ChE 32 Lecture Notes 01 - INTRODUCTION C + O2 CO2

H2 + 0.5O2 H2O
Introduction to the Combustion Process (if with S) S + O2 SO2*

Combustion – chemical process in which a substance reacts *although SO2 is still combustible, it is considered a product of
complete combustion because it is more stable than SO3.
rapidly with oxygen and gives off heat; accompanied by
**N2 does not participate in the combustion process and leaves
evolution of light and heat; generally used in generation of
furnace as plain N2 gas
heat to supply energy in the industry
ii. Incomplete combustion – too much fuel for given
I. Components of Combustion oxygen or inefficient system; there is loss of heat due to
a. Fuel – usually hydrocarbon burned to generate thermal incomplete combustion; additional products include H2 and
energy; in given percentages composition, assume % mol if CO.
gases and assume % mass for solid and liquid unless iii. Orsat technique – determines specific amounts
otherwise stated; if amount is unstated, choose your basis of different components of combustion gases by measuring a
wisely decrease in volume of gas sample as it passes over selective
b. Air – can be assumed to be 21% O2 and 79% N2 since we liquid absorbent in series; dry basis (the percentage result
can assume CH4, Ar, Ne to be negligible (unless explicitly does not reflect water vapor although it might actually be
stated to include other compounds); assume dry air (without present)
water) if condition is not stated
i. Theoretical Oxygen (O2) – mol of oxygen required Liquid Absorbent Gas Absorbed
for fuel to undergo complete combustion based on balanced Caustic solution Carbon dioxide
combustion reaction Pyrogallol Oxygen
ii. Theoretical Air – mol of air containing theoretical Cuprous chloride Carbon monoxide
oxygen Conc. sulfuric acid Water vapor
--------------------------------------------------------------------------- Lead dioxide Sulfur dioxide
Example 1: Determine the theoretical oxygen and theoretical
air required for combustion of 1 mol of refinery gases d. Reactor – called furnace, engine, boiler depending on use
containing 6% H2S, 5% H2, 57% C3H8, 2% CO2 and 30% C4H10.
Ans. 4.915 mol O2, 23.405 mol air II. Dew point of wet flue gas
-------------------------------------------------------------------------- - Temperature at which the water vapor in the
iii. Excess air – amount of air used above that wet flue gas begins to condense
theoretically needed for complete combustion; excess Wet flue gas = Dry flue gas + water vapor
amount is used in order to surround the fuel with sufficient Mol frac of water vapor (ywater) = (mol water vapor)/(mol wet flue
gas)
air for combustion; difference between supplied and
Mol frac of water vapor (ywater) = Partial pressurewater/PressureTotal
thoeretical air
At dew point, Ppartial of water = VP at saturation
𝑠𝑢𝑝𝑝𝑙𝑖𝑒𝑑 𝑎𝑖𝑟−𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑎𝑖𝑟
%excess air = 𝑥 100% At partial saturation, Ppartial of water = VP X (%RH/100)
𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑎𝑖𝑟
𝑠𝑢𝑝𝑝𝑙𝑖𝑒𝑑 𝑜𝑥𝑦𝑔𝑒𝑛−𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑜𝑥𝑦𝑔𝑒𝑛
= 𝑥 100% STP is 0°C, 760 mmHg
𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑜𝑥𝑦𝑔𝑒𝑛

How to determine dew point or VP? Antoine equation

c. Combustion products – depends on the type of
log VP = A – [(B)/(C + T)] ; where A,B,C are constants (Perry’s
combustion; keep in mind that aside from the products of
Handbook), T is in degrees Celsius and VP in mmHg
reaction, exiting gas can contain unreacted compounds like
For water: A = 7.96681; B = 1668.21; C = 228
nitrogen and excess compounds like oxygen if applicable;
exiting gas has many names inlcuding flue gas, producer gas,
III. Net Hydrogen – amount of hydrogen in fuel which reacts
exhaust gas and stack gas.
with oxygen in air during combustion
IV. Combined water –amount of hydrogen in fuel that is
i. complete or perfect combustion – obtained by
combined with oxygen in fuel to form water (only
mixing and burning right proportions of fuel and oxygen
hypothetical; serves to simplify calculation)
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Example 2: Natural gas (92% CH4, 6.5% C2H6, 1.5% C3H8) is
burned in the presence of 40% excess air. Assuming complete
combustion, determine the mol of each compound in the
stack gas.
Ans: CO2 – 109.5 mol; H2O – 209.5 mol; N2 – 1,128.38 mol; O2 – 85.7
mol
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Energy in the Combustion Process
I. Energy considered in the combustion calculations
a. Latent heat - heat required to change a quantity of a
substance from 1 state to another
b. Sensible heat – change in internal energy or enthalpy of a
substance if it is heated or cooled from one temperature to
another without undergoing change in state or composition;
there is only change in temperature
c. Heat of combustion – heat generated from combustion of
fuel
II. Calorific Value (CV) or Heating Value (HV)
The heat given off by the complete combustion of a unit
quantity of the fuel at some reference temperature (25°C).
a. Gross calorific value (GCV) or higher heating value (HHV)
- Quantity of heat generated by the combustion and
subsequent cooling of the products of combustion to a
certain temperature (usually 25 deg C)
- The products of combustion are brought back to the pre-
combustion temperature (cooled since product gases are hot)
causing the water vapor to component of the exhaust gas to
condense (this is where dew point comes in!)
- takes into account the energy required to heat the
combustion air and the exhaust gases and heat generated by
the evaporation or condensation of water
- the water component of the products of combustion is
cooled to liquid state
b. Net calorific value (NCV) or lower heating value (LHV)
- indicates the heat quantity of the fuel that can actually be
utilized
- the water component of the products of combustion is
retained as vapor
*When the CV is unstated, by default we assume it to be HHV
since it is the one usually reported
2
c. Equations
For gaseous mixtures of fuel, the following equations are
applied:
GCV = ∑ 𝑯𝑪𝒊 𝒏𝒊
Where HCi = heat of combustion of component i
ni = mol fraction of component i
𝒎𝒐𝒍 𝒐𝒇 𝒘𝒂𝒕𝒆𝒓 𝒇𝒓𝒐𝒎 𝒄𝒐𝒎𝒃𝒖𝒔𝒕𝒊𝒐𝒏 𝒐𝒇 𝒇𝒖𝒆𝒍 𝒙 𝑳𝑪 𝒘𝒂𝒕𝒆𝒓
NCV = GCV –
𝒕𝒐𝒕𝒂𝒍 𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒇𝒖𝒆𝒍
Where LC water = latent heat of condensation of water
= 44.04 MJ/kmol
d. Expressing GCV and NCV
- magnitude of GCV is always greater than NCV
- calorific value units in SI are expressed on a dry* (Mega
Joules/ dry standard cubic meter or MJ/dSCM) or wet basis
(MJ/SCM) at 15.56 deg C, 760 mmHg and 100%RH** (Laurito,
1994)
- other units include MJ/kmol; kcal/gmol and MJ/kg
*dry basis – water is not included in the calculation of percentages
in composition although it might be present in the system
**RH or relative humidity is the ratio of the partial pressure of water
vapor to the equilibrium vapor pressure of water at the same
temperature. A reading of 100 percent relative humidity means that
the air is totally saturated with water vapor and cannot hold any
more.
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Example 3: Calculate the gross and net calorific value of a
natural gas at 25 deg C which has the following composition:
89.4%CH4, 5%C2H6, 1.9%C3H8, 0.4%i-C4H10, 0.6%n-C4H10,
0.7%CO2 and 2%N2 in:
a. MJ/kmol (Ans. GCV – 945.52, NCV – 854.62)
b. kcal/gmol (Ans. GCV – 225.82, NCV – 204.11)
c. MJ/kg (Ans. GCV – 52.27, NCV – 47.28)
d. MJ/dSCM (Ans. GCV – 39.93, NCV – 36.06)
e. MJ/SCM (Ans. GCV – 39.21, NCV – 35.44)
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III. Losses in Calorific Value
a. CV lost due to incomplete combustion – losses manifested
by the formation of carbon monoxide or hydrogen gas in
exhaust gas; presence of unburned combustibles constitute
CV loss because had these substances been completely
burned, they would have given off additional heat
CV loss due to:
CO: mol CO formed x 283.18 MJ/kmol
H2: mol H2 formed x 286.03 MJ/kmol

b. CV lost due to sensible heat (SH) - part of the heat

generated by the combustion reaction is absorbed by the
exhaust gas which leaves the chimney or stack at high
temperatures

CV lost due to SH =Σ niCpi (Tfg – T0)

Where ni = mol of component i in flue gas
Cpi = specific heat of component i
Tfg = temperature of flue gas
T0 = reference temperature 25 deg C

c. CV lost due to Uncondensed water vapor – part of the

heat generated is used to remove the uncondensed water
vapor in flue gas

CV lost due to undcondensed water vapor = moles water

from combustion x 44.04 MJ/kmol*
*latent heat of vaporization
**all the calculations of the CV including CV losses will be
incorporated in the 3 cases for gaseous fuel combustion

After this introduction to the elements and calculation

considerations for combustion, we are now prepared to solve
for the 3 cases for gaseous fuels covered in lecture 2.