Thermo Lecture 3

Engineering Thermodynamics
MEC 1203
Joseph Arineitwe
Liquid Biofuels
• Liquid biofuels are produced from biomass feedstock.
• They can complement and/or replace fossil fuels and
reduce carbon emissions in the transport sector with only
modest changes to vehicle technology (i.e. engines) and to
existing infrastructure for fuel distribution.
• Depending on the feedstock type and the maturity and
sustainability of the production process, biofuels are
referred to as conventional(1st generation) or advanced
(2nd and 3rd generation).
• Conventional biofuels are based on commercial feedstock
and processes currently in use in many countries.
• They include
– bioethanol from sugar- and starchy crops,
– Biodiesel from oil crops and waste oil
Liquid biofuels
• Advanced biofuels promise to be more sustainable,
with higher emissions reductions.
• They are based on biomass resources and land not used
for other primary needs, such as food production and
farming.
• Feedstock includes ligno-cellulosic residues from
agriculture and forestry, fast-rotation non-food crops
(possibly grown on marginal, non-arable land), organic
fraction of urban waste and micro-algae.
• The conversion of these resources into biofuels requires
processes that are currently under commercial
demonstration or under development, with small plants
in operation and large plants under construction or
planned all over the world
Bioethanal
• Commercial bioethanol can be produced from many types
of feedstock, including sugarcane, sugar beets, corn
(maize), wheat, potatoes, sorghum and cassava.
• Production from sugar crops (i.e. sugarcane, sugar beet,
sorghum) is based on the fermentation of sucrose followed
by distillation to fuel-grade ethanol.
• Production from sugarcane is particularly easy and efficient
because a considerable amount of sucrose is readily
available, and crushed stalk (bagasse) can be used to
provide heat and power to the process, as well as to other
energy uses.
• If starchy crops (e.g. corn) are used as the feedstock, an
additional step (hydrolysis) is needed to convert starch into
sugar, followed by fermentation and distillation
Bioethanol
Bioethanol
• Bioethanol is a fuel used to replace and complement
gasoline in spark ignition engines and to reduce CO2
emissions.
• Oxygen in its molecular form enables a relatively low-
temperature combustion, which also reduces the
emissions of CO, NOx and volatile organic compounds
(VOC).
• Benefits from ethanol combustion (e.g. high
compression ratio) compensate for the low energy
content compared to gasoline
• Conventional spark-ignition engines can run with 5-
10% (E5, E10) ethanol-gasoline blends with almost no
technical changes
Bioethanol
Biodiesel
Biodiesel
Biodiesel
• Biodiesel is a fuel, which can be fully blended
with fossil diesel to run compression ignition
engines.
• It offers low emissions of GHG, sulphur
compounds and particulate matter compared
with fossil diesel.
• In current practice, a 5-20% (B5, to B20) 1st
generation biodiesel (fatty acid methyl ester,
FAME) is blended with fossil diesel.
• A full blending (up to B100) is possible for
advanced biodiesel.
Biodiesel
• Commercial production of biodiesel is based on
trans-esterification of vegetable oils (chemically or
mechanically extracted from rapeseed, palm seeds,
sunflowers, etc.), animal fats and waste oil through
the addition of methanol (also biomethanol or other
alcohols) and catalysts, with glycerine as a by-
product.
• Biodiesel production from animal fats and waste oils
is cheaper and more efficient, but the basic
feedstock is limited.
• In principle, some vegetable oils could be used
directly as a fuel, but this would involve risks for the
vehicle engine
Biodiesel
Biodiesel
Dimethyl ether (DME)
• Dimethyl ether (typically abbreviated as DME), also
known as methoxymethane, wood ether, dimethyl
oxide or methyl ether, is the simplest ether.
• It is a colourless, slightly narcotic, non-toxic, highly
flammable gas at ambient conditions, but can be
handled as a liquid when lightly pressurized.
• The properties of DME are similar to those of
Liquefied Petroleum Gas (LPG).
• DME is degradable in the atmosphere and is not a
greenhouse gas
Molecular Formula
• DME is primarily produced by converting natural gas,
organic waste or biomass to synthesis gas (syngas).
• The syngas is then converted into DME via a two-step
synthesis, first to methanol in the presence of catalyst
(usually copper-based), and then by subsequent
methanol dehydration in the presence of a different
catalyst (for example, silica-alumina) into DME.
2H2+ CO --------- CH3OH
2CH3OH ---------- CH3OCH3 + H2O
CO+H2O --------- CO2+H2

• Alternatively, DME can be produced through direct
synthesis using a dual-catalyst system which permits
both methanol synthesis and dehydration in the same
process unit, with no intermediate methanol separation,
a procedure that, by eliminating the intermediate
methanol synthesis stage, the licensors claim promises
efficiency advantages and cost benefits.
• Both the one-step and two-step processes are
commercially available.
• DME can also be converted itself into olefins and
synthetic hydrocarbons.
• Due to its good ignition quality, with a high cetane number,
DME can be used in diesel engines as a substitute for
conventional diesel fuel.
• However, compared to diesel fuel. DME has a lower viscosity
(insufficient), and poor lubricity.
• Like LPG for gasoline engines, DME is stored in the liquid
state under relatively low pressure of 0.5 MPa.
• This helps to limit the number of modifications required to
the engine.
• Still, some slight engine modifications are necessary,
primarily relating to the injection pump and the installation
of a pressure tank, similar to that for LPG.
• The fuel line must also be adapted with specific elastomers.
• DME in diesel engine burns very cleanly with no soot.
• The infrastructure of LPG can be used for DME.
• DME production is being optimized, especially for use as
a transport fuel.
Petroleum fuels
Petroleum liquid fuels
• Gasolines are colourless blends of volatile fractions,
which boil within the temperature range of about 20-
200 C.
• For overall average properties, gasolines are often
approximated to octane.
• The major application for gasoline is the spark-
ignition reciprocating-piston engine used for
transport.
• ‘Unleaded’ gasoline is now widely used due to health
concerns.
• Formula: C8H18
• Kerosines are colourless blends of relatively
involatile petroleum fractions, which boil
between about 150-250 C.
• The average properties of kerosene and high-
flash kerosene are very roughly equivalent to
dodecane and tridecane respectively.
• Applications include domestic heating, cookers,
camping stoves, some heavy SI engine
applications and most notably as aviation fuel.
• Formula: C12H26
• Diesel fuels are darkish-brown petroleum
fractions with minimum flash-point of about
60C.
• Applications include heavy, large engines
employed in marine and stationary electricity
generating installations, operating at low
rotational speeds, and which are less reliant on
fuel quality.
• Industrial heating, hot-water boilers and drying
processes are others applications.
• Formula: C12H23
• Residual Fuel Oils are brownish-black petroleum

fractions with minimum flashpoint of 66C.
• High sulphur content – up to 3.5% - can be
prohibitive in terms of corrosion.
• Applications include heating, and steam-raising
in ships, industrial process heating and power
generation.
Gaseous fuels
• Natural (natural gas, mine gas, liquid gases),
• Synthetic (town gas, coke gas, hydrogen)
Natural gas
• The major compounds of natural gas are:
• methane (>96% CH4) and its homologous C3-C7
• Non-combustible compounds of are: nitrogen,
CO2, water.
• An important compound (pollutant) of is: H2S
• Natural gas can occur:
– separately,
– diluted in oil,
– diluted in water,
– diluted in rocks (in coal)
Mine gas
• In some hard coal deposits, methane is absorbed in
coal under great pressure.
• Mine-methane is obtained in the process of de-
methanization of coal mines.
– To make the process of de-methanization more effective
the coal field is shaken using explosives.
– Mine-methane is collected in the steel pipelines and
transported from the mine
• The methane content in coal depends on the coal
field features.
• The mine-methane comprises:
– 96% CH4
– 3% N2
– other compounds.
Gaseous fuels
• Town gas (or producer gas) is obtained at low-
and medium temperature gasification
– Limited air supply
– Temperature 800-1200oC
• Town gas composition
– H2, CH4, CO, N2, H20, CO2
• Coke gas is obtained at the high temperature
coal gasification.
• Composition and properties similar to the
properties of town gas
Hydrogen gas
• Hydrogen as a fuel of the future
– environmental friendly,
– high caloric value,
– Fuel cells applications.
• Hydrogen is produced on the industrial size by
reforming of natural gas (methane).
• Reforming means acting of water steam on
natural gas in the presence of nickel catalyst at
the temperature approx. 800 °C.
Landfill gas
Landfill gas
• Landfill gas production results from chemical reactions and
microbes acting upon the waste as the biodegradable materials
begins to break down in the landfill
• The rate of production is affected by waste composition and
landfill geometry, which in turn influence the microbial
populations within it, chemical make-up of waste, thermal range
of physical conditions, and the biological ecosystems co-existing
simultaneously within most sites.
• Landfill gas is approximately 40-60% methane (CH4), with the
remainder being mostly carbon dioxide (CO2).
• Landfill gas also contains varying amounts of nitrogen (N2) and
oxygen gas (O2), water vapour (H20), hydrogen sulphide (H2S),
and other contaminants
Landfill gas
Biogas
• Biogas typically refers to a mixture of gases
produced by the breakdown of organic matter
in the absence of oxygen
• The gases include 40-60%, the rest being CO2,
H20 and traces of H2S
• Biogas is produced in a process called
anaerobic digestions.
Biogas
Biogas digester - biolatrine
Biogas digester – fixed dome
Biogas digester -Floating drum
Biogas digester - tubular

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Engineering Thermodynamics

2CH3OH ---------- CH3OCH3 + H2O

CO+H2O --------- CO2+H2

• Residual Fuel Oils are brownish-black petroleum

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