Energy Sources, Part A, 30:1876–1883, 2008

Copyright © Taylor & Francis Group, LLC

ISSN: 1556-7036 print/1556-7230 online
DOI: 10.1080/10916460701462846

Relationships Proximate Analysis Results and

Higher Heating Values of Lignites

A. DEMIRBAS1
1
Sila Science, Trabzon, Turkey

Abstract In this study, the higher heating values (HHVs) of 26 lignite samples
were calculated by using the proximate and elemental analyses data. The proximate
analysis results such as volatile materials (VM), fixed carbon (FC) and HHV and the
elemental analysis results such as carbon (C), hydrogen (H), oxygen (O), nitrogen
(N) and sulfur (S) were determined for 26 lignite samples from different areas of
Turkey. The lignite samples have been tested with particle size of 0–0.05 mm. The
HHVs of 26 lignite samples obtained from different Turkish sources were determined
experimentally and calculated from both ultimate and proximate analyses. HHVs of 26
the lignite samples can be calculated from the Equation based modeling. The HHVs
(MJ/kg) of the lignite samples as a function of fixed carbon (FC, wt%) or volatile
materials (VM, %) was calculated from the following equations:

HH V D 0:300F C C 11:117 (1)

HH V D 0:323VM C 42:223 (2)

where the correlation coefficients for Eqs. (1) and (2) were 0.9907 and 0.9862,
respectively. The combustion heats calculated from Eqs. (1) and (2) showed mean
differences of C3.9% and C0.3%, respectively. The HHVs (MJ/kg) of the lignite
samples as a function of C, H, O, N, and S were calculated from the following
equation:

HH V D 31:6.C / C 142:3.H / C 30:8.S/ 15:4.O/ 14:5.N / (3)

where the correlation coefficients for Eq. (3) was 0.9891. HHVs calculated from
Eq. (3) showed a mean deviation of C0.1.

Keywords higher heating value, lignite, modeling, proximate analysis

Introduction
The heating values of coals can be determined experimentally or can be calculated from
the ultimate or proximate analyses. Various formulae for calculating heating values of
coals from their proximate analyses have been proposed by different authors (Selvig and
Gibson, 1945; Elliott and Yohe, 1981; Kucukbayrak et al., 1991; Channiwala and Parikh,
2002):

HHV D 76:56 1:3.VM C ash/ C 7:03  10 3 .VM C ash/2 : (1)

Address correspondence to Professor Ayhan Demirbas, P. K. 216, TR-61035 Trabzon, Turkey.

E-mail: ayhandemirbas@hotmail.com

1876
 Heating Value of Lignite Based on Proximate Analysis 1877

The most important fuel properties of coals are ultimate and proximate analyses,
analyses of conversion products, overall heating value and heating values of the volatiles.
Proximate analysis gives the weight fraction of moisture, volatile matter (VM) including
liquids and tar, fixed carbon (FC), and ash. The yield of volatile materials from coals
can be increased by increasing the heating rate and the temperature of pyrolysis. The
experimental determination of combustion heats and ultimate analyses requires special
instrumentation such as calorimeter and elemental analyzer, whereas proximate analysis
data can be obtained relatively easily using common laboratory equipment.
The formula proposed by Goutal is one of the oldest and best known that is based on
proximate analysis of materials (Demirbas, 1997). The most common methods currently
being practiced to evaluate the heating value of lignite are derived from the mathematical
equations by Dulong and Goutal. The original formula-based elemental analysis was
proposed by Dulong:

HHV D 8,080.C/ C 34,460.H/ 4,308.O/ C 2,250.S/; (2)

where HHV is the higher heating value in kcal/kg and C, H, O, and S is carbon, hydrogen,
oxygen, and sulfur contents (wt%), respectively. Elemental composition equations based
mathematical models are the most reported with Dulong’s equation being among the first
available to calculate the calorific value of coal. Dulong’s formulae for coals define the
HHV as a function of carbon, hydrogen, oxygen and sulfur contents (Demirbas, 2006):

HHV.kcal=kg/ D 81.C/ C 342:5.H O=8/ C 22:5.S/ 6.9H W/; (3)

where W is water content of the sample, HHV is higher heating value in MJ/kg, C, H, O,
and S is carbon, hydrogen, oxygen and sulfur in the coal sample (wt%), respectively. The
formula proposed by Goutal is one of the oldest for calculating the higher heating value
that is based on proximate analysis of material (Demirbas, 1997; Khan and Abu-Ghararah,
1991):

HHV D 147:6.FC/ C K.VM/; (4)

where HHV is the higher heating value in Btu/lb, FC is fixed carbon (wt%), VM is
volatile material (wt%), and K is a constant that varies with the value of VM.

Experimental
For use in the experiments, 26 lignite samples were obtained from different areas of
Turkey (Sensogut et al., 2007). The samples were ground and sieved into a powder with
a particle size of 0–0.05 mm. The proximate and elemental analyses of the samples were
performed according to ASTM standards (ASTM, 1993).
The HHVs were measured by bomb calorimeter according to the ASTM D2015
standard method.
The proximate analysis results such as VM, FC, and HHV and the elemental analysis
results such as C, H, O, N, and S were determined for 26 lignite samples from different
areas of Turkey. The HHVs of the lignite samples were calculated from the proximate
and elemental analyses data.
1878 A. Demirbas

Results and Discussion

The proximate analysis, moisture, and ash and sulfur content of the lignite samples are
shown in Table 1. In general, the calorific value of a carbonaceous fuel is a function
of fixed carbon (FC, wt%) and its HHV increases as the FC content of fuel increases
(Demirbas, 1997; 1998). The calorific values of lignite samples decrease with increasing
ash and moisture contents. The highest and the lowest HHVs of the lignite samples were
29.5 and 22.4 MJ/kg.
Table 2 shows the VM, FC, and HHVs of lignite samples in % dry and ashless
basis. The HHVs of the lignite samples can be calculated from the proximate analysis
data given in Table 2. The HHVs (MJ/kg) of the lignite samples as a function of fixed
carbon (FC, wt%) can be calculated from:

HHV D 0:300.FC/ C 11:117: (5)

Equation (5) represents the correlation obtained by means of regression analysis.

Table 3 shows the HHVs (MJ/kg) measured and calculated from proximate analysis.

Table 1
Proximate analysis, moisture, ash and sulfur contents of lignite samples

Source Moisture, % Ash, % Total S, % Organic S, %

Beysehir 38.2 23.6 1.28 1.23

Kangal 42.8 13.5 2.41 2.37
Ilgin 37.4 8.8 2.54 2.50
Yalvac 13.8 2.3 0.48 0.42
Ibribey 25.7 19.1 2.30 2.20
Maymundere 14.0 45.8 0.78 0.74
Gediz 32.7 17.2 5.24 5.17
Goynuk 27.3 15.2 1.85 1.82
Mihaliccik 21.6 24.7 1.47 1.42
Damlarca 28.5 17.5 1.57 1.52
Cayirhan 32.8 12.9 2.98 2.94
Yenikoy 29.5 6.2 0.59 0.57
Batkin 32.8 11.3 0.46 0.44
Seyitomer 14.1 17.0 2.38 2.33
Soke 22.2 12.1 5.00 4.93
Gemerek 24.2 12.5 2.96 2.78
Dodurga 19.9 18.7 1.15 1.08
Afsin-Elbistan 16.3 12.9 6.13 6.06
Yatagan 12.6 13.5 1.40 1.36
Beypazari 14.1 12.5 10.25 10.13
Ermenek 18.0 13.3 1.25 1.19
Soma 15.1 11.6 1.43 1.39
Can 29.8 7.5 0.86 0.84
Dadagi 16.8 8.3 4.16 4.07
Tuncbilek 15.9 16.3 1.39 1.34
Yeniceltek 12.5 9.6 3.18 3.11
 Heating Value of Lignite Based on Proximate Analysis 1879

Table 2
VM, FC, and HHV of lignite samples,
% of dry and ashless (daf) basis

Lignite
source VM, % FC, % HHV, MJ/kg

Beysehir 62.4 37.6 22.4

Kangal 64.1 35.9 22.6
Ilgin 59.1 40.9 23.3
Yalvac 58.8 41.2 23.4
Ibribey 57.3 42.7 23.6
Maymundere 57.1 42.9 23.7
Gediz 54.3 45.7 24.8
Goynuk 53.2 46.8 24.8
Mihaliccik 52.9 47.1 24.9
Damlarca 53.0 47.0 24.9
Cayirhan 52.2 47.8 25.0
Yenikoy 52.1 47.9 25.1
Batkin 51.6 48.4 25.3
Seyitomer 51.2 48.8 25.5
Soke 50.8 49.2 25.6
Gemerek 50.3 49.7 25.9
Dodurga 50.1 49.9 26.0
Afsin-Elbistan 49.5 50.5 26.3
Yatagan 49.0 51.0 26.4
Beypazari 48.8 51.2 26.5
Ermenek 48.5 51.2 26.7
Soma 47.5 52.5 27.1
Can 47.1 52.9 27.3
Dadagi 43.1 56.9 28.2
Tuncbilek 44.2 55.8 29.4
Yeniceltek 38.7 61.3 29.5

Figure 1 shows the plot for fixed carbon and higher heating values of lignite samples.
The correlation coefficient (r) is 0.9907. The HHVs calculated using Eq. (5) showed a
mean difference of C3.9% (Table 3).
The HHVs (MJ/kg) of the lignite samples as a function of volatile matter (VM, wt%)
can be calculated from:

HHV D 0:323.VM/ C 42:223 (6)

Equation (6) represents the correlation obtained by means of regression analysis.

Figure 2 shows the plot for volatile materials and HHVs of lignite samples. The corre-
lation coefficient (r) is 0.9862. The calorific values calculated using Eq. (6) also showed
a mean difference of C0.3% (Table 3).
1880 A. Demirbas

Table 3
HHVs (MJ/kg) measured and calculated from proximate analysis

Source of From Difference, From Difference,

lignite Experimental Eq. (1) % Eq. (2) %

Beysehir 22.4 22.4 0.0 22.1 1.4

Kangal 22.6 21.9 3.0 21.9 3.0
Ilgin 23.3 23.1 0.8 23.4 C0.4
Yalvac 23.4 23.5 C0.4 23.3 0.4
Ibribey 23.6 23.9 C1.3 23.7 C0.4
Maymundere 23.7 24.0 C1.3 23.8 C0.4
Gediz 24.8 24.8 0.0 24.7 0.4
Goynuk 24.8 25.1 C1.3 25.0 C0.8
Mihaliccik 24.9 25.2 C1.3 25.2 C1.3
Damlarca 24.9 25.2 C1.3 25.1 C0.8
Cayirhan 25.0 25.4 C1.6 25.4 C1.6
Yenikoy 25.1 25.5 C1.6 25.4 C1.3
Batkin 25.3 25.6 C1.3 25.6 C1.3
Seyitomer 25.5 25.7 C0.8 25.7 C0.8
Soke 25.6 25.9 C1.3 25.8 C0.8
Gemerek 25.9 26.0 C0.4 26.0 C0.4
Dodurga 26.0 26.1 C0.4 26.1 C0.4
Afsin-Elbistan 26.3 26.3 0.0 26.2 0.4
Yatagan 26.4 26.4 0.0 26.4 0.0
Beypazari 26.5 26.5 0.0 26.5 0.0
Ermenek 26.7 26.5 0.7 26.6 0.4
Soma 27.1 26.9 0.7 26.9 0.7
Can 27.3 27.0 1.1 27.0 1.1
Dadagi 28.2 28.2 0.0 28.3 C0.4
Tuncbilek 29.4 27.9 5.1 28.3 3.7
Yeniceltek 29.5 29.5 0.0 29.7 C0.7

According to the equation proposed by Goutal, heating value is a function of FC

and VM of the dry and ash-free coals. It is seen that the HHV is also a function of FC
and VM for biomass fuel.
The HHVs of a carbonaceous fuel is a function of C, H, S, O, and N contents of the
fuel and its HHV increases as the C, H, and S contents of fuel increases. Table 4 shows
the elemental composition of lignite samples from Turkish resources. The calorific values
of lignite samples decrease with increasing their O and N contents. The HHVs (MJ/kg)
of the lignite samples as a function of C, H, S, O, and N (wt%) can be calculated from:

HHV D 31:6.C/ C 142:3.H/ C 30:8.S/ 15:4.O/ 14:5.N/: (7)

Equation (7) represents the correlation obtained by means of regression analysis. The
correlation coefficient (r) is 0.9891. The calorific values calculated using Eq. (7) showed
 Heating Value of Lignite Based on Proximate Analysis 1881

Table 4
Elemental composition of lignite samples
from Turkish resources (wt%)

O
Source of lignite C H N S (by diff.)

Beysehir 60.5 5.6 1.8 0.9 31.2

Kangal 62.0 5.4 1.9 1.8 28.3
Ilgin 62.4 5.7 1.9 0.7 29.3
Yalvac 63.0 5.6 2.1 1.4 27.9
Ibribey 63.4 5.5 2.4 2.1 26.9
Maymundere 62.8 5.6 1.7 2.8 27.1
Gediz 64.7 5.0 1.6 4.2 24.5
Goynuk 61.0 5.6 1.7 3.3 28.4
Mihaliccik 65.2 5.5 1.6 1.3 26.4
Damlarca 65.4 5.6 1.4 1.9 25.7
Cayirhan 65.6 5.5 1.9 2.2 24.9
Yenikoy 65.7 5.5 2.1 2.0 24.7
Batkin 65.9 5.6 2.0 2.6 23.9
Seyitomer 71.0 5.2 2.1 1.7 20.1
Soke 65.5 5.5 1.4 2.3 25.3
Gemerek 66.3 5.6 1.7 2.1 24.3
Dodurga 67.0 5.6 1.6 2.5 24.5
Afsin-Elbistan 68.9 4.6 1.8 5.2 19.5
Yatagan 65.3 5.1 1.5 5.5 22.7
Beypazari 62.5 5.3 2.1 9.1 21.0
Ermenek 66.5 5.7 1.8 0.8 25.2
Soma 71.6 5.2 1.8 3.7 17.7
Can 72.6 5.2 2.3 3.5 16.3
Dadagi 71.3 5.3 1.7 3.3 18.4
Tuncbilek 71.9 5.4 2.6 3.2 16.9
Yeniceltek 74.0 5.8 2.8 2.3 15.2

a mean deviation of C0.1. The results showed that the correlation from the elemental
analysis gave the best correlation coefficient.
In earlier works (Demirbas et al., 1997), formulae were also developed for estimating
the HHVs of fuels from different lignocellulosic materials by using their chemical analysis
data:

HHV D 33:5.C/ C 142:3.H/ 15:4.O/ 14:5.N/; (8)

where (C) is carbon content (wt%), (H) is hydrogen content (wt%), (O) is oxygen content
(wt%), and (N) is nitrogen content (wt%). 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.
1882 A. Demirbas

Figure 1. Plot for FC and HHVs of lignite samples.

Figure 2. Plot for VM and HHVS of lignite samples.

 Heating Value of Lignite Based on Proximate Analysis 1883

Comparing Eqs. (7) and (8), the first term with C is higher in Eq. (8) than that of
Eq. (7). The coals certainly have aromatic structure. The HHVs of aromatic compounds
are lower than aliphatic compounds. The HHV decreases with the increase of aromaticity
of a coal fuel.

Conclusions
In this study, the mathematical equations have been developed to calculate the HHVs of
the lignite samples from proximate and elemental analysis (ultimate analysis) data.
The HHVs of the lignite samples can be calculated by using the FC and VM obtained
from simple chemical analyses. The results showed that the correlation from the proximate
analysis gave the best correlation coefficient. The HHVs of the lignite samples can be
calculated as a function of C, H, S, O and N.
Elemental composition-based mathematical models are the most reported, with Du-
long’s equation being among the first available to calculate the HHV of coal. However,
ultimate analysis is more expensive than bomb calorimeter method and tedious and needs
skilled workers to carry out the analysis. It is difficult to make accurately an ultimate
analysis of a fuel sample.
Applied analytical method is important when determining the accuracy and validity
of the data. The experimental determination of HHVs and combustible elements of
lignites require special instrumentation, whereas proximate analysis data can be obtained
relatively easily by using common laboratory equipments.

References
ASTM. 1993. Annual Book of ASTM standards, Vol. 1994, Section 5. Philadelphia: American
Society of Testing Materials, pp. D3172–D3189.
Channiwala, S. A., and Parikh, P. P. 2002. A unified correlation for estimating HHV of solid, liquid
and gaseous fuels. Fuel 81:1051–1063.
Demirbas, A. 1997. Calculation of higher heating values of biomass fuel. Fuel 76:431–434.
Demirbas, A. 1998. Determination of combustion heat of fuels by using non-calorimetric experi-
mental data. Energy Edu. Sci. Technol. 1:7–12.
Demirbas, A. 2006. Theoretical heating values and impacts of pure compounds and fuels. Energy
Sources, Part A 28:459–467.
Demirbas, A., Gullu, D., Caglar, A., and Akdeniz, F. 1997. Determination of calorific values of
fuel from lignocellulosics. Energy Sources 19:765–770.
Elliott, M. A., and Yohe, G. R. 1981. Chemistry of Coal Utilization, 2nd Supp. Vol., Elliott, M. A.
(Ed.). New York: Wiley-Interscience.
Khan, M. Z. A., and Abu-Ghararah, Z. H. 1991. New approach for estimating energy of municipal
solid waste. J. Environ. Engng. 3:376–380.
Kucukbayrak, S., Durus, B., Mericboyu, A.E., and Kadioglu, E. 1991. Estimation of calorific values
of Turkish lignites. Fuel 70:979–781.
Selvig, W. A., and Gibson, F. H. 1945. Chemistry of Coal Utilization, Vol. I, Ch. 4, Lowry, H. H.
(Ed.). New York: Wiley.
Sensogut, C., Ozsen, H., and Demirbas, A. 2008. Determination of some combustion characteristics
of 24 lignite samples. Energy Sources 30:420–428.
Tillman, D. A. 1978. Wood as an Energy Resource. New York: Academic Press.