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Alcohols as fuels
Methanol, Ethanol, Propanol, and Butanol are widely used as fuels
They can be synthesized chemically or biologically
When obtained from biological materials and/or biological processes, they are known
as bio alcohols
There is no chemical difference between biologically produced and chemically
produced alcohols
They have characteristics which allow them to be used in internal combustion engines
The general chemical formula for alcohol fuel is CnH2n+1OH
They have high octane rating resulting in better fuel economy in terms of kmpl
Alcohols as fuels
The physical and chemical characteristics of alcohols make them
better suited for SI engines rather than CI engines
The ignition quality of alcohols being poor, these cannot replace diesel fuels directly
The stoichiometric air-fuel ratio due to presence of oxygen in the
molecule is much lower than gasoline.
The latent heat of vaporization of methanol and ethanol is
nearly 4 and 2.7 times,
respectively compared to gasoline
When used in spark ignition engines alcohols have the potential to
reduce NOx, CO, HC and particulates
Properties of ethanol
Formula C2H5OH
Molecular Weight 46.07
Carbon 52.2
Hydrogen 13.1
Oxygen 34.7
Boiling Point (°C) 78
Freezing Point (°C) -114
Viscosity, mPa-s at 20 °C 2.4
Latent heat of 923
Flash Point (°C)
vaporization, kJ/kg 13
Autoignition Temperature 423
Stoichiometric
(°C) air fuel 9
Flame
ratio visibility Difficult to see in daylight
Octane Number 108.6
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The alcohol from the top of the column passes through a dehydration
system where the remaining water will be removed
Most ethanol plants use a molecular sieve to capture the last bit of water in the
ethanol
The alcohol product at this stage is called anhydrous ethanol
(pure, without water)
Denaturing
Ethanol that will be used for fuel must the denature or made unfit for human
consumption with a small amount of gasoline (2 to 5%)
This is done at the ethanol plant
Centrifuges
The stillage from the bottom of the distillation columns contain solids from
the grain and added yeast, as well as liquid from the water added during the
process.
It's then sent and separated through the centrifuges into thin stillage (a liquid
with 5-10% solids) and wet distillers grain
Evaporators
The liquid that is not routed back to the cook/slurry tanks is sent through a
multiple-effect evaporation system where it is concentrated into syrup
containing 25-50% solids
Syrup Tanks
The syrup, which is high in protein and fat content, is then mixed back in
with the wet distiller’s grain.
Grain Drying
The wet cake is conveyed to dryers where it is converted into a low-moisture
(10-12%) product called dried distillers grains with soluble.
Evaporators
The liquid that is not routed back to the cook/slurry tanks is sent through
a multiple-effect evaporation system where it is concentrated into syrup
containing 25-50% solids
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Co-products
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Advantages of Ethanol
Production of methanol
Methanol is produced from synthesis gas which is a mixture of
carbon monoxide and hydrogen
The feedstock, over the last 40 or more years, has been oil or
natural gas
Particularly in China, coal, rather than natural gas or oil is being used.
Any solid biomass including for example agricultural, city and
industrial waste can be used to make synthesis gas using
techniques similar to its production from coal
Production of methanol
At moderate pressure of 1 to 2 MPa and high temperatures around 850 °C,
methane reacts with steam on a nickel catalyst to produce syngas according to
the following chemical equation
CH4 + H2O CO + 3H2O
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Properties of Methanol
Formula CH3OH
Molecular Weight 32.04
Carbon 37.45
Hydrogen 12.5
Oxygen 50
Boiling Point (°F) 149
Freezing Point (°C) -143
Liquid Viscosity at 60 °F
0.59 centipoise Latent heat of
vaporization, at 60 °F 3340
Btu/gallon Flash Point (°F)
52
Autoignition Temperature (°F) 867
Stoichiometric air fuel ratio 6.45
Flammability Limit (% in air) 7.3 to 36
Octane Number 106
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Uses of methanol
M-85 is a mixture of methanol (85%) and petrol used in many cars in China
Pure methanol is used in diesel engines in some buses in China
Methanol is used to produce a variety of chemicals, including formaldehyde
and acetic acid
Formaldehyde is added to adhesives used in the wood industry, such as
plywood, particle board and laminates
Formaldehyde is also a key component of resins used to coat paper and
plastic products
Industrial uses of acetic acid include preparing metal acetates, used in some
printing processes; vinyl acetate, used to produce plastics; and cellulose
acetate, used in photographic films and textiles; and butyl acetates, widely
used as solvents in paints, lacquers and resins.
Globally, methanol is also used to produce chemicals used to manufacture
polyester fabrics and fibers; acrylic plastics; pesticides; textile solvents;
pharmaceuticals; and windshield wiper fluid
Methanol is also used as a direct fuel for automobile engines, as a blended
fuel with gasoline (M85), and as an octane booster/additive in MTBE
(methyl tertiary butyl ether) reformulated gasoline.
Methanol is primarily used as an industrial solvent for inks, resins,
adhesives to wood items, and dyes.
Methanol is used as an antifreeze for automotive radiators, an
ingredient of gasoline
Methanol is also an ingredient in paint and varnish remover
Advantages of methanol
Methanol is a liquid under normal conditions, allowing it to be
stored, transported and dispensed easily, much like gasoline
It has a higher octane number
It can be produced from a wide variety of sources including
fossil fuels like coal, wood and municipal waste
The volumetric energy density of methanol is considerably
higher than liquid hydrogen
It has a lower temperature catalytic reforming than gasoline,
hence making it a better fuel for fuel cells
It can be blended with gasoline (M85)
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Disadvantages of methanol
Methanol combustion
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Fuel properties
Auto Ignition Temperature
It is a minimum temperature of a substance to initiate self-
sustained combustion independent of any ignition source
Boiling Temperature
The boiling point of a substance is the temperature at which the vapor
pressure of the liquid equals the pressure surrounding the liquid and the liquid
changes into a vapor
Fuels that are pure compounds (such as methanol) have a single temperature as
their boiling point
Fuels with mixtures of several hydrocarbons (such as gasoline) have boiling
points of each individual compound in the mixture. For these mixtures, the 10%
point of distillation is often used as the boiling point of the fuel
FlameVisibility
It is a degree to which combustion of a substance under various
conditions can be seen
Odor Recognition
It is the degree of smell associated with that of fuel vapor
Flammability Limits
Minimum and maximum concentrations of vapor on air below and
above which the mixtures are unignitable
A vapor-air concentration below the lower flammable limits is too lean to ignite
A vapor-air concentration above the upper flammable limits is too rich to ignite
Flash point
It is the minimum temperature of a liquid at which sufficient vapor as produced to
form a flammable mixture with air
Freezing Point
It is the temperature where a liquid can exist as both a liquid and a solid in
equilibrium
Heating Value
It is the heat released when a fuel is combusted completely corrected to standard
pressure and temperature
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Volatility
A fuel’s ability to vaporize or change from liquid to vapor is referred to as its volatility
Fuels that do not vaporize readily may cause hard starting of cold engines and poor
vehicle driveability during warm-up and acceleration
Fuels that vaporize too readily at higher operating temperatures will cause too much
vapor to form causing a decrease in fuel f low to the engine (known as ―vapor lock’)
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These extremes of difficult starts on the one hand and vapor lock on
the other can be minimized by changing fuel volatility specifications
for seasonal, geographical, and elevation considerations
Therefore, it is important that a fuel’s tendency to evaporate is controlled to certain
standards
Gasoline is composed of a number of compounds having boiling points ranging
from approximately 27- 225°C(80-437°F)
Unlike gasoline, methanol and ethanol are single compounds that boil at
64.7°C (149°F) and 78.3°C (173°F), respectively
In fuel applications, alcohols lack the light fractions with boiling points near 38°C
(100°F) which are essential for starting spark-ignited engines in severe cold
Volatility
ASTM Distillation Curves for Gasoline and Alcoho
Calorific Value
When the alcohol is burned, the hydroxyl combines with a hydrogen atom to
form a molecule of water
Thus, the oxygen contained in the alcohol contributes nothing to the fuel value
The relative atomic weights of the atoms involved are: hydrogen, 1 ; carbon,
12; and oxygen, 16
Since methyl alcohol has an atomic weight of 32, half the molecule cannot
be
"Burned" and does not contribute any fuel value
As expected, methanol has less than half the heat value (expressed in Btu/lb)
of gasoline
Ethanol, with 35% oxygen, is slightly better with 60% of the heat value of
gasoline
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Vapor Pressure
A fuel’s tendency to vaporize is measured by Reid Vapor Pressure (RVP)
The Reid Vapor Pressure or RVP (ASTM D 323) is a measurement of a
fuel’s
frontend volatility
The determination of RVP is performed by submerging a fuel sample (sealed
in a f lask) in a 100°F water bath
More volatile fuels will vaporize more readily, producing higher pressure
readings.
Less volatile fuels will not create as much readings.
Alcohols have a very low vapor pressure because of their high boiling point and
high latent heat of vaporization
This makes alcohol unsuitable for severe cold environment operation
When alcohol is added to gasoline in small amount it tends to increase the RVP
of t fuel
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This power gain due to increased volumetric mass efficiency is the primary
reason for the popularity of methyl alcohol
Water Content
Gasoline and water free alcohol are miscible in all proportions over a wide
range of temperatures
However, even a small addition of water to this blended fuel causes separation
of the alcohol and gasoline which can be one of most difficult problems for the
blends to be used as motor fuels
Octane Number
The Octane number of methanol and ethanol are higher than gasoline
Hence higher compression ratios can be used with alcohols resulting in higher
thermal efficiency
Alcohols have the ability to raise considerably the octane ratings of gasoline’s
with which they are mixed
The effect is greatest on the poorer grades of gasoline
A 25% blend of ethanol and 40 octane gasoline will have a net increase of
almost 30 points!
This increase is one of the major advantages of "gasohol―
The ability to increase octane rating means that:
A lower (therefore cheaper) grade of gasoline can be used to obtain a fuel with a
certain octane rating
The use of traditional pollution producing anti-knock additives such as
tetraethyl lead can be eliminated
Flammability limits
Alcohols have extended f flammability limits
They can be combusted with very leaner mixture
This results in the reduction of emissions
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Figure shows the relation between equivalence ratio and thermal efficiency for methanol
and gasoline
The maximum efficiency attainable by a lean mixture of gasoline (27%) can be attained
with rich mixtures of methanol
Work conducted on a test engine operating on ethanol produced similar results
Because the efficiency values are measured at the fuel’s knock limited compression
ratio (KLCR), the second figure is included to discriminate between the effect of the fuel
and the effect of KLCR on efficiency
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Figure shows the relation between equivalence ratio and power for methanol and
gasoline
The peak power achieved with gasoline was attained by the fuels containing
methanol at much leaner conditions
Again, because an increase in compression ratio is accompanied by an increase in
power
The right hand illustration in Figure shows the contribution of the compression
ratio vs. the methanol fuel content
Figure shows a plot of 198 proof (99%) ethyl alcohol as compared to gasoline
"Mean effective Pressure" in the graph is a direct indication of the power
produced
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Hot Smoke
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Hot Smoke results from incomplete combustion during heavy engine loads or
from an over-rich fuel mixture
Insufficient oxygen prevents the diesel fuel from completely oxidizing
Besides generating particulate pollution, hot smoke performs no useful work;
it reduces net engine power and lowers vehicle mpg
Traditional engine adjustments do nothing to hot smoke production
Fumigation reduces most hot smoke production resulting in reduced pollution
and increased vehicle mpg
Cold Smoke
Smoke produced during light engine loads is called "cold smoke"
Traditional engine adjustments (engine timing and advance), leaking injectors,
and poor quality diesel fuel are the contributors to cold smoke
Cold smoke produces the same emission pollutant particulate matter
Fumigation does not abate cold smoke
A fumigation system injects a gaseous or liquid fuel into the intake air stream
of a compression ignited engine
This fuel burns and becomes a part-contributor to the power producing fuel
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Fumigation
Fumigation, is a process where a part of the fuel in a diesel engine is supplied by
alcohol through engine air intake
The remaining diesel fuel is delivered normally by a high-pressure injection
system into the engine cylinder.
The energy released from alcohol addition reduces the diesel fuel consumption,
and thus fumigation presents a relatively easy method to burn lower proof
alcohol without requiring major engine modifications
While alcohol and gasoline may be used, gaseous fumigation seems to exhibit the
best overall power yields, performance, and emissions benefits
LPG (Liquified Petroleum Gas) or CNG (Compressed Natural Gas) is used.
The fumigation process is divided into major fraction and minor fraction
fumigation
When more than 50% gaseous injection is used, it is known as major
fraction fumigation
Minor fraction fumigation is under 50% gaseous injection
Fumigation
In 1980, researchers at IIT Madras embarked on a collaborative project with the
erstwhile Standard Motor Company and Carburettors Ltd on the vehicular
application of ethanol in diesel vehicle by fumigation and conduct the road trials
The heart of the technique was a special air-alcohol inductor, designed after
extensive tests on a laboratory dynamometer
The novelty of this gadget is that under starting and idling conditions, the throttle
of the single jet carburettor is closed and there is no f low of alcohol and the
vehicle works on neat diesel oil
The throttle in the air arm is fully open when the throttle in the carburettor arm is
fully closed
Together, they are linked by a flexible coaxial cable to the control lever of the diesel
injection system which, in turn, is linked to the accelerator pedal.
The relative sizes of the venturi and the carburettor jet, and its position relative to
the venturi, are designed such that the jet does not allow any alcohol till the
predetermined speed compatible to efficiency and smoke number (as determined
by the static dynamometer tests) is reached
At speeds higher than this, there is automatic controlled f low of pre-
determined alcohol f low conducive to the fuel efficiency and low smoke
number
This technique permits complete working on diesel fuel in case of disruption in the
supply of alcohol
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Carburetor
A conventional carburetor is employed to supply an alcohol/air mixture to the engine
However, it is necessary to throttle a pair of the air f low to ensure adequate air supply
through the carburetor, and this may present problems
The carburetor can also be preceded by a heat exchanger to transfer heat from the
exhaust gas to the intake air
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The engine was found to run smoothly on ethanol with performance compared
to diesel operation
Observations made on using alcohol in hot surface ignition engine:
Ignition characteristics of ethanol affected by fuel amount, injection timing,
position and length of glow plug, glow plug temperature and water content in
ethanol
Engine speed, fuel injection timing and position of the glow plugs have a strong
effect on the ignition characteristics.
Combustion difficulties appear as the load decreases, making idling impossible
Glow plug surface temperature for proper ignition is around 850oC
Brake thermal efficiency is comparable to that of diesel
Higher carbon monoxide and hydrocarbon emissions
Larger reduction in NOx emissions
Soot free combustion
Quieter operation
Longer ignition delay
Dual-fuel mode
The dual fuel engine is an ideal multi-fuel engine that can operate effectively on
a wide range of fuels with the flexibility of operating it as a conventional diesel
engine
The main aim is to minimize the use of diesel fuel and maximize its
replacement by alternative fuel throughout the load and speed ranges
The energy release by combustion comes about partly from the combustion of
either carburated or manifold injected alternative fuel, while the remaining part
of the energy release comes from diesel fuel throughout, through timed
cylinder injection
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IGNITION IMPROVERS
Ethanol has too low an ignition quality for use in a diesel engine
The ignition quality of ethanol is increased by adding ignition improvers to
ethanol or by the introduction of ignition improvers that have very low self-
ignition temperatures, into the intake manifold
Isoamyl nitrate, Ethyl nitrate, Butyl nitrate, Di-Ethylene Glycol Di-Nitrate
(DEGDN), Tri-Ethylene Glycol Di-Nitrate (TEGDN) and Kerobrisol are some
good ignition improvers, but can aggravate NOx emissions
With the addition of upto 25 % by volume it is possible to increase the cetane
number of ethanol to about 60
Di-Methyl ether (DME) and Di-Ethyl ether (DEE) are the ignition improvers that
have very low self-ignition temperatures and wider flammability limits are
introduced in a small quantity into the intake manifold, that mixes with the
combustion air
This mixture would begin a slow combustion in the compression stroke forming a
pool of species and raising the temperature and pressure inside the engine cylinder
This would create an ideal environment for igniting the subsequently injected
ethanol
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SPARK IGNITION
For smooth operation of an engine, combustion must spread smoothly throughout
the combustion chamber
This is accomplished in a gasoline engine by having a homogeneous mixture in the
cylinder ignited by means of a spark
The heterogeneous mixture in a diesel engine, when using high cetane fuels,
combustion depends upon simultaneous auto ignition at different locations rather
than a f lame propagation
When using low cetane fuels like alcohol in a diesel engine with spark ignition, the f
lame propagate from the f lame nucleus fast enough to achieve smooth combustion
and rapidly induce auto ignition in the rest of the mixture
Thus, for spark assisted diesel, smooth operation depends upon the formation of air
vapour mixture through which the f lame can propagate
The literature survey made on spark plug assisted alcohol
operation shows the following points as made compared to diesel
operation:
Proper timing of both injection and ignition is vital for ignition of alcohol fuel
Injection timing to be advanced
Higher efficiency at full load
More unburnt hydrocarbons
Reduced NOx and noise
Shorter ignition delay
Lower maximum pressure, temperature and rate of pressure rise
Emulsification
An emulsion is a mixture of two or more liquids that are normally immiscible
(unmixable or unblendable)
The dispersion produces a continuous and finely dispersed droplets phase
An emulsifier (also known as an "emulgent") is a substance that stabilizes an
emulsion by increasing its kinetic stability
One class of emulsifiers is known as "surface active agents", or surfactants
Surfactants are compounds that lower the surface tension (or interfacial tension)
between two liquids or between a liquid and a solid. Surfactants may act as
detergents, wetting agents, emulsifiers, foaming agents, and dispersants
A surfactant added to the mixture reduces the oil and water surface tension, activates
their surfaces and maximizes their superficial contact areas to make emulsion
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Most of the properties of emulsion systems (stability, viscosity etc) depend on the
droplet size and size distribution
Emulsification
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