CatalysisMaterialsReaction Engineering Research in Chemical Engineering

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Catalysis/Materials/Reaction Engineering
Research in Chemical Engineering

• Kerry Dooley - dooley_at_lsu.edu
• Others Jerry Spivey, K.T. Valsaraj, F.C. Knopf,
  Lisa Podlaha-Murphy, Judy Wornat, Greg Griffin,
  Doug Harrison

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AREAS OF EXPERTISE

• Dooley Supported metal oxides, metals, and
  solid acids for oxidation, condensation, and
  hydrogenation.
• Griffin - CVD synthesis of thin metal films
• Knopf Novel microreactor development,
  especially for gas-liquid reactions.
• Podlaha-Murphy - electrodeposition of
  nanostructured metal alloys and metal matrix
  composites
• Spivey NO decomposition, fuel processing
  (selective CO oxidation), oxygenate synthesis
  from biomass-derived syngas, Fischer-Tropsch.
• Valsaraj mesoporous materials synthesis.
• Wornat - pyrolysis and combustion of fuels,
  especially aromatics

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Capabilities at LSU Catalysis
Capabilities at LSU Experimental

• Catalyst testing low and high pressure
  microreactor systems - gas-solid,
  gas-liquid-solid GC, GC-MS, LC product
  characterization.
• Catalyst characterization (TPR, FTIR, TGA,
  chemisorption, etc.).
• Environmental SEM/EDAX (and several other
  microscopy facilities on campus)
• XPS, UV-Vis and other spectroscopic techniques

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Major Equipment Fabrication for Microreactors,
Spectroscopic Cells, etc. Major Equipment
Major Equipment Fabrication for Microreactors,
Spectroscopic Cells, etc.
We have 3 full-time machinists with CNC lathes,
3- and 4-axis milling machines, and water-jet
cutter.

• Six GCs and one MS for online analysis
• Thermogravimetric analyzer chemisorption
  apparatus
• Haake torque rheometer/twin screw extruder/high
  shear mixer for reactive extrusion and
  compounding.
• FTIR controlled environment transmission,
  DRIFTS ATR
• Parallel fixed bed reactor system (8), low
  pressures (lt2 atm).
• High-pressure (to 4 MPa) microreactor facility,
  for gas/liquid reactions.
• Two other low pressure microreactor facilities
  with flow, temperature, pressure controls
• Cat. Prep. Facilities vacuum lines, glove box,
  3-zone furnace, autoclaves.

Poly. Reactor facility, fabrication and assembly
by Che shop ?
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Major Equipment Synchrotron Beamlines and
Microfabrication Facilities(Center for Advanced
Microstructures and Devices)
Major Equipment Synchrotron Beamlines and
Microfabrication Facilities (Center for Advanced
Microstructures and Devices) e.g. DCM Beamline
for X-ray Absorption Spectroscopy, High
Resolution XRD, Tomography

• Six GCs and one MS for online analysis
• Thermogravimetric analyzer chemisorption
  apparatus
• Haake torque rheometer/twin screw extruder/high
  shear mixer for reactive extrusion and
  compounding.
• FTIR controlled environment transmission,
  DRIFTS ATR
• Parallel fixed bed reactor system (8), low
  pressures (lt2 atm).
• High-pressure (to 4 MPa) microreactor facility,
  for gas/liquid reactions.
• Two other low pressure microreactor facilities
  with flow, temperature, pressure controls
• Cat. Prep. Facilities vacuum lines, glove box,
  3-zone furnace, autoclaves.

Microfab Heat Exchanger, cross-section view (from
Kevin Kelley, ME)
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XANES/XAFS Effect of Metal Doping on Rare Earth
Oxide Condensation (to Ketone) Catalysts (Dooley)

Pseudo Radial Distribution Function for Co from
FT-XAFS (c(k), k3 weighting) data. The magnitude
of the first Co shell is small, suggesting
dispersion in CeO2.
Co K-edge XANES, Co/CeO2/Al2O3 catalysts, showing
reduced state of doped Co.
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Direct Synthesis of Acetic Acid from CO2
Methane - Spivey

• Vinyl Acetate Production

• Cyclic
• Adsorption/Desorption

CO2 CH4 ? CH3COOH
CH3COOH C2H2 ? CH3CO2CH3
CO2(g) CH4(g) C2H2(g) ? CH3CO2CH3 (g)
?H298 -73.7 kJ/mol ?G298 6.98 kJ/mol
XCH4 99.6 at 5 atm, 300K
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Meso/Megaporous Synthesis of Catalyst
Supports(Valsaraj, Dooley)
Studying dual surfactant (polyaphron) methods and
all alkoxide synthesis routes for
hydroxyapatites, CeO2/ZrO2, other rare earth
oxides.
GEL FORMATION
TEMPLATE REMOVAL
Polyaphron silica synthesis, megaporous
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HYDROGENATION IN ACTIVELY FORCED (PULSED)
MICROREACTORS (Knopf/Dooley)

• Adaptable to slurry bubble columns, monolith and
  microreactors. Beneficial effects on gas
  distribution, catalyst wetting, mass transfer
  rates in either small channels or bulk liquid.
• Future hydrogenation/dehydrogenation reactions
  involve high MW materials bio-derived oils and
  waxes, biomass etc. Active forcing can make
  gas/liquid processing of them in microchannels
  possible.

Gas Flow Visualization, Microchannel Assembly,
without (left) and with (right) active forcing
121 channels, 1.59 mm dia., Amplitude 2.46
mm, Frequency 2 Hz Gas flow rate 15 mL/s.
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Capabilities at LSU (Lisa Podlaha)
Capabilities at LSU Alloy Electrodeposition
(Podlaha-Murphy)
Nanowire with nanometric multilayers 2 nm Cu / 4
nm CoNiFe
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LSU Capabilities Atomic level resolution STM
LSU Capabilities Atomic level resolution STM

• Atomic level resolution STM

hexagonal Fe3O4 on Cu (001)
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Conclusion versatility, broad experience and
range of experimental capabilities in Catalysis,
Materials, Reaction Engineering
Conclusion versatility, broad experience and
range of experimental capabilities in Catalysis,
Materials, Reaction Engineering
CVD Reactor Facility Griffin Lab