Thermochemistry

Lecture 4

By M Ayub, Lecturer, MED, UOL 1

Contents:
• Fuels

• Calculation of Air Fuel Ratio and stochiometric ratio

• Gasoline
• Octane Rating

• How to decide Octane Rating for an Engine

• Diesel
• Cetane Rating

• Methane

• Bio Diesel
By M Ayub, Lecturer, MED, UOL 2
Fuels for IC Engines

Any liquid or gas that can burn with air and release enough energy to
do work.
• Gasoline

• Diesel

• Methane (Natural Gas)

• Ethanol

By M Ayub, Lecturer, MED, UOL 3

Mole & Mass
1 KG Mole = 6.02 X 1026 molecules
1 lb Mole = 2.73 X 1026 molecules
m= NM

m = mass
N = Number of Moles
M = Molecular Weight

By M Ayub, Lecturer, MED, UOL 4

Composition of air
Nitrogen (by Weight) 78%
Oxygen 21%
Argon 01%
Traces of CO2, Ne, CH4, He, H2O etc.

So in every combustion with air all these gases will be included. Argon is also neutral. For simplifying
calculations:

Or for every 21 gram of oxygen, Nitrogen is = 79

For every 1 Gram of Oxygen, Nitrogen is = 79/21 = 3.76

Please note that Nitrogen and Argon are mostly chemically inert gases.
(Nitrogen reacts at very high temp.)

Weight of 1K Mole of Nitorgen = 28.01 KG/KMole

Weight of 1K Mole of Oxygen = 16 KG/KMole
By M Ayub, Lecturer, MED, UOL 5
Molecular Weight
Substance Symbol Molecular Weight
(Kg/Kg Mole)

Air 28.97
Argon Ar 39.95
Carbon C 12.01
Carbon Monooxide CO 28.01
Carbon Dioxide CO2 44.01
Hydrogen H2 2.02
Water Vapour H2O 18.02
Nitrogen N2 28.01
Helium He 4.00

By M Ayub, Lecturer, MED, UOL 6

Gasoline
Gasoline consists of a number of Iso octanes.
Chemical Reaction of combustion is given by:

C8H18 + 12.5 O2 + (3.76) 12.5 N2 = 8CO2 + 9 H2O + 12.5 (3.76) N2

Energy liberated: 35 MJ/L
or (46.6 MJ/kg, or 9.7 kWh/L, 13 kWh/kg, 132 MJ/US gal, 36.6 kWh/US gal)

AIR:
FUEL: 12.5 O2 – oxygen 12.5 ( 16 x 2 ) = 400
(3.76) 12.5 N2 - Nitrogen 12.5 x 3.76 (14 x 2) = 1316
C8H18 – carbon 12 x 8 = 96, hydrogen 1 x 18 = 18 Total weight = 96 + 18 = 114 Weight of air = weight of oxygen + weight of nitrogen = 400 + 1316 = 1716

Stoichiometric Ratio:
For 114 gram of C8H18 air requires 1716 gram air.
for 1 gram of C8H18 air required is 1716/114= 15.02 grams

By M Ayub, Lecturer, MED, UOL 7

Increasing Fuel as compare to Air

C8H18 + 10 O2 + (3.76) 10 N2 = 3CO2 + 9 H2O + 5CO + 10 (3.76) N2

If air is reduced, CO is produced.

CO is colorless and odorless gas which can be further burnt to CO2.

Ø = (FA) act / (FA) stoich = (AF) stoich / (AF)act

Ø < 1 running lean, oxygen in access

Ø > 1 running rich, oxygen deficiency, CO is exhaust along with fuel

Ø = 1 maximum energy released from fuel

Normal engines run on 0.9 to 1.2 depending upon the type of condition.
By M Ayub, Lecturer, MED, UOL 8
By M Ayub, Lecturer, MED, UOL 9
By M Ayub, Lecturer, MED, UOL 10
Power &
Air Fuel Ratio

By M Ayub, Lecturer, MED, UOL 11

Gasoline Composition C4 – C12
Gasoline consists of Hydrocarbons, with between 4 and 12 carbon atoms
per molecule (commonly referred to as C4-C12).

It is a mixture of:

paraffins (alkanes) cycloalkanes (naphthenes) olefins (alkanes)

where the usage of the terms paraffin and olefin is particular to the oil industry.

The actual ratio depends on:

• the oil refinery that makes the gasoline, as not all refineries have the same set of processing units;

• the crude oil feed used by the refinery;

• the grade of gasoline, in particular, the octane rating.

By M Ayub, Lecturer, MED, UOL 12
Components of Fuel

Some of the main components of gasoline:

Iso-octane, butane,
3-ethyltoluene, MTBE (octane enhancer)
MTBE is almost exclusively used as a fuel component in fuel for gasoline engines. It is one of a group of
chemicals commonly known as oxygenates because they raise the oxygen content of gasoline.

Alternatively ethanol can be used.

By M Ayub, Lecturer, MED, UOL 13

High octane rating allows high compression ratio.
Composition of Gasoline
Octane Rating: Octane rating is measured relative to a mixture of:

• 2,2,4-trimethylpentane (an isomer of octane) | Octane Rating:100

• n-heptane | Octane Rating: 0

2,2,4-Trimethylpentane, also known as isooctane, Octane Rating: 100

iso-octane, is an organic compound with the formula (CH3)3CCH2CH(CH3)2. It is one of several isomers of octane (C8H18).

• This particular isomer is the standard 100 point on the octane rating scale (the zero point is n-heptane).

• It is an important component of gasoline, frequently used in relatively large proportions to increase

the knock resistance of the fuel.

Octane Rating: 0
n-Heptane is the straight-chain alkane with the chemical formula H C(CH ) CH 3 2 5 3 or C7H16

It is undesirable in petrol, because it burns explosively causing engine knocking, as opposed to branched-

chain octane isomers, which burn more slowly and give better performance.
By M Ayub, Lecturer, MED, UOL 14
SIT
Temperature and
Ignition Delay

By M Ayub, Lecturer, MED, UOL 15

Self Ignition and
Octane Number
Raised AF Mixture Temp. – Self Ignition will start. (Gasoline will burn by itself without spark plug as it happens in Diesel Engine)

Temp at which Self Ignition occurs: SIT (Self Ignition Temperature)

Therefore Compression Ratio of SI Engine may be limited to 11:1

Self ignition can cause higher pressure in combustion chamber.

If mixture is heated to a temp above SIT, self ignition will be done after Ignition Delay (ID) time

Higher the temp. Shorter is the ID.

Values of SIT and ID are ambiguous depending upon:

Temp, Pressure, Density, Turbulence, Swirl, Fuel Air Ratio & presence of Inert Gases

By M Ayub, Lecturer, MED, UOL 16

Combustion and
Self Ignition
If a combustible air-fuel mixture is heated to a:

• temperature less than SIT, no ignition will occur and the mixture will cool off.

• temperature above SIT, self-ignition will occur after a short time delay called ignition delay (ID).
• The higher the initial temperature rise above SIT, the shorter will be ID.
• The values for SIT and ID for a given air-fuel mixture are ambiguous, depending on many variables which include temperature, pressure, density,
turbulence, swirl, fuel-air ratio, presence of inert gases, etc. [93].

Ignition delay is generally a very small fraction of a second. During this time:
• Pre-ignition reactions occur, including oxidation of some fuel components and

• cracking of some large hydrocarbon components into smaller HC molecules.

• These preignition reactions raise the temperature at local spots, which then promotes additional reactions until, finally, the actual combustion
reaction occurs.

By M Ayub, Lecturer, MED, UOL 17

Continued
Without Self Ignition Engine Operations are smooth:

With no self-ignition the pressure force on the piston follows a smooth curve, resulting in smooth engine
operation.

SELF-IGNITION Causes Engine Knock:

When self-ignition does occur, pressure forces on the piston are not smooth and engine knock occurs.

Before Self Ignition, Pre-ignition occurs including oxidation of some of the fuel components and breaking of large

molecules.

Pre-ignition raises temperature. at local spots, promoting addition reaction until final combustion reaction
occurs.
By M Ayub, Lecturer, MED, UOL 18
By M Ayub, Lecturer, MED, UOL 19
How to Decide Octane Rating for an Engine
Combustion Process in SI Engine (SIT and Knock)
Combustion chamber can be divided into 4 equal mass units, occupying equal mass.

Combustion starts on spark plugs at left side and flame front travels from left to right.

As combustion occurs, temperature of gases increases to a high value.

This in turn raises pressure and expands the volume of that mass.

Un-burnt gas in front of the flame front are compressed by this higher pressure and compressive heating raises the temp. of

the gas.

Temp. of the un-burnt gas further raises by the radiation of the heating from the flame and this then raises the

pressure even higher.

Heat transfer by conduction and convection are not important during this process due to short time interval involved.

By M Ayub, Lecturer, MED, UOL 20

Continued
The flame front moving through the second mass of air fuel does so at an accelerated rate because of higher temp. and

pressure, which increases reaction rate. This in turn further compresses and heats the un-burnt gases in front of the flame.

Energy released in combustion process further raises temp. and pressure of burnt gases behind the flame front. This occurs

by compressive heating and radiation.

Thus flame front continues to travel through the un-burnt mixture that is progressively higher in temp. and pressure.

By the time flame front reaches the last portion of un-burnt gas, this gas is at very high temp. and pressure. In this end , near

the end of combustion process, knocking and self ignition occurs.

By M Ayub, Lecturer, MED, UOL 21

By M Ayub, Lecturer, MED, UOL 22
Engine Knocking
• Engine knocking characteristics depend upon:
• Engine Combustion Chamber Geometry
• Swirl Produced in it
• Temp.
• Pressure
• Turbulence
• Density
• AFR
• Presence of inert gases etc.

By M Ayub, Lecturer, MED, UOL 23

Octane Rating Methods

RON (Research Octane Number)

MON (Motor Octane Number)

AON (Aviation Octane Number

By M Ayub, Lecturer, MED, UOL 24

Finding Octane Number
The test engine is run at specified conditions using the fuel being tested.

Compression ratio is adjusted until a standard level of knock is experienced.

The test fuel is then replaced with a mixture of the two standard fuels. The intake system of the engine is

designed such that the blend of the two standard fuels can be varied to any percent from all isooctane to all

n-heptane.

The blend of fuels is varied until the same knock characteristics are observed as with the test fuel.

The percent of isooctane in the fuel blend is the ON given to the test fuel.

For instance, a fuel that has the same knock characteristics as a blend of 87% isooctane and 13% n-heptane

would have an ON of 87.

By M Ayub, Lecturer, MED, UOL 25
RON and MON Rating Measurement
Test Conditions for RON & MON
RON MON
Engine Speed 600 900
Inlet Air Temperature (C) 52 149
Coolant Temperature (C ) 100 100
Oil Temperature 57 57
Ignition Timing 13bTDC 19 – 26 bTDC
Spark Plug Gap 0.508 0.508
Inlet Air Pressure Atmospheric Pressure
Air Fuel Ratio Adjusted for max. knock
Compression Ratio Adjusted to get standard knock

By M Ayub, Lecturer, MED, UOL 26

Composition of Gasoline
Octane Rating is identified as RON (Research Octane Number).

It determines if fuel will self ignite or not. Higher octane number means no self ignition.

Self Igntion is not desirable in SI Engines.

Higher temperature (and pressure) cause self ignition. Therefore compression ratio is limited to 11.1 to avoid self ignition.

• RON 88

• RON 91 - standard unleaded gasoline in UK

• RON 95 - premium unleaded gasoline in UK

• RON 98 - super unleaded gasoline in UK

• RON 102 - Produced by Shell & BP for high performance cars

By M Ayub, Lecturer, MED, UOL 27

Gasoline and Octane Rating
A gasoline's octane number is a measure of its ability to resist knocking as it burns in the combustion chamber of an engine. A
spark from the spark plug starts normal combustion. The flame travels across the combustion chamber rapidly and smoothly
until all the fuel is consumed.

The higher the octane number, the more compression the fuel can withstand before detonating (igniting).

Higher the octane rating more stable the fuel is under high temperature and pressure conditions. In other words it is knock resistance of
the fuel.

Ethanol is a natural octane enhancer - adding ethanol to petrol boosts the octane number and its performance.

According to Pakwheels forums, in Pakistan:

• Gasoline is RON87

• Hi-octane is RON97

• According to Total Parco their product Hi-super is RON90.

• Honda Civic 2013 requires RON87 fuel

By M Ayub, Lecturer, MED, UOL 28
Octane Rating and
Performance
What Are Octane Ratings? Octane ratings measure a gasoline's ability to resist engine knock, a rattling or pinging sound that results from premature
ignition of the compressed fuel-air mixture in one or more cylinders. Most gas stations offer three octane grades: regular, usually 87 octane, mid-grade,
usually 89 octane and premium, usually 92 or 93. The ratings must be posted on bright yellow stickers on each gasoline pump.
What's The Right Octane Level For Your Car?
Check your owner's manual to determine the right octane level for your car. Regular octane is recommended for most cars. However, some cars with high
compression engines, like sports cars and certain luxury cars, need mid-grade or premium gasoline to prevent knock.
How Can You Tell If You're Using The Right Octane Level?
Listen to your car's engine. If it doesn't knock when you use the recommended octane, you're using the right grade of gasoline.
Will Higher Octane Gasoline Clean Your Engine Better?
As a rule, high-octane gasoline does not outperform regular octane in preventing engine deposits from forming, in removing them, or in cleaning your car's
engine. In fact, the U.S. Environmental Protection Agency requires that all octane grades of all brands of gasoline contain engine cleaning detergent additives
to protect against the build-up of harmful levels of engine deposits during the expected life of your car.
Should You Ever Switch To A Higher Octane Gasoline?
A few car engines may knock or ping, even if you use the recommended octane. If this happens, try switching to the next highest octane grade. In many
cases, switching to the mid-grade or premium-grade gasoline will eliminate the knock. If the knocking or pinging continues after one or two fill-ups, you may
need a tune-up or some other repair. After that work is done, go back to the lowest octane grade at which your engine runs without knocking.
Is Knocking Harmful?
Occasional light knocking or pinging won't harm your engine, and doesn't indicate a need for higher octane. But don't ignore severe knocking. A heavy or
persistent knock can lead to engine worn-out.

By M Ayub, Lecturer, MED, UOL 29

RON
• RON is tested on special single cylinder engine.

By M Ayub, Lecturer, MED, UOL 30

Diesel Fuel QUALITY MEASURE : CETANE INDEX - CI

Larger the Cetane number, shorter is the Ignition Delay (ID) and

quicker the fuel will self ignite in the combustion environment.

Lower Cetane number means fuel will have longer Ignition Delay.

European (EN 590 standard) road diesel has a minimum Cetane number of 51.

Fuels with higher Cetane numbers, normally "premium" diesel fuels with
additional cleaning agents and some synthetic content, are available in some
markets.

By M Ayub, Lecturer, MED, UOL 31

Diesel Fuel
In compression ignition engine correct cetane number is required for self
ignition at compression.
• Large Cetane number – better self ignition

• Smaller Cetane Number – Ignition Delay

• C16H34 (hexa decane) is given cetane number value of 100.

• C12H34 (Heptamethylenonane) is given the value of 15

Cetane Rating of Fuel = (Percent of n-cetane) + (0.15)(percent of HMN)

By M Ayub, Lecturer, MED, UOL 32

By M Ayub, Lecturer, MED, UOL 33
Cetane Rating Measurement (ASTM
D613)
Cetane Rating is done by using special engine which has the capability to change compression ratio.

Fuel being rated is injected at 13bTDC.

Compression ratio is then varied until combustion starts at TDC, giving an Ignition Delay (ID) of 13
degree of Engine rotation.

Without changing compression ratio, the fuel is then replaced with a blend of the two reference
fuels.

Using the two fuel tanks and two flow controls the blend of the two reference fuels is varied until
combustion is again obtained at TDC and ID of 13.
By M Ayub, Lecturer, MED, UOL 34
Affect of Cetane Number on Engine
Normal Cetane Number range for vehicle fuel is about 40 to 60.

Cetane number of the fuel can be raised by using nitrates and nitrites.

LOW CETANE NUMBER FUEL:

For a given engine injection timing and rate, if the cetane number of the fuel is low, then the ignition delay will be too long. When this occurs more

fuel than desirable will be injected into the cylinder before the first fuel particles ignite causing a very large, fast pressure rise at the start of

combustion. This results in low thermal efficiency and rough running engine.

Long ignition delay of fuels with cetane numbers below 40 results in a very rich fuel-air mixture in the cylinder when ignition finally occurs. This results

in unacceptable exhaust smoke and these fuels are illegal by many emission laws.

HIGHER CETANE NUMBER FUEL:

If the CN of the fuel is high, combustion will start too soon in the cycle. Pressure will rise in the cylinder and more work will be required in the

compression stroke.

By M Ayub, Lecturer, MED, UOL 35

Cetane Index
Emperical Method of Measuring Cetane

CI = -420.34 + 0.016G2 + 0.192 G (log 10Tmp) + 65.01 (log10Tmp)2 – 0.0001809T2mp

Where:

• G= (141.5/Sg) – 131.5

• Sg = Specific Gravity

• Tmp = Midpoint boiling temp. in F

By M Ayub, Lecturer, MED, UOL 36

DIESEL ENGINE:
Calculation of Ignition Delay
ID (ca) = (0.36 + 0.22 Up) exp { EA [(1/Ru Ti rc k-1) – (1/17190)] [ (21.2)/(Pirck - 12.4)]0.63 }
Where
• ID – Ignition Delay

• EA = (608 840) / (CN + 25) = Activation Energy

• CN = Cetane number

• Up = Average Piston Speed in m/sec = 2SN

• Ru = Universal Gas Constant = 8.314 KJ/kgmole – K

• Ti, Pi = Temp (K) and Pressure (bars) at start of compression stroke

• rc = compression ratio

• K = cp/cv = 1.35 in air standard analysis

For an engine Speed in N (rpm) ignition delay in millisecond is

ID(ms) = ID (ca) / (0.006 N)

By M Ayub, Lecturer, MED, UOL 37

Natural Gas - Methane

CH4 + 2O2 + 2 (3.76) N2 = CO2 + 2 H2O + 2 (3.76) N2

By M Ayub, Lecturer, MED, UOL 38

Methane - CH4 60 to 98%
Natural Gas - N2
CO2
Methane He
Sulfur (Litter amount is called Sweet, Large Amount is called Sour)
Traces of Other Gases

Natural Gas is a mixture of components, consisting mainly of methane (60-98%) with small
amounts of other hydrocarbon fuel components.

In addition it contains various amounts of N2, CO2, He and traces of other gases.

Sulfur contents range may vary from little (sweet) to larger amounts (Sour).

STORAGE:

CNG (compressed Natural Gas) is stored at pressures of (16 to 25 Mpa)

LNG (liquid Natural Gas) is stored at pressure of 70 to 210 Kpa and a temp around -160C.
By M Ayub, Lecturer, MED, UOL 39
Natural Gas as a fuel
Advantages
It works best in an engine system with single throttle body injector which gives longer mixing time.

Octane Number is 120 which makes it very good for SI engine.

It has fast flame speed and engine can operate at higher compression ratios.

Low engine emissions, less aldehydes than with methanol and less CO2.

Cleaner than both gasoline and diesel engines. Also, none of the smog-forming contaminates are emitted.

Natural gas is lighter than air and can be mixed together.

Fuel can be made from Coal.

By M Ayub, Lecturer, MED, UOL 40

Natural Gas as a Fuel
Dis-advantages
• Low Energy Density resulting in low engine performance

• Low engine Volumatric Efficiency because it is a gaseous fuel

• Need a large pressurized storage tank. Safety is concern.

• Inconsistent fuel properties

• Refueling is slow process.

By M Ayub, Lecturer, MED, UOL 41

Shale Gas
Shale gas is Natural Gas that is found trapped within Shale formations.

Increasingly important source of natural gas in the United States since the start of this century:

• In Year 2000 shale gas provided only 1% of U.S. natural gas production;

• By 2010 it was over 20%

• U.S. government's Energy Information Administration predicts that by 2035, 46% of the United States' natural gas supply will come

from shale gas.

• Shales are fine-grained sedimentary rocks that can be rich resources of petroleum and natural gas. Sedimentary rocks are

rocks formed by the accumulation of sediments at the Earth's surface and within bodies of water. Common sedimentary

rocks include sandstone, limestone, and shale.

• China is expected to have largest shale gas reserves.

By M Ayub, Lecturer, MED, UOL 42

By M Ayub, Lecturer, MED, UOL 43
Shale Gas in Pakistan
• More recent estimates as of November 2015, point to over 10000 TCF
of Shale gas reserves, of which about 205 Tcf is technically
recoverable as reported recently by Pakistan's Minister of Petroleum
and Natural Resources, Shahid Khaqan Abbasi. Exploratory drilling
continues.

• Pakistan stands 19th in terms of recoverable shale gas and oil reserves.

By M Ayub, Lecturer, MED, UOL 44

By M Ayub, Lecturer, MED, UOL 45
Alcohols
(Methanol, Ethanol)
Alcohols are an attractive alternate fuel because they can be obtained
from a number of sources, both natural and manufactured. Types of
alcohols:
Methanol - Methyl alcohol

Enthanol - Ethyl Alcohol

By M Ayub, Lecturer, MED, UOL 46

Advantages of Alcohol
• Can be obtained from a number of sources, both natural and manufactured.

• Is a high octane fuel with anti-knock index number (octane number on fuel pump) of over 100.

• High octane numbers result at least in part from the high flame speed of alcohol. Engine using high-octane fuel can

run more efficiently by using high compression ratios.

• Generally lower overall emissions compared with those of gasoline.

• When burned, it forms more moles of exhaust which give higher pressure and more power in expansion stroke.

• Has high evaporative cooling (hfg) which results in a cooler intake process and compression stroke. This raises the

volumetric efficiency of the engine and reduces the work input in the compression stroke.

• Low sulfer contents in the fuel.

By M Ayub, Lecturer, MED, UOL 47
Dis-advantages of Alcohol fuel
• Low energy content of the fuel. This means almost twice as much alcohol as gasoline must be burned to give the same energy input to the

engine. Therefore:

• With equl thermal efficiency and similar engine output usage, twice as much fuel would have to be purchased and the distance which could be driven

with a fuel tank volume would be cut in half.

• Alcohol contains oxygen and thus requires less air for stoichiometric combustion. More fuel can be burnt with same amount of air.

Therefore engine power for a given displacement would be same.

• More aldehydes in the exhaust. If as much fuel was consumed as gasoline, aldehyde emission would be a serious exhaust pollution

problem.

• Much more corossive than gasoline on copper, brass, aluminium, rubber and many plastics. This puts some restriction on the design and

manufacturing of engines to be used with this fuel. Fuel lines, tanks, gasket and even engine metal parts can be deteriorated with long

term alcohol use.

• Methanol is very corossive on metals. This is because it reacts with the exhaust CO2 and H2O and forms formic acid (CH2O2) and carbonic
By M Ayub, Lecturer, MED, UOL 48
acid (H2CO3).
Dis-advantages of Alcohol
• Poor cold weather starting characteristics due to low vapor pressure and evaporation. Alcohol-fueled engine starting at temepratures
below 10C. For cold starting small amount of gasoline can be added. This need to do this reduces it as an attractive fuel.

• Poor ignition characteristics in general.

• Almost invisible flame which is considered dangerous when handling fuel. (small amount of gasoline removes this danger)

• Danger of storage tank flammability due to lower vapor pressure. Air can leak into storage tank and creates a combustible mixture.

• Lower flame temperature which generates less Nox but the resulting lower exhaust temperatures take longer to heat the catalytic
converter to an efficient operating temperature.

• Strong, possibly offensive ordor. Headache and dizziness have been experienced when refueling an automobile.

• Vapor lock in fuel delivery systems.

• Mixes with water. So any leakage can contaminate groundwater.

By M Ayub, Lecturer, MED, UOL 49

Methanol – CH3OH
CH3OH + 1.5 (O2 + 3.773 N2) = CO2 + 2H2O + 5.66N2 (Stoichiometric A/F Ratio = 9.0)

• One of the most promising alternate fuel.

• Pure methanol and mixtures of methanol with gasoline are extensively tested. Most common mixtures are:

• M85 – 85% methanol, 15% gasoline

• M10 – 10% methanol, 90% gasoline

Their data is compare with M0 (pure gasoline) and M100 (100% methanol).

Some smart flexible fuel, variable fuel engines are capable of using any random mixture of methanol with gasoline ranging from pure methanol to pure gasoline.

Two fuel tanks are used and various flowrates of the fuel can be pumped to the engine, passing through the mixture. Using information from intake and exhaust, EMS adjusts the proper mixture being

used.

• In Alcohol-gasoline mixture alcohol has the tandency to combine with any water present. When this happens, alcohol separates from gasoline , resulting in non-homogeneous mixture. This causes

engine to run erratically.

• Methanol can be obtained from many sources, both fossil and renewable. These include coal, petroleum, natural gas, biomass, wood, landfills and even the ocean. However any source requires

extensive process ing, raising its price.

• M10 fuels produce almost same emissions as gasoline. It decrease HC and CO emissions. However it increases Nox and a large increase in formaldehydes formation.

• Methanol can also be used with small amount of CI which produces good results for ignotion.
By M Ayub, Lecturer, MED, UOL 50
Ethanol – C2H5OH
C2H5OH + 3(O2 + 3.773N2) = 2CO2 + 3H2O + 11.32N2 (Stoichiometric A/F Ratio
= 6.47)
• Ethanol is used as an automotive fuel In Brazil and many parts of the world. In Brazil there were more than 4.5 million vehicles in 1990s using

more than 93% ethanol as fuel.

• In many parts of USA (Midwest, corn producing states) gasohol has been available for many years. Gasohol is 90% gasoline and 10% ethanol.

• Most common combinations are:

• E85 (85% ethanol, 15% fuel) – to reduce cold start problem and tank flammability

• E10 (10%ethanol, 90% fuel)

• E10 does not require any modification in the engine.

• Ethanol can be made from ethylene or from fermentation of grains and sugar. Sources include corn, sugar, beets, cane and cellulose (wood

and paper). Corn is major source in USA.

• Current cost of ethanol is higher due to manufacturing and processing required. It may be reduced if quantity is increased.

• Ethanol has less HC emissions than gasoline but more than methanol.

By M Ayub, Lecturer, MED, UOL 51

Hydrogen
H2 + ½ (O2+3.773N2) = H2O + 1.887N2 (Stoichiometric A/F Ratio
34.3)
Projected as a major fuel of future to replace gasoline supplies.
It can fuel IC Engines or Fuel Cells.
It offers HIGH OCTANE number.
No CO, CO2 or HC emissions.
Two major issues are:
• Fuel Storage
• Refueling
BMW is leading automotive company to make prototypes using hydrogen fuel. It is developing duel fuel (gasoline or hydrogen)
vehicle.
Mazda has adapted an experimental rotary Wankel engine to run on hydrogen fuel as this was a good type of engine for this fuel; fuel
intake is on the opposite side of the engine from where the combustion occurs, lowering the chance of pre-ignition from a hot engine
block.
Hydrogen fuel ignites very easily.
It takes 140 liters of hydrogen to carry same energy content as gasoline.
Fuel storage can be done in any of the three phases: Gaseous, liquid and solid.
Several of the presnet experimental automobiles store onboard fuel as a cryogenic liquid. At atmospheric pressure this can be done
at a temperature of -250C (23K or 420F) ,requiring bulky super insulated fuel tank. If pressurized, storage temperature can be raised.

By M Ayub, Lecturer, MED, UOL 52

Advantages of Hydrogen
• High Octane number. When used at a fuel equivalence ratio of 0.6 (67% excess air), compression ratios of

about 14:1 can be utilized without serious knock issues. This makes high thermal efficiency.

• Low emissions. No CO, CO2, HC in exhaust. No carbon in fuel NOx emissions can be kept low if the engine is

operated at low fuel equivalence ratio. Need for catalytic convertor can be eliminated. Most exhaust would

be H2O and N2.

• FUEL AVAILABILITY: Hydrogen can be obtained from natural gas and electrolysis of water. (however when

total energy and environmental picture is considered in converting natural gas as the engine fuel, it can be

argued that natural gas may be used directly as an engine fuel. Solar energy or improved fuel cell technology

could diminish this problem.

• Fuel leakage to the environment is not pollutant.

By M Ayub, Lecturer, MED, UOL 53
Dis-advantages of Hydrogen as fuel
• Heavy bulky fuel storage, both in vehicle and at service stations. This
would be much less for a stationary engine.

• Difficult to refuel.

• Poor engine volumetric efficiency. Any time a gaseous fuel is used in

an engine, fuel will displace some of the inlet air and poorer
volumetric efficiency will result. This is especially true for hydrogen
fuel which is generally burned with large amount of air.

• High fuel cost, given present day technology and availability.

• Fuel can detonate. By M Ayub, Lecturer, MED, UOL 54

Bio-
Diesel

By M Ayub, Lecturer, MED, UOL 55

Diesel vs Bio-Diesel

By M Ayub, Lecturer, MED, UOL 56

Bio Diesel
• Biodiesel refers to a vegetable oil - or animal fat-based diesel fuel
consisting of long-chain alkyl (methyl, ethyl, or propyl) esters.
• Biodiesel is typically made by chemically reacting lipids (e.g.,
vegetable oil, soybean oil, animal fat (tallow)) with an alcohol
producing fatty acid esters.

By M Ayub, Lecturer, MED, UOL 57

Blends of Bio-Diesel
Blends of biodiesel and conventional hydrocarbon-based diesel are known as the "B" factor to state the amount of biodiesel

in any fuel mix:

• 100% biodiesel is referred to as B100

• 20% biodiesel, 80% petrodiesel is labeled B20

• 5% biodiesel, 95% petrodiesel is labeled B5

• 2% biodiesel, 98% petrodiesel is labeled B2

Blends of 20% biodiesel and lower can be used in diesel equipment with no, or only minor modifications, although certain

manufacturers do not extend warranty coverage if equipment is damaged by these blends.

The B6 to B20 blends are covered by the ASTM D7467 specification.

By M Ayub, Lecturer, MED, UOL 58

By M Ayub, Lecturer, MED, UOL 59
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By M Ayub, Lecturer, MED, UOL 61
By M Ayub, Lecturer, MED, UOL 62
Bio Diesel Production
Transesterification
• Chemical reaction between methanol or ethanol and a
vegetable Oil or animal fat
• Requires a catalyst, such as caustic soda (NaOH) or KOH
• Removal of glycerin

By M Ayub, Lecturer, MED, UOL 63

Bio Diesel Production
Chemically, transesterified biodiesel comprises a mix of mono-alkyl esters of long chain fatty acids.

• The most common form uses methanol (converted to sodium methoxide) to produce methyl
esters (commonly referred to as Fatty Acid Methyl Easter - FAME) as it is the cheapest alcohol
available,

• Ethanol can be used to produce an ethyl ester (commonly referred to as Fatty Acid Ethyl Ester -
FAEE) biodiesel

• Higher alcohols such as isopropanol and butanol have also been used.

• Using alcohols of higher molecular weights improves the cold flow properties of the resulting
ester, at the cost of a less efficient transesterification reaction.

By M Ayub, Lecturer, MED, UOL 64

Bio Diesel
• A lipid transesterification production process is used to convert the base oil to the desired esters.

• Any free fatty acids (FFAs) in the base oil are either converted to soap and removed from the process, or they are esterified

(yielding more biodiesel) using an acidic catalyst.

• After this processing, unlike straight vegetable oil, biodiesel has combustion properties very similar to those of petroleum

diesel, and can replace it in most current uses.

• The methanol used in most biodiesel production processes is made using fossil fuel inputs. However, there are sources

of renewable methanol made using carbon dioxide or biomass as feedstock, making their production processes free of

fossil fuels.

• A by-product of the transesterification process is the production of glycerol . For every 1 tonne of biodiesel that is

manufactured, 100 kg of glycerol are produced.

By M Ayub, Lecturer, MED, UOL 65

Transesterification Process

• In the transesterification mechanism, the carbonyl carbon of the starting ester (RCOOR1) undergoes nucleophilic attack by the incoming alkoxide (R2O−) to give a

tetrahedral intermediate, which either reverts to the starting material, or proceeds to the transesterified product (RCOOR2).

• The various species exist in equilibrium, and the product distribution depends on the relative energies of the reactant and product.

• Strong acids catalyse the reaction by donating a proton to the carbonyl group, thus making it a more potent electrophile, whereas bases catalyse the reaction by

removing a proton from the alcohol, thus making it more nucleophilic.

• Esters with larger alkoxy groups can be made from methyl or ethyl esters in high purity by heating the mixture of ester, acid/base, and large alcohol and evaporating
By M Ayub, Lecturer, MED, UOL 66
the small alcohol to drive equilibrium.
By M Ayub, Lecturer, MED, UOL 67
Source Materials for Bio-Diesel Production
A variety of oils can be used to produce biodiesel. These include:
• Virgin oil feedstock – rapeseed and soyabean oils are most commonly used.
soybean oil accounting for about half of U.S. production.
• It also can be obtained from Pongamia, field Pennycress and Jatropa and other crops such
as mustard, jojoba, flax, sunflower, palm oil, coconut and hemp
• Waste vegetable oil (WVO)
• Animal fats including tallow, lard, yellow grease, chicken fat, and the by-products of the production of Omega-3-
fatty acids from fish oil.
• Algae, which can be grown using waste materials such as sewage and without displacing land currently used for
food production.
• Oil from halophytes such as Salicornia bigelovii, which can be grown using saltwater in coastal areas where
conventional crops cannot be grown, with yields equal to the yields of soybeans and other oilseeds grown using
freshwater irrigation
• Sewage Sludge - The sewage-to-biofuel field is attracting interest from major companies like Waste Management
and startups like InfoSpi, which are betting that renewable sewage biodiesel can become competitive with
petroleum diesel on price. By M Ayub, Lecturer, MED, UOL 68
Source Materials for Bio-Diesel Production

Jojoba

Soyabean

By M Ayub, Lecturer, MED, UOL 69

Dis-advantages
• Bio Diesel is not that stable. Additives help solving this problem.
• There can be water contamination.

By M Ayub, Lecturer, MED, UOL 70

By M Ayub, Lecturer, MED, UOL 71
Comparison of Fuel

(*) Diesel fuel is not used in a gasoline engine, so its low octane By M isAyub,
rating not anLecturer,
issue; the MED,
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metric for diesel engines is the cetane number 72
By M Ayub, Lecturer, MED, UOL 73
By M Ayub, Lecturer, MED, UOL 74
By M Ayub, Lecturer, MED, UOL 75
Thank you

By M Ayub, Lecturer, MED, UOL 76