10 1016@j Rser 2015 09 016

Renewable and Sustainable Energy Reviews 53 (2016) 801–822
Contents lists available at ScienceDirect
Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser
Bio-jet fuel conversion technologies

Wei-Cheng Wang a,b,n, Ling Tao c
a
Department of Aeronautics and Astronautics, National Cheng Kung University, No.1, University Road, Tainan 70101, Taiwan
b
Research Center for Energy Technology and Strategy, National Cheng Kung University, Tainan 70101, Taiwan
c
National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, CO 80401, United States
art ic l e i nf o a b s t r a c t
Article history: Biomass-derived jet (bio-jet) fuel has become a key element in the aviation industry's strategy to reduce
Received 10 June 2014 operating costs and environmental impacts. Researchers from the oil-refining industry, the aviation
Received in revised form industry, government, biofuel companies, agricultural organizations, and academia are working toward
9 March 2015
developing a commercially viable and sustainable process that produces a long-lasting renewable jet fuel
Accepted 16 September 2015
with low production costs and low greenhouse emissions. This jet fuel, additionally, must meet ASTM
International specifications and potentially be a 100% drop-in replacement for current petroleum jet fuel.
Keywords: In this study, the current technologies for producing renewable jet fuels, categorized by alcohols-to-jet,
Bio-jet fuel oil-to-jet, syngas-to-jet, and sugar-to-jet pathways are reviewed. The main challenges for each tech-
Alcohol-to-jet
nology pathway, including conceptual process design, process economics and life-cycle assessment of
Hydro-processed renewable jet
greenhouse gas emissions are discussed. Although the feedstock price and availability and energy
Fischer–Tropsch
Catalytic upgrading sugars to hydrocarbons intensity of the process are significant barriers, biomass-derived jet fuel has the potential to replace a
Direct sugar to hydrocarbon significant portion of conventional jet fuel required to meet commercial and military demand.
& 2015 Elsevier Ltd. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 802
1.1. Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 802
1.2. Jet fuel specifications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 802
1.3. Bio-derived jet fuel conversion pathways . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 804
2. Conversion pathways to bio-jet fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 807
2.1. Alcohol-to-jet (ATJ) fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 807
2.1.1. Process description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 807
2.1.2. Economic analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 808
2.1.3. Life-cycle assessment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 809
2.2. Oil-to-jet (OTJ) fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 809
2.3. Gas-to-jet (GTJ) fuel. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 811
2.4. Sugar-to-jet fuel. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 813
3. Summary of all bio-jet fuel production pathways . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 818
n
Corresponding author. Tel.: þ 886 6 2757575x63628.
E-mail address: wilsonwang@mail.ncku.edu.tw (W.-C. Wang).
http://dx.doi.org/10.1016/j.rser.2015.09.016
1364-0321/& 2015 Elsevier Ltd. All rights reserved.
802 W.-C. Wang, L. Tao / Renewable and Sustainable Energy Reviews 53 (2016) 801–822
4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 818
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 819
Appendix A. Supplementary material. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 819
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 819
1. Introduction of feedstock; (2) process design; (3) conversion efficiency or pro-

duct yield; (4) valorization of co-products; and (5) energy con-
1.1. Background servation. Therefore, decreasing the production cost of bio-jet fuel
depends on synergistic efforts in all areas, including improve-
Fuel is one of the biggest operating costs for the aviation ments in the areas of feedstock productivity, extraction yield of oil
industry. Aviation fuel, a petroleum-based fuel used to power or sugar yield from the crops, process energy conservation, and
aircraft, has stricter quality requirements than fuels used in road balance between jet fuel product and value-added co-products.
transport. Jet fuel, a type of aviation fuel designed specifically to In addition, there is a growing awareness of important envir-
power the gas-turbine engines, will be the primary subject of this onmental issues, including improving air quality in and around
review. According to a report from the U.S. Department of Energy's airports and determining the aviation industry's contribution to
(DOE's) Bioenergy Technologies Office [1], out of one barrel of greenhouse gas (GHG) emissions globally. It has been estimated
crude oil, 4 gallons are used to produce jet fuel. The worldwide that commercial aviation has contributed approximately 2–6% to
aviation industry consumes approximately 1.5–1.7 billion barrels total global carbon emissions [11]. Jet fuels derived from renew-
(47.25–53.55 billion gallons) of conventional jet fuel per year [2,3]. able resources may offer the potential to reduce the GHG emis-
The challenges of crude oil prices, national security, environmental sions from aviation. A life-cycle assessment (LCA) that considers
impact, and sustainability make it difficult to have a long term emissions from the field where the feedstock is harvested to the
plan and budget for operating expenses. Sustainable biofuels wake behind the aircraft can provide the change in GHG emissions
produced globally offer a solution to these issues. Biomass-derived due to the use of alternative fuels [3], usually known as well-to-
jet fuels (bio-jet fuels) are a potential alternative to petroleum wake (WTW) analysis. The WTW analysis can be split into two
jet fuel. parts: well-to-tank (WTT) and tank-to-wake (TTW) [12]. To com-
Many process technologies that convert biomass-based mate- pare the GHG emissions due to bio-jet fuels with that of conven-
rials into jet fuel substitutes are available. Some are available at tional jet fuels, it is necessary to consider emissions from the
commercial or pre-commercial scale, and others are still in the whole production chain. In the WTT portion, feedstock production,
research and development stage. These technologies are varied land use change, and conversion processes contribute significantly
and depend strongly on the type of feedstock. Oil-based feedstocks to GHG emissions. In the TTW portion, emissions from burning jet
are converted into bio-jet fuels through hydro-processing tech- fuels are considered [12]. The WTW GHG emissions from con-
nologies, including hydro-treating, deoxygenation, and iso- ventional jet fuel are reported to be 87.5 g carbon dioxide
merization/hydrocracking. Processes such as catalytic hydro- equivalent per megajoule (gCO2e/MJ) [13], including 14.3 gCO2e/
thermolysis (CH) have also been developed to treat triglyceride- MJ WTT GHG emissions and 73.2 gCO2e/MJ TTW GHG emissions
based oils. Solid-based feedstocks are converted into biomass [14]. When bio-jet fuel is used for aviation, the GHG emissions can
derived intermediate through gasification, into alcohols through be reduced to 1.5 gCO2e/MJ (open pond algal oil case), a 98%
biochemical or thermochemical processes, into sugars through reduction relative to conventional jet fuel [15]. Different conver-
biochemical processes, and into bio-oils through pyrolysis pro- sion technologies may result in different amounts and types of
cesses. Syngas, alcohols, sugars, and bio-oils can be further GHG emissions due to the variety of feedstocks and reaction pro-
upgraded to bio-jet fuel via a variety of synthesis, fermentative, or cesses. Reviewing the GHG emissions data from the conversion
catalytic processes. So far, bio-jet fuels from Fischer–Tropsch (F–T) pathways will help determine the optimal platforms for producing
synthesis and oil hydro-processing technologies have been bio-jet fuel.
approved by ASTM International (ASTM) Method D7566 [4] for Groups such as aircraft manufacturers, airline companies, aca-
blending into jet at levels up to 50%. Hydro-processing technolo- demic institutions, fuel refining companies, agricultural compa-
gies using vegetable and waste oils represent the only conversion nies, farmers groups, and local/regional/national departments of
pathways ready for large-scale deployment [5]. Industries are agriculture, defense, transport, economic development, and
currently working on developing optimal processes that utilize enterprise are working together to develop commercially feasible
sustainable feedstocks and can be produced economically. bio-jet fuel [16]. The level of bio-jet fuel commercialization
Production cost is a key parameter of the commercial feasibility depends on feedstock availability, conversion technology devel-
of a bio-jet fuel. U.S. passenger and cargo airlines require more opment, reduction of GHG emissions, and policy. Conversion
than 18 billion gallons of jet fuel annually. Therefore, every penny technologies for transportation biofuels such as ethanol [17] and
increase in the price of jet fuel results in an additional $180 million biodiesel [18] have been reviewed and compared extensively. For
in annual fuel costs for U.S. airlines [6]. The price of petroleum- future development and deployment of bio-jet fuel, it is important
derived jet fuel is directly correlated with the price of crude oil [7]. to review and understand the maturity and uncertainty of all
Changes in crude oil price make it difficult to plan and budget pathways to assess impacts on commercialization.
long-term operating expenses for jet fuel refining. In 2012, the
annual fuel cost for all airlines was around $47 billion [8]. It is 1.2. Jet fuel specifications
predicted that by 2030, the bio-jet fuel production cost may drop
to as low as $2.54/gal due to improved conversion technology [9], In addition to define target compositions, jet fuel specifications and
and 30% of annual airline fuel consumption can be replaced by bio- requirements are mostly defined in terms of required performance
jet fuel [2]. Following the same pattern for bioethanol production properties. The specifications required for jet fuels are (1) acceptable
[10], the variation in the bio-jet production cost would be highly minimum energy density by mass, (2) maximum allowable freeze
dependent on the following parameters: (1) composition and cost point temperature, (3) maximum allowable deposits in standard
W.-C. Wang, L. Tao / Renewable and Sustainable Energy Reviews 53 (2016) 801–822 803
Acronyms GJ gigajoules
GTJ gas-to-jet
ABE acetone-butanol-ethanol GTL gas-to-liquid
AFRL U.S. Air Force Research Laboratory H2 hydrogen
APR aqueous phase reforming HDCJ hydrotreated depolymerized cellulosic jet
ASTM ASTM International HEFA hydroprocessed esters and fatty acids
ATJ alcohol-to-jet HMF 5-hydroxymethylfurfural
BIRD Binational Industrial Research and Development HRJ hydroprocessed renewable jet
BTL biomass-to-liquid LCA life-cycle assessment
CH catalytic hydrothermolysis LHV lower heating value
CLEEN Continuous Lower Energy, Emissions and Noise MIL military
CO carbon monoxide MJ megajoules
CO2 carbon dioxide NAWCWD Naval Air Warfare Center Weapons Division
CTL coal-to-liquid NOx oxides of nitrogen
DARPA Defense Advanced Research Projects Agency NETL National Energy Technology Laboratory
DCN Derived Cetane Number NRC National Research Council Canada
DMF 2,5-dimethylfuran NREL National Renewable Energy Laboratory
DOE U.S. Department of Energy OTJ oil-to-jet
DSH Direct Sugar to Hydrocarbons READI renewable, aromatic, and drop-in
E. coli Escherichia coli RTP rapid thermal processing
FAA Federal Aviation Administration SPK synthetic paraffinic kerosene
FFA free fatty acid STJ sugar-to-jet
F-T Fischer–Tropsch TTW tank-to-wake
gCO2e grams carbon dioxide equivalent WTT well-to-tank
GGE gallon of gasoline equivalent WTW well-to-wake
GHG greenhouse gas
Table 1
Jet fuel specifications [19,22–24,26].
Jet A-1 JP-8
ASTM D1655-04a IATA Def Stan 91–91 ASTM D7566 MIL-DTL- 83,133E specification
Composition
Acidity, total (mg KOH/g) 0.1, max 0.015, max 0.012, max 0.1, max 0.015, max
Aromatics (vol %) 25, max 25, max 25, max 25, max (8, min) 25, max
Sulfur, total (wt %) 0.3, max 0.3, max 0.3, max 0.3, max 0.3, max
Volatility
Distillation temperature:
10% Recovery (°C) 205, max 205, max 205, max 205, max 205, max
20% Recovery (°C) – – – – –
50% Recovery (°C) – – – (15, min) –
90% Recovery (°C) – – – (40, min) –
Final BP (°C) 300, max 300, max 300, max 300, max 300, max
Flash point (°C) 38, min 38, min 38, min 38, min 38, min
Density @ 15 °C (kg/m3) 775–840 775–840 775–840 775–840 775–840
Fluidity
Freezing point (°C), max 47 47 47 40 Jet A ; 47 Jet A 1 47
Viscosity @ 20 °C (cSt) 8, max 8, max 8, max 8, max 8, max
Combustion
Net heat of comb. (MJ/kg) 42.8, min 42.8, min 42.8, min 42.8, min 42.8, min
Smoke point (mm) 25, min 25, min 25, min 25, min 25, min
Smoke point (mm) and naphthalenes (vol%) 19 (min), 3 (max) 19 (min), 3 (max) 19 (min), 3 (max) 18 (min), 3 (max) 19 (min), 3 (max)
Thermal stability
JFTOT Delta P @ 260 °C (mm Hg) 25, max 25, max 25, max 25, max 25, max
Tube deposit Rating (Visual) o3 o3 o3 o3 o3
Conductivity
Conductivity (pS/m) 50–450 50–450 50–600 – –
Lubricity
BOCLE wear scar diameter (mm) – 0.85, max 0.85, max 0.85, max –
(Note: MIL-DTL-83133E is the standard specifically for JP-8 fuel).
heating tests, (4) maximum allowable viscosity, (5) maximum allow- are three standards for certifying aviation fuel: ASTM D1655 [20,21],
able sulfur and aromatics content, (6) maximum allowable amount of International Air Transport Association Guidance Material (Kerosene
wear in standardized test, (7) maximum acidity and mercaptan con- Type) [20,21], and the United Kingdom Ministry of Defense, Defence
centration, (8) minimum aromatics content, (9) minimum fuel elec- Standard (Def Stan) 91–91 [22]. ASTM Specification D7566 (Standard
trical conductivity, and (10) minimum allowable flash point [19]. There Specification for Aviation Turbine Fuel Containing Synthesized
Ethanol C4-C8 Olefins
Ethanol Ethylene α-olefins

Dehydration Oligomerization Distillation
>C16 Olefins C9-C16 Olefins
Hydrogenation
Diesel Blendstock Jet Blendstock
Dimerization C16H32
C8 Olefins
of C8
N-Butanol
1-butene C8, C12, C16, C20, C8, C12 and
2-butene
N-butanol Dehydration Oligomerization C24, C28, C32 Olefins Distillation Hydrogenation C16 Alkanes
[123, 124]
C8, C12, C16, C20,

C24, C28, C32 Olefins
C8H18
Gasoline Blendstock
Distillation C12H26, C16H34
C20H42, C24H50,
Diesel Blendstock
C28H58, C32H66
or Lubricants
C8 Olefins Dimerizationof C16H32

Iso-butanol C8
Isobutene, 1-butene,
Trans-2-butene,
C8, C12, C16
Cis-2-butene Oligomerization C8, C12and
Iso-butanol Olefins
Dehydration Distillation
C16 Alkanes
C12 Olefins Hydrogenation
C16 Olefins
Distillation
Gasoline Blendstock
Jet Blendstock
Diesel Blendstock
Fig. 1. Alcohol to jet processes: (1a) ethanol to jet; (1b) n-butanol to jet; (1c) iso-butanol to jet [35,38,60–63,65–69,71,72,74,77–81].
Hydrocarbons), which targets alternative jet fuel, lists the fuel prop- flow properties, such as a lower freezing point, to ensure the fuel can
erties and criteria required to control the production and quality of a flow at high altitude [25].
renewable fuel for aviation safety [23]. There might be other fuel
standards, and Table 1 shows the specifications for two typical jet fuels 1.3. Bio-derived jet fuel conversion pathways
for commercial and military aircraft. Jet fuel requires a high flash point
due to the fire-hazard consideration [24]. Major fuel properties are Biomass-derived jet fuel can provide a near-term and even
similar across different standards, but there are some differences. For long-term solution to the airline industry and the military with a
instance, D7566 is an expansion of D1655 to include fuel specifications lower environmental impact than petroleum fuels. Many bio-jet
required of the SPK blendstocks. In addition, jet fuel needs good cold fuel conversion technologies, whether in the research and devel-
opment, demonstration, or commercial stages, are described in the
Table 2
(a) Flight tests with bio-jet fuels through different conversion pathways [58] by commercial airlines.
Commercial airline Aircraft Partners Year Feedstocks Bio-jet fuel Conversion pathway
content
Virgin Atlantic B747-400 Boeing, GE Aviation 2008 Coconut & Babassu 20% Oil to Jet
Air New Zealand B747-400 Boeing Ralls-Royce, UOP 2008 Jatropha 50% Oil to Jet
Continental airlines B737-800 Boeing, GE Aviation, CFM, Honeywell UOP 2009 2.5% Algae & 47.5% 50% Oil to Jet
Jatropha
JAL B747-400 Boeing, Pratt & Whitney, Honeywell UOP, Nikki 2009 42% Camelina, 8% 50% Oil to Jet
Universal Jatropha/Algae
KLM B747-400 GE, Honeywell UOP 2009 Camelina 50% Oil to Jet
KLM B737-800 2011 Waste cooking oil 50% Oil to Jet
TAM airlines A-320 Airbus, CFM 2010 Jatropha 50% Oil to Jet
Jet blue airways A-320 Airbus, IAE, Honeywell UOP 2010 TBC Oil to Jet
Boeing B747-8F 2011 Camelina 15% Oil to Jet
Interjet A-320 CFM, Safran, EADS, Airbus, Honeywell UOP 2011 Jatropha, Halophyte 30% Oil to Jet
Air France A-321 2011 Waste cooking oil 50% Oil to Jet
Honeywell Gulfstream G450 2011 Camelina 50% Oil to Jet
Finnair A-319 2011 Waste cooking oil 50% Oil to Jet
Air Mexico B777-200 2011 Jatropha Oil to Jet
Thomson airways B757-200 SkyNRG 2011 Waste cooking oil Oil to Jet
Porter airlines Bombardier Q400 2012 Camelina Oil to Jet
Air China B747-400 Boeing, PetroChina 2012 Jatropha 50% Oil to Jet
NRC Canada Falcon 20, T-33 Aemetis, AFRL, Rolls-Royce, FAA-CLEEN, Agri- 2012 Carinata 100% Oil to Jet (CH)
soma Biosciences, Applied Research Assoc.,
Chevron Lummus Global
Lufthansa A-321 Neste Oil 2011 Jatropha, camelina & 50% Oil to Jet
animal fats
Azul airlines E195 Jet Amyris, Embraer, GE 2012 Sugarcane Sugar to Jet
Continental airlines B737-800 Solazyme, United Airlines 2011 Algae Alcohol to Jet
Alaska airlines B737, Bombardier Dynamic Fuels, Horizon Air 2011 Algae & waste cook- 20% Oil to Jet
Q400 ing oil
Virgin Atlantic Lanza Tech, Swedish Biofuels 2011 Industrial waste gas Gas to Jet (gas
fermentation)
Etihad airways B777-300ER 2012 vegetable oil Oil to Jet
British airways TBD Solena TBD Factory waste TBD Gas to Jet (F-T)
Paramus flying club Cessna 182 2013 Waste cooking oil 50% Oil to Jet
(b) Flight tests with bio-jet fuels through different conversion pathways [58] by military Aircrafts types.
Military Aircraft Aircraft Partners Year Feedstocks Bio-jet Fuel Conversion Pathway
Content
U.S. Navy F/A-18 Honeywell UOP 2010 Camelina 50% Oil to Jet
U.S. Air Force A-10C Honeywell UOP 2010 Camelina, waste 50% Oil to Jet
cooking oil
U.S. Air Force F-22 Honeywell UOP 2011 Camelina 50% Oil to Jet
U.S. Navy MH60S Seahawk 2010 Camelina 50% Oil to Jet
Helicopter
U.S. Navy MH60S Seahawk Solazyme 2011 Algae 50% Oil to Jet
Helicopter
U.S. Navy T-45 2011 Camelina 50% Oil to Jet
U.S. Navy AV-8D 2011 Camelina Oil to Jet
Netherland Air AH-64D Apache Honeywell UOP 2010 Waste cooking oil 50% Oil to Jet
Force Helicopter
U.S. Air Force A-10C Gevo 2012 cellulose-derived Alcohol to Jet
alcohol
U.S. Air Force B-52 Syntroleum 2006 natural gas 50% Gas to Jet (F–T)
U.S. Air Force TBD Swedish Biofuels TBD Biomass-derived 100% Alcohol to Jet
sugar
NASA DC-8 2011 Chicken and beef Oil to Jet
tallow
Dutch Military Ah-64 Apache 2010 Waste cooking oil Oil to Jet
helicopter
EADs Diamond D42 2010 Algae Oil to Jet
literature. Jet fuel blended with up to 50% bio-jet fuel from an F–T joint ventures by biofuel and oil companies [41–48]. Two recently
process was certified in August 2009 [12,27–29]. Bio-jet fuels from proposed processes, CH and hydro-treated depolymerized cellu-
hydro-processing technologies, such as hydro-treated esters and losic jet (HDCJ), also called pyrolysis, have not yet been approved
fatty acids (HEFA) or hydro-processed renewable jet (HRJ), were by ASTM, but several companies and research institutes are
also studied extensively [30–33]. Conversion of alcohol to jet fuel, working on this technology [49–52]. Currently bio-jet fuels from
called alcohol-to-jet (ATJ), has also been developed at commercial ATJ, HRJ, and F–T synthesis have been used for commercial and
scale and was flight-tested by the U.S. Air Force in July 2012 [34– military flights, as shown in Table 2.
38]. Fuel produced by two recently proposed sugar-to-jet (STJ) fuel Some of the technologies that convert bio-based feedstocks to
processes, fermentation of sugars to hydrocarbons [39] and cata- jet fuel have been reviewed in the literature in areas including
lytic conversion of sugars to fuels [40], have been developed in feedstock availability, upgrading technology, process economics,
Table 3
Summary of jet fuel production pathways reviewed in this work.
Category Pathways Companies U.S. or international Airline companies/manufacturers

agencies
Alcohol Ethanol to Jet Terrabon/MixAlco; Lanza Tech/Swedish Bio- Defense Advanced Boeing, Virgin Atlantic
to Jet fuels; Coskata Research Projects
Agency, FAA
Butanol to Jet Gevo; Byogy; Albemarle/Colbalt; Solazyme Navy/NAWCWD, AFRL, Continental Airlines; United Airlines
DLA, USAF
Oil-to- Hydro-processed UOP; SG Biofuels; AltAir Fuels; Agrisoma U.S. Navy, USAF, Neth- Boeing, Lufthansa, Virgin Atlantic, Virgin Blue, GE Aviation,
Jet Renewable Jet (HRJ) Biosciences; Neste Oil; PetroChina; Sapphire erland Air Force, NASA, Air New Zealand, Rolls-Royce, Continental, CFM, JAL, Air-
Energy, Syntroleum/Tyson Food; PEMEX; ASA Dutch Military, EADs bus, KLM, Interjet, Pratt & Whitney, Air China, TAM Air-
lines, Jet Blue Airways, IAE, United Airlines, Air France,
Finnair, Air Mexico, Thomson Airways, Porter Airlines,
Alaska Airlines, Horizon Air, Etihad Airways, Romanian Air,
Bombardier
Catalytic Hydro-ther- Applied Research Assoc., Aemetis/Chevron FAA CLEEN, NRC Rolls-Royce, Pratt & Whitney
molysis (CH) Lummus Global Canada, AFRL
Hydro-treated Depo- Kior/Hunt Refining/Petrotech, Envergent, GTI, FAA N/A
lymerized Cellulosic Dynamotive
Jet (Pyrolysis) (HDCJ)
Gas to Fischer–Tropsch Syntroleum; SynFuels; Rentech; Shell; Solena U.S. DOE, U.S. DOD, Qatar Airways, United Airlines, Airbus, British Airways
Jet Synthesis USAF, Ontario
government
Gas Fermentation Coskata; IneosBio/Lanza Tech; Swedish N/A Virgin Atlantic
Biofuels
Sugar to Catalytic Upgrading Virent/Shell, Virdia AFRL, U.S. DOE N/A
Jet of Sugar to Jet
Direct Sugar to Amyris/Total, Solazyme, LS9 Navy, FAA Boeing; Embraer; Azul Airlines; GE; Trip Airlines
Hydrocarbons
Residue Residue Post By Products

Treatment
CO2
H2 & H2O
C3H8 Catalyst H2 Catalyst
H2 Catalyst H2 Catalyst CO
Saturated
Biomass Oil Triglycerides FFA Decarboxylation Or Hydrodeoxygenation
Crude Oils Hydrogenation Propane Cleave
Extraction
C17H36 C18H38
H2 Hydro-
Catalyst isomerization
& Hydrocracking
Paraffins, Iso-paraffins,
Cracking Products
Hydro-
isomerization
& Hydrocracking
Light Gases Naphtha Jet fuel Diesel
Fig. 2. Hydro-processed renewable jet (HRJ) process.
lifecycle GHG analysis, and commercial progress [5,11,12,21,53– pathways are classified as one of four types, based on the feed-
57]. Most literature has focused on approved technologies such as stocks and conversion processes: (1) alcohol-to-jet (ATJ), (2) oil-to-
F–T synthesis and HRJ processes; few literature references are jet (OTJ), (3) gas-to-jet (GTJ), and (4) sugar-to-jet (STJ) (shown in
available for either ATJ or STJ processes because they are still in the Table 3). Detailed information and literature data, such as potential
development stage. To fully understand current biomass-to-jet feedstocks, process technologies, cost analysis comparisons, life-
fuel development, it is necessary to have an overview of all of the cycle assessment studies, and pre-commercial or commercial
upgrading technologies, both approved and pending approval, demonstrations for each pathway, are described in this report in
from laboratory to commercial scale. In this review, the upgrading the following sections.
Table 4
Bio-jet fuels from the CH process [107, 108].
JP-8 From Soybean From Jatropha From Tung From Camelina From Carinata MIL-DTL-83133H spec requirement
Aromatics 18.8 (vol%) 2.6 (wt %) 10.8 (wt%) 61.7 (wt%) 24.2 (vol%) 16.8 (vol%) r 25.0
Paraffins (normal þiso) N/A 40.0 (vol%) 32.8 (wt%) 16.2 (wt%) N/A N/A N/A
Olefins 0.8 (vol%) N/A N/A N/A 1.3 (vol%) 1.8 (vol%) r 5.0 (vol%)
Cycloparaffins N/A 52.0 (vol%) 39.2 (wt%) 16.7 (wt%) N/A N/A N/A
Dicycloparaffins, vol% N/A 5.9 (vol%) N/A N/A N/A N/A N/A
Heat of Combustion, MJ/kg 43.3 43.4 43.4 42.3 42.9 43.2 Z 42.8
Smoke Point, mm 22 430 28 N/A 22 26 Z 19
Freeze Point, C 51 o 47 39 o 66 54 57 r 47
Flash Point, C 51 438 45 39 48 46 Z 38
Distillation (D2887, D86) N/A pass 195–229 187–252 N/A N/A N/A
Density, kg/L 0.804 40.775 0.804 0.839 0.818 0.802 0.775–0.840
Acid Number, mg of KOH/g 0.003 o 0.010 o 0.010 N/A 0.011 0.012 r 0.015
Hydrogen, wt% 13.8 N/A 14 13.3 13.8 Z 13.4
Viscosity at 40C, cSt 9.9 N/A N/A N/A 7.4 6.5 r 12.0
Cetane Index N/A N/A 43.9 34.2 N/A N/A N/A
2. Conversion pathways to bio-jet fuel processes, broader carbon number distributions are produced,
such as 5% C4; 50% C6–C10; 30% C12 and C14; 12% C16 and C18; and
2.1. Alcohol-to-jet (ATJ) fuel 3% C20 and C20 þ [63], at 200 °C and 250 bar. The resulting olefins
are distilled to diesel- and jet-range fuels and light olefins [66].
ATJ fuel, also called alcohol oligomerization, is fuel converted Light olefins (C4–C8) separated by distillation are recycled back to
from alcohols, such as methanol, ethanol, butanol, and long-chain the oligomerization step, shown in Fig. 1a. Jet fuel range products
fatty alcohols. The maximum use of ethanol is 10–15% for the (C9–C16) can be subjected to hydrogenation, which operates at
majority of gasoline-powered vehicles on the road today, which temperatures of 370 °C and WHSV of 3 h 1 with feeding hydrogen
creates a blend wall that makes it difficult to achieve further over 5% by weight of palladium or platinum on activated carbon
market penetration of ethanol as a blend stock for gasoline. catalyst [67]. The C9–C16 alkanes produced from the hydrogenation
Therefore, upgrading ethanol to jet fuel blend stock presents a step are suitable for renewable jet fuels.
potential pathway for developing drop-in or fungible fuels for the N-butanol can be dehydrated to 1-butene at 380 °C and 2.1 bar
jet fuel market. In this review, ethanol and butanol are the two over the γ-alumina catalyst [68]. The highest yield of biobutenes is
primary alcohols discussed for jet fuel conversion. 98%, with 95% selectivity of 1-butene [68]. The rest of the product
is 2-butene isomerized from 1-butene. The 1-butene is subjected
2.1.1. Process description to the oligomerization process to produce olefins ranging from C8
To make drop-in alternative jet fuel from alcohols, the differ- to C32 with the conversion of 97% [69]. The product distributions of
ences in the physical and chemical properties between alcohols the mixed olefins are 26.46% C8, 25.48% C12, 17.64% C16, 11.76% C20,
and conventional jet fuel have to be minimized. In the United 7.84% C24, 4.9% C28 and 3.92% C32 [38]. The reaction is operated at
States, anhydrous ethanol, at 99.5–99.9% purity, is required to ambient temperature with stirring for 16 h over the Group 4
blend with gasoline to avoid separation [59]. However, for transition-metal catalysts in the presence of methylaluminoxane
upgrading to jet fuel products, the necessity of high-purity ethanol (Cp2ZrCl2/MAO) [70]. The 2-butene, containing cis- and trans-2-
is still uncertain. A typical three-step ATJ process that converts butenes, are considered as unreacted olefins and separated by
alcohols to jet fuel has been demonstrated [35]. The process temperature controlled distillation [71]. The C8 olefin, 2-ethyl-1-
includes alcohol dehydration, oligomerization, and hydrogenation. hexene, is distillated and sent to the dimerization reactor [69,72].
The overall process diagram for ethanol to jet fuel is shown in The dimerization is operated at 116 °C for 2 h over Nafion catalyst.
Fig. 1. The advantage is that all of these process steps have been The C8 olefin is 100% converted, yielding to 90% of C16H32 [72]. The
demonstrated on a commercially relevant scale and the risk of products from 1-butene oligomerization, ranging from C12 to C32,
scale-up is expected to be reduced. However, the development and together with C16 olefins produced from dimerization, are sent to
demonstration of the integrated process on biomass derived hydrogenation process [72] over 0.08 wt% PtO2 catalyst. The
intermediates is necessary [35]. resulting C12–C16 paraffins can be blended with jet fuel and the
Catalysts for upgrading alcohols to hydrocarbons are important. C20–C32 alkanes are separated and sold as lubricants [69]. In
Studies on dehydration catalysis started with alumina and transi- addition, n-butanol from ABE fermentation can be dehy-
tion metal oxides and moved to silicoaluminophosphates (SAPO), drogenated over a Pd/C–K3PO4 catalyst, producing C5–C11 ketones
H-ZSM-5 zeolite catalyst, and heteropolyacid catalysts [60]. The [73]. These ketones can be deoxygenated to produce normal par-
most promising case was found to be the 0.5%La–2%P H-ZSM-5 affins, similar to the components of jet, gasoline, and diesel fuels.
catalyst. Approximately 100% conversion and 99.9% ethylene Iso-butanol produced from a process such as Escherichia coli
fermentation is dehydrated to a mixture of isobutene, n-butene (1-
selectivity are approached at 250 °C and 2 h 1 weight hourly
butene), and 2-butene (cis-2-butene and trans-2-butene) [74].
space velocity [61,62]. The dehydrated ethylene can be turned into
Acidic catalyst such as ZSM-5 zeolites, Y-type zeolites, and
linear α-olefins via a catalytic oligomerization process [63]. Cur-
Amberlyst acidic resins can be used to catalyze a dehydration
rent commercial processes for making α-olefins are focused on
reaction, and different catalysts affect the selectivity of isobutene
both homogeneous and heterogeneous catalysts [35]. Catalysts
and the overall linear butenes [74] 1. With the overall isobutanol
such as a Ziegler Natta-type catalyst [64], chromium diphosphine
dehydration yield of 99.1%, the selectivity is reported to be
catalyst [65], and zeolites [35] have been studied extensively. With
95.1% isobutene, 1.6% 1-butene, 0.5% trans-2-butene, and 1.9%
a temperature of 90–110 °C and a pressure of 89 bar over a Ziegler
Natta-type catalyst, 96–97% yield of linear α-olefins was produced
with a carbon range of C4–C20 [64]. In industrial oligomerization 1
Unless specified, all selectivities are mass %.
Triglycerides Catalytic Cyclization/ Catalyst/Non-Catalyst

Conjugation X-Linking
Organic
Phase Hydrogenation,
Catalytic
Decarboxylation, Fractionation
Hydrothermolysis
Hydrotreatment
Alkenes
Triglycerides
Processing Waste Aqueous
Anaerobic Decarboxylation Water
Phase
Fermentation or Dehydration
Naphtha
Jet Fuel
Diesel Fuel
H2
Fig. 3. Catalytic hydro-thermolysis to jet fuel [107,108].
External H2
Bio-Gas H2
Cellulosic
Biomass Bio-Oil Bio-Oil Bio-Oil Hydrocarbons
Pyrolysis Hydrotreating Fractionation Jet Fuel
Recovery
Bio-Char Steam
Fuel Gas
Fuel Gas/NG
Reforming
External NG
Fig. 4. Pyrolysis-to-jet process [52].
cis-2-butene at 325 °C using ZSM-5 catalyst at 2 h 1 WHSV [74]. In (n-butanol and iso-butanol) needs to be determined. The techno-
addition, Armstrong reports that isobutanol can be converted into economic analysis of both biochemical and thermochemical pro-
isobutylene through the dehydration process operated at 310 °C cesses [82,83] for ethanol production(from starch or cellulosic
over γ-Alumina catalyst, resulting in 98% isobutanol conversion feedstocks) has been studied extensively [10,82–90]. Most reports
and 92 mol% isobutylene selectivity [75]. The isobutene can be calculate a minimum selling price of the fuel based on a number of
converted to oligomers, trimmers, and tetramers at 100 °C using economic assumptions. The minimum ethanol selling price for the
an Amberlyst-35 catalyst at a WHSV of 2 h 1, producing 20%, 70%,
biochemical conversion of lignocellulosic biomass was recently
and 10% for C8, C12, and C16 olefins, respectively [66,67]. The 1-
reported to be $2.15/gal or $3.27/gal of gasoline equivalent (GGE)
butene is converted into 25%, 24%, 17%, and 25% to C8, C12, C16, and
in 2007 US dollars ($2.76/gal or $4.18/GGE in 2011 US dollars) [83].
C20 olefins, respectively, resulting in an overall 1-butene yield of
96% with 4% unreacted. To increase the jet and diesel yields, the C8 The minimum ethanol selling price for the thermochemical route
olefins can be distilled and sent to one additional dimerization was reported to be $2.05/gal or $3.11/GGE in 2007 US dollars ($2.5/
process, operating at 116 °C over a Nafion catalyst [72]. Alter- gal or $3.8/GGE on 2011 US dollars) [85].
natively, C8 olefins can be either converted into C16H32 through The selling price of butanol from ABE fermentation is projected
dimerization or reacted with butenes to produce C12 olefins, to be $0.34/kg ($1.04/gal) based on the corn feedstock cost of
leading to the increase of C12 and C16 for the jet-range chemicals $79.23/ton [91]. For cellulosic biomass, the price becomes $3.7/gal
[66]. or $4.1/GGE (2011 US dollars) [92]. According to the current mar-
Another source for producing 1-butene reported by researchers ket demand and the fluctuation of agricultural prices, cheaper
at the University of Wisconsin–Madison is γ-valerolactone [76]. feedstocks such as agricultural waste or algal biomass [93] are
The γ-valerolactone produced from biomass-derived carbohy- desired due to their renewability and non-competition with food.
drates is converted into 96% butene and CO2 through the dec- The substrate cost [91], credit for by-products [94], solvent
arboxylation process over a silica/alumina catalyst at a pressure of recovery technology [91], and product molar ratio [95] are
36 bar and temperature of 375 °C. The resulting butene is subse-
important factors for economic evaluation of butanol production.
quently oligomerized over an Amberlyst-70 catalyst at 170 °C and
To evaluate the overall ATJ conversion pathway and estimate
17 bar, resulting in 99% conversion of butene and 71% yield of C8–
the commercial feasibility, the economics of the fuel upgrading
C16 alkenes, which can be targeted for jet fuel application.
processes such as dehydration, oligomerization, dimerization, and
2.1.2. Economic analysis hydrogenation also have to be considered. Because these processes
To evaluate the production cost for the bio-jet fuel derived from are still under development, more research efforts are required to
alcohols, the cost of making alcohols, such as ethanol and butanol complete this target.
Table 5
Oil selling price [118–123].
Jatropha Palm Camelina Algae Waste cooking oil Soybean Rapeseed Pyrolysis oil
Oil Price ($/kg) 0.50 0.79 1.75 3.55 0.115–0.472 1.14 1.72 0.26
2.1.3. Life-cycle assessment A representative process flow diagram is shown in Fig. 2.

LCA studies for the ATJ process are primarily focused on pro- Renewable fats and oils that have different degrees of unsaturation
duction of ethanol [96,97], n-butanol [98], and iso-butanol [92]. The require the hydrogenation process to completely saturate the
LCA for fuel alcohol production can be categorized into four areas double bonds [32]. Catalytic hydrogenation could be used to
[92]: (1) feedstock (land-use-change), (2) on-site enzyme produc- convert liquid-phase unsaturated fatty acids or glycerides into
tion, (3) biorefinery process, and (4) biorefinery co-product credits. saturated ones [32] with the addition of hydrogen. The next step is
If different pathways are considered, the biochemical process has to cleave the propane and produce three moles of FFAs [100]. The
slightly different performance from the thermochemical process glycerol portion of the triglyceride molecule is turned into pro-
with respect to GHG emissions, fossil fuel consumption and water pane by adding H2. Alternative route to convert the glycerides to
consumption [99]. FFAs is thermal hydrolysis [101–103]. Oils and fats that contain
For n-butanol and iso-butanol conversion, studies have focused mostly triglycerides are converted into three moles of FFAs and
on emissions, consumptive water use, global warming potential, one mole of glycerol by processing the feedstocks with three
and fossil energy consumption [92]. The n-butanol production moles of water. The hydrogen ion from the water is attached on
process releases more direct emissions, such as CO2, nitrogen the glycerol backbone and forms one mole of glycerol, where the
dioxide, and sulfur dioxide, than the iso-butanol production pro- hydroxyl ion from the water is added to the ester group and
cess does. CO2 is produced during the cellulase (or enzyme) pro- produces three moles of FFAs. High temperature (250–260 °C) is
duction and cellulase seed fermentation, but is largely from required for water to dissolve in the oil phase. High pressure is also
combustion [92]. Nitrogen dioxide is formed through high tem- necessary to maintain the reactants in liquid phase. The by-
perature oxidation of the diatomic nitrogen in the combustion air. product glycerol has many pharmaceutical, technical, and perso-
Sulfur dioxide emissions strongly depend on the amount of sul- nal care product applications. The glycerol purification process is
furic acid used in the pretreatment process. However, the bioenergy intensive, adding cost to overall process, but might be
refining of n-butanol consumes more water than iso-butanol offset by glycerol selling value [104].
refining does. The biomass feedstock is responsible for most of To meet the jet fuel specification, the produced bio-jet fuel has
the global warming potential and fossil energy consumption [92]. to have not only a high flash point, but also good cold flow
Conversion of iso-butanol consumes 5.15 MJ/GGE more fossil fuel properties. Therefore, it is required to hydrocrack and hydro-
than n-butanol conversion does. isomerize the normal paraffins produced from deoxygenation to
The LCA of the ATJ fuel upgrading processes is still unknown a synthetic paraffinic kerosene (SPK) product with carbon chains
and requires more attention in future studies. ranging from C9 to C15 [100]. The cracking and isomerization
reactions are either concurrent or sequential [32]. Studies have
2.2. Oil-to-jet (OTJ) fuel shown that isomerization of straight-chain alkanes occurs first and
cracking is a consecutive reaction. The isomerization process takes
In this review, three processes are classified into the OTJ con- the straight-chain hydrocarbons and turns them into the branched
version pathway: HRJ, also known as HEFA; catalytic hydro- structures to reduce the freeze point to meet the jet fuel standard
thermolysis (CH), also termed hydrothermal liquefaction; and [105]. It is accompanied by a hydrocracking reaction, which results
hydro-treated depolymerized cellulosic jet (HDCJ), also known as in more or less yield from the isomerized species. The hydro-
fast pyrolysis with upgrading to jet fuel. Currently, only products cracking reactions are exothermic and result in the production of
from the HRJ pathway have been approved for blending and have a lighter liquids and gas products. They are relatively slow reactions;
defined ASTM specification. thus, most of the hydrocracking takes place in the last section of
the reactor. The hydrocracking reactions primarily involve cracking
2.2.1. Process description and saturation of paraffins. Overcracking will result in low yields
Both HRJ and CH processes employ triglyceride-based feed- of jet-fuel-range alkanes and high yields of light species ranging
stocks, but the free fatty acids (FFAs) are produced differently. FFAs from C1 to C4 and naphtha ranging from C5 to C8. Both of these are
in the HRJ process are made by propane cleavage of glycerides, out of jet fuel range and also have lower economic value than
whereas in the CH process FFAs are formed by thermal hydrolysis. diesel or jet fuel.
The bio-oil in the HDCJ process is produced by pyrolyzing the Bifunctional catalysts containing metallic sites for hydrogena-
biomass feedstock. The downstream hydro-treating processes are tion/dehydrogenation and acid sites for skeletal isomerization via
similar in all three processes. The HRJ, CH, and HDCJ processes are carbenium ions are used in isomerization. In a typical isomeriza-
discussed separately below. tion reaction, normal paraffins are dehydrogenated on the metal
sites of the catalyst and reacting on the acid sites to produce
2.2.1.1. Hydroprocessed renewable jet (HRJ). HRJ conversion tech- olefins protonate with formation of the alkylcarbenium ion. The
nology is at a relatively high maturity level, is commercially alkylcarbenium ion is rearranged to monobranched, dibranched,
available, and was recently used to produce jet fuel for military and tribranched alkylcarbenium ions on the acid site. The bran-
flights [57]. HRJ fuel is equivalent to conventional petroleum in ched alkylcarbenium ions are deprotonated and hydrogenated to
properties, but has the advantages of higher cetane number, lower produce the corresponding paraffins [106]. The choice of catalyst
aromatic content, lower sulfur content, and potentially lower GHG will result in variation of cracking at the end of the paraffin
emissions [100]. molecule and therefore adjust the yield of jet fuel range product
Over the past 60 years, a large variety of catalytic hydrogena- [32]. The hydro-isomerization and hydrocracking processes are
tion, deoxygenation, hydro-isomerization, and hydrocracking followed by a fractionation process to separate the mixtures to
processes have been successfully developed and commercialized.
paraffinic kerosene (HRJ SPK), paraffinic diesel, naphtha, and petroleum gas, propane, and diesel—have more credits than gly-
light gases. cerol from the transesterification process [55]. Feedstock costs
contribute a significant part of the production cost. For example,
2.2.1.2. Catalytic hydrothermolysis (CH). Catalytic hydro-thermolysis 70–80% of the total production cost for biodiesel production
(CH), also named hydrothermal liquefaction, is a novel process that results from the cost of feedstocks [114–117]. Edible and non-
has been developed and patented by Applied Research Associates, edible oils are becoming promising alternatives to biofuel because
Inc., for producing “renewable, aromatic, and drop-in” fuels (known they are renewable in nature and can be produced locally and in
as ReadiJet or ReadiDiesel) from plant or algal oils [51]. The environmentally friendly ways. Table 5 shows the unit oil prices
hydrothermal process (Fig. 3), contains a series of reactions, for plant oils, algae oil, waste cooking oil, and pyrolysis oil.
including cracking, hydrolysis, decarboxylation, isomerization, and Obviously, higher oil yield leads to lower operating cost.
cyclization, that turn triglycerides into a mixture of straight chain, By-products from the HRJ process can be upgraded to increase
branched, and cyclic hydrocarbons [107]. The CH reaction is con- overall yield or sold as a high-value-added co-product. Depending
ducted at temperatures from 450 °C to 475 °C and pressures of on the conversion technology, the by-products include:
210 bar with water and a catalyst (or without a catalyst). The
resulting products—including carboxylic acids, oxygenated species, 1. Propane, which is created by breaking the carbon backbone of
and unsaturated molecules—are sent to decarboxylation and hydro- the triglyceride or formed in the fractionation step. It accounts
treating processes for saturation and oxygen removal. The treated for 4% of the products [100]. The current residential propane
products, ranging from 6 to 28 carbon numbers, contain n-alkanes, price is $2.48/gal [124].
iso-alkanes, cyclo-alkanes, and aromatics, which require a fractio- 2. Liquefied natural gas (LNG), which is produced in the product
nation step for separation to naphtha, jet fuel, and diesel fuel. The separation step. LNG will increase to 6% if the diesel fuel is
jet fuel made from the CH process meets ASTM and military (MIL) cracked down to the jet fuel range [100]. The current price of
specifications and has excellent combustion quality, cold flow LNG is $4.58 per thousand cubic feet [125].
properties, and stability [50]. Research has shown that through the 3. Naphtha, which is also formed in the distillation step. The price
CH process, bio-jet fuels can be produced from a variety of of naphtha is $2.03/gal [100].
triglyceride-based feedstocks such as soybean oil, jatropha oil, 4. Diesel, which is separated in the fractionation step. The current
camelina oil, and tung oil (shown in Table 4) [107,108]. price of biodiesel is around $3.64/gal [126].
2.2.1.3. Hydro-treated depolymerized cellulosic jet (fast pyrolysis with 2.2.3. Life-cycle assessment
upgrading to jet fuel). Hydro-treated depolymerized cellulosic jet Several research groups have developed a GHG emissions
(HDCJis a recent technology developed by Kior to convert the analysis on a life cycle basis [3,56,100,127]. The GHG emissions for
cellulosic biomass into renewable gasoline, diesel, and jet fuels soybean oil are about 40% to 80% of those of conventional jet fuel
[52]. The HDCJ jet fuel has not yet been approved by ASTM. Bio- (89 gCO2e/MJ for Jet A fuel ) [56], resulting from the soybean yield,
oils from the pyrolysis process undergo a series of hydro-treating N2O emissions from fertilizer, liming emissions, and H2 require-
processes to produce jet-fuel-range products. If no further catalytic ments in the hydro-treating process. The GHG emissions increase
upgrading is applied, pyrolysis oils undergo hydro-treating and when land use change is considered. One study shows low soy-
fractionation to form jet blend stocks, as shown in Fig. 4. In bean yield from tropical rainforest results in 800% more emissions
addition, UOP LLC, PNNL, Ensyn, and Tesoro have been working on
than conventional jet fuel [56]. The emissions of the palm oil to jet
upgrading pyrolysis oil to hydrocarbon fuels, including jet fuel,
fuel process are about 30–40% of those of conventional jet fuel
through integrated pyrolysis and hydro-conversion [109–111].
production processes, resulting from palm fresh-fruit-bunch yield
Utilizing feedstocks including corn stover, cane bagasse, switch-
per acre, farming energy, methane emissions from palm oil-mill
grass, guinea grass, algae biomass, and forest residue, this inte-
effluent treatment, H2 requirements in the hydro-treating process,
grated biorefinery system combines commercial RTP (Rapid
and hydro-processing fuel yield. GHG emissions increase to the
Thermal Processing) pyrolysis technology with catalytic hydro-
range of 40–800% of those of conventional jet fuel when
conversion. Approximately 42.4–44.2 wt% jet fuel was separated
accounting for land use change [3]. For rapeseed oil, the emissions
by batch vacuum distillation [109–111].
are around 45–87% of those of conventional jet fuels [3] and
increase to 87– 147% when considering land use change. For
2.2.2. Economic analysis
jatropha oil, the emissions are 36–52% of those from conventional
An economic analysis of HRJ fuel is described in the literature
[112]. The HEFA fuel price was found to be $3.85/gal ($4.1/gal or jet fuel, and N2O emissions represent more than 20% of the total
$3.6/GGE on 2011 U.S. dollars) for the plant capacity of emissions. Zero emissions from land use change are assumed due
98.28 MM gal/yr and $4.46/gal ($4.8/gal or $4.2/GGE on 2011 U.S. to the assumption that marginal land will be used. Other research
dollars) for the plant capacity of 30.16 MM gal/yr. Additional $0.27/ shows the emissions from jatropha OTJ conversion were 40 gCO2e/
gal $0.31/gal is required to produce maximum jet fuel because of MJ of fuel produced [127], approximately 45% of that of conven-
the increased hydrogen use and decreased yields of jet and diesel tional jet fuel. For algal oil, the emissions range from 16% to 220%
fuels. The economic analysis of bio-jet fuels from microalgae and of those from conventional jet fuel. The wide range results from
pongamia oils are also studied [113]. The minimum selling prices the uncertainty of emissions from CO2 injection and dewatering
for jet fuels derived from microalgae and pongamia oils are esti- and drying processes [3]. For salicornia oil, the emissions range
mated to be $31.98/gallon or $28.3/GGE and $8.9/gallon or $7.9/ from 35% to 76% of those from conventional jet fuel [3]. The GHG
GGE (2011 U.S. dollars), respectively. The development of tech- emissions of liquid fuel production via fast pyrolysis of cellulosic
nology and market will decrease the prices to be $9.2/gallon or biomass have been studied by researchers at Argonne National
$8.1/GGE and $6.07/gallon or $5.4/GGE (2011 U.S. dollars), Laboratory [128]. When hydrogen is generated from natural gas
respectively. Unlike biodiesel production through transesterifica- and bio-char is used to support the process energy, the GHG
tion, HRJ biofuel production requires hydrogen to hydro-treat the emissions are reduced by 45% relative to conventional fuels. When
biomass. It is suggested that the capital cost for HRJ is 20% higher hydrogen is produced from reforming of pyrolysis oil and bio-char
than that of biodiesel production due to the hydro-treating pro- is applied as the fertilizer, the GHG emissions are reduced by 103%
cess. However, the by-products from HRJ—naphtha, liquefied relative to conventional fuels [128].
2.3. Gas-to-jet (GTJ) fuel self-sufficient, improved capital cost associated with the smaller
process scale, and neutral electrical energy [86].
The GTJ pathway presented here describes the conversion After syngas is produced, it is polished with zinc oxide and an
processes that turn biogas, natural gas, or syngas into bio-jet fuel. activated carbon sorbent and compressed to 25 bar, the F–T
The F–T and gas fermentation processes are classified in this operating pressure. H2 used in hydro-processing stage can be
pathway and are reviewed here. purified through a pressure swing adsorption. The syngas is then
processed by F–T synthesis to produce liquid fuel [129,131], as
2.3.1. Process description illustrated in Fig. 5.
2.3.1.1. Fisher Tropsch biomass to liquid (FT-BTL) process. The F–T F–T synthesis is a set of catalytic processes for converting
process is capable of producing liquid hydrocarbon fuels from syngas into liquid hydrocarbons. There are two well-known F–T
syngas. F–T fuels are typically free of sulfur and contain very few operating modes [134]; high temperature and low temperature.
aromatics compared to gasoline and diesel, which leads to lower The high-temperature process runs at 300–350 °C with iron-based
emissions when used in jet engines [12]. Some recent studies catalysts. Gasoline and linear low-molecular-mass olefins are
point out that the use of the F–T technology to convert biomass to produced in this process. The low-temperature process operates at
synthetic fuels may provide a promising carbon-neutral alter- 200–240 °C with either iron or cobalt catalysts. Linear waxes
native to conventional diesel, kerosene, and gasoline [129–131]. produced in the low-temperature process have higher molecular
The process reviewed here is the FT-BTL process. mass than those produced in the high-temperature process. In the
In the FT-BTL process (Fig. 5), biomass feedstocks are first dried F–T process, the products range from methane to long-chain
to reduce the particle sizes during pretreatment [132]. Multiple hydrocarbons. Besides alkanes and alkenes, oxygenated com-
gasification technologies exist to convert the biomass to syngas. In pounds such as alcohols, aldehydes, and carboxylic acids are also
a high- temperature (slagging) gasification process, the dried formed. Aromatics and ketones are also produced in the high
biomass is pressurized and converted into raw synthesis gas dur- temperature process. The F–T process is a highly exothermic pro-
ing gasification at temperatures around 1300C in the presence of cess; therefore, the heat of reaction has to be removed quickly to
high purity oxygen and steam. A combustor is included to provide avoid overheating and deactivating the catalyst and also to prevent
heat to dry the biomass. The direct-quench syngas cooling system production of undesired methane [135]. Traditional F–T catalysts,
next to the gasifier removes ash and tars. A water-gas-shift system such as iron-, cobalt-, nickel- and ruthenium-based catalysts, have
after quench is applied to adjust the H2:CO ratio to 2.1:1 [132]. been extensively studied in the literature [130,134,136–143]. Pro-
NREL has conducted an investigation on indirect gasification and duct selectivity and product distribution depend strongly on the
tar reforming [85]. In this design, the endothermic gasification operating temperature and the partial pressure of the gases that
process is indirectly-heated by the circulation of hot olivine and contact the catalyst.
the material in the gasifier is fluidized by the steam. Gasification After F–T synthesis, a portion of the unconverted syngas is
occurs at atmospheric conditions and at 880*C. The syngas is returned to the F–T reactor, and part of it is sent to the acid gas
further conditioned such that the residual tars, methane and light removal system [131]. The remaining portion flows into the power
hydrocarbons are reformed to syngas in a fluid catalytic cracker. generation area, providing power for the air separation unit [131].
Water gas shift also occurs in the reformer. Compared to the high Conventional refinery processes, such as hydrocracking, iso-
temperature gasification, this design has the benefits of energy merization, hydrogenation, and fractionation, can be applied to
Fig. 5. FT-BTL process [133].

Lanza Tech Technology
Ethanol
Woody Biomass CO and H2 Fermentation 2,3-Butanediol
Gasification Gas Reception (Acetogenic
Bacteria)
α – Olefins
(C4~C20) Ethylene
C9-C16 Olefins Dehydration
Distillation Oligomerization
Hydrogenation
Jet Fuel Swedish Biofuels Technology
Fig. 6. Gas fermentation to bio-jet fuel.
upgrade the F–T synthesis product to high-quality, low-aromatic, energy efficiencies with smaller plants and the higher capital cost
and almost zero-sulfur-content fuels [144]. Hydrocracking/iso- of gasification [56]. The jet fuel production cost of CTL is estimated
merization is used to convert the wax into lighter products with as $1.70 to $2.04/gal ($2.26 to $2.72/gal on 2011 U.S. dollars),
shorter chain length and lower boiling points. Products from the whereas for CBTL it is estimated as $1.99/gal to $2.34/gal ($2.65 to
hydrocracking/isomerization reactor are heated and distilled to $3.11/gal on 2011 U.S. dollars) [56]. The temperature of gasification
produce jet fuel, diesel fuel, and lubricants. Hydrogenation is also has a high impact on the cost analysis of the BTL F–T process
applied to produce naphtha from the F–T liquid. The F–T tail gas, [90,149]. A low-temperature gasifier has several constraints, such
which contains H2, water, methane, CO, CO2, nitrogen, argon, and as the limitation of reaction kinetics and the formation/flow of slag
heavier hydrocarbons, is recycled back to the syngas generation [90]. Based on processing 2000 metric tons per day of corn stover,
system. H2 in the tail gas can be purified through the pressure the total capital investment for the high-temperature ( 1300 °C),
swing absorber and can be further used in the hydrocracking/ slagging, entrained flow gasification process, including feedstock
isomerization process. handling, solids feeding, gasification, amine scrubbing, sour water-
gas-shift, pressure swing adsorption, F–T synthesis, hydrocracking,
2.3.1.2. Gas fermentation process. Instead of catalytically upgrading and air separation/power generation, is $500 million (2007 basis)
F–T syngas to bio-jet fuel, it is also possible to ferment syngas to [149]. The total capital investment for the low temperature
liquid biofuels (Fig. 6). If lignocellulosic biomass is used as the (870 °C), non-slagging, direct fluidized bed gasification process is
feedstock, it is first converted into syngas via gasification. The $610 million. With the same capacity, high-temperature (1300 °C)
cooled syngas can be fermented to ethanol or butanol by aceto- indirect gasification has total capital investment of $516 million
genic bacteria [145]. The acetogenic bacteria Clostridium is used to (2007 basis) [85]. Compared to the pyrolysis and biochemical
consume CO and H2 to produce ethanol and 2,3-butanediol [145]. processes, gasification has the highest capital cost [150]. Followed
Other products such as acetate, acetone, isopropanol, and butanol by catalytic F–T synthesis and hydro-processing to naphtha-range
can be produced by other biosynthetic pathways with different and distillate-range liquid fractions, the product values for the
microbe strains [146]. The mixed alcohol, ethanol, or 2,3-butane- high temperature and low temperature direct gasifiers are $4.50/
diol can be upgraded into jet fuel via the ATJ technology described GGE and $5.00/GGE ($5.50/GGE and $6.10/GGE on 2011 US dol-
in Section 2.1.2, which includes dehydration, oligomerization, lars), respectively. Tijmensen et al. [151], pointed out that the
distillation, and hydrogenation processes [147]. Gas fermentation pretreatment, gasification with oxygen, and gas cleaning sections
has several potential advantages. It is able to produce more pro- account for approximately 75% of total capital cost. The production
ducts than the traditional biochemical or thermochemical path- cost of F–T liquids in this study ranged from $9/GJ to $16/GJ ($1.86/
ways can [148], and it has an overall energy efficiency of 57%, gal to $3.30/gal on 2011 US dollars).
while the F–T process has a relative overall energy efficiency of
45% [146]. The process requires lower temperature and pressure, 2.3.3. Life-cycle assessment
as well as less expensive enzymes [148]. Gas fermentation can In the syngas production and fuel synthesis processes, the GHG
convert not only energy crops and typical agricultural wastes, but emissions considered are [152] (1) CO2 emissions from gasifica-
also municipal and industrial organic waste [148]. tion, F–T synthesis, fossil fuel combustion, and venting from nat-
ural gas production; (2) methane emissions from fugitive plant
2.3.2. Economic analysis and pipeline emissions, incomplete combustion, and coal bed
The production cost of BTL jet fuel has been reported based on methane releases; and (3) N2O emissions from fuel combustion
BTL diesel production due to the similarity of the processes [12]. and the cultivation of biomass. The F–T CTL and F–T GTL processes
The feedstock price, as shown in the report, has a significant effect have high life-cycle GHG emissions [152,153]. The F–T CTL process
on the cost of the BTL fuel. High-cost energy crops contribute has GHG emissions 10% higher than those of conventional jet fuel
about 70% more to the cost of the fuel than high-cost forestry with carbon capture and 120% higher without carbon capture.
residues and wastes [12]. In addition, production costs are reduced GHG emissions from the F–T BTL process are 92–95% less than
with the reduction of the conversion cost and improvement of the those of conventional jet fuel because the feedstock for F–T BTL,
energy crop yield. It is estimated that the conversion cost will be either woody biomass or forestry residues, has a very low con-
reduced by 26% from 2012 to 2026 [12]. The unit production cost tribution [12]. This is also because 48% of the energy consumed for
of BTL is expected to be higher than that of CTL due to the lower the conversion processes, either gasification or F–T synthesis,
comes from the biomass itself [12]. The life-cycle GHG emissions and upgraded into hydrocarbon fuels through aqueous phase
from the use of corn stover, forest residue, and switchgrass are 9.0, reforming (APR). The process has been operated by companies
12.2, and 2.0 gCO2e/MJ, respectively (with a soil carbon-change such as Virent and Virdia. The jet fuel produced from the pro-
credit, the CO2 sequestration arising from land use change dom- cess has been tested in AFRL and passed the relevant specifi-
inates the GHG emissions), which are about 10%, 14%, and 2% of cations of Jet A1 fuel.
those of conventional jet fuel, respectively [3]. It is also suggested 2. Fermentation of sugars to hydrocarbons: the sugars from bio-
that identifying strategies and technologies, such as carbon mass are fermented directly to hydrocarbon fuels or hydrocarbon
sequestration, co-production of fuels and power, co-processing of intermediates, recovered, purified, and further upgraded to drop-
coal and biomass, and improved vehicle technology will help in hydrocarbon fuels. This process has been operated by compa-
reduce GHG and other emissions from the F–T process [154]. nies such as LS9 and Amyris, and the renewable jet fuel produced
When switchgrass is used as the feedstock, the WTW GHG emis- by the process from a sugarcane feedstock has been used in an
sions range from 11.9 gCO2e/MJ to 26 gCO2e/MJ without soil car- Embraer E195 jet operated by Azul Brazilian Airline [158].
bon sequestration and from 1.7 gCO2 to 4.4 gCO2e/MJ with soil
carbon sequestration [3]. HRJ fuel has higher GHG emissions, 2.4.1. Process description
about 62–92% more than F–T BTL [21] due to higher fertilizer and The STJ processes include (1) catalytic upgrading of sugars to
chemical use. The effect of carbon capture and storage on climate, hydrocarbons, (2) fermentation of sugars to hydrocarbons, and (3)
estimated in terms of radiative forcing of the production and uti- sugar-to-sugar intermediate and upgrading to fuel.
lization chains of the F–T fuel based on GHG emissions, has been
studied [155]. It is concluded that without carbon capture and 2.4.1.1. Catalytic upgrading of sugars to hydrocarbons. Lignocellulosic
storage, the climate impacts of F–T fuel from peat are 30–40% sugars are typically produced by pretreatment and enzymatic
lower than from petroleum fuels. With carbon capture and sto- hydrolysis of biomass feedstocks. A certain level of purification and
rage, the climate impacts of peat-based F–T fuels are 50–84% lower concentration of biomass sugars is often needed before catalytically
than petroleum diesel. upgrading sugar to hydrocarbons, which converts sugar or its
intermediates to a range of hydrocarbon molecules and hydrogen in
2.4. Sugar-to-jet fuel an APR process. The hydrocarbon molecules are separated in a
fractionation process to jet, gasoline, and diesel fuels. Bio-derived
The biological and catalytic conversion of sugars to hydro- chemicals, such as para-xylene for polyethylene-terephthalate-
carbons provide a biochemical route to the production of liquid saturated polyester polymers, are also produced [40] and can be
transportation fuels and chemicals [17,43–48,156,157]. According credited as co-products. Closed loop processes that recover and
to reports by DOE's Office of Energy Efficiency & Renewable Energy recycle the unreacted species are significant to improve the process
Bioenergy Technologies Office [39,40], STJ fuel can be processed economics [17], but separation of the product mixtures can be
via two pathways: technically challenging.
Virent's BioForming platform is one example of a process that
1. Catalytic upgrading of sugars or sugar intermediates to hydro- turns the plant sugars into high-energy hydrocarbon mixtures
carbons: sugars are separated from biomass (e.g., milled corn (Fig. 7) [44,48,144,159]. Following the pretreatment and fractio-
stover) through a series of chemical and biochemical processes nation processes, lignocellulosic biomass is converted and
Generate
Process Heat
Lignin H2
Short-Chain Oxygenated Compounds
Biomass
(Glycerol, Propylene, Glycol, Ethylene Glycol)
(Lignocellulosic Hydrogenolysis
Materials, Soluble Biomass
Sugars, Starches) Pretreatment, Aqueous Phase
Conditioning and Reforming
Fractionation
Polyhydric Alcohols
Hydrogenation
Alkenes
Oligomerization Dehydration
Cyclization and
Aromatics
Jet Fuel Dehydrogenation
Cracking Alkanes Oxygenates
Isomerization
Alkanes Alkanes
Hydrogen-
and Iso-alkanes
Transfer
Ketone or β-hydroxyketone or
Dehydration/ Alkehyde Conjugated Enone β-hydroxyalkehyde Aldol
Hydrogenation or Hydrogenation Dehydration
Condensation
Hydrogenolysis
Alkenes or
Alkanes Alkenes Alkanes Dehydration or
Hydrogenation Oligomerization
Hydrogenation-
Dehydration
Fig. 7. Catalytic upgrading of sugars to jet fuel (Virent BioForming Process). Note: Blue line represents the hydrogen supply. (For interpretation of the references to color in
this figure legend, the reader is referred to the web version of this article.)
separated to cellulose, hemi-cellulose, and lignin. Lignin, in this contaminants, including sulfur, nitrogen and ash. In addition, the
process, is sent to the combustor to provide process heat. Using ideal catalyst should be able to handle lignin and its decomposed
enzymatic or acid hydrolysis, the fractionated cellulose and products with high carbon efficiency and long catalyst lifetime [17].
hemicellulose are turned into sugars with five and six carbons. The Researchers at the University of Wisconsin-Madison developed
carbohydrates are converted into polyhydric alcohols via hydro- a two-stage process that converts sugar derived from biomass into
genation [160] or short-chain oxygenates via hydrogenolysis [161]. 2,5-dimethylfuran (DMF) [169]. The fructose, obtained directly
The key step in the BioForming platform is APR. Through APR, the from biomass or by isomerizing of glucose, was dehydrated to
product stream from the hydro-treating step is reacted with water form 5-hydroxymethylfurfural (HMF) by removing five oxygen
over a proper heterogeneous catalyst at temperatures of 450– atoms over an acid catalyst. HMF was then turned into DMF
575 K and pressures of 10–90 bar. The APR reaction includes through hydrogenolysis over a CuRu catalyst. The resulting DMF
reforming to produce hydrogen, dehydrogenation of alcohols/ has higher energy density by 40% and a higher boiling point by
hydrogenation of carbonyls, deoxygenation, hydrogenolysis, and 20 K than ethanol, and it is not water soluble [169]. This study
cyclization [161]. Products that form in APR are hydrogen, carbon created a new path for the production of DMF as a replacement for
dioxide, alcohols, ketones, alkehydes, alkanes, organic acids, and traditional petroleum transportation fuels.
furans [162]. Hydrogen produced from APR will support the hydro-
treating process before the APR step and hydro-refining processes 2.4.1.2. Direct sugar to hydrocarbons (DSH). In the direct sugar-to-
after the APR step. The lighter alkanes from APR, such as C1–C4 hydrocarbons process, biomass cell walls are broken down and
hydrocarbons, are sent to the combustor to provide additional hemicellulose sugars are released. After enzymatic hydrolysis,
process heat [163]. which removes solid materials, liquid sugars are often concentrated
Based on the available open literatures, there are three poten- by removing 50% of the water. Hydrocarbon intermediates are
tial routes to convert the oxygenates from the APR step into jet- produced by processing concentrated sugars through an aerobic
fuel-range hydrocarbons. As shown in Fig. 7, the first route is acid fermentation process using fed-batch or continuous fermentation.
condensation, which turns the oxygenates into alkanes, iso- The resulting products are then sent to a phase separation stage to
alkanes, and aromatics with a zeolite ZSM-5 catalyst. The reactions recover the hydrocarbon fuels [39].
include dehydration of oxygenates to alkenes, oligomerization of The processes developed by Amyris and LS9 successfully trans-
the alkenes to heavier alkenes, cracking, cyclization and dehy- forms sugars to hydrocarbon fuel [170,171]. There are two pathways
drogenation of heavier alkenes to aromatics, alkane isomerization, to produce isopentenyl pyrophosphate (IPP), the precursor of liquid
and hydrogen-transfer to form alkanes [162,164,165]. The heavier fuel: the mevalonic acid (MVA) pathway and the deoxyxylulose-5-
species of the products can be distilled and blended into jet fuel. phosphate (DXP) pathway [172]. The three-carbon compound pyr-
The second route is direct catalytic condensation over multi- uvate derived from glycolysis of glucose is turned into three moles
functional solid-base catalysts [81,166]. There are several con- of acetyl-CoA. The mevalonate pathway employs three moles of
densation reactions occurring: (1) aldol condensation to produce a acetyl-CoA and produces the five-carbon IPP [17]. The DXP pathway
β–hydroxyketone or β–hydroxyaldehyde, (2) dehydration of β– produces IPP via condensing pyruvate and D-glyceraldehyde-3-
hydroxyketone or β–hydroxyaldehyde to produce a conjugated phosphate from glycolysis [17]. The DXP pathway has higher carbon
enone, (3) hydrogenation of the conjugated enone to produce efficiency (83%) than the MVA pathway does (56%) [17]. The ter-
ketone or aldehyde, and (4) removal of hydroxyls by dehydration/ penes, assembled by condensing IPP and its isomer dimethylallyl
hydrogenation or hydrogenolysis to form alkanes [81,166]. The pyrophosphate, represent the candidates of biologically-derived
products from this route are mostly in the jet fuel range. The third fuel [17]. Large terpenes can be cracked to liquid fuel and the
route is to convert the oxygenates from APR to alkanes and alkenes branched olefins can be hydrogenated to isoparaffins [17,171]. Fig. 8
via dehydration and hydrogenation-dehydration reactions. The shows an example of sugar fermentation to hydrocarbons in which
alkenes are oligomerized to produce kerosene with solid phos- the sugar sirup is processed through the MVA and converted into
phoric or zeolite catalysts [167,168]. artemisinic acid, isopentenyl pyrophosphate, and jet/gasoline pre-
To obtain high selectivity to fuels, a catalyst that helps generate cursors. The artemisinic acid is then turned into an anti-malarial
hydrocarbons with low oxygen content and with the appropriate drug, and isopentenyl pyrophosphate is further transformed into
amount of branching, cyclic, and aromatic content is needed [17]. farnesenyl pyrophosphate and C15 isoprenoids, which are the pre-
The catalyst should be able to deal with a wide range of sugars and cursors of diesel and chemicals [170]. The fermentation waste could
Sugars in
Aqueous Phase Juice
Fermentation Separation Purification Hydroprocessing Jet fuel
Evaporation
Fermentation
Waste
Anaerobic
Digestion
Biogas Steam-Methane H2
Reforming
Fig. 8. Direct sugar-to-jet fuel.

Table 6
Production Yields from Various Biomass Feedstocks Using Various Pathways.
Pathway Biomass Intermediate Yield Jet FuelAYield [gal/ Ref.

[GGE/BDT] BDT]/[GGE/BDT]
Alcohol to Jet Ethanol to Jet Dry Mill — — [38, 61, 63, 64, 71, 83, 85, 177,
CornB 77.5 39.6/44.7 178]
Unrefined Sugar 13.9 7.1/8.0
SwitchgrassB 55.9 28.5/32.2
N-butanol to Jet (Dehydrated over a Corn StoverC 120.9 74.1/83.7 [73, 179–185]
Pd/C- K3PO4 catalyst) Corn FiberC 57.2 34.2/38.6
GlucoseC 112.7 69.0/78
Wheat StrawC 112.7 69.0/78
Liquefied Corn StarchC 112.7 69.0/78
SwitchgrassC 101.6 62.3/70.4
Barley StrawC 118.1 72.4/81.8
Sweet Potato SlurryC 53.5 32.8/37.1
Whey PermeateC 120.9 74.1/83.7
N-Butanol to Jet (Oliomerization Corn FiberC 57.2 10.0/11.3 [38, 68, 71, 72, 80, 179–185]
Reaction) GlucoseC 112.7 19.5/22
Wheat StrawC 112.7 19.5/22
Liquefied Corn StarchC 112.7 19.5/22
SwitchgrassC 101.6 17.6/19.9
Corn StoverC 120.9 21.0/23.7
Barley StrawC 118.1 20.5/23.2
Sweet PotatoC 53.5 9.3/10.5
Whey PermeateC 120.9 21.0/23.7
Isobutanol to Jet Dry Mill — — [38, 68, 71, 72, 77, 92, 133, 178,
CornD 163.6 51.9/58.6 181]
Unrefined SugarcaneD 29.4 9.3/10.5
SwitchgrassD 118.4 14.4/16.3
Methanol to Jet Woody BiomassE 79.2 45.4/51.3 [83, 186–189]
Oil to Jet HRJ Vegatable Oil — — [3, 21, 100, 190–199]
Palm SeedF,G (22% Oil) 58.3 41.9/47.3
F,G
Rapeseed (45% Oil) 127.9 75.2/85
SoybeanF,G (18% Oil) 49.8 29.9/33.8
Jatropha SeedF,G (35% Oil) 92.0 59.9/67.7

Camelina SeedF,G (29% Oil) 85.9 47.2/53.3
Camelina SeedF,G (41% Oil) 121.4 66.2/74.8
AlgalF,G (25% Oil) 61.9 44.3/50
Salicornia SeedF,G (28.2% Oil) 61.6 45.0/50.8
CH Soybean (18% Oil) 28.7 7.6H/8.6 [3, 107, 200]

Jatropha Seed (35% Oil) 56.0 8.9H/10.1
Tung Seed (40.4% Oil) 102.1 15.2H/17.2
HDCJ Dry WoodI 93.5 41.1H/46.4 [201–209]
Corn StoverI 71.8 36.4H/41.1
SwitchgrassI 74.8 37.9H/42.8
Sugarcane BagasseI 62.3 31.6H/35.7
Algae 18% Oil ContentI 22.5 11.4H/12.9
Algae 24% Oil ContentI 29.9 15.2H/17.2
Forest Residue LowI 74.8 37.9H/42.8
Forest Residue HighI 81.1 41.1H/46.4
Gas to Jet F-T to Jet Natural Gas — 156.4/176.7 [3, 55, 131, 210–215]
CoalJ — 84.1K/95
HardwoodL — 63.9/72.2
Switchgrass — —
Gas Fermentation Natural GasM,B 306.8 139.5N/157.6 [38, 61, 63, 64, 68, 71, 72, 77,
204.5O/231 133, 143, 145, 146, 177, 178,
P,B
Natural Gas 259.1 117.8N/133.1 181, 216–218]
172.7O/195.1
BiomassB Feedstock/Soft- 65.8 29.9N/33.8
wood From Coskata
43.8O/39.8
HardwoodB 77.3 35.2N/39.8
51.5O/58.2
Biomass FeedstockB 52.7 23.9N/27
35.1O/39.7
Biomass FeedstockB 46.8 21.3N/24.1
31.2O/35.2
Sugar to Jet Catalytic Upgrading Corn StoverQ,R 91.8 52.7/59.5 [162, 219–222]
Sugarcane Bagasse 62.8 49.0/55.4
HardwoodQ,R 75.3 41.7/47.1
SwitchgrassQ,R 81.5 48.1/54.3
Table 6 (continued )
SugarcaneQ,S 65.8 44.5/50.3

Sugar BeetQ,S 54.8 37.1/41.9
Cellulosic MassT,U 26.9 13.8/15.6 [81, 175]
Corn StoverV,R 91.8 21.9/24.7 [162, 223]
Direct Sugar to Jet Corn StoverW,R 91.8 36.9/41.7 [172, 220]
Corn StoverX,Y 56.4 18.5/20.9
Notes:
— Data not available.
A
Unless otherwise stated “Jet Fuel” is defined as C9-C15 n-alkanes.
B
Starting Intermediate: Ethanol.
C
Starting Intermediate: A:B:E (Acetone:Butanol:Ethanol).
D
Starting Intermediate: Ethanol-Isobutanol.
E
Starting Intermediate: Methanol.
F
Uses the decarboxylation pathway.
G
Starting Intermediate: Triglyceride Oil.
H
Jet range based off of boiling point.
I
Starting Intermediate: Liquid Pyrolysis Oil.
J
The average of six notable sources for the production of CTL fuel from coal.
K
Coal to Liquid Fuel (CTL), unknown ranges of gasoline, diesel, and jet.
L
The average of several design cases for hardwood gasification.
M
90% of Carbon Conversion to Syngas.
N
Using Ethanol to Jet Pathway to create Jet Fuel C9-C15 alkanes.
O
Using Isobutanol to Jet Pathway, Jet Fuel C9-C15 alkanes.
P
76% of Carbon Conversion to Syngas.
Q
Catalytic Upgrading Using Virent Pathway.
R
Starting Intermediate: Glucose: Xylose.
S
Starting Intermediate: Sucrose.
T
Catalytic Upgrading Condensation to HMF to Jet.
U
Starting Intermediate: Fructose.
V
Catalytic Upgrading non-fermentation of biomass.
W
Direct Sugar to Jet Mevalonic (MVA) Pathway.
X
Direct Sugar to Jet Deoxysylulose-5-phosphate (DXP) Pathway.
Y
Starting Intermediate: Glucose: Xylose: Fructose.
be optionally processed with anaerobic digestion to reduce the 100

GHG emissions (kgCO2/GJ)
effluent. After purification, through downstream hydro-processing, 90

the jet/gasoline precursors can be turned into bio-jet fuel. 80
70 Upgrading
An engineered E. coli fatty acid pathway has been developed to Process
produce fatty esters, fatty alcohols, and waxes from sugars [17,173]. 60
Through combining the thioesterase-catalyzed hydrolysis of fatty 50
acyl-ACP, with fatty acyl-CoA-synthase-catalyzed reactivation of the 40
30
fatty acid carboxylate group, fatty acyl-CoA was converted from
20
fatty acid metabolism. Fatty esters were produced by applying an
10
acyltransferase with an alcohol-forming pathway; fatty alcohols
0
were produced from fatty acyl-CoAs by expressing fatty acyl-CoA ATJ OTJ GTJ STJ Conv. Jet
reductases; and wax was produced through the fatty alcohol
Fig. 9. GHG emissions of jet fuel from various pathways. ([3,12,14,21,33,43, 55–
pathway [173]. Through the pathway consisting of acyl–acyl carrier
57,92,127,128,199,241–243]). Note: AFor ATJ pathway, the higher and lower end
protein reductase and an aldehyde decarbonylase, the C13–C17 uncertainties represents GHG emissions of n-butanol and ethanol, respectively.
mixtures of alkanes and alkenes, part of the component of jet fuel, B
For OTJ pathway, the higher and lower end uncertainties represents GHG emis-
are produced from these intermediates of fatty acid metabolism sions of rapeseed and palm oils, respectively. CFor the GHG emissions of OTJ and
[171]. This invention, developed by LS9, enables the conversion of GTJ pathways, without land use change is considered. DFor GTJ pathways, switch-
grass is selected as the feedstock; without soil carbon sequestration is considered.
biomass into jet fuels without the need for chemical conversion
technologies such as distillation or hydrogenation.
attention [17]. Separation of decomposed biomass slurries sometimes
Scientists in Berkeley have developed a novel process that
accounts for 50–70% of capital and operating costs at a biorefinery
integrates ABE fermentation and chemical catalysis to selectively
produce jet, diesel, and gasoline products from lignocellulosic and [174]. Decreasing viscosities, increasing fluxes, and avoiding formation
cane sugars [73]. Glyceryl tributyrate has been used to efficiently of precipitants are ways to increase the efficiency of separation at high
separate acetone and n-butanol from ethanol and to remove sev- temperatures [174]. NREL and Virent are currently conducting a pro-
eral inhibitors of fermentation found in acid-pretreated lig- cess economic analysis for Virent's BioForming technology [144]. Four
nocellulosic biomass, such as furfural, p-coumaric acid, and ferulic main process steps, (1) pretreatment/fractionation, (2) hydrogenation,
acid. Acetone and butanol from ABE fermentation are converted (3) APR, and (4) acid catalyzed dehydration/condensations, are con-
into ketone through a condensation reaction over K3PO4 and a sidered to affect the production cost significantly [144]. Additionally,
palladium catalyst. The resulting products, a C11 compound with a researchers from Iowa State University and the University of
ketone in the middle, can be fed into the refinery infrastructure as Wisconsin-Madison conducted a techno-economic study of DMF and
a feedstock to produce renewable jet fuel [73]. HMF production [175]. Based on the process capacity of 300 metric
ton/day of fructose and an operating period of 20 years, the resulting
2.4.2. Economic analysis minimum selling prices for HMF and DMF were estimated to be
When analyzing the process economics of STJ, separation of the $5.03/gal ($6.2/gal or $4.8/GGE on 2011 US dollars) and $7.63/gal
sugar and sugar intermediates from other compounds needs more ($9.4/gal or $9.9/GGE on 2011 US dollars), respectively. The cost of the
copper–ruthenium–carbon catalyst used in the DMF process might 2.4.3. Life-cycle assessment
play an important role in the final production cost. This study pro- The Institute for International Trade Negotiations conducted a
vides a single point on the TEA associated with catalytic upgrading of study of life-cycle GHG emissions of bio-jet fuel produced from
a pure expensive clean sugar to a single product at a small scale. sugarcane sugars based on the Amyris process parameters [43].
Other comparative analysis shows that the production of levulinic The results showed that the life-cycle GHG emissions are around
acid from biomass costs approximately $4.31/GGE [176]. For the DSH 15 gCO2e/MJ, an approximate 82% reduction compared with con-
pathway, the techno-economic analysis is conducted to evaluate the ventional Jet A/A-1 fuels [43]. However, sugarcane could induce
selling price of bio-jet fuel derived from sugarcane, resulting in $7.16/ land use change, which was not considered in the study above. The
gallon ($7.2/gal or $6.3/GGE on 2011 US dollars) for the base case and GHG emissions associated with sugarcane production and trans-
$4.00/gallon ($4.0/gal or $3.5/GGE on 2011 US dollars) with the port, according to the study, are primarily dominated by farm
development of the technology and the market [113]. NREL in support input and the emissions of N2O from the soil, which contribute 32
of the NABC efforts, in collaboration with Virent and Amyris, is also gCO2e/MJ and 45 gCO2e/MJ, respectively [41]. This research helps
conducting process economics studies for a direct sugar to fuel pro- improve the knowledge of the carbon footprint of a renewable
cess [144]. The target is to find the low-cost routes for biomass aviation fuel derived from sugarcane.
hydrolysate streams and low-cost mitigation strategies for fermen-
tation inhibitors that are compatible with the current state of the art.
Future work should consider the catalytic upgrading of biomass-
derived sugars to a slate of fuel components, specifically jet fuel.
Table 7
Lower heating values of the intermediates.
Lower heating value MMBTU/gal Refs.
Gasoline heating value 0.12 [83]

Ethanol heating value 0.08 [83]
Acetone heating value 0.08 [224]
n-butanol heating value 0.10 [95]
Isobutanol heating value 0.10 [92]
Methanol heating value 0.06 [224]
Palm oil heating value 0.12 [225]
Rapeseed oil heating value 0.13 [225]
Soybean oil heating value 0.13 [225]
Jatropha oil heating value 0.12 [226]
Camelina oil heating value 0.14 [227]
Algal oil heating value 0.12 [228]
Salicornia oil heating value 0.12 [3]
Tung oil heating value 0.12 [229]
Pyrolysis oil heating value 0.07 [230]
Glucose heating value 0.09 [231]
Xylose heating value 0.08 [83]
Sucrose heating value 0.09 [83]
Fructose heating value 0.09 [232]
Jet fuel heating value 0.13 [20]
Table 8
Production costs of jet fuel from various pathways.
Category Pathways Intermediate Interm. CostA($/gal) [($/GGE)] Final jet fuel cost ($/gal) Refs.
[(($/GGE)]
ATJ Ethanol to Jet EthanolB 2.5–2.6 (3.8–4.0) Not Available [83,85]

n-Butanol to Jet N-butanolB 3.7 (4.1) [92]
Iso-Butanol to Jet IsobutanolB 3.6 (4.0) [92]
Methanol to Jet Methanol 1.5 (3.0) [233]
OTJ HRJ Bio-OilC 4.3–8.5 (4.0–8.2) 4.3–9.2 (4.0–8.5) [100,112,113, 234]
CH Bio-OilD 1.7–4.3 (1.6–3.9) Not available [113,235]
HDCJ Pyrolysis Oil 1.0–1.5 (1.8–2.6) [118,201,236]
GTJ F–T to Jet (BTL) Syngas derived diesel 6.4–6.7 (6.0–6.2) Not available [56]
Gas Fermentation Ethanol from syngas 2.8–3.1 (4.3–4.8) [237,238]
fermentation
STJ Catalytic Upgrading of Sugar to HMF and DMF 6.2–9.4 (4.8–9.9) Not available [175]
Jet
E F
DSH Hydrocarbons 4.6 (4.4) 7.2 (6.6) [113,239]
Note:
A
The cost numbers are inflated to 2011 U.S. dollars using the industrial inorganic Chemical Index for SRI Consulting [240].
B
The alcohol intermediates are produced from cellulosic biomass.
C
Soybean and algal oils are selected for the lower and higher end bio-oils.
D
Jatropha and soybean oils are selected for the lower and higher end bio-oils.
E
Pentadecane.
F
Target value of the product.
3. Summary of all bio-jet fuel production pathways pathway has higher intermediate cost due to the early stage of
technology development and the HDCJ (one of the OTJ technolo-
Production yields, including intermediate and jet fuel yields, gies) has a lower intermediate cost because the selling price of
production costs and GHG emissions for the conversion technol- pyrolysis oil is reported to be very low in the literature. As seen in
ogies reviewed in this work are summarized in Table 6 for yields the table, only HRJ and DSH processes have some reported num-
(details explained in Supplementary materials), Table 8 for pro- bers for jet fuel blendstock production cost. HRJ fuel can be pro-
duction cost and Fig. 9 for GHG emission. duced for $4.3–$9.2/gal (equivalent to $3.8–$8.1/GGE in 2011 US
Feedstock is the most important parameter when considering dollars) [112,113], which is expected to decrease once the tech-
the commercial feasibility of bio-jet fuel production. Agricultural nology can be further improved. STJ fuel through DSH process was
and forest feedstocks as well as algal biomass are major feedstocks
evaluated to be $7.2/gal (equivalent to $6.3/GGE in 2011 US dol-
for producing alcohol fuels, able to provide large amounts of
lars) [113] and this can be reduced when the technology and
alcohols for converting into jet fuel. Plant oils, animal fats, waste
market are further developed. As seen in Table 8, the production
cooking oils, algal oil, and pyrolysis oils are the predominant
costs from intermediates to final products increase slightly for HRJ
feedstocks for oil-related conversion processes such as HRJ, CH,
process and increase significantly for DSH process. The credits
and HDCJ. Agricultural and forest residues can serve as major
feedstocks for producing syngas or biogas. There is an abundance obtained from the co-products in the HRJ process lowers the cost
of sources of sugars (lignocellulosic or grain sugar) to ferment or of the upgrading processes from intermediates to jet fuel and
synthesize to jet fuels via the STJ process. From the variable benefits the entire conversion process. The cost estimates for the
feedstocks, the sum of all the intermediates per dry ton biomass other upgrading processes are not available and require future
for each pathway is demonstrated in Table 6, using energy basis, investigation.
i.e., GGE per dry ton biomass (BDT). Based on these literature data, The GHG emissions of jet fuels from the reviewed pathways are
ethanol from syngas fermentation has the highest reported yield compared in Fig. 9, using gCO2/MJ basis. The GHG emission of ATJ
(306.8 GGE/BDT) due to the 90% carbon conversion. On the other pathway is currently not available, so only the data for process to
hand, algal oil has relatively low yield (22.5–29.9 GGE/BDT) make alcohols is reported here. A potential penalty, expected for
because of the low oil content reported. Table 6 not only reports upgrading alcohols to jet fuels, is roughly estimated based on the
the yields of intermediates, but also summarizes the jet fuel yield environmental impact of the refinery processes, including dehy-
after upgrading intermediates to finished products. The jet fuel dration, oligomerization and hydro-treating. It is presented as a
yields demonstrate the jet fuel production from literature reported dashed line box, shown in Fig. 9. GHG emissions primarily come
data or several assumptions for the calculating intermediates to jet from the farm input, land use change, and biorefinery processes.
productions. Detailed analyses can be found in the Supplementary The GHG emissions from HRJ pathways range from 16% to 800% of
materials. For example, the jet fuel yield from palm seed results those from conventional jet fuel depending on the feedstocks as
from the calculation of the product yield from palm oil through well as coproducts [3]. For F–T BTL, the life-cycle GHG emissions
deoxygenation and hydro-treating processes. The jet fuel yield are 2–12.2 gCO2e/MJ from the use of corn stover, forest residue,
from corn stover derived isobutanol comes from the estimation of
and switchgrass, approximately 2% to 14% of those of conven-
the product yield through dehydration, oligomerization and
tional jet fuel [3]. The STJ process through the direct sugar-to-
hydro-treating processes. For consistent purpose, the units are
hydrocarbons process contributes 15 gCO2e/MJ GHG emissions
normalized from volumetric basis (gallon) to energy basis (GGE)
[43], about an 82% reduction from conventional jet fuel. Appar-
by dividing the lower heating value (LHV) of the products (Table 7)
ently the GHG emissions are reduced when using the bio-jet fuel
by the LHV of gasoline. The yield values provide a general idea of
and STJ pathway has the highest reduction.
the pathway/feedstock that most final products can be obtained
from. The HRJ process with palm seed as the feedstock has the
highest conversion from intermediate to final products (67.8%) due
to the high carbon conversion. The CH process with jatropha seed 4. Conclusion
as the feedstock has the lowest intermediate-to-jet conversion
(8.0%) because most of the carbon distributes out of the jet The issues of jet fuel cost, energy supply, energy security, and
fuel pool. aviation emissions have driven the development of aircraft and
The maturity of a conversion process controls the process engine technologies throughout the history of flight. Sustainable
economics. FT-to-jet fuel (as an example of GTJ) has first been biomass-derived bio-jet fuel represents a major opportunity to
proved by ASTM as a promising technology. Product selection, resolve these issues. Many conversion technologies that turn bio-
which leads to the yield of jet fuel, is strongly dependent upon the mass into jet fuels have been developed, and some of them are
operating temperature, partial pressure of syngas, and the applied
commercially viable. In this review, most of the current technol-
catalyst. The HRJ process is also an approved process, representing
ogies have been classified into four major categories: ATJ, OTJ, GTJ,
one of the OTJ technologies. The use of hydrogen and selection of a
and STJ. Each category has been described and reviewed with
catalyst contribute to a significant part of the production costs. ATJ
regard to feedstocks, upgrading processes, production costs when
and STJ processes are at the R&D stage, and may be the next
available, sustainability, and commercial readiness.
processes being approved. The jet fuel product yield, which
Sustainable bio-jet fuel not only brings environmental benefits
depends on the catalyst or enzyme used, has attracted more and
more interest and driven more research efforts. for aviation, but helps the development of a new industry. There is
The production cost for intermediates and final jet fuel from still a considerable way to proceed before renewable aviation fuels
each pathway are summarized in Table 8. If the feedstock costs, become economically viable. Through the combination of exper-
financial assumptions, and analysis methodologies are not nor- tize of the aviation industry, government, biofuel companies,
malized, the cost numbers cannot be compared consistently. Both agriculture organizations, and academic systems, along with
volumetric basis and energy basis units are presented in the table encouragement from regional banks, progress is being made
for consistency. All the cost numbers are adjusted to 2011 US toward an optimal process that utilizes the most effective feed-
dollars. Both the feedstock cost and conversion technology con- stock sources, is amenable with current infrastructure, and pro-
tribute a significant portion of each production cost. The STJ duces renewable aviation fuels.
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Renewable and Sustainable Energy Reviews 53 (2016) 801–822

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

Bio-jet fuel conversion technologies

1. Introduction of feedstock; (2) process design; (3) conversion efﬁciency or pro-

Jet A-1 JP-8

(Note: MIL-DTL-83133E is the standard speciﬁcally for JP-8 fuel).

Ethanol C4-C8 Olefins

Ethanol Ethylene α-olefins

>C16 Olefins C9-C16 Olefins

Diesel Blendstock Jet Blendstock

C8, C12, C16, C20,

Distillation C12H26, C16H34

C8 Olefins Dimerizationof C16H32

Category Pathways Companies U.S. or international Airline companies/manufacturers

Residue Residue Post By Products

Light Gases Naphtha Jet fuel Diesel

Fig. 2. Hydro-processed renewable jet (HRJ) process.

Triglycerides Catalytic Cyclization/ Catalyst/Non-Catalyst

Fig. 3. Catalytic hydro-thermolysis to jet fuel [107,108].

Fig. 4. Pyrolysis-to-jet process [52].

2.1.3. Life-cycle assessment A representative process ﬂow diagram is shown in Fig. 2.

Fig. 5. FT-BTL process [133].

Lanza Tech Technology

Jet Fuel Swedish Biofuels Technology

Fig. 6. Gas fermentation to bio-jet fuel.

Cracking Alkanes Oxygenates

Fig. 8. Direct sugar-to-jet fuel.

Pathway Biomass Intermediate Yield Jet FuelAYield [gal/ Ref.

Palm SeedF,G (22% Oil) 58.3 41.9/47.3

SoybeanF,G (18% Oil) 49.8 29.9/33.8

Jatropha SeedF,G (35% Oil) 92.0 59.9/67.7

CH Soybean (18% Oil) 28.7 7.6H/8.6 [3, 107, 200]

SugarcaneQ,S 65.8 44.5/50.3

be optionally processed with anaerobic digestion to reduce the 100

efﬂuent. After puriﬁcation, through downstream hydro-processing, 90

Lower heating value MMBTU/gal Refs.

Gasoline heating value 0.12 [83]

ATJ Ethanol to Jet EthanolB 2.5–2.6 (3.8–4.0) Not Available [83,85]

Acknowledgment [30] UOP LLC. Green Jet Fuel; 2010.

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