J Therm Anal Calorim (2009) 97:661–665

DOI 10.1007/s10973-009-0346-3

Characterization of sugarcane and coconut fibers by thermal

analysis and FTIR
Cheila G. Mothé Æ Iara C. de Miranda

ICTAC2008 Conference

Akadémiai Kiadó, Budapest, Hungary 2009

Abstract Pyrolysis of sugarcane bagasse and coconut environment [2]. The use of biomass as energy source is of
fiber was studied by thermal analysis in order to charac- interest due to the following envisaged benefits: (i) biomass
terize their thermal behavior and to identify their constit- is a renewable, potentially sustainable and relatively
uents by the aid of their thermogravimetric curves and environmentally benign source of energy; (ii) a huge array
to determine their heat capacity by means of DSC. The of diverse materials, frequently stereo chemically defined
Fourier Transform Infrared Spectrum (FTIR) was used to are available from the biomass giving the user many new
determine the main constituents present in both residues. structural features to exploit [3]; (iii) increased use of
The thermal degradation of sugarcane bagasse and coconut biomass would extend the lifetime of diminishing crude oil
fiber presents two mass loss steps attributed to the release supplies; (iv) biomass fuels have negligible sulfur content
of humidity and to the decomposition of organic material and therefore, do not contribute to sulfur dioxide emissions
(hemicellulose, cellulose and lignin). It was expected that that cause acid rain; (v) the combustion of biomass pro-
the results of DSC analysis were almost the same for both duces less ash than coal combustion and the ash produced
types of biomasses. can be used as a soil additive in fields, etc.; (vi) the com-
bustion of agricultural and forestry residues and municipal
Keywords Biomass
FTIR
Thermal analysis
solid wastes (MSW) for energy production is an effective
Pyrolysis use of waste products that reduces the significant problem
of waste disposal, particularly in municipal areas;
(vii) biomass provides a clean, renewable energy source
Introduction that could improve our environment, economy and energy
securities [4, 5] and (viii) use of biomass could be a way to
There are several different ways in which the abundance of prevent more carbon dioxide production in the atmosphere
energy surrounding us can be stored, converted and as it does not increase the atmospheric carbon dioxide
amplified for our use. Energy sources will play an impor- level. Biomasses are known to grow is a sustained way
tant role in the future life of the World. The energy sources through the fixation and release of CO2, mitigating global
have been split into three categories: fossil fuels, renewable warming problems. In fact, the amount of CO2 produced
sources and nuclear sources [1]. The cost of producing during the combustion of the fuels is the same amount
energy from fossil fuel usually exceeds the cost of biomass absorbed during the gromassh of the plants. This is partic-
fuels. Besides, the burning of fossil fuels causes green ularly the case of energy crops and agricultural residues [6].
house gas emission which has remarkable effect to the The biomass can be defined as a hydrocarbon, which
consists mainly of carbon, hydrogen, oxygen and nitrogen.
Some types of biomass present significant proportions of
C. G. Mothé (&)
I. C. de Miranda inorganic species. The concentration of ashes generated for
Organic Process Department, School of Chemistry, Federal
this inorganic goes since \1% in softwoods until 15% in
University of Rio de Janeiro, Rio de Janeiro, RJ 21949-900,
Brazil herbaceous biomass and agro-industrial residues [7]. Bio-
e-mail: [email protected] mass is the fourth largest energy source in the world after

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662 C. G. Mothé, I. C. Miranda

coal, petroleum and natural gas, providing about 14% of extracted from either mature or immature fruits (for
the world’s primary energy consumption. Renewable bio- example, they are sold in Brazil though obtained from
mass is being considered as an important energy resource green fruits used for their water, which is one of the pop-
all over the world. Biomass is used to meet a variety of ular refreshments and has therapeutic properties).
energy needs, including generating electricity, fueling Between the more than a hundred products made
vehicles and providing process heat for industries [8, 9]. directly or indirectly of coconut fiber can to be outstanding:
Among all the renewable energy sources biomass is unique cords, carpets, plant pots, brushes, brooms, automotive
as it effectively stores solar energy. It is the only renewable upholstery, painting of civil construction, plates of fiber-
source of carbon that can be converted into convenient resin, plates of fiber-cement between others due to the good
solid, liquid and gaseous fuels through different conversion water retention property [14].
processes [10]. Pyrolysis which according to its physical-chemical sub-
Sugarcane bagasse, an abundant agricultural lignocel- stance belongs among thermic processes, is one of the ways
lulosic byproduct is a fibrous residue of cane stalks left that may lead to transformation of certain kinds of bioma-
over after crushing and extraction process of the juice from terials into a more refined form of energy [17]. The basic
sugarcane. About 54 million dry tons of bagasse is pro- thermochemical process is for converting biomass to a more
duced annually throughout the world [11]. Is a complex useful fuel. The pyrolysis method has been used for com-
material being the main product of the sugarcane industry mercial production of a wide range of fuels, solvents,
and generated in large quantities during the processing of chemicals and other products from biomass feed stocks.
sugarcane in sugar mill. Bagasse offers the advantage of Pyrolysis produces energy fuels with high fuel-to-feed ratios
being a cheap, plentiful and low polluting fuel. On making in the most efficient process for biomass conversion
the average, bagasse contains about 45–50% moisture, and the method most capable of competing with and even-
43–52% fiber, and 2–6% soluble solids. The typical com- tually replacing non-renewable fossil fuel resources [1].
position of bagasse fiber is about of 26.6–54.3% cellulose, Conventional pyrolysis consists of the slow, irreversible
22.3–29.7% hemicellulose and 14.3–24.45% lignin [12]. thermal decomposition of the organic components in bio-
Bagasse has a net calorific value of around 8,000 kJ/kg, mass. Slow pyrolysis has traditionally been used for the
with a moisture content of around 50 mass% and ash production of charcoal. Fast pyrolysis is characterized by
content in the range of 4–5 mass%. It is therefore utilized high heating rates and rapid quenching of the liquid products
as a fuel in boilers in the sugar mills to generate steam and to terminate the secondary conversion of the products [7].
electricity [13]. Bagasse is characterized as a low-density Depending on the pyrolysis temperature, the char frac-
fiber and by its wide particle size distribution (\100 lm to tion contains ashed inorganic materials in different degrees,
larger than 10 cm). Is used primarily in the sugar mill to any unconverted organic solid and carbonaceous residues
cover the own energy requirement of the sugar production produced from thermal decomposition of the organic
process [12]. Burning of bagasse in cogeneration process components. The liquid fraction is a complex mixture of
for meeting internal energy needs and is inefficient and water and organic chemicals. For highly cellulosic biomass
wasteful. There has been a significant interest in converting feed stocks the liquid fraction usually contains acids,
this residue into higher energy dense products by means of alcohols, aldehydes, ketones, esters, heterocyclic deriva-
pyrolysis, carbonization, liquefaction, gasification and tives and phenolic compounds. The liquid products of
combustion. This study is focused on the pyrolysis of pyrolysis are complex mixtures of oxygenated aliphatic
bagasse and coconut fiber. and aromatic compounds. The tars contain native resins,
The coconut fiber is a short fiber; a little flexible and intermediate carbohydrates, phenols, aromatics, aldehydes,
hard when compared to the others fibers. Their hardness is their condensation products and other derivatives.
associated mainly to the presence of lignin, which is also Pyroligeneous acids can consist of 50% CH3OH, C3H6O
responsible for the yellowish color and for the brown color (acetone), phenols and water. CH3OH can be produced by
to the mature coconut [14]. Coconut is a common and pyrolysis of biomass. CH3OH arises from the methoxyl
abundant fruit. The fiber is the inner part which covers the groups of uronic acid and from the breakdown of methyl
shell containing of the nut. This fibrous part is generated as esters and/or ethers from decomposition of pectin-like
a waste in the processing of coconut fruit. The composition plant materials. Acetic acids come from the acetyl groups
of the fiber is about 5% of water soluble; 3% of pectin and of hemicelluloses. The pyrolysis gas mainly contains
related compounds; 0.3% of hemicellulose; 46% of lignin CO2, CO, CH4, H2, C2H6, C2H4, minor amounts of higher
and 2% of ash [15]. Thus, coconut fiber is classified as a gaseous organics and water vapors [7].
lignocellulosic material. The production of electricity in large scale from biomass
In Brazil annually about 1.5 billion coconuts (Cocos (and this include, obviously sugarcane bagasse and coconut
nucifera) are produced [16]. Coconut fibers (coir) can be fiber) having a large interest consequently is a topic which

123
Characterization of sugarcane and coconut fibers by thermal analysis and FTIR 663

has been studied in the recent years. This interest focused The thermal degradation of sugarcane bagasse and
the attention of several factors: (i) production of electricity coconut fiber were studied between 303 and 1,073 K under
from biomass, which has a practically closed carbon cycle nitrogen flow in a TA model SDT 2960 Simultaneous
and with low or almost zero amount of SOx emission; DTA-TGA analyzer by using of 283 K min-1 heating rate
besides, the amount of residual ash is lower than the gen- and 120 mL min-1 gas flow. The sample masses were
erated amount when mineral coal is used; (ii) the increase approximately 10 mg.
of the energy produced by bio-resources may lead to save The specific heat determinations have been done by
some crude oil and other fossil energy bearers. using TA DSC 2010 Differential Scanning Calorimeter,
The objective of this paper is to characterize sugarcane TA Instruments in nitrogen atmosphere applying
bagasse and coconut fiber samples, to determine calori- 283 K min-1 heating rate until 673 K.
metric properties of the sugarcane bagasse and coconut The FTIR analysis was carried out in a Spectrum One
fiber through DSC analysis, to monitor the decomposition FTIR Spectrometer (PerkinElmer). It was used in the
products of pyrolysis and to obtain the related kinetics Attenuated Total Reflectance Method (ATD) with appli-
parameters. cation of noise’s attenuating (Automatic Smooth).

Experimental
Results and discussion
The biomass residues used in the study were:
Thermal analysis
• Sugarcane bagasse originating from Campinas’ region
in Brazil and As it can be seen in Fig. 2 the TG curve of the sugarcane
• Coconut fiber originating from Rio de Janeiro state, bagasse presented three mass loss steps. The first one up to
Brazil 373 K is attributed to the moisture elimination accompa-
nied by 7.7% of mass loss. The second step occurring
For their characterization thermoanalytical techniques
between 473 and 523 K and representative for the release
(TG/DTG, DTA and DSC) and Fourier Transform Infrared
of many organic extractives e.g. fats, waxes, alkaloids,
Spectroscopy (FTIR) were used.
terpenes, glycosides, etc. The resulted mass change is
The treatment of raw material covered two steps: in the
around 25%. The third step appearing in the 523–653 K
first one is the drying of the sugarcane bagasse on the sun
temperature range is attributed to the decomposition of
(Fig. 1a). The second was the grinding of the sun-dried
lignin, hemicellulose and cellulose. Is important to
material (Fig. 1b) in a mill. Coconut fiber was received air-
emphasize that the thermal degradation of hemicellulose
dry (Fig. 1c). The coconut fiber was also ground in a mill.
and cellulose takes place in very near temperatures around
Both the milling processes (sugarcane bagasse and coconut
under 603 K (see DTG curves in Fig. 2), depending of the
fiber) were conducted in a knife granulator mill, with
nature of the heteropolymers presents in the biomass. In
granulometry of 2 mm, provided by Embrapa in Rio de
such case is not possible to detect separated peaks for these
Janeiro.
compounds. The residue of pyrolysis process accomplishes
15% of initial mass and consists of inorganic compounds in
the form of oxides. Table 1 shows the results of X-ray
fluorescence analysis of the ashes.

1.2
– – ] Temperature Difference (°C/mg)

100
[ - - - - ] Deriv. Mass (%/°C)

1.0

80 0.0
0.8
Mass (%)

60
-0.1 0.6

40
0.4
-0.2
20 0.2
[

0 0.0
273 473 673 873 1073
Exo Up Temperature (K) Universal V4.2E TA Instruments
Fig. 1 a Dry sugarcane bagasse, b ground sugarcane bagasse, c dry
coconut Fiber Fig. 2 TG, DTG and DTA of sugarcane bagasse

123
664 C. G. Mothé, I. C. Miranda

Table 1 XRF analysis of ashes of sugarcane bagasse Table 3 Specific heat capacity of sugarcane bagasse
Elements Concentration in ashes T/K CP sugarcane bagasse/J g-1 K-1
of sugarcane bagasse/%
423.08 2.24485
K2O 60.9 448.03 2.524433
CaO 28.9 462.96 2.610374
ScO2 2.9 Mean = 2.459886
SO 2.6
MnO2 2.2
Fe2O3 1.7 Table 4 Specific heat capacity of coconut fiber
CuO 0.8 T/K CP coconut fiber/J g-1 K-1

458.06 3.240422
1.0
– – ] Temperature Difference (°C/mg) 462.96 3.206149
100
468.08 3.215612

[ - - - - ] Deriv. Mass (%/°C)

0.8
80
0.0 Mean = 3.220728

0.6
Mass (%)

60
-0.1 The specific heat capacities of sugarcane bagasse and
40
0.4 coconut fiber were determined by DSC ant the relevant rata
-0.2
at three different temperatures as well as their average are
20 0.2 given in Tables 3 and 4.
[

0 0.0
273 473 673 873 1073
Exo Up Temperature (K) Universal V4.2E TA Instruments FTIR spectroscopy studies
Fig. 3 TG, DTG and DTA of coconut fiber
This technique was used for structural characterization of
the sugarcane bagasse and the coconut fiber.
Table 2 XRF analysis of ashes of coconut fiber The absorption spectrum on the infrared region of the
sugarcane bagasse, can be observed in the Fig. 4. The main
Elements Concentration in ashes
of coconut fiber/%
characteristics are attributed to the presence of lignin,
hemicellulose and cellulose, characteristic of natural fibers.
K2O 71.5 In general, the IR spectra for the native and the chemically
CaO 12.8 modified fibers are representative in the 3,200–3,600 cm-1
Cl2O 11.2 range. The large band is attributed to the axial deformation
Fe2O3 1.5 of the O–H group. For the sugarcane bagasse used in the
SO 1.2 study this peak appeared at 3,330 cm-1. At 2,888 cm-1 the
ScO2 0.8 observed absorption band is related to the axial deforma-
CuO 0.3 tion of C–H group. The peak at 1,721 cm-1 is
ZnO 0.2
BrO 0.2 99,8
99
RbO2 0.2 98 1721,03;99,91
97
96
95 2888,88;97,15 1602,21;96,28
94 1423,98;95,32
330,99;94,82
For the coconut fiber (see Fig. 3) the TG curve shows 93
92
1511,80;97,13
1318,08;94,23
1369,74;94,36
two stages of decomposition: the first stage around 323 K 91
90 899,63;92,36
%T

89
corresponds to moisture elimination. The second one 88
1243,13;92,70
87 1155,35;91,16
between 523 and 643 K is attributed to decomposition of 86
85
organic materials which is the superposition of two parallel 84
83
processes (see DTG curve of Fig. 3). In this step, the mass 82
81
80 1033,88;79,27
loss caused by organic species presents in the raw material: 79.0
4000,0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600,0
lignin, hemicellulose and cellulose. The residues is about –1
cm
20% of initial sample mass and its composition is shown in
Table 2. Fig. 4 FTIR of sugarcane bagasse

123
Characterization of sugarcane and coconut fibers by thermal analysis and FTIR 665

128,1 Acknowledgements The authors would like to thank the Brazilians

126 Agencies: Coordenação de Aperfeiçoamento de Pessoal de Nivel
124
Superior (CAPES) and Conselho Nacional de Desenvolvimento
122 2103,35;125,80

120 2325,58;112,18
Cientı́fico e Tecnológico (CNPq) for their financial support.
118
767,89;109,12
116
2919,89;117,58
114
3731,26;117,15
112
3334,62;117,78 1620,29;113,96 References
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sugarcane bagasse and 20% residue was determined for the
coconut fiber.

123