A unied correlation for estimating HHV of solid, liquid

and gaseous fuels

q
S.A. Channiwala
a,
*
, P.P. Parikh
b
a
Department of Mechanical Engineering, S.V.R. College of Engineering and Technology, Surat 395 007, Gujarat, India
b
Department of Mechanical Engineering, IIT, Powai, Mumbai 400 076, India
Received 10 January 2001; accepted 3 August 2001; available online 28 August 2001
Abstract
A unied correlation for computation of higher heating value (HHV) from elemental analysis of fuels is proposed in this paper. This
correlation has been derived using 225 data points and validated for additional 50 data points. The entire spectrum of fuels ranging from
gaseous, liquid, coals, biomass material, char to residue-derived fuels has been considered in derivation of present correlation. The validity
of this correlation has been established for fuels having wide range of elemental composition, i.e. C 0.0092.25%, H 0.4325.15%,
O 0.0050.00%, N 0.005.60%, S 0.0094.08% and Ash 0.0071.4%. The correlation offers an average absolute error of
1.45% and bias error as 0.00% and thereby establishes its versatility. Complete details of few salient data points, the methodology used for
derivation of the correlation and the base assumptions made for derivation are the important constituents of this work. A summary of
published correlations along with their basis also forms an important component of present work. q 2001 Published by Elsevier Science Ltd.
Keywords: Unied correlation; Higher heating value; Thermal systems
1. Introduction
Higher heating value (HHV) is an important fuel property
which denes the energy content of the fuel. Estimation of
HHV from the elemental composition of fuel is one of the
basic steps in performance modelling and calculations on
thermal systems. Numerous correlations for calculation of
HHV from elemental composition are available in the litera-
ture [128], out of which the 22 important ones have been
presented with their corresponding basis and assumptions in
Table 1. Most of these relations have been derived for coals.
Studies related with comparison and validity of these corre-
lations for coals as well as other fuels have drawn attention
of many researchers. Selvig [1] in 1945 compared the valid-
ity of Dulong [1], Strache and Lant [2], Steuer [3], Vondra-
cek [4], D'Huart [5], Schuster [6,7], Grummel and Davis
[8,9], Gumz [11], Sumegi [12] and Mott and Spooner's [13]
correlations for wide range of coals. He concluded that
Vondracek [4] and Grummel and Davis [8,9] correlation
offer better predictions as compared to other ones. Himus
[25] in 1958 while comparing the validity of aforesaid as
well as Seylor's correlation [10], again recommended use of
Grummel and Davis [8,9] correlation for coals. Grummel
and Davis correlation [8,9] has also been recommended for
coal chars by IGT [26], whose comparative analysis
included Dulong [1], Mott and Spooner [13], Grummel
and Davis [8,9] and Boie's [14] correlations. Applicability
of various correlations for wider range of fuels was tested by
Van Krevelon [27], who found Boie's correlation [14] to be
applicable to coals as well as hydrocarbon fuels. Such
comparative validity analysis for biomass materials was
carried out by Grabosky and Bain [15] with reference to
the correlations of Dulong [1], Dulong-Berthelot [15,27],
IGT [16] and Tillman [17]. IGT [16] correlation was stated
to be reasonably valid for biomass materials and chars.
Grabosky and Bain [15] observed existence of nearly linear
relationship between enthalpy of formation and molar (C/
H)
p
ratio of biomass materials. Based on this important
observation and using the pertinent combustion reactions,
Grabosky et. al. [15] proposed their own correlation which
is claimed to offer predictions within 2% accuracy. Jenkins
[18,19] based on his doctoral work and later based on the
analysis of some 57 biomass materials has also derived
HHV correlations for biomass materials. Beckman et al.
[20] have recently reported a HHV correlation for biomass
derived oils. Wilson [21], Chang [22], Khan and Abu
Fuel 81 (2002) 10511063
0016-2361/02/$ - see front matter q 2001 Published by Elsevier Science Ltd.
PII: S0016-2361(01)00131-4
www.fuelrst.com
* Corresponding author. Present address: Department of Material
Systems and Life Science School of Engineering, Toyama University,
Gofuku, Toyama 930-8555, Japan.
E-mail address: sac@svrec.ernet.in (S.A. Channiwala).
q
Published rst on the web via Fuelrst.comhttp://www.fuelrst.com
S.A. Channiwala, P.P. Parikh / Fuel 81 (2002) 10511063 1052
Table 1
Survey of published HHV correlations (Note: (i) HHV is in MJ/kg expressed on dry basis. (ii) C,H,O,N,S, A, Cl and P represent carbon, hydrogen, oxygen,
nitrogen, sulphur, ash, chlorine and phosphorous content of material, respectively, expressed in % by mass on dry basis. (iii) Co and Ci represents organic and
inorganic Carbon, respectively, expressed in % by mass on dry basis. (iv) F, represented foods in waste, expressed in % by mass on dry basis. (v) CP represents
mass percent of cardboard and paper on dry basis in waste. (vi) PLR represents mass percent of plastic, rubber and leather in the dry waste mixture. (vii) All the
reported HHV correlations are converted to MJ/kg with the following conversion factor.1 Btu=lbm 2:3261 10
23
MJ=kg; 1 cal=kg 4:186 10
23
MJ=kg:
(viii) p indicates composition in % by mass on dry, ash free basis)
Sr. No. Name of
investigator
Correlation Basis and assumptions
1 Dulong's (1880) [1] HHV
p
0:3383C
p
11:443H
p
2O
p
=8 1
0:0942S
p
MJ=kg
The correlation is based on pertinent combustion reactions
and concept of available hydrogen. It is derived from coal
properties and has the accuracy of ^1.5% for low oxygen
coals. For high oxygen coals deviations are as large as 57%
2 Strache and Lant
(1924) [2]
HHV
p
0:3406C
p
11:4324H
p
20:1532O
p
1
0:1047S
p
MJ=kg
This is the modied version of Dulong's correlation. It has the
accuracy of 2% for whole range of coals
3 Steuer (1926) [3] HHV
p
0:3391C
p
23=8O
p
1
0:23863=8O
p
11:444H
p
21=16O
p
1
0:1047S
p
MJ=kg
This is modied version of Dulong's correlation in which
association of oxygen is considered with both carbon and
hydrogen. This correlation predicts HHV within 2% for entire
range of coals
4 Vondrecek (1927)
[4]
HHV
p
0:373 20:00026 C
p
C
p
11:444H
p
2
1=10O
p
10:1047S
p
MJ=kg
This correlation allows for bond energy of carbon and
considers more availability of hydrogen as compared to
Dulong's. The predication of this correlation are found to be
within 1.5% for whole range of coals
5 D'Huart (1930) [5] HHV
p
0:3391C
p
11:4337H
p
10:0931S
p
2
0:1273O
p
This is modied version of Dulong's correlation. It covers
complete range of coals and predicts HHV within 2%
6 Schuster (1931)
[6,7]
HHV
p
1:0632 11:486 10
23
O
p
C
p
=3 1
H
p
2O
p
2S
p
=8 MJ=kg
This is a different type of correlation based on the assumption
that the amount of heat evolved by fuels on complete
combustion is proportional to the amount of oxygen or air
consumed and that this constant of proportionality depends on
oxygen content of the fuel. Predictions of this correlation are
claimed to be superior than that of Dulong's correlation
7 Grummel and Davis
(1933) [8,9]
HHV
p
0:0152H
p
10:9875C
p
=3 1H
p
2
O
p
2S
p
=8 MJ=kg
This correlation is also derived based on the same assumption
that the amount of heat evolved by fuels on complete
combustion is proportional to the oxygen or air consumed.
However the constant of proportionality is assumed to be
proportional to the hydrogen content of the fuel and not on
oxygen content as assumed by Schuster. The predictions of
HHV by this correlation lie within 1.3% for whole range of
coals
8 Seyler (1938) [10] HHV
p
0:519C
p
11:625H
p
10:001O
p2
2
17:87 MJ=kg
Seyler in 1938 found that the ratio of the heat of formation to
the percentage of fuel oxygen was a linear function of the
oxygen content of fuel. This correlation is based on this
nding and predicts HHV within 1% (as claimed by Seyler)
9 Gumz (1938) [11] HHV
p
0:3403C
p
11:2432H
p
10:0628N
p
1
0:1909S
p
20:0984O
p
MJ=kg
This correlation incorporates the effect of fuel nitrogen and
predicts HHV within 2% for whole range of coals
10 Sumegi (1939) [12] HHV
p
0:3391C
p
20:75O
p
=21
1:444H 20:125O
p
=2 10:1047S
p
This is a modied version of Steuers correlation and is derived
on the basis of association of oxygen with both carbon and
hydrogen. The correlation predicts within 2% for whole range
of coals
11 Mott and Spooner
(1940) [13]
HHV
p
0:3361C
p
11:419H
p
20:1453O
p
1
0:0942S
p
MJ=kg O
p
# 15% 0:3361C
p
1
1:419H
p
20:1532 20:0007O
p
O
p
1
0:0942S
p
MJ=kg O
p
. 15%
This correlation is developed on the assumption that two third
of the oxygen is associated with the hydrogen and one third
with the carbon of coal. The caloric value of carbon in
bituminous coals is taken as 33.61 MJ/kg which takes are for
heat of decomposition of coal. The prediction of this
correlation are claimed to be within 1.2%
12 Boie (1953) [14] HHV
p
0:3517C
p
11:1626H
p
10:1047S
p
2
0:111O
p
MJ=kg
This is a more general correlation as it is derived based on the
properties of hydrocarbon fuels. The predictions of this
correlation usually lie within 1.8%
13 Dulong-Berthelot
[15,27]
HHV
p
0:3414C
p
11:4445 H
p
2
N
p
1O
p
21
8
10:093 S
p
MJ=kg
This is a modied version of Dulong's correlation in which
effect of fuel nitrogen is introduced. The predictions of this
correlation are claimed to be superior than that of Dulong's
correlation
Gharah [23] and Niessen [24] presents the correlation for
municipal waste, refuse and sludge.
Buckley et al. [28] presents detailed discussion by Rigo
HG on evaluation of data on HHVs and elemental analyses
for refuse derived fuels. They observed Chang [22] correla-
tion as superior one for refuse with error levels of 1.48%.
Niessen [24] carried out similar study and found that for
sludge most of existing correlation over predicts the HHV
values and based on this observation he derived his own
corelation which under predicts the HHV only by 6% for
over 80 sludge samples.
Study of the published correlations and the com-
parative analysis presented by Selvig [1], Himus [25],
Krevelon [27], IGT [26], Grabosky and Bain [15],
Buckley et al. [28] and Niessen [24] highlights the
following points:
1. The published correlations can be divided in two main
categories:
(a) The correlations based upon the combustion reac-
tions of C, H and S to CO
2
, H
2
O and SO
2
, respectively,
with different assumptions regarding association of
oxygen with hydrogen or carbon [15,1016,1820].
(b) The correlations based on the assumption that
the HHV of fuel is proportional to the amount of
oxygen/air required for its complete combustion, the
constant of proportionality being represented either as
a function of oxygen or hydrogen content in the fuel
[69].
2. Except a few [14,15,17,1924] all other correlations are
derived for coals. When applied to biomass materials
they under predict the HHV [17] and over predicts for
refuse and sludge [24].
3. Except IGT [16], by and large all the correlations are
based on limited and/or investigator's own data points.
Application of these correlations to a wider spectrum of
fuels result in larger errors in estimation of HHV.
The analysis as above focuses the need for development
of a unied correlation which can encompass the entire
spectrum of solid, liquid and gaseous fuels. It is in
this context that the present work has its relevance. The
S.A. Channiwala, P.P. Parikh / Fuel 81 (2002) 10511063 1053
Table 1 (continued)
Sr. No. Name of
investigator
Correlation Basis and assumptions
14 IGT (1978) [16] HHV 0:341C 11:323H 10:0685 20:0153A2
0:1194O 1N MJ=kg
This is perhaps the most general HHV correlation derived
from the properties of more than 700 coal samples. The
predictions of this correlation usually lie within 1.2% for
whole range of coals
15 Tillman (1978) [17] HHV 0:4373C 20:3059 MJ=kg a; HHV
0:4373 C 21:6701 MJ=kg b (modied)
Tillman observed that the HHV of biomass materials is a very
strong function of its carbon content and based on this he
derived the correlation (a) for wood and wood barks and later
on modied as (b) to cover whole range of biomass materials.
The predictions of this correlation for biomass materials are
found to be within 5%
16 Jenkins (1980) [18]
(1985) [19]
HHV 0:4791C 10:6676H 10:0589O2
1:2077S 28:42 MJ=kg a; HHV 20:763 1
0:301C 10:525H 10:064O MJ=kg b
This correlation is derived based on 19 data points of biomass
material and using the multiple regression analysis. The
predictions of this correlation are found to be within 7%. Later
he derived a more general correlation using 57 data points
pertaining to biomass materials
17 Grabosky and Bain
(1981) [13]
HHV 0:328C 11:4306H 20:0237N1
0:0929S 21 2A=10040:11H=C 1
0:3466 MJ=kg
This correlation is derived for biomass materials based on the
pertinent reactions of C, H, S and N to CO
2
, H
2
O, SO
2
and
NO
2
. The predictions of this correlations are claimed to be
within 1.5%
18 Beckman et al.
(1990) [20]
HHV 0:352C 10:944H 10:105S 2O This correlation is derived for biomass derived oils. The
predictions are observed to be within 5%
19 Wilson (1972) [21] HHV 0:352Co 11:507H 20:1384O2
0:1485Ci 10:09263S 10:02419N MJ=kg
This correlation is derived for municipal solid waste. It is
derived from thermo chemical principles, heating value of
carbon and sulphur, types of carbon present and the formation
of water
20 Chang (1979) [22] HHV
p
35:8368 10:7523H
p
20:2674S
p
2
0:4654O
p
20:3814Cl
p
20:2802N
p
MJ=kg
This correlation is derived for waste material and its
predictions for 150 pure organic compounds are found to be
within 1.48%
21 Khan and Abu-
Gharah (1991) [23]
HHV 0:0535F 132:6CP 10:3722PLR MJ=kg This is a new approach for estimating HHV of municipal solid
waste based on the primary combustible components such as
paper, plastic, rubber, leather and food
22 Niessen (1995) [24] HHV
p
0:2322C
p
10:7655H
p
20:072O
p
2
0:0419N
p
10:0698S
p
10:0262Cl
p
1
0:1814P
p
MJ=kg
This correlation is derived for waste water sludges on dry and
ash free basis. It showed an under prediction by 6% when
tested for 80 data points of such sludges
following sections describe the evolution of a unied corre-
lation for estimating HHV of solid, liquid and gaseous fuels
from their elemental composition.
2. Derivation of unied correlation
Steps involved in development and derivation of unied
correlation are listed below:
2.1. Step 1: collection and generation of data
Collection of data. Data pertaining to large number of
solid, liquid and gaseous fuels were collected from the
published literature. The major sources of data are:
JANAF Tables [29], Refs. [1820,24,26,3039].
Generation of data. The data points generated during the
present work can be divided in two classes. Class I refers to
the biomass materials while Class II to the biomass chars.
Since there are no standard sampling procedures specied
for biomass materials, the samples of both the classes were
collected with due care to get the most representative
samples. Preparation of samples was carried out in accor-
dance with ASTM D 2013-86 [40] for both the classes. The
procedure requires samples to be in powder form of upto
250 mm grain size. Some difculties were encountered in
preparation of 250 mm size samples of brous materials like
bagasse, coconut bre and cottongin waste. These samples
were cut to approximately 1 mm size using stainless steel
scissors and used for analysis. The proximate analysis of all
the samples were carried out in accordance with ASTM D
3172-73 (84) [41] Standard. The moisture content in test
samples was determined according to ASTM D 3173-87
[42] method in a Sartorious infrared moisture meter. The
volatile matter contents in the test samples were determined
according to ASTM D 3175-89 [43] modied method for
sparking fuels. This method was programmed in DuPont
series 9900 thermal analyser. All the samples except coco-
nut shell, bre, pith and bagasse, were analysed with this
program. For Coconut shell, bre, pith and bagasse, ash
fusion was observed at 9508C and hence these samples
were analysed for volatile matter contents only upto
7508C. Determination of the ash content in the test samples
was carried out according to ASTM D 3174-89 [44] method
in the electric mufe furnace. The xed carbon content of
the test samples was calculated by difference [44]. The ulti-
mate analysis of these samples was carried out according to
ASTM Standard D 3176 to 7984 [4548] using Carlo Erba
elemental analyser Model 1106. The HHV of these materi-
als was determined according to ASTM D 2015-85 [49]
method in a parr microprocessor controlled Oxygen Bomb
Calorimeter, Model 1241 EF.
Table 2 gives the data on proximate and ultimate analysis
along with the measured HHV values for the materials
analysed during the course of this work.
2.2. Step 2: selection of suitable data
Through the process of collection and generation of data,
information about over 300 fuels was collected. Out of
these, 225 data points have been used for the purpose of
the derivation of the correlation, while 50 were used for
validation of the correlation. The selected data points satis-
ed the following criteria:
1. If it is a published data, adherence to the procedures of
ultimate analysis has been clearly stated by the corre-
sponding author (ASTM D 3176-84, D 3177-84, D
3178-84, D 3179-84 [4548]. Similarly adherence to
ASTM D 2015-85 [49] or D 3286-85 [50] is stated
with reference to bomb calorimetry, were strictly
observed. For the data points generated in the course of
present work, all the above procedures were strictly
observed.
2. One of the most proved correlation was selected for each
of the gaseous, liquid and solid fuels and ensured that the
published data points reasonably satisfy the correspond-
ing correlation. This method crosschecked the accuracy
of the data points. Boie's [14] correlation has been used
for gaseous and liquid fuels, IGT correlation [16] for
coals, Tillman [17] and Jenkins [18,19] for biomass
materials and Grummel and Davis [8,9] correlation for
chars. The error level of all the selected data was limited
to 5%.
In order to develop a generalised and unied correlation
to the extent possible, care was taken to include data points
of widest range of elemental composition and HHV. Table 3
presents the summary of few such data points used for deri-
vation and validation of the unied correlation. In total 225
data points comprising of 6 data points for gaseous fuels, 40
data points for liquid fuels, 49 data points for coals and
cokes, 95 data points for terrestrial and aquatic biomass
material, 21 data points for industrial waste, municipal
solid waste, refuse and sludge and 14 data points for chars
have been used for derivation of the correlation and 50
data points comprising of 5 gaseous fuels, 11 liquid fuels,
13 coals and cokes, 16 biomass materials, 3 refuse materials
and 2 chars have been used for validation of the correlation.
It is worth mentioning over here that equal weightage is
given to matured form of fuels like coals, liquid and
gaseous fuels and immatured form of fuels like biomass
(95 data points for each form). Further, the composite
fuels like industrial and municipal solid waste refuse
derived fuels and sludge as well as articially prepared
chars are also included as data points in derivation of this
unied correlation.
The spectrum of fuel is so selected that it approximately
represents the relative proportions of their occurrence in
nature and thus permits the derivation of a truly unied
correlation.
S.A. Channiwala, P.P. Parikh / Fuel 81 (2002) 10511063 1054
S.A. Channiwala, P.P. Parikh / Fuel 81 (2002) 10511063 1055
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S.A. Channiwala, P.P. Parikh / Fuel 81 (2002) 10511063 1056
Table 3
Summary of few salient data used for derivation and validation of unied correlation
Sr.No. Fuel name Proximate analysis
(% by mass, dry basis)
Ultimately analysis
(% by mass, dry basis)
Measured HHV
(dry basis) (MJ/kg)
Ref.
FC% VM% ASH% C% H% O% N% S%
Gaseous fuels
1 Methane, CH
4
74.85 25.15 0.00 0.00 0.00 55.345 [30]
2 Propane,C
3
H
8
81.70 18.30 0.00 0.00 0.00 50.237 [30]
3 LPG (ethane, C
2
H
6
0.57% propane,
C
3
H
8
30.94%, isobutane,
C
4
H
10
62.69%, n-butane,
C
4
H
10
5.8% by vol.)
82.40 17.60 0.00 0.00 0.00 49.602 [51]
4 Hydrogen sulphide, H
2
S 0.00 5.92 0.00 0.00 94.08 16.410 [29]
Liquid fuels
5 n-Pentane, C
5
H
12
83.22 16.78 0.00 0.00 0.00 48.539 [30]
6 n-Eicosane, C
20
H
42
85.01 14.99 0.00 0.00 0.00 47.04 [30]
7 Benzene, C
6
H
6
92.25 7.75 0.00 0.00 0.00 41.788 [30]
8 n-Octyl benzene, C
14
H
22
88.34 11.66 0.00 0.00 0.00 44.525 [30]
9 Aviation gasoline 85.10 14.90 0.00 0.00 0.00 47.302 [30]
10 Diesel oil 86.50 13.20 0.00 0.00 0.00 45.700 [30]
11 Heavy fuel oil 0.04 85.40 11.40 0.20 0.16 2.80 42.900 [30]
12 Methanol 37.50 12.50 50.00 0.00 0.00 22.69 [30]
13 Pyrolytic oil 0.50 57.00 7.70 33.20 1.10 0.20 24.700 [52]
14 Wood-tar 39.58 42.61 17.84 63.03 5.31 12.06 1.76 0.00 25.722 [39]
15 Oil from digested sludge 71.40 8.80 14.20 5.60 34.300 [53]
Solid fuels: coal/coke
16 Anthracite coal 90.60 1.34 8.06 86.78 1.63 1.96 0.65 0.92 31.840 [38]
17 Pittsburgh seam coal 55.80 33.90 10.30 75.50 5.00 4.90 1.20 3.10 31.751 [17]
18 Northumberland No. 8 Anth. Coal 84.59 7.09 8.32 83.67 3.56 2.84 0.55 1.05 32.856 [26]
19 Northumerland No. 81/2 Sem. Anth.
Coal
63.14 9.12 27.74 62.45 2.83 3.82 0.94 2.17 24.726 [26]
20 German-HVB bittu minus 60.25 33.45 6.30 76.65 4.78 10.87 0.54 0.42 31.00 [55]
21 Jefferson, Pratl -mvb coal 4.58 85.29 4.55 3.16 1.45 0.96 34.594 [26]
22 Green Ind. No. 3 -hvBb coal 41.53 40.93 17.55 62.70 4.84 6.29 1.36 7.17 27.357 [26]
23 Converse School Sub C Coal 23.39 52.57 24.04 53.07 4.09 17.53 0.55 0.72 21.672 [26]
24 Jhanjra Bonbahal Seam Coal R- VII 24.92 59.37 3.68 10.11 1.41 0.43 24.082 [54]
25 German Braunkohole lignite 46.03 49.47 4.50 63.89 4.97 24.54 0.57 0.48 25.10 [55]
26 Coke 91.47 0.92 7.61 89.13 0.43 0.98 0.85 1.00 31.124 [55]
27 Charcoal 89.10 9.88 1.02 92.04 2.45 2.96 0.53 1.00 34.388 [30]
Biomass material
28 Peat 3.00 56.00 5.00 35.00 1.00 0.00 20.667 [56]
29 Coconut shell 22.10 77.19 0.71 50.22 5.70 43.37 0.00 0.00 20.498 [39]
30 Oak bark 5.30 49.70 5.40 39.30 0.20 0.10 19.420 [57]
31 Western Hemlock wood 15.20 84.80 2.20 50.40 5.80 41.40 0.10 0.10 20.051 [17]
32 Douglass r wood 12.60 87.30 0.10 50.64 6.18 43.00 0.06 0.02 20.377 [32]
33 Chaparral wood 18.68 75.19 6.13 46.90 5.08 40.17 0.54 0.03 18.610 [19]
34 Eucalyptus Globulus wood 17.30 81.60 1.10 48.18 5.92 44.18 0.39 0.01 19.23 [19]
35 Cotton stalks 19.90 62.90 17.20 39.47 5.07 38.09 1.25 0.02 15.831 [18]
36 Bagasse 14.95 73.78 11.27 44.80 5.35 39.55 0.38 0.01 17.330 [19]
37 Rice husks Patni-23 14.90 69.30 15.80 38.92 5.10 37.89 2.17 0.12 15.673 [58]
38 Dry Subabul wood 18.52 81.02 1.20 48.15 5.87 44.75 0.03 0.00 19.777 [39]
39 Ply wood 15.77 82.14 2.09 48.13 5.87 42.46 1.45 0.00 18.955 [39]
40 Saw dust 5.83 47.13 5.86 40.35 0.65 0.16 19.970 [61]
41 Soquel point Giant Brown Kelp 57.90 42.10 27.80 3.73 23.69 1.63 1.05 10.747 [62]
Refuse, MSW, animal waste etc.
42 MSW 12.00 47.60 6.00 32.90 1.20 0.30 19.879 [59]
43 Sewage sludge 71.40 14.20 2.10 10.50 1.10 0.70 4.745 [17]
44 Missippi hyacinth digested slurry 60.70 39.30 31.70 3.82 23.20 1.98 0.00 12.28 [60]
45 RDF 17.60 72.00 10.40 44.72 6.21 38.36 0.69 0.00 19.495 [18]
46 Animal waste 23.50 35.10 5.30 38.70 2.50 0.40 13.400 [63]
Chars
47 Red wood char (8001725 F) 72.0 23.90 4.10 78.80 3.50 13.20 0.20 0.20 30.472 [35]
48 MSW char 41.20 54.90 0.80 1.80 1.10 0.20 18.655 [59]
49 ERCO char 57.76 24.00 18.26 65.86 2.57 12.80 0.40 0.10 24.161 [64]
50 Lignite char 89.00 1.10 8.90 0.70 0.30 31.30 [55]
2.3. Step 3: selection of suitable forms of correlations
Assumption made in published correlations were used for
formulation of 18 different algebraic expressions (correla-
tions) relating HHV and elemental composition of fuels.
Table 4 presents these expressions along with the assump-
tions based upon which the corresponding formulation has
been carried out. An exhaustive computer algorithm has
been developed based on generalised method of least
sequares to evaluate the constants of these assumed algebric
expressions. It is worth to note that the algorithm is capable
to incorporate any number of variables and data points.
Using this algorithm and 225 data points the constants of
these 18 algebraic expressions were evaluated.
2.4. Step 4: selection of the best correlation
To facilitate the selection of unied correlation, the aver-
age absolute and bias errors for each of these 18 correlations
S.A. Channiwala, P.P. Parikh / Fuel 81 (2002) 10511063 1057
Table 4
Details of assumed correlations (Note: (i) C, H, O,N,S, and Arepresents carbon, hydrogen, oxygen, nitrogen, sulphur and ash, respectively, in %by mass on dry
basis. (ii) a
i
represent a constant in ith term)
Sr. No. Correlation Criteria for selection
1 HHV 0:328C 11:419H10:0928S Basic correlation based on pertinent combustion reactions of C, H, and
S to, CO
2
, H
2
O, and SO
2
, respectively. Effect of bond energies and
presence of O, N, and A in fuel is neglected
2 HHV 0:328C 11:419H10:0928S 2a
1
O 1N 1a
2
A 1a
3
Based on pertinent combustion reactions of C, H, and S to CO
2
, H
2
O
and SO
2
, respectively. The effect of O, N, A and bond energies are
introduced through constants a
1
, a
2
, and a
3
, respectively
3 HHV a
1
0:328C 11:419H 10:0928S 1a
2
O 1N 1a
3
A Based pertinent combustion reactions of C, H, and S to CO
2
, H
2
O and
SO
2
, respectively. The effect of bond energies, O, N and A introduced
through constants a
1
, a
2
and a
3
, respectively
4 HHV a
1
0:328C 11:419H 10:0928S 20:0238N1a
2
O 1a
3
A Based on pertinent combustion reaction of C, H and S to CO
2
, H
2
O an
SO
2
, respectively. The effect of CH bond and A is introduced through
constants a
1
, a
2
and a
3
, respectively, while effect of N is introduced
based on endothermic reaction of N to NO
2
5 HHV a
1
C 2a
2
H 1a
3
S 1a
4
O 1a
5
N 1a
6
A 1a
7
Assuming fuel HHV to be linear function of its constituents
6 HHV a
1
C 1a
2
H 1a
3
S 1a
4
O 1a
5
N 1a
6
A Assuming HHV to be the linear function of its constituents
7 HHV a
1
C 1a
2
H 1a
3
S 1a
4
O 1N 1a
5
A 1a
6
Assuming fuel HHV to be linear function of its constituents and
combining the effect of O and N
8 HHV a
1
C 1a
2
H 1a
3
S 1a
4
O 1N 1a
5
A Assuming fuel HHV to be linear function of its constituents and
combing the effect of O and N
9
HHV a
1
C 1a
2
H 2
O
8

1a
3
S
Based on DULONG'S criteria of available hydrogen
10 HHV a
1
C 1a
2
H 1a
3
S 1a
4
O Modied version of DULONG'S correlation
11 HHV a
1
H=1 2A=100 1a
2
C=3 1H 2O 2S=8 Assuming fuel HHV to be proportional to the amount of oxygen or air
required for the complete combustion and the constant of
proportionality to be proportional to hydrogen content of the fuel
(based on Grummel and Davis criteria)
12 HHV a
1
O=1 2A=100 1a
2
C=3 1H 2O 2S=8 Assuming fuel HHV to be proportional to the amount of oxygen or air
required for the complete combustion and the constant of
proportionality to be proportional to oxygen content of the fuel (based
on SCHUSTER'S criteria)
13 HHV a
1
C=1 2A=100 1a
2
C=3 1H 2O 2S=8 Assuming fuel HHV to be proportional to the amount of oxygen or air
required for the complete combustion and the constant of
proportionality to be proportional to carbon content of the fuel
14 HHV a
1
C=1 2A=100 1a
2
H=1 2A=100 1a
2
O 1N=
1 2A=100 1a
4
S=1 2A=100 1a
5
C=3 1H 2O2S=8
Assuming fuel HHV to be proportional to the amount of oxygen or air
required for the complete combustion and the constants of
proportionality to be proportional to fuel constituents
15 HHV a
1
C 1a
2
H 1a
3
O
2
=1 2A=100 1a
4
1 2A=100 Assuming enthalpy of formation to be linear function of fuel oxygen as
observed by SEYLOR
16 HHV a
1
C 1a
2
H 1a
3
O 1a
4
O
2
=1 2A=100 1a
5
S Based on MOTT and SPOONERS criteria of nonlinear effect of O
2
on
HHV of highly oxygenated fuels
17 HHV a
1
C 1a
2
Assuming fuel HHV to be linear function of carbon only (based on
TILLMAN'S criteria)
18
HHV a
1
C
p
H
" #
1a
2
O 1N 1a
3
A
Assuming fuel HHV to be dependent on degree of maturity of fuel i.e.
(C/H)
*
molar ratio and considering the effect of O, N, and A on Fuel
(Based on Grabosky's criteria)
as derived above were computed as follows:
Average absolute error
1
n
X
n
i1
HHV
c
2HHV
HHV

100% 1
Average bias error
1
n
X
n
i1
HHV
c
2HHV
HHV

100% 2
The correlation giving minimum error levels over 225
data points was selected as the best one.
The following is the correlation which turned out to be
the best in this manner with an average absolute error of
1.45% and bias error of 0.00% with respect to measured
values of HHV:
HHV 0:3491C 11:1783H 10:1005S
20:1034O20:0151N 20:0211A MJ=kg 3
0% # C # 92.25%, 0.43% # H # 25.15%, 0.00% #
O # 50.00%,0.00%#N #5.60%, 0.00%#S #94.08%,
0.00%#A #71.4%, 4.745 MJ/kg #HHV #55.345 MJ/
kg where, C, H, O, N, S and A represents carbon, hydrogen,
oxygen, nitrogen, sulphur and ash contents of material,
respectively, expressed in mass percentages on dry basis.
3. Validation of the unied correlation
Validation of the unied correlation developed under the
S.A. Channiwala, P.P. Parikh / Fuel 81 (2002) 10511063 1058
Fig. 1. Comparison between measured and predicted HHV (gaseous fuels).
Fig. 2. Comparison between measured and predicted HHV (liquid fuels).
Fig. 3. Comparison between measured and predicted HHV (coals).
Fig. 4. ComparisonbetweenmeasuredandpredictedHHV(biomass material).
present work has been carried out by comparison of
computed and measured values of HHV over 275 data
points which include 225 data points used for the derivation
and 50 data points, specially used for the validation of the
correlation. The measured and computed values of HHV
data has been presented graphically at Figs. 16 for
gaseous, liquid and solid fuels, the solid fuels being further
sub-divided into coals, biomass, refuse and chars, respec-
tively. Fig. 7 presents this comparison for whole range of
fuels. The error band of ^3% has been also shown on these
gures to indicate the error limits. The study of this compar-
ison indicates that the average absolute deviation a for
gaseous fuels, liquid fuels, coals, biomass, refuse, chars
and entire spectrum of fuels are 0.588, 0.299, 0.295,
0.369, 0.406, 0.241 and 0.337 MJ/kg, respectively, while
bias deviations are of the order of 20.445, 0.00, 0.045,
20.026, 0.164, 0.031 and 0.00 MJ/kg, respectively. Simi-
larly the average absolute error for gaseous fuels, liquid
fuels, coals, biomass, refuse, chars and entire spectrum of
fuels are 1.18, 0.772, 1.04, 1.94, 2.58, 0.951, and 1.45%,
respectively, except for few gaseous fuels like CO, C
2
H
2
and C
2
H
4
. The bias errors for these categories are found
to be 20.92, 0.00, 0.14, 20.17, 1.30, 0.08, 0.00%,
respectively.
It is worth mentioning over here that the ASTM bomb
calorimeter standards [49,50] specify the reproducibility
limit of 240 J/g while the present correlation for the entire
range of solid, liquid and gaseous fuels offers the prediction
within 337 J/g which is quite comparable with the measure-
ment uncertainties if one consider the widely varying nature
of data and the source of its collection.
The validation of present unied correlation has further
been established by comparing its predictions with the
predictions of few widely used correlations. However, it is
to be noted here that the published correlations are valid
only for the fuels for which they are derived. Hence, this
comparison is purely for academic interest. It is observed
that the average absolute error for Dulong's [1], Vondrecek
[4], Grummel and Davis [8,9], Boie [14], IGT [26], Tillman
[17], Jenkins [18,19] and Niesson [24] for the entire
spectrum of fuels considered herein are of the order of
6.94, 1.89, 5.65, 1.93, 2.15, 7.26, 12.34 and 33.6%, respec-
tively, while the bias error for the same correlations are
found to be 24.33, 0.07, 21.47, 0.13, 20.39, 22.95,
210.60 and 233.6%, respectively. The comparison was
also made for different categories of fuels for which above
correlations were derived and it was observed that irre-
spective of the fact whether the fuel falls under the classi-
cation of gaseous, liquid, coal, biomass, refuse or chars,
the values of average absolute and bias error with the
present unied correlation are either minimum or compar-
able to minimum.
It must, however, be emphasised that when taken over the
whole range of fuels, the proposed unied correlations gives
the absolute and bias errors which are the lowest as
compared to any published correlation. With these mini-
mum values of average absolute and bias error as 1.45
and 0.00%, respectively, the validity and merits of the
proposed unied correlation stands established.
The validity of proposed unied correlation is also
examined for the materials like, graphite, mixed garbage,
mixed paper, waste water sludges, plastic, leather, rubber,
polyvinyl chloride, polyurethane, and others as presented in
Table 5 which are not generally classied as recognised
fuels and further that these data points are not used in deri-
vation and validation of present unied correlation. It is
observed that except for few materials where bond energies
and/or ash levels are quite high, the present unied correla-
tion handles the predictions within ^3%. It's validity is
observed even for very high chlorine content materials
like polyvinyl chloride Cl 45:41%:
S.A. Channiwala, P.P. Parikh / Fuel 81 (2002) 10511063 1059
Fig. 5. Comparison between measured and predicted HHV (residue).
Fig. 6. Comparison between measured and predicted HHV (chars).
4. Utility of the proposed unied correlation
Having established the validity and merits of the
proposed unied correlation, few of its applications have
been summarised below:
(i) The correlation can be used for HHV computation of
any solid, liquid and gaseous fuel, from its elemental
composition.
(ii) The correlation can also be used to verify the accuracy
of measured data of HHV and elemental composition.
(iii) In performance modelling exercise of combustion,
gasication and pyrolysis process, the correlation pro-
vides the facility of using HHV as an algebraic expression
in terms of fuel constituents which in turn is useful in
studying the inuence of elemental composition of the
fuel on process performance.
5. Conclusions
The present correlation has been derived based upon a
large number of data points having widely varying elemen-
tal composition and encompassing all categories of solid,
liquid and gaseous fuels. This means in that, within the speci-
ed ranges of C, H, O, N, S and Ash as 0.0092.25, 0.43
25.15, 0.0050.00, 0.005.60, 0.0094.08 and 0.0071.4%,
respectively, and within the stated absolute error limit of
1.45%, the present correlation may be accepted as `unied
correlation' for estimating HHV of solid, liquid and gaseous
fuels from their ultimate analysis, expressed on dry basis.
6. Limitations of the present unied correlation
Though the correlation has been derived over the entire
spectrum of solid, liquid and gaseous fuels, it does suffer
from the following limitations:
(i) Beyond the specied ranges of C, H, O, N, S and Ash,
the predictive accuracy of the correlation does not hold
good. For example HHV of H
2
H 100%; CO C
42:86; O 57:14% and municipal metallic waste A
90:49% as predicted by the present correlation has the
error of the order of 216.59, 210.88 and 2101.41%,
respectively.
(ii) For highly unsaturated hydrocarbon fuels like acetyl-
ene (C
2
H
2
) and ethylene (C
2
H
4
), the correlation is
S.A. Channiwala, P.P. Parikh / Fuel 81 (2002) 10511063 1060
Fig. 7. Comparison between measured and predicted HHV (whole range of fuels).
S.A. Channiwala, P.P. Parikh / Fuel 81 (2002) 10511063 1061
T
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observed to be under predicting the HHV by 17.74 and
6.85%, respectively. This is due to their bond energy
levels being less than that of normal fuels.
(iii) For combustible material likes certain category of
leather, plastic, rubber and minerals where oxygen pene-
tration for combustion of C, H, and S is difcult either due
to very strong CH bond or due to very high ash content,
the predictions of present correlation does not hold good.
(iv) In general, for the materials whose bond energy
levels are lower than the normal fuels, the present corre-
lation under predicts the HHV values while for the
materials whose bond energy levels are substantially
higher than the normal fuels, the present unied correla-
tion is found to over predict the HHV values.
Acknowledgements
Authors gratefully acknowledges the physical and moral
support provided by the staff of Biomass Gasication
Project, I.C. Engine laboratory and Chemical Laboratory
of IIT, Mumbai. The nancial support provided by depart-
ment of non-conventional energy sources, Government of
India is also gratefully acknowledged.
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