New Advances for Fischer Tropsch Catalysis Office of Research and - - PowerPoint PPT Presentation

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New Advances for Fischer Tropsch Catalysis Office of Research and - - PowerPoint PPT Presentation

Driving Innovation Delivering Results New Advances for Fischer Tropsch Catalysis Office of Research and Development Christopher Matranga & Dushyant Shekhawat August 2015 National Energy Technology Laboratory A Simplified View of


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National Energy Technology Laboratory

Driving Innovation ♦ Delivering Results Christopher Matranga & Dushyant Shekhawat

Office of Research and Development August 2015

New Advances for Fischer‐Tropsch Catalysis

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National Energy Technology Laboratory

A Simplified View of Fischer‐Tropsch Mechanistic Chemistry

Figure from Weckhuysen Chem. Soc. Rev., 2008, 37, pgs 2758–2781

6 general rxn steps: (independent of model, catalysts, rxn conditions)

  • Adsorption/activation
  • Chain initiation
  • Chain growth
  • Product desorption
  • Chain termination
  • Readsorption/further rxn

3 widely considered mechanisms on Fe:

  • Surface carbide (shown)
  • Surface enol
  • CO insertion

https://youtu.be/44OU4JxEK4k Youtube Movie Credit: I. Filot, E. Hensen, R. van Santen Institute for Complex Molecular Systems, Eindhoven University of Technology

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National Energy Technology Laboratory

A Simplified View of Fischer‐Tropsch Mechanistic Chemistry

Figure from Weckhuysen Chem. Soc. Rev., 2008, 37, pgs 2758–2781

6 general rxn steps: (independent of model, catalysts, rxn conditions)

  • Adsorption/activation
  • Chain initiation
  • Chain growth
  • Product desorption
  • Chain termination
  • Readsorption/further rxn

3 widely considered mechanisms on Fe:

  • Surface carbide (shown)
  • Surface enol
  • CO insertion

Surface Carbide Mechanism

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National Energy Technology Laboratory

Anderson‐Shulz‐Flory (ASF) Product Distributions

Figures from R. De Deugd PhD Dissertation, Technical University of Delft, 2004

  • Radical polymerization type distro
  • Chain termination/progation are

critical/rate‐determining steps

  • Occur for fully thermalized,

“equilibrium” or “steady state” conditions

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National Energy Technology Laboratory

Are Controlled Deviations from ASF Possible?

Image from Wang et. al. ChemCatChem Doi: 10.1002/cctc.201000071

Nano‐structured Catalyst Materials Potential Benefits

  • Non Anderson‐Shulz‐Flory Product Distributions
  • Stabilization of active catalyst phase
  • Controlled production of oxygenates/aromatics
  • Improved reactivity & conversion

Non‐equilibrium Reactors (Microwave‐MW)

Solid = microwaves Dashed = thermal

Potential Benefits

  • Non‐thermal & Non‐ASF Product Distributions
  • Lowered reactor temperatures
  • Improved kinetics, reactivity & conversion
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National Energy Technology Laboratory

Motivation from Previous Literature: Process Intensification w/Nano‐Catalysis

Data & Images from Bao et. al. JACS, doi: 10.1021/ja8008192

Fe2O3 in Carbon Nanotubes Fe2O3 outside Carbon Nanotubes

Fe & Fe‐carbide form at lower T For Fe2O3 inside CNTs

Altered Product Distros

Legend: Black = Fe inside CNTs Red = Fe outside CNTs Blue = Fe on act. carbon

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National Energy Technology Laboratory

Recent Nano‐catalyst results from ORD

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National Energy Technology Laboratory

Layered Graphene Catalyst Supports for Breaking ASF Distributions

Layered graphene controls surface mobility of FT‐type species (Li et. al., Science, 2013)

Can this be exploited for FT ?

Adsorption Isotherms in Graphene Oxides

  • Surface mobility disrupted (kinetic effect)
  • More H2 adsorbed than N2 (size exclusion)
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National Energy Technology Laboratory

Nanostructured Fe5C2 “Häggs Phase”

10 nm Fe5C2 20 nm Fe5C2

  • Fe5C2 Häggs phase one of most active phases for FT
  • ORD synthesis produces high yield, gram, batches of nearly pure Fe5C2
  • Nanoparticle shell is a mixed amorphous Fe‐carbide/oxide
  • Future work will incorporate into layered graphene and/or carbon nanotube supports

X‐ray diffraction confirms nano‐Fe5C2 structure

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National Energy Technology Laboratory

Synchrotron X‐ray characterization of nano‐ Fe5C2

705 710 715 720 725 730

20 nm Fe-carbide 10 nm Fe-carbide Fe3C Fe3O4 Fe2O3 FeO

Normalized Absorbance Photon Energy (eV)

Fe

Fe L edge X‐ray absorbance

525 530 535 540 545 550 555

20 nm Fe-carbide 10 nm Fe-carbide Fe3C Fe3O4 Fe2O3 FeO

Normalized Absorbance Photon Energy (eV)

Fe

O K edge X‐ray absorbance

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National Energy Technology Laboratory

Summary

  • ASF arises from a radical chain polymerization process at

thermal equilibrium

  • Deviations from ASF require disrupting molecular processes
  • n catalyst/support surface (adsorption, diffusion, etc)
  • Microwave reactors offer additional opportunities to deviate

from ASF

  • Nano‐structured Graphene and Fe5C2 have been synthesized

and initial characterization started.