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Energy Sources, Part A: Recovery, Utilization, and

Environmental Effects
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Effects of Moisture and Hydrogen Content on the

Heating Value of Fuels
a
A. Demirbas
a
Department of Chemical Engineering , Selcuk University , Konya, Turkey
Published online: 04 Apr 2007.

To cite this article: A. Demirbas (2007) Effects of Moisture and Hydrogen Content on the Heating Value of Fuels, Energy
Sources, Part A: Recovery, Utilization, and Environmental Effects, 29:7, 649-655, DOI: 10.1080/009083190957801

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 Energy Sources, Part A, 29:649–655, 2007
Copyright © Taylor & Francis Group, LLC
ISSN: 1556-7036 print/1556-7230 online
DOI: 10.1080/009083190957801

Effects of Moisture and Hydrogen Content on the

Heating Value of Fuels

A. DEMIRBAS
Department of Chemical Engineering
Selcuk University
Konya, Turkey
Downloaded by [University of New Mexico] at 08:08 01 December 2014

Abstract In this work, effects of moisture and hydrogen contents on lower heating
value (LHV) of fuels were investigated. The LHV at constant pressure measures the
enthalpy change of combustion with and without water condensed, respectively. Mois-
ture in biomass generally decreases its heating value. Moisture in biomass is stored in
spaces within the dead cells and within the cell walls. Higher heating value (HHV) of
a fuel decreases with increasing of its moisture content. The LHV of a fuel increases
with increasing of its hydrogen content. The LHV of a fuel depends on its oxygen
content and the LHV of a fuel decreases with increasing of its oxygen content. The
LHV of a fuel increases with increasing the hydrogen content due to cause combustion
water. Moisture in a fuel generally decreases its HHV. The LHV of a fuel increases
with increasing the sulfur content due to cause SOx gases absorbed by water.

Keywords biomass, coal, hydrogen, lower heating value, moisture, reaction water

Introduction
Coal and biomass combustion is a series of chemical reactions by which carbon is
oxidized to carbon dioxide, and hydrogen is oxidized to water. Oxygen deficiency leads
to incomplete combustion and the formation of many products of incomplete combustion
(Demirbas, 2000).
The heating value is obtained by the complete combustion of a unit quantity of fuel
in an oxygen-bomb colorimeter under carefully defined conditions. The standard measure
of the energy content of a fuel is its heating value, sometimes called the calorific value
or heat of combustion. The “gross” or “high” heating value is obtained by this method,
as the latent heat of moisture in the combustion products is condensed. The results may
be expressed on the “as received” or “dry” or “dry and ash free” basis. The higher
heating value (HHV) and the lower heating value (LHV) at constant pressure measures
the enthalpy change of combustion with and without water condensed, respectively. The
enthalpy (heat) of vaporization of water as a function of temperature (Marsh, 1987) is
tabulated in Table 1.
The enthalpy of vaporization of water is given as a function of temperature by apply-
ing the Clapeyron equation to the Clausius-Clapeyron regression of the data. The relation
between the equilibrium pressure and temperature is given exactly by the Clapeyron equa-
tion (Smith and Van Ness, 1975).

Address correspondence to Professor Ayhan Demirbas, Department of Chemical Engineering,

Selcuk University, Campus, 42031 Konya, Turkey. E-mail: ayhandemirbas@hotmail.com

649
 650 A. Demirbas

Table 1
Enthalpy (heat) of vaporization of water

Temperature
Hvapor , Hvapor , Hvapor ,
◦C K J/mol J/g cal/g

0 273.2 45,054 2,500.78 597.41

20 298.2 43,990 2,441.72 583.31
40 311.2 43,350 2,406.19 574.82
60 331.2 42,482 2,358.13 563.34
80 351.2 41,585 2,308.23 551.42
100 373.2 40,657 2256.72 539.11
140 413.2 38,643 2,144.93 512.41
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180 453.2 36,304 2,015.10 481.39

220 493.2 33,468 1,857.68 443.78
260 533.2 29,930 1,661.30 396.87
300 573.2 25,300 1,404.31 335.48
340 613.2 18,502 1,026.98 245.34
360 633.2 12,966 719.69 171.93
374 647.2 2,066 114.68 27.40

The heat content is related to the oxidation state of the natural fuels in which carbon
atoms generally dominate and overshadow small variations of hydrogen content. On the
basis of literature values for different species of wood, Tillman (1978) also found a linear
relationship between HHV and carbon content.
Biomass fuels are composed of biopolymers that consist of various types of cells and
the cell walls are built of cellulose, hemicelluloses, and lignin. HHVs of biomass fuels
increase as increase lignin contents (Demirbas, 2003a, 2003b). In general, the HHV of
fuels increases with increase in their FC contents (Demirbas, 1997). Moisture, ash and
HHVs analysis of the biomass fuels are given in Table 2 (Demirbas, 1997, 2002a, 2003c;
Baxter et al., 1998). The moisture content in test samples was determined according to
ASTM D (3173-87) standard test method in sartorious infrared moisture meter (ASTM,
1989a). The HHV of biomass materials is determined according to ASTM D (2015-
85) standard test method in a parr microprocessor controlled oxygen bomb calorimeter
(Model 1241 EF) (ASTM, 1989b).
In earlier work (UNDP, 2000), formulae were developed for estimating the HHVs of
various lignocellulosic materials, using their ultimate analysis data. The relation between
the observed HHV and C, H, and O contents of the samples (wt%) was investigated. Thus
the HHV (MJ/kg) of lignocellulosic materials including C, H, and O can be calculated
from Eq. (1):

HHV = 0.335 C + 1.423 H − 0.154 O (1)

Experimental
Since there are no standard sampling procedures specified for fuel materials, the samples
were collected with due care to get the most representative samples. Preparation of
 Effects of Moisture and Hydrogen Content on HV 651

Table 2
Moisture, ash and higher heating value (HHV) analysis of biomass fuels

Moisture, Ash, HHV,

Fuel common/scientific name wt% of fuel wt% of dry fuel MJ/kg, daf

Almond shells/Pranus dulcis 7.5 2.9 19.8

Almond hulls/Pranus dulcis 8.0 5.8 20.0
Beech wood/Fagus orientalis 6.5 0.6 19.6
Hazelnut shell/Corylus avellena 7.2 1.4 19.5
Oak wood/Quersus predunculata 6.0 1.7 19.8
Oak bark/Quersus predunculata 5.6 9.1 22.0
Olive husk/Olea europaea 6.8 2.1 21.8
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Rice straw/Oryza sativa 11.2 19.2 18.7

Spruce wood/Picea orientalis 6.7 0.5 20.5
Wheat straw/Triticum aestivum 6.4 8.1 19.3
Sources: Demirbas, 1997, 2002a, 2003c.

samples was carried out in accordance with ASTM D (2013-86) standard test method
(ASTM, 1989c).
The higher heating values of extractive free samples were determined by forming
the samples into pellets weighing approximately 0.5 g each, and burning the pellets in
an adiabatic oxygen bomb calorimeter according to the ASTM D (2015-66) standard test
method (ASTM, 1977). Heat of combustion of liquid hydrocarbon by bomb calorimeter
was determined according to the ASTM D (240-64) and ASTM D (240-76) standard test
methods (ASTM, 1982; ASTM, 1983).
Direct moisture content measurement of wood and wood base materials was deter-
mined according to the ASTM D (4442-92) standard test method (ASTM, 1997a). Total
sulfur in the analysis sample of coal and coke was determined according to the ASTM D
(3177-75) standard test method (ASTM, 1997b). Volatile matter in the analysis sample
of particulate wood fuel was determined according to the ASTM D (872-82) standard
test method (ASTM, 1998a). Ash in biomass was determined according to the ASTM D
(1755-95) standard test method (ASTM, 1998b). The fixed carbon content of the test
samples was calculated by difference.
The proximate analysis of samples were carried out in accordance with ASTM D
(3172-73) standard test method (ASTM, 1989d).

Results and Discussion

The elemental analysis, ash and moisture contents, and HHVs and LHVs of fuels are
tabulated in Table 3. Biomass fuel properties vary significantly more than those of coal
do (Liu, 2004). As examples, ash contents vary from less than 1% to over 16%, oxygen
contents vary from less 35% to over 43% and fuel nitrogen varies from around 0.2%
to over 1.2% (Table 3). Other notable properties of biomass relative to coal are high
moisture content, low heating value, and low bulk density.
Table 4 shows the mathematical equations for calculating lower heating values
(LHVs, kJ/kg)) of different types of fuels:
 652 A. Demirbas

Table 3
Elemental analysis, ash and moisture contents, higher and lower heating values
(HHV and LHV, MJ/kg) of fuels

C H N O S Ash Moisture HHV LHV

Coal 77.6 3.8 1.1 3.1 2.9 6.7 4.8 31.9 30.8
Lignite 61.5 4.2 1.6 7.8 6.1 12.6 6.2 25.1 23.9
Beech wood 48.4 5.9 0.3 38.7 — 0.6 6.1 18.7 17.2
Spruce wood 49.3 5.8 0.2 37.8 — 0.5 6.4 19.1 17.6
Grass 42.2 5.1 1.1 36.9 — 8.2 6.7 16.4 15.0
Hazelnut shell 46.9 5.3 1.2 39.1 — 1.5 6.0 18.2 16.8
Corncob 44.1 5.6 0.5 42.8 — 1.3 5.7 17.7 16.2
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Wheat straw 41.8 4.8 0.5 38.0 — 8.6 6.3 17.0 15.7
Corn stover 41.3 5.3 0.6 40.8 0.1 5.2 6.7 16.2 14.8
Methanol 37.5 12.5 — 50.0 — — — 22.7 20.0

Table 4
Equations for calculating of lower heating values (LHVs)
different types of fuels

LHV of fuel Higher heating value (HHV) − HVapor (9H + W)

LHVCoal HHV − 2,851 (9H + W)

LHVLignite HHV − 2,803 (9H + W)
LHVBiomass HHV − 2,535 (9H + W)
LHVMethanol HHV − 2,437 (9H + W)

For coal:

LHVCoal = HHV − 2,851 (9H + W) (2)

For lignite:

LHVLignite = HHV − 2,803 (9H + W) (3)

For biomass:

LHVBiomass = HHV − 2,535 (9H + W) (4)

For methanol:

LHVMethanol = HHV − 2,437 (9H + W) (5)

in which Eqs. (2)–(5), HHV (kJ/kg) is higher heating value of fuel, H and W are hydrogen
and water (hygroscopic moisture) contents (% by weight) of fuel, respectively.
 Effects of Moisture and Hydrogen Content on HV 653
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Figure 1. Plot of vaporization heat of water versus oxygen content of fuel.

Figure 1 shows the plot of vaporization heat of water versus oxygen content of fuel.
The LHV of a fuel depends on its oxygen content. As seen from Figure 1, the LHV
of a fuel decreases with increasing of its oxygen content. The LHV of a fuel increases
with increasing the hydrogen content due to cause combustion water. The LHV of a fuel
increases with increasing the sulfur content due to cause SOx gases absorbed by water.
The carbon content of fuel also contributes to increase the LHV due to release CO2 after
combustion.
Moisture in a fuel generally decreases its HHV (Demirbas, 2002b). Moisture in
biomass is stored in spaces within the dead cells and within the cell walls. When the fuel
is dried, the stored moisture equilibrates with the ambient relative humidity. Equilibrium
is usually about 20% in air dried fuel.
Moisture percentage of the wood species originally varied from 41.27 to 70.20%
(Demirbas, 2003c). The HHV of a wood fuel decreases with increasing of moisture
content of the wood. Moisture content varies from one tree part to another. It is often
the lowest in the stem and increases toward the roots and the crown.
The presence of water in biomass influences its behavior during pyrolysis and affects
the physical properties and quality of the pyrolysis liquid: qualitative observations show
that dry feed material led to the production of very viscous oil, particularly at higher
reaction temperatures. The results obtained show that for higher initial moisture contents
the maximum liquid yield on a dry feed basis occurs at lower pyrolysis temperatures
between 691 K and 702 K (Demirbas, 2004).
The most important characteristic temperatures of a burning profile are ignition
temperature and peak temperature for fuels (Haykırı-Açma et al., 2001). The ignition
temperature corresponds to the point at which the burning profile underwent a sudden
rise. The ignition temperatures of samples were determined from their burning profiles.
After releasing the moisture, some small losses in the mass of the sample occurred due
to desorption of the adsorbed gases. A sudden loss in the mass of the samples started
at the temperatures between 450–500 K, representing the release of some volatiles and
 654 A. Demirbas

their ignition. In the rapid burning region, the rate of mass loss proceeded so rapidly that
it reached to its maximum value. Rapid loss of mass immediately slowed down at the
temperatures between 600 K and 700 K. After then, burning rate apparently decreased
and consequently some small losses in the mass of the sample continuously went on
as long as temperature was increased up to 1,273 K, indicating the slow burning of the
partly carbonized residue. At the end of hold time at 1,273 K, samples reached to the
constant weight after given periods (Haykırı-Açma, 2003).

Conclusion
The effects of moisture and hydrogen contents on lower heating value of fuels were
investigated. Moisture in biomass generally decreases its heating value. Higher heating
value of a fuel decreases with increasing of its moisture content. The LHV of a fuel
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increases with increasing of its hydrogen content. The LHV of a fuel depends on its
oxygen content and the LHV of a fuel decreases with increasing of its oxygen content. The
LHV of a fuel increases with increasing the hydrogen content due to cause combustion
water. Moisture in a fuel generally decreases its HHV.
The LHV of a fuel increases with increasing the sulfur content due to cause SOx
gases absorbed by water. The carbon content of fuel also contributes to increase the LHV
due to release CO2 after combustion.

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