Biomass and Bioenergy 85 (2016) 178e186

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Biomass and Bioenergy

journal homepage: http://www.elsevier.com/locate/biombioe

Research paper

Production of bio-oil and activated carbon from sugarcane bagasse

and molasses
Gilberto da Cunha Gonalves a, *, Nehemias Curvelo Pereira b, Ma

rcia Teresinha Veit c
a
Laboratory of Chemical Process, Federal Technological University of Parana, Toledo, PR, Brazil
b
Department of Chemical Engineering, State University of Maringa, Maringa
, PR, Brazil
c
Department of Chemical Engineering, Western Parana
State University, Toledo, PR, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: In this study, the production of bio-oil and activated carbon from sugarcane bagasse and molasses was
Received 31 December 2014 investigated via pyrolysis and CO2 activation. The pyrolysis process yielded char, bio-oil, and gases in
Received in revised form 25.90, 41.11, and 32.99 wt%, respectively. The properties and characteristics of obtained bio-oil are
24 November 2015
comparable with the proposed specications of the various grades of pyrolysis oils and could nd po-
Accepted 9 December 2015
Available online 24 December 2015
tential application as fuel or source of a number of valuable chemicals. The activation process with CO2
showed it was possible to obtain activated carbon with surface area up to 900 m2 g
1 over 4.5 h acti-
vation time with a predominance of micro- and mesopores. The bagasse-based activated carbon was
Keywords:
Activated carbon
found to be efcient in comparison to commercial activated carbon in removing molasses color, and
Bio-oil might provide a lower-cost alternative adsorbent for use in sugar decolorization in raw sugar rening.
Pyrolysis 2015 Elsevier Ltd. All rights reserved.
CO2 activation
Sugarcane bagasse
Decolorization

1. Introduction
The Brazilian agribusiness produces a substantial amount of
byproducts in the form of cake, bran, pulp, bones, guts, and
feathers, among others, which represents economic losses in the
production process. These byproducts may contribute to environ-
mental problems because of their pollution potential if they do not
receive due attention to their proper disposal. In this context, we
can highlight the ethanol and sugarcane industries, with an esti-
mated production of over 658 million tons of sugarcane crop in the
2013/14 season [1].
The major by-product of the sugarcane industry is sugarcane
bagasse, the brous materials that remains after sugarcane is
crushed to extract their juice, with an estimated production of 164
million tons per year. A part of the bagasse is used for steam-power
generation within the ethanol and sugar industries for self-use,
while the remainder can be transformed into a high-density sec-
ondary energy source that could signicantly increase the total
energy yield and protability of sugarcane mills [2]. In order to
* Corresponding author. Laborato
rio de Processos Qumicos, UTFPR, Rua Cristo
Rei, 19, 87020-900, Toledo, PR, Brazil.
E-mail address: cunha@utfpr.edu.br (G.C. Gonalves).
create a higher value for this byproduct excess, several studies have
been conducted, exploring the conversion of bagasse into useful
products such as oil and char by pyrolysis [2e6].
During the pyrolysis process, the bagasse material is heated to
high temperatures in the absence of oxygen, which initiates ther-
mal decomposition of the material, producing char and volatile
matter. A part of the volatiles are condensed as oil, while the bal-
ance remains in gas form. The pyrolytic oil produced (also referred
to as bio-oil) is a complex mixture of organic compounds with a
molecular mass of up to 2000 g/mol. The bio-oil contains signicant
amounts of water (10e35 wt%) and oxygenated compounds [7].
This pyrolytic oil may be used as liquid fuel in turbines and in
boilers [6,8].
The char produced can be used commercially, or be subjected to
an activation process for producing activated carbon. Activated
carbon is a predominantly amorphous solid with a large internal
surface area and pore volume. Activated carbon are produced in the
form of powder or granules. Because of its good adsorption prop-
erties, it is extensively used as a versatile adsorbent for gas-phase
and liquid-phase applications. Granular activated carbons are
generally considered more versatile than the powdered carbons
due to their regenerability [9]. In the production of granular acti-
vated carbon from low-density agricultural by-products such as

http://dx.doi.org/10.1016/j.biombioe.2015.12.013
0961-9534/ 2015 Elsevier Ltd. All rights reserved.
 G.C. Gonalves et al. / Biomass and Bioenergy 85 (2016) 178e186
sugarcane bagasse, it must be mixed with binders and compressed
to produce a hard, higher density briquette or pellet before pyrol-
ysis and activation. These binders ensure intimate contact of the
lignocellulosic particles during pyrolysis [9].
In recent years, many studies have been reported, relating to the
preparation and characterization of powdered activated carbon
materials from agricultural wastes, including sugarcane bagasse
[3,5,7,10e13]. Few studies were conducted to prepare granular
activated carbons from sugarcane bagasse using molasses, a by-
product of sugar production, as binder [9,14e17]. It has been re-
ported that the sugarcane bagasse and molasses-based granular
activated carbon presents goods physical, chemical and adsorptive
properties and may be used as sugar decolorizers in the industrial
process of raw sugar decolorization. However, the characterization
of bio-oil produced from pyrolysis of sucarcane bagasse and
molasses has received little attention. Therefore, the current paper
aims to the production and characterization of bio-oil and activated
carbon from of bagasses and molasses pellets using CO2 as acti-
vating agent in a single and two-stage process.
2. Experimental
2.1. Materials
The sugarcane bagasse and molasses used in this study were
furnished by Alto Alegre Sugar Mill, ColoradoePR, Brazil. The
bagasse was dried at 105  C and stored in plastic sacks. The
molasses was freeze-stored at
10  C in plastic bottles. A com-
mercial granular activated carbon made from animal bone char was
used as the reference carbon.
2.2. Apparatus
The experiments were carried out in a laboratory xed-bed
reactor, according to the layout shown in Fig. 1. This reactor is
composed of a quartz tube (4.7 cm i.d.) inserted in an electric
horizontal tubular furnace. The samples were introduced into the
Fig. 1. Layout of the experimental unit for pyrolysis/activation of pellets.
179
quartz tube and the temperature was controlled using a thermo-
couple near the samples. A owmeter was used to control the gas
uxes in the reactor. The condensable volatile products were
collected in a glass ask, and the gases were bubbled in water to
maintain atmospheric pressure while exiting the system.
2.3. Preparation of pellets
Sugarcane bagasse was sieved to 10 mesh (1.68 mm), dried at
105  C for 1.0 h, and mixed with molasses in a bagasse/molasses
ratio of 1:0.5. The mixture was dried at 105  C for 1.0 h and press-
molded in a stainless-steel cylinder of 1.5 cm diameter using a
laboratory press. A pressure of 850 kg cm
2 was applied to the
cylinder contents for 1.0 min, forming pellets with 1.5 cm diameter
and 1.0 cm height that were stored in desiccators.
2.4. Pyrolysis and activation of pellets in a two-stage process
2.4.1. Pyrolysis of pellets
The pyrolysis conditions were established based on our previous
studies [16,17]. About 62e74 g of the pellets was placed in the
reactor, which was then purged with N2 (150 mL min
1) at room
temperature for 5 min. Pyrolysis was effected under N2 ow
(150 mL min
1), wherein the temperature was increased linearly at
a rate of 14  C min
1 until 850  C and maintained at this level for
1.0 h. During the pyrolysis process, the bio-oil (condensable prod-
ucts) was collected in a glass ask. Finally, the carbonized pellets
and collected oil were cooled and weighed. Four runs were per-
formed under the same pyrolysis conditions to produce the char-
coal pellets used in the next stage (activation with CO2).
At this stage, the charcoal and bio-oil (condensable products)
yields were calculated according to Equations (1) and (2), respec-
tively. The gas (non-condensable components) yield was deter-
mined by subtracting the charcoal and bio-oil yields from 100:
180 G.C. Gonalves et al. / Biomass and Bioenergy 85 (2016) 178e186
 
mCarbonized
Charcoal Yield % *100 (1)
mPellet
 
mBio
oil
Bio
oil Yield % *100 (2)
mPellet
2.4.2. Activation of carbonized pellets
Prior to the activation tests, the charcoal pellets were dried at
105  C for 12 h. Approximately 16 g of the charcoal pellets was
placed in the reactor, which was purged under N2 ow
(150 mL min
1) at room temperature for 5 min. Then, the charcoal
pellets were heated under N2 ow (150 mL min
1) at a heating rate
of 14  C min
1 until 850  C. Once reaching this temperature, the gas
ow was changed to CO2 (75 mL min
1) and activation was realized
over reaction times from 0.5 to 4.0 h. After the activation time, the
gas ow was returned to N2 (150 mL min
1), and the reactor was
cooled to room temperature. Once cooled, the activated pellets
were weighed, crushed, and sieved to 7e16 mesh in order to pro-
duce samples in the size range of 1.0e2.8 mm. Activated carbon
samples were denoted CA-0.0, CA-0.5, CA-1.0, CA-2.0, and CA-4.0,
where the numeral corresponds to activation time.
At this stage, the burn-off gradedthe weight losses due to the
activation processdand activated carbon yield values were calcu-
lated according to Equations (3) and (4), respectively:
 
mCarbonized
mActivated
Burn
off % *100 (3)
mCarbonized
Charcoal Yield  100
Burn_Off
Activated Carbon Yield %
100
(4)
2.4.3. Treatment of activated carbons
Each as-prepared activated carbon sample was divided in two
equal portions. One of these portions was transferred to a 100 mL
beaker to which was added a HCl solution (0.1 M) and stirred for
5.0 min. These samples were than washed with water and dried at
105  C for 3.0 h. The other portion was tested without treatment.
2.5. Pyrolysis and activation of pellets in a single-stage process
For production of activated carbon and bio-oil in a single-stage
process, the bagasse/molasses pellets were subjected to activation
with CO2 immediately after the pyrolysis.
Approximately 85 g of bagasse/molasses pellets was placed in
reactor and pyrolyzed under a N2 ow of 150 mL min
1. The tem-
perature was increased linearly at a rate of 14  C min
1 until 850  C,
and maintained at this level for 1.0 h. After this time, the gas ow
was changed to CO2 (75 mL min
1) and activation was realized over
4.5 h. After the activation time, the gas ow was returned to N2
(150 mL min
1) and the reactor was cooled to room temperature.
After cooling, the obtained activated pellets and bio-oil were
weighed; the activated carbon and bio-oil yields were calculated
according to Equations (5) and (2), respectively. The activated
pellets were crushed and sieved to 7e16 mesh in order to produce
samples in the size range of 1.0e2.8 mm and subjected to HCl
treatment (0.1 M) in the same manner as described above. A dia-
gram of pyrolysis and activation of pellets with nomenclature of
samples produced was presented in Fig. 2.
 
mActivated Pellet
Activated Carbon Yield % *100 (5)
mPellet
2.6. Characterization of bio-oil
The densities, acid value, loss by evaporation, ash, and pH value
of bio-oil were measured. The density was measured by a pyc-
nometer at 28  C. The acid value of the pyrolysis oil was determined
by direct titration with a standard KOH solution (0.8 mol L
1), using
phenolphthalein as indicator. The loss by evaporation was realized
in an oven at 105  C. Ash content was measured by burning the bio-
oil sample in a mufe furnace at 550  C for 2 h. The pH value of bio-
oil was measured with a digital pH meter (DIGIMED- Model - DM-
20).
2.7. Characterization of the activated carbon
2.7.1. Determination of surface areas and pore volumes
The as-prepared activated carbon materials (110e160 mg) were
dried overnight under vacuum at 110  C and transferred to an
automatic volumetric sorption analyzer (Quantachrome, NOVA-
1200); the N2 adsorption isotherms at 77 K were then measured.
The following parameters were determined using software Auto-
sorb for Windows (Version 1.19):
 The specic surface area (SBET): according to the Bru-
nauereEmmetteTeller (BET) multipoint method in the relative
pressure range of 0.01e0.2 [18].
 The micropore surface area (SMicro): calculated from the t-plot
method [19].
 The external surface area (SExt): determined by subtracting
SMicro from SBET.
 The pore volume distribution and average pore diameter (Dav):
obtained using the BarretteJoynereHalenda (BJH) method [20].
2.7.2. Determination of pH
Analysis of pH was carried out by placing 0.5 g of activated
carbon and 50 mL of neutralized water (pH 7.0) in a 125 mL
Erlenmeyer ask that was stirred for 20.0 min at 90  C using a
thermostat bath (Dubnoff-TE053, TECNAL). After cooling to room
temperature, the suspension pH was measured with a pH meter
(DIGIMED, Model e DM-20).
2.7.3. Measurement of adsorptive capacity: molasses test
A modication of the molasses test of Pendyal et al. [15] was
used to measure adsorptive capacities of the activated carbon
materials. The molasses solution was prepared by dissolving 10.0 g
of sugarcane molasses and 15.0 g of disodium phosphate (Na2HPO4)
in 500 mL of water; the pH of the resulting mixture was adjusted to
6.5 with phosphoric acid (H3PO4). The mixture was diluted with
water to 1.0 L and ltered through a lter paper in a Bchner funnel.
The obtained solution was stored at 4  C. For molasses tests, 0.5 g of
activated carbon and 50 mL of the as-prepared molasses solution
was placed in a 125 mL Erlenmeyer ask that was stirred for
30.0 min at 80  C using a thermostat bath (Dubnoff-TE053, TEC-
NAL). A blank sample with no carbon added was also prepared in a
similar manner. Next, the solutions were vacuum-ltered through a
0.45 mm membrane and cooled to room temperature. The solution
pH was adjusted to 7.0 0.1 with HCl or NaOH solutions. The
absorbance was measured in a 1 cm cell at 420 nm using a spec-
trophotometer (SHIMADZU, UV-1203). The molasses tests were
 G.C. Gonalves et al. / Biomass and Bioenergy 85 (2016) 178e186 181

SUGARCANE BAGASSE PELLETS

1.0:0.5
MOLASSES

Two-stage Process Single-stage Process

PYROLYSIS Bio-oil PYROLYSIS +

ACTIVATION

PYROLYZED PELLETS

ACTIVATION WITH CO2

4.5h
0.0h 0.5h 1.0h 2.0h 4.0h CPA-4.5A
CA-0.0A CA-0.5A CA-1.0A CA-2.0A CA-4.0A

TREATMENT WITH
TREATMENT WITH HCl (0.1 mol.L-1) HCl (0.1 mol.L-1)

CA-0.0B CA-0.5B CA-1.0B CA-2.0B CA-4.0B CPA-4.5B

Fig. 2. Diagram of pyrolysis and activation of pellets with nomenclature of samples produced.

carried out in duplicate; the percent molasses color removed
(PMCR) was calculated using Equation (6).
 
ABSBlank
ABSSample
PMCR % *100
ABSBlank
2.7.4. Structural features of activated carbon surfaces
Scanning electron microscopy (SEM) was used to study the
surface structural features of the activated carbon materials. The
samples were gold-coated for electrical conduction, placed under a
scanning electron microscope (SHIMADZU, SS-550), and the gran-
ular morphology was observed.
3. Results and discussion
3.1. Pyrolysis process yields
A series of four pyrolysis experiments were carried out using the
as-prepared bagasse/molasses sugarcane pellets (1:0.5 bag-
asse:molasses ratio). The thermal decomposition of pellets was
performed in a reactor heated at a rate of 14  C min
1 from room
temperature to 850  C under N2 ow. A thick white smoke was
observed at a reactor temperature of ca. 250  C, indicating that
bagasse decomposition had begun. During pellet pyrolysis, charcoal
formation proceeds simultaneously with liberation of volatile
products (gas, vapors, and aerosols). In fact, several studies con-
cerning the pyrolysis of sugarcane bagasse monitored by ther-
mogravimetric analysis have indicated that the thermal
decomposition of bagasse can be divided into three stages: drying
(26e102  C), heating and pyrolysis of hemicelluloses and celluloses
(221e384  C), and depolymerization of lignin (386e548  C) [2,21].
After cooling, most volatiles could be condensed to a dark brown
liquid referred to as bio-oil, which presented a pungent smoky
odor. The remaining gases were identied as a mixture of carbon
monoxide, carbon dioxide, methane, ethane, ethane, propane,
(6)
propene, etc. [6].
The product distribution of pellet pyrolysis is presented in
Table 1. The average charcoal yield for pyrolysis of bagasse/
molasses pellets was 25.9% (pellet anhydrous basis) at a nal
temperature of 850  C. The result obtained for charcoal yield was
slightly superior to the results for bagasse pyrolysis at high tem-
peratures reported by Asadullah et al. [6] (22.86% at 600  C), Erlich
et al. [22] (18.3e23.0% at 800  C), and Strezov et al. [23] (16.1e19.4%
at 900  C). The higher charcoal yield is therefore suggested to be
due to a deposition of molasses pyrolysis products on the bagasse
char. For pyrolysis of bagasse at lower temperatures, previously
reported results have indicated that a higher charcoal yield can be
obtained: 30% at 400  C [24]; 25.7e28.9% at 450  C [22]; 19.4% at
500  C [25]; 20e26% at 500  C [26]; 25.9e29.7% at 500  C [23];
24.9% at 500  C [6]; 35.4% at 530  C [2]. In this work, the temper-
ature of pyrolysis (the same temperature of activation) was main-
tained at 850  C.
The average values for bio-oil and gas yields were 41.11 and
32.99% (pellet anhydrous basis), respectively. Several bagasse py-
rolysis studies have indicated that the bio-oil yields could reach
values above 60% when an efcient condenser system is used to
reduce the vapor temperature [6,21,23,25]. Consequently, an in-
crease in bio-oil yields causes a decrease in gas yields.
In the current work, pyrolysis experiments were performed to
obtain information about the potential yields of charcoal and bio-
oil from bagasse/molasses pellets only. It should be mentioned
that no attempt was made to optimize the pyrolysis conditions with
respect to product yields. It is reasonable to assume that an
182 G.C. Gonalves et al. / Biomass and Bioenergy 85 (2016) 178e186

Table 1
Product distribution of pellet pyrolysis.

Runs Mass of pellets (g) Mass of charcoal (g) Mass of bio-oil (g) Charcoal yield (wt%) Bio-oil yield (wt%) Gas yield (wt%)a

1 62.20 16.12 n.d.b 25.91 n.d. n.d.

2 73.55 19.14 31.63 26.02 43.00 30.98
3 73.91 19.15 30.34 25.91 41.05 33.04
4 70.10 18.07 27.52 25.78 39.27 34.96
Average e e e 25.90 41.11 32.99
a
Calculated by difference.
b
n.d. Not determined.

improvement in gas cooling will increase bio-oil yield. (a)

280
260 CA-4.0
3.2. Characteristics of the activated carbon

Volume Adsorbed (cm .g )

-1
240
220

3
The charcoals were activated at 850  C with CO2 over different CA-2.0
200
time intervals of 0.5e4.0 h. The evolution of burn-off grade and
180
activated carbon yield as a function of activation time is shown in
160 CA-1.0
Fig. 3. An increasing activation time progressively increases the
140
burn-off grade and reduces the yield of activated carbon; this was
120 CA-0.5
expected, since an increase in burn-off represents an increase in the
100
weight losses due to the activation process, thereby resulting in a
80
decreasing yield. It was observed that the relationship between
60
burn-off and activation time was linear.
40
Pendyal et al. [14] veried that an activation time of 6.0 h was
20 CA-0.0
necessary for the production of granular activated carbon from
0
sugarcane bagasse/molasses (1:0.5 ratio) with a burn-off grade of 0.0 0.2 0.4 0.6 0.8 1.0
26%; however, the researchers used a 13% CO2 and 87% N2 gas
Relative pressure P/P0
mixture for pyrolyzed carbon activation. In our case, the carbon
materials were activated with pure CO2, with a burn-off of 25% (b)
obtained in 2.0 h. 280
The N2 adsorption isotherms of the activated carbon samples CA-4.0
260
Volume adsorbed (cm .g )
-1

prepared over different activation times without treatment and 240

washed with HCl are shown in Fig. 4(a) and (b), respectively. It can 220
3

CA-2.0
be seen that the shape of the activated carbon adsorption isotherms 200
are approximately Type I isotherms, according to the International 180 CA-1.0
Union of Pure and Applied Chemistry (IUPAC); these isotherms are 160 CA-0.5
typical of microporous materials, in that micropore lling occurs 140
signicantly at low relative pressures (P/P0 < 0.1) [27]. Samples CA- 120
0.0A, which represents the pyrolyzed carbon, presented a low 100
volume of adsorbed N2; however, the adsorption capacity iso- 80
therms were found to signicantly increase as the activation time 60
40
20 CA-0.0
70 35 0
0.0 0.2 0.4 0.6 0.8 1.0
Activated Carbon Yield (%)

60 30 Relative pressure P/P0

50 25 Fig. 4. Effect of activation time on the N2 adsorption isotherms at 77 K of activated
carbon: (a) without treatment and (b) washed with 0.1 M HCl solution.
Burn-off (%)

40 20

30 15 increased, a behavior indicating developing porosity characteristics

of the activated carbon. The activated carbon subjected to washing
20 10 with 0.1 M HCl solution e Fig. 4(b) e presented an increase in
volume of N2 adsorbed, indicating an improvement in porosity.
10 5 The physical and chemical properties of the carbon materials
prepared at different activation times are given in Table 2. As ex-
0 0 pected from the isotherms, CA-0.0 (pyrolyzed carbon) exhibited a
low surface area and pore volume. Activation with CO2 afforded
0 1 2 3 4 5 6
materials with greater porosity, improving both surface area and
Activation Time (h) pore volume. It was veried that the pores formed are predomi-
nantly microporous, contributing up to 93% of the total surface area.

Fig. 3. Evolution of burn-off ( ) and activated carbon yield ( ) as a function of
Increasing the activation time contributed to the appearance of
activation time.
 G.C. Gonalves et al. / Biomass and Bioenergy 85 (2016) 178e186 183

Table 2
Physical and chemical properties of activated carbon samples subjected to different activation times and HCl treatment.

Nomenclature Surface areas (m2 g
1) Pore volume (m3 g
1) Dav () pH

SBET SMicro SExt VTotal VMicro VMeso VMacro

CA-0.0 Aa 4.3 0.2 4.1 0.006 0.001 0.005 0.001 22.05 9.61
Ba 7.1 5.5 1.6 0.007 0.002 0.004 0.000 19.51 9.36
CA-0.5 A 354.2 331.6 22.7 0.083 0.048 0.033 0.003 14.57 9.66
B 471.6 453.8 17.8 0.087 0.036 0.046 0.004 16.86 9.17
CA-1.0 A 472.7 452.3 20.5 0.059 0.026 0.031 0.002 15.29 9.82
B 585.4 564.6 20.8 0.078 0.032 0.041 0.005 14.54 9.13
CA-2.0 A 625.6 586.4 39.3 0.097 0.040 0.053 0.004 14.54 10.08
B 670.6 650.3 20.3 0.083 0.031 0.047 0.005 14.74 9.07
CA-4.0 A 823.2 774.0 49.3 0.152 0.080 0.069 0.003 14.54 10.29
B 844.0 813.8 30.2 0.108 0.043 0.061 0.004 15.19 8.51
a
(A) without treatment, (B) washed with 0.1 M HCl solution.

new micropores instead of enlarging the initial pores, as was The pH values of activated carbon samples without treatment
veried by a higher surface area percentage of micropores on the varied from 9.6 to 10.3 with an increase in activation time. How-
activated carbon with higher activation times. It was possible to ever, pH values for carbon materials washed with 0.1 M HCl solu-
obtain an activated carbon material with surface area up to tion were lower, decreasing from 9.4 to 8.5. The treatment with HCl
800 m2 g
1 over an activation time of 4.0 h. The pore volume dis- solution could dissolve minerals from the carbon surface; the
tribution showed a predominance of micro and mesopores; the presence of these minerals in the water could increase the pH.
macropore volume was inferior, accounting for 6% of the total
volume. The average activated carbon pore diameter was about
15 .
The relationships between both surface area and pore volume
and the extent of activated carbon burn-off are shown in Fig. 5. 3.3. Adsorptive properties of the activated carbon
Increasing the extent of burn-off (i.e., activation time) progressively
increased both surface area and pore volume. Bernardo et al. [5] The adsorptive properties of activated carbon were determined
reported similar observations, which veries that there is a direct by the molasses test. According to Ahmedna et al. [9], this test is
relationship between activation time and surface area indicating generally an indicator of the ability of activated carbon to adsorb
the development of porosity. Washing the activated carbon mate- colored material, especially sugar colorants. Carbons with high
rials with the HCl solution propitiated an increase in the surface molasses color removal properties are potentially good de-
area; however, a small drop in pore volume was observed at burn- colorizers. A comparison of molasses color removal by the as-
off up to 20%. prepared activated carbon samples and a commercial bone-char
The pH values of the activated carbon materials were alkaline, a carbon are shown in Fig. 6. As observed, pyrolyzed carbon (CA-
similar observation reported by both Pendyal et al. [14] and 0.0) exhibited relatively low decolorization capacity; however, the
Ahmedna el al [9]. They veried that activated carbon derived from percent molasses color removal (PMCR) was improved by an in-
sugarcane bagasse in which cane molasses were used as binder crease in activation time. The molasses color uptake of carbon
generally had pH values above 8.0. The alkaline pH of activated prepared with 2.0 h activation time (CA-2.0) was similar to that of
carbon is attributable to inorganic constituents originating from the reference carbon. Carbon prepared with 4.0 h activation time
the precursor or added during manufacture. A neutral pH range of (CA-4.0) was the most efcient in removing molasses color,
6e8 is recommended for sugar decolorization, which in acid so- achieving decolorization efciencies superior to that of the refer-
lution can lead to inversion of sucrose; above pH 8.5, undesirable ence carbon. Washing with 0.1 M HCl solution improved the
highly colored products can be generated from the destruction of decolorization capacity of experimentally prepared activated car-
reducing sugars [28]. bon, mainly for carbon materials with low activation times.

900 0.22
800 0.20
Surface Area (m .g )

0.18
Pore Volume (cm .g )
-1

-1

700
0.16
2

600
0.14
500 0.12
400 0.10
300 0.08
0.06
200
0.04
100
0.02
0 0.00
0 10 20 30 40 50

Burn-off (%)
Fig. 5. Relationship between surface area and pore volume and extent of activated Fig. 6. Molasses color removal by commercial bone-char carbon and experimentally

carbon burn-off: without treatment ( ) and washed with 0.1 M HCl solution ( ). prepared activated carbon.
184 G.C. Gonalves et al. / Biomass and Bioenergy 85 (2016) 178e186

Fig. 7. SEM images for experimentally prepared activated carbon samples washed with 0.1 M HCl solution: (a) CA-0.0B (500); (b) CA-0.5B (100); (c) CA-0.5B (2400); (d) CA-
4.0B (15000).

3.4. Surface features of experimental activated carbon
The surface morphology of experimentally prepared activated
carbon materials was observed using SEM. The microstructures of
the char and carbon prepared with activation times of 0.5 and 4.0 h
are shown in Fig. 7(a)e(d). The surface morphology of pyrolyzed
carbon is showed in Fig. 7(a) at a magnication of 500. According
to the micrograph, the surface was irregular, with numerous
channels of different shapes originating from structures of bagasse
bers and rudimentary pores due to the release of volatiles.
Fig. 7(b) and (c) show the SEM images of carbon activated over 0.5 h
at low (100) and high (2400) magnications, respectively. Many
channels originating from the char were clearly distributed over
the surfaces. Activation resulted in the creation of more pores,
mainly micropores. Fig. 7(d) depicts the surface image of carbon
activated over 4.0 h captured at a higher magnication (15000);
small macroporous structures (~0.1 mm in diameter) created by
gasication could be observed. Microporosity, the dominant factor
responsible for surface area and adsorption capacity, cannot be
resolved by SEM analysis.
3.5. Single-step production of activated carbon and bio-oil
A series of 21 experiments of single-step pyrolysis (850  C for
1.0 h) and activation with CO2 (850  C for 4.5 h) were carried out
using bagasse/molasses sugarcane pellets (1:0.5 bagasse:molasses
ratio). The product distribution of the experiments is presented in
Table 3. In this process, activated pellets and bio-oil were produced
simultaneously in the same reactor, yielding about 17.5% and 37.5%
(pellet anhydrous basis), respectively. As mentioned previously,

Table 3
Product distribution of single-step pyrolysis and activation of sugarcane bagasse and molasses pellets.

Runs Mass of pellets (g) Mass of activated pellets(g) Mass of bio-oil (g) Activated pellets yield (wt%) Bio-oil yield (wt%) Gas yield (wt%)a

1 80.20 15.50 27.44 19.33 34.21 46.46

2 81.40 15.31 29.56 18.81 36.31 44.88
3 86.25 16.16 34.61 18.74 40.13 41.14
4 81.42 14.64 33.28 17.98 40.88 41.14
5 87.33 14.92 33.91 17.08 38.83 44.09
6 83.62 13.96 32.99 16.70 39.45 43.85
7 83.89 14.54 32.95 17.34 39.27 43.39
8 84.79 14.45 33.55 17.04 39.57 43.39
9 86.21 15.31 31.55 17.76 36.60 45.65
10 77.34 13.50 30.17 17.46 39.01 43.53
11 83.45 14.72 26.94 17.63 32.29 50.08
12 84.20 14.49 32.05 17.21 38.07 44.73
13 84.67 14.33 33.15 16.93 39.15 43.92
14 86.79 14.31 24.97 16.49 28.77 54.74
15 83.55 14.44 31.66 17.29 37.89 44.82
16 82.81 13.85 31.50 16.73 38.04 45.24
17 82.58 15.82 33.67 19.16 40.77 40.06
18 85.28 14.59 31.25 17.11 36.65 46.24
19 92.21 15.96 36.96 17.30 40.08 42.62
20 87.38 14.69 30.97 16.81 35.44 47.74
21 88.02 14.69 31.20 16.69 35.44 47.87
Average e e e 17.50 37.47 45.03
a
Calculated by difference.
 G.C. Gonalves et al. / Biomass and Bioenergy 85 (2016) 178e186 185

bio-oil yields are expected to improve by implementing an efcient

Fig. 8. Products of sugarcane bagasse and molasses pyrolysis/activation: (a) activated
carbon, (b) bio-oil.
system for gas cooling. The activated bagasse/molasses pellets
produced from the 21 experiments were crushed, sieved to 7e16
mesh, and subjected to treatment with HCl solution (0.1 M), pro-
ducing granular activated carbon in the size range of 1.0e2.8 mm.
Visual characteristics of the as-prepared activated carbon and
bio-oil are shown in Fig. 8; the properties and characteristics of the
bio-oil are presented in Table 4. The bio-oil obtained appears as a
viscous liquid with dark-brown coloration. According to Bridgwater
[8], the coloration of bio-oil can vary from dark brown to dark green
depending on the raw materials used and the conditions of pyrol-
ysis. Another remarkable feature of the bio-oil is a strong smoky
odordwhich is characteristic of liquids obtained by the pyrolysis
processdthat can cause eye irritation on prolonged exposed. Ac-
cording to Bridgwater [8], the odor is due to the presence of alde-
hydes and low-molecular-weight acids.
The density of bio-oil produced from bagasse/molasses pellets
was found to be 1.09 g cm
3 as measured by a pycnometer at 28  C.
This value is consistent with density of other bio-oils obtained from
biomass [6,8,29]; however this value is higher than that of light fuel
oil (around 0.850 g cm
3) and could be attributed to the high ox-
ygen content in the bio-oil (usually 45e50 wt%) [6,8].
The bio-oil usually presents acid characteristics due to the
presence substantial amounts of organic acids, mostly acetic and
formic acid, which results in a pH of 2e3 [6,8]. The pH and acid
value of the bio-oil was found to be around 1.9 and 146.70 mg
KOH$g
1, respectively; this pH value is lower than that of sugarcane
bagasse pyrolysis liquid (3.5e4.5) [6]. The ash content in the bio-oil
was found to be 0.04 (wt%). A low ash content in bio-oil is expected,
since the ash present in the biomass is associated with the char at
the end of the pyrolysis process [6,8]. Thus, bio-oil produced from
the pyrolysis of bagasse/molasses pellets could be used as liquid
fuel for boilers, diesel engines, or gas turbine applications, but
would rst require chemical treatment for lowering the acidity
[6,8]. In addition, this bio-oil can be a potential source of a number
of valuable chemicals that offer more interesting commercial op-
portunities [8]. The optimization of the pyrolysis conditions and the
physico-chemical characterization of the bio-oil will be investi-
gated in a separate paper.
The physical and chemical properties of the activated carbon
materials are presented in Table 5. It was possible to obtain acti-
vated carbon with a surface area up to 900 m2 g
1 with a pre-
dominance of micro and mesopore structures. The average pore
diameter of the activated carbon was about 15 .
The experimentally prepared activated carbon presented the
ability to removal molasses color similar to commercial activated
carbon. This similarity suggests that activated carbon from bagasse/
molasses sugarcane could be a useful adsorbent substitute for use

Table 4
Properties and characteristics of bio-oil produced from pyrolysis of bagasse and molasses pellets and other bio-oils from pyrolysis of sugarcane bagasse.

Properties Bio-oil from pyrolysis/activation of bagasse and molasses Bio-oil from pyrolysis of Bio-oil from vacuum pyrolysis of sugarcane bagasse
pellets sugarcane bagasse [6] [29]

Appearance Dark, brown liquid e e e

Odor Strong smoky smell e e e
Density (g cm
3) 1.09 (at 28  C) 1.13 (at 1.05 (at 1.21 (at 20  C)
20  C) 20  C)
Acid value (mg KOH$g
1) 146.70 137.35 117.51 e
pH 1.90 3.50 4.50 2.70
Loss by evaporation (wt%) 2.50 e e e
Ash content (wt%) 0.042 0.030 0.020 0.050
Water Content (wt%) e 15.00 11.00 13.80
Gross caloric value e 17.25 19.91 22.4
(MJ kg
1)
186 G.C. Gonalves et al. / Biomass and Bioenergy 85 (2016) 178e186

Table 5
Physical and chemical properties of activated carbon produced by single-step py-
rolysis and activation of bagasse/molasses pellets.
Properties Value
Surface area (m2/g) SBET 906.10
Pore volume (cm3/g) VTotal 0.174
VMicro 0.059
VMeso 0.107
VMacro 0.007
Average pore volume () Dav 15.05
pH 6.58
Molasses color removed (%) 27.51
in the industrial process for sugar decolorization.
4. Conclusions
Sugarcane bagasses and molasses was successfully tested as
feedstock for bio-oil and GAC production. For pyrolysis and CO2
activation using single-stage process, the yields of bio-oil, GAC and
gases were around 37.5, 17.5, and 45.0 wt%, respectively. The
properties and characteristics of the obtained bio-oil are compa-
rable to the proposed specications of the various grades of py-
rolysis oils and could nd potential application as fuel or source of a
number of valuable chemicals. GAC with a surface area of up to
900 m2 g
1 was obtained after 4.5 h of activation. Micro and
mesopores were predominant in the pore-size distribution. The
bagasse-based GAC demonstrated excellent sugar decolorization
performance that was improved by washing with HCl solution.
Bagasse-based GAC might provide a lower cost alternative to
commercial activated carbon used in sugar decolorization during
raw sugar rening.
Acknowledgments
The authors are grateful for the nancial support of the Federal
Technological University of Parana.
References
[1] National Supply Company e CONAB, Ministry of Agriculture, Livestock and
Supply, Brazilian Sugarcane Crop 2013/2014, 2013.
[2] J. Zandersons, J. Gravitis, A. Kokorevics, A. Zhurinsh, O. Bikovens, A. Tardenaka,
B. Spince, Studies of the Brazilian sugarcane bagasse carbonisation process
and products properties, Biomass Bioenergy 17 (3) (1999) 209e219.
[3] Q. Mortley, W.A. Mellowes, S. Thomas, Activated carbons from materials of
varying morphological structure, Thermochim. Acta 129 (2) (1988) 173e186.
[4] J. Piskorz, P. Majerski, D. Radlein, D.S. Scott, A.V. Bridgwater, Fast pyrolysis of
sweet sorghum and sweet sorghum bagasse, J. Anal. Appl. Pyrol. 46 (1) (1998)
15e29.
[5] E.C. Bernardo, R. Egashira, J. Kawasaki, Decolorization of molasses' wastewater
using activated carbon prepared from cane bagasse, Carbon 35 (9) (1997)
1217e1221.
[6] M. Asadullah, M.A. Rahman, M.M. Ali, M.S. Rahman, M.A. Motin, M.B. Sultan,
M.R. Alam, Production of bio-oil from xed bed pyrolisis of bagasse, Fuel 86
(2007) 2514e2520.
[7] K. Gergova, A. Galushko, N. Petrov, V. Minkova, Investigation of the porous
structure of activated carbons prepared by pyrolysis of agricultural by-
products in a stream of water vapor, Carbon 30 (5) (1992) 721e727.
[8] A.V. Bridgwater, Biomass fast pyrolysis, Therm. Sci. 8 (2) (2004) 21e49.
[9] M. Ahmedna, W.E. Marshall, R.M. Rao, Production of granular activated car-
bons from select agricultural by-products and evaluation of their physical,
chemical and adsorption properties, Bioresour. Technol. 71 (2000) 103e123.
[10] M. Ahmedna, M.M. Johns, S.J. Clarke, W.E. Marshall, R.M. Rao, Potential of
agricultural by-product-based activated carbons for use in raw sugar decol-
ourisation, J. Sci. Food Agric. 75 (1) (1997) 117e124.
[11] J.C. Gonzales, M.T. Gonzales, M. Molina-Sabio, F. Rodriguez-Reinoso,
A. Sepulveda-Escribano, Porosity of activated carbons prepared from different
lignocellulosic materials, Carbon 33 (8) (1995) 1175e1177.
[12] F. Rodrigues-Reinoso, M. Molina-Sabio, M.T. Gonz
alez, The use of steam and
CO2 as activating agents in the preparation of activated carbons, Carbon 33 (1)
(1995) 15e23.
[13] R.-S. Juang, F.-C. Wu, R.-L. Tseng, Characterization and use of activated carbons
prepared from bagasses for liquid-phase adsorption, Colloids Surf. A Phys-
icochem. Eng. Aspects 201 (1e3) (2002) 191e199.
[14] B. Pendyal, M.M. Johns, W.E. Marshall, M. Ahmedna, R.M. Rao, The effect of
binders and agricultural by-products on physical and chemical properties of
granular activated carbons, Bioresour. Technol. 68 (1999) 247e254.
[15] B. Pendyal, M.M. Johns, W.E. Marshall, M. Ahmedna, R.M. Rao, Removal of
sugar colorants by granular activated carbons made from binders and agri-
cultural by-products, Bioresour. Technol. 69 (1999) 45e51.
[16] G.C. Gonalves, E.E. Mendes, N.C. Pereira, J.C. Sousa, Produ~ ao de carva~o ati-
vado a partir de bagao e melao de cana-de-acar, Acta Sci. Technol. 28 (1)
(2006) 21e27.
[17] J.C. Sousa, N.C. Pereira, M.L.M.C. Silva, R. Ferro, Production and characteriza-
tion of water-steam activated carbons made from sugarcane bagasse and
molasses pellets, Acta Sci. Technol. 34 (1) (2012) 13e20.
[18] S. Brunauer, P. Emmett, E. Teller, Adsorption of gases in multimolecular layers,
J. Am. Chem. Soc. 60 (1938) 309e319.
[19] D.G. Halsey, Physical adsorption on non-uniform surfaces, J. Chem. Phys. 16
(10) (1948) 931e937.
[20] E.P. Barrett, L.G. Joyner, P.P. Halenda, The determination of pore volume and
area distributions in porous substances. I. Computations from nitrogen iso-
therms, J. Am. Chem. Soc. 73 (1) (1951) 373e380.
[21] M. Garca-Pe rez, A. Chaala, J. Yang, C. Roy, Co-pyrolysis of sugarcane bagasse
with petroleum residue. Part I: thermogravimetric analysis, Fuel 80 (9) (2001)
1245e1258.
[22] rnbom, D. Bolado, M. Giner, T.H. Fransson, Pyrolysis and gasi-
C. Erlich, E. Bjo
cation of pellets from sugar cane bagasse and wood, Fuel 85 (2006)
1535e1540.
[23] V. Strezov, M. Patterson, V. Zymla, K. Fisher, T.J. Evans, P.F. Nelson, Funda-
mental aspects of biomass carbonisation, J. Anal. Appl. Pyrol. 79 (1e2) (2007)
91e100.
[24] L.E. Brossard, L.A.B. Cortez, Potential for the use of pyrolytic bio oil from
bagasse in industry, Biomass Bioenergy 12 (5) (1997) 363e366.
[25] H. Darmstadt, M. Garca-Pe rez, A. Chaala, N. Cao, C. Roy, Co-pyrolysis under
vacuum of sugar cane bagasse and petroleum residue. Properties of the char
and activated char products, Carbon 39 (2001) 815e825.
[26] M. Garca-Pe rez, A. Chaala, C. Roy, Co-pyrolysis of sugarcane bagasse with
petroleum residue. Part II. Product yields and properties, Fuel 81 (2002)
893e907.
[27] J.F. Byrne, H. Marsh, Introductory overwiew, in: J.W. Patrick (Ed.), Porosity in
Carbons: Characterization and Applications, John Wiley & Sons, New York,
1995, pp. 1e48.
[28] F.G. Carpenter, Cane sugar rening II: decolorization, in: J.C.P. Chen (Ed.), Cane
Sugar Handbook, eleventh ed., John Wiley & Sons, New York, 1985, pp.
571e609.
[29] M. Garca-Pe rez, A. Chaala, C. Roy, Vacuum pyrolysis of sugarcane bagasse,
J. Anal. Appl. Pyrol. 65 (2) (2002) 111e136.