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
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.
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:
c) Ash Content:
Ash is an impurity that will not burn. Typical range is 5 to 40%. Ash
d) Moisture Content:
e) Sulphur Content:
Ultimate Analysis:
COMBUSTION
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
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%
CO2 0.03%
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.
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
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,
SCH1204 CHEMICAL PROCESS CALCULATIONS UNIT IV FUELS AND COMBUSTION
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.
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.
Percent Excess
Actual air supplied = Theoretical Air Requirement (1 + )
100
SCH1204 CHEMICAL PROCESS CALCULATIONS UNIT IV FUELS AND COMBUSTION
Note that the percent excess air identical to the 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
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
If there are no experimental data for GCV and NCV, they can be easily
calculated by using the following formulae:
where:
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.
SCH1204 CHEMICAL PROCESS CALCULATIONS UNIT IV FUELS AND COMBUSTION
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 %).
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.