Alternative Fuels Research: Practical Applications and Foundational Questions
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Alternative Fuels Research: Practical Applications and Foundational Questions. Ohio Center for Intelligent Propulsion and Advanced Life Management Ohio Third Frontier Program Review Heinz J. Robota, Ph.D. Ohio Research Scholar in Alternative Fuels Group Leader: Alternative Fuels Synthesis

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Ohio center for intelligent propulsion and advanced life management

Alternative Fuels Research: Practical Applications and Foundational Questions

  • Ohio Center for Intelligent Propulsion and Advanced Life Management

  • Ohio Third Frontier Program Review

    Heinz J. Robota, Ph.D.

    Ohio Research Scholar in Alternative Fuels

    Group Leader: Alternative Fuels Synthesis

    University of Dayton Research Institute

    University of Cincinnati

    14 May 2013


Overview

Overview

  • Alternative Fuels in Aviation

    • Fuel types and specifications

  • Facilities

  • Practical Scale Preparations

    • Fischer-Tropsch Synthetic Paraffinic Kerosene

    • Unique “single carbon number, narrow boiling” fuels

    • True “drop-in” renewable Jet-A

  • Foundational Research

    • Algae oil to jet and diesel

    • Kinetics of stearic acid deoxygenation

  • Summary


The origination of the assured aerospace fuels research facility

The Origination of the Assured Aerospace Fuels Research Facility

Generate practical sample quantities of jet boiling range material for evaluation and demonstration


Alternative fuels approved by type for use in a blend with petroleum fuel

Alternative Fuels Approved by “type” for use in a blend with petroleum fuel

  • USAF leadership from properties, characteristics, specifications, through flight approval – commercial aviation now implementing slowly

  • Approved or nearly approved fuels categorized as “Synthetic Paraffinic Kerosene” (SPK)

    • Aliphatic hydrocarbons – negligible aromatic content

    • Highly isomerized alkanes – for low temperature properties

    • Type Specifications accommodate the peculiarities of the fuel chemical constituents

  • Fischer-Tropsch SPK – First type to be approved

  • Hydrotreated Renewable Jet (HRJ) or Hydrotreated Esters and Fatty Acids (HEFA) – second to be approved

    • Spec has added requirements related to: Gum, FAME content

  • Nearly approved Alcohol-to-Jet (ATJ) – allows higher cycloparaffins

  • Otherwise, these specs are the SAME


Shroyer park center catalyst preparation and testing capabilities

Shroyer Park Center Catalyst Preparation and Testing Capabilities

4 Fixed bed reactors with concurrent liquid and gaseous feed

2 Fixed bed FT synthesis reactors and 2 CSTRs available for swap

Continuous off-gas monitoring with on-line GC

Micromeritics ASAP 2020 textural analysis and chemisorption analysis system being installed

Surface Area

Pore Volume

Pore size distribution

Metal Catalyst dispersion

Mix-muller for 1-3 kg preparation of extrudable catalyst/binder aggregate

1” laboratory extruder for making shaped catalyst for use in AAFRF or other practical-scale fixed bed reactors reactors

High resolution FTIR with heated multi-path gas cell for trace gas contaminant analysis – NH3,HCN, CO, CO2

Usable for condensed phase research as well


Facilities assured aerospace fuels research facility aafrf

Facilities: Assured Aerospace Fuels Research Facility - AAFRF

  • What Is The AAFRF?

    • SPU, Facility and Team

      • Skilled and experience team (USAF, UDRI and BMI)

    • Answer practical questions about fuels from alternative sources

    • Producing practical quantities of demonstration fuelfor testing and demonstrating synthetic routes

    • Assess catalyst –related technology through formulation and evaluation. Lab at Shroyer Park Center


Aafrf spu designed with ft upgrading in mind

AAFRF-SPU Designed with FT Upgrading in Mind


Aafrf commissioned making spk from genuine f t wax

AAFRF Commissioned making SPK from Genuine F-T Wax

AAFRF SPK properties are nearly identical to other non JP-8 jet fuels

  • Validated design criteria

  • Validated catalyst function

  • Required Heat Trace everywhere

  • Distillation heater required higher

    • output than original design

  • Validated automation system

  • Ready for production research!


Preparing a c 14 narrow boiling spk maximizing isomer yield

Preparing a C14 narrow boiling SPK: Maximizing Isomer Yield

Synthetic approach demonstrated at SPC Lab scale – in house catalysts scaled to multi kg lots

Outstanding performance scalability from lab to AAFRF scale

Fed roughly 2200 gal n-C14 - recovered 1700 gal of mixed C14 isomers


Preparing a c 14 narrow boiling spk final product by distillation

Preparing a C14 narrow boiling SPK: Final Product by Distillation

A consolidated 500 gal batch with freezing point of -41.7 °C – meets Jet-A Specification

Isomer distribution is different from a solvent-dewaxed product in a desirable way – multi-branched isomers dominate

Distillation Gradient T90-T10 = 17 °C – meets the narrow boiling target

From concept discussions to fuel delivery in 18 months

A successful campaign and project!


Supporting commercialization finishing a prospective true renewable drop in jet a

Supporting Commercialization: Finishing a Prospective True Renewable “Drop-in” Jet-A

1750 gallons of “CH Crude” delivered for Total Acid Number (TAN) reduction and separation of the Jet-A Specification –compliant fraction

Delivered TAN 140 mg/g

Required reduction to <0.10 mg/g

Distilled fraction to meet Jet-A Specification


Supporting commercialization finishing a prospective true renewable drop in jet a1

Supporting Commercialization: Finishing a Prospective True Renewable “Drop-in” Jet-A

Delivered 525 gallons of a theoretical 565 max, >90%

Cumulative TAN 0.005 mg KOH/g – an effective overall conversion of 99.996% !!

First use of a sulfided catalyst in the system

Fuel met all applicable JET-A specifications

Flash point and Freezing point set the bounds on allowable composition


Converting algal oil to fuels first to n alkanes

Converting Algal Oil to Fuels: First to n-Alkanes

Algae provided by USAF from Phycal production

Output of a Third Frontier development program

Processed ~ 2.5 L of algal oil

Product Alkanes reflect oil composition and a

changing catalyst selectivity with time-on-stream


Converting algal oil to fuels n alkanes to fuel

Converting Algal Oil to Fuels: n-Alkanes to Fuel

All methods and catalysts used are readily scalable

n-C17

n-C18

n-C15

n-C16

Deoxygenated alkane mixture hydro-converted to isomers and cracked products with Pt/US-Y

A Practical Diesel Fuel

Selective removal of n-alkanes improves cold weather flow – Arctic Grade Diesel Fuel


Elucidating reaction kinetics of a complex reaction network

Elucidating Reaction Kinetics of a Complex Reaction Network

Fitting power law kinetics with the effects of T, concentration of reactants

Rigorous control of all reaction variables to produce reproducible reaction rates allowing parameter extraction


Summary

Summary

  • Established a laboratory infrastructure to make and investigate fuel-making catalysts and catalyst processes

  • Brought to operation the AAFRF-SPU within the design envelope by making genuine Fischer-Tropsch SPK

  • Successfully produced two unique research fuels for composition-property research

  • Delivered 525 gallons of genuine drop-in renewable Jet-A for an industrial collaborator

  • Established foundational research related to liquid fuel-making catalytic chemsitries


Acknowledgements

Acknowledgements

This research was supported, in part, by the U. S. Air Force Cooperative Grant Numbers F33615-03-2-2347 and FA8650-10-2-2934 with Mr. Robert W. Morris Jr. serving as the Air Force Grant Monitor. The research was also sponsored by the State of Ohio Subrecipient Award No. COEUS # 005909 to the University of Dayton (Dr. Dilip Ballal as the Grant Monitor) under the “Center for Intelligent Propulsion and Advanced Life Management,” program with the University of Cincinnati (Prime Award NO. TECH 09-022). We gratefully acknowledge this support.

Thank you to UDRI personnel: Steve Zabarnick, Matthew de Witt, Rich Striebich, Linda Shafer, Ryan Adams, Zachary West, Dave Thomas, Gordon Dieterle, James Shardo, Jerry Grieselhuber, Jeff Coleman, Jeff Unroe, Alan Wendel, Dennis Davis, Ted Williams, David Gasper, Scott Breitfield, Rhonda Cook, Zachary Sander, Jhoanna Alger, Andrew Palermo, Albert Vam, Roger Carr, Becki Glagola, Sam Tanner, Drew Allen

Thank you to Battelle personnel: Satya Chauhan, Eric Griesenbrock, Nick Conkle, Grady Marcum, Bill Jones, George Wrenn, Sarah Nejfelt, Cory Kuhnell, Stephen M. Howe, Erik Edwards, J. Boyce, C. Lukuch

Thank you to Air Force Personnel: Robert W. Morris, Jr., Lt. Mark Roosz, Lt. Adam Parks, Milissa Flake

Thank you to UTC Personnel: Jennifer Kelley, Steve Procuniar


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