PNNL-SA-106313

Renewable routes to jet fuel
JOHNATHAN HOLLADAY, KARL ALBRECHT, RICH HALLEN
Japan Aviation Environmental Workshop—Innovative concepts for carbon neutral growth
5 November 2014

November 5, 20141

Outline
Jet fuel
Pathways
Fuel properties
Pathways correlate to product and feedstock
Energy carriers: syn gas, fats, sugars,
whole biomass

Conclusions

November 5, 20142

Fuel characteristics
Desired Characteristics
Miscible with petroleum-based fuels and transportable in current pipelines
Meet performance & storability criteria designed for jet engines—it must be jet fuelOptimize desired hydrocarbon chain/boiling point for aviation (mid-distillates)
Lower cost
• Reduce H2 demand and pressure• Improve product quality

3Compound classes in jet fuels
Ideal Carbon Length C8-C16
Paraffins
70 - 85%

Normal Paraffins

Iso-paraffins

Cyclic Paraffins

Aromatic< 25%
Olefins< 5%
S, N, O containing
Compounds < 5%November 5, 2014

We desire fuels with composition similar to above(i.e. a replacement or “drop-in” fuel)4

Typical petroleum jet fuel: JetA and JP-8
Ideal Carbon Length C8-C16
Fractions vary!

cycloparaffinsn-paraffins(C8-C16)aromatics
iso-paraffins• Iso-paraffins and n-paraffins are good(Btu content)• Aromatics are bad above certain amount(minimum needed to ensure seal swell )Jet is designed around
propulsion system
Hydrocarbon mixture gives
properties needed
Energy density
Freeze point
Flash point
Lubricity
etc
Source: Dr. Timothy Edwards, Air Force ResearchLaboratory

Routes to fuels (energy carriers)
Lignocellulose
Gasification Liquefaction (pyrolysis)

Syn-gasBio-oils

FischerTropsch

H2Upgrading

Gasoline/jet/diesel

Fats/ oils

sugarsfermentation

catalytic

OXYGENREMOVAL

Single molecules

lipds

CHEMICALPLATFORMS

Various catalytic
processes (H2)

C-C
manipulations(coupling)

Industrial Chemicals

Products

Catalytic

monofunctionals

Various catalytic
processes (H2)Heating Oils

Jet/diesel

Optimal choices vary by region and are afunction of feedstock and product slate
Lignocellulose• Simple sugars
Catalytic likefermentation
cane juice• Biomass-sugars
in development

Gasification Liquefaction (pyrolysis)• High temperatures• Whole biomass• Cyclic-rich hydrocarbons

Syn-gasBio-oils• Very high temperatures• Broad feedstock options• Paraffinic-rich product

FischerTropsch

H2Upgrading

Gasoline/jet/diesel

Fats/ oils

sugarsmonofunctionals

Single molecules• Range of products• Paraffinic to cyclic andaromatic

Various catalytic
processes (H2)Heating Oils

Jet/diesel

OXYGEN• Sourcingof fats/oils?
catalytic
REMOVAL• Algae in development

lipds

CHEMICALPLATFORMS• Paraffinic

Various catalytic
processes (H2)

C-C
manipulations(coupling)

Industrial Chemicals

Products

Fischer-Tropsch (FT) jet fuelFT converts syngas to fuelApproved for 50% blends
Process is complex
Gasification (O2 plant)
FT synthesis (C-C coupling,cracklng, isom)
Heat integration required

Inefficiencies favor large
scale
Chemistry favors wax ormethane
Perego, C.; Bortolo, R.; Zennaro, R., Catalysis Today 2009, 142, (1,2), 9-16

nCO + (2n +1)H2
carbonmonoxide

H—(CH2)—H + nH2Ohydrogenheatparaffin(wax)water(steam)Hydrocracking and isomerization improves
cold temperature properties
Freeze Point, °C

C10H22

Jet AFPC12H26FP

C14H30

FP-30-10-5.5-72-46-26-40(max)Jet A1-47(max)FT Synthetic paraffinic kerosene (SPK)jet fuel
FT jet fuelJet A, JP-8

cycloparaffinsn-paraffins

Approved for 50% blend

Feedstocks

FT SPK(coal to liquid)aromatics

Dry biomass
iso-paraffins

FT SPK(gas to liquid)

Municipal solid waste
Source: Dr. Timothy Edwards, Air Force Research Laboratory

FT has a history of escalating capital costs
Robert Malina, Nov. 27, 2012

Nominal BPD costs ($/bpd)$250,000$200,000$150,000$100,000$50,000

1996

2000

2004

2008

2012

Capital cost perspective

Some capital cost estimates inUS$ per barrel per day ($/bpd)
Greenfield refinery: $25,000-40,000/bpd
FT (Biomass to liquid, 5,000 bpd plant):$68,000 — 408,000/bpd Robert MalinaCorn ethanol: $16,000 — 34,000/bpd
http://www.usda.gov/oce/reports/energy/
EthanolSugarFeasibilityReport3.pdf
Cellulosic ethanol: $77,000 — 285,000(US Department of energy)

November 5, 201412

U.S. Department of Defense awards
Capacity (milliongallons/year)

Project

LocationFeedstock

Fulcrum

McCarran, NV

Municipal solidwaste

10Red RockLakeview, ORWoody biomass

12EmeraldGulf CoastFats, oils, andgreases82 Production anticipated to begin in 2016/2017
 These fuels have been approved for use as jet fuel by ASTM at up to50/50 blends Fuels successfully demonstrated during Rim of the Pacific (RIMPAC)
demonstration in 2012 for ships and planes
 Fuels can be utilized in Navy’s warfighting platforms with nodegradation to performance or mission

Hydroprocessed esters and fatty acids (HEFA)
June 2011—ASTM D7566 approves HEFA
50% blendallows fuels from fats derived from jatropha,camelina and other fats
Sometimes called HRJ (hydrotreatedrenewable jet) or Bio-SPK (syntheticparaffinic kerosene)

November 5, 201414

Chemistry to make HEFA jet fuelParaffins (lipid)
Vegetable oil (triglyceride)

isoParaffins
Courtesy of NAABB/UOPHEFA product slate(LNG, naphtha, jet fuel, diesel fuel)The technology is welldemonstrated andcommerciallypracticed
The product slate canbe adjusted

Malina; Source: Pearlson (2011) and Pearlson et al. (2012)
Fractionation results via spinning-band distillation of hydrotreatedand isomerized N. oceanica (low lipid) HTL bio-oil.
FractionBoiling Range Mass %Noncondensable material (gas) -6%
NaphthaIBP–150 °C
4%
Jet (SPK)
150–250 °C
26%Diesel
250–350 °C
47%Heavies350+°C

17%

Challenge is the costand availability of thefeedstock
Algae potential sourcein the future
Regional (niche)
opportunities
NAABB

HEFA jet fuel summary
Jet A, JP-8
cycloparaffins

Productn-paraffinsn-paraffinsaromatics

HEFA
iso-paraffins

iso-paraffins

Challenge isfeedstock cost/
availability
Source: Dr. Timothy Edwards, Air Force Research Laboratory

FeedstockDirect sugar to hydrocarbon (DSHC)Sugar
YEAST CELL

Farnesene

Mevalonate Pathway

Farnesene
Synthase

Diesel, jet & Chemical
Precursor

Fermentation of Sugars
 Require pretreatment torelease sugars
 Lignin is not converted Organism development
needed for complex sugars[1] Cane juice[2] Fermentation broth[3] Separations
18[4] Purification

Amyris-Total and DSHC fuelTotal Major oil/chemical company
300 airports in 75 countries
1.5 million refuelings each year
Relationship with Amyris since 2010

June 16, 2014—Revised standard toASTM D7566 allowing 10% blend
Next jet fuel approved by ASTM afterHEFA2012—demonstrated in GE-powered
Embraer (Azul airlines)
2013—demonstrated in an Airbus A321
2014—demonstrated in a Boeing 777 (EtihadAirlines)
2014—KLM collaboration, intent to fly

Renewable farnesane can reducegreenhouse gas emissions by 50%
10% blend reduces GHG by 5%
10% blend reduces particulate matter by 3%
November 5, 2014

Farnesane (a sesquiterpene)

Rather than a fuel with a broad
range of hydrocarbons,farnesane is a single molecule
approved for blending at 10%19DSHC (direct sugar to hydrocarbon) summary
Jet A, JP-8ProductFeedstockfarnesol

cycloparaffinsn-paraffins
DSHC jetaromatics

Cane juice
iso-paraffins

10% DSHC in Jet A

Blending DSHC increases
the good components
Source: Dr. Timothy Edwards, Air Force Research Laboratory

Agriculture residues?
(future)Renewable paraffins and naphthenes (RPN)

175 - 300°C
10 – 90 bar© Virent 2014

Catalytic Conversion of Sugars (not approved today) APR/HDO makes a mixtures of oxygenated compounds
 Further catalytic upgrading gives hydrocarbon fuels

Renewables paraffins and naphthenes (RPN)
cycloparaffin-rich fractionStable operation (2 months)

15 gal/day liquid fuel (20x lab)
100 gal jet fuel produced
Renewable paraffins and naphthenes (RPN) consisting of C9-C16
Aromatic renewable jet blendstock (ARJB) consisting of C9 - C11
Freezing point = −71°C; flash point = 50°C; density = 812 (kg/m3);
thermal stability pass at 325°C; density
November 5, 201422

RPN (renewable paraffins and naphthalenes)summary
Jet A, JP-8
cycloparaffins

ProductFeedstock

RPN
Jet fuel)sugarsn-paraffinsaromatics
iso-paraffins

Unlike previous technologies,
this produces a cyclic-richproduct

Agriculture residues(future unless very clean)
Source: Dr. Timothy Edwards, Air Force Research Laboratory

Liquefaction (pyrolysis) technologies

Pyrolysis and Liquefaction
 Multiple variants Yield depends on quality ofbiomass feedstock andvariant of technology
 T = typically 500 C, short
residence time (1 sec)

Potential for distributed bio-oil
production with processing incentral facility

Produce hydrocarbon fuels fromlow quality bio-oil, but…
• Catalyst life is too short
24 is too slow
• Catalyst rateLiquefaction technologies (pyrolysis)
UOP and Kior have submitted fuels(variants of pyrolysis/upgrading)

All variants produce highamounts of cyclics / aromatics
November 5, 2014

PNNL and Genifuel are also
developing a wet variant25

Liquefaction (pyrolysis) summary
Jet A, JP-8

cycloparaffins

ProductsFeedstock

HDCJ(Kior)n-paraffins

Forest residues

aromatics
iso-paraffins
CH(UOP)

Agriculture residues

Source: Dr. Timothy Edwards, Air Force Research Laboratory

Pyrolytic methods makecyclics and aromatics

Alcohol to jet
catalyst

catalystheatCan makeisoparaffins orcyclics dependent
on reaction
conditions

Dimer (C8)
1. Distillation
2. H2 catalyst

Trimer (C12)

Tetramer (C16)

C4—butanol, i-butanol• Cobalt, Gevo , et al• fuel primarily C12 andC16 (limited mol. chains)

C2—ethanol• Swedish Biofuels (+CO/H2)• PNNL/ Imperium (SPK)• broad chain lengthMany routes to alcohols—LanzaTech highlighted
Industrial Natural Gas, CH4
Waste Gas

Steel, PVC,
Ferroalloys

AssociatedGas,
BiogasSolid Waste

Inorganic CO2

Industrial,MSW, DSW

Biomass

Renewable
Electricity
COCO + H2

CO2 + H2CO + H2 + CO2

CO2 + H2O + e-Gas Fermentation

Source: LanzaTech

Fuels

Chemicals28Jet fuel production from waste gasGas
fermentation

Catalyticupgrading “Fuel is very stable, wide boiling isoparaffinickerosene” (C10-C16)
 Exceeds D1655 standards including 325 JFTOT(thermal oxidation), high flashpoint (56°C), lowfreezing (<-70°C), no gum, “not easy to do”
 72% GHG reduction (biomass gasification)

fractionation

ATJ summary
Jet A, JP-8

cycloparaffins

ProductFeedstock

ATJ-SKA(Swedish)Butanol /ethanoln-paraffinsaromatics
iso-paraffinscellulosic ethanol
ATJ-SPK
Hydrocarbon mix
depends on the technology
butanol-produces C8,12 and16
Ethanol give range of hydrocarbons
Source: Dr. Timothy Edwards, Air Force Research Laboratory

gas fermentation

Many routes to fuels (energy carriers)
Lignocellulose
Gasification Liquefaction (pyrolysis)

Syn-gasBio-oils

FischerTropsch

H2
UpgradingGasoline/jet/diesel

Fats/ oils

sugarsfermentation

catalytic

OXYGENREMOVAL

Single molecules

lipds

CHEMICALPLATFORMS

Various catalytic
processes (H2)

C-C
manipulations(coupling)Industrial Chemicals

Products

Catalytic

monofunctionals

Various catalytic
processes (H2)Heating Oils

Jet/diesel

Conclusions
Lignocellulose
Gasification Liquefaction (pyrolysis)

Syn-gas• FT approved today (50% blend)• Paraffins/isoparaffins• Very high capital• Broad range of feedstocks(municipalFischer- solid waste)
H2

TropschUpgradingfermentation

Catalytic• Liquefaction technologies
produce cycloparaffins andaromatics• Can have high H2 demand• Dry biomass or wet biomass

Bio-oils

Fats/ oils

sugarsmonofunctionals• Direct sugar to jet fuelapproved at 10% blend• Today:cane juice• Single molecule• HEFA fuels approved
OXYGENfor catalytic
50% blend
REMOVAL• Feedstock expensive• Niche opportunities

lipds

CHEMICALPLATFORMS

Various catalytic
processes (H2)

C-C
manipulations(coupling)Single molecules• Alcohol to jet next inapproval process• Isoparaffins and/or cyclics

Various catalytic
processes (H2)

• The “right” solution is regionally dependent• Feedstock sourcing, product slate, business cases

Gasoline/jet/diesel

Heating Oils

Jet/diesel

Industrial Chemicals

Products

Questions?
There are a number of viable routes to make renewable jet fueltoday
Range of feedstocks that are suitable for each technology
Product slate differs dramaticallyThree technologies are approved for commercial use
Two others are in the process for approval
All still have unique challenges—including high cost
The right solution depends on the region
Feedstock sourcing, tax structure, product slate

November 5, 201433

Thank you

November 5, 201434

ASTM D7566 TASK FORCES

Adapted from Brown, Iowa State, 2012
and Tim Edwards, USAF/AFRL

Alternative Jet Fuel Pathways

Crude oil

Draft ASTM Research Report

B

Re Rpt & Spec Balloted

carbohydrate-based fuelslipid-based fuelscamelina,
algae, etc.

Rsugar cane, etc.

bagassecoal, natural gas

lignocellulosic biomass

lipidsCatalytic
Hydrothermolysis

saccharification

Thermalcatalytic or
pyrolysis

gasification

sugarsbio-oilsyngashydroprocessing
fermentation
HEFA
Annex A2

CHTaskForceJuly 2011

Co-Procss’dTask ForceARA

May 9, 2013

Chevron, BP, Phillips66

DSHC/SIP
Annex A3
June 2014

alcoholcatalytic upgrading

ATJ
SKA Task
Force

SK, SAKTask Force

SPK

VirentR

Byogy,LanzaTech, Swed
Biofuels

GEVO, Cobalt/USN,UOP, LanzaTech, Swed
Biofuels

HDCJ
Task Force

RR

KiOR,UOPFT-SKA
Task ForceFT-SPK
Annex A1RSept2009

SASOL,Rentech

Annual U.S. greenhouse gas emissions(Tg CO2 equivalent, 2006)
U.S. GHG Emissions (7,054; 100.0%)
CO2 (5,983; 84.8%)
Fossil Fuel Combustion (5,638; 79.9%)
HFCs,

Transportation (1,856; 26.4%)
Diesel (463;6.6%)

Gasoline (1,170; 16.6%)
Cars (630; 8.9%)

Light Duty Trucks(488; 6.9%)

Industrial (862; 22.2%)

Other(52;0.7%)

Med. And Heavy
Trucks (365; 5.2%)

Gasoline
automobiles

Rail (46;0.7%)

Other(52;0.7%)

USTerrit

Jet Fuel(168;2.4%)

Natural Gas(389; 5.5%)

Petroleum(351; 5.0%)

Coal(122;1.7%)

Electricity (705; 10.0%)
Residential (825; 11.7%)

Diesel rail

Industrial NG
combustion

All otherdieselIndustrial
petroleum
combustion
Industrial coal
combustion

Diesel medium
and heavytrucksJet fuel
aircraft

Transportation(1,856 Tg, 26%)

Natural Gas(392; 5.6%)

Electricity (1,618; 22.9%)

Aircraft(168; 2.4%)

Gasoline light
duty trucks
All othergasoline

Buildings (537; 30.5%)

Residential(238; 3.4%)

Commercial (793; 11.2%)

Petroleu ories(55;m (138;0.8%)
2.0%)

All other CH4 (555; 7.9%) N2O (368; andPFCs,SF6(148;5.2%) 2.1%)
sources(345;4.9%)

Commercial Resident Commer
ial (89; cial (50;(154; 2.2%) 1.3%) 0.7%)

CH4

N2O

Electricity Generation (2,328; 33.0%)
Coal (1,932; 27.4%)

Natural Gas(340; 4.8%)

Other(56;0.8%)

HFCs, PFCs, andSF6

Coal fueled
electricity
Naturalgas fueled
electricity

All other fossil
fuels electricity

ResidentialNGcombustion

Residential
petroleum
combustion

Commercial
NG combustion

Electricity Generation(2,328 Tg, 33%)

CO2 from all sources
except fossil fuelcombustion
Fossil fuelcombustion in US
Territories
Commercial
petroleum
combustionPyrolysis enables 100% renewable jet

The hydroplane ran on 98% Bio-SPK and 2% renewable aromatics

Freeze Point (oC)Flash Point (oC)November 5, 2014
Density(g/mL)

Jet A1
Spec-47390.775

Starting
SPK-63420.753

Woody Pyrolysis Oil
Aromatics-SPK-53
52
370.863

Fuel Properties
Ethanol to Gasoline (61666-113-D1H)1
PNNL-SA-105930

RON = 85
MON = 81
Final Octane (R+M)/2 = 83 (Regular unleaded is 87; Premium unleaded is 91)

Ethanol to Jet (61666-107-ETJ-FIN)2
Density = 0.782 (0.775-0.840 for Jet A/JP-8/Jet A-1)
Flash Point = 56°C (ASTM D1655 requires > 38°C)
Freeze Point = < -70°C (ASTM D1655 requires < -40°C)

Ethanol to Diesel (61666-77-H7)3
Cetane = 53.6 (Diesel fuels are typically in the 40-55 range)
Cloud Point = -60.1°C (ASTM D 975 is regional, but an extreme case is< -28°C for MN. European standard EN 590 specifies < -34°C for Class 4 arcticdiesel)
Pour Point = -66.0°C
1RON and MON determined via NIR method for correlated
11/5/2014

octane number
2Ethanol to Jet data generated by the Air Force ResearchLaboratory
3Cetane determined by closed cup derived cetane method

38

Yields from HEFA

November 5, 201439

Transportation energy use by type
U.S.Fuel
FuelUsed
Consumption
for U.S. (2012) Transportation
Gasoline (134 billiongallons)(2011)
 Diesel (53 billion gallons) Jet (22 billion gallons

Diesel/Jet
consumption forecast
growth / consistent
with scale of biomass

November 5, 2014

Source: U.S. Energy Information Administration40
http://www.eia.gov/energyexplained/index.cfm?page=us_energy_transportation

Upgraded HTL oil from algae: 85% diesel(NAABB: Solix, Cellana and TAMU)HT ProductHigh paraffin HTL Products

Fractionated Product

June 14, 2012

Diesel Fuel

41

Catalysis of sugars

APR/HDO produces a complex mixture of oxygenates
November 5, 201442

Fermentation of sugars

Yield today from complex sugars (not indicative of yield from sugar cane)
November 5, 201443

Fischer-Tropsch (FT) jet fuelSyngas based route
Broad range of feedstocks
Complex
airC
feedAir
separation
unit

Biomassformating

FT gastreatment

FischerTropschsynthesis

Syngasproduction

Hydrogenproduction

Product
work-up

Effluent
treatment
Utilities