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 lsre@fe.up.pt

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

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

UiO66-NH2(powder): CO2

UiO66-NH2(shaped): CO2

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

UiO66-NH2(powder): CH4

UiO66-NH2(shaped): CH4

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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

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Calo Vert: UiO66-NH2 (-) / Carbon Dioxide / 30°C

UiO66-NH2 (powder)

UiO66-NH2 (shaped)

UiO66-NH2 (shaped)0

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

UiO66-NH2 (powder)

UiO66-NH2 (shaped)

UiO66-NH2 (shaped)0

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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

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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

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Relative pressure, p/p°

MIL-101(Cr)HKUST-1MIL-47(V) - 303KUIO-66(Zr)MIL-53(Al)

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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

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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

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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

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Relative pressure, p/p°

o-xylene

m-xylene

p-xylene

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nt / m

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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