experimental conditions Column length : 25 cm T = 180°C N2 flow = 30 cm3.min-1
List of publications The adsorption and separation of hexane/benzene mixture onto MIL-101(Cr) : An experimental and computational study Naseem A. Ramsahye, Philippe Gonzalez, Hichem Belarbi, Céline Shepherd, Jong-San Chang and Philippe Trens. To be submitted before summer. Influence of the nature of ligands towards the adsorption of n-alkanes over flexible MOFS: The example of the MIL-88(Fe) (A, B, C) materials Naseem A. Ramsahye, Thuy Khuong Trung, Farid Nouar, Thomas Devic, Patricia Horcajada, Christian Serre, Philippe Trens. To be submitted before summer. Separation of alkanes by MIL-125 and UIO66: a chromatographic and computational study Naseem A. Ramsahye, Céline Shepherd, Thuy Khuong Trung, Thomas Devic, Patricia Horcajada, Christian Serre, François Fajula, Philippe Trens, In preparation. Staff involved 0 postdoc
2 PhD Students : T. K. Trung, H. Belarbi 1 Master student : C. Shepherd