Novel carbon nanomaterials for selective CO capture

CARBON 2011-Shanghai JAS

Novel carbon nanomaterials for selective CO2 capture

A. Wahby, J.M. Ramos-Fernández, M. Martínez-Escandell, F. Rodríguez-Reinoso and J. Silvestre-Albero

Laboratorio de Materiales AvanzadosDepartamento de Química Inorgánica-Instituto Universitario de Materiales

Universidad de Alicante (Spain)

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Introduction

Carbon Dioxide PollutionCO2 is a greenhouse gas which is a major

contributor to global warming

Combustion of fossil fuel(coal, oil, gas in power plants,

automobiles and industrial facilities)

Main Source

2ºSAASA, San Luis-2013

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Introduction

Carbon Dioxide Solutions

- Carbon Dioxide Sequestration (e.g. injection into deep underground reservoirs)

Capture and concentration of CO2 from large emission sources, such as power plants

Requirements

!!!!CO2 is accompanied by other gases: N2, O2, H2O, NOx, SOx, particulate!!!!


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Introduction

Selective CO2 capture

PorousStructure

SurfaceChemistry


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Introduction Effect of pore size

TiC-CDCT=273K

(a-d) 1 bar(e-h) 0.1 bar

a)

b)

c)

d)

e)

f)

g)

h)Presser et al. Energy & Environ. Sci. 4, 3059-3066 (2011)


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Introduction

Carbon Dioxide Solutions

- Carbon Dioxide Sequestration (e.g. injection into deep underground reservoirs)

Capture and concentration of CO2 from large emission sources, such as power plants

Requirements

!!!!CO2 is accompanied by other gases: N2, O2, H2O, NOx, SOx, particulate!!!!

0.36 nm

0.33 nmC CO

0.39 nmCH

H

HH


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Introduction

Molecular Sieves

Microporous solids with a very narrow pore size distribution, the dimension of micropores being

similar to the molecules to be adsorbed/separated.

Molecular discrimination caused by:

molecular dimensionmolecular shapekinetics of adsorption


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Introduction

Molecular Sieves


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p/p0 p/p0 p/p0

n ads n ads n adsBz

2,2DMB

n-butane

i-butane

N2

o2

Introduction

Molecular Sieves: Equilibrium adsorption isotherms


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0.4 nm

Introduction

Selectivity by molecular shape


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0.4 nm

Introduction

Selectivity by molecular size


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0.4 nm

Introduction

Selectivity by different kinetics


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Introduction

Why carbon molecular sieves?Slit-shaped micropores

Porosity can be tailored

Rather “inert” surface

Adsorption of non-polar species favoured,

Surface chemistry can be easily modified,

Many physical forms (granular, pellets, fibres, cloth, felt, monoliths, etc.)

Unparallelled flexibility2ºSAASA, San Luis-2013

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Objective

Synthesis of very high porosity CMS from petroleum residues for selective CO2 adsorption vs. other molecules of

similar molecular dimensions (N2 and CH4)

Synthesis of monolithic CMS without the use of a binder:


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Effect of theactivationconditions

Novel CarbonMaterials

Effect of thepetroleum pitch


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Effect of theactivationconditions

Novel CarbonMaterials

Effect of thepetroleum pitch


JASJ.M. Ramos-Fernández et al., Carbon 46 (2008) 384

Experimental Section440ºC, 1 MPa,

2-4 Hours. Ball Milling

Mesophase pitchØ≤500µm

MP-2 (2 h) VR-5; DO-10MP-4 (4 h) VR-93; DO-88

VR (vacuum residue)DO (decanted oil)


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VR-5 VR-93

DO-10 DO-88

A. Wahby et al. ChemSusChem 3, 974-981 (2010)

Experimental Section


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+ KOH

30 min, 300 rpm

1

2

3

45 6

7

8

9

1 102

3

45 6

7

8

9

11

ACM

J.M. Ramos-Fernández et al., Carbon 46 (2008) 384

MP + KOH (1:3)(VR-5, VR-93, DO-10, DO-88)

Experimental Section

Conforming Press400 MPa

Activation 800ºC, 2 Hours

Washing


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Results and discussion

J.M. Ramos-Fernández et al., Carbon 46 (2008) 3842ºSAASA, San Luis-2013

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Scanning Electron Microscopy


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0.0 0.2 0.4 0.6 0.8 1.00

10

20

30

40

50

VR-5

0.0 0.2 0.4 0.6 0.8 1.00

10

20

30

40

50

VR-93

0.0 0.2 0.4 0.6 0.8 1.00

10

20

30

40

0.0 0.2 0.4 0.6 0.8 1.00

10

20

30

40

DO-10-mix DO-88

monolithpowder

powder

monolith

monolith

powder

p/p0 p/p0

p/p0p/p0

nads(mmol/g)

nads(mmol/g)

nads(mmol/g)

nads(mmol/g)

Results and discussionN2 adsorption/desorption isotherms at 77 K

A. Wahby et al. ChemSusChem 3, 974-981 (2010) 2ºSAASA, San Luis-2013

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Muestra SBET (m2/g) V0 (cm3/g) Vt (cm3/g) Vn (cm3/g)

VR-5-P 3100 1.45/1.02 1.57 0.85

VR-5-M 2450 1.03 1.12 0.95

VR-93-P 2895 1.28/1.06 1.42 0.80

VR-93-M 2720 1.21 1.22 1.08

DO-10-mix 2600 1.16/0.93 1.16 0.75

DO-88-P 2440 1.09/0.88 1.14 0.69

DO-88-M 2660 1.16/1.00 1.16 0.74

Results and discussionTextural characteristics N2 and CO2 data


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Muestra SBET (m2/g) V0 (cm3/g) Vt (cm3/g) Vn (cm3/g)

VR-5-P 3100 1.45/1.02 1.57 0.85

VR-5-M 2450 1.03 1.12 0.95

VR-93-P 2895 1.28/1.06 1.42 0.80

VR-93-M 2720 1.21 1.22 1.08

DO-10-mix 2600 1.16/0.93 1.16 0.75

DO-88-P 2440 1.09/0.88 1.14 0.69

DO-88-M 2660 1.16/1.00 1.16 0.74

Results and discussionTextural characteristics N2 and CO2 data


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0.00 0.01 0.02 0.030

100

200

300

0.00 0.01 0.02 0.030

100

200

300

nads(mg/g)

p/p0

nads(mg/g)

323 K

VR-93-P

298 K

273 K

VR-93-M

323 K

298 K

273 K

p/p0


CO2 adsorption isotherms at different temperatures (VR-93)


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0.00 0.01 0.02 0.030

100

200

300

400

0.00 0.01 0.02 0.030

100

200

300

400

p/p0

nads(mg/g)

VR-5-P

323 K

298 K

273 K

p/p0

nads(mg/g)

VR-5-M

323 K

298 K

273 K


A. Wahby et al. ChemSusChem 3, 974-981 (2010)

CO2 adsorption isotherms at different temperatures (VR-5)


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0.3 0.4 0.5 0.6 0.70

50

100

150

200

250

300

350

VR-5-P VR-5-M VR-93-P VR-93-M DO-88-P DO-88-M DO-10-mix

Molecular dimension (nm)

DCM BZ 22DMB α-pinene-DHimm

(J/g)


Immersion calorimetry into different liquids


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0.0 0.2 0.4 0.6 0.8 1.00

100

200

300

400

nads

(m

g/g)

VR-5-M

Zeolite 13X

Zeolite 5A

Pressure (bar)


Carbon Molecular Sieves vs. Zeolites


JASJ. Silvestre-Albero et al. ChemComm 47, 6840-6842 (2011)

0.0 0.2 0.4 0.6 0.8 1.00

50

100

150

200

250

U

ptak

e (m

g/g)

Pressure (bar)

MOF-200 MOF-177 MAXSORB VR-5 VR-93


Carbon molecular sieves vs. MOFs materials


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0 10 20 30 40 500

400

800

1200

1600

2000

2400 MOF-200 MOF-177 MAXSORB VR-5 VR-93

Upt

ake

(mg/

g)

Pressure (bar)



J. Silvestre-Albero et al. ChemComm 47, 6840-6842 (2011) 2ºSAASA, San Luis-2013

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0 10 20 30 40 500

100

200

300

400

500

C

O2 u

ptak

e (c

m3 (S

TP)/c

m3 )

Pressure (bar)

MOF-200 MOF-177 MAXSORB VR-5 VR-93




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0 10 20 30 40 500

100

200

300

400

500

CO

2 upt

ake

(cm

3 (STP

)/cm

3 )

Pressure (bar)

1st cycle 2nd cycle 3rd cycle


Regeneration of the carbon molecular sieves


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0 100 200 300 4000

1

2

3

4

5

CO2

N2

CH4

0 100 200 300 4000

1

2

3

4

5

CH4

N2

CO2

Time (s)

nads(mmol/g)

Time (s)

nads(mmol/g)

VR-93-P VR-93-M


Kinetics of adsorption of CO2, N2 and CH4 at 298 K(VR-93)


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0 100 200 300 4000

1

2

3

4

5

CO2

N2

CH4

0 100 200 300 4000

1

2

3

4

5

CH4

N2

CO2

VR-5-MVR-5-P

Time (s)

nads(mmol/g)

Time (s)

nads(mmol/g)


Kinetics of adsorption of CO2, N2 and CH4 at 298 K(VR-5)


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SummaryHigh surface area (up to 3000 m2/g) carbon molecular sieves can be prepared from petroleum pitch using KOH as activating agent.

These carbon molecular sieves exhibit an extremely high CO2 adsorption capacity (up to 380 mg/g).

Either at low (1 bar) and high (50 bar) pressure, CMSs are able to overcome the incomparable adsorption behavior described for MOFs materials.

CMSs are able to discriminate CO2 for molecules of similar dimensions (e.g. CH4 and N2).

The size of the pore entrance on these CMSs highly depends on the petroleum residue, the pyrolysis conditions used and the activation degree. For samples VR it is below 0.56 nm.


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AcknowledgementNational Projects:NAN2004-09267-C03-03MAT2007-61734

EU Projects: FRESP (Advanced First Response Respiratory Protection)

Laboratorio de Materiales Avanzados


10th International Symposium on the Characterization of Porous

Solids (COPS-X)

Granada (Spain)11-14 May 2014

Location

Granada is located in the South of Spain in the “Andalucia Region”

How to arrive:

-Granada is located 434 Km south from Madrid. There are several daily trains from Madrid to Granada (4h 25 min; shorter time in 2014)-Granada´s airport is 17 Km from the city. There are direct national flights to Madrid (Iberia), Barcelona (Vueling) and Palma de Mallorca (Iberia, Air Europa). There are also International connections with Paris (Vueling), Milano (Ryanair) and Bologna (Ryanair)-International airport of Malaga is located 125 Km from Granada.

The City of Granada

The “Alhambra”Palace

The Catedral Generalife Palace Albaicín

Granada Congress Centre

The “Tapas”

Around Granada

Sierra Nevada The Alpujarras

Organization

Local Scientific Committee:-Dr. Francisco Carrasco-Marín, University of Granada-Dr. Agustín F. Pérez Cadenas, University of Granada

International Scientific Committee:-Dr. Tina Düren, University of Edinburgh, UK-Dr. Stefan Kaskel, TU Dresden, Germany-Dr. Philip Llewellyn, University of Provence, France-Dr. Joaquín Silvestre-Albero, University of Alicante, Spain

Honorary Scientific Committee:-Prof. Dr. Francisco Rodríguez-Reinoso, Spain-Prof. Dr. Jean Rouquerol, France-Prof. Dr. Kenneth Sing, UK-Prof. Dr. Klaus K. Unger, Germany

Revista del Grupo Especializado de Adsorción de la RSEQISSN:2173-0253

Artículos Espacio PredocArtículos recientes destacadosBolsa de trabajoNovedades tecnológicas

Tesis doctoralesReseñas de congresosCuriosidades científicasAgenda de actividad

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COPS 2011- Dresden JAS

Thank you very much foryour attention!!!

email: [email protected]

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Novel carbon nanomaterials for selective CO capture

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