WP4: Application of MOF materials in gas or vapor recovery & separation

Task 4.1: MOF screening CNRS-LCP & CNRS-ILV

T4.2: Propane/propylene separation

T4.3: Acid gas separation & recovery: H2S/CO2

T4.4. CO2 and H2 purification

T4.5: N2 recovery from light hydrocarbons

T4.6: C6/aliphatics separation

CNRS-ILV

CO2 CNRS-LCP

Lab scale CNRS-LCP

Lab scale CNRS-LCP

Lab scale CNRS-IGCM

FEUP

CO2 & H2S FPMS

Lab-pilot scale FPMS

Lab-pilot scale FPMS

Upscaling FEUP

WP7. Gas-phase separation pilot plant TOTAL-PF

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 2011
WP4.4 D4.4 Process operation of PSA and SMB propane/propylene-lab scale units (first generation MOFs) D4.13 CO2/CO separation using 5 different MOF phases in powder form Faculdade de Engenharia da Universidade do Porto Laboratoire Chimie Provence July 2011 29/07/2011 WP4.13 July 2011 20/12/2011

D4.17 Comparison of N2/C3H6 WP4.17 separation using five different MOF phases in powder form WP4.5 D4.5 Development of propane/propylene gas phase separations (PSA and SMB) with first generation MOFs shaped

Laboratoire Chimie Provence

December 2011

19/03/2012

Faculdade de Engenharia da Universidade do Porto

January 2012

30/12/2011

WP4.9

CO2/H2S separation using 5 different Facult Polytechnique de Mons MOF phases in powder form

July 2012

Deliverables 2012
WP4.6 WP4.14 WP4.20 WP4.21 WP4.10 WP4.18 WP4.2 WP4.2 D4.6 Process operation of PSA and SMB Faculdade de Engenharia da propane/propylene-lab scale units (2nd generation Universidade do Porto MOFs) D4.14 Comparison of CO2/CO separation using 5 Laboratoire Chimie Provence different MOF phases in powder and shaped form Comparison of benzene/light olefins adsorption using 5 different MOF phases in powder and shaped form Comparison of alkylbenzenes separation using 5 different MOF phases in powder and shaped form Comparison of CO2/ H2S separation using 5 different MOF phases in powder and shaped form Institut Charles Gerhardt Institut Charles Gerhardt Facult Polytechnique de Mons July 2012 July 2012 July 2012 July 2012 November 2012

Lab pilot scale separation of N2/C3H6 using second Laboratoire Chimie Provence November 2012 generation MOFs Final analysis of high throughput experiments carried Laboratoire Chimie Provence out on new MOF phases Final analysis of high throughput experiments carried out on new MOF phases Institut Lavoisier January 2013 January 2013

T4.2 Propane/ Propylene

Business cases: Polyolefins:
Case Case 1 C3 splitter: debottlenecking taken out from the top of the column Case 2 C3 splitter: debottlenecking taken out from the reactor
* From polymerization catalyst

Reference material: 13X zeolite (SMB), 4A zeolite (PSA)

inlet Composition (%wt) outlet Composition (%wt) C3-: 96-97% C3-: 96

T (C) 36, 34-38 20

P (barg)

Impurities tracks of TriEthylAluminium* and oligomers

P (barg) 20 20

20 (liquid) C3-: 85 95 14 (flash) C3+: 5-15 22 C3-: 82 C3+: 18

Business cases: Basechemicals:

Case Case 1 C3 splitter: debottlenecking taken out from the bottom of the column Case 2 C3 splitter: debottlenecking taken out from the bottom of the column Case 3 C3 splitter: quality improvement taken out from the reactor T (C) 58 P (barg) 22 inlet Composition (%wt) C3-: 30 C3+: 70 C3-: 10 C3+: 90*** C3-: 92 C3+: 8 Impurities tracks of TriEthylAluminium*, oligomers, sylanes tracks of TriEthylAluminium* and oligomers P (barg) >12 outlet Composition (%wt) n.a.**

31

12.6

any

n.a.**

23

12

any

n.a.**

* 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

T (C) 50 P (bar) 80 inlet Composition (%wt) CO2: 5 CH4: 94 H2S: 1 H2O: 0 CO2: 40 CH4: 50 H2S: 10 H2O: 0

Reference material: none

outlet Composition (%wt) CO2<1 CH4>99 H2S: 1 ppm CO2: 2 CH4: 95 H2S: 1 ppm

Case Case 1 Low contaminant Case 2 High contaminant

Impurities Mercaptan, hydrocarbons, BTX Mercaptan, hydrocarbons, BTX

P (bar) <80

50

80

<80

T4.4 Syngas purification

T (C) 50 P (bar) 65 inlet Composition (%mol) H2: 57 CO2: 39 CO: 3 H2S: 0.7 H2: 47 CO2: 30 CO: 22 H2S: 0.7

Reference material: Activated carbon (Norit R2030)

Outlet Composition (%mol) H2>90%, Rec> 95% H2S<1ppm CO2<5 H2S<1ppm

Case Case 1 Methanol Case 2 Fisher-Tropsch

Impurities CH4, N2, COS, H2O

P (bar) 60

50

33

CH4, N2, COS, H2O

26

T4.5 N2 recovery from light hydrocarbons

Reference material: none

Case Polypropylene Polyethylene

T (C) 70 70

P (bar) 1 1

inlet Composition (%wt) N2: 70 C3H6: 30 N2: 70 C4: 24 C6: 6

Impurities C6

P (bar) 1 1

Outlet Composition (%mol) N2: >95 N2: >95

T4.6 C6/aliphatics separation

inlet Composition (%mol)

Reference material: 5A zeolite, BEA (linear/branched hexane isomers)

P (bar) outlet Composition (%mol)

Case Linear/ branched hexane isomers n-paraffins from fuel Aromatics/olefins Normal and branched alkylbenzene

T (C) 50-150 50-150 50-150 50-150

P (bar) 1 1 1 1

Impurities

June 2011 - Today PRODUCTS DELIVERED FROM ILV (WP4)

Group Leader

Type of Sample and Amount

MIL-88B(Fe)(CH3)4 1g

Sample Name

Date

P. Llewelyn (Marseille, France)

FA395

27.03.2012

UiO-66(Zr) (CO2)H 1g

P. Llewelyn (Marseille, France)

CLH54

13.03.2012

UiO-66(Zr) (CO2H)2

P. Llewelyn (Marseille, France) G. De Weirield (Mons, Belgium)

1g

CLH11
20g

09.01.2011

Departamento de Engenharia Qumica Rua Dr. Roberto Frias, S/N | 4200-465 Porto| Portugal

http://lsre.fe.up.pt lsre@fe.up.pt

Propane/propylene gas phase separation

Alrio E. Rodrigues, Jos M. Loureiro, Joo 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)
(act 423 K) (act 553 K)

UIO-66 Powder (KRICT)

MIL-125(Ti)_NH2 Spheres (KRICT)

Propane

323 K 348 K 373 K 323 K 348 K 373 K 323 K 348 K 373 K 323 K 348 K 373 K

323 K 348 K 373 K 323 K 348 K 373 K 323 K 348 K 373 K 323 K 348 K 373 K

373 K

373 K

(act 423 K)

373 K

(act 423 K)

373 K

Propylene

373 K
(act 423 K)

373 K

(act 423 K)

373 K

(act 423 K)

373 K

(act 553 K)

Isobutane

Butane

Adsorption isotherms: KRICT Cu-BTC tablets (D4.5)

5 4 3 2 1 0 0 100 323 K (adsorption) 323 K (desorption) 348 K (adsorption) 348 K (desorption) 373 K (adsorption) 373 K (desorption) 200 300 Pressure (kPa) 400 500

Amount adsorbed (mol kg-1)

Amount adsorbed (mol kg-1)

Amount adsorbed (mol kg-1 )

Amount adsorbed (mol kg-1 )

Propane
4 3 2 1 0 0 100 323 K (adsorption) 323 K (desorption) 348 K (adsorption) 348 K (desorption) 373 K (adsorption) 373 K (desorption) 200 300 Pressure (kPa) 400 500

Propylene

Isobutane
4 3 2 1 0 0 100 323 K (adsorption) 323 K (desorption) 348 K (adsorption) 348K (desorption 373 K (adsorption) 373 K (desorption) 200 300 Pressure (kPa) 400 500

Butane
4 3 2 1 0 0 100 323 K (adsorption) 323 K (desorption) 348 K (adsorption) 348 K (desorption) 373 K (adsorption) 373 K (desorption) 200 300 Pressure (kPa) 400 500

Isosteric heat of adsorption (kJ mol-1 )

Isosteric heat of adsorption (kJ mol-1 )

Isosteric heat of adsorption (kJ mol-1 )

60 50 40 30 20 10 0 0

Propane

60 50 40 30 20 10 0 0

Propylene

60 50 40 30 20 10 0 0

Isobutane

Isosteric heat of adsorption (kJ mol-1 )

70

70

70

70 60 50 40 30 20 10 0 0 1 Experimental Klein et al. 2 3 Loading (mol kg-1 ) 4

Butane

Experimental Wagener et al. 1 2 3 Loading(mol kg-1 ) 4

Experimental Wagener et al. 1 2 3 Loading (mol kg-1 ) 4

Experimental Hartmann et al. 1 2 3 Loading (mol kg-1 ) 4

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.

Adsorption isotherms: Cu-BTC spheres KRICT (D4.5)

9
Adsorbed amount (mol kg-1 ) Adsorbed amount (mol kg-1 )

Adsorbed amount (mol kg-1 )

Adsorbed amount (mol kg-1 )

8 7 6 5 4 3 2 1 0 0

Propane

8 7 6 5 4 3 2 1 0 0

Propylene

9 8 7 6 5 4 3 2 1 0 0 100 323 K (adsorption) 323 K (desorption) 348 K (adsorption) 348 K (desorption) 373 K (adsorption) 373 K (desorption) 200 300 Pressure (kPa) 400 500

Isobutane

8 7 6 5 4 3 2 1 0 0

Butane

323 K (desorption) 323 K (adsorption) 348 K (adsorption) 348 K (desorption) 373K (adsorption) 373 K (desorption) 100 200 300 Pressure (kPa) 400 500

323 K (adsorption) 323 K (desorption) 348 K (adsorption) 348 K (desorption) 373 K (adsorption) 373 K (desorption) 100 200 300 Pressure (kPa) 400 500

323 K (adsorption) 323 K (desorption) 348 K (adsorption) 348 K (desorption) 373 K (adsorption) 373 K (desorption) 100 200 300 Pressure (kPa) 400 500

Isosteric heat of adsorption (kJ mol-1 )

Isosteric heat of adsorption (kJ mol-1 )

Isosteric heat of adsorption (kJ mol-1 )

Isosteric heat of adsorption (kJ mol-1 )

70 60 50 40 30 20 10 0 0 1 2 Experimental Wagener et al 3 4 5 6 Loading (mol kg-1 ) 7 8

70 60 50 40 30 20 10 0 0 1 2 Experimental Wagener et al. 3 4 5 6 Loading (mol kg-1 ) 7 8

70 60 50 40 30 20 10 0 0 1 2 3 4 Loading (mol kg-1 ) 5 6 Experimental Hartmann et al.

70 60 50 40 30 20 10 0 0 1 Experimental Klein et al 2 3 4 Loading (mol kg-1 ) 5 6

Propane

Propylene

Isobutane

Butane

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.

Adsorption isotherms: UiO-66 (Zr) KRICT (D4.5)

3.0 3.0

Adsorbed amount (mol kg-1 )

Adsorbed amount (mol kg-1 )

2.5 2.0 1.5 1.0 0.5 0.0 0

Effect of activation:
Higher activation temperatures do not increase adsorption capacity

UiO-66 (Zr) tablets Propane adsorption at 373 K

2.5 2.0 1.5 1.0 0.5 0.0

UiO-66(Zr) tablets Propylene adsorption at 373 K

Activation at 423 K Activation at 553 K 100 200 300 Pressure (kPa) 2.0 400

Activation at 423 K Activation at 553 K 0 100 200 Pressure (kPa) 300 400

Effect of shaping:
Adsorbed amount (mol kg-1 )

1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 0

UiO-66 (Zr) activated at 423 K

Shaping reduces the adsorption capacity in near 15 %

Propane (powder) Propylene (powder) Propane (tablets) Propylene (tablets) 20 40 60 80 100 120 140 160 Pressure (kPa)

UiO-66 (Zr) is not selective

Adsorption isotherms: MIL-125(Ti)_NH2 KRICT (D4.5)

Adsorption equilibrium measurements of propane, propylene at 100 C and different pressures (from 0 to 5 bar) in: MIL-125(Ti)_NH2 spheres from KRICT

5 Adsorbed amount (mol kg-1) 4 3 2 1 0 0

MIL-125(Ti)-NH2 at 373 K

Propane Propylene 100 200 300 400 500 600

Pressure (kPa)

Fixed bed unit

SV1 - In CV1 Filter

SV3 - Out

Exhaustion system

Oven

FID
Comburent Combustible Make-up

Carrier gas F
V-24

GC Chompack CP9001
SP

Vacuum pump

MFC1 F MFC2
MR8 MR7 MR6

Carrier gas

SV7

F MFC3

K T1

MR5 MR1 MR2 I-29

K T2

Air

MR3

He

H2

MFC4
MR4

K T3

iC4H10

C 3H 8

C 3H 6

SV5

N2

SV6 RV

CV3

Diapragm Vacuum Pump

SV2 - In

CV2

Filter SV4 - Out

16

C 2H 6

Back Pressure Regulator

Breakthrough curves (D4.5)

Cu-BTC spheres KRICT Single component Binary C3 Pseudobinary C3/C4 Pseudoternary C3/C4
Propane Propylene Isobutane Butane Propane / Propylene Propane / Isobutane Isobutane / Propane Propylene / Isobutane Isobutane /Propylene Propane + Propylene / Isobutane Isobutane / Propane + Propylene Propane + Propylene / Butane
F
V-24

SV1 - In CV1 Filter

SV3 - Out

Exhaustion system

Oven

FID
Comburent Combustible Make-up

Carrier gas

GC Chompack CP9001
SP

Vacuum pump

MFC1 F MFC2
MR8 MR7 MR6

Carrier gas

SV7

F MFC3

K T1

MR5 MR1 MR2 I-29

K T2

Air

MR3

He

H2

MFC4
MR4

K T3

C 3H 6

iC4H10

C 3H 8

SV5

N2

SV6 RV

CV3

Diapragm Vacuum Pump

SV2 - In

CV2

Filter SV4 - Out

C 2H 6

Back Pressure Regulator

Cu-BTC spheres from KRICT (D4.5)

1.0 0.9 1.0 1.0 0.9

Molar flowrate (mmol/s)

Molar flowrate (mmol/s)

0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 0 440 430 Bottom Middle 500

0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 0 440 430 500

Molar flowrate (mmol/s)

0.9

0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 0 500

Propane adsorption 373 K & 150 kPa Q = 1SLPM

1000 1500 2000 2500 3000 Time (s)

Propylene adsorption 373K & 150 kPa Q = 1SLPM

1000 1500 2000 2500 3000 Time (s) Bottom Middle Top (wall)

Isobutane adsorption 373 K & 150 kPa Q = 1SLPM

1000 1500 2000 2500 3000 Time (s)

440 430 Bottom Middle Top (wall)

Temperature (K)

Temperature (K)

Top (wall)

410 400 390 380 370 0 500 1000 1500 2000 2500 3000 Time (s)

410 400 390 380 370 0 500 1000 1500 2000 2500 3000 Time (s)

Temperature (K)

420

420

420 410 400 390 380 370 0 500

1000 1500 2000 2500 3000 Time (s)

Mass of adsorbent: 0.122 kg

Highlights lab-scale 1C-PSA

Highlights lab-scale 1C-PSA

MACADEMIA annual meeting : Work Package 3 : FPMs

Non permanent Staff

PhD student : Sbastien Vaesen (12 months) PhD student : Nicolas Heymans (3 months)

Publications WP4 implication

A complete procedure for acidic gas separation by adsorption on MIL-53 (Al), Micropor. Mesopor. Mat. , 154, 2012, 93-09

22

Universit de Mons

Deliverables
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)
23

Universit de Mons

Results : UiO-66(Zr) BTEC

Outgassing : 100C Isotherms : 30C H2S: regenerable

24

Universit de Mons

Comparison between the 3 samples :

Results : MIL-125(Ti)_NH2

VG761 from IL (SBET : 1244 m/g) Powder from KRICT (SBET : 1472 m/g) Pellets from KRICT (SBET : 1187 m/g) Same outgassing conditions (200C/8h under vacuum). Properties of MOF from KRICT are close to the sample from Versailles.

25

Universit de Mons

Conclusions and Perspectives

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 ?

26

Universit de Mons

Andrew Wiersum

Estelle Lenoir

Supervision : Christelle Vagner Sandrine Bourrelly Philip Llewellyn

Experiments summary

Estelle Soubeyrand-Lenoir, Christelle Vagner, Philip Llewellyn

Laboratoire MADIREL, Universit Aix-Marseille / CNRS UMR 7246

WP4 Progress London June 2012

Target : Evaluation of the impact of water vapour on MOFs

Estelle Lenoir

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
CO2 H2O

H2O

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

Estelle Soubeyrand-Lenoir, Christelle Vagner, Philip Llewellyn

Laboratoire MADIREL, Universit Aix-Marseille / CNRS UMR 7246

WP4 Progress London June 2012

NaX

CO2 Sorption with Humidity

High uptake & Low Energetic price

MIL-100(Fe)

CO2 H2 O

HKUST-1(Cu)

MIL-101(Cr)

UiO-66(Zr)

MIL-127(Fe)

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)

Estelle Soubeyrand-Lenoir, Christelle Vagner, Philip Llewellyn

Laboratoire MADIREL, Universit Aix-Marseille / CNRS UMR 7246

WP4 Progress London June 2012

Recent work of A. Wiersum

Pure component adsorption isotherms on shaped samples (KRICT) SCREENING UiO-66, UiO-66-NH2, MIL-100(Fe), Discovery and research for new MIL-125(Ti)-NH2, MIL-127(Fe) samples of interest Mixture predictions/comparison with experiments EVALUATION Optimisation of the UiO-66-NH2(shaped): CO2/CH4 and CO2/N2 adsorbents Evaluation of shaped MOFs for C3=/N2 separation TESTS UiO-66-NH2 Deliverable D4.17 MIL-127(Fe) Number of samples High throughput evaluation of MOFs CAU-10 with different functionalized ligands (Kiel) UiO-66-BTeC activated at different temperatures (ILV)
Andrew Wiersum

Precision of information

Laboratoire MADIREL, Universit Aix-Marseille / CNRS UMR 7246

Andrew Wiersum, Sandrine Bourrelly, Philip Llewellyn

WP4 Progress London June 2012

Sample
MOF NaX NaY Takeda 5A MIL-47(V) Zr-BDC UiO-66(Zr) UiO-66(Zr) (hydrox) UiO-66(Zr) UiO-66(Zr) UiO-66(Zr)-NH2 UiO-66(Zr)-NH2 (hydrox) UiO-66(Zr)-NH2 UiO-66(Zr)-Br UiO-66(Zr)-Br (hydrox) Cu-BTC Cu-BTC CAU-1 Basolite F300 MIL-53(Al) MIL-100(Al) MIL-100(Fe)-HF (150C) MIL-100(Fe)-HF (250C) MIL-100(Fe)-HF MIL-101(Cr) MIL-125(Ti) MIL-125(Ti) MIL-125(Ti)-NH2 MIL-125(Ti)-NH2 MIL-127(Fe) MIL-127(Fe) MIL-100(Al) MIL-100(Cr) MIL-100(V)-HQ MIL-100(V)-LQ MIL-100(Fe)-F MIL-53(Al)-Cl MIL-53(Al)-Br MIL-53(Al)-NH2 MIL-53(Al)-Me MIL-53(Al)-COOH MIL-53(Al)-(OH)2 CAU-10-H CAU-10-OH CAU-10-NH2 CAU-10-NO2 CAU-10-CH3 CAU-10-OCH3 MIL-100(Fe) no F MIL-100(Fe) no F UiO-66(Zr)-BTeC MIL88B-(CH3)4 UiO-66(Zr) UiO-66(Zr)-NH2 Cu-BTC Batch Origin powder/shaped

Char.
ATG BET

High-throughput
C2H6 C3H6 C3H8 CO2 CH4 N2 N2 He He

Gravimetry
C4H10 C2H6 C3H6 C3H8 CO2 CH4 CO CO N2 He

Calorimetry
CO2 / CH4 CO2 / CO C4H10 C2H6 C3H4 C3H6 C3H8 CO2 CH4

Mixtures
CO2 / N2 CO / CH4 C3= / N2 C3= / C3 CO / N2

70C
C3H6 10C 20C N2

CO2
40C 50C 1 1 70C 1

1 shaped powder powder powder powder powder shaped powder powder shaped powder powder powder powder powder powder powder powder powder powder shaped powder powder powder powder shaped powder shaped powder powder powder powder powder powder powder powder powder powder powder powder powder powder powder powder powder powder shaped powder powder powder powder 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 1 1 1 1 1 1 1 1 1 1 1 1 0.5 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 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 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 1 1 1 1 1 1 1 0.5 0.5 0.5 1 1 0.5 0.5 0.5 0.5 1 1 1 1 0.5 1 1 0 0 1 0

ILV ILV ILV ILV KRICT EC 146 ILV EC 146 ILV KRICT FR 121 ILV FR 121 ILV RO 53 ILV KRICT Kiel BASF Kiel Kiel KRICT KRICT KRICT KRICT MDH 465 A ILV KRICT FR 72 ILV KRICT CH 52 ILV KRICT KRICT KRICT KRICT KRICT KRICT Kiel Kiel Kiel Kiel Kiel Kiel Kiel Kiel Kiel Kiel Kiel Kiel KRICT KRICT CLH 11 ILV FA395 ILV new KRICT new KRICT new KRICT

VG 982 VG 862 VG 862 FR 49

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 0.5 0.5 1 1 1 1 1 1

1 1 1 1 1

0.5 0.5 0.5 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

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 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

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

1 1 1 1 1 1 1

1 1 1

1 1 1 1 1

1 1 1

1 1 1

1 1 1

0.5

1 1 1

1 1 1

1 1 1

1 1 1

1 1 1 0.5 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 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 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 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

Laboratoire MADIREL, Universit Aix-Marseille / CNRS UMR 7246

Andrew Wiersum, Sandrine Bourrelly, Philip Llewellyn

WP4 Progress London June 2012

Adsorption measurements on shaped MOFs: UiO-66-NH2

9 8 7 5

UiO66-NH2(powder) / UiO66NH2(shaped) comparison: CO2 at 303K

6

UiO66-NH2(powder) / UiO66NH2(shaped) comparison: CH4 at 303K

7.0 6.0 5.0

UiO66-NH2(powder) / UiO66NH2(shaped) comparison: C3s at 303K

nads / mmol.g-1

nads / mmol.g-1

nads / mmol.g-1

6 5 4 3 2 1 0 0 10 20 30 40 50 60 70
UiO66-NH2(powder): CO2 UiO66-NH2(shaped): CO2

4.0 3.0 2.0

UiO66-NH2(powder): C3H6 UiO66-NH2(powder): C3H8

2
UiO66-NH2(powder): CH4 UiO66-NH2(shaped): CH4

1.0 0.0

0 0 10 20 30 40 50 60 70

10

Pressure / bar

Pressure / bar

Pressure / bar

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)
Andrew Wiersum, Sandrine Bourrelly, Philip Llewellyn
WP4 Progress London June 2012

Laboratoire MADIREL, Universit Aix-Marseille / CNRS UMR 7246

Adsorption measurements on shaped MOFs: UiO-66-NH2

Calo Vert: UiO66-NH2 (-) / Carbon Dioxide / 30C
40 35 30 30 25 20 15 10 5 0 8.0 0.0 1.0 2.0
UiO66-NH2 (powder) UiO66-NH2 (shaped) UiO66-NH2 (shaped)

Calo Vert: UiO66-NH2 (-) / Methane / 30C

Calo Vert: UiO66-NH2 (-) / Propane / 30C

60 50 40 30 20 10 0 4.0 0.0 1.0 2.0 3.0
UiO66-NH2 (powder) UiO66-NH2 (shaped) UiO66-NH2 (shaped)

-Qads / kJ.mol-1

25 20 15 10 5 0 0.0 2.0 4.0

UiO66-NH2 (powder) UiO66-NH2 (shaped) UiO66-NH2 (shaped)

-Qads / kJ.mol-1

-Qads / kJ.mol-1

6.0
-1

3.0
-1

4.0
-1

5.0

6.0

n ads / mmol.g

n ads / mmol.g

n ads / mmol.g

Similar enthalpies for CO2 and CH4 Different enthalpies, especially at high coverage, for C3s

Laboratoire MADIREL, Universit Aix-Marseille / CNRS UMR 7246

Andrew Wiersum, Sandrine Bourrelly, Philip Llewellyn

WP4 Progress London June 2012

Deliverables CNRS-Marseille
D4.13: CO2/CO separation using 5 different MOF phases in powder form Delivered December 2011 (on time) D4.17: Comparison of N2/C3H6 separation using 5 different MOF phases in powder and shaped form Delivered March 2012 (3 months late) due to extra experiments on shaped samples at 70C 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 MOFs 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

Laboratoire des Matriaux Avancs pour la Catalyse et la Sant

UMR 5253 - Institut de Chimie Molculaire et des Matriaux de Montpellier

Adsorption and separation of light hydrocarbons from the vapour phase using different MOFs D4.19 D4.21
Thuy Khuong Trung, Philippe Gonzales, Naseem Ramsahye Franois Fajula, Philippe Trens
7th Framework Programme

D-4.19. Monocomponents adsorption of light hydrocarbons using 5 MOFs Comparison Benzene / n-hexane

n-Hexane adsorption at 313 K

1000 900 800 MIL-101(Cr) HKUST-1 MIL-47(V) - 303K UIO-66(Zr) MIL-53(Al)

800 700
Adsorbed amount / mg.g-1

Benzene adsorption at 313 K

MIL-101(Cr) HKUST-1 MIL-53(Al) UIO-66(Zr)

Adsorbed amount / mg.g-1

700 600 500 400 300 200 100 0 0 0.2 0.4

600 500 400 300 200 100 0

MIL-47(V) MIL-125(Ti)-NH2

0.6

0.8

0.2

Relative pressure, p/p

0.4 0.6 0.8 Relative pressure, p/p

D-4.19: Coadsorption of Benzene / n-hexane using 5 MOFs Results : Co adsorption of n-hexane/Benzene (66%) on MIL-101(Cr)
160 140 80 70 60 50 40 30 20 10 0 50 100 Pressure / Torr 150 200 250 0

Adsorbed amount / cm3.g-1

120 100 80 60 40 20 0

Enthalpy of adsorption / -kJ.mol-1

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

350 300

Adsorbed amount / mg.g-1

250 200 150 100 50 0 n-hexane 1-hexene Toluene Methylcyclohexane Cyclohexane Benzene 0 0.1 0.2 0.3 0.4 0.5 0.6 Relative pressure, p/p 0.7 0.8 0.9 1

Cyclohexene and methyl-1 cyclohexene still to come..

Deliverable D4.21: Comparison of alkylbenzenes separation using 5 different MOF phases in powder and shaped form
Vapour adsorption of xylenes at 313 K
1400 1200 1000 800 600 400 p-Xylene 200 0 o-Xylene m-Xylene 0 0.2 0.4 0.6 Relative pressure, p/p 0.8 1

MIL-101(Cr) Powder form

350 300 250 200 150 100 50 0

UIO-66(Zr) Powder form

Adsorbed amount / mg.g-1

Adsorbed amount / mg.g-1

o-xylene m-xylene p-xylene 0 0.2 0.4 0.6 Relative pressure, p/p 0.8 1

MIL-125(Ti) to be done soon

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)

Hydrocarbon Experimental conditions Column length : 25 cm T = 180C N2 flow = 30 cm3.min-1 Hexene Benzene Cyclohexene Toluene Methylcyclohexane 1methyl1cyclohexene M-Xylene P-Xylene O-Xylene

Retention time SP (Mins) 2,338 4,005 10,243 7,243 23,643 13,52 6,452 5,420 17,976

The adsorption and separation of hexane/benzene mixture onto MIL-101(Cr) : An experimental and computational study Naseem A. Ramsahye, Philippe Gonzalez, Hichem Belarbi, Cline 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, Cline Shepherd, Thuy Khuong Trung, Thomas Devic, Patricia Horcajada, Christian Serre, Franois Fajula, Philippe Trens, In preparation.

List of publications

Staff involved 0 postdoc 2 PhD Students : T. K. Trung, H. Belarbi 1 Master student : C. Shepherd