Kul-14.

4700
Transport Biofuels, Combustion
and Emission Control
Lecture 7: Alternative fuel basics
4.11.2015 Aki Tilli
LEARNING OBJECTIVES:
After this lecture, you should be able to...
• ...write down, what is meant by the terms ”biofuel”, ”biodiesel”,
”alternative fuel”, ”renewable fuel” and ”renewable diesel”
• ...list the most important alternative fuels and
• …describe and compare their chemical and physical characteristics
• …list the some of the characteristics’ effects on engine operation
• ...list the feedstocks for different alternative fuels
• ...compare and list the pros and cons of the use, production and
environmental impacts of different fuels
Terms...
• Biofuel?
Terms...
• Biofuel?
– Fuel, whose feedstocks are (short carbon cycle) organic materials
• Renewable fuel?
Terms...
• Biofuel?
– Fuel, whose feedstocks are (short carbon cycle) organic materials
• Renewable fuel?
– Larger category!
– A fuel is renewable, if its energy source is replaced by natural
processes at a rate comparable or faster than its rate of
consumption by humans
• For instance, hydrogen
from water, if the energy
to produce the hydrogen
is from a renewable
source
• Alternative fuel?
Terms...
• Alternative fuel?
– A fuel seen as an alternative for traditionally produced (fossil) fuels
– Not necessarily renewable!
• Biodiesel?
Terms...
• Alternative fuel?
– A fuel seen as an alternative for traditionally produced (fossil) fuels
– Not necessarily renewable!
• Biodiesel?
– Defined by legislation:
FAME!!!
– Controversy in literature
– For more developed diesels:
bio-based diesel,
renewable diesel,
green diesel
(another controversy...)
Alternatives to fossil
gasoline (in SI-engines)?
(Bio)Ethanol (C2H5OH) added to gasoline
• Almost all the world’s grain ethanol used as gasoline additive
• EN228: maximum ethanol 10% (E10)
– 10 % => possible VERY slight consumption increase
(depends on engine and its parameters)
• 10 - 25 % => changes needed (seals, tanks...)
• E85 = max. 85 % ethanol
– gasoline needed for cold starts (25% in very cold)
• FFV Differences:
– tanks, hoses, seals, nozzles, control, valve sockets
– oil change ~twice as often
– E85: ~40 % greater fuel consumption
• Ethanol must be 99,7 % pure!

Source: VTT
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 Ethanol
Traditional Source: Castle Rock Renewable Fuels
fermentation
process
• Uses
foodstuffs
(sugar) to
produce fuel
=> food
price, land
use problems
• In many
cases
inefficient in
decreasing
GHG –
emissions!
Ethanol
Cellulosic ethanol
• From cellulose into
fermentable sugars via heat
and/or chemicals (...like
sulfuric acid) and/or enzymes

• ...or via gasification and

synthesis.

• production emerging, tech:

development stage
• Still high investment,
operation costs (enzymes
etc.)
 Ethanol
• Cultivation cycle emissions => inefficient in decreasing GHG!
– Fertilizer industry emissions; carbon dioxide (CO2 ), nitrous oxide (N2O)
– Cultivation CO2, N2O, grain drying energy…
• VTT, MTT 2006: negative grain ethanol GHG balance
– Presumptions + boundary conditions = huge impact on LCA results!
• Reductions in CO, HC, PM,
NOx and aromatics (vs. fossil)
• Increase in acetaldehyde,
Source: US Environmental
evaporative emissions, Protection Agency

cold start emissions

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Butanol
• Commonly produced using fossil fuels
• Biobutanol production emerging
• Fermentation, same feedstocks as ethanol—corn etc.
• Can also be produced from cellulosic raw materials.
• Energy density only 10%–20% lower than gasoline.
• Lower vapor pressure => lower evaporative emissions.
• Butanol is being studied, less (of the same) problems in
gasoline engines than ethanol (up to 15%-vol)
• Production entirely with solar energy and nutrients, from
algae? (Current yield is very low…)
 Methanol
• Synthesis gas => reactor+catalyst => methanol+water
• Many feedstocks, natural gas the most economical.
• Low production costs (vs. other alternative fuels)
• Low flammability (vs. gasoline), toxic,corrosive (eg.
aluminium)
• High heat of
vaporization
• Now not preferred as
gasoline component
• Energy carrier?
• Fuel cells?
Liquid gasoline alternative properties
 Biogas and natural gas
• Mainly methane: in end use, chemically the same!
– colourless, non-toxic, weight ~ half of air
• Need to be cleaned before use in transport
– CO2 N2, water, oil, mud, CO2 , H2S, mercury…
,

Raw biogas Raw natural gas Dry (purified) gas

Gas composition % (vol.) Methane 50-75 70…98 90…98
Higher alkanes ~0 0-20 0…3
Carbon dioxide 25-50 1…8 0…0,5
Nitrogen 0-30 1…5 0…1,5
Hydrogen sulphide 0-5 0-5 ~0
Properties Lower Heating value (MJ/kg) ~35 30…50 ~50
Density (kg/Nm^3) ~1,15...1,3 0,73...1,1 0,73

• Ignites well with spark => Mainly in Otto engines

– logistics, fuel injection differences!
• Dual-fuel: diesel –gas engine, diesel fuel ignition
– energy mainly (cars 90%, ships 99%) from gas
• Performance can be enhanced by adding hydrogen.

16
 Biogas & Natural gas
• Biogas: Life cycle GHG ~ the best option available
– production may in some cases lessen GHG in atmosphere!

17
 Biogas & Natural gas: local emissions
• Very low PM emissions (vs. diesel vehicles)
• NOx emissions depend on technology (very low with
stoichiometric combustion and 3-way-Cat)
• Unregulated emissions extremely low; methane slip problem

OECD/IEA 2010 The contribution of natural gas

18 vehicles to sustainable transport
Biogas production
– Sewage treatment sludges, landfill gas, agricultural (easily decomposed)
biomasses, food industry byproducts.
– Biogas reactor: anaerobic (fermentation):

Pfeifer, B.
2008.
Basics of
the biogas
process.
International
training
course 1519
September
2008.

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 CNG, LNG, LPG
• CNG: compressed natural gas
– compressed to < 1% of the volume
– store and distribute p = 200–248 bar
• LNG: liquefied natural gas
– ~1/600 vol, low p (atm), ~ −162 °C.
– The reduction in volume:
• cost efficient in long distance transport.
• specially designed vessels and tankers.
• LPG: liquefied petroleum gas
– propane, butane, or both from refining
crude oil or oil/gas fields
– Gaseous in atmospheric T and p;
• vapour pressures: butane 2.1 bar,
propane 8,1 bar at 20 °
• LPG is heavier than air

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Alternatives to fossil
diesel (in CI-engines)?
 Renewable diesel fuels
Term ”biodiesel” in legislation:
”traditional” fatty acid ester diesels
• FAME = fatty acid methyl ester
Synthetic diesel: paraffinic hydrocarbons
• Produced from any carbon-based combustable
matter
• Fischer-Tropsch (FT) –diesel
– Biomass-to-liquids BTL
– Gas-to-liquids GTL
– Coal-to-liquids CTL
Hydrotreated vegetable oil (HVO)
• Feedstocks like FAME
• End-product like synthetic diesel
DME
• Different fuel, from methanol or FT-synthesis

* Place your footnotes / notes here

22
Trad biodiesel = FAME
–Thermodynamically ~ trad. diesel
–Non-toxic and biodegradable
–Improves lubricity when
blended with other diesel fuels
–High density, viscosity, low compressibility
⇒ Faster and bigger p-changes, higher max p in fuel
injection system, faster start of injection
⇒ Bigger droplets, narrower opening angle, longer
penetration, decreased mixing in fuel sprays
–Chemical properties: as such problematic for fuel injection
systems, may require material changes
 Trad biodiesel = FAME
–Less emissions than
with regular diesel
• particulate matter (PM), HC, CO;
• oxygen content important!
Source: US EPA
– ...but
• NOx –increase in most cases
• in engines: cold property problems, oil dilution, rubber part brittlement,
corrosion, carbon deposits
• LCA’s: no lower CO2 always
• oil plant cultivation vs.
food production
• storage problems
(biodegradable, water...)
• EU: max. 7% in any diesel
Trad biodiesel = FAME

• Production: simple and

easy process
Hydrotreated vegetable oil: HVO

– Neste oil: NEXBTL

• ”As an anwer to the
demand for high
quality renewable
diesel produced at
refinery volumes”
• Production
integrated with a
trad. oil refinery =>
hydrogen, heat,
infrastructure
 Hydrotreated vegetable oil: HVO
– T, p control =>
chain length,
isomerization
=> properties
• Catalysts e.g.
NiMo/Al2 O3 ,
CoMo/ Al2 O3
Hydrotreated vegetable oil: HVO
– Lower density, more compressible => injection later (in older engines)
– HC chain length and branching (= cold properties) adjustable (process T
ja p => isomerization)
– Chemistry: combustion, ignition easier => Less PM; Lower adiabatic
flame T = >lower NOx
– Paraffinic HC => high CN => possibilities to decrease NOx with
technologies lowering T and worse combustion conditions (EGR, Miller)
– lower density, viscosity, faster vaporization => increased spray angle,
decreased penetration,
smaller droplets
⇒ good mixing, no wall
interactions => PM, NO,
HC –decrease
– Low lubricity => need of
additives (as usual)
 Hydrotreated vegetable oil: HVO
– LCA’s (according to Neste Oil): CO –emissions -33%...-90%
2

• indirect land-use changes (deforestration) hard to calculate, not taken into

account!
• palm oil => deforestration? => ??
– Feedstocks are oils; competition with food industry;
• however, wider feedstock possibilities (good quality fuel) than with FAME
– Emission studies (VTT, Scania):
• standard high –duty engine, no optimization for new properties!

regulated not regulated

• NOx - 0 ... - 20 % • Aldehydes - 40 ... - 45 %
• Particles - 17 ... - 30 % • Benzene - 40 ... - 45 %
• CO - 45 ... - 55 % • PAH less
• HC - 45 ... -55 % • Mutagens less
Fischer-Tropsch (FT) -diesel
– Biomass to liquids (BTL), Gas to liduids (GTL), Coal to Liquids (CTL)
= same end-product as HVO, same properties
– raw material gasification => CO ja H (Synthesis gas, ”Syngas”) => Cleaning
2

(BTL: problem with tar) => FT-process => (iso)paraffinic HC:s

 Fischer-Tropsch-diesel
–High-grade fuel (~HVO), but
costs ~ 3x trad diesel
• Small volumes, raw material
production scattered (BTL)
• Costly technology (catalysts etc.)
• Energy efficiency?
• GTL or CTL has been in production
stage already very long ago (China,
South Africa, WW II germany)
–Research and development
ongoing
• GTL produced already: Sasol, Shell,
BTL: Choren, (Neste Oil+Stora Enso)
 DME – dimethyl ether
• Structurally the simplest ether
– one component => more controllable in-cylinder phenomena
• Production from methanol or straight syngas synthesis
• Compatible to diesel process: high CN
• Very low exhaust emissions (comparable with biogas)
– No particulate matter (PM); very low NOx; no SOx)
– Low CO2 emissions
– Low engine noise
– High fuel economy
– High WTW efficiency
– Thermal efficiency and
ignition like diesel

Sivu 32
Source: Volvo
 DME – dimethyl ether
• Use as a heating fuel and as an aerosol propellant
⇒ already widespread production!
• Gaseous in normal conditions, pressurized (like LPG)
⇒ logistics and storage properties: like LPG, infra exists in many places!
• Already eg. Sweden (Volvo) has BioDME-trucks
• Problems
– High compressibility, vapour pressure => cavitation problem?
– Low viscosity (=> leaks), incompatible with some materials
(elastomers) => need for new materials in fuel injection
– density, heating value low
⇒ need of longer injection
for same power
– Need of pressurized tanks

Sivu 33
Japan DME Forum
Biobased diesel fuel comparison
 Biobased diesel fuel comparison
FAME HVO BTL
Process route Transesterification Hydrotreatment Gasification, FT
Feed Product Vegetable oils Oils, fats Biomass
Isomerized Isomerized
Product
Fatty acid methyl esters paraffinic paraffinic
(type)
hydrocarbons hydrocarbons
Product Consistency and
High High
quality stability issues
CO2 0.3-1.5 kg
1.6-2.3 kg CO2/kg oil 0.5-1.5 kg CO2/kg
emissions CO2/kg oil
equivalent oil equivalent
(LCA) equivalent
Note: Fossil diesel fuel value reported as 3.8 kg CO2 / kg oil equivalent (Bown
D. 2007)
 Biobased diesel fuel comparison
FAME Typical
NExBTL GTL FT (RME) diesel
Diesel Typical Typical fuel EN 590
Density at +15°C (kg/m3) 780 - 785 770- 785 n. 885 n. 835 820-845
Viscosity at +40°C
(mm2/s) 3.0 - 3.5 n. 3.2- 4.5 n. 4.5 n. 3.5 2.0-4.5
Cetane number 98 - 99 n. 73 - 81 n. 51 n. 53 >51
10 % distillation (°C) n. 260- 270 n. 260 n. 340 n. 200
90 % distillation (°C) 295 - 300 325 - 330 n. 355 n. 350
Cloud point (°C) n. - 15 n. 0 ... +3 n. 0 ... - 5 n. - 5
Heating value (MJ/kg) n. 44 n. 43 n. 38 n. 43
Heating value (MJ/l) n. 34,5 n. 33,8 n. 34 n. 36
Polyaromatic content (wt-
%) n. 0 n. 0 n. 0 n. 4 <11
Oxygen content (wt-%) n. 0 n. 0 n. 11 0
Sulfur content (mg/kg) < 10 < 10 < 10 < 10 <50
GHG and cost of GHG avoided
 Bio-based diesels, in short
• FAME
– Production: oil+alcohol => fatty acid ester (+glycerol)
– ☺ simple production, low emissions
–  quality, food vs. fuel, enough feedstocks? NOx?
• HVO
– oils/fats + hydrotreatment => paraffin HC
– ☺ quality, emissions low, production at refinery levels
–  food vs. fuel, enough feedstocks?, deforestration, price?
• BTL
– Biomass => gasification => syngas (CO +H2) => (Fischer –Tropsch synthesis) => paraffin HC
– ☺ quality, emissions, any biomass ok!
–  price, development stage, difficult process, small production scale so far
• DME
– From syngas or direct synthesis from methanol
– ☺ quality, emissions, any biomass ok, existing production, no new logistics solutions (vs.
LPG)!
–  Logistics and production in a new scale, requires pressurized systems, engine adaptation
requirement, difficult process

* Place your footnotes / notes here

39
 Thank you!
Trad diesel vs. synthetic diesel