An Approach to the Characterization of

Biochar and Bio-Oil

Didem zimen
Bioengineering Department
Yildiz Technical University, Turkey

Introduction

Biomass energy is a type of the alternative energy produced from renewable resources. Valuable products such as biochar and bio-oil can be obtained from pyrolysis/carbonization of biomass sources. Biochar and bio-oil products are usually used as alternative fuel to fossil-based fuels, however, biochar as
carbon source for producing different carbon materials, and bio-oil as chemical feedstock for valuable
chemicals can be also utilized. This study has focused on the physical and chemical characteristics of
biochar and bio-oil products, generally relevant to fuel applications, to evaluate their use as alternative
fuel to conventional fossil fuels. Most of the characterization properties of biochar products, such as elemental analysis, proximate analysis, heating value, bulk density and surface properties analysis (BET
surface area, porosity and SEM etc.) were presented in detail. And also standard test methods applied to
bio-oil samples such as density, viscosity, pour point, Conradson carbon residue, heating value, flash
point, pH value, water content, ash, metal and elemental analysis, FTIR analysis and column chromatography analysis were indicated. Moreover, the characterization values for various biomass derived biochar
and bio-oils in the literature studies were tabulated for comparison between different biomass feedstocks.
This study provides a comprehensive overview of biochar and bio-oil characterization with acknowledged standard test methods and can be used to get ideas about the properties of biochar and bio-oil obtained from biomass pyrolysis/carbonization.
1.1

Biomass Energy

Due to the depletion of fossil fuels which meet most of our energy requirements in near future and the
environmental pollution, the usage of alternative renewable energy sources is inevitable important. Solar,
wind, hydro, geothermal, wave, hydrogen and biomass energy are the most important renewable energy
resources. All renewable resources have different advantages and disadvantages as compared with fossil
energy sources and it is very important to choose the sustainable and environmental friendly energy
source. In this context, biomass is considered as an important alternative energy source to fossil fuels.
Biomass which has many applications is a very strategic energy source, since it is cultivated in everywhere and provides the social and economical development. Furthermore, many chemicals and bio-fuels
are produced by using biomass which mainly consists of carbon, hydrogen, oxygen and nitrogen with
small proportions of inorganic species. The chemical structure and major organic components in biomass
are extremely important in the development of processes for producing derived fuels and chemicals
(zimen & Meriboyu, 2010). Biomass resources are essentially composed of cellulose, hemicelluloses,
lignin and extractive and they include various natural and derived materials. Woody and herbaceous species, wood wastes, energy crops, bagasse, agricultural and industrial residues, waste paper, municipal
solid waste, sawdust, biosolids, grass, waste from food processing, animal wastes, aquatic plants and algae etc. are different kinds of biomass resources (Yaman, 2004).

What is the Pyrolysis/Carbonization?

To produce energy, biomass resources are used directly or after many conversion processes. Thermochemical conversion processes are applied to produce liquid, gas and solid products, which are used in
many applications. Carbonization and pyrolysis are the thermochemical processes that convert biomass

into liquid, charcoal and non-condensable gases by heating the biomass in the absence of air. If the purpose is to maximize the solid product yield, a low temperature and low heating rate process which is
called carbonization would be preferred. However, pyrolysis at low temperature and high heating rate
process is to maximize the yield of liquid product (Bridgwater & Bridge, 1991).
Biomass resources can be converted into valuable products by using different conversion technologies such as biochemical and thermochemical processes. Biochemical processes include two process
types (i.e., digestion and fermentation) which give the major products such as biogas, hydrogen and ethanol. Combustion, carbonization/pyrolysis, gasification and liquefaction are considered as thermochemical
conversion processes. Liquid products (e.g., wood tar, tar, bio-oil and pyrolytic oil), gas products (e.g.,
wood and pyrolytic gases) and solid products (e.g., biochar and charcoal) are produced by applying of
thermochemical processes to biomass resources (Klass, 1998).
2.1

Biochar Properties

Biochar, which is called solid product of biomass carbonization, is used in many commercial applications
such as: metallurgical, domestic and chemical. And also it can be used to produce activated carbon and
different carbonaceous materials. Biochars can be alternative to the conventional fuels partially due to
their high fixed carbon content and high calorific value. Although biochars have many physical and
chemical properties, this section has mostly focused on the fuel properties of biochars.
In this section of the study, heating value, bulk density, elemental analysis, proximate analysis,
analysis of the surface properties (BET surface area, porosity and SEM etc.) of biochars and standard
methods applied to the biochar products were presented. Also the values for various biomass derived biochars in the literature were given in Table 1 to make a comparison between different biomass feedstocks.
It was observed from the previous studies that the standard methods developed mainly for coal samples
were also used for biomass derived biochars.
2.1.1

Heating Value

Heating value is the amount of heat produced by a complete combustion of fuel and it is measured as a
unit of energy per unit mass or volume of substance (e.g., kcal/kg, kJ/kg, J/mol and Btu/m). The heat of
combustion of fuels is expressed by the higher and lower heating values (HHV and LHV). The higher
heating value is also known as the gross calorific value. The higher heating value (HHV) is measured
using a bomb calorimeter; and defined as the amount of heat released when fuel is combusted and the
products have returned to a temperature of 25C. The heat of condensation of the water is included in the
total measured heat. The lower heating value (LHV) is defined as the net calorific value and is determined by subtracting the heat of vaporization of water vapor (generated during combustion of fuel) from
the higher heating value (Meriboyu et al., 1998). Same types of fuels can usually be compared according to their HHV, whereas the different types of fuels are usually compared according to their LHV. Because hydrogen contents of the different types of fuels are different from each other (e.g. oil and coal);
therefore, it is necessary to determine the hydrogen content of the fuel for calculating the LHV.
The heating values of the various types of fuels are determined according to the ASTM E 711,
ASTM D 240, ASTM D 3523, ASTM D 5865. The heating values for various biochar samples were presented in Table 1. As can be seen from Table 1, the heating values of biomass derived biochars in the
literature vary between 11.83 and 44.2 (MJ/kg), whereas the values for coal and charcoal vary between

14 and 35 (MJ/kg) (Speight, 2005). Generally, the high heating values of biochars make them attractive
feeds for clean energy production instead of fossil-based solid fuels.
2.1.2

Bulk Density

Bulk density is defined as the weight per unit volume of material. It is primarily used for powder and
pellet materials. The test of bulk density can reflect the flow consistency and packaging quantity of solid
fuel material. It is expressed in kilograms per cubic meter (kg/m3) and can be determined according to the
ASTM D 1895 standard method. There are differences between bulk density values of various types of
solid fuel. For instance, the bulk density of rapeseed cake biochar is 467 (kg/m3) (zimen &
Karaosmanolu, 2004), whereas the bulk density of coal is in the range from about 600 to 800 (kg/m3)
(Speight, 2005).
2.1.3

Elemental Analysis

Elemental or ultimate analysis includes the quantitative determination of carbon, hydrogen, nitrogen, sulfur and oxygen within a fuel material. Almost all of the heat being formed from combustion of biomass
products is obtained from carbon and hydrogen burning. For this reason, characterizing the elemental
composition of products from biomass carbonization/pyrolysis is important to evaluate their fuel potentials. Furthermore, measuring nitrogen and sulfur contents in the structure of fuels is crucial for environmental pollution, since nitrogen and sulfur oxides are formed because of the nitrogen and sulfur in the
structure of fuel when fuel is burned.
Elemental analysis of the biochar or bio-oil products can be performed according to ASTM D
5373 and ASTM D 5291 standard test methods. Composition is determined according to ASTM D 3176.
Empirical formula, H/C and O/C molar ratios are calculated from elemental composition. Oxygen content of fuel is generally calculated as O (%) =100-[ash%+moisture%+C%+H%+N%+S%], instead of
direct analysis (Meriboyu et al., 1998). Generally the high oxygen content of biomass samples results in
a low heating value (Czernik & Bridgwater, 2004). Total sulfur of biochar and bio-oil samples can be
determined according to ASTM D 3177 and ASTM D 4294, respectively. Nitrogen content could be determined according to ASTM D 3179, but this standard method has been removed from ASTM standards.
The elemental analysis values for various biochar samples were given in Table 1. From the elemental
analysis data given in Table 1, the values for C, H, N, S are in the range of 8.45-87.2 (wt%) for C, 0.544.26 (wt%) for H, 0.08-6.94 (wt%) for N, 5-89.9 (wt%) for O and 0-0.35 (wt%) for S, respectively.

Raw material of
biochar

HHV
(MJ/kg)

Elemental analysis (wt%)

C

Ash

5
-

26.5
8.47

1.1
-

89.9
-

84
5.36

60.32

7.7
34.32

50.96

39.45

63.16

30.26

Bird et al., 2010

zimen & Meriboyu,
2010
Herod et al., 2004
zimen & Meriboyu,
2010
Agblevor et al., 2010
Raveendran & Ganesh,
1996
Raveendran & Ganesh,
1996
Mullen et al., 2010
Ptn et al., 1997
Mullen et al., 2010
Ptn et al., 1996
zimen & Meriboyu,
2010
Raveendran & Ganesh,
1996
Agblevor et al., 2010
zimen & Meriboyu,
2010
Ertas & Alma, 2010

39.38 20.17
12.11
34.82
25.6 21.8
20.04 17.6

66.33
64.6
63.7

13.5
13.6
18.7

Kwapinski et al., 2010

Uzun et al., 2007
Kwapinski et al., 2010
ensz, 2003
Thangalazhy et al., 2010
Liu & Zhang, 2009
Sanchez et al., 2009
Uar & Ozkan, 2008

34.73 17.91

57.08

25.01

57.7
-

13.4
-

zimen &
Karaosmanoglu, 2004
Onay & Kokar, 2003
Raveendran & Ganesh,
1996
Liu & Zhang, 2009
Beis et al., 2002
Sanchez et al., 2009
Gerel, 2002
Inyang et al., 2010
Sensoz & Kaynar, 2006
Kwapinski et al., 2010

30.76

28.9
-

Cattle bone
Chestnut shell

25.86

8.45 0.54
-

Chicken litter
Coir pith

11.83
25

23.4 1.36 1.73 0.83 27.36 43.79

-

Corn cob

28.6

Corn cob
Cotton seed cake
Corn stover
Euphorbia rigida
Grapeseed

30
21
26.73

Groundnut shell

27.4

Hardwood bedding
Hazelnut shell

23.49
29.08

44.6 1.96 1.18 0.28 23.51 27.28

6.58

Laurel extraction
residue
Mistcanthus
Olive oil residue
Pine
Pine bark
Pine wood
Pine wood
Rape residue
Rapeseed cake

20.75

56.29 3.57 3.13

29.9
15.18
30.4
30.73
24.39
25.3

76.3
59.01
81.4
84.99
61.6
72.2
54.9

Rapeseed cake

24.12

55.85 2.75 6.47

Rapeseed
Rice husk

36.9
44.2

87.2
-

2.4
-

5.4
-

Rice husk
Safflower seed
Sunflower residue
Sunflower oil cake
Sugarcane bagasse
Soybean oil cake
Willow

26.41
23.87
31

51.62
77.44
63.4
75.4
76.45
58.92
79.9

2.08
2.17
0.7
1.7
2.93
1.82
3.34

0.11
4.22
1.6
3.4
0.79
6.94
0.97

0.1
-

77.6 3.05 0.85 0.02

75.8 1.7 5.3
57.29 2.86 1.47 0.15
82.7
2
2.1
-

4.26
1.61
3.38
2.82
3.42
0.9
2.14

0.4
0.47 0.08 0.16 13
0
4.97 0.35
0.2

5.11 13.34
17.2
5.45 32.78
13.2
9.59
-

37.01

5
-

23.82
16.17
34.3 28.9
19.5
19.83
32.32
-

Volatile
matter
19.83

References

Fixed
carbon
71.7

Algae
Apricot stone

2.8
-

Proximate analysis (wt%)

Table 1. The properties of various biomass derived biochars.

2.1.4

Proximate Analysis

The parameters of proximate analysis are moisture, volatile matter, ash, and fixed carbon. The proximate
analysis of different materials is done according to a group of test methods ASTM D 5142 and ASTM D
3172, or ASTM D 3173 and ASTM D 4442 for measuring moisture content, ASTM D 3174 and ASTM
E 1755 for measuring ash content, ASTM D 872 and ASTM D 3175 for measuring volatile matter, respectively.
Proximate analysis values for some biochar samples in the literature are given in Table 2. According to the proximate analysis data of biochar samples given in Table 2, the volatile matter contents are in
the range between 7.7 and 39.45 (wt%), the fixed carbon contents in the range between 50.96 and 71.70
(wt%). The change interval of the ash contents are between 5.36 and 84 (wt%), whereas the proximate
analysis values of different coal samples (from anthracite to lignite) in the literature are in the range of 245 (wt%) for volatile matter content, 25-85 (wt%) for fixed carbon content and 3-15 (wt%) for ash content, respectively (Speight, 2005).

Porosity
(%)
0.13
0.17
0.13
0.11
-

Biochar
Algal biochar
Apricot stone
Chestnut shell
Corn stover
Grapeseed
Hazelnut shell
Mistcanthus
Pine
Sugarcane bagasse
Willow

Total pore
volume (m3)
0.18
0.18
0.16
0.12
-

BET surface
area (m2/g)
1.15
11.24
0.67
3.1
14.47
14.68
1.65
1.93
14.07
1.41

Reference
Bird et al., 2010
zimen & Meriboyu, 2010
zimen & Meriboyu, 2010
Mullen et al., 2010
zimen & Meriboyu, 2010
zimen & Meriboyu, 2010
Kwapinski et al., 2010
Kwapinski et al., 2010
Inyang et al., 2010
Kwapinski et al., 2010

Table 2. Surface properties of biomass derived biochars.

2.1.5

Surface Properties

Since the physical properties affect the combustion characteristics of solid fuels (Blake et al., 1967), the
physical properties of biochar samples such as porosity, total pore volume and surface area should be
determined. For instance, the porosity can help combustion event because more porosity causes more
active combustion (zimen, 2010).
Some surface properties of biochar samples in the literature such as porosity, total pore volume
and surface area were presented in Table 2. From this table it can be seen that porosity values of biochar
samples change from 0.13 to 0.17 (%), BET surface areas and total pore volume values are in the range
of 0.6714.68 (m2/g), 0.12-0.18 (m3), respectively.
Also, SEM analysis can be done for biochar samples. Scanning electron microscopy (SEM) is a
potential technique for studying morphology of solid fuel particles. SEM analysis has been especially
used to evaluate the structural variations in biochar particles after different thermal treatments and SEM

images are very useful to obtain accurate details about pore structure of biochars (zimen & Meriboyu,
2010).
2.2

Bio-oil Properties

Reference

1.85

Elemental
analysis
(wt%)

Ash (wt%)

Water (wt%)

Density (kg/m3)

pH

Viscosity (cSt)

24.44
22.72

Flash point
(0C)
Pour point (0C)

HHV (MJ/kg)

Raw material
of bio-oil

Bio-oil is a renewable liquid fuel produced from biomass carbonization/pyrolysis. It has different compositions due to different feedstocks and production conditions. It can be used as a source of high quality
chemicals. In addition, bio-oil can be used as an alternative fuel directly or generally after application of
some purifying and improving processes. Some properties of bio-oils can result in several significant
problems during its use as fuel in boiler, engine and gas turbine equipments constructed for combustion
of petroleum derived fuels. Because bio-oils has poor volatility, high viscosity, coking and corrosiveness
compared to petroleum derived fuels (Czernik & Bridgwater, 2004).
So, it is necessary to describe important physical and chemical properties of bio-oils, but
mostly fuel properties. In this context, viscosity, density, pour point, heating value, flash point, Conradson carbon residue, pH value, water content, elemental analysis, ash and metals, FTIR analysis,
column chromatography analysis and standards applied to the bio-oil products will be presented in
this section, and also the characterization values for various biomass derived bio-oils in the literature
were given in Table 3.

Cattle bone
Cashew nut shell
Chestnut shell

40 39 (60C) 987 164 -5

26.72
- 2.63

Chicken litter
Corn cobs
Corn
Corn stover
Corn stover
Cottonseed cake
Euphorbia rigida
Euphorbia rigida
Empty fruit bunches
Eucalyptus
Grapeseed

28.25
26.2
13.85
1200
17.51 60 (50C) 1250
24.3
30.35
39.66
37.7
31.44
-

6.1
- <0.09
0.08
2.3
2.87 15.2 0.04
- <0.09
3.6 5.2 0.10

C
H
N
S
O
58.8 6.9 0.6 <0.1 33.7 Maggi & Delmon, 1994
57.95 7.44 1.87
- 32.74 Ozbay ,2008
- zimen & Meriboyu,
2010
44
6.9 <0.1
0
49 Oasmaa & Czernik,
1999
73.3 10.1 11.3
5.3 Herod et al., 2004
79.9 11.8 <0.2
8.1 Das & Ganesh, 2003
- zimen & Meriboyu,
2010
63.24 7.22 5.05 0.46 23.89 Agblevor et al., 2010
55.14 7.56 0.56 <0.05 36.9 Mullen et al., 2010
33.25 9.18 1.1 0.03 56.43 Zhang et al., 2009
60.66 7.7 2.02 0.15
- Yu et al., 2007
53.97 6.92 1.18 <0.05 37.94 Mullen et al., 2010
65
8.4 5.8
20.8 Ptn et al., 1997
75.5 11.1 2.8
10.6 Ptn et al., 2001
74.1 9.3 2.2
14.4 Ptn et al., 1996
68.26 8.02 2.02 0.03 21.57 Khor et al., 2009

29.76

3.23

63.9
-

Acacia
Apricot pulp
Apricot stone
Birch

28 (50C) 1250 62 -24 2.5 18.9 0.004

0.01
-

7.8
-

0.6
-

<0.1 27.7 Maggi & Delmon, 1994

- zimen & Meriboyu,
2010

Hardwood bedding 22.64

Hazelnut shell
26.79
Hazelnut shell
Laurel extraction
residue
Microalgae

26.31
31.04

Olive oil residue

Olive husk
Palm shell

32.13
30.2
-

Palm shell
Peach pulp
Pine bark
Pine/spruce wood
Pine
Pine/spruce wood
Pine wood

61
1133 65
(40 C)
30.74
1180 -

2.7
2.95

<0.08 55.25 6.54 <0.5 <0.05 37.58 Agblevor et al., 2010

- zimen & Meriboyu,
2010
64.9 6.5 0.7
27.9 Ptn et al., 2001
3.12 none - 69.65 8.1
5
- 17.25 Ertas & Alma, 2010
3.5- 8.73 0.2- 63.55 7.66 3.71
4.2
0.5
- 69.52 8.62 0.62
0.3 66.5 8.1 3.2
4.2
0.09
-

0.8
- <
(50 C)
-2
22.1
14.4
- 2.35 0.1
(40 C)
22.27
- 54.77 7.27 0.53
63.3 7.2 0.8 <0.1
17.9 30 (40C) 1200 - 2.2 20.7
- 28 (50C) 1240 95 -19 2.4 17 0.03 45.7
7
<0.1 0.02

16.6 73 (20C)
22.49
55.2
(50C)
Pine wood
19.7
Pistachio shell
30
Poplar
13.5
(50C)
Rapeseed cake
36.4 38 (50C)
62
(37.8C)
Rapeseed
37.9
Rape residue
37.2
Rapeseed cake
33.17
Rice husk
19.9
86.6
(40C)
Rice husk
Rice husk
16.5
13.2
(40C)
Rice husk
12.94
Robinia
Safflower seed
41.09
Safflower seed
40.9 33 (50C)
Safflower seed
36
225
(50C)
Scrap tyre
43.41
6.66
(40C)
Soybean cake
33.26
Soybean oil cake
33.6
72.38
(50C)
Sugarcane bagasse 20.08
89.4
(50C)
Sugarcane bagasse 17.25
3.9
(20C)

1200
1180

993 62

2.4 20.6 0.11

- Thangalazhy et al., 2010
- 67.44 7.82 0.42
- 24.32 Apaydin et al., 2007
2.8 18.9 0.01 46.5 7.2 0.15 0.02 46.1 Oasmaa & Czernik,
1999
0.3 73.74 10.69 4.65 0.11 10.51 zimen &
Karaosmanoglu, 2004

1107 63

2.25

2.8 25.2
41.7 7.7 0.3 0.2 50.3 Ji-lu, 2007
3.2 28 0.25 39.92 8.15 0.61 0.03
- Qiang et al., 2008

1198 105 -24

1130

1100 - 2..5 1020 76 -16 1079 58 - none

-

zbay et al., 2008

Maggi & Delmon, 1994
Morris, 1999
Oasmaa & Czernik,
1999
Morris et al., 2000
Hassan et al., 2009

1190 1140 68

37.43
28.7
47

Islam et al., 1999

1138 1200 64

2.3 23.3 <0.02

3.08 16.9
-

21.24 Uzun et al., 2007

21.9 Demirba et al., 2000
- Islam & Ani, 1998

25.08 Shuping et al., 2010

5.34 - none

72.8 10.8 3.3

13.1 Onay & Kokar, 2003
78.4 9.3 2.4 0.4 8.5 Sanchez et al., 2009
66.8 8.72 9.05 0.59 14.84 Uar & Ozkan, 2008
0.06
Islam et al., 1999

32.35
63.5
75.52
76.8
66.98

0.05

8.36 1.19 0.03 58.06 Zhang et al., 2009

7.4 0.9 <0.1 28.2 Maggi & Delmon, 1994
12.1 1.72
- 10.66 Beis et al., 2002
12.1 2.6
8.5 Onay, 2007
6.29 4.58
- 22.15 Sensoz & Angn, 2008
-

55.88 7.45 8.08

67.89 7.77 10.84
46.27 6.55

3.5

15

0.03

0
-

Islam et al., 1999

28.59 Ptn et al., 2003

13.5 Sensoz & Kaynar, 2006

0.76 46.94 Islam et al., 2001

-

Asadullah et al., 2007

Sunflower pressed
bagasse
Sunflower oil cake
Sunflower pressed
bagasse
Sunflower residue
Swine manure
Tea waste
Waste paper oil

37.65

74.5

9.9

5.3

10.3 Ptn et al., 2001

32.15
35.01

66.5
70

9.2
9.8

4.5
4.8

19.8 Gerel, 2002

15.4 Gerel, 2002

10
-

0.13
0.35

74.7
72.58
69.26
40.8

9.3 5.9
9.76 4.47
8.97 6.19
6.29
0

36.6
36.05
29.59
13.1

89.34 1205 200

(35 0C)

- 5.04
-8 1.5

0.3
9 Sanchez et al., 2009
1319 Xiu et al., 2010
- 15.58 Uzun et al., 2010
- 52.91 Islam et al., 2005

Table 3. Properties of various biomass derived bio-oils.

2.2.1

Viscosity

Viscosity, a measure of the resistance of a fluid to flow, is an important one of the fuel properties of biooil. Viscosity values of bio-oils are needed to be in definite range since very viscous bio-oils cant be
pumped easily. Depending on the biomass feedstocks and process conditions, the viscosities of bio-oils
vary in a large range. It decreases at high temperatures and by addition of some polar sol-vents such as
methanol or acetone (Czernik & Bridgwater, 2004). Also, the viscosity is reduced in the bio-oils with
higher water con-tent and less water insoluble components (Sipilae et al., 1998). However, this value
generally increases when the oils are stored or handled at high temperatures because of chemical reactions between various compounds present in the oil, leading to the formation of larger molecules (Czernik & Bridgwater, 2004). So, it is recommended in ASTM D 7544 standard test method that bio-oil
should be stored in the storage temperature of 15 to 200C and in containers made of corrosion resistant
materials.
The viscosity of standard fuels is typically measured as kinematic viscosity according to ASTM D
445 (Das & Ganesh, 2003; Islam et al., 1999; Oasmaa & Peacock, 2001), also the Saybold viscosity according to ASTM D 88 was used in various literatures (Ertas & Alma, 2010; zimen &
Karaosmanolu, 2004; Sensoz & Kaynar, 2006; Onay, 2007).
The viscosity values for various bio-oil samples were given in Table 3. As can be seen from Table
3, the viscosity values vary in a large range depending on temperature and biomass feedstock. ASTM D
7544 standard suggested that the limit value of the kinematic viscosity at 400C for bio-oil samples should
not exceed 125 (cSt).
2.2.2

Density

Density is one of the physical properties of bio-oil liquids. It is used for mass volume relationship of biofuel. It is affected by water content of bio-oil. When the water content of bio-oil increases, the density
generally decreases (Oasmaa et al., 1997). The density of bio-oil can be measured according to ASTM D
4052. However, it was generally measured according to ASTM D 1298 standard method in the literature.
Also IP 365 standard test method was used to measure the density of bio-oils in the literature (Das &
Ganesh 2003; Das et al., 2004).
The density values for various bio-oil samples were presented in Table 3. The density values are in
the range of 987-1250 (kg/m3) for various bio-oil samples obtained from different biomass raw materials.

If the density values of bio-oil samples in the literature were compared with a recently published
ASTM D 7544 standard, bio-oils generally meet density value suggested by the standard specification
(1100-1300 kg/m3).
2.2.3

Pour Point

The pour point of bio-oil is the lowest temperature at which bio-oil may pour and pumpable under standard conditions. Generally, the low viscosity is an indication of low pour point (Oasmaa & Peacock,
2001). Pour point is determined according to ASTM D 97. The pour point values for various bio-oil samples in Table 3 are in the range between -24 and -20C, although ASTM D 7544 standard specification
suggested that the pour point of bio-oil sample should not exceed -9 0C.
2.2.4

Heating Value

The heating value subject was explained in detail in the biochar section. The heating value of bio-oil liquids is measured according to ASTM D 240. The higher heating values of bio-oils obtained from various
biomass feedstocks at different process conditions were presented in Table 3. Table 3 indicates that the
heating values of bio-oils vary between 13.85 and 43.41 (MJ/kg), whereas this value for heavy fuel oil
are almost 42-43 (MJ/kg) (Islam et al., 2005). When the heating values of bio-oil samples in Table 3 are
compared with ASTM D 7544 standard, bio-oils generally meet heating value suggested by the standard
(min. 15 MJ/kg).
2.2.5

Flash Point

The flash point of bio-oil liquid is usually used to characterize its fire hazards and safety requirements
during usage, storage, and transportation. Flash point value is the lowest temperature at which liquid fuel
has enough flammable vapour to form an ignitable mixture in air, in the presence of an ignition source.
The flash point of bio-oil liquids in the literature is generally determined according to ASTM D
93. There are two basic types of flash point measurement: open cup and closed cup. Determination of
flash point is detailed in relevant standard.
Osmaa et al. (1997) stated that flash point values of pyrolysis liquids change from 40 up to 1000C.
The flash points for various bio-oil samples reported in the literature were given in Table 3. As can be
seen from Table 3, the flash point values vary between 58 and 2000C for bio-oils. To compare the flash
point of bio-oil with that of the fossil based liquid fuels, zimen (2004) determined the flash points of
fuel oil (No: 6) and heating fuel as 660C and 620C, respectively. ASTM D 7544 standard suggested that
flash point of bio-oil sample should be min. 450C.
2.2.6

Conradson Carbon Residue

Conradson carbon residue test is made for measuring of carbonaceous material left in fuels after removing all the volatile components. The amount of Condradson carbon residue was performed according to
the ASTM D 189. The carbon residue values for bio-oil samples in the literature generally vary over a
wide range of 5-20 (%) depending on the feedstock and process conditions. Conradson carbon residue
value was obtained as 20 (wt%) for birch bio-oil, 16 (wt%) for pine bio-oil (Oasmaa & Czernik, 1999)
and 5.2 (wt%) for rapeseed cake bio-oil (zimen & Karaosmanolu, 2004).

2.2.7

pH Value

Pyrolysis liquids have generally acidic character and they contain also different amounts of organic acids, mostly acetic and formic acids, that commonly result in low pH (2-3). Because of the low pH, bio-oil
is corrosive to some construction materials like carbon steal and aluminum (Czernik & Bridgwater,
2004; Oasmaa & Czernik, 1999). The pH value can be measured in accordance with ASTM E 70 standard test method. The pH values of various bio-oil samples, obtained from literatures, presented in Table 3
are in the range of 1.85-6.1.
2.2.8

Water Content

Bio-oil has a content of water as high as 1530 (wt %) depending on the feedstock and process conditions. The presence of water has a negative effect on the heating value, it lowers the heating value and
very high water content can cause the phase separation. However, it has positive effect in reducing the
viscosity of bio-oil. Also water content of bio-oil enhances the fluidity and combustion (pumping and
atomization) (Czernik & Bridgwater, 2004; Oasmaa & Czernik, 1999; Qi et al., 2007).
Water content can be determined according to ASTM D 4928 or ASTM E 203 standard methods.
The water content values for various bio-oil samples reported in the literatures are given in Table 3. As
can be seen from Table 3, the water content values vary between 0 and 28 (wt %) for different biomass
derived bio-oils.
If the water content of bio-oil samples are compared with ASTM D 7544 standard results, bio-oils
meet water content suggested by the standard (max. 30 wt%).
2.2.9

Elemental Analysis

In the biochar section, the elemental analysis of fuels was explained in detail. The elemental analysis values obtained for various bio-oil samples were presented in Table 3. From the elemental analysis results
given in Table 3, the C, H, N, S values are in the range of 32.35-79.9 (wt% ) for C, 6.29-11.8 (wt%) for
H, 0.1-10.84 (wt%) for N, 5.3-58.06 (wt%) for O and 0-0.76 (wt%) for S.
2.2.10

Ash and Metals

Ash content value represents the residue after combustion of a fuel. High ash content in liquid fuels like
as bio-oil can cause high wear in pumps and injectors, deposits and corrosion in combustion equipment
due to alkali metals in ash (Oasmaa & Peacock, 2001). Ash content also gives the total mineral composition of a solid fuel. Minerals may have a catalytic effect on the reactivity of solid fuels such as coal. The
reactivity of solid fuels can be differed according to their ash contents (Sekine et al., 2006). Also, it is
important to determine the ash content of fuels for disposal and environmental reasons. The elements Ca,
K and Na strongly enhance char reaction rates by their catalytic effects (Sekine et al., 2006).
Ash content can be determined according to ASTM D 482 method. The ash content values for various bio-oil samples reported in the literature were presented in Table 3. The ash content values vary between 0.004 and 0.30 (wt %) for biomass derived bio-oils. ASTM D 7544 standard suggested that ash
content of bio-oil sample should not exceed 0.25 (wt %).

2.2.11

FTIR Analysis

The chemical composition of the bio-oil can be investigated using spectroscopic techniques like as Fourier Transform Infrared Spectroscopy (FTIR). FTIR is an analytical technique used mainly to identify
organic materials. FTIR identifies chemical bonds and functional groups in a bio-oil sample by producing an infrared absorption spectrum and it gives a view about the chemical properties of bio-oil. The
functional groups that were identified from the FTIR spectra of bio-oil samples were reported in some
literature (zimen & Meriboyu, 2010; Ptn, 1997; Erta & Alma, 2010; zimen & Karaosmanolu,
2004; Beis, 2002; Sensoz & Kaynar, 2006; Maggi & Delmon, 1994; zbay et al., 2008; Shuping et al.,
2010; Islam et al., 1999; Apaydin et al., 2007; Hassan et al., 2009).
Figure 1 and Table 4 show the FTIR analysis results of a bio-oil sample (zimen & Meriboyu,
2010; zimen, 2007).

Figure 1: FTIR spectrum of hazelnut shell bio-oil (zimen & Meriboyu 2010; zimen
2007).

Wave numbers (cm-1)

2926
2855
1710
1514
1377
1231
1114
1019
736
Table 4. The functional groups of
(zimen & Meriboyu, 2010).

Functional groups
Aliphatic CH stretching
Aliphatic CH stretching
Aromatic carbonyl/carboxyl C=O stretching
Aromatic C=C ring stretching
Aliphatic CH3 deformation
Aromatic CO stretching
Ketone or ester bonding
Aliphatic ether CO and alcohol CO stretching
4 adjacent aromatic H deformation
hazelnut shell bio-oil determined by the FTIR analysis

2.2.12

Column Chromatography

The chemical composition of the bio-oil can be also investigated using chromatographic techniques like
as column chromatography. The column chromatography for bio-oils can be performed to identify the
contents of aromatic, aliphatic and polar ratios of bio-oil samples. Determining these ratios are important
for a liquid fuels since the heating values of these structures may be different. Onay (2007) found that
calorific value of aliphatic sub-fraction is significantly higher than that of aromatic and polar sub-fraction
of safflower seed. The sub-fractions obtained by column chromatography can be also characterized by
FTIR, GC, GC/MS and H-NMR techniques and so further structural analysis can be obtained (Ptn,
1997; Ptn, 1996; Onay & Kokar, 2003; Beis, 2002; Ozbay et al., 2008; Ptn et al., 2003).
Some bio-oil samples in the literature were also fractionated using column chromatography and
the results of these samples were summarized in Table 5. The column chromatography results of bio-oils
show that the aliphatic ratios (n-pentane eluate) of bio-oil samples change between 11 and 36 (%), the
aromatic (toluene eluate) and polar ratios (methanol eluate) of bio-oils change between 31 and 66 (%), 22
and 45 (%), respectively.

Bio-oil
Arid land plant

Asphaltane
(%)

n-Pentane
eluate (%)

n-pentane soluble
Toluene
Methanol
eluate (%) eluate (%)

References

40

36

32

32

Apricot stone

37.75

15.6

41.5

42.9

zimen & Meriboyu, 2010

Chestnut shell

40.53

16.2

41.1

42.7

zimen & Meriboyu, 2010

Grapeseed

28.5

14.1

42.75

43.15

zimen & Meriboyu, 2010

Hazelnut shell

38.4

16.5

40.65

42.85

zimen & Meriboyu, 2010

Laurel ext. residue

52.24

21.6

54.05

24.35

Erta &Alma, 2010

35

37

31

32

Uzun et al., 2007

Rapeseed cake

23.08

12.5

42.5

45

zimen & Karaosmanolu, 2004

Safflower seed

24.9

12.5

54.5

33

Onay, 2007

Safflower seed

62.5

11.1

66.7

22.2

46

20

55

25

Olive oil residue

Tea waste

Ptn et al., 1996

ensz & Angn, 2008

Uzun et al., 2010

Table 5. The column chromatography results of various bio-oil samples

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