Lesson 2 Classification and Properties of Analysis of Composition of Solid Fuels

Fuels (Fuels and Combustion) Proximate analysis. (ASTM D3173-11) is an

analysis of the composition of the fuel which
Introduction gives, on mass basis, the relative amount of
Fuel is any substance, natural or artificial the moisture content, volatile matter, fixed
which upon combustion, release heat energy. carbon and ash. This analysis enables the
It is a substance which, when burnt, i.e. on engineer to predict the behavior of fuel in the
coming in contact and reacting with oxygen furnace to a certain degree. The proximate
or air, produces heat. Thus, the substances analysis provides a useful comparison
classified as fuel must necessarily contain one between fuels.
or several of the combustible elements:
carbon, hydrogen, sulfur. Procedure.
Step 1. A sample of coal is crushed and dried
A. Solid Fuels - Solid Fuels refers to various in an oven at 105 to 110C to constant weight
forms of solid material that can be burnt to for 1 hour to determine residual moisture.
release energy, providing heat and light Step 2. The sample is then heated in a covered
through the process of combustion. Solid crucible at 900C for 7 minutes to constant
fuels can be contrasted with liquid fuels and weight. This weight loss is referred as volatile
gaseous fuels. Common examples of solid matter.
fuels include wood, charcoal, peat, coal, Step 3. The remaining sample is then placed in
Hexamine fuel tablets, wood pellets, corn, an oven at 750C with the cover off so that the
wheat, rye, and other grains. sample is combusted. The weight loss upon
combustion is termed fixed carbon or char.
Types of Solid Fuels
Step 4. The remaining residue is defined as ash
1. Biomass - is a cellulose material which can be
broadly classified as woody and non woody Moisture
biomass.
2. Wood - Although wood is a form of biomass,
but the term usually refers to other natural
plant material that can be burnt for fuel. Volatile matter
3. Charcoal - is made by heating wood in the
absence of air to produce char. Charcoal is
relatively clean burning fuel.
4. Peat - also known as turf, is an accumulation Ash
of partially decayed vegetation or organic
matter. It is unique to natural areas called
peatlands, bogs, mires, moors, or muskegs. Fixed Carbon
5. Coke is a grey, hard, and porous fuel with a high
carbon content and few impurities, made by
heating coal or oil in the absence of air a Hydrogen
destructive distillation process.
6. Coal is the most plentiful fuel available on Earth.
but it is a finite, non-renewable and very-
polluting source. Fuel composition is reported on as – received
6.1. Types of Coal. basis (mas received), on a dry basis (mdry basis), or
Anthracite. This is the hardest, purest, more on a dry ash -free basis (mdaf)
brittle and scarce coal; too precious for a
fuel (it is used for chemicals). mas received = mfuel = mdaf + MC + Ash
Bituminous coal. Bituminous coal is a dense
black solid that frequently contains bright mdry basis = mdaf + Ash
bands with a brilliant luster.
Lignite. Lignite, or brown coal, is the most
abundant form of coal. It has some 40-60%
of trapped water.
 Sample problems. The heating value of solid fuel can be obtained
1. Wood chips with a 40% moisture (as – by:
received) are supplied to a biomass power
Dulong’s Formula:
plant. What is the moisture content on a
dry basis? HHV=GCV=Qh= 14,540C + 62,000(H-O/8) +
4050S BTU/lb
Ultimate Analysis
The ultimate analysis (ASTM 3176) is an analysis HHV=GCV=Qh=33,820C + 144,212(H-O/8) +
of the composition of fuel which gives on mass 9,304S KJ/kg
basis the relative amount of carbon, hydrogen, Lower Heating Value
oxygen, nitrogen, sulfur, ash and moisture.
Procedure. Carbon and hydrogen are QL = QH – 9%H (2442) Kj/Kg
determined by burning the sample in oxygen in QL = QH – 9%H (1050) BTU/Lbm
a closed system and quantitatively measuring
the combustion products. The carbon includes Example.
organic carbon as well as carbon from the
1. Calculate the HHV, LHV (in KJ/Kg) given the
mineral carbonates. The hydrogen includes
ultimate analysis C= 71.5% O= 7% S=3.6%
organic hydrogen as well as hydrogen from the
H=5.0% N= 1.3% Ash=8.2%.
moisture of the dried sample and mineral
hydrates. The extraneous carbon and hydrogen
2. A solid fuel contains 6% hydrogen, 30%
are usually negligible. Nitrogen and sulfur are
moisture, and 10% ash has a higher heating
determined chemically. Oxygen is determined
value of 5000 Btu/lbm (all wt % as received).
by the differences between 100 and the sum of
Determine the lower heating value (LHV)
C,H,N and S. Sometimes, chlorine is included in
based on Dry ash free basis.
the ultimate analysis.
Liquid Fuels
Gravimetric analysis – yields the percentage of
composition based on mass.
Petroleum Oil - (Crude oil) is a mixture of
Mass fraction (Mf) =
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑒𝑙𝑒𝑚𝑒𝑛𝑡 numerous hydro carbons, each having its
𝑇𝑜𝑡𝑎𝑙 𝑀𝑎𝑠𝑠
chemical and physical properties including
molecular form. It is a natural mineral oil which
Volumetric Analysis -Yields the percentage of exists in varying depth in many areas of the
composition based on Yields. earth. Crude oil as extracted from wells
consists essentially of carbons and hydrogen,
𝑁𝑜. 𝑜𝑓 𝑚𝑜𝑙𝑒 𝑒𝑙𝑒𝑚𝑒𝑛𝑡 with small amount of sulfur, oxygen, water in
Mole fraction (Nf) = 𝑇𝑜𝑡𝑎𝑙 𝑛𝑜. 𝑜𝑓 𝑚𝑜𝑙𝑒
emulsion and silt.

Sample Problems.
Composition. Each crude-oil field has a
2. Determine the mole fraction of a gas
different composition that can be established
consisting of a mole oxygen, eight moles
by a combination of gas-chromatography,
of nitrogen, a mole of CO and two moles
fluorescence-spectroscopy and infrared-
of CO2. Determine also the mass fraction.
spectroscopy techniques, and that may be
And what is the average molecular weight
used, for instance, in forensic analysis of oil
of the gas?
spills at sea (even after refining, crude-oil
derivatives may be associated to their source
Heating Value/Calorific Value of Solid Fuels
field)
Calorific value (CV) or Heating Value (HV) is a
direct indication of the heat content (energy Groups of Petroleum
value) of a fuel.
a. Paraffin Based- Those containing
Gross Calorific Value/Higher Heating Value. The relatively high percentage of aliphatic
GCV assumes that all of the vapor produced hydrocarbons and low percentage of
from coal moisture during the combustion cyclic hydrocarbons.
process is fully condensed.
b. Intermediate Based - Those contains both
paraffinic and asphaltic hydrocarbons and
are generally rich in semi-solid waxes.
c. Asphalt Based -It contains mainly
cycloparaffins or napthenes with smaller
amount of paraffin’s and aromatic
hydrocarbons.
Viscosity. Viscosity of a liquid indicates the
Characterization of Liquid Fuels resistance to flow.

Specific Gravity. This also known as the relative Absolute viscosity. Viscosity which is
density. determined by direct measurement of
shear resistance.

Kinematic viscosity. Absolute viscosity

divided by density. Kinematic viscosity is
expressed in stoke or centistoke.

Viscosity Index. The rate at which

The Specific Gravity (S.G.) of liquid fuels at viscosity change with temperature.
Temperature (t) can be obtained by:
Flash Point. Flash point is the temperature at which
ignition of the fuel vapor rising above the heated oil
occurs when exposed to open flame.

Pour Point. The pour point of a fuel is the lowest

temperature at which it will pour or flow when
cooled under prescribed conditions.

Specific heat. Specific heat is the amount of energy

Calorific Value or Heating Value This is the in kCals needed to raise the temperature of 1 kg of
energy liberated by a complete combustion of oil by 1 0C.
a unit of weight or volume of fuel.
Higher Heating Value or Gross Calorific Value, Auto ignition Temperature. This is the lowest
HHV or Qh-is the heating value obtained when temperature required to initiate self-
the water in the product of combustion is in sustained combustion in a standard container
liquid state. in atmospheric air in the absence of spark or
Lower Heating Value or Net Calorific Value. flame. i.e. the auto ignition temperature of
LHV or QL. This is the heating value obtained gasoline is 37°C.
when the water in the product of combustion
is in vapor state. Ignition Quality. As a means of controlling the
ignition quality of fuel, cetane number and
The higher heating value of fuel can be diesel index are widely used.
obtained by the ff.:
Sulphur Content. The amount of sulphur in
ASME Formula for Petroleum Products: the fuel oil depends mainly on the source of
the crude oil and to a lesser extent on the
refining process.

Bureau of Standards Formula: Ash Content. The ash value is related to the
inorganic material or salts in the fuel oil. The
ash levels in distillate fuels are negligible.
Lower Heating Value of Liquid Fuels, QL
 Liquid Fuel Types of the fuel is 19,500 Btu/lb and the over-
all efficiency of the diesel electric unit is
1. Gasoline - The straight run gasoline is obtained 30%.
either from distillation of crude petroleum or by
synthesis. It is a blend of paraffins, olefins, Gaseous Fuels - is any fuels that under ordinary
naphthenes, and aromatics which varies from conditions are gaseous. The main gaseous fuels
are natural gas and liquefied petroleum gas.
company to company and by location and
Gaseous fuels are also produced from coal and
season of the year.
wood, and from petroleum and natural gas.
Gasoline varies greatly in characteristics
depending upon the nature of crude oil and Types of Gaseous Fuels
process of preparation. Gasoline must be volatile Two broad classes of fuel gases based on their
enough to vaporize readily in the engine but not sources and the way they are produced.
so volatile as to cause danger of detonation
during handling. A. Natural gas and petroleum gases

Natural gas is a naturally occurring hydrocarbon

Other properties of gasoline are: gas mixture consisting primarily of methane, but
commonly including varying amounts of other
Octane number. The ignition quality rating of higher alkanes, and sometimes a small
gasoline, which is the percentage by volume of percentage of carbon dioxide, nitrogen, hydrogen
isooctane (C8H18 )in a mixture of iso-octane and sulfide, or helium.
heptane(C7H16) that matches the gasoline in
anti -knock quality. Additional fuel gases can result as a process of
Bioethanol. Bioethanol is bio-fuel substitute of refining natural gas or petroleum:
gasoline; i.e. it is ethanol obtained from biomass
1. Propane - Propane is a three-carbon
(not from fossil fuels), and used as a gasoline
alkane with the molecular formula C3H8.
blend.
It is a gas at standard temperature and
pressure, but compressible to a
2. Diesel Fuel - is a mixture of light
transportable liquid.
distillate hydrocarbons with a higher boiling
2. Butane is an organic compound with the
point range than gasoline.
formula C4H10 that is an alkane with four
Cetane Number (CN). this is the ignition quality
carbon atoms.
rating of diesel which is the percent of cetane in
3. Liquefied Petroleum Gas (LPG) - LPG is a
the standard fuel. Low cetane number cause
petroleum-derived product distributed
cold starting problem, increase engine
and stored as a liquid in pressurized
roughness, peak pressure and NO emissions.
containers.
𝐶𝑁=−420.34+0.016(𝐴𝑃𝐼)2+0.192(𝐴𝑃𝐼)𝑙𝑜𝑔10(𝑇)+
B. Manufactured fuel gas - Manufactured fuel
65.01(𝑙𝑜𝑔10𝑇)2− 0.0001809(𝑇)2
gases are those produced through an artificial
Where; T = in °F process, usually gasification, at a location known
as a gasworks.
Sample Problems
1. Coal gas - is a flammable gaseous fuel made
1. Find the gravity in oAPI and °BAUME for from coal and supplied to the user via a piped
oil having a specific gravity of 0.84. distribution system. It is produced when coal is
2. A fuel with 28°API has temperature of heated strongly in the absence of air.
4°C.Determine the density, 𝜌 (kg/m3) and 2. Water gas is a mixture of carbon monoxide and
higher heating value (kCal/kg) of this
hydrogen produced from synthesis gas. Synthesis
fuel?
gas is a useful product, but requires careful
3. A fuel has an API gravity of 35.7 and a
50% distillation temperature of 529K. handling due to its flammability and the risk of
Calculate its cetane number (CN) of this carbon monoxide poisoning. Syngas, or synthesis
fuel. gas is a fuel gas mixture consisting primarily of
4. How many cubic feet of fuel oil with 320 hydrogen, carbon monoxide, and very often some
Baume are supplied to produce 3,780 carbon dioxide.
kW-hrs of electricity, if the heating value
3. Producer gas is fuel gas that is manufactured Actual Weight of Air:
from material such as coal.
The weight of air supplied for combustion is
4. Wood gas is a syngas fuel which can be used as necessarily in excess of what is theoretically
a fuel for furnaces, stoves and vehicles in place of required. The volumetric analysis of the dry flue
gasoline, diesel or other fuels. gas can be used to calculate the actual weight air.

5. Biogas refers to a mixture of different gases

produced by the breakdown of organic matter in
the absence of oxygen.
Where:
6. Blast furnace gas (BFG) is a by-product of blast
furnaces that is generated when the iron ore is Waa = actual weight of air including the excess
reduced with coke to metallic iron.
C = weight of carbon per kg of fuel from the
7. Acetylene is the chemical compound with the ultimate analysis.
formula C2H2. It is a hydrocarbon and the
simplest alkyne. N2, CO2 and CO are percentages by volume of the
component gases in the flue gas as obtained by
8. Hydrogen is manufactured by reforming Orsat Analysis.
natural gas, partial oxidation of liquid
hydrocarbons, or coal gasification. ANALYSIS OF FLUE GAS

Gaseous products of combustion are analyzed

Theoretical Weight of Air
using gas analyzer known as the Orsat apparatus.
The theoretical weight of air is the exact The combustion products contain CO2, SO2, N2,
theoretical amount as determined from the O2, CO, and water vapor.
combustion reaction of air needed to burn a unit
The result of the analysis of dry flue gas by
amount of fuel.
volume can be expressed by the equation:
If the Ultimate Analysis of coal is available, the
theoretical weight of air required to completely
oxidize the fuel can be calculated as:

Sample Problems

1. The bituminous coal has the following

compositions:
where:
C= 71.5% O= 7% S=3.6% W=3.4%
Wta = ideal proportion of air to completely burn
the fuel H=5.0% N= 1.3% Ash=8.2%
C, H, O and S are proportions by weight of Carbon, Calculate for complete combustion the
Hydrogen, Oxygen and Sulfur per kg of fuel from theoretical weight of air required in Kgair/Kgfuel
the ultimate analysis.
2. If the theoretical air- fuel ratio is 15, what is
If the Ultimate Analysis of coal is not available, an the approximate higher heating value in
approximate formula to obtain the theoretical air- KJ/Kgfuel?
fuel ratio when the heating value of fuel is known:

COMBUSTION STOICHIMETRY

Combustion. Combustion is a chemical reaction

between fuel and oxygen which is accompanied
by heat and light.
Oxidizers. As the name of this reactants
suggests, molecular oxygen (O2) is the oxidizer
present in most combustion processes.
Products. When a hydrocarbon fuel burns, the 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑜𝑓 𝐶𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛
carbon reacts with the oxidizer to create first
carbon monoxide (CO) and then carbon dioxide bCO2 + cH2O+ a(3.76N2)
(CO2)-note that although CO is a product of
hydrocarbon combustion, it is also a fuel in its B. Actual balance with excess air.
own right because it can further oxidize to CO2.
CnHm + a(1+e)O2 + a(1+e)(3.76)N2
The hydrogen in the fuel reacts to form water,
H2O. bCO2 +cH2O + a(1+e)(3.76)N2 + a(e)O2
Complete Combustion. This refers to the
Where:
condition of having the fuel completely oxidized;
that is all the carbon in the fuel becomes carbon E = excess air
dioxide (CO2) and all the hydrogen in the fuel
becomes (H2O). For any given combustion situation, two air-fuel ratios
Perfect Combustion. This refers to the condition exist: one based on the number of moles of each
of complete combustion occurring with no substance and one based on the mass of each
additional oxygen present. Perfect combustion substance in the reactants.
can also be referred as stoichiometric On mass basis;
combustion. The products of perfect combustion
of a hydrocarbon fuel in air are considered to be
only CO2, H2O and N2
Lean Combustion. The term for combustion
when there is more oxygen (or air) presents in
On mole basis;
the reactants than what is required to produce
complete combustion
Rich Combustion. The term for combustion
when there is less oxygen (or air) present in the
reactants than what is required to produce sample problems
complete combustion. 1. Typical fuel oil 𝐶8𝐻18 is burned with the correct
amount of air. A. Find Combustion equation. B.
Balancing Combustion Reactions 25% excess.
To determine the global chemical reaction 2. Propane, C3H8, burns to completion with 110%
governing a combustion process, we must theoretical air. Write the chemical reaction for
consider the expected appropriate expected this process and determine the ff.: (a) actual air-
outputs and the number of atoms of each type fuel ratio on mass basis, (b)actual air-fuel ratio
must be equal in the products and the reactants. on mole basis (c) theoretical air-fuel ratio (mass
This process, called atom balancing, allows to basis), (d) theoretical air-fuel ratio (mole basis),
determine the coefficients in front of each and (d) The equivalence ratio.
compound in the chemical equation.

Typical combustion reaction of a fuel with known List of Gaseous Hydrocarbon Fuels
1. Methane (CH₄)
chemical formula:
2. Ethane (C₂H₆)
𝐹𝑢𝑒𝑙 + 𝑎𝑖𝑟 ⟶ 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑜𝑓 𝑐𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛
3. Propane (C₃H₈)
4. Butane (C₄H₁₀)
A. Theoretical Balance of Hydrocarbons 5. Pentane (C₅H₁₂)
6. Isobutane (C₄H₁₀)

where:
a, b, and c represent number of moles.
𝐹𝑢𝑒𝑙 ⟶ 𝐶n𝐻m
𝐴𝑖𝑟 ⟶ a𝑂2 + b(3.76)𝑁2