Optimization of Bioenergy Use

Lecture : Transport Biofuel Basics

17.8.2012 Martti Larmi and Aki Tilli
Aalto University, Department of Energy
Technology
Additional reading
VTT research notes 2426

Nylund, Aakko-Saksa, Sipilä:

“Status and outlook for biofuels, other alternative fuels and new
vehicles”. VTT 2008

http://www.vtt.fi/inf/pdf/tiedotteet/2008/T2426.pdf
SI Combustion basics

• SI engine = spark ignition engine

• Combustion = turbulent premixed combustion initiated
by spark. => flame propagation.
• Stoiciometric combustion.
• Knock = autoignition of fuel during flame propagation
resulting in heavy pressure oscillation and uncontrolled
combustion.
• SI engine fuels: resistant againts autoignition, Octane
Number (ON), fuel should be easily evaporated and
mixed with air before combustion.
CI Combustion basics

• CI engine = compression ignition engine

• Combustion = turbulent mixing controlled combustion
initiated by autoignition => mixing control combustion.
• Lean combustion. Flame is still close to stoichiometric.
• Fuel injection is the key issue that affects mixing.
• CI engine fuels: easily ignitable, Cetane Number (CN).
Fuel should also be easily injected and mixed with air
during combustion.
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
– Renewable diesel
• Alternative fuel?
Terms...

• Alternative fuel?
– A fuel seen as an alternative for traditionally produced (fossil)
fuels
– Not necessarily renewable!
• Biodiesel?
– Defined by US legistlation: FAME!!!
– Controversy in literature
– For more developed diesels: bio-based diesel, renewable diesel,
green diesel (another controversy...)
 Ethanol
(Bio)Ethanol added to gasoline

• Almost all the world’s ethanol from grain is used as gasoline additive
• Previously in Eutope maximum ethanol amount 5%, in the future 10%
(E10)
– Transition: in Finland beginning of 2011, many EU countries (e.g. Sweden) 2012
• 5 % => no fuel consumption changes, 10 % => increase
• Increase of gasoline vaporization and vaporized emissions
– E5 ... 10 => old car carburetor adjusted to richer, new cars (~ < 15 years) ok
– 10 - 25 % ethanol => changes to fuel injection system (seals, tanks...)
• Ethanol must be 99,7 % pure!
– Special process needed for water removal
– Fuel logistics: clean, no water!

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 Ethanol

E85, FFV (Flexible Fuel Vehicle)

• E85 = 85 % ethanol + 15 % gasoline

– gasoline needed for cold starts (25% in very cold conditions)
• Injection lenghts, ignition advance etc. automatically controlled
• Differences:
– fuel tanks, fuel hoses, seals, nozzles, engine control, valve sockets
– oil change twice as often
– E85: 40 % greater fuel consumption
• Otto engine efficiency less than for diesel, for instance:
– Ford Focus FFV; with E85 10 l / 100 km
– with gasoline 7 l / 100 km
– TDI with biodiesel 5 l / 100 km

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 Ethanol

• Mainly because of the cultivation cycle emissions grain ethanol is quite

inefficient in decreasing GHG!
– Fertilizer industry emissions; carbon dioxide (CO2 ), nitrous oxide (N2O)
– Cultivation CO2, N2O (whitewash)
– Grain drying
• VTT, MTT 2006: negative grain ethanol GHG balance
– The presumptions and boundary conditions have a huge impact on the life
cycle analysis’ results!
• Cellulose –based ethanol production
– technically in development stage
– high investment and operation costs (enzymes etc.)

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 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
– Biogas: CO N 2, 2

– Natural gas: water, oil, mud, CO2 , H2S, mercury.

• Fits well to Otto-cycle engines
– logistics, fuel injection differences!
• Dual-fuel: diesel –gas engine, diesel fuel ignition
– energy mainly from (cars 90%, ships 99%) from gas
• Bifuel: otto engine able to use both gasoline and gas
– (cold) start often with gasoline
• Heavy duty gas engines mainly modified diesel engines
– spark + compression ratio decrease => efficiency decrease

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 CNG, LNG and LPG
• CNG: compressed natural gas
– compressed to less than 1% of the volume at standard atmospheric pressure.
– stored and distributed in hard containers at a pressure of 200–248 bar
• LNG: liquefied natural gas
– Takes up about 1/600th the volume of natural gas in the gaseous state.
– The gas cooled down in stages until it is liquefied.
• close to atmospheric pressure (maximum transport pressure set at around 25 kPa)
• approximately −162 °C.
– The reduction in volume:
• cost efficient to transport over long distances.
• specially designed cryogenic sea vessels (LNG carriers) or cryogenic road tankers.
• LPG: liquefied petroleum gas
– propane, butane, or both propane and butane
– Synthesised by refining petroleum or "wet" natural gas
• manufactured during the refining of crude oil, or extracted from oil or gas streams as
they emerge from the ground
– Gaseous in atmospheric T and p;
• vapour pressures: 2.2 bar butane at 20 °C (68 °F), 22 bar for propane at 55 °C
• LPG is heavier than air, and thus will flow along floors and tend to settle in low spots,
such as basements. This can cause ignition or suffocation hazards if not dealt with

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 Renewable diesel fuels
Term ”biodiesel” in legistlation: ”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

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Trad biodiesel = FAME
fatty acid methyl ester
– non-toxic biodegradable, simple and easy process
 Trad biodiesel = FAME
– Less emissions than with regular diesel
• particulate matter (PM), HC, CO;
– oxygen content important!
– ...but
• life cycle analysis’ (LCA): CO2 not necessarily decreased
• NOx –increase in most cases
• oil plant cultivation: competition with food production
• in engines: cold property problems, engine oil deterioration, rubber
part embrittlement, corrosion, carbon deposits
• storage problems (biodegradable, water...)
• standards (EU): max. 7% in any diesel
 Trad biodiesel = FAME
– Thermodynamically ~ trad. diesel
– Blended with other diesel fuels: lubricity improver
– 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
• seals, rubber parts
• small amounts (according to EN 590) should be ok
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

Reinhart et al.
2006
 Hydrotreated vegetable oil: HVO
Production: oil/fat pretreatment => fatty acid hydrotreatment =>
paraffin-HC => isomerisation

Mikkonen, 2007
 Hydrotreated vegetable oil: HVO
– T, p control => chain length, isomerization => properties
• Catalysts e.g. NiMo/Al2 O3 , CoMo/ Al2 O3

Oja & Rouhiainen

2005
Hydrotreated vegetable oil: HVO
– Lower density, more compressible => injection later (especially in older
engines)
– HC chain length and branching (= cold properties) adjustable (process T
ja p => isomerization)
– Low lubricity => need of additives (as usual)
– Chemistry: combustion, ignition easier => Less PM
– Paraffinic HC => high CN
⇒ possibilities to decrease NOx with technologies lowering T and
worsening 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
 Hydrotreated vegetable oil: HVO
– LCA’s: CO –emissions -33%...-80%
2

• indirect land-use changes (deforestration) hard to calculate, not taken into account!
• palm oil => deforestration? => ??
– Feedstocks oils; competition with food industry;
• however, wider feedstock possibilities (good quality fuel)
– 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
Hydrotreated vegetable oil: HVO Aatola, 2008
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”) => FT-process
2

=> (iso)paraffinic HC:s

Fischer-Tropsch-diesel
Synthesis gas production, gasification
– C + H2O → CO + H2 , ∆H = 135,1 kJ/mol
– C + 2 H2O → CO2 + 2 H2 , ∆H = 96,2 kJ/mol
– C + CO2 → 2 CO , ∆H = 173,2 kJ/mol
– C + ½ O2 → CO , ∆H = -110,5 kJ/mol
– C + O2 → CO2 , ∆H = -393,7 kJ/mol
– CO + H2O → CO2 + H2 , ∆H = -42 kJ/mol (Water-Gas Shift)
– CO + 3 H2 → CH4 + H2O , ∆H = -217,6 kJ/mol (methane!)
=> Synthesis gas cleaning; e.g. tar problem with BTL
 Fischer-Tropsch-diesel
Synthesis gas production

Vessia, 2005
Fischer-Tropsch-diesel
Fischer-Tropsch -synthesis
–473-523 K, 25-60 bar; conditions (T, p) => quality
–Paraffins: n CO + (2n +1) H2 → CnH2n+2 + n H2O
–Olefins: n CO + (2n) H2 → CnH2n + n H2O
–Alcohols: n CO + (2n) H2 → CnH2n+1OH + (n-1) H2O
=> polymerization
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 the easiest (cleaning not so difficult)
• CTL has been in production stage already very long ago (South Africa,
WW II germany)
–Research and development ongoing
• GTL: Sasol, Shell, BTL: Choren, Neste Oil+Stora Enso
Biobased diesel fuel comparison

Juva, 2007
 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
 DME – dimethyl ether
• Use as a heating fuel and as an aerosol propellant
⇒ already widespread production!
• Gaseous in normal conditions, needs to be pressurized
(like LPG)
⇒ logistical and storage properties: like LPG, infra exists!
• Problems
– Need of pressurized tanks
– 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
– High compressibility, vapour pressure => cavitation problem?
 DME – dimethyl ether
• Structurally the simplest ether
– one component => more controllable in-cylinder phenomena
• 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 well-to-wheel efficiency
– Thermal efficiency equivalent to diesel engine performance
– Ignition characteristics equivalent to diesel engine performance
 DME – dimethyl ether
Property DME Propane Butane
Boiling Point, oC -24.9 -42.1 -0.5
Vapor Pressure @ 20 oC, bar 5.1 8.4 2.1
Liquid Density, @ 20 oC , kg/m3 668 501 610
Specific density, gas 1.59 1.52 2.01
Lower Heating Value, kJ/kg 28,430 46,360 45,740
Auto Ignition Temperature @ 1 atm, oC 235-350 470 365
Explosion/Flammability Limit in air, vol % 3.4-17 2.1-9.4 1.9-8.4

Sivu 32
 DME – dimethyl ether
Production:
• straight synthesis from methanol (exothermic
reactions)...
– CO2+ 3 H2 => CH3OH + H2O
– H2O + CO => H2 + CO2
– 2 CH3OH => CH3OCH3 + H2O

• ...or synthesis gas and synthesis

– 3 CO + 3 H2 => CH3OCH3 + CO2
– 2 CO + 4 H2 => CH3OCH3 + H2O
– 2 CO + 4 H2 => 2 CH3OH + CO2
– 2 CH3OH => CH3OCH3 + H2O

• Life cycle GHG–emissions very low, when production

wholly biomass -based (studies e.g. Volvo+Chalmers)
 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

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References
Juva A: “Neste Oilin Biopolttoaineet”, handouts, Neste Oil, 25.4.2007
Oja S, Rouhiainen J: “NExBTL - Renewable Synthetic Diesel”, handouts, Neste Oil,
2005.
Mikkonen S: “NExBTL – Second Generation Biodiesel”, handouts, Neste Oil, 2007
Reinhardt G, Gärtner S, Helms H, Rettenmaier N, “Final Report – An Assessment
of Energy and Greenhouse Gases of NExBTL”, Institute for Energy and
Environmental Research, Heidelberg GmbH, Germany, June 2006.
Vessia Ø, “Biofuels from lignocellulosic material - In the Norwegian context 2010 –
Technology, Potential and Costs”, Norwegian University of Science and
Technology, Department of electrical engineering, Trondheim, 2005.
Aatola & al.: Hydrotreated Vegetable Oil (HVO) as a Renewable Diesel Fuel:
Trade-off between NOx, Particulate Emission, and Fuel Consumption of a
Heavy Duty Engine, SAE Technical Paper Series 2008-01-2500, 2008

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 Thank you!
Trad diesel vs. synthetic diesel