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UK Norway Collaboration Post-Combustion Carbon Capture Using MOFs, Carlos Grande (Sintef) UK/Norway/Canada Meeting 18/19 March 2015

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UK Carbon Capture and Storage Research Centre
UK Carbon Capture and Storage Research Centre

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

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Technology for a better society UK-Canada-Norway meeting on CO2 capture research, 19th March 2015 1 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
Technology for a better society  Technical introduction  Project description  Project data & partners  Some results  Conclusions  Acknowledgments  Other related projects 2 Outline
Technology for a better society CO2 capture possibilities 3
Technology for a better society 4 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
Technology for a better society 5 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
Technology for a better society  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. 6 The "CO2 selective" adsorbent
Technology for a better society  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. 7 The "CO2 selective" adsorbent challenges
Technology for a better society  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 8 The project: data & partners
Technology for a better society  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) 9 The project: work-packages
Technology for a better society  MOF formulation: the alginate method 10 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…..
Technology for a better society MOF formulation by molecular gastronomy methods…… 11
Technology for a better society 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 12 Spjelkavik, Didriksen, Aarti, Divekar, Blom. Chem. Eur. J. 2014, 20, 8973
Technology for a better society  Measure pure gas adsorption isotherms  Very high selectivity towards CO2 was observed 13 Adsorption equilibrium CPO-27-Mg is not so stable and is much more expensive to produce
Technology for a better society 14 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
Technology for a better society 15 Dual piston VPSA Pure CO2 and N2 experiments at 35°C Cycle time 10s, Pistons in Phase, Stroke length 100 mm
Technology for a better society 16 Initial VSA process simulations Bench scale Vacuum swing adsorption (VSA) cycle simulator. Very high purity in the evacuation step.
Technology for a better society Acknowledgements 17 To all funding entities of this project under the FENCO.net programme: NFR, EPSRC and NCRD
Technology for a better society 18 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

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UK Norway Collaboration Post-Combustion Carbon Capture Using MOFs, Carlos Grande (Sintef) UK/Norway/Canada Meeting 18/19 March 2015

  • 1. Technology for a better society UK-Canada-Norway meeting on CO2 capture research, 19th March 2015 1 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
  • 2. Technology for a better society  Technical introduction  Project description  Project data & partners  Some results  Conclusions  Acknowledgments  Other related projects 2 Outline
  • 3. Technology for a better society CO2 capture possibilities 3
  • 4. Technology for a better society 4 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
  • 5. Technology for a better society 5 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
  • 6. Technology for a better society  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. 6 The "CO2 selective" adsorbent
  • 7. Technology for a better society  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. 7 The "CO2 selective" adsorbent challenges
  • 8. Technology for a better society  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 8 The project: data & partners
  • 9. Technology for a better society  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) 9 The project: work-packages
  • 10. Technology for a better society  MOF formulation: the alginate method 10 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…..
  • 11. Technology for a better society MOF formulation by molecular gastronomy methods…… 11
  • 12. Technology for a better society 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 12 Spjelkavik, Didriksen, Aarti, Divekar, Blom. Chem. Eur. J. 2014, 20, 8973
  • 13. Technology for a better society  Measure pure gas adsorption isotherms  Very high selectivity towards CO2 was observed 13 Adsorption equilibrium CPO-27-Mg is not so stable and is much more expensive to produce
  • 14. Technology for a better society 14 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
  • 15. Technology for a better society 15 Dual piston VPSA Pure CO2 and N2 experiments at 35°C Cycle time 10s, Pistons in Phase, Stroke length 100 mm
  • 16. Technology for a better society 16 Initial VSA process simulations Bench scale Vacuum swing adsorption (VSA) cycle simulator. Very high purity in the evacuation step.
  • 17. Technology for a better society Acknowledgements 17 To all funding entities of this project under the FENCO.net programme: NFR, EPSRC and NCRD
  • 18. Technology for a better society 18 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