Center for Advancing Research

in Transportation Emissions,
Energy, and Health
A USDOT University Transportation Center

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Lecture #57: Alternative and Emerging Fuels

Georgios Karavalakis, Ph.D.

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 Introduction
• Fuel is a material that carries energy in chemical form.
• When the fuel is reacted (e.g., through combustion), most of the energy is released as heat.
o Though sometimes e.g., in fuel cells or flow batteries it can be released as electric power

Fuels suitable for fast chemical reaction have to be used in internal combustion engines:
• Hydrocarbons fuels derived from the crude petroleum by proper refining process such as
thermal and catalytic cracking method, polymerization, alkylation, isomerization, reforming
and blending.
• Alternative fuels such as
o Alcohols (methanol, ethanol)
o Biodiesel
o Natural gas (methane)
o LPG (propane, butane)
o Hydrogen
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 What Properties Do We Desire in a Fuel?
• Prefer not to carry more than one reactant on vehicle; take second reactant from the
atmosphere.
o Air is 78% N2, 21% O2, 1% Ar. N2 is poor reactant (N≡N bond too strong), Ar is unreactive,
leaves O2.
• Fuel should have highly exothermic reaction with O2
• Fuel should be abundant in nature or easy to make. And cheap.
o We need millions of tons every day.
• Fuel itself should be environmentally benign and renewable
• Prefer to dump exhaust so we don’t have to carry its weight. Exhaust should be
environmentally benign (even if we carry it: we are making Mtons/day!)
• Both fuel & exhaust must be liquids or gases: no solids handling!

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 Alternative Fuels - Liquids
Conventional and Cellulosic Ethanol
• Typically made from corn in U.S. or sugarcane in Brazil
o Produced by fermenting almost any material that contains starch
• Domestically produced, renewable, nontoxic, biodegradable, sulfur and
aromatics free
• Blended into conventional gasoline at 10% rate (E10)
• Flexible fuel vehicles (FFVs) can operate up to 85% of ethanol (E85)
• Higher octane number than gasoline, but lower heating value
• Cellulosic ethanol is made from waste, agricultural residue or other non-food
materials
o Technology is relative new, with few plants operational in U.S.
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 Alternative Fuels - Liquids
Conventional and Cellulosic Ethanol
• Studies have shown that ethanol combustion results in lower emissions of CO,
THC, and soot, as well as achieves moderate reductions in NOx and GHG
emissions
• Although CO2 is released during ethanol production and combustion, it is
recaptured as a nutrient to the crops that are used in its production, thus
ethanol results in lower increases to the carbon cycle
• CE-CERT’s researchers have shown that high levels of ethanol will reduce the
formation of secondary organic aerosol from gasoline vehicles [Roth et al.,
2020]
• Studies have also shown that ethanol blending shows no toxic effects in
particulate matter (PM) emissions [Roth et al., 2017; Bisig et al., 2016]
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 Alternative Fuels - Liquids
Methanol
• Methanol (methyl alcohol) produced mostly from natural gas, but it can be produced from renewable
sources.
• Good combustion characteristics
o High octane number (ON=99)
o Cleaner exhaust: lower CO and HC emissions
• Problems
o Lower heating value than gasoline (about half)
o Toxic and corrosive
o Cold-start difficulties
• Overall:
o Not an attractive intermediate alternative because:
 Needs expensive retrofit of existing engine
o Not good log term prospect; not efficient use of energy source 7
 Alternative Fuels - Liquids
Butanol
• A four carbon alcohol (C4H9OH), colorless, neutral liquid of medium volatility
with a characteristic banana-like odor.
• Traditionally petrochemically derived - generally used to make other chemicals,
or used as a solvent or an ingredient in formulated products such as cosmetics.
• Butanol exists in four (4) different isomers:
• Attractive biofuel that more closely
resembles the properties of gasoline
• High water tolerance, higher energy
content, and less corrosive compared to
ethanol
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 Alternative Fuels - Liquids
Biodiesel
• Biodiesel or fatty acid methyl esters (FAME) is considered the biofuel of choice for
compression ignition (diesel) engines
• Biodiesel is produced via the transesterification reaction of vegetable oils, waste
cooking oils, and animal fats and methanol with the use of an acidic or alkaline
catalyst.
• Biodiesel is used in Europe up to 7% with diesel and in the U.S. up to 20%.
• Biodiesel has better lubricity properties and a higher cetane number (ignition
quality) than diesel fuel
• Nontoxic, biodegradable, aromatics and sulfur free
• Biodiesel offers reductions in CO, THC, and soot emissions, moderate reductions in
CO2 emissions, and increases in NOx emissions [Karavalakis et al., 2017; 2011]
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 Alternative Fuels - Liquids
Renewable Diesel or Hydrogenated Vegetable Oil (HVO)
• HVO is made from biomass sources (vegetable oils, animal fats, agricultural
waste) via hydrotreating refining process
• Commercially available with a fast growth in global scale
• HVO is a highly paraffinic (saturated) fuel, and free of aromatic hydrocarbons
and sulfur
• HVO has an exceptional cetane number (greater than 65 – diesel spec limit is
40)
• Compatible with existing distribution systems and engines
• Offers carbon emissions reductions, THC, NOx, and soot emission reductions
[Karavalakis et al., 2016]
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 Alternative Fuels – Non-Liquids
Fossil Natural Gas
• Produced domestically and often is less expensive than gasoline
• Natural gas is available through established distribution networks
• Methane is the major part of natural gas – clean burning fuel
• Other hydrocarbons also present (i.e., ethane, propane, isobutane, etc.), CO2, nitrogen,
and hydrogen sulfide
• It has to be stored in a compressed state (CNG) or in a liquefied state (LNG)
o CNG (natural gas concentrated by pressure): used in light- and heavy-duty applications
o LNG (natural gas concentrated by extremely cold temperatures): used only in heavy-duty
applications
• Elevated methane emissions (methane leakage) – methane is a potent GHG
• High octane rating, nontoxic, lower ozone-forming emissions than gasoline 11
 Alternative Fuels – Non-Liquids
Renewable Natural Gas (RNG)
• Produced by anaerobic digestion of organic material, like food waste, green
waste or animal manure
o Sources of RNG include: landfills, wastewater treatment plants, livestock facilities, and
commercial and residential food waste
• For energy purposes, RNG is chemically identical to pipeline quality natural gas
o RNG uses the same infrastructure as fossil natural gas (pipelines, refueling stations, and
vehicle technology)
• Purification from contaminants (i.e., CO2, siloxanes, etc.) is needed to meet
pipeline standards
• Lower local pollutant emissions and lower GHG emissions – combat climate
change
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 Alternative Fuels – Non-Liquids
Hydrogen
• Excellent fuel for combustion engines or fuel cells – commonly produced from reforming
fossil or renewable natural gas with steam
o Can be produced from electricity and water, gasification of coal
• Strictly, hydrogen is not a ‘fuel’, but an energy storage medium (a means of transferring
energy from an energy source to an energy user)
• Need to generate energy from sources (coal, natural gas, etc.) to:
o Power a mechanism like electrolysis or natural gas reforming
o Extract the hydrogen from a source material like water or natural gas
• Stored in tanks (cryogenic, high pressure cylinders) – bulky and expensive
• Very low calorific value
• Hydrogen is used in fuel cell vehicles and also as a fuel mixture with natural gas in ICEs
• No tailpipe pollutants and GHG emissions
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 Alternative Fuels – Non-Liquids
Electricity
• Electric drive vehicles (EDVs) categorized into three groups: hybrid electric
vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and battery electric
vehicles (BEVs)
• All EDVs utilize electric motors and energy storage systems
o HEVs : utilize internal combustion engines (ICEs) along with an electric motor; use
another fuel to power the ICE (gasoline or diesel); better fuel economy than
conventional vehicles; lower emissions
o PHEVs: Use batteries to power an electric motor; use another fuel to power the ICE
(gasoline or diesel); batteries are charged when plugged in; low emissions
o BEVs: use a battery to store the electrical energy that powers the motor; do not use
other fuels (no ICE); batteries are charged by plugging the vehicle into an electric power
source; limited battery range; produce no direct exhaust emissions
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Discussion
• Ethanol is a promising biofuel that will offer lower exhaust emissions,
including mobile source air toxics (benzene, toluene, 1,3-butadiene,
etc.) and GHG
o Ethanol is precursor for acetaldehyde, which is considered a possibly carcinogen
to humans (Group 2B) by the International Agency for Research on Cancer
o Low levels of ethanol blends may increase particulate emissions because of
ethanol’s higher heat of vaporization, which will cause a charge cooling effect in
the cylinder [Yang et al., 2019]
• Butanol use will result in lower gaseous and particulate emissions
compared to gasoline
o Butanol fuels will likely result in butyraldehyde emission increases.
Butyraldehyde posses similar reactivity and mutagenicity to acetaldehyde

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Discussion
• The use of biodiesel in modern technology diesel engines will offer reductions in
most harmful pollutants, as well as GHG emissions
o NOx emissions will show moderate increases with biodiesel compared to petroleum diesel due
to the presence of oxygen in biodiesel
• Renewable diesel or HVO will offer similar reductions in exhaust emissions and GHG.
o Due to the high cetane number of HVO, NOx emissions will be lower compared to diesel fuel
• Current natural gas engines offer important emissions reductions
o Ultra-low NOx technology drives heavy-duty vehicle market with significant reductions in NOx
and GHG emissions
o Elevated ammonia (NH3) emissions from natural gas engines; Ammonia is a precursor of
secondary inorganic PM emissions
o Concern about ultrafine particles of very small sizes that will likely adversely impact human
health
o Gas composition may affect emissions; the increasingly use of RNG in heavy-duty applications
could be a concern due to variations in gas composition
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Discussion
• Hydrogen-fuel cell vehicles can help achieve reductions of GHG emissions in
the transportation sector and contribute to the diversification of
transportation energy sources to reduce petroleum consumption and
promote U.S. energy security
o Challenges include hydrogen infrastructure cost & reliability, fuel cell durability &
reliability
• EDVs will offer fewer emissions – effects of air pollution and climate change
are lessened
o HEVs and PHEVs have advantages over BEVs because consumers are already
comfortable with gasoline or diesel fueled vehicles
o HEVs and PHEVs may have elevated ultrafine particle emissions when the electric
motor transitions to the ICE, especially in urban and heavily populated areas
o BEVs have losses related to charging, which is ~90% efficient, and battery leakage
(batteries lose their charge over time)
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Research Gaps and Future Directions
• Better understand the effects of liquid biofuels on ultrafine particle
emissions from current and future engine technologies
• Promote near-zero emission natural gas engines
• Development of natural gas-hybrid vehicles
• Better understand the emissions impacts from EDVs under real-world
conditions

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Take-Home Messages
• Liquid biofuels will play a major role in powering the transportation
sector for the foreseeable future
o Liquid fuels are considered energy dense, allowing vehicles to be driven long
distances before refuelling
o Ethanol, biodiesel, and HVO will be the biofuels of choice for gasoline and diesel
engines
• Near-zero natural gas engines could play a major role in heavy-duty
applications, especially for goods movement and ports activities
• The market share of EDVs will see a significant growth in the next
decade
o PHEVs will likely dominate the light-duty vehicle market
o BEVs have serious challenges: their cost and driving range
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List of Abbreviations
• Particulate Matter (PM); volatile organic compounds (VOCs);
oxides of nitrogen (NOx); carbon monoxide (CO); carbon
dioxide (CO2); total hydrocarbons (THC); greenhouse gas
(GHG); fatty acid methyl esters (FAME); Hydrogenated
Vegetable Oil (HVO); compressed natural gas (CNG); liquified
natural gas (LNG); renewable natural gas (RNG); internal
combustion engines (ICEs); electric drive vehicles (EDVs);
hybrid electric vehicles (HEVs); plug-in hybrid electric
vehicles (PHEVs); battery electric vehicles (BEVs); ammonia
(NH3)

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References
Bisig C., et al., 2016. Hazard assessment of exhausts from gasoline-ethanol fuel blends using a 3D human lung
model. Environ. Res., 151, 789-796.
Karavalakis G., et al. , 2017. Impact of Biodiesel on Regulated and Unregulated Emissions, and Redox and
Proinflammatory Properties of PM Emitted from Heavy-Duty Vehicles. Science of the Total Environment, 584-
585, 1230-1238.
Karavalakis G., et al., 2016. Emissions and Fuel Economy Evaluation from Two Current Technology Heavy-Duty
Trucks Operated on HVO and FAME Blends. SAE Int. J. Fuels Lubr., 9(1), 177-190, doi:10.4271/2016-01-0876.
Karavalakis G., et al., 2011. Biodiesel emissions profile in modern diesel vehicles. Part 2: Effect of biodiesel
origin on carbonyl, PAH, nitro-PAH and oxy-PAH emissions. Science of the Total Environment, 409(4), 738-747.
Roth P., et al., 2020. Intermediate and high ethanol blends reduce secondary organic aerosol formation from
gasoline direct injection vehicles. Atmospheric Environment, 220, 117064.
Roth M., et al., 2017. Effects of gasoline and ethanol-gasoline exhaust exposure on human bronchial epithelial
and natural killer cells in vitro. Toxicology in Vitro, 45, 101-110.
Yang J., et al., 2019. Impacts of Gasoline Aromatic and Ethanol Levels on the Emissions from GDI Vehicles: Part
2. Influence on Particulate Matter, Black Carbon, and Nanoparticle Emissions. Fuel, 252, 812-820.

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 Reading List
• Kakaee et al. The influence of fuel composition on the combustion and emission characteristics of natural gas fueled engines. Renewable and Sustainable Energy Reviews 2014, 38, 64-
78.
• Korakianitis et al. Natural-gas fueled spark-ignition (SI) and compression-ignition (CI) engine performance and emissions. Progress in Energy and Combustion Science 2011, 37, 89-112.
• Hartikka et al. Technical Performance of HVO (Hydrotreated Vegetable Oil) in Diesel Engines. SAE Technical Paper 2012-01-1585, 2012
• Suarez-Bertoa et al. Impact of HVO blends on modern diesel passenger cars emissions during real world operation. Fuel 2019, 235, 1427-1435.
• Ashraful et al. Production and comparison of fuel properties, engine performance, and emission characteristics of biodiesel from various non-edible vegetable oils: A review. Energy
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• Sun et al. Oxides of nitrogen emissions from biodiesel-fuelled diesel engines. Progress in Energy and Combustion Science 2010, 36, 677-695.
• Karavalakis and Stournas. Impact of Antioxidant Additives on the Oxidation Stability of Diesel/Biodiesel Blends. Energy and Fuels 2010, 24, 3682-3686.
• Karavalakis et al. Evaluating the regulated emissions, air toxics, ultrafine particles, and black carbon from SI-PFI and SI-DI vehicles operating on different ethanol and iso-butanol blends. Fuel
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• Cardona and Sanchez. Fuel ethanol production: Process design trends and integration opportunities. Bioresource Technology 2007, 98, 2415-2457.
• Karavalakis et al., Assessing the Impacts of Ethanol and Isobutanol on Gaseous and Particulate Emissions from Flexible Fuel Vehicles. Environ. Sci. Technol. 2014, 48, 14016-14024.
• Marchetti et al. Possible methods for biodiesel production. Renewable and Sustainable Energy Reviews 2007, 11, 1300-1311.
• Grunditz and Thiringer. Performance Analysis of Current BEVs Based on a Comprehensive Review of Specifications. IEEE Transactions on Transportation Electrification 2016, 2, 270-289.
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• Requia et al. Carbon dioxide emissions of plug-in hybrid electric vehicles: A life-cycle analysis in eight Canadian cities. Renewable and Sustainable Energy Reviews 2017, 78, 1390-1396.
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• Sobrino et al. Critical analysis on hydrogen as an alternative to fossil fuels and biofuels for vehicles in Europe. Renewable and Sustainable Energy Reviews 2010, 14, 772-780.
• Contestabile et al. Battery electric vehicles, hydrogen fuel cells and biofuels. Which will be the winner? Energy and Environmental Science 2011, 4, 3754-3772.

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