This document summarizes a project on using metal-organic frameworks (MOFs) for post-combustion carbon capture. It discusses (1) developing MOF materials with high CO2 selectivity and capacity through scale-up synthesis and formulation methods, (2) testing MOF performance for CO2/N2 separation through breakthrough experiments using a dual-piston vacuum swing adsorption system, and (3) optimizing the vacuum pressure swing adsorption process through modeling. The project involves partners from the University of Edinburgh, SINTEF Materials and Chemistry, and the Centre for Research and Technology. Some results showed the successful formulation of MOFs into stable spheres using an alginate method and their high CO2 ad

1. Technology for a better society
UK-Canada-Norway meeting on CO2 capture research, 19th March 2015
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Carlos A. Grande
SINTEF Materials and Chemistry. Forskningsveien 1, Oslo (0373), Norway.
E-mail: carlos.grande@sintef.no
Tel: +4793207532
Richard Blom, Stefano Brandani, Eusthatios Kikkinides, Michail Georgiadis, Shreenath
Krishnamurthy, Aud Spjelkavik and Terje Didriksen
Post-Combustion Capture using MOFs
UK-Norway-Greece Collaboration

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 Technical introduction
 Project description
 Project data & partners
 Some results
 Conclusions
 Acknowledgments
 Other related projects
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Outline

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CO2 capture possibilities
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PSA process fundamentals
CO2 is initially adsorbed in a selective porous material and after
is concentrated and before it escapes from the column, it is
recovered with high purity.
DesorptionAdsorption
Feed
CO2,
> 95%
Production
step
Regeneration
steps
No / little
CO2

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Simultaneous water removal is possible? YES
►Zeolites used in H2 purification cannot handle water
 A pre-layer is placed to selectively remove water
 Same strategy can be used for post-combustion capture
Alumina / silica gel
Activated carbon
Zeolite (5A or 13X)
Feed: H2, CO2, CH4,
CO, H2O (N2, O2, etc).
Product: H2 > 99,99%
H2O
CO2
CH4
CO
N2, lights
Alumina / silica gel
Selective CO2
adsorbent
Feed: O2, N2, Ar, CO2,
H2O
CO2 free stream
H2O
CO2

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 The adsorbent is "the heart" of an adsorption process. Several
porous materials with large surface area like zeolites can selectively
adsorb CO2, but they are very difficult to regenerate.
 Metal-organic frameworks have already demonstrated that they can
haver extremely large capacity of CO2 and is possible to regenerate
them without extreme power consumption.
 The structure of the material can be tuned for specific conditions.
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The "CO2 selective" adsorbent

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 Very few MOF materials are commercial (in powder form).
Unfortunately they are not good for CCS applications.
 So, material scale-up, formulation and efficient utilization is
necessary.
 The main objective of our project "Post-Combustion Carbon Capture
Using MOFs: Materials and Process Development" is to address all
the challenges in using MOF materials: large-scale (kg) synthesis,
formulation, stability and process design, modelling and
verification.
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The "CO2 selective" adsorbent challenges

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 Project identification: 230940 - " Post-Combustion Carbon Capture
Using MOFs: Materials and Process Development "
 Partners:
The University of Edinburgh, UK. Prof. Brandani
SINTEF Materials and Chemistry, Norway. Dr. Blom
Centre for Research and Technology, Greece. Prof. Kikkinides
 Project budget: 605 k€. Support from FENCO-NET project:
244 kEuro RCN, 251 kEuro EPSRC, 110 kEuro NCRD
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The project: data & partners

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 Materials synthesis & testing (SINTEF)
Select, produce and scale-up to 0.2-1 kg of formulated and
stable MOF material (CPO-27-Ni)
 VSA dynamics (UoE)
Use the MOF to measure breakthrough and test its performance
in dual-piston VSA
 Process optimization & benchmarking (CERTH)
Develop a detailed modelling framework to optimize the PSA
performance and benchmark it with existing technologies.
 Project management & dissemination (UoE)
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The project: work-packages

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 MOF formulation: the alginate method
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Some results
Molecular Formula:
(C6H8O6)n
• Discovery of alginates were done by Edward Stanford in 1883
• Polymerizes into a three dimentional metal-bioorganic network in the
presence of cations such as Ca2+
• Used in molecular gastronomy for ages…..

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MOF formulation by molecular gastronomy
methods……
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Looking into the spheres: CPO-27-Ni / alginate
• The interior has
macro-pores that
give fast gas
diffusion
• The alginate matrix
seems evenly
distributed and
glue to MOF
crystallites together
• Still, there is a lot to
gain on increasing
the particle density
through
optimisation of the
procedure
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Spjelkavik, Didriksen, Aarti, Divekar, Blom. Chem. Eur. J. 2014, 20, 8973

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 Measure pure gas adsorption isotherms
 Very high selectivity towards CO2 was observed
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Adsorption equilibrium
CPO-27-Mg is not so stable and is much more expensive to produce

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Dual piston VPSA
 Separation efficiency of MOFs for CO2 capture
 Determination of equilibrium and kinetics
 Pure component and mixtures can be tested
 Different combinations of cycle times, phase angles (Pistons in phase/out of phase)
and stroke lengths possible
Dual piston apparatus
Pellets on thermocouples
Packed column
11.8g sample

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Dual piston VPSA
Pure CO2 and N2 experiments at 35°C
Cycle time 10s, Pistons in Phase, Stroke length 100 mm

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Initial VSA process simulations
Bench scale Vacuum swing adsorption (VSA) cycle simulator.
Very high purity in the evacuation step.

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Acknowledgements
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To all funding entities of this project under the FENCO.net
programme: NFR, EPSRC and NCRD

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Other related projects: NORWAY – UK collaboration
MATESA: Advanced Materials and Electric Swing
Adsorption Process for CO2 Capture
FP7 – Energy funded project.
Coordinated by SINTEF Materials and Chemistry
Partner from UK: PSE Enterprise, London.
Electrically conducting monoliths containing
MOF materials for post-combustion capture.
PSA process for natural gas upgrading
Performed by SINTEF
Tender launched by IEAGHG. Report to be
released in 2015.
Topic: CO2 removal from natural gas for EOR
using adsorption processes