EEE 22-2 body 8-6-04 10:28 am Page 135

ENERGY EXPLORATION & EXPLOITATION · Volume 22 · Number 2· 2004 135

Estimating the Calorific Values of Lignocellulosic Fuels

Ayhan Demirbaş and A. Hilal Demirbaş
P. K. 216, 61035 Trabzon, Turkey

ABSTRACT
Ultimate analysis based mathematical models are the most reported with
Dulong’s equation being among the first available to calculate the calorific
value of coal or biomass. The higher heating value (HHV) at constant pressure
measures the enthalpy change of combustion with water condensed. The HHVs
(MJ/kg) of the lignocellulosic fuels as a function of carbon (C) or carbon +
hydrogen (C + H) contents (wt%) were calculated using the following
equations:

HHV = 0.3699 (C) + 1.3178 (1)

HHV = 0.3856 (C + H) – 1.6938 (2)

for Equations (1 and 2) which in square of the correlation coefficients (r2) were
0.9734 and 0.9814, respectively. There is a highly significant correlation
between the HHV of the lignocellulosic fuels and their carbon or (carbon +
hydrogen) contents.

INTRODUCTION
The standards measure of the energy content of a fuel is its heating value (HV),
sometimes called the calorific value or heat of combustion. In fact, there are multiple
values for the HV, depending on whether it measures the enthalpy of combustion, the
internal energy of combustion, and whether for a fuel containing hydrogen, product
water is accounted for in the vapor phase or the condensed (liquid) phase. With water
in the vapor phase, the lower heating value (LHV) at constant pressure measures the
enthalpy change due to combustion (Jenkins et al., 1998). The heating value is
obtained by complete combustion of a unit quantity of solid fuel in an oxygen-bomb
calorimeter under controlled conditions. The “gross” or “high” heating value is
obtained by this method, as the latent heat of moisture in the combustion products is
recovered. The results may be expressed on the “as received” or “dry” or “dry and ash
free” basis. The Higher Heating Value (HHV) at constant pressure measures the
enthalpy change of combustion with water condensed. Fuel values of lignocellulosic
fuels are greatly dependent on their heating values and are generally believed to be one
of the parameters to compare one fuel with another. In the earlier works, relationships
between lignin contents and higher heating values (HHVs) of biomass, and aqueous
EEE 22-2 body 8-6-04 10:28 am Page 136

136 Estimating the Calorific Values of Lignocellulosic Fuels

liquefaction products of biomass have been studied and the mathematical equations
have been developed to calculated the HHVs of various lignocellulosic fuels from
their chemical analyses data (Demirbaş, 2001; Demirbaş, 2000a).
Data on the higher heating values (HHVs) of lignocellulosic materials have been
extensively investigated in the earlier studies (Parr and Davidson, 1922; Howard,
1973; White, 1987; Demirbaş et al., 1997; Raveendran and Ganesh, 1996; Demirbaş,
1997; Kathiravale et al., 2003; Demirbaş, 1998a; Barnes and Singlair, 1984; Demirbaş,
2001; Harris, 1984; Demirbaş, 2002; Ince, 1979; Demirbaş, 2003).
In the earlier works (Demirbaş, 1997; Demirbaş, 1998b; Demirbaş, 1998c),
formulae were also developed for estimating the HHVs of fuels from different
lignocellulosic materials, vegetable oils and diesel fuels using their chemical analysis
data. For fuels such as coal, the Dulong’s formulae (Perry and Chilton, 1973) define
the HHV as a function of the carbon, hydrogen, oxygen, and sulphur contents:

HHV (kcal/kg) = 8,080(C) + 34,460(H) – 4,308(O) + 2250(S) (1)

HHV (kcal/kg) = 81(C) + 342.5(H – O/8) + 22.5(S) – 6(9H – W) (2)

On the basis of literature values for different species of wood, Tillman (1978) also
found a linear relationship between HHV and carbon content. The HHVs foe
extractives, lignin, and holocellulose are consistent with their carbon content (White,
1987).

EXPERIMENTAL
The elementary composition, ash, volatile material, and fixed carbon contents of
charcoals from the lignocellulosic materials in relation to the carbonization
temperature and their HHVs are determined by bomb calorimeter according to the
ASTM D2015 standard method. Calculations are done using the ultimate and
proximate analysis data as given in the earlier studies (Demirbas¸, 1997; Demirbas¸ et
al., 1997).
Part of the sample is ground to pass through a 0.2 mm sieve and about 0.5 g of
ground material is pressed into a pellet and burnt in a an adiabatic oxygen bomb
calorimeter according to the ASTM D2015 standard test method for determination of
higher heating value (HHV).
Chemical analyses of the samples are carried out according to the ASTM D1103-
80 and ASTM D1104-56 standard test methods, respectively. The methods of
lignocellulosic fuel analyses are listed Table 1.

RESULTS AND DISCUSSION

The proximate and ultimate analyses and HHVs of lignocellulosic fuels are listed in
Table 2. Figures 1a and 1b show the plot of higher heating values versus carbon
contents of lignocellulosic fuels. The plot of higher heating values versus (carbon +
hydrogen) contents of lignocellulosic fuels are depicted in Figures 2a and 2b.
EEE 22-2 body 8-6-04 10:28 am Page 137

ENERGY EXPLORATION & EXPLOITATION · Volume 22 · Number 2 · 2004 137

Table 1. Methods of lignocellulosic fuel analyses

Property Analytical method

Heating value ASTM D 2015, E 711
Proximate analysis
Ash ASTM D1102 (873 K), ASTM E830 (848 K)
Volatile matter ASTM E 872, ASTM E 897
Fixed carbon by difference
Ultimate elemental analysis
Carbon, Hydrogen ASTM E 777
Nitrogen ASTM E 778
Sulfur ASTM E 775
Chloride ASTM E776
Oxygen by difference

Table 2. Proximate and ultimate analyses and higher h

eating values (HHVs) of lignocellulosic fuels

Sample C H O N Ash FC VM HHV

(MJ/kg)
Cellulose 44.4 6.2 49.4 – – – – 17.7
Hardwood lignin 59.8 6.4 33.7 – – – – 24.9
Softwood lignin 63.8 6.3 29.9 – – – – 26.6
Beech wood 51.6 6.3 41.5 0.3 0.7 24.6 74.0 19.9
Spruce wood 52.1 6.2 40.7 0.2 0.5 28.3 70.2 20.3
Yellow pine 52.6 7.0 40.1 0.2 0.8 29.2 69.1 21.5
Poplar wood 51.7 6.2 41.4 0.3 0.6 25.0 73.8 20.1
Pine bark 56.3 5.6 37.7 0.2 0.4 33.9 54.7 21.9
Wood pyrolytic oil 72.3 8.6 17.6 0.2 0.8 – – 33.5
Wood charcoal 92.0 2.5 3.0 0.5 1.0 89.3 – 34.4
Cotton stalk 43.6 5.8 43.9 0.1 6.7 22.4 70.9 18.2
Rice hulls 38.3 4.4 35.5 0.8 20.6 15.8 63.6 14.9
Grass 44.6 5.4 39.2 1.2 8.7 18.6 72.8 17.4
Hazelnut shell 49.9 5.6 41.6 1.3 1.6 26.3 72.3 19.3
Walnut shell 51.1 5.7 42.2 0.4 0.6 21.2 78.3 19.9
Olive husk 49.4 6.2 39.2 1.6 3.6 26.1 70.3 19.0
Corncob 46.6 5.9 45.5 0.5 1.4 18.5 80.1 18.7
Wheat straw 43.2 5.0 39.4 0.6 8.9 19.8 71.3 17.5
Corn stover 43.7 5.6 43.3 0.6 5.6 19.3 75.2 17.7
Sugarcane bagasse 44.8 5.4 39.6 0.4 11.3 15.0 73.8 17.9
Pine needless 50.2 6.6 41.7 0.2 1.4 26.1 72.4 20.0
Sources: Paul and Buchele, 1980; LePori, 1980; Maschio et al., 1994; Demirbaş, 1997.
EEE 22-2 body 8-6-04 10:28 am Page 138

138 Estimating the Calorific Values of Lignocellulosic Fuels

35
Higher heating value, MJ/kg

30

25

20

15

40 50 60 70 80 90

Carbon content, wt%

Figure 1a. Plot of higher heating values versus
carbon contents of lignocellulosic fuels

40

35
Higher heating value, MJ/kg

30

25

20

15

10
30 40 50 60 70 80 90 100

Carbon content, wt%

Figure 1b. Plot of higher heating values versus
carbon contents of lignocellulosic fuels
EEE 22-2 body 8-6-04 10:28 am Page 139

ENERGY EXPLORATION & EXPLOITATION · Volume 22 · Number 2 · 2004 139

40

35
Higher heating value, MJ/kg

30

25

20

15

10
40 50 60 70 80 90 100

Carbon + hydrogen content, wt%

Figure 2a. Plot of higher heating values versus carbon +
hydrogen contents of lignocellulosic fuels

40

35
Higher heating value, MJ/kg

30

25

20

15

10
40 50 60 70 80 90 100

Carbon + hydrogen content, wt%

Figure 2b. Plot of higher heating values versus carbon +
hydrogen contents of lignocellulosic fuels
EEE 22-2 body 8-6-04 10:28 am Page 140

140 Estimating the Calorific Values of Lignocellulosic Fuels

The mathematical models available from literature for estimation calorific values
of lignocellulosic fuels were based on ultimate analysis, proximate analysis, physical
composition, chemical composition or structural analyses.
Equations based on ultimate analysis are:

HHV (Btu/lb) = 188.0C – 131.5 (Tillman, 1978) (3)

HHV (kcal/kg) = 83.22C + 274.3H –

25.8O +15N + 9.4Cl + 65P (Corbitt, 1989) (4)

HHV (MJ/kg) = 33.5 (C) + 142.3 (H) –

15.4 (O) – 24.5N (Demirbaş et al., 1997) (5)

where HHV is the higher heating value of fuel and C, H, O, N, Cl, and P is carbon,
hydrogen, oxygen, nitrogen, chlorine, and phosphor contents (wt% of fuel),
respectively.
Equations based on proximate analysis are:

HHV (MJ/kg) = 0.196FC + 14.119 (Demirbaş, 1997) (6)

HHV (MJ/kg) =
0.312FC + 0.1534VM (Demirbaş, 1997) (7)

where HHV is the higher heating value of lignocellulosic fuel, FC is fixed carbon
(wt% of fuel) and VM is volatile materials (wt% of fuel).
Equations for vegetable oils, alcohols and alkanes based on physical composition
are:

For vegetable oils:

HHV (MJ/kg) = 79.014 – 43.126d (Demirbaş, 2000b) (8)

HHV (MJ/kg) = 37.945 + 0.0491µ (Demirbaş, 2000b) (9)

For alcohols:
HHV (MJ/kg) =
–220.981 + 316.050d (Demirbaş, 2000b) (10)

For alkanes:
HHV (MJ/kg) =
55.750 – 11.051d (Demirbaş, 2000b) (11)

where HHV is the higher heating value of the fuel, d is density of the fuel (g/cm3) and
µ is viscosity (mm2/s) of the fuel.
EEE 22-2 body 8-6-04 10:28 am Page 141

ENERGY EXPLORATION & EXPLOITATION · Volume 22 · Number 2 · 2004 141

Equation based on chemical composition of vegetable oils is:

HHV (MJ/kg) = 49.43 –
0.041SV + 0.015IV (Demirbaş, 1998c) (12)

where HHV is the higher heating value of vegetable fuel, SV is saponification value
of oil and IV is iodine value of oil).
Equations based on structural composition of lignocellulosic fuels are:

For woody lignocellulosic fuels:

HHV (MJ/kg) =
0.0893L + 16.9742 (Demirbaş, 2001) (13)

(HHV (MJ/kg) = 0.00639E2 +

0.223E + 0.691 (Demirbaş, 2002) (14)

For non-wood lignocellulosic fuels:

HHV (MJ/kg) =
0.0877L + 16.4951 (Demirbaş, 2001) (15)

where HHV is the higher heating value of lignocellulosic fuel, L is lignin content (wt%
of the fuel), ∆HHV is differential HHV of the fuel and E is extractive content (wt% of
the fuel).
As seen Figures (1-4), the HHVs (in MJ/kg) of the lignocellulosic fuels as a
function of carbon (C) or carbon + hydrogen (C + H) contents (wt%) were calculated
using the following equations:

From Figure 1a:

HHV = 0.4084 (C) – 0.459 (16)

From Figure 1b:

HHV = 0.3699 (C) + 1.3178 (17)

From Figure 2a:

HHV = 0.4182 (C + H) – 3.4085 (18)

From Figure 2b:

HHV = 0.3856 (C + H) – 1.6938 (19)

For Equations (16, 17, 18 and 19) the correlation coefficients (r2) were 0.9335,
0.9734, 0.9631 and 0.9814, respectively. There is a highly significant correlation
between the HHV of the lignocellulosic fuels and their carbon or (carbon + hydrogen)
contents. One point showed extreme (see Table 2: wood pyrolytic oil) deviate from the
others and was not taken into account when HHVs calculated for Equations (17 and
19).
EEE 22-2 body 8-6-04 10:28 am Page 142

142 Estimating the Calorific Values of Lignocellulosic Fuels

CONCLUSION
The mathematical models available from literature for estimation calorific values of
lignocellulosic fuels were based on ultimate analysis, proximate analysis, physical
composition, chemical composition or structural analyses.
The higher heating value (HHV) at constant pressure measures the enthalpy change
of combustion with water condensed. There are linear functions between the HHVs of
the lignocellulosic fuels and carbon (C) or carbon + hydrogen (C + H) contents (wt%).
Using regression analysis, the results showed that there is a highly significant
correlation between the HHV of the lignocellulosic fuels and their carbon or (carbon
+ hydrogen) contents.
Fuel value of a lignocellulosic material is greatly dependent on its heating value
and is generally believed to be one of the parameters to compare one fuel with another.
Moisture in biomas generally decreases its heating value. Ash and extractive content
are two important parameters directly affecting the heating value. High ash content of
a plant part makes it less desirable as fuel, whereas high extractive content adds to its
desirability. Again the heat content, which is a very important factor affecting
utilization of any material as a fuel, is affected by the proportion of extractives present
in it. Extractives raised the higher heating values (HHVs) of the biomass samples.

REFERENCES
Barnes, D. P. and Sinclair, S. A. (1984). “Gross heat of combustion of living and
spruce budworm-killed balsam fir”, Wood Fiber Sci, Vol. 16, pp. 518-522.
Corbitt, R. A. (1989). “Standard handfbook of environmental engineering”, McGraw-
Hill, USA.
Demirbaş, A., Güllü, D., Çaşlar, A., and Akdeniz, F. (1997). “Estimation of calorific
values of fuel from lignocellulosics”, Energy Sources, Vol. 19, pp. 765-770.
Demirbaş, A. (1997).”Calculation of higher heating values of biomass fuels”, Fuel,
Vol. 76, pp. 431-434.
Demirbaş, A. (1998a). “Determination of combustion heat of fuels by using non-
calorimetric experimental data”, Energy Edu Sci Technol, Vol. 1, pp. 7-12.
Demirbaş, A. (1998b). “Fuel properties and calculation higher heating values of
vegetable oils”, Fuel, Vol. 77, pp. 1117-1120.
Demirbaş, A. (1998c). “Combustion properties and calculation of higher heating
values of diesel Fuels”, Petroleum Sci Technol, Vol. 16, pp. 785-797.
Demirbaş, A. (2000a). “Effect of lignin content on aqueous liquefaction products of
biomass”, Energy Convers Mgmt, Vol. 41, pp. 1601-1607.
Demirbaş, A. (2000b). “A direct route to the calculation of heating values of liquid
fuels by using their density and viscosity measurements”, Energy Convers
Mgmt, Vol. 41,pp. 1609-1614.
Demirbaş, A. (2001). “Relationships between lignin contents and heating values of
Biomass”, Energy Convers Mngt, Vol. 42, pp. 183-188.
Demirbaş, A. (2002). “Relationships between heating value and lignin, moisture, ash and
extractive contents of biomass fuels”, Energy Explor Exploit, Vol. 20, pp. 105-111.
EEE 22-2 body 8-6-04 10:28 am Page 143

ENERGY EXPLORATION & EXPLOITATION · Volume 22 · Number 2 · 2004 143

Demirbaş, A. (2003). “Relationships between lignin contents and fixed carbons of

biomass Samples”, Energy Convers Mgmt, Vol. 44, pp. 1481-1486.
Haris, R. A. (1984). “Fuel values of stems and branches in white oak, yellow-poplar,
and sweetcum”, Forest Prod J, Vol. 34, pp. 25-26.
Howard, E. T. (1973). “Heat of combustion of various southern pine materials”, Wood
Sci, Vol. 5, pp. 194-197
Ince, P. J. (1979). “How to estimate recoverable heat energy in wood or bark fuels”,
USDA Forest Serv. Gen. Tech. Rep. FPL 29. Forest Prod. Lab. Madison,WI.
Jenkins, B. M., L. L. Baxter, T. R. Miles, Jr., and T. R. Miles. (1998). “Combustion
properties of Biomass”, Fuel Process Technol, Vol. 54, pp. 17-46.
LePori, W. A. (1980). “Fluidized bed combustion and gasification of biosolid”, Agric
Energy, Vol. 2, pp. 330-334.
Maschio, G., A. Lucchesi, and G. Stoppato. (1994). “Production of syngas from
biodiesel”, Bioresource Technol, Vol. 48, pp. 898-902.
Kathiravale, S., Yunus, M. N. M., Sopianb, K., Samsuddin, A. H., and Rahman, R. A.
(2003). “Modeling the heating value of municipal solid waste”, Fuel (in pres).
Parr, S. W. and Davidson C. N. (1922). “The calorific value of American woods”, J
Ind Eng Chem, Vol. 14, pp. 935-936.
Perry, S. W. and Chilton, C. N. (1973). “Chemical Engineers’ Handbook”, 5th ed.
McGraw-Hill, New York.
Paul, W. C. and W. F. Buchele. (1980). “Development of a concentric vortex agri-
residue furnace”, Agric Energy, Vol. 2, pp. 349-356.
Raveendran, K and Ganesh A. (1996). “Heating value of biomass and biomass
pyrolysis products”, Fuel, Vol. 75, pp. 1715-1720.
Tillman, D. A. (1978). “Wood as an Energy Resource”, Academic Press, New York.
White, R. H. (1987). “Effect of lignin content and extractives on the higher heating
value of wood”, Wood Fiber Sci, Vol. 19, pp. 446-452.