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EN ERGY EXPLORATION & EXPLOITATION Volume 20 Number 1 2002

105

Relationships Between Heating Value and Lignin,


Moisture, Ash and Extractive Contents of Biomass Fuels
Ayhan Demirbas
P. K. 216, TR-61035 Trabzon, Turkey

ABSTRACT
Various fuel characteristics, such as moisture, ash, lignin, holocellulose and
extractive contents of different biomass species were determined on ash-free dry
weight and extractive-free dry weight basis to find out relationship, if any,
between ash and extractive content with the higher heating value. Moisture in
biomass 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 of the
biomass samples.

INTRODUCTION
Biomass is the most abundant renewable energy resource available in the world.
Biomass can be utilized by direct combustion, co-firing with coal, carbonization,
liquefaction and gasification in order to obtain heat, fuels and chemicals. So far, most
attention has been focussed on the various ways of steam gasifying or liquefying
biomass (Wang et al., 1997). Steam gasification of biomass produces CO, which
together with H2 constitutes syngas, the feed in fuel syntheses processes.
In earlier works, relationships between lignin contents and higher heating values
(HHVs) of biomass, and aqueous 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 (Demirbas,, 2001;
Demirbas,, 2000a ). Lignocellulosic biomass consists of three structural components:
lignin, cellulose and hemicelluloses.
There has been many attempts at correlating the heating value with the composition
(Georing et al., 1982; Demirbas,, 1997; Demirbas,; 1998a; Demirbas,, 1998b). Formulas
developed for coal, such as the Dulong equation (Perry and Chilton, 1973), typically
do not do well for biomass. The increase in heat content results from a high increase
in the number of carbons and hydrogens, as well as an increase in the ratio of these
elements relative to oxygen. A decrease in heat content is the result of fewer hydrogen
atoms (i.e., greater unsaturation ) in the fuel molecule. Determination of data obtained
for a great many compounds has shown that the HHV of an aliphatic hydrocarbon

106

Relationships Between Biomass Fuels

agrees rather closely with that calculated by assuming a certain characteristic


contribution from each structural unit (Morrison and Boyd, 1983).
EXPERIMENTAL
Moisture content was determined by drying the wood sample at 353K to constant
weight. Ash content was determined by burning 1g of ground sample in a muffle
furnace at 825K for 4h. Extractives were obtained by extracting the ground sample
with alcohol-benzene (1/1, v/v) in a Soxhlet extractor for 18 hours (at least 15
cycles/hour).
The extractive-free samples were further used for determination of lignin, by
digesting with 72% sulfuric acid for 2h and holocellulose by chlorination and
extraction in ethanol and ethanolamine (Kataki and Konwer, 2001).
Part of the sample was ground to pass through a 0.2mm sieve and about 0.5g of
ground material was pelleted 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 and structural analyses of the samples were carried out according to the
ASTM D1103-80 and ASTM D1104-56 standard test methods, respectively. The other
standard test methods for biomass fuel analysis are presented in Table 1.
Table 1 Standard test methods of biomass fuel analyses
Property
Heating value
Proximate analysis
Moisture
Ash
Volatile matter
Fixed carbon
Ultimate elemental analysis
Carbon, Hydrogen
Nitrogen
Oxygen

Analytical method
ASTM D 2015
ASTM E871
ASTM D1102
ASTM E 872
by difference
ASTM E 777
ASTM E 778
by difference

RESULTS AND DISCUSSION


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 higher heating value
(HHV) at constant pressure measures the enthalpy change of combustion with water
condensed at initial temperature and pressure.
The average ultimate and proximate including fixed carbon and volatile material

EN ERGY EXPLORATION & EXPLOITATION Volume 20 Number 1 2002

107

contents analyses results are given in Table 2. Table 3 shows the average structural,
extractive and ash content analyses results and HHVs.
Table 2 Average proximate and ultimate
analyses results (wt. % dry basis)
Sample
Spruce trunkwood
Spruce trunk bark
Beech trunk wood
Beech trunk bark
Ailanthus trunk wood
Sunflower shell
Almond shell
Hazelnut shell
Olive husk
Hazelnut kernel husk
Walnut shell

C
51.9
53.8
49.5
52.9
49.5
47.4
47.9
51.6
52.8
51.0
53.5

H
6.1
6.0
6.2
6.1
6.2
5.8
6.0
6.2
6.7
5.4
6.6

O
40.9
40.0
41.2
40 8
41.0
41.4
41.6
40.2
36.7
42.3
35.5

N
0.3
0.2
0.4
0.3
0.3
1.4
1.1
1.6
0.5
1.3
1.5

Fixed carbon
28.5
30.2
24.8
29.5
24.9
21.5
22.7
28.3
32.9
27 4
37.9

Volatile material
70.7
64.6
74.4
64.1
74.5
78.0
74.1
70 3
63.9
71.2
59.3

The HHVs of extractive-free samples reflect the HHV of lignin relative to cellulose
and hemicelluloses. It was reported that (Demirbas, 2001) , cellulose and
hemicelluloses (holocellulose) have a HHV of 18.60 MJ/kg, whereas lignin has a
HHV of 23.26 to 25.58 MT/kg. As discussed by Baker (1982), HHVs reported for a
given species reflect only the samples tested and not the entire population of the
species. The HHV of a lignocellulosic fuel is a function of its lignin content.
Using linear regression analysis, it can be compared the HHVs with the chemical
composition data. In general, the HHVs of lignocellulosic fuels increase with increase
of their lignin contents and the HHV is highly correlated with lignin content. For the
model including the lignin content, the regression equation is
HHV - 0.0889 (LC) +16.8218,

(1)

where HHV is the higher heating value of fuel sample (MJ/kg)) and LC is lignin
content (wt % daf and extractive-free sample basis).
For the wood samples, the regression equation is

HHV = 0.0893 (LC) + 16.9742

(2)

For the non-wood biomass samples, the regression equation is

HHV = 0.0877 (L ) + 16.4951

(3)

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Relationships Between Biomass Fuels

For Eqn (1), correlation coefficient (r) is 0.9504. The HHVs calculated with Eqn
(1) showed a mean difference of 0.056 %. For Eqns (2 and 3), r is 0.9658 and 0.9302,
and mean difference is 0.045 and 0.067 % respectively.
There are no direct relations between HHV and the holocellulose of the
lignocellulosic fuels, but there are good relations between the lignin contents and the
determined HHVs of the wood samples (Demirbas,, 2001b).
The plots of HHVs of biomass samples versus percentages of carbon + hydrogen,
lignin, and fixed carbon are given in Figure 1. The HHV (MJ/kg) of the biomass fuels
as a function of fixed carbon content (FCC, wt%) was calculated from Equation (4):

HHV= 0.196 (FCC) + 14.119

(4)

Figure 1. Plots of HHVs of biomass samples versus percentages of carbon +


hydrogen, lignin, and fixed carbonAs seen from Figure 1, HHV increases as increase
(C + H) contents of the samples.

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109

The differential higher heating values (HHVs in MJ/kg) of various biomass


species vs percent extractive content are given in Figure 2. The HHVs of the
extractive-free samples were found to be lower than those of the unextracted samples
which indicate a likely positive contribution of extractives towards the increase of
HHV. The HHV (MJ/kg) of the biomass samples as a function of extractive content
(EC, wt%) can be calculated from Equation 5:
HHV = 0.00639 (EC)2 + 0.223 (EC) + 0.691

(5)

For Eqn (5), in a square of the correlation coefficient (r2) was 0.9748.
Apart from physiological differences that might cause variation in moisture content
in different plant parts, seasonal changes and geographic location also contribute
towards the difference in moisture content among different species and their
plant parts (Diaz and Golueke, 1981). Moisture in biomass generally decreases its
heating value.

Figure 2. Plot of increase of higher heating values of various biomass species versus
Percentage of extractive content

110

Relationships Between Biomass Fuels

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 (Table 3). 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.
Table 3 Average structural, extractive and ash content analyses results and
HHVs (wt % dry basis)
Sample
Holocellulose Lignin Extractivesa
Spruce trunk wood
70.12
26.93
2.14
Sprucetrunkbark
51.54
38.37
3.97
Beechtrunkwood
75.15
21.11
2.92
Beech trunk bark
57.40
32.79
3.45
Ailanthus trunk wood
72.35
24.48
2.61
Sunflower shell
81.05
15.72
2.69
Almond shell
75.12
19.21
2.43
Hazelnut shell
55.27
40.12
3.25
Olive husk
45.08
42.29
9.35
Hazelnut kernel husk
37.63
42.38
18.56
Walnut shell
44.81
49.13
3.31

Ash
0.81
6.12
0.82
6.36
0.56
0.54
3.24
1.36
3.28
1.43
2.75

HHVb
19.92
21.90
19.33
21.38
19.43
18.75
21.68
20.49
21.61
20.83
22.22

HHVC
18.09
18.84
18.23
19.85
18.32
17.60
20.58
19.09
20.16
13.78
20.74

aAlcohol/Benzene

(1/1, vlv ) extractives


Higher Heating Value on ash free basis (MJ/kg)
cHHV: Higher Heating Value on extractive free basis (MJ/kg )
b HHV:

For the samples tested in this study, the mean difference in HHVs of the softwoods,
hardwoods, and non-wood biomass fuels was primarily caused by their difference in
lignin contents. There are many different types of lignins and extractives in structures
of different species of lignocellulosic materials. The lignins from grasses, softwoods,
and hardwoods differ somewhat in composition, chiefly in methoxyl substitution and
the degree of carbon-carbon linkage between phenyl groups. The aromatic and
phenolic character is apparent in conifer (softwood and spruce wood) lignin, as is the
covalent carbon-carbon bonding that prevents reversion to monomers by mild
processing. In conifers the precursors is principally coniferyl alcohol (3-methoxy-4hydroxycinnamyl alcohol) that yields the so-called guaiacyl lignin.

CONCLUSION
Fuel value of biomass 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
biomass 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.

EN ERGY EXPLORATION & EXPLOITATION Volume 20 Number 1 2002

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There are no direct relations between HHV and the holocellulose of the
lignocellulosic fuels, but there are good relations between the lignin contents and
determined HHVs of the lignocellulosic fuel samples. Thus the HHVs of the
renewable natural fuels can be calculated by using the lignin content obtained from
simple chemical analysis. The experimental determination of HHV requires special
instrumentation, whereas chemical analysis data can be obtained relatively easily by
available laboratory equipment.

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