Research Journal of Agriculture and Environmental Management. Vol. 2(10), pp.

295-301, October, 2013

Available online at http://www.apexjournal.org
ISSN 2315 - 8719 2013 Apex Journal

Full Length Research Paper

New Van Krevelen diagram and its correlation with the

heating value of biomass
Marliati Ahmad1,* and Handoko Subawi2
1

Riau Islamic University, Pekanbaru Indonesia.

Indonesia Aerospace, Jl. Pajajaran, No. 154 Bandung Indonesia.

Accepted 17 July, 2013

This study was aimed to propose new Van Krevelen diagram on biomass by involving proximate and
ultimate analysis data. The biomass groups were stratified into (a) coals and fuel, (b) organic waste and
chemicals, and (c) wood and biofiber. The basic diagram correlates a hydrogen to oxygen content, all
compared to carbon content in biomass with refers to ultimate analysis. The profiles of basic elements
in biomass were also examined and to explore its corelation with heating value parameter by
accomodating ash content on biomass. This study did not discuss moisture removal from biomass.
Key words: Biomass, bioenergy, carbon content, ash content, heating value, fuel.
INTRODUCTION
A biomass is defined as part of agricultural product
including waste and the rest of biodegradable animals,
plants, forestry and municipal wastes. Biomass is
renewable feedstock of bioenergy mainly waste of human
activities and nature containing carbon. Nowadays,
biomass feedstock covers 14% of global energy and
contributes up to 38% of energy supply in developing
countries (Beena and Bharat, 2012).
Utilization of agriculture and horticulture wastes
provides large opportunities of huge renewable bioenergy
in Indonesia. The utilization of oil palm waste through
biogas processing offers electrical power generation up
to 380 MW, excluding direct utilization as bioenergy
feedstock for fuel, or its opportunity for animals feedstock
(Alexis and Pierre, 1819). Potential bioenergy from
biomass is intended to contribute to the increasing global
energy consumption that is still dominated by fossil fuels
(Handoko and Marliati, 2012).
The heating value potential of substances has being
studied by researchers since long time ago. Initial study
by Pierre Louis Dulong and Alexis Thrse Petit
examined heating content of substances in the form of
heating capacity parameter. They proposed hypothesis

about heating capacity of substances and predicted that

volumetric heating capacity of all materials has the same
value of 3 for solid materials (Handoko, 2013). Law of
Dulong-Petit (1819) currently does not prevail anymore
due to more detail measurement that shows the broad
range of values. This study focused on relationship
between elements and the heating value of biomass. In
parallel, the heating value data can be predicted by
accomodating the elements and ash content of variety of
biomass by means of proximate and ultimate analyses.
MATERIAL AND METHODS
This study employed two groups of data: i) Data of
proximate analysis per ASTM D3175 providing fixed
carbon content, volatile matter and ash content; ii) Data
of ultimate analysis providing element content of carbon
(C), hydrogen (H), oxygen (O), nitrogen (N) and sulphur
(S). The ash content was analysed per ASTM D1102-90
to describe elements included in ash of biomass.
Correlation of the element content with heating value
of biomass

*Corresponding author. Email: marliatiahmad@yahoo.com

Determination

of

heating value of biomass can be

296

Res. J. Agric. Environ. Manage.

obtained through measurement (HHVmeasured) or by

means of calculation (HHVcalculated) by accomodating
parameters of carbon, hydrogen, oxygen, nitrogen,
sulphur and ash content. High heating value (HHV) is
obtained from completely oxidation of biomass sample
yielding carbon dioxide gas and water liquid. The high
heating value (HHV) is different with low heating value
(LHV) that correlate with the heat released while
hydrogen burned and turns to gas phase, and can be
calculated based on HHV value and hydrogen fraction.
The prediction method was used to determine
HHVcalculated as a comparison to the measured HHVmeasured
in the laboratory.
RESULTS
The analysis data of biomass consist of proximate,
ultimate analysis and heating value. The main constraint
in empowering
biomass feedstock either for heat
sources or electricity, is burning efficiency level that has
not been sufficiently competitive with the wood solid fuel.
The constraint is indicated by parameter of ash content.
Most of ash content is silica. High content of silica, kalium
and also chlor in biomass will overlap to cause a clogging
and slagging in a heating equipment with temperature
over the melting point of ash. Biomass will be competitive
and compatible with advanced technology if the high ash
removal has been overcomed. Table 1 covers test result
of ash, fixed carbon content and elements analysis in
biomass (Jigisha et al., 2005; Woodgas, 2007 and
Kirubakaran et al., 2009)The carbon content, volatile
matter and ash content in percentage values based on
dry basis. It means excluding moisture content of each
biomass.
DISCUSSION
In parallel experiment, it was found that the removal of
high ash content in biomass can be performed through
immersion in diluted alkaline solution at low temperature.
An effort to remove ash content is strategically to
maintain the heating facility. An experience in electrical
power generation in Denmark (1997) found that straw
biomass contained kalium over limit value of 0.2% and
chlor more than 0.1%. Figure 1 shows relationship
between ash content and heating value of biomass.
The figure indicates that the lower ash content
correlates with an increase of heating value of biomass.
Biomass with lower ash content shows variety of heating
value parameter. Heating value of biomass varies from
10 MJ/kg until 50 MJ/kg. The ash content in biomass are
mostly less than 20% dry basis. The lower the ash
content, the higher effectivity of oxidation process.
Out of the variety of biomass, rice hull, rice husk, and

rice straw have high ash content of about 23.5%, 20.6%

and 19.8% respectively. Not all ash contains high silica.
However, the rice straw, rice husk and rice hull show
predominantly high silica content in its ash, beside kalium
and chlor. The removal of ash content is very important
in the empowerment of natural fiber such as feedstock in
industry, or solid fuel.
Oxidation elements contribute in burning process
performance. The important elements in this case consist
of carbon (C), hydrogen (H), oxygen (O), nitrogen (N) and
sulphur (S). Van Krevelen (1950) tried to stratify soild fuel
of biomass in simple diagram to correlate between
parameter of H/C to parameter of O/C (Figure 2.).
On the diagram, comparism between natural fuel and
fossil fuel such as coals was illustrated. The diagram
shows clearly the comparison between oxygen to
hydrogen, based on carbon content. The lower heating
value seems due to carbon-to- oxygen and carbon-tohydrogen bonds compared with carbon-to-carbon bond
(Van Krevelen, 1950; Peter, 2002).
This diagram differentiates groups of (a) biomass, (b)
peat, lignite, (c) coal, and (d) anthracite. Anthracite
contains lowest oxygen and hydrogen elements than
other solid fuels.
This study evaluated variety of biomass and fuels as a
comparison on a diagram called new Van Krevelen
diagram shown at Figure 3. The diagram has clear
boundary line than Van Krevelen diagram. All data were
grouped into (a) wood, (b) biofiber, (c) fuel, (d) coal, (e)
organic chemicals and (f) organic waste. The new
diagram identified wood as part of biofiber, and coal as
part of fuel, whereas in the narrower range of oxygen and
hydrogen there is organic waste as a part of organic
chemical group.
Groups of wood and biofiber contain varied oxygen, as
O/C, between 0.75 and 1.50, in the range of certain
hydrogen content. On the other hand, fuel groups
including coals, char and tar have oxygen content, as
O/C, from 0 until 0.30, with certain range of hydrogen.
The relationship of HHV can be traced from carbon
content as shown at Figure 4a. It followed a trend; the
higher the carbon content, the higher heating value HHV.
However this trend is more clear when sum of carbon
and hydrogen content was compared Figure 4c.. Further,
Figure 4b shows that higher oxygen content tends to
decrease heating value. However, comparison between
sum of oxygen and ash content made it clearer as shown
at Figure 4d.
The correlation of biomass elements content to the
heating value, HHV, was formulated by Channiwala
(1992) by involving fraction of carbon, hydrogen, oxygen,
ash, sulphur and nitrogen that were obtained from
ultimate analysis (Channiwala, 1992). Higher carbon
content in biomass can be reached in char such as 89 to
92% in charcoal or 83 to 87% in coconut shell char. This
is higher than 84 to 85% in anthracite.

Ahmad and Subawi

297

Tabel 1. Biomass component analysis and thermal measurement.

Volatile
matter %

Feedstock

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30

Acetone
Acetic acid
D-glucose
Phenol
Cellulose
Lignin (softwood)
Lignin(hardwood)
Coal Pittsburgh seam
Peat S-H3
Charcoal
Oak char (565C)
Casuarina char (950C)
Coconut shell char (750C)
Eucalyptus char (950oC)
Northumberland no.8-Anth.
Coal
Coal sample
L14
Charcoal
Redwood char-790-1020oF
Oak char-820-1185oF
Coconut shell char-750oC
QrC550
PhC300
EsC700
Bagasse
Coconut coir
Corn stalks
Rice straw
Wheat straw

31

Wheat straw

71.3

8.9

19.8

43.2

32
33
34

Cotton stalk
Sugarcane baggase
Water hyacinth

70.9
73.8
80.4

6.7
11.3
19.6

22.4
15.0
0.0

43.6
44.8
40.3

35

Brown kelp, soquel point

57.9

42.1

0.0

27.8

36
37
38
39
40
41
42
43
44

Wheat straw
Paddy straw
Cotton stalk
Mulberry stick
Coconut coir
Sena leaves
Sugarcane leaves
Dallake weed
Tea bush

63.0
72.7
65.4
75.1
66.6
57.2
77.4
47.7
76.5

13.50
15.50
17.30
2.10
3.72
17.30
7.70
48.70
1.70

23.5
11.8
17.3
22.8
29.7
25.5
14.9
3.6
21.8

45

Salseed husk

62.5

9.40

46

Eucalyptus sawdust

83.6

0.20

33.9
70.1
93.9
27.1
15.2
93.0
19.2
7.1
12.0
49.5
9.9
0.9
30.0
25.8
9.9
14.7
68.1
6.6
84.2
82.8
80.1
80.2
83.9

Ash %

Fixed
Carbon
%
0.0
0.0
0.0
0.0
0.0
0.0
0.0
55.8
26.9
89.3
55.6
71.5
87.2
70.3
84.59
79.6
46.03
89.1
91.47
67.7
59.3
87.17
82.2
31.3
91.5
15.8
17.2
19.9
19.8
16.1

No

0.6
0.6
0.2
0.9
16.2
0.0
0.0
10.3
3.0
1.0
17.3
13.2
2.9
10.5
8.32
8.40
4.50
1.02
7.61
2.30
14.90
2.90
3.10
0.60
1.90
2.9
0.9
6.8
19.8
11.2

Measured
HHV (MJ/kg)

62.1
40.0
40.0
76.6
44.4
63.8
59.8
75.5
54.8
92.0
64.6
77.5
89.0
76.1
83.7
82.6
63.9
92.0
89.1
75.6
67.7
88.9
87.1
57.8
92.7
43.8
47.6
41.9
36.9
47.5

10.3
6.7
6.7
6.4
6.2
6.3
6.4
5.0
5.4
2.5
2.1
0.9
0.7
1.3
3.56
3.02
4.97
2.45
0.43
3.3
2.4
0.73
2.4
5
1.6
5.8
5.7
5.3
5.0
5.4

27.6
53.3
53.3
17.0
49.4
29.9
33.7
4.9
35.8
3.0
15.5
5.6
6.0
11.1
2.84
3.66
24.54
2.96
0.98
18.4
14.4
6.04
6.9
36.5
3.3
47.1
45.6
46.0
37.9
35.8

4.28
2.09
6.70
7.30

7.38
3.48
3.72
7.76

1.20
0.89
0.53
0.40
2.67
1.38
1.02
0.55
0.92
0.57
0.53
0.85
0.20
0.40
1.38
0.50
0.20
0.40
0.40
0.20
0.40
0.10

3.10
0.11
1.00
0.10
1.05
0.73
0.48
1.00
1.00
0.20
0.20

5.0

39.4

0.61

0.11

17.51

5.8
5.4
4.6

43.9
39.6
34.0

0.38
1.51

0.01
-

18.26
17.33
14.86

3.8

23.7

4.63

1.05

10.75

45.5
36.0
39.4
44.2
50.2
36.2
39.7
19.1
47.6

5.1
5.28
5.07
6.61
5.05
4.72
5.55
2
6.13

34.1
43.08
39.14
46.25
39.63
37.49
46.82
25.96
43.16

1.80
0.17
1.20
0.51
0.45
4.29
0.17
4.22
1.33

0.02

0.16

17.00
14.52
15.83
18.36
20.05
18.13
17.41
8.89
19.84

28.06

48.1

6.55

35.93

20.60

16.2

49.3

6.4

42.01

2.02

18.50

30.90
14.60
15.60
32.50
17.68
26.60
24.93
31.75
22.00
34.39
23.05
27.12
31.12
27.60
32.86
33.00
25.10
34.39
31.12
28.84
24.80
31.12
32.72
22.84
32.20
16.29
14.67
16.54
16.78
17.99

298

Res. J. Agric. Environ. Manage.

Table 1. Contd.

47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96

N-octane
Benzene
Motor gasoline
Kerosene
Methanol
Ethanol
LBL wood oil
BOM wood oil
Coke oven tar
Low temp tar
Carbonmonoxide
Acetylene
Carbon
Carbondioxide
Coconut shell
Coir pith
Corn cob
Groundnut shell
Millet husk
Rice husk
Peach pits
Walnut shells
Corn cobs
Rice hulls
Pine needles
PeachPit
Macadamia shell
Pistachio shell
Cottonshells
Spire-mint
Corncob
Corncob
Cottongin waste
Douglass fir bark
Loblolly pinebark
Eucalyptus camaldulensis
Sudan grass
Almond prunings
Black walnut prunings
Corn stover
Cottongin trash
Eucatlyptus bark
Almond
Cabernet Sauvignon
Teawaste
Cottongin waste
Cottongin trash
Alabama Oakwood waste
Subabul wood
Black locust

80.2
73.3
85.4
83.0
80.7
81.6
79.1
78.3
80.1
63.6
72.4
75.9
82.0
69.3
70.1
80.1
86.5
76.4
88.0
73.0
54.7
81.4
72.8
76.8
80.7
75.2
67.3
76.8
78.6
78.5
85.0
83.4
67.3
74.7
85.6
80.9

0.0
0.0
0.0
0.0
0.0
0.0
0.8
0.7
0.3
0.0
0.0
0.0
0.0
0.0
0.7
7.1
2.8
5.9
18.1
23.5
1.0
0.6
1.4
20.6
1.5
0.40
1.13
1.40
18.10
1.36
1.00
0.10
5.4
1.2
0.4
0.8
8.7
1.6
0.8
5.6
17.6
1.63
2.17
0.70
1.40
1.61
17.60
3.30
0.9
0.8

0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
19.8
26.7
14.6
17.0
19.3
18.4
19.9
21.2
18.5
15.8
26.1
23.68
16.84
28.3
11.8
18.54
12.5
23.5
12.0
25.8
33.9
17.8
18.6
21.5
18.6
19.3
15.1
21.54
19.2
20.8
13.6
14.97
15.1
22
14.4
18.3

84.1
92.3
85.5
85.8
37.5
52.2
72.3
82.0
91.8
83.0
42.9
92.3
100.0
27.3
50.2
44.0
47.6
48.3
42.7
38.9
53.0
50.0
46.6
38.3
48.2
54.4
48.8
52.9
37.2
46.6
49.0
48.1
42.7
56.2
56.3
49.0
44.6
51.3
49.8
43.6
39.6
51.3
46.6
48.2
48.6
42.6
39.5
49.5
48.2
50.7

15.9
7.8
14.4
14.1
12.5
13.0
8.6
8.8
5.5
8.2
7.8
5.7
4.7
5.0
5.7
6.0
5.1
5.9
5.7
5.9
4.4
6.6
4.99
5.91
5.6
5.34
5.87
5.4
5.99
6.0
5.9
5.6
5.9
5.4
5.3
5.8
5.6
5.3
5.29
5.85
6.25
5.5
6.05
5.26
5.7
5.9
5.7

50.0
34.8
17.6
9.2
0.8
7.4
57.1
72.7
43.4
43.4
44.6
39.4
33.0
32.0
39.1
43.4
45.5
35.5
43.7
39.69
43.41
42.7
33.38
45.46
44.6
45.74
49.5
36.7
37.7
44.0
39.2
40.9
43.4
43.3
36.4
40.9
43.9
43.24
39.5
49.5
36.38
41.3
45.1
41.9

0.20
0.60
0.90
0.60
-

0.10
0.10
0.01
0.80
0.80
-

0.70
0.80
0.10
0.60
0.32
0.21
0.47
0.83

0.05
0.01
0.01
0.06

0.36
0.56
1.40
5.95
0.47
0.40
0.08
0.10
0.30
1.21
0.66
0.22
0.61
2.09
0.66
0.83
1.61
0.50
0.18
2.09
0.20
0.57

0.01
0.01

0.01

0.01
0.01
0.01
0.01
0.01
0.01
0.04

0.01

47.80
41.79
46.88
46.50
22.69
30.15
33.70
36.80
38.20
38.75
10.16
49.60
32.81
9.45
20.50
18.07
15.65
18.65
17.48
15.29
20.82
20.18
18.77
14.89
20.12
21.01
19.26
19.30
15.53
18.77
17.00
19.92
17.48
22.10
21.78
19.42
17.39
20.01
19.83
17.65
16.42
20.01
19.03
19.97
17.10
17.48
16.42
19.23
19.78
19.71

Ahmad and Subawi

299

Table 1. Contd.

97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114

Douglas fir
Ponderosa pine
Red alder
Redwood
WesternHemcock
White fir
White oak
Madrone
Mango wood
Casuarina
Poplar
Plywood
Pressmud briquettes
Plywood
Wood Chips
Canyonlive Oak
Redwood
Softwood

81.5
82.5
87.1
83.5
84.8
83.2
81.3
87.8
85.6
78.6
82.3
82.1
83.3
79.1
88.2
79.7
70.0
70.2

0.8
0.3
0.4
0.4
2.2
0.3
1.5
0.2
3.0
1.8
1.3
2.1
2.09
1.10
0.50
0.36
1.70
1.50

17.7
17.2
12.5
16.1
15.2
16.6
17.2
12.0
11.4
19.6
16.4
15.7
14.59
19.8
11.3
19.92
28.1
28.3

52.3
49.2
49.6
53.5
50.4
49.0
49.5
48.9
46.2
48.5
48.5
48.1
46.9
49.1
47.8
50.6
52.1
51.9

6.3
6.0
6.1
5.9
5.8
6.0
5.4
6.0
6.1
6.0
5.9
5.9
6.07
6.34
5.8
5.98
6.1
6.1

40.5
44.4
43.8
40.3
41.1
44.8
43.1
44.8
44.4
43.3
43.7
42.5
43.99
43.52
45.76
42.88
41
40.9

0.10
0.06
0.13
0.10
0.10
0.05
0.35
0.05
0.28
0.31
0.47
1.45
0.95
0.48
0.07
0.05
0.20
0.30

0.03
0.07
0.10
0.01
0.01
0.02
0.01
0.02
0.03

21.05
20.02
19.30
21.03
20.05
19.95
19.42
19.51
19.17
18.77
19.38
18.96
18.26
19.42
18.98
20.72
20.00
20.10

115

Spruce wood

82.0

0.10

17.9

47.3

46.5

0.10

20.08

116
117
118
119
120
121
122
123
124
125
126
127
128

Pinewood
Subabul wood
Eucalyptus
Eucalyptus-Grandis
Subabul
Douglas Fir
White Fir
Tan Oak
Beech
Hickory
Maple
Poplar
Yellow pine

81.0
75.4
82.6
72.8
73.0
65.7
83.2
90.6

1.20
3.35
0.52
8.65
1.20
0.40
0.25
0.20
0.7
0.7
1.4
0.7
1.3

18.52
21.3
16.93
18.6
25.8
33.9
16.58
9.2
0.0
0.0
0.0
0.0
0.0

48.2
46.0
48.3
44.6
56.2
56.3
49.0
48.6
51.6
47.7
50.6
51.6
52.6

5.87
5.82
5.89
5.35
5.9
5.6
5.98
6.03
6.3
6.5
6.0
6.3
7.0

44.75
44.49
45.13
39.18
36.7
37.7
44.75
44.99
41.4
43.1
41.7
41.5
40.1

0.03
0.30
0.15
1.21
0.05
0.06
0.25
-

0.01
0.01

0.01
0.04
-

19.78
18.64
19.35
17.39
22.10
21.77
19.95
18.93
20.38
20.17
19.96
20.75
22.30

Source: Jigisha Parikha (2005), Woodgas (2007), and Kirubakaran et al. (2009).

50

HHV (MJ/kg)

40
30
20
10
-

10

20

30

40

50

Ash content (%)

Figure 1. Ash content in biomass.

Figure 2. Old Van Krevelen diagram of biomass.

Source: Van (1950), McKendry (2002).

Res. J. Agric. Environ. Manage.

50

40

40

50

HHV (MJ/kg)

HHV (MJ/kg)

Figure 3. New Van Krevelen diagram of biomass.

30
20
10

20

20

40

60

80

100

C (%)

40 60
O (%)

(4a)

(4b)
50

40

40

50

HHV (MJ/kg)

30

10

HHV (MJ/kg)

300

30
20
10
-

20

80

100

40 60 80
O + A (%)

100

30
20
10
-

20

40 60 80
H + C (%)

100

(4c)
Figure 4. Diagram of HHV to biomass component.

20

(4d)

Ahmad and Subawi

The fixed carbon in rice straw reaches 12 to 20%.

Sugarcane baggase has fixed carbon about 15%. Most of
biomass contains fixed carbon from 10 until 30%. During
long period, carbon content may reach to the value of
100% such as anthracite, or by heat treatment such as
char formation or through chemical processing to remove
ash content in rice straw, etc through chemical immersion
in diluted alkaline solution (Jan et al., 2006).
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