SCH1204 CHEMICAL PROCESS CALCULATIONS UNIT IV FUELS AND COMBUSTION

PREPARED BY: P.SENTHILKUMAR PAGE: 1 OF 10

FUELS

A fuel is any material that can be made to react with other substances so that
it releases chemical or nuclear energy as heat or to be used for work. The
concept was originally applied solely to those materials capable of
releasing chemical energy but has since also been applied to other sources of
heat energy such as nuclear energy. The heat energy released by reactions of
fuels is converted into mechanical energy via a heat engine. Other times the
heat itself is valued for warmth, cooking, or industrial processes, as well as the
illumination that comes with combustion. Chemical fuels are divided in two
ways. First, by their physical properties, as a solid, liquid or gas. Secondly, on
the basis of their occurrence: primary (natural fuel) and secondary (artificial
fuel).

COAL ANALYSES

It is often difficult to obtain representative samples of coal because of

composition variations from location to location even within a given seam. As a
result there are limits on the accuracy and adequacy of coal analyses in
assessing coal behavior in a given application. Before discussing the nature of
these analyses, it is important to establish the basis on which they are
conducted.

Coal contains varying amounts of loosely held moisture and noncombustible

materials or mineral matter (ash), which are of little or no use. The basis of an
analysis helps to specify the conditions under which the coal is tested. The coal
sample may be freshly taken from the mine, the as-mined basis. It may have
resided in a coal pile for months, and be analyzed just before burning, the as-
fired basis. It may be examined immediately after transport from the mine, the
as-received basis. Exposure to rain or dry periods, weathering, and separation
and loss of noncombustible mineral matter through abrasion and the shifting
of loads during transport and storage may cause the same load of coal to have
changing mineral matter and moisture content over time. It is therefore
important to specify the basis for any test that is conducted. Published
tabulations of coal properties are frequently presented on a dry, ash-free, or
dry and ash-free basis, that is, in the absence of water and/or noncombustible
mineral matter.

Coal ranking and analysis of combustion processes rely on two types of

analysis of coal composition: the proximate analysis and the ultimate analysis.
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Proximate Analysis

The proximate analysis starts with a representative sample of coal. The sample
is first weighed, then raised to a temperature high enough to drive off water,
and then reweighed. The weight loss divided by the initial weight gives the coal
moisture content, M. The remaining material is then heated at a much higher
temperature, in the absence of oxygen, for a time long enough to drive off
gases. The resulting weight-loss fraction gives the volatile matter content, VM,
of the coal. The remainder of the sample is then burned in air until only
noncombustibles remain. The weight loss gives the fixed carbon, FC, and the
remaining material is identified as non-combustible mineral matter or ash, A.

The proximate analysis may be reported as percentages (or fractions) of the

four quantities moisture, ash, volatile matter, and fixed carbon or without ash
and moisture and with the FC and VM normalized to 100%. Sulfur, as a
fraction of the coal mass, is sometimes reported with the proximate analysis.
The proximate analysis, while providing very limited information, can be
performed with limited laboratory resources.

Significance of Various Parameters in Proximate Analysis

a) Fixed carbon:

Fixed carbon is the solid fuel left in the furnace after volatile matter is distilled
off. It consists mostly of carbon but also contains some hydrogen, oxygen,
sulphur and nitrogen not driven off with the gases. Fixed carbon gives a rough
estimate of heating value of coal.

b) Volatile Matter:

Volatile matters are the methane, hydrocarbons, hydrogen and carbon

monoxide, and incombustible gases like carbon dioxide and nitrogen found in
coal. Thus the volatile matter is an index of the gaseous fuels present. Typical
range of volatile matter is 20 to 35%. Volatile Matter

• Proportionately increases flame length, and helps in easier ignition of

coal.
• Sets minimum limit on the furnace height and volume.
• Influences secondary air requirement and distribution aspects.
• Influences secondary oil support.
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c) Ash Content:
Ash is an impurity that will not burn. Typical range is 5 to 40%. Ash

• Reduces handling and burning capacity.

• Increases handling costs.
• Affects combustion efficiency and boiler efficiency
• Causes clinkering and slagging.

d) Moisture Content:

Moisture in coal must be transported, handled and stored. Since it replaces

combustible matter, it decreases the heat content per kg of coal. Typical range
is 0.5 to 10%. Moisture

• Increases heat loss, due to evaporation and superheating of vapour

• Helps, to a limit, in binding fines.
• Aids radiation heat transfer.

e) Sulphur Content:

Typical range is 0.5 to 0.8% normally. Sulphur

• Affects clinkering and slagging tendencies

• Corrodes chimney and other equipment such as air heaters and
economisers
• Limits exit flue gas temperature.

Ultimate Analysis:

A more sophisticated and useful analysis is the ultimate analysis, a chemical

analysis that provides the elemental mass fractions of carbon, hydrogen,
nitrogen, oxygen, and sulfur, usually on a dry, ash-free basis. The ash content
of the coal and heating value are sometimes provided also. It is useful in
determining the quantity of air required for combustion and the volume and
composition of the combustion gases. This information is required for the
calculation of flame temperature and the flue duct design etc.

COMBUSTION

Combustion is the conversion of a substance called a fuel into chemical

compounds known as products of combustion by combination with an oxidizer.
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The combustion process is an exothermic chemical reaction, i.e., a reaction

that releases energy as it occurs. Thus combustion may be represented
symbolically by:

Fuel + Oxidizer → Products of combustion + Energy

Here the fuel and the oxidizer are reactants, i.e., the substances present before
the reaction takes place. This relation indicates that the reactants produce
combustion products and energy. Fuels are evaluated, in part, based on the
amount of energy or heat that they release per unit mass or per mole during
combustion of the fuel. Such a quantity is known as the fuel's calorific value or
heat of reaction or heating value.

Combustion Chemistry

Most of the fuel used in power plant combustion furnaces is either coal
(carbon, some hydrogen and sulfur, and various noncombustible materials),
fuel oil (mostly high molecular weight hydrocarbons, some sulfur), gaseous fuel
(such as natural gas, which is primarily methane), or liquefied petroleum gas,
which is usually propane and/or butane.

When a fuel is burned, carbon in the fuel reacts to form either CO2 or CO,
hydrogen forms H2O, and sulfur forms SO. At temperatures greater than
approximately 1800oC, some of the nitrogen in the air reacts to form nitric acid
(NO). A combustion reaction in which CO is formed from a hydrocarbon is
referred to as partial combustion or incomplete combustion of the
hydrocarbon.

Examples

C + O2 → CO2 Complete combustion of carbon

C3H8 + 5O2 → 3CO2 + 4H2O Complete combustion of propane

C3H8 + 3.5O2 → 3CO + 4H2O Partial combustion of propane

CS2 + 3O2 → CO2 + 2SO2 Complete combustion of carbon

disulfide
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For obvious economic reasons, air is the source of oxygen in most combustion
reactors. Dry air has the following average molar composition:

N2 78.03%

O2 20.99%

Ar 0.94% Average molecular weight = 29

CO2 0.03%

H2, He, Ne, Kr, Xe 0.01%

In most combustion calculations, it is acceptable to simplify this composition

to 79% N2, 21% O2 or 79 moles N2/21 moles O2 or 3.76 moles N2/mole O2.

The term composition on a wet basis is commonly used to denote the

component mole fractions of a gas that contains water, and composition on a
dry basis signifies the component mole fractions of the same gas without the
water. For example, a gas that contains 33.3 mole% CO2, 33.3% N2, and 33.3%
H2O (wet basis) contains 50% CO2 and 50% N2 on a dry basis.

Flue Gas Analysis by Orsat Apparatus

The product gas that leaves a combustion furnace is referred to as the stack
gas or flue gas. This contains gases like SO2, CO2, O2, CO etc.

Importance of Flue Gas Analysis:

 The analysis gives the idea of whether a combustion process is complete

or not.
 The C and H present in a fuel undergo combustion forming CO2 and H2O
respectively. Any N present is not at all involved in the combustion. ie.,
the products of combustion are CO2, H2O and N2.
 If analysis of a flue gas indicates the presence of CO; it is suggestive of
incomplete combustion. (wastage of heat is inferred) 26
 If there is considerable amount of oxygen, it shows that there is excess
supply of O2 although combustion would have been complete.

Analysis:

The flue gas analysis is carried out by using Orsat’s apparatus. The analysis of
flue gas generally deals with the determination of CO2, O2 and CO by absorbing
SCH1204 CHEMICAL PROCESS CALCULATIONS UNIT IV FUELS AND COMBUSTION

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them in the respective solution of KOH, alkaline pyrogallol and ammonium

cuprous chloride.

Description of Orsat’s apparatus:

Orsat’s apparatus consists of a horizontal tube having 3 way stopcock at one

end and a water jacketed measuring burette at the other end. The horizontal
tube is connected to three different absorption bulbs for the absorption of CO2,
O2 and CO respectively. The lower end of the burette is connected to the
leveling bottle by means of rubber tube. The level of water in the leveling bottle
(water reservoir) can be raised or lowered by raising or lowering the water
reservoir. By changing the level of water, the flue gas can be moved into various
parts of the apparatus during analysis.

It is essential to follow the order of absorbing the gases- CO2 first; O2 second
and CO last. This is because the absorbent used for O2 (ie., alkaline pyrogallol)
can also absorb some amount of CO2 and the percentage of CO2 left would be
less.

Absorption of CO2: Flue gas is passed into the bulb A via its stopcock by
raising the water reservoir. CO2 present in the flue gas is absorbed by KOH
(usually 250 g KOH in 500 mL distilled water). The gas is again sent to the
burette and then again sent to bulb A. This process is repeated several times,
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by raising or lowering of water reservoir so as to ensure complete absorption of

CO2 in KOH. Now, the stopcock of bulb A is closed. The volume of residual
gases in the burette is taken by equalizing the water level both in the burette
and in the water reservoir. The difference between original volume and the
volume of the gases after CO2 absorption gives the volume of CO2 absorbed.

Absorption of O2: Stopcock of bulb A is closed and bulb B is opened. Oxygen

present in the flue gas is absorbed by alkaline pyrogallol (25 g pyrogallol +200 g
KOH in 500 mL distilled water). The absorption process is same as in bulb A.

Absorption of CO: Now the stopcock of bulb B is closed and stopcock of bulb C
is opened. Carbon monoxide present in the flue gas is absorbed by ammoniacal
cuprous chloride (100 g Cu2Cl2 + 125 mL liquid NH3 + 375 mL water). Here
also absorption process is same as in bulb A.

Since the total volume of the gas taken for analysis is 100 mL, the volumes of
the constituents are their percentage. The residual gas after the above three
determinations is taken as nitrogen. Further, as the content of CO in the flue
gas would be very low, it should be measured quite carefully.

Theoretical Air and Air-Fuel Ratio

The minimum amount of air which will allow the complete combustion of the
fuel is called the Theoretical Air (also referred to as Stoichiometric Air). In this
case the products do not contain any oxygen. If we supply less than theoretical
air then the products could include carbon monoxide (CO), thus it is normal
practice to supply more than theoretical air to prevent this occurrence.
This Excess Air will result in oxygen appearing in the products.

Theoretical Oxygen Requirement in moles

Theoretical Air Requirement in moles =
0.21
The amount of air in excess of the stoichiometric air is called excess air. It is
usually expressed in terms of the stoichiometric air as percent excess air.
Amount of air less than stoichiometric are called deficiency of air.

Actual air supply − Theoretical Air Requirement

Percent excess air = ( )
Theoretical Air Requirement

Percent Excess
Actual air supplied = Theoretical Air Requirement (1 + )
100
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Note that the percent excess air identical to the percent excess O2

Percent Excess Air = Percent Excess O2

CALORIFIC VALUE
In combustion discussions reference is frequently made to gross calorific value
(or higher heating value) and net calorific value (or lower heating values). The
term gross calorific value, GCV, refers to a heating value measurement in
which the product water vapor is allowed to condense. As a consequence, the
heat of vaporization of the water is released and becomes part of the heating
value. The net calorific value, NCV, corresponds to a heating value in which the
water remains a vapor and does not yield its heat of vaporization. Thus the
energy difference between the two values is due to the heat of vaporization of
water, and

GCV = NCV + n∆Hv

where n is the mol of water produced during combustion, ∆Hv is the latent heat
of vaporization of water at 298 K in kJ/mol.

If ‘m’ is the quantity of water produced in kg when a unit mass of fuel is burnt
and ‘λ’ is the latent heat of condensation of water vapour at 298 K in kJ/kg,
then

GCV = NCV + mλ

In practice, heat transferred for combustion of fuel is measured experimentally

either at constant volume for solid and liquid fuels or at constant pressure for
gaseous fuels.

If there are no experimental data for GCV and NCV, they can be easily
calculated by using the following formulae:

Solid and liquid fuels

O MJ
NCV = 33.9 C + 117 (H − ) + 10.5 S − 2.5 W [ ]
8 kg of fuel
MJ
GCV = NCV + 2.5 (9 H + W) [ ]
kg of fuel

where:

C = Mass of Carbon per 1 kilogram of fuel

H = Mass of Hydrogen per 1 kilogram of fuel
S = Mass of Sulfur per 1 kilogram of fuel
O = Mass of Oxygen per 1 kilogram of fuel
W = Mass of Water per 1 kilogram of fuel
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EXERCISE
1. Explain proximate and ultimate analysis of coal.
2. Distinguish between gross and net calorific values
3. If methane gas is burnt with the theoretical amount of air determine the
percentage composition by volume of the flue gases obtained.
4. Define Calorific value of fuel.
5. Write short notes about Orsat analysis.
6. Distinguish between proximate and ultimate analysis of coal.
7. Express the constituents of coal as given by ultimate and proximate
analysis.
8. Define excess air.

9. 500kg/h of pure sulfur is burned with 25% excess air. Based on S to SO2
5% sulfur is oxidized to SO3 and rest to SO2. Find the exit gas analysis.
10. A furnace is fired with a natural gas that consist entirely of hydrocarbons.
The flue gas consists of 9.5% CO2, 2%O2 and 1.8%CO.
(a) Calculate the molor ration of net hydrogen to carbon in the
fuel.
(b) Find the percentage excess air.
11. What was the % excess air used if 40 kg of butane is burnt with 1300 kg
of air to produce 92 kg of CO2 and 20 kg of CO?
12. The gases from a sulphur burner in a sulphuric acid plant has the
following composition by volume : SO2 – 6.5%; SO3 – 2.78%; O2 – 10.65%;
and N2 – 80.07%. Calculate the following:
a) percentage oxidation of sulphur to SO2;
b) percent excess air supplied over that required for complete oxidation
of sulphur to SO3 and
c) volume of gases leaving the burner at 450oC and 740 mm Hg pressure
per 100 kg of sulphur burnt.
13. (a) A fuel is burnt with O2 to give CO2 and H2O with ratio of 2:3. Find C: H
ratio of the fuel.
(b) Natural gas containing 90% CH4, 6% C2H6 and 4% C3H8 is burnt with
40% excess air. If 90% of the hydrocarbons are converted to CO2 and the
rest to CO, calculate the Orsat analysis of the flue gas.
14. The analysis of a gas entering the converter in a contact H2SO4 plant is 4%
SO2, 13% O2 and 83% N2 by volume. The gas leaving the converter
contains 0.45% SO2 by volume on SO3 free basis. Calculate the percentage
of SO2 entering the converter that gets converted to SO3.

15. Butane gas is burnt with 80% of the theoretical air required for
complete combustion. If all the hydrogen present in butane gets converted
to water vapour determine the complete analysis by volume of the flue
gases.
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16. A gas containing 80% ethane and 20% oxygen is burned with 200% excess
air. 80% of ethane goes to CO2, 10% to CO and the rest remains unburnt.
Calculate the dry exhaust gas analysis.

17. A fuel contains 70% CH4, 20% C2H2 and 10% O2. The fuel – air mixture
contains 200% excess O2 before combustion. 10% of the hydrocarbon
remains unburnt. Of the total carbon burnt 90% forms CO2 and the rest
forms CO. Calculate the composition of the flue gas on dry and wet basis.
The reactions taking place are
CH4 + 2O2 → CO2 + 2H2O
CH4 + 1.5O2 → CO + 2H2O
C2H6 + 3.5O2 → 2CO2 + 2H2O
C2H6 + 2.5O2 → 2CO + 3H2O

18. The Orsat analysis of the flue gases from a boiler house chimney gives
CO2: 11.4%, O2 : 4.2% and N2 : 84.4% (mole %).

Assuming that complete combustion has taken place

(i) Calculate the % excess air and
(ii) Find the C : H ratio in the fuel
Give detailed account of Orsat analysis with schematic diagram. Explain how it
is used for automobile exhaust gas analysis.
19. A petroleum refinery burns a gas mixture containing C5H12 7%, C4H10
10%, C3H8 16%, C2H6 9%, CH4 55% and N23% at the rate of 200m3/hr at
4.5 bar pressure and 30°C temperature. The air rate is adjusted so that
15% excess air is used and under the conditions the ratio of moles of CO2
to CO is 20:1 in the flue gas. Calculate
(a) m3/hr of air introduced at 30°C and 1 atmospheric pressure and
(b) Composition of flue gas on dry basis.

20. A furnace uses coke containing 80% Carbon, 5% Hydrogen and remaining
ash. The furnace operates with 50% excess air of that required for
complete combustion of all the carbon charged. The solid residue (ash)
contains 2% carbon. Of the carbon burnt 5% goes to CO. Calculate :
(a) composition of the flue gas;
(b) ash produced;
(c) kg carbon lost per kg of coke burnt.
21. Natural gas, consists entirely of hydrocarbons, is burnt in a furnace. The
flue gas analysis is CO2-9.5%, O2-1.4%, and CO-1.9%. Calculate the
following
(a) the atomic ratio of H2 to carbon in the fuel
(b) % excess air
(c) the composition of the fuel gas in the form CxHy.