Chemical elements that are

contained in fuels, and

combustion effects

Reference
• Thompson EV, Ceckler
WH. 1985. Introduction
To Chemical
Engineering. McGraw-
Hill Book Co, Singapore,
Singapore.

1
 Reference
Leighou RB. 1953.
Chemistry of Engineering
Materials. McGraw-Hill
Book Company, Inc, New
York, US

Refinery Products
The production of petroleum products (before 1978):
Percent by weight
Refinery Products United
Europe Japan
States
Gasoline 42 35
Kerosene 8
Diesel fuel 21
Fuel oil 7 16 > 52
Other 22

The primary crude oil elements: C, H (Hydrocarbon)

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 Processing Steps within the Refinery
Crude Oil Gas
Light Naphtha
Heavy Naphtha
Fractionation and separation Kerosene
(into 7 fractions) Fuel Oil
Gas Oil
Topped Crude Oil
Desulfurization
Alkylation
Chemical modification (if Catalytic reforming
necessary) Catalytic cracking
Catalytic hydrogen cracking
Fractionation into products
and recycle streams

Oil Refining – Overall Material Balance

8 H2, etc
3 Ethane, etc Gases = 13
2 Pentane
6 Alkylate
9 St.-run gas

Gasoline = 41
13 Reformed gas
13 Cat.-cr. gas
7 St.-run. kero
12 St.-run. d.fuel Jet and diesel fuel,
5 Cat.-cr. d.fuel
kerosene = 24
9 Fuel oil
4 Fuel oil Fuel oil = 13

3 Lub. oil
6 Asphalt Residuals = 9
100

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 Specific Refinery Products
• Gasoline
– Aviation gasoline
• For small civilian aircraft: blend of catalytically
cracked and straight-run gasoline with some alkylate
• For large civilian aircraft: blend of catalytically
cracked gasoline and alkylate
• For combat aircraft: essentially pure alkylate

Specific Refinery Products

• Gasoline
– Automobile gasoline
• Regular grade, for passenger cars and truks (with
compression ratios up to 9:1): blend of catalytically
cracked, reformed and straight-run gasolines
• Premium or high-test grade (with compression
ratios greater than 9:1): blend of catalytically
cracked, reformed, straight-run gasolines and
alkylate

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 Specific Refinery Products
• Kerosene
– Illuminating oil and fuel for various types of stoves
and heaters: straight-run kerosene
– Aviation turbine fuel, for jet propulsion aircraft: high-
boiling fractions of straight-run kerosene, sometimes
with straight-run gasoline

Specific Refinery Products

• Diesel Fuel
– Grade no. 1-D, for small and medium-sized trucks:
blend of straight-run kerosene and straight-run diesel
fuel
– Grade no. 2-D, for industrial use and for large trucks:
blend of straight-run and catalytically cracked diesel
fuels
– Grade no. 4-D, for large industrial installation: blend of
catalytically cracked deisel fuel and residual oil

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 Specific Refinery Products
• Fuel Oil
– Gas-turbine fuel oil, for all types of gas turbine: fuel
oil, sometimes with residual oil
– Fuel oil no. 1, for vaporizing pot-type burners: blend
of straight-run kerosesn and fuel oil
– Fuel oil no. 2, for home furnaces: catalytic cracked
diesel fuel and fuel oil
– Fuel oil no. 6, industrial burners using high-viscosity
fuels: principally residual oil, sometimes with high-
boiling fractions of fuel oil

Specific Refinery Products

• Fuel Oil
– Gas-turbine engine

– Home furnace

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 Specific Refinery Products
• Others
– Liquified petroleum gas, for residential and commercial
use: propane and butane
– Solvents, aromatic solvents (e.g., benzene and
toluene): derived from various aromatization processes
– Solvents, petroleum spirits (e.g., mineral spirits for
paints and varnish thinners): derived from straight-run
and reformed gasolines
– Lubricants, automotive lubricants (e.g., transmission
lubricants) and industrial lubricants (e.g., machine,
engine oils, greases): well-fractionated and well-
refined cuts from lubricating and residual oils

Specific Refinery Products

• Others
– Waxes, parrafin waxes for paper coatings, electrical
insulation, in rubber compounding, as a sealer for food
products: highly refined mixtures from residual oil
– Waxes, microcrystalline waxes for waterproofing of
coating material: highly refined mixtures from residual
oil, but of somewhat higher molecular weight

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 Specific Refinery Products
• Others
– Building materials, roofing asphalt and joint-filler for
building constructions and emulsified asphalts and
dust-laying oils for road construction: mostly refined
from asphalt and residual oil

Compression Ratio
• A ratio between the volume of a combustion chamber and
cylinder, when the piston is at the bottom of its stroke and
the volume when the piston is at the top of its stroke, or
• A ratio by which the air/fuel mixture is compressed before it
is ignited
• The higher the compression ratio, the more mechanical
energy an engine can squeeze from its air-fuel mixture.
• Higher compression ratios, however, also make detonation
more likely.
• A reduction in fuel consumption is achieved by increasing
the work output and/or decreasing the frictional and
pumping losses.

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 Fuel Consumption Reduction Strategies
Fuel Consumption Sources of effectiveness
Reduction Strategy
1 Increased effective Improved indicated
expansion ratio efficiency
2 Downsizing • Pumping losses reduction
• Internal heat transfer
surface reduction
• Flame travel distance
reduction
• Friction losses reduction
3 Downspeeding •Pumping losses reduction
•Friction losses reduction
4 Unthrottled load •Pumping losses reduction
control
5 Engine mechanical •Friction losses reduction
efficiency improvement
Engine strategies
•High Fixed Compression Ratio
(FCR)
•Variable Compression Ratio
•High supercharging
•Increased average BMEP
•10:1 Compression Ratio (FCR)
•From 8:1 to 16:1 Compression
Ratio (VCR)
•High supercharging
•Increased average BMEP
•Load control by air/fuel ratio
•Load control by Late Intake
Valve Closing
•Reduction of all friction sources

Combustion Effect
Combustion is a chemical reaction of “rapid
oxygenation/oxidation”
• Compounds move from a high to a low energy
state by releasing some energy
• Usually produces visible radiance
• The primary combustion elements: C, H, and
small part of S

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Typical Analyses of Common Gaseous Fuels
Gaseous Carburated Natural Natural Natural
Coal gas
Fuel water gas gas I gas II gas III
CH4 34.0 14.8 - 32.3 83.5
Constituent (% by volume)

C2H6 - - 31.8 67.0 12.5

C3H8 - - 77.7 - -
C2H4 6.6 12.8 - - -
CO 9.0 33.9 - - -
CO2 1.1 1.5 - - 0.2
H2 47.0 35.2 - - -
O2 - - - - -
N2 2.3 1.8 0.5 0.7 3.8
Theoretical flame
temperature (°F) 3910 4090 3840 3770 3740

Combustion Chemistry
The generalized combustion reaction for
hydrocarbon fuels can be shown as:
CxHy + O2  CO2 + H2O + Energy
• CxHy:the hydrocarbon fuel; O2: oxygen
(The actual conversion of hydrocarbon molecules in
the combustion process is more complex as there
are many intermediate conversions that take place)

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 Combustion Efficiency
It is affected by the manner in which the
combustion occurs, that is, the
• air:fuel ratio
• degree of atomizing (for liquid fuels only)
• fuel-air mixing
• flame temperature
• flame shape
• fuel residence time in the combustion zone
• amount of heat lost out of the system

Air:Fuel Ratio
The theoretical air:fuel ratio for complete combustion is
known as the “STOICHIOMETRIC” ratio
• In practice this ratio does not achieve complete
combustion as the degree of mixing is never sufficient to
allow every oxygen molecule to come into contact with a
fuel molecule
• Thus a certain amount of excess oxygen (air) is required
to achieve full combustion
• Too much excess air is undesirable as it reduces
efficiency by absorbing and carrying away heat

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 Atomizing
• It is required to generate an even spray of
droplets sufficiently small to allow good
mixing with the oxygen to achieve complete
combustion (usually <50 microns in diameter)
• The burner must provide a stable spray of
atomized fuel particles expanding into the
combustion air in a manner that will sustain
good combustion

Fuel-Air Mixing
• It is affected the efficient combustion
• The chimney helps sustain the shape of the flame
necessary for good combustion
Causes of poor mixing:
• Imbalanced air:fuel pressures
• Incorrectly set up burners
• Worn burner parts
• Damaged or badly made burner tile (quarl)
• Dirty or blocked swirl plates

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 Flame Characteristics
• Heavy fuel oils require more time than light oils
and gas to achieve full combustion (respectively,
0,1s – 0,01s – 0,001s).
• Flame shapes are important, as short flames may
not provide sufficient residence time for full
combustion and “woolly” flames allow unburnt
fuel mixture to escape from the side of the flame.

Heat Losses
Useful energy (heat) is lost in the following manner:
• Poor combustion (0% - 20%)
• Insufficient radiance (5% - 15%)
• Poor insulation (2,5% - 15%)
• Heating up excess air (0,5% - 3%)

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 Ignition Temperature
(Kindling Temperature)
• Definition: the temperature at which a substance
ignites and continues to burn without further
addition of heat
For gases, it depends on:
• Pressure; increase P  decrease ignition
temperature
• The ratio of combustible gas to air
• The size and shape of the vessel
• The presence of a catalyst; lower the ignition
temperature

Types of Ignition
Spontaneous Ignition
Also known as auto-ignition or self-ignition.
• It occurs as a result of increasing the temperature in
hot boundaries, because the heat generation rate in a
strong exponential function of temperature, whereas
the heat loss rate is a simple linear function
• Once the generation rate exceeds the loss rate,
ignition occurs in the whole volume almost
instantaneously.
• The reaction then proceeds by itself without any
further external heating.

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 Types of Ignition
Forced Ignition
• It occurs when there is an external energy
addition, such as an electrically heated wire, an
electric spark, an incandescent particle, etc.
• A flame is initiated locally near the ignition source
and it propagates into the rest of the mixture

The General Gas Equation

PV = nRT
where, P = absolute pressure
V = volume
n = number of moles of gas
R = gas constant, 0729
T = absolute temperature

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 Gay-Lussac’s Law
“At constant temeprature and pressure, the volumes
of reacting gases or gaseous reaction products are to
each other as the coefficients in the balanced
chemical equation representing the reaction”

Example
Calculate the theoretical volume of oxygen and of
air required at 80 F and 1 atm, for the combustion
of 100 lb coal. The coal’s composition:
– C 69%
– H 5.4% Reaction:
– S 1.0% C + O2  CO2
– N 1.6% H2 + ½ O2  H2O
S + O2  SO2
– O 15%
– Ash 8%

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 Gas Constant
Units Units
Values of R Values of R
[VPT-1n-1] [VPT-1n-1]
8.3144621(75) J K-1 mol-1 84.78402×10−6 m3 kgf/cm2 K-1 mol-1
5.189×1019 eV K-1 mol-1 8.3144621(75)×10−2 L bar K−1 mol−1
0.08205746(14) L atm K-1 mol-1 62.36367(11) L mmHg K−1 mol−1
1.9858775(34) cal K-1 mol-1 62.36367(11) L Torr K−1 mol−1
1.9858775(34)×10−3 kcal K-1 mol-1 6.132440(10) ft lbf  K−1 g-mol−1
8.3144621(75)×107 erg K-1 mol-1 1,545.34896(3) ft lbf  R−1 lb-mol−1
8.3144621(75) L kPa K-1 mol-1 10.73159(2) ft3 psi °R−1 lb-mol−1
8.3144621(75) m3 Pa K-1 mol-1 0.7302413(12) ft3 atm °R−1 lb-mol−1
8.3144621(75) cm3 MPa K-1 mol-1 1.31443 ft3 atm K−1 lb-mol−1
ft3  mmHg K−1 lb-
8.3144621(75)×10−5 m3 bar K-1 mol-1 998.9701(17)
mol−1
8.205746×10−5 m3 atm K-1 mol-1 1.986 Btu °R−1 lb-mol−1
82.05746 cm3 atm K-1 mol-1 *value(standard deviation)

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