Ohio Center for Intelligent Propulsion and Advanced Life ManagementOhio Third Frontier Program Review

Heinz J. Robota, Ph.D.Ohio Research Scholar in Alternative FuelsGroup Leader: Alternative Fuels Synthesis

University of Dayton Research Institute

University of Cincinnati14 May 2013

Alternative Fuels Research: Practical Applications and Foundational Questions

•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

Overview

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

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 contentHighly isomerized alkanes – for low temperature properties Type Specifications accommodate the peculiarities of the fuel chemical constituents

Fischer-Tropsch SPK – First type to be approvedHydrotreated Renewable Jet (HRJ) or Hydrotreated Esters and Fatty Acids (HEFA) – second to be approved

Spec has added requirements related to: Gum, FAME contentNearly approved Alcohol-to-Jet (ATJ) – allows higher cycloparaffins

Otherwise, these specs are the SAME

Shroyer Park Center Catalyst Preparation and Testing Capabilities

4 Fixed bed reactors with concurrent liquid and gaseous feed2 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 AreaPore VolumePore size distributionMetal 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

• 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 fuel for 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 Commissioned making SPK from Genuine F-T Wax

AAFRF SPK properties are nearly identical to other non JP-8 jet fuelsValidated design criteria

Validated catalyst functionRequired Heat Trace everywhereDistillation heater required higher

output than original designValidated automation systemReady for production research!

Preparing a C14 narrow boiling SPK: Maximizing Isomer Yield

0.40 0.50 0.60 0.70 0.80 0.90 1.000

102030405060708090

100

Comparing the Lab Basis with AAFRF-SPU Performance in n-tetradecane isomerization

basis crackSPU crackbasis total isoSPU total isobasis multiSPU multibasis monoSPU mono

Conversion

% S

elec

tivity

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

0 100 200 300 400 500 600 700 800 900100010

20

30

40

50

60

70

80

90Time Behavior of n-tetradecane con-

versioncracktotal isomultimonoconvEaster

Hours on Stream

% S

elce

tivity

Preparing a C14 narrow boiling SPK: Final Product by Distillation

6.5 7 7.5 80

0.5

1

1.5

2

2.5

3

3.5

4n-C14 can be sufficiently reduced by distilla-

tion to meet Jet-A Freezing Point Specification

Isomerized tetradecane product

Distilled refined tetradecane

Retention time (minutes)

Nor

mal

ized

FID

cur

rent

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

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-A

Parameter, Requirements J-1 J-2 J-3 J-4 J-5 J-6 J-7

Freezing point, max. -40°C -38.5(a) -41 -45.1 -44.4 -43.1 -42 -46.2Total Acid Number, max 0.1 mg KOH/g max

0.002 0.0060.004 0.004 0.002 0.002 0.004

Flash point, min. 38°C 52 45 37 43 42 46 46Density at 15°C, 775–840 kg/m3 804 804 803 802 802 805 804Distillation temperature, °C          

10 % recovered, max. 205°C 175 167 165 164 164 166 16850 % recovered(b)

208 204 201 200 201 203 20190 % recovered(b)

254 252 246 248 250 252 246Final boiling point, max. 300°C 267 276 264 264 264 266 261Distillation residue, max. 1.5% 1.2 1.2 1.2 1.2 1.3 1.0 1.1Distillation loss, max. 1.5% 0.7 0.4 0.7 0.7 0.3 0.8 0.6

Requirements J-8 J-9 J-10 J-11 J-12 Cumulative(d)

Freezing point, max. -40°C -42.9

(c)

-43.4 -43.5 -43.4 -43.0Total Acid Number, max 0.1 mg KOH/g max 0.011 0.008 0.009 0.004 0.005

Flash point, min. 38°C 48 44 42 42 44Density at 15°C, 775–840 kg/m3 808 806 805 803 804Distillation temperature, °C          

10 % recovered, max. 205°C 175 168 162 163 16750 % recovered(b) 206 201 199 200 20290 % recovered(b) 251 248 249 249 250Final boiling point, max. 300°C 268 263 264 264 266Distillation residue, max. 1.5% 1.0 1.1 1.3 1.2 1.2Distillation loss, max. 1.5% 0.7 0.2 0.6 0.3 0.5

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

CH2-COOR1 R1-COOH|CH -COOR2 R2-COOH + CH3-CH2-CH3

|CH2-COOR3 R3-COOH C17H36

Triglyceride

C18H38

C17H35-COOH C17H35-CHO

C18H37-COO-C17H35 C17H35-CH2OH

C18H38

Pd/C + H2

Pd/C + H2

Pd/C -/+ H2

Decarbonylation

Hydrogenation/ dehydrogenation

Reduction

C17H35-COOH

HeatH2O

Pd/C + H2

Esterfication

HydrogenolysisHydrodeoxyagenation

Pd/C + H2

3H2

HydrogenolysisAlgae provided by USAF from Phycal production

Output of a Third Frontier development program

0 50 100 150 2000

20406080

100n-C18 n-C17 n-C16 n-C15 n-alkane total

Time on Stream (hours)

Mas

s % in

Pro

duct

Processed ~ 2.5 L of algal oil

Product Alkanes reflect oil composition and achanging catalyst selectivity with time-on-stream

Converting Algal Oil to Fuels: n-Alkanes to Fuel

n-C15 n-C16

n-C17

n-C18

A Practical Diesel Fuel

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

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

All methods and catalysts used are readily scalable

Elucidating Reaction Kinetics of a Complex Reaction Network

C17H36

C18H38

C17H35-COOH C17H35-CHO

C17H35-COO-C18H37 C17H35-CH2OH

C18H38

Pd/C + H2

Pd/C + H2

Pd/C -/+ H2

Decarbonylation

Hydrogenation/ dehydrogenation

Reduction

C17H35-COOH

HeatH2O

Pd/C + H2 EsterficationHydrogenolysis

Decarboxylation

Pd/C + H2

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

•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

AcknowledgementsThis 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