Heating

Value Estimation for Natural Gas Applications

Jayanthi Vijay Sarathy, M.E, CEng, MIChemE, Chartered Chemical Engineer, IChemE, UK
For natural gas custody transfer applications, Estimating Fuel Calorific Values
the gross calorific or gross heating value is The Gross calorific value (GCV) in mass terms
necessary for both the buyer and seller to can be computed as per ISO 6976:1995 at
estimate the sales price of natural gas. In case 1.01325 bara & 15 0C (referred to as Standard
of fuel suppliers, heat content is expressed in Conditions as per ISO 6976), as follows,
terms of Higher Heating value (HHV) to ∑ %! ×'()![#$%]
estimate fuel charges in kWh. Whereas Lower 𝐺𝐶𝑉!"## = ∑ %! ×*!
(1)
Heating Value (LHV) is employed to estimate
Where,
fuel requirements since the total energy input
for a specific power output is already fixed. Xi = Molar fraction of component ‘i’
To understand how fuel heating values are GCVi[mol] = Molar Gross calorific value of
affected, LHV and HHV is explained as, component ‘i', [kJ/mol]
1. The lower heating value (LHV) or net Mi = Molecular mass of component ‘i’ [g/mol]
calorific value (NCV) of a fuel is defined as However in this article, the standard
the amount of heat released by combusting temperature is taken as 250C and the heating
a specified quantity at 25°C and returning values are estimated based on a
the temperature of combustion products to stoichiometric balance instead of ISO
150°C, with the assumption that latent 6976:1995 method. Taking the following
heat of vaporization of water in the natural gas composition,
reaction products is not recovered, i.e.,
Table 1. Natural Gas Composition
when water in the combustion product, is
Component MW Mol%
in its vapour form, it is called LHV/NCV.
LHV is a better indication of a fuel’s useful - kg/kmol %
heat since the combustion products are Methane [CH4] 16.043 85.0
above the boiling point of water. Ethane [C2H6] 30.070 5.0
2. The higher heating value or gross calorific Propane [C3H8] 44.097 3.0
value (GCV) of a fuel is defined as the
n-Butane [n-C4H10] 58.123 1.0
amount of heat released by combusting a
i-Butane [i-C4H10] 58.123 1.0
specified quantity at 25°C and the products
have returned to a temperature of 25°C, n-Pentane [n-C5H12] 72.15 0.5

taking into account the latent heat of i-Pentane [i-C5H12] 72.15 0.3
vaporization of water in the products. i.e., Hydrogen [H2] 2.016 0.1
when water in the combustion product, is Carbon monoxide [CO] 28.011 0.1
in its vapour form, it is called HHV/GCV.
Carbon dioxide [CO2] 44.011 0.2
Presence of water is detrimental to a fuel’s
Nitrogen [N2] 28.0135 3.8
heating value, since with high combustion
Mixture MW [kg/kmol] 19.385
temperatures, water turns into steam & eats
away a portion of the energy released as To estimate the heat of reaction, the
latent heat of vaporization [DHV], i.e., HHV combustion of hydrocarbons follow the below
includes latent heat of vaporization of water. stoichiometric balance as,
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 3𝑛 + 1 i-Pentane [i-C5H12] -154.40
𝐶! 𝐻"!#" + $ ) 𝑂" → 𝑛𝐶𝑂" + [𝑛 + 1]𝐻" 𝑂
2
Carbon monoxide [CO] -110.52
To estimate the natural gas calorific value, the
Hydrogen [H2] 0.00
calculations require,
Oxygen [O2] 0.00
1. Natural gas Composition
Nitrogen [N2] 0.00
2. Heat of formation [DH0 f] at Ref. Conditions Carbon dioxide [CO2] -393.51
3. Heat of Reaction per mole computed as, Water Vapour [H2O (g)] -241.83
) ) )
𝛥𝐻$%!,"'℃ = ∑ 𝑋*,+ ∆𝐻,,+ − ∑ 𝑋*,$ ∆𝐻,,$ (1) Water [H2O (l)] -285.84

4. Based on per mole heat of reaction for each Performing a stoichiometric balance of the
combustible species/component, the combustion reactions,
individual mole fraction of each Table 3. Combustion Reaction Set
component is multiplied with the
CH4 + 2 O2 → 1 CO2 + 2 H2O(g)
respective heat of reaction and summed up
C2H6 + 3½ O2 → 2 CO2 + 3 H2O(g)
to arrive at the Net Calorific Value (NCV) or
Lower Heating Value (LHV). A negative C3H8 + 5 O2 → 3 CO2 + 4 H2O(g)
sign in the LHV/NCV value indicates, heat nC4H10 + 6½ O2 → 4 CO2 + 5 H2O(g)
is released due to the combustion process.
iC4H10 + 6½ O2 → 4 CO2 + 5 H2O(g)
5. To estimate the HHV, firstly, the hydrogen
nC5H12 + 8 O2 → 5 CO2 + 6 H2O(g)
content in each component of the natural
gas mixture (which forms water) is iC5H12 + 8 O2 → 5 CO2 + 6 H2O(g)
multiplied by its respective component’s H2 + ½ O2 → 1 H2O(g)
mole fraction, summed up, divided by 2
CO + ½ O2 → 1 CO2
and multiplied with the heat of reaction
H2O(g) → 1 H2O(l)
from the conversion of H20(g) ® H20(l),
i.e., [DHRxn,250C = DH0f,H2O(l) - DH0f,H2O(g)]. Quoting a sample case for methane at 250C,
Followed by, subtracting the above +
∑ 𝑋',) ∆𝐻*,) = [(1 × −74.84) + (2 × 0)] (2)
estimate from the modulus (positive) value
of LHV/NCV. %
∑ 𝑋!,# ∆𝐻$,# = [(2 × −241.83) + (1 × −393.51)] (3)

The standard heat of formation [DH0f] at 250C %

𝛥𝐻&'( = [−877.162] − [−74.84] = −802.32
)*
(4)
+,-
for the reactants and products are as follows,
For the case of H2 at 250C,
Table 2. Standard Heat of Formation [250C]
+
∑ 𝑋',) ∆𝐻*,) = [(1 × 0) + (0.5 × 0)] (5)
Component DH0f,250C
+
- kJ/mol ∑ 𝑋',, ∆𝐻*,, = [1 × −241.83] (6)
Methane [CH4] -74.84 + /0
𝛥𝐻)-. = [−241.83 − 0] = −241.83 123 (7)
Ethane [C2H6] -84.67
For the case of H2O(g) to H2O(l) at 250C,
Propane [C3H8] -103.85
+
∑ 𝑋',) ∆𝐻*,) = −241.83 (8)
n-Butane [n-C4H10] -124.73
+
i-Butane [i-C4H10] -134.50 ∑ 𝑋',, ∆𝐻*,, = −285.84 (9)
)*
n-Pentane [n-C5H12] -146.40 %
𝛥𝐻&'( = [−285.84 − (−241.83)] = −44.01 +,- (10)

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Similarly, performing calculations for other n-Butane [n-C4H10] 0.010 ´ 10 0.1
components to yields,
i-Butane [i-C4H10] 0.010 ´ 10 0.1
Table 4. Heat of Reaction Summary
n-Pentane [n-C5H12] 0.005 ´ 12 0.06
Component ΔH0Rxn, 250C [kJ/mol] i-Pentane [i-C5H12] 0.003 ´ 12 0.036
CH4 -802.32 Hydrogen [H2] 0.0010 ´ 2 0.002
C2H6 -1,427.83 Total 4.238

C3H8 -2,043.98 The HHV/GCV is now calculated as,

nC4H10 -2,658.44 𝐻𝐻𝑉 = 894.43 − ;
4.678×:44.+;4 /0
< = 987.70 123 (11)
6
iC4H10 -2,648.67
Expressing in mass terms [kJ/kg], the heating
nC5H12 -3,272.11 values are as follows,
iC5H12 -3,264.11 8<4.47×;+++
𝐿𝐻𝑉/𝑁𝐶𝑉 = ;<.78=
= 46,140 𝑘𝐽/𝑘𝑔 (12)
H2 -241.83 <8>.>×;+++
𝐻𝐻𝑉/𝐺𝐶𝑉 = = 50,951𝑘𝐽/𝑘𝑔 (13)
;<.78=
CO -282.99
References
H2O(g) -44.014
1. “Principles of Chemical Engineering
Therefore the LHV/NCV is computed as, Processes”, Nayef Ghasem, Redhouane
Table 5. LHV/NCV Estimation Henda, 2nd Edition, Taylor & Francis Group
Component 𝑿𝒊 ∆𝑯𝟎𝑹 2. ISO 6976 (1995) Natural gas - Calculation
- [kJ/mol] of calorific values, density, relative density
Methane [CH4] 0.85 ´ -802.32 -681.974
and Wobbe index from composition

Ethane [C2H6] 0.050 ´ -1,427.83 -71.392 3. https://www.clarke-energy.com/heating-

value/
Propane [C3H8] 0.030 ´ -2,043.98 -61.320
4. https://www.industrialheating.com/articl
n-Butane [n-C4H10] 0.010 ´ -2,658.44 -26.584
es/90561-calculating-the-heat-of-
i-Butane [i-C4H10] 0.010 ´ -2,648.67 -26.487
combustion-for-natural-gas
n-Pentane [n-C5H12] 0.005 ´ -3,272.11 -16.361

i-Pentane [i-C5H12] 0.003 ´ -3,264.11 -9.792
Hydrogen [H2] 0.001 ´ -241.83 -0.242

Carbon monoxide 0.001 ´ -282.99 -0.283

Carbon dioxide 0.000 0.000
Nitrogen [N2] 0.000 0.000
𝑳𝒐𝒘𝒆𝒓 𝑯𝒆𝒂𝒕𝒊𝒏𝒈 𝑽𝒂𝒍𝒖𝒆 (𝑳𝑯𝑽) = 3 𝑿𝒊 ∆𝑯𝟎𝑹 -894.43
The higher heating value (HHV) is computed
by initially making a hydrogen balance as,

Component Hydrogen Balance

Methane [CH4] 0.850 ´ 4 3.4

Ethane [C2H6] 0.050 ´ 6 0.3

Propane [C3H8] 0.030 ´ 8 0.24
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Appendix A

Natural Gas Calorific Value Calculations

Enthalpy of Formation [250C] ΔH0Rxn, 250 C Components MW Mole %Mole FractionXi × ΔH0R
Reaction Set
Component ΔH0f [kJ/mol] [kJ/mol] [kg/kmol] [%] [-] [kJ/mol]
Methane [CH 4] -74.84 1 CH 4 + 2 O2 → 1 CO2 + 2 H 2O (g) -802.32 Methane [CH4] 16.043 85.0 0.850 -681.974
Ethane [C2H 6] -84.67 1 C2H 6 + 3.5 O2 → 2 CO2 + 3 H 2O (g) -1427.83 Ethane [C 2H6] 30.07 5.0 0.050 -71.392
Propane [C3H 8] -103.85 1 C3H 8 + 5 O2 → 3 CO2 + 4 H 2O (g) -2043.98 Propane [C 3H8] 44.097 3.0 0.030 -61.320
n-Butane [n-C4H 10] -124.73 1 n-C4H 10 + 6.5 O2 → 4 CO2 + 5 H 2O (g) -2658.44 n-Butane [n-C 4H10] 58.123 1.0 0.010 -26.584
i-Butane [i-C4H 10] -134.50 1 i-C4H 10 + 6.5 O2 → 4 CO2 + 5 H 2O (g) -2648.67 i-Butane [i-C 4H10] 58.123 1.0 0.010 -26.487
n-Pentane [n-C5H 12] -146.40 1 n-C5H 12 + 8 O2 → 5 CO2 + 6 H 2O (g) -3272.11 n-Pentane [C 5H12] 72.15 0.5 0.005 -16.361
i-Pentane [i-C5H 12] -154.40 1 i-C5H 12 + 8 O2 → 5 CO2 + 6 H 2O (g) -3264.11 i-Pentane [i-C 5H12] 72.15 0.3 0.003 -9.792
Carbon monoxide [CO] -110.52 1 H2 + 0.5 O2 → 1 H 2O (g) -241.83 Hydrogen [H2] 2.016 0.1 0.001 -0.242
Hydrogen [H 2] 0.00 1 CO + 0.5 O2 → 1 CO2 -282.99 Carbon Monoxide [CO] 28.011 0.1 0.001 -0.283
Oxygen [O2] 0.00 1 H 2O (g) → 1 H 2O (l) -44.014 Carbon dioxide [CO 2] 44.011 0.2 0.002 0.000
Nitrogen [N2] 0.00 Nitrogen [N2] 28.014 3.8 0.038 0.000
Carbon dioxide [CO2] -393.51 Legend 100 1.000 -894.43
Water Vapour [H 2O (g)] -241.83 Input Input Data
Water [H 2O (l)] -285.84 GCV/HHV Gross Calorific Value / Higher Heating Value Results
NCV/LHV Net Calorific Value / Lower Heating Value NG Mixture MW 19.385 kg/kmol
Enthaply of Reaxtion ΔH0Rxn, 25 0C Notes NCV/LHV 894.43 kJ/mol 46,140 kJ/kg
Enthalpy of Formation is taken at 1.01325 bara/250C GCV/HHV 987.70 kJ/mol 50,951 kJ/kg

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