Renewable Energy 130 (2019) 510e523

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Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Simultaneously carbonized and sulfonated sugarcane bagasse as solid

acid catalyst for the esterification of oleic acid with methanol
Ken P. Flores a, Jan Laurence O. Omega a, Luis K. Cabatingan a, **, Alchris W. Go a, *,
Ramelito C. Agapay a, b, Yi-Hsu Ju c
a
Department of Chemical Engineering, University of San Carlos, Talamban, Cebu City, 6000, Philippines
b
Department of Chemical Engineering, National Taiwan University of Science and Technology, No. 43, Keelung Road, Section 4, Daan District, Taipei, 106-07,
Taiwan
c
Graduate Institute of Applied Science and Technology, National Taiwan University of Science and Technology, No. 43, Keelung Road, Section 4, Daan
District, Taipei, 106-07, Taiwan

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

Article history: Solid acid catalyst was synthesized from sugarcane bagasse, a residue left behind during sugar milling,
Received 23 January 2018 through a simpler and less energy-intensive one-step process, simultaneous carbonization-sulfonation. A
Received in revised form range of synthesis temperature (150, 200, 250
C) and time (4, 6, 8 h) were investigated in the prepa-
18 April 2018
ration of the catalyst to determine their effects on the catalytic activity and conversion during esterifi-
Accepted 21 June 2018
cation of oleic acid and methanol. Extensive washing of the freshly synthesized catalyst have significant
Available online 26 June 2018
influence on the performance of the catalyst, as loosely bound acid sites are removed in the process
lowering its activity but improving its stability. The catalyst synthesized at 150
C for 8 h, having a sul-
Keywords:
Solid acid catalyst
fonic acid density of 0.59 mmol/g, exhibited the best performance during a 4-h esterification assay using
Sugarcane bagasse oleic acid and methanol, resulting in an FFA conversion of 46.5% and catalytic activity of 4.62 mmol oleic
Catalytic activity acid/mmol-SO3H $h. Additionally, the catalyst could be used for at least five 24-h esterification cycles,
Biodiesel production where an FFA conversion of as high as 87% was achieved. The catalyst retained 76.5 and 86% of its initial
FFA conversion catalytic performance and sulfonic acid density, respectively, after the fourth cycle, offering good oper-
Carbon-based catalyst ational stability.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction
Heterogeneous acid catalysts for biodiesel production have
gained increasing attention owing to their significant advantages of
eliminating separation, corrosion, toxicity and reduce environ-
mental problems posed by their homogeneous counterparts. In
addition, these catalysts can simultaneously catalyze both esteri-
fication and transesterification reactions, making them compatible
for use with high acid value oils in the production of biodiesel.
Traditional solid acid catalysts include zeolites, mesoporous silica,
and polystyrene resins. These catalysts generally possess one or
more problems of small pore size, low acid density, poor opera-
tional stability, bad tolerance to water, and high cost [1e3].
* Corresponding author.
** Corresponding author.
E-mail addresses: lkcabatingan@usc.edu.ph (L.K. Cabatingan), alchrisgo@yahoo.
com, awgo@usc.edu.ph (A.W. Go).
Recently, there has been a growing interest in the use of carbon
as the catalyst support material. This led to the emergence of a new
class of catalysts derived from natural products having well-
defined chemical structures such as sugar, starch, and cellulose.
These catalysts can be readily prepared by sulfonation of partially
carbonized organic matter using concentrated sulfuric acid.
Carbon-based catalysts from glucose [4], sucrose, cellulose, starch
[5], and Kraft lignin [6] exhibited high catalytic performance in the
esterification of oleic acid (95e96% FFA conversion), outperforming
the aforementioned traditional solid acid catalysts. Since these
catalysts are derived from major constituents of lignocellulosic
biomass, there is a potential for utilizing agricultural residues in the
synthesis of such catalysts. In the recent years, several studies have
been conducted on using agricultural residues such as coconut shell
[7], oil palm trunk [8], rice husk [9], corn straw [10], bamboo [11],
spent coffee grounds [12], waste Jatropha curcas seed shells [13],
and sugarcane bagasse [14] as the starting material for synthesis of
solid acid catalyst (SAC). The catalysts prepared from these
materials demonstrated good catalytic performance towards

https://doi.org/10.1016/j.renene.2018.06.093
0960-1481/© 2018 Elsevier Ltd. All rights reserved.
 K.P. Flores et al. / Renewable Energy 130 (2019) 510e523
esterification of high FFA oils, with FFA conversions ranging from 71
to 98%. Esterification reactions involving the use of these catalysts
typically require 0.005 to 0.09 w/w of catalyst, a methanol to oil
ratio of 1e20, and a reaction time of 2e8 h at 60e110
C [7e14].
Although catalysts synthesized from different biomass residues
as starting material and carbon source may have certain advantages
of their own, their potential for later local application is hinged on
the availability of the raw material in a given locality. In this regard,
sugarcane bagasse (SCB) would be a practical candidate as starting
material in the Philippine context as it is available locally (4.45
millions tons/year), given that sugarcane is the top agricultural
product of the country (22.7 million tons/year) from 2007 to 2016
[15e17]. The utilization of agricultural residues such as SCB in the
synthesis of solid acid catalysts (SAC) is attractive owing to the
material's low cost and availability, which could potentially lead to
a greener process for the production of biodiesel [18]. Moreover,
this could lead to the valorization of these waste materials while at
the same time addressing waste management concerns.
Several studies have been conducted on the use of sulfonated
activated carbon from sugarcane bagasse (SAC-SCB) for the (trans)
esterification of oils [5,8,14,19]. The catalysts exhibited desirable
catalytic performance ranging from 80 to 96% conversion,
depending on the catalyst preparation conditions and reaction
parameters. The catalytic activity of a sulfonated activated carbon
like that of SAC-SCB is attributed to the presence of sulfonic acid
(eSO3H) functional groups [20], which are introduced via sulfo-
nation of partially carbonized material.
In view of catalyst synthesis, SAC-SCB is typically synthesized
via a two-step process involving partial carbonization of crushed
SCB at temperatures of 300e800
C for about 0.5e20 h and sub-
sequent sulfonation at temperatures of 120e200
C for a duration
of 3e20 h [8,14,19]. Partial carbonization is employed to induce
formation of small polycyclic aromatic rings to serve as backbone or
support for the active sites [22]. Sulfonation using sulfuric acid is
then carried out to introduce the sulfonic acid (eSO3H) functional
groups into the polycyclic aromatic rings through covalent attach-
ment by substitution of hydrogen in the CeH bonds of the catalyst
structure [14]. Another approach in the preparation of SAC-SCB
involves carrying out dilute acid hydrothermal pretreatment step
prior to carbonization and sulfonation. However, the synthesized
catalyst only had minimal improvement in performance (from 90.3
to 93.2% FFA conversion), and required an additional processing
time of 10 h at 200
C for the pretreatment step [21]. Considering
the processing conditions (temperature and time) required of the
carbonization and sulfonation steps, there are overlaps and could
potentially be taken advantaged of by combining the two pro-
cessing steps. An alternative to the above described preparation
schemes is the simultaneous carbonization and sulfonation (SCS) of
SCB as proposed by Savaliya and Dholakiya [23] in which both
carbonization and sulfonation are carried out in one single step.
Table 1
Typical operating conditions for different synthesis methods in the preparation of SAC-SCB.
Method of Synthesis Carbonization-Sulfonation Carbonization-Sulfonation with hydrothermal pre-treatment
[8,14,21] [21]
No. of steps 2 3
Pre-treatment Time e 10 h
Pre-treatment e 200
C
Temperature
Carbonization Time 0.5e20 h 5h
Sulfonation Time 3e20 h 5e15 h
Total synthesis time 3.5e23 h 20e30 h
Carbonization 300e800
C 400e800
C
Temperature
Sulfonation Temperature 100e200
C 120e200
C
Operating Temperature 100e800
C 120e800
C
511
This approach greatly reduces the preparation time as well as the
energy requirements of the synthesis of SAC-SCB. A comparison of
the different synthesis schemes in the preparation of SAC-SCB is
presented in Table 1.
In the preparation of SAC-SCB through SCS, a mixture of baggase
and sulfuric acid is heated at an elevated temperature under a
stream of nitrogen [23]. Through the SCS scheme of synthesizing
SAC-SCB the synthesis or preparation could be greatly reduced
from almost 30 h to as short as 10 h. Moreover, the main processing
steps could be greatly reduced from a synthesis scheme requiring 3
major steps to a one-step synthesis. Furthermore, taking account
the fact that sulfuric acid is a dehydrating agent, this would result in
the hastening of the carbonization process, whereby removing the
inherent hydrogen and oxygen groups present while simulta-
neously attaching to the carbon backbone. A successful imple-
mentation of this approach would result in a cost-effective and
more environmentally friendly process, considering the initial in-
vestments and capital cost that could be reduced by reducing the
required processing steps and the reduction of the energy re-
quirements and emissions entailed in the conventional approach.
As of this writing, the effects of time and temperature during SCS
on the catalytic activity of SAC-SCB during SCS has not been
investigated. Moreover, most of the above mentioned catalyst
preparation schemes were typically carried out under oxygen-free
atmosphere by continuously purging with nitrogen gas, which
would also entail additional cost in the catalyst production. It
would be of interest to explore the possibility of preparing SAC-SCB
through SCS without the use of purge gas [21,24] to further reduce
the preparation cost.
In view of the existing gaps in the conditions for the synthesis of
SAC-SCB through SCS, this study aims to determine the effects of
time and temperature during SCS under minimized oxidative con-
dition on the catalytic performance (FFA conversion) and activity
(sulfonic acid activity) of the SAC-SCB in the esterification of oleic
acid. Furthermore, the reusability of SAC-SCB in the esterification of
oleic acid was also looked into. Moreover, during the course of this
study, the importance of incorporating an extensive washing step to
produce catalyst of good stability was also elucidated.
2. Material and methods
Sugarcane bagasse was collected from a local sugarcane juice
vendor in Cebu. Ethanol 99.9 %v/v, methanol 99.8%, n-Hexane 96%,
Scharlau, Spain and chemical reagents (Sulfuric acid 95e98 %w/w;
hydrochloric acid 36e39 %w/w; barium chloride dihydrate 99.0%;
anhydrous sodium carbonate 99.8%; oleic acid AV 195e204, Ajax,
Sydney, Australia and sodium chloride 99.5%; magnesium oxide
96e100.5%; sodium hydroxide pellets 97%, Scharlau, Spain) used
were obtained through local suppliers.
Simultaneous Carbonization-Sulfonation
[23]
1
e
e
e
e
10 h
e
e
180
C
512 K.P. Flores et al. / Renewable Energy 130 (2019) 510e523
2.1. Collection, storage, and characterization of sugarcane bagasse
Sugarcane bagasse samples were collected fresh right after
pressing of its juice. Collected samples were oven-dried at 60
C for
3 days or until a moisture content of less than 10% w/w was ach-
ieved. Dried samples were milled through a 2-mm mesh using a
Willey mill, stored at room temperature in a polypropylene box and
tightly covered.
2.1.1. Particle size distribution
About 50 g of milled bagasse was sieved through pre-weighed
standard Tyler sieves (850, 450, 250, and 180 mm), stacked in
ascending order of mesh size, with the receiver placed at the bot-
tom. The sample was loaded on the topmost sieve and covered. The
sieve set was securely mounted on the sieve shaker (Mod.A5911,
Intertest Benelux, Netherlands) and operated for 15 min. The sieves
containing the samples were weighed and the mean particle size
(dm ) was calculated using Equation (1).
X mi
mean particle size ðdm Þ ¼ di
mT
where mi and mT are the mass of the retained samples in a given
sieve and the total sample mass, respectively. Diameter di is the
average mesh aperture between two sieves.
2.1.2. Proximate components
About 1 g of powdered bagasse was weighed (to the nearest
0.0001 g) into pre-fired and pre-weighed 30-mL porcelain cruci-
bles. The crucibles containing the samples were heated in an oven
at 105
C for 2 h, transferred to a desiccator and allowed to cool for
an hour prior to weighing. This drying procedure was repeated
until the change in weight was less than or equal to 0.0005 g. The
moisture content (%M), of the sample was calculated using Equa-
tion (2).
 
ms  mcs;105
C  mc
%M ð%w=wÞ ¼  100%
ms
where, ms is the initial mass of the sample, mc is the mass of the
pre-fired crucible and mcs;105
C is the mass of the crucible con-
taining the sample after drying at 105
C.
For the determination of volatile matter content, the crucibles
were covered with pre-fired crucible lids before being placed into a
pre-heated furnace (950
C). With the furnace door open, the cru-
cibles were placed on the outer ledge of the furnace for 2 min,
transferred to the edge of the furnace for 3 min, and then moved to
the rear of the furnace with the muffle door closed for 6 min. The
crucibles were then taken out of the furnace, allowed to cool for
15 min, transferred to a desiccator and allowed to cool for an
additional 30 min before weighing. Volatile matter content (%VM)
was calculated using Equation (3).
mcs;105
C  mcs;950
C
%VM ð%w=wÞ ¼  100%
ms
where, mcs;950
C is the mass of the covered crucible containing the
sample after heating at 950
C.
For the determination of ash content, the uncovered crucibles
containing the samples used for the determination of volatile
matter were placed in the furnace and heated at 750
C for 6 h.
After heating, the crucibles were then taken out of the furnace,
allowed to cool for 15 min, transferred to a desiccator and allowed
to cool for an additional 30 min prior to weighing. Ash content
(%Ash) and fixed carbon (%FC) was calculated using Equation (4)
and Equation (5), respectively.
mcs;750
C  mc
%Ash ð%w=wÞ ¼  100% (4)
ms
%FC ð%w=wÞ ¼ 100  %M  %VM  %Ash (5)
where mcs;750
C is the weight of the crucible containing the sample
after firing at 750
C.
2.2. Simultaneous carbonization and sulfonation of SCB
About 3 g of powdered bagasse (644 ± 15 mm) with a moisture
content of 8.70 ± 0.20% w/w was weighed and transferred into a
Kjeldahl digestion flask, 50 mL concentrated H2SO4 was then added
to act as the sulfonating agent. To ensure minimized oxidative
conditions, the powdered bagasse was fully immersed in the sul-
fonating agent. Eight flasks containing the SCB-sulfuric acid
mixture were loaded into the Kjehldahl digester for simultaneous
carbonization and sulfonation. The digester was heated to a pre-
(1) determined temperature (150, 200, or 250
C) and held at the set
temperature for a duration of 4, 6, or 8 h. After simultaneous
carbonization and sulfonation, the flasks containing the mixture
were allowed to cool to room temperature. About 180 mL of
distilled water was slowly added to each flask with continuous
stirring. The solids in the diluted mixture were then recovered via
centrifugation or filtration; the recovered solids are then referred to
as the solid acid catalyst from sugarcane bagasse (SAC-SCB). For
SAC-SCB synthesized at 150
C, solids were recovered via filtration
using grade 4 filter paper (pore size ¼ 20e25 mm) and continuously
washed with hot water (90
C) until the pH of the washings was
above 5. In the case of SAC-SCB synthesized at 200 and 250
C,
particles were too fine for filtration, thus requiring the aid of
centrifuge for its recovery. Likewise, the collected solids were
repeatedly washed with hot water to remove most of the free acids.
The collected solids were partially dried overnight in a convection
oven (UM500, Memmert, USA) at 80
C for ease of recovery. The
(2) partially dried solids were then packed in pre-weighed cellulose
extraction thimbles (Whatman 25  80 mm Cat No: 2800258) for
subsequent washing with distilled water in a Soxhlet extractor
operated under continuous reflux (~100
C) for 12 h. Washing with
the aid of a Soxhlet extractor was carried out in order to further
remove residual acids, loosely bound active sites [25], and other
water-soluble materials. After extraction, the thimbles containing
the washed SAC-SCB were oven-dried at 80
C until constant
weight. Catalyst yield (Y SAC=SCB ) was calculated using Equation (6)
P 
total SAC­SCB mT;SAC  mT
Y SAC=SCB ðw=wÞ ¼ ¼ (6)
mSCB mSCB
where, mSCB is the total mass of SCB subjected to simultaneous
carbonization and sulfonation in a given condition, mT is the mass
of the extraction thimble and mT;SAC is the mass of the extraction
thimble containing the dried SAC-SCB after washing in a Soxhlet
(3) extractor. Collected catalysts were stored in glass vials for further
characterization and use. The synthesized solid acid catalysts from
sugarcane bagasse (SAC-SCB) were designated as SAC-SCB-tt-TTT,
to indicate the sulfonation time (t) and temperature (T). As an
example, SAC-SCB-08-150 is used to designate the catalyst syn-
thesized for a duration of 8 h at 150
C.
2.3. Catalyst characterization
The synthesized acid catalysts were characterized for its sulfur
content and total acid density. Sulfur content was determined by
 K.P. Flores et al. / Renewable Energy 130 (2019) 510e523
Eschka method as described in ASTM D3177-02 [26] with slight
modification. The total acid density was determined by following
the method used by Savaliya et al. [23].
2.3.1. Sulfur content and sulfonic acid density
About 1 g of SAC-SCB (weighed to the nearest 0.0001 g) was
mixed with 3 g of Eschka mixture (composed of 2 parts by weight
MgO and 1 part anhydrous Na2CO3) in a 30-mL porcelain crucible
and then covered with 1 g Eschka mixture layer on top. The crucible
containing the mixture was then heated in a muffle furnace. The
temperature inside the furnace was raised to 800
C at a heating
rate of 10
C/min and held at the set temperature for 4 h to
completely oxidize the SAC-SCB. The crucible was then allowed to
cool for an hour.
The contents of the cooled crucible were transferred to a 250-
mL beaker containing 100 mL of hot water and the mixture was
thoroughly stirred. The mixture in the beaker was then heated in a
water bath (90
C) for 45 min and was stirred occasionally (5-min
interval). The solids in the mixture were allowed to settle and
then the liquid was decanted to a 600-mL beaker, passing through a
grade 4 filter paper (pore size ¼ 20e25 mm). The remaining solids
were washed four times with 50 mL hot water, with the washings
decanted to the 600-mL beaker and passing through the filter paper
in between washings. The collected filtrate was added with 30 mL
of 1 M HCl. The solution was then heated to 90
C in a water bath
and was slowly added with 15 mL of BaCl2 solution (100 g/L) to
precipitate the dissolved sulfates as BaSO4. The solution was
allowed to stand in the heating bath for 2.5 h. After heating, the
settled solids were filtered through an ashless filter paper (What-
man 42) with the aid of a vacuum pump. The solids were washed
with hot water until 10 mL of the collected filtrate was clear when
added with 1 drop of 0.1 AgNO3 solution. The ashless filter paper
containing the recovered solids was folded and placed in a pre-fired
and pre-weighed 30-mL porcelain crucible. The crucible was placed
in a furnace and the temperature inside the furnace was then raised
from room temperature to 800
C (heating rate of 15
C/min) and
held at this temperature for 30 min to burn off the ashless filter
paper and dry the recovered solids. Sulfur content (%S), sulfonic
acid density (rSO3H ), and extent of sulfonation (xs ) was calculated
using Equation (7), Equation (8), and Equation (9), respectively.
  MW S
mc;BaSO4  mc  MW
%S ðw=wÞ ¼ BaSO4
 100% (7)
mSAC
 
mmol %S 1000 1 mmol SO3 H
rSO3H ¼   (8)
g SAC 100 MW S 1 mmol S
%S SAC
xs ¼ (9)
%S SCB
where, mSAC is the mass of SAC-SCB sample, mc is the mass of the
pre-fired crucible, mc;BaSO4 is the mass of the crucible containing
the BaSO4 precipitates, MW S and MW BaSO4 is the molar mass of
sulfur and barium sulfate, respectively, and %S SAC and %S SCB is the
sulfur content of the SAC-SCB and sugarcane bagasse, respectively.
The sulfonic acid density (rSO3H ) was calculated based from the
sulfur content (%S) with the assumption that all the sulfur present
in the catalyst are in the form of sulfonic acid (eSO3H) moiety.
2.3.2. Total acid density
About 0.5 g of SAC-SCB was weighed in a 125-mL Erlenmeyer flask
and was added with 50 mL of 2 N NaCl solution. The mixture was
shaken at 200 rpm for 24 h (R-2 New Brunswick Scientific, New Jer-
sey, USA) and filtered using a grade 4 filter paper (pore
513
size ¼ 20e25 mm) to remove the solids. A 15-mL aliquot from the
filtrate was added with 3 drops of phenolphthalein indicator and then
titrated with standardized 0.01 M NaOH solution until endpoint. Total
acid density of SAC-SCB (racid ) was calculated using Equation (10).
 
mmol V NaOH C NaOH  VV as
racid ¼ (10)
g SAC mSAC
where, V s is the volume of the NaCl solution added to the SAC-SCB,
V a is the volume of the aliquot titrated with NaOH solution, V NaOH
is the volume of the NaOH solution titrated, C NaOH is the concen-
tration of the titrant NaOH solution.
2.3.3. FTIR
Bio-Rad Excalibur FTS 3500 Spectrometer was used to perform
FT-IR analysis of selected catalyst samples of washed and unwashed
catalyst to verify the presence of functional groups. Infrared scans
were carried out over the wavenumbers of 2700 to 400 cm1,
employing the attenuated total reflectance (ATR) technique with a
scanning resolution of 4 cm 1.
2.4. Esterification of oleic acid with SAC-SCB
In a 250-mL screw-capped Erlenmeyer flask, 30 g of oleic acid
was added with 85 mL methanol (methanol to oil molar ratio of
20:1). Oleic acid was selected as the model substrate considering
that it is the primary fatty acid found in most vegetable oils [27] and
WCO [28]. The flask was loaded in a pre-warmed incubator shaker
(New Brunswick Scientific Co. Inc, Model-G25) set at 65
C and
200 rpm for incubation. After an incubation time of 30 min, 3 g of
SAC-SCB (10% w/w with respect to the amount of oleic acid) was
added to the mixture in the flask to start the esterification reaction.
The reaction was kept at the set temperature for 6 h. After the set
reaction time, the flask was removed from the shaker and cooled in
an ice bath to stop the reaction. The cooled mixture was then
filtered through a grade 4 filter paper (pore size ¼ 20e25 mm) and
into a 250-mL separation funnel. The remaining oil and solid cat-
alysts were recovered by washing the flask with n-hexane, with the
washings filtered through the filter paper to the separation funnel
between washings. The collected catalysts (spent SAC-SCB) were
rinsed three times with 15 mL of n-hexane to further remove the
methyl oleate and unreacted oleic acid from the catalyst surface.
The spent SAC-SCB was dried and was analyzed for its sulfur con-
tent and total acid density.
The mixture in the separation funnel was added with 20 mL of
aqueous NaCl solution (5 %w/w) to induce phase separation. The
mixture was gently swirled and allowed to settle, forming an
organic phase (n-hexane layer) and an aqueous phase. The aqueous
phase containing the methanol (lower layer) was discarded.
Washing with 20 mL NaCl was done three times to ensure the
removal of methanol and leached acids. The n-hexane layer was
recovered and transferred into a pre-weighed evaporation flask and
concentrated with the aid of a rotary evaporator (VV-micro, Hei-
dolph, England). The recovered oil sample was weighed and was
transferred in screw-capped glass vials for analysis of FFA content.
Crude yield (%Y crude ), conversion (X FFA ), and FAME yield (Y FAME )
were calculated using Equation (11), Equation (12), and Equation
(13), respectively while catalyst activity as catalytic activity (AC )
and sulfonic acid activity (ASO3 H ) were calculated using Equation
(14) and Equation (15), respectively.
mproduct
%Y crude ðw=wÞ ¼  100 % (11)
mOA
514 K.P. Flores et al. / Renewable Energy 130 (2019) 510e523
AV i  AV f
X FFA ðw=wÞ ¼
AV i
MW MO
Y FAME ðw=wÞ ¼ X FFA 
MW OA
X  mOA
AC ðmmol=g$hrÞ ¼ MW FFA
OA
1000  m SAC  t e
AC
ASO3 H ðmmol=mmol SO3 H$hrÞ ¼
rSO3H
where, mproduct and mOA are the masses of the concentrated
product and initial oleic acid, respectively; AV i and AV f is the acid
value of the oil before and after esterification, respectively; MW MO
and MW OA is the molar mass of the product methyl oleate and oleic
acid, respectively; and t e is the esterification time in hours.
2.5. Free fatty acid content and acid value determination
FFA content of oil samples was determined via titration as
described in AOAC Official Method 940.28 [29]. About 0.5e1 g
(accurately weighed to the nearest 0.0001 g) of oil sample was
weighed into a 125-mL flask and was added with 25 mL of
neutralized ethanol (99%). Neutralization of the alcohol was done
by adding 10 drops of phenolphthalein indicator solution to 250 mL
of boiled alcohol and titrated with 0.1 M ethanolic NaOH. The oil-
ethanol mixture was added with 2e3 drops of phenolphthalein
indicator solution and was titrated with 0.075 M ethanolic NaOH
until endpoint. Acid value of the oil sample (AV) was calculated
using Equation (16) and free fatty acid content (%FFA) was deter-
mined using the calculated acid value (Equation (17)).
 
mg KOH C  V NaOH  MW KOH
AV ¼ NaOH
g moil
w  AV MW OA
%FFA ¼   100%
w 1000 MW KOH
where, V NaOH is the volume of the NaOH solution titrated, C NaOH is
the concentration of the titrant NaOH solution, moil is the mass of
the oil sample, MW OA and MW KOH is the molar mass of oleic acid
and KOH, respectively.
2.6. Reusability of SAC-SCB
Catalyst reusability was tested using the SAC-SCB with a high
catalytic activity, lowest reduction in sulfonic acid groups after
esterification and at an esterification time where maximum con-
version of oleic acid was achieved. To determine the minimum
esterification time, esterification of oleic acid using the selected
SAC-SCB was first carried out at 2, 4, 6, 8, 12, and 24 h. Reactions
were carried out in duplicates. The reaction condition providing the
highest conversion of FFA was adopted for the reusability test.
To determine the reusability of the catalyst, the same esterifi-
cation procedure as described in Section 2.4 was followed. For the
first cycle, 6 sets of reaction mixtures were subjected to the ester-
ification reaction. Spent catalysts were washed with n-hexane,
dried, and pooled to be used in the next cycle and was analyzed for
its sulfur content. For every cycle, the number of prepared reaction
mixtures was reduced by one set in order to have enough spent
catalysts for sulfur content analysis. SAC-SCB was used for up to 5
reaction cycles.
2.7. Data and statistical analysis
(12)
To aid in the determination of the influence of sulfonation time
and temperature on the acid densities and the catalytic activity,
two-way analysis of variance (ANOVA) with replication was
(13)
employed. Microsoft Excel with data analysis package was used for
all ANOVA analyses.
(14) 3. Results and discussion
Sugarcane bagasse used in this study was determined of its
proximate components and was found to have the following
(15)
composition: 17.31 ± 1.02 FC, 79.90 ± 1.06 VM, and 2.79 ± 0.08 ash,
in % w/w (dry basis). These results are within values reported in
literature (14.95e18.1% FC, 73.78e78.6% VM, 3.3e11.27% ash)
[30,31]. In the synthesis of carbon-based SAC, an important
consideration is the carbon content of the catalyst support. How-
ever, not all carbon remains during the synthesis of the catalyst,
considering that the synthesis of SAC-SCB involves the volatiliza-
tion of volatile organics during partial carbonization. Among the
proximate components, special interest is given to the fixed carbon
content, as it allows the estimation of the minimum amount of
catalyst that could be obtained after catalyst synthesis. Apart from
the fixed carbon, of importance is the presence of sulfonic acid
groups in carbon-based SAC, and is estimated based on the sulfur
content. Sulfur content of SCB was found to be 0.13% w/w (dry
basis). This amount is considerably low, requiring a sulfonation step
to increase the amount of sulfur in the biomass support.
3.1. Catalyst yield and extent of sulfonation
In this study, simultaneous carbonization and sulfonation (SCS)
was adopted to dehydrate, devolatilize, carbonize, and incorporate
sulfur sites in SCB. Nine types of SAC-SCB were prepared by varying
the sulfonation temperature and time. In general, the catalyst yield
(16) decreased from ~51 to ~20% (g SAC-SCB/g SCB) when the SCS
temperature was increased from 150 to 250
C (Fig. 1). It is inter-
esting to note that the catalyst yield approaches the fixed carbon
content (17.3 %w/w) of the raw SCB, implying that as the SCS
(17)
temperature is increased, the synthesized catalysts become more
carbonized, resulting to a more rigid structure. The resulting cata-
lysts could have lower sulfonic acid (eSO3H) densities [14] and
consequently lower activities, suggesting that higher sulfonation
temperatures beyond 250
C may not be necessary in the synthesis
of SAC-SCB.
In view of sulfonation time, sulfonation of SCB beyond 4 h did
not result in significant effects on the catalyst yield (p > 0.05). These
results are comparable to the results reported in a study done by
Savaliya et al. [23], where a yield of 25e35% was achieved during
the synthesis of SAC-SCB through SCS at 180
C for 10 h. Discrep-
ancies in the catalyst yields may be due to mass losses incurred
during the recovery and washing of catalysts as these are carried
out differently by different researchers. Unfortunately, most studies
involving the synthesis of SAC-SCB, whether direct or indirect
sulfonation, do not account for catalyst yield. However, it may be
inferred from the results of this study that SCS may be favorable
when compared to conventional two-step approaches requiring
the separate carbonization and sulfonation steps at high tempera-
tures beyond 250
C and total synthesis time of up to 30 h.
Although catalyst yield is an important parameter in view of
process performance of the synthesis step, the effectiveness of the
sulfonation process would best be evaluated through the successful
incorporation of the sulfur sites in SAC-SCB, as the catalytic activity
is attributed to sulfonic acid (eSO3H) functional groups [14,21]. In
order to assess the extent of sulfonation (x), the prepared catalysts
 K.P. Flores et al. / Renewable Energy 130 (2019) 510e523 515

Fig. 1. Yield of SAC-SCB during simultaneous carbonization-sulfonation at various temperature and time.

Fig. 2. Sulfur content ratio (SAC-SCB:SCB) at varying SCS conditions.

were analyzed for their sulfur content, and evaluated by deter-
mining the sulfur content ratio of SAC-SCB to raw SCB (Fig. 2).
Compared to the initial sulfur content (0.13 %w/w) of SCB, a
remarkable increase as high as ~18 times was achieved through
SCS. This suggests the successful incorporation of sulfonic acid
functional groups into the carbonized SCB. In addition to the
introduction of the main functional group, sulfonation also allowed
for the formation of weak acid groups such as carboxylic (eCOOH)
and hydroxyl (eOH) [8,14,21].
3.2. Characterization of SAC-SCB
Apart from process performance during catalyst synthesis, also
of importance is the actual activity of the synthesized catalyst,
whereby this activity is oftentimes attributed to its acid density
(Fig. 3). In view of the effects of sulfonation temperature and time
on the total acid density, no significant difference was observed
(p > 0.05). However, separately evaluating the strong acid sites
(sulfonic acid density) and weak acid sites (weak acid density), it

Fig. 3. Sulfonic acid (SO3H), weak acid, and total acid density of SAC-SCB synthesized at different SCS conditions. SAC-SCB-(Time, hr)-(Temp,
C).
516 K.P. Flores et al. / Renewable Energy 130 (2019) 510e523
could be observed that at lower temperatures of 150
C, the acid
sites are predominantly of the sulfonic acid group (71e77%), which
decreases to as low as 47% when the temperature is increased to
250
C.
High sulfonic acid densities (0.57e0.67 mmol/g SAC-SCB) are
obtained when synthesis was carried out at 150
C, which generally
decreases as temperature is increased. In a related study, Lou et al.
[14] observed that during sulfonation, the introduction of eSO3H
brought about a corresponding decrease in CeH bonds. This sug-
gests that sulfonation is achieved through covalent attachment of
eSO3H in the carbon framework by substitution of hydrogen in the
CeH bonds [14]. Increasing the sulfonation temperature leads to
the graphitization of the biomass and cross-linking of carbon
sheets, as the CeH bonds are eliminated prior to attachment of the
sulfonic acid groups, resulting in a more rigid carbon framework,
which in effect results to a low sulfonic acid density [14,21]. At this
point, it can be inferred that in the SCS of SCB, the temperature
should not go beyond 150
C. This coincides with the study of Lou
et al. [14], whereby 150
C was determined to be the optimum
sulfonation temperature in a two-step preparation of SAC-SCB,
which had a sulfonic acid density of 1.06 mmol/g.
Varying the sulfonation time did not significantly influence the
sulfonic acid density of the synthesized catalysts. Although an in-
crease in sulfonic acid density is observed during synthesis at
200
C from 4 to 6 h, statistical analysis indicated that there is no
significant difference (p > 0.05) between the synthesized catalysts.
However, the increase and decrease in the different acid sites is
influenced by various factors during sulfonation which includes
devolatilization, thermal decomposition, and changes in
morphology. In various studies, sulfonation of carbon-based ma-
terials resulted to sulfonic acid densities ranging from 0.48 to
1.83 mmol/g, depending on the material and the sulfonation con-
ditions [8,14,25]. In view of SAC-SCB prepared via conventional
process, SAC-SCB having sulfonic acid densities ranging from 1.06
to 1.54 mmol/g were found to have good catalytic performance
(>90% conversion) in the esterification of FFA [14,21]. Meanwhile,
Savaliya et al. [23] reported a sulfonic and total acid density of 0.90
and 1.90 mmol/g, respectively, for the SAC-SCB synthesized via SCS
at 180
C for 12 h.
The difference in the determined acid density is largely
dependent on the washing step after the synthesis process, as
sulfur-containing moieties such as polycyclic aromatic hydrocar-
bons (PAH) may have been removed during the process of washing
[25]. However, there is no consensus as to how the washing step is
carried out. Typically, synthesized catalyst is filtered and continu-
ously washed with hot water (~80
C) until the pH of the washings
reach neutral [19,21], or in some cases, the washings are tested for
presence of sulfate ions through the addition of barium chloride
[8,14,23]. Despite these attempts to eliminate residual acids, these
approaches face challenges in view of achieving a good consistency
and repeatability owing to the mode of contact and exposure
during washing. In light of this, filtered catalysts recovered after
washing with hot water (~95
C) were compared with catalysts
exhaustively washed using a Soxhlet extractor operated under
reflux (~100
C) for 12 h (Fig. 4).
As could be observed, even after washing with hot water until
neutral pH, a decrease in sulfonic acid density was still observed
after exhaustive washing using Soxhlet extractor. This will poten-
tially lead to a decrease in the actual performance and activity of
the catalyst. Moreover, from these results, it could be inferred that
an effective washing process should be developed so not to jeop-
ardize the characterization and later assessment of the catalyst
performance and activity.
Fig. 4. Sulfonic aicd density of SAC-SCB* (washed until neutral pH) and SAC-SCB
(exhaustively washed using Soxhlet extractor for 12 h) synthesized at 150
C over
various sulfonation times (4,6,8 h).
3.3. Catalytic activity of SAC-SCB
Catalytic activity of a SAC is oftentimes attributed to the pres-
ence of the sulfonic acid group. However, the actual activity is best
determined through its performance when used for its intended
application. In view of biodiesel production and in the reduction of
FFA in low quality oils, esterification of oleic acid was carried out
with the synthesized catalysts to determine its catalytic perfor-
mance (FFA conversion) and activity (sulfonic acid activity). The
sulfonic acid activity of SAC-SCB was calculated to determine the
FFA conversion brought about by its sulfonic acid functional groups.
This provides a more objective comparison of the synthesized
catalysts, considering that the catalysts synthesized were of varying
sulfonic acid densities.
As presented in Fig. 5, FFA conversion reached as high as ~90%,
translating to a catalytic activity of 6.6e7.5 mmol FFA/mmol
SO3H$h with the catalyst (SAC-SCB*) prepared at 150
C without
being exhaustively washed in a Soxhlet extractor. The conversion
and activity significantly decreased to as low as 44e53% and
~4.5 mmol FFA/mmol SO3H$h, respectively, when the synthesized
catalysts were subjected to exhaustive washing prior to use in the
esterification of oleic acid at 45 ± 5
C for 6 h. The decrease can be
attributed to the relatively lower sulfonic acid density, which
resulted from the removal of sulfur-containing moieties during
extensive washing (Figs. 5 and 6).
To further support the presence of sulfonic groups and their
removal during washing, FTIR spectra of the catalysts washed with
hot water and extensively washed with an aid of a Soxhlet appa-
ratus was obtained and presented in Fig. 7. As could be observed,
bands at 1030, 1056 and 1111 cm1 indicates the presence of sulfur
groups in the form of sulfoxide or sulfone (S]O) [11,14,23], while
bands at 1350 and 600 cm1 indicates that these sulfur groups are
that of the sufonic acid group (eSO3H) [12].
Catalysts obtained after exhaustive washing resulted in the
decrease in the intensities of these bands suggesting that some of
these groups have been removed. Furthermore, observed bands for
aromatic C]C (1600e1700 cm1) and CeH (680e850 cm1) are
also observed to have decreased suggesting that the sulfonic groups
that were removed are those attached to aromatic rings, which are
expected to form during carbonization and serves as the support
for the active moiety. The decrease in the band intensities suggests
that these groups or a portion of these might have been solubilized
and washed out during the washing process. Another mechanism
by which the sulfonic acid groups might have been removed could
be through hydrolysis, where aromatic C]C bending at 1600 cm1
is observed after exhaustive washing. Some of the carboxylic
moiety's might have also been solubilized considering that band
 K.P. Flores et al. / Renewable Energy 130 (2019) 510e523 517

Fig. 5. Catalytic performance (a) and activity (b) of SAC-SCB* (washed until neutral pH) and SAC-SCB (exhaustively washed using Soxhlet extractor for 12 h) synthesized at 150
C at
various sulfonation times (4,6,8 h).

Fig. 6. Sulfonic acid density of fresh and spent catalyst of SAC-SCB* (washed until neutral pH), (a) and SAC-SCB (exhaustively washed using Soxhlet extractor for 12 h, (b) syn-
thesized at 150
C over various sulfonation times (4,6,8 h).

Fig. 7. FTIR spectra of SAC-SCB synthesized at 150
C and 8 h.

518 K.P. Flores et al. / Renewable Energy 130 (2019) 510e523
intensity of carboxyl groups (C]O, 1795 and OeC, 1200 to
1350 cm1) also decreased.
In a related study by Mo et al. [25], sulfonated D-glucose was
washed with methanol for 24 h at 60
C prior to use in esterification
were found to have lower activities than the unwashed catalysts by
12e20%. Moreover, the authors confirmed the leaching of catalytic
species by using the recovered methanol from the washing in the
esterification of acetic acid. It was found that the methanol from the
washings had active agents in catalyzing the reaction. Deactivation
of the catalyst is primarily caused by leaching out of polar sulfonic
groups to gain better stability through hydrogen bonding with polar
solvents such as alcohol or water [25]. Leaching of the active sites
poses a challenge in the effective use of SAC in biodiesel production
as this would lead to poor catalytic performance and stability, in
view of catalyst reuse, and contamination of the products, which
defeats the primary purpose of employing SAC. In relation to this,
the sulfonic acid densities of SAC-SCB* and SAC-SCB after esterifi-
cation of oleic acid with methanol were also looked into (Fig. 6).
Following the use of the synthesized catalysts in the esterifica-
tion of oleic acid with methanol, a reduction in sulfonic acid density
was observed in both SAC-SCB* and SAC-SCB. However, the
reduction in sulfonic acid density of the catalysts which were
extensively washed (SAC-SCB) was not as pronounced when
compared to those that were only washed until a neutral pH. This
suggests that exhaustive washing with an aid of a Sohxlet extractor
is an effective means of removing weakly attached sulfur-
containing groups. Moreover, it could be observed that from
Fig. 6b, sulfonation at prolonged time of 8 h resulted in lesser
amounts of sulfonic acids removed, with 93% of the original sul-
fonic groups retained after the reaction. This also suggests better
stability of the synthesized catalysts. Comparing SAC-SCB* and
SAC-SCB sulfonated for 6 and 8 h, the spent catalysts resulted in
similar sulfonic acid densities (0.48e0.54 mmol/g), further sug-
gesting the need to ensure the removal of loosely bound acid
groups prior to catalyst evaluation and use. As such, washing by
Soxhlet extraction was employed in the preparation of the catalysts
synthesized at higher temperatures.
The performance and activity of SAC-SCB prepared at varying
SCS conditions are presented in Fig. 8. As could be observed, FFA
conversion is positively correlated (r ¼ 0.75) with the catalysts'
sulfonic acid densities. The highest conversion of 54% was achieved
at an SCS temperature of 150
C for 4 h, where sulfonic acid density
was also found to be the highest. At an SCS time of 4 h, increasing
the temperature from 150 to 200
C resulted in the decrease of FFA
Fig. 8. Effect of SCS conditions on (a) performance and (b) sulfonic acid activity of SAC-SCB.
conversion from ~54% to ~44%. Further increasing the sulfonation
temperature to 250
C caused a significant drop in FFA conversion
to ~7%. A similar behavior was exhibited by the catalysts synthe-
sized for a duration of 8 h. In contrast, these observations could not
be observed from the catalytic performance of the catalysts pre-
pared at an SCS time of 6 h. Nevertheless, the conversions brought
about by these catalysts (synthesized for 6 h) are still in agreement
with their corresponding sulfonic acid densities.
Similar to what has been observed on the sulfonic acid densities
of SAC-SCB, the effect of SCS time on FFA conversion is not as
pronounced as those brought about by SCS temperature. At 150
C,
increasing the SCS time from 4 to 6 h resulted to a decrease in FFA
conversion from 54 to 44%. Prolonging the SCS further to 8 h did not
have a significant effect on the FFA conversion (p > 0.05). At an SCS
temperature of 200
C, increasing the SCS time from 4 to 6 h
resulted in a catalyst rendering higher conversion (~50%) of oleic
acid during esterification. However, a prolonged SCS time of 8 h
resulted in a catalyst of poor catalytic performance (~38% conver-
sion). On the other hand, at 250
C, varying the SCS time did not
have a considerable effect on the FFA conversion (p > 0.05).
In view of catalytic activity (Fig. 8b), an abrupt decrease in ac-
tivity was observed when the temperature during SCS was
increased to 250
C. As for sulfonation time, it was found to
generally not have an influence in the catalytic activity of the
synthesized catalysts. However, at 200
C, peculiar differences
could be observed where an increase in SCS time from 4 to 6 h
resulted in a decrease in catalytic activity from 5.78 to 4.62 mmol
FFA/mmol SO3H$h, which then again increased to 5.38 mmol FFA/
mmol SO3H$h when the SCS time was increased further to 8 h.
Catalytic activity provides an idea on the ability of the available
active sites in catalyzing the esterification reaction. However, this is
greatly influenced by various factors which includes catalyst
morphology (surface area, pore size, and particle size) and distri-
bution of active sites. Moreover, active sites were only estimated
based on the total sulfur content, which may not be in its active
form as attached on the catalyst. For instance, although the cata-
lysts synthesized at 250
C have sulfonic acid densities comparable
to SAC-SCB-4-200 and SAC-SCB-8-200 (Fig. 3), their performances
are considerably lower. This could indicate differences in the
catalyst structure and sulfur moiety between the two groups of
catalysts. The higher SCS temperature may have produced catalysts
which are more rigid in structure and less flexible due to the
stacking of carbon sheets, which presumably may have prevented
large reactant molecules from coming into contact with the eSO3H
 K.P. Flores et al. / Renewable Energy 130 (2019) 510e523
groups [14]. Moreover, these catalysts have significantly lower
performances as compared to those synthesized at 150
C, despite
having about twice the weak acid density. Having a high weak acid
density (eCOOH) could enhance the catalytic performance of the
catalysts as it tends to attract methanol or by enhancing the oleic
acid-methanol interaction. However, this could also imply the
presence of high amounts of eOH groups, which could potentially
attract water molecules formed during the reaction, preventing
hydrophobic reactants such as that of oleic acid from accessing the
main functional groups [14].
Nevertheless, the above results further support the premise that
the catalytic activity of SAC-SCB is attributed to its sulfonic acid
density [8,14,21]. Both catalytic activity and conversion are
important response parameters to consider in the selection of
catalyst. However, stability of the catalyst should also be taken into
consideration. In view of catalyst stability, the spent catalysts were
reanalyzed of their sulfur content after its use in the esterification
of oleic acid (Fig. 9).
Analysis of sulfur content reveals a decrease in sulfonic acid
density of all the SAC-SCB's following their use in catalyzing the
esterification reaction of oleic acid with methanol. Among the
catalysts, SAC-SCB-04-150 and SAC-SCB-06-200 had the highest
reduction in sulfonic acid density (41.3 and 37.9%, respectively). In
the case of SAC-SCB-06-200, its sulfonic acid density after the re-
action is close to those of the other catalysts synthesized at 200
C,
despite having a relatively greater initial sulfonic acid density.
Therefore, if these catalysts were reused, they can be expected to
have comparable activities. In relation to this, if the catalysts syn-
thesized at 150
C were to be reused, SAC-SCB-04-150 would have
the lowest activity in the group. Thus in view of a good balance in
conversion, stability, and activity, SAC-SCB-08-150 is the most
promising among the catalysts synthesized.
3.4. Reusability of SAC-SCB
As for the reusability study, a suitable candidate among the syn-
thesized catalysts was chosen for use in 5 successive esterification
cycles. In terms of catalytic activity, the catalysts synthesized at 150
and 200
C showed potential (Fig. 8b). However, in view of stability,
SAC-SCB-6-150 and SAC-SCB-8-150 were found to be superior, as the
rest of the catalysts considered were found to have relatively greater
reduction in sulfonic acid densities after one cycle of use (Fig. 9).
Fig. 9. Sulfonic acid density of unused and spent SAC-SCB.
519
Furthermore, SAC-SCB-6-150 and SAC-SCB-8-150 have the advantage
with regard to catalyst preparation, owing to their relatively lower
synthesis energy requirement. Statistical tests would dictate that
there is no significant difference between SAC-SCB-6-150 and SAC-
SCB-8-150 in terms of activity (p > 0.05) or stability with reference
to reduction of sulfonic acid density (p > 0.05). Nevertheless, SAC-
SCB-8-150 was selected for the reusability study owing to its slight
advantage over SAC-SCB-6-150 in both aspects.
Prior to the reusability test, SAC-SCB-08-150 was used in the
esterification of oleic acid with methanol over a period of 24 h to
determine the highest possible conversion achievable at the
selected esterifiction conditions (Fig. 10a). As could be observed in
Fig. 10a, the conversion increased with increasing esterification
time, having a conversion of 85% after 24 h. Although much higher
conversions could have been achieved, prolonged reaction times
beyond 24 h may not be practical for industrial applications.
Nevertheless, these results provide an idea on the stability of the
catalyst over a 24-h reaction period. In Fig. 10b, the sulfur density
only slightly decreased from 0.59 to 0.56 mmol SO3H/g SAC but
eventually reached a stable sulfur density of ~0.53 mmol SO3H/g
SAC. These results further suggest the importance of washing to
ensure no loosely bound sulfur-containing moieties are present in
the final catalyst to be used.
For stability, in view of catalyst reusability, each esterification
cycle was conducted for 24 h (Fig. 11a). Initially, conversion
decreased by ~17% after the first cycle. However, the reduction in
performance diminished in each successive cycle. After the third
cycle, the catalytic performance of SAC-SCB-08-150 remained
essentially stable at ~67% (p > 0.05), resulting to a 76.5% retention of
the original performance. Meanwhile, Savaliya et al. reported a
retention of ~87% of the original performance of SAC-SCB synthe-
sized through SCS, after 4 cycles of use [23]. The relatively higher
stability of the catalyst reported in literature may be due the
employed reactivation step, whereby the recovered catalysts were
washed with methylene dichloride and dried at 80
C for 10 h prior
to use in the subsequent cycle [23]. Deactivation of the catalyst may
be caused by several factors which includes catalyst poisoning,
whereby sulfonate esters are formed, rendering the available sulfur
sites inactive. This potentially occurs by esterification of the cata-
lyst's sulfonic acid groups in an alcohol rich environment, such as
that of esterification oleic acid with methanol [32]. Another pos-
sibility would be the clogging of pores by the reactants or products,
520 K.P. Flores et al. / Renewable Energy 130 (2019) 510e523

Fig. 10. (a) Performance and (b) sulfonic acid density of SAC-SCB-08-150 over a 24-h esterification period.

Fig. 11. (a) Performance and (b) sulfonic acid density of SAC-SCB-08-150 in successive 24-h esterification cycles.

resulting in hindered access to the active sites. Although washing of
the catalyst prior to its reuse was carried out, there was no means of
determining the adequacy of the washing.
A similar behavior to the catalytic performance was observed in
the sulfonic acid density of SAC-SCB-8-150 (Fig. 10b). The sulfonic
acid density, initially at 0.59 mmol/g, remained unchanged
(p > 0.05) at ~0.51 mmol/g after the third cycle. Ultimately, 86% of
the initial sulfonic acid density of SAC-SCB-8-150 was retained after
5 cycles of use. This is in agreement with the results of the study by
Mo et al. [25], whereby ~80% of the initial active sites of a sulfonated
D-glucose pre-washed with methanol was retained after 8 cycles of
use. Apart from washing with water after catalyst synthesis,
washing with methanol may also be necessary to ensure complete
removal of loosely attached active sites.
3.5. Comparison of SAC-SCB with other carbon-based solid acid
catalysts
Summarized in Table 2 are some of the biomass-derived solid
acid catalysts reported in literature. Among those listed, the highest
specific catalytic activity (AC) and sulfonic acid activity (ASO3H) was
exhibited by the SAC derived from waste Jatropha curcas seed shells.
This was followed by the catalyst synthesized from spent coffee
grounds (SCG) and the bamboo-derived catalyst, which had rela-
tively high activities owing to their use in short reaction periods of
2e4 h. The relatively greater activity exhibited by the SAC derived
from waste Jatropha curcas seed shells was also due to short reac-
tion time of 2 h, in addition to the minimal amount of the catalyst
used (0.005 w/w), and its relatively high sulfonic acid density of
2.0 mmol/g. However, as what has been observed in this study, a
high sulfonic acid density may not always result to a high sulfonic
acid activity. On one hand, The SAC synthesized from corn straw
had a relatively lower sulfonic acid activity of 5.08 mmol/mmol$h
despite having the highest sulfonic acid density of 2.44 mmol/g. On
the other hand, SAC from SCG had the second highest sulfonic acid
activity of 55.09 mmol/mmol$h despite having the lowest sulfonic
acid density of 0.45 mmol/g. These results further support the idea
that the catalytic activity of a SAC is also greatly influenced by other
factors such as catalyst morphology (surface area, pore size, and
particle size) and availability of active sites. Unfortunately, this
 K.P. Flores et al. / Renewable Energy 130 (2019) 510e523 521

Table 2
Solid acid catalysts derived from agricultural waste residues.

Catalyst Source SCc T (
C)/t (h) ECd T (
C)/t Substrate Alcohol Cycles/ XFFA (%)g ACi ASO3Hj Ref
(h) Washing

Sugarcane bagasse rSO3Ha: 1.06 racidb: 3.69 Ck: 375/0.5 Sl: 80/6 Oleic acid w/we: Methanol n/nf: 8 n-hexane 95 (85.5)h 11.21 10.57 [14]
150/15 0.05 10
Waste Jatropha curcas seed shells rSO3H: 2.0 C: 350/5 S: 100/8 80/2 Oleic acid w/w: Methanol n/n: 4 methanol 95.7 338.76 169.38 [13]
racid: n.s. 0.005 1 (95.1)
Corn Straw rSO3H: 2.44 racid: 2.64 C: 300/1 S: 80/4 60/4 Oleic Acid w/w: 0.07 Methanol n/n: e 98 12.39 5.08 [10]
7
Bamboo rSO3H: 1.82 racid: 1.74 C: 350/2 S: 105/2 90/2 Oleic acid w/w: 0.06 Ethanol n/n: 7 5 ethanol 98.4 29.03 15.95 [11]
(27.8)
Oil Palm Trunk rSO3H: 1.41 racid: 5.31 C: 400/4 S: 150/15 65/5 Palmitic Acid w/w: Methanol n/n: 6 n-hexane 88.8 7.70 5.46 [8]
0.09 18 (~79.5)
Spent coffee grounds rSO3H: 0.45 racid: 0.99 C: 600/4 S: 200/18 60/4 Caprylic Acid w/w: Methanol n/n: 5 methanol 71.5 24.79 55.09 [12]
0.05 3 (>20)
Sugarcane bagasse rSO3H: 0.59 racid: 0.79 S: 150/8 45 ± 5/24 Oleic acid w/w: 0.10 Methanol n/n: 5 n-hexane 85.1 1.26 2.14 This
(soxhlet)m 20 (66.6) study
Sugarcane bagasse rSO3H: 0.70 racid: 1.12 S: 150/8 45 ± 5/6 Oleic acid w/w: 0.10 Methanol n/n: e 89.1 5.26 7.49
20
a
SO3H density as mmol eSO3H per g catalyst.
b
Total acid density as mmol acid/g catalyst.
c
Catalyst synthesis conditions (temperature and time).
d
Esterification temperature and time.
e
Catalyst loading as g catalyst per g oil/substrate.
f
Alcohol to oil ratio as mol alcohol per mol oil.
g
Percent FFA conversion.
h
FFA conversion after several cycles of use.
i
Catalytic activity as mmol FAME per g catalyst per hour.
j
Sulfonic acid activity as mmol FAME per mmol SO3H per hour.
k
Carbonization temperature and time.
l
Sulfonation temperature and time.
m
Catalyst is exhaustively washed using Soxhlet apparatus.

could not be looked into, as the relevant data are not reported in
most of the studies. For this reason, and in addition to the varying
reaction parameters, an objective comparison between the cata-
lysts with reference to performance and activity is difficult.
In view of catalyst reusability, the SAC derived from Jatropha
curcas seed shells exhibited the highest stability, being able to
retain almost all of its initial performance after 4 cycles of use. This
was followed by the SCB and oil palm trunk-derived catalysts,
which retained ~90% of their original performance after 8 and 6
cycles of use, respectively. Meanwhile, SAC-SCB-08-150 offered
better stability (78% retention) as compared to both SCG and
bamboo-derived catalysts, which retained only ~28% of their initial
performance after 5 cycles.
Although SAC-SCB-08-150 exhibited the lowest catalytic activ-
ity, its main advantage is on the required synthesis conditions.
Other biomass-derived catalysts were prepared via the conven-
tional two-step approach of carbonization and subsequent sulfo-
nation, with total synthesis times ranging from 4 to 22 h and
energy-intensive conditions requiring a synthesis temperature of
up to 600
C. Meanwhile, SAC-SCB-08-150 can be prepared under a
milder and less energy-intensive process at 150
C for 8 h.
Biomass-derived SACs prepared through SCS are presented in
Table 3. The peanut shell-derived catalyst showed the highest
specific activity and sulfonic acid activity owing to its high sulfonic
acid density of 2.13 mmol/g, minimal amount of catalyst used (0.04
w/w), and a short reaction time of 3 h. However, the high activity
could also be due to the high esterification temperature of 85
C.
Meanwhile, SAC-SCB-08-150 was used in a 6-h esterification re-
action with the lowest temperature of 45 ± 5
C. Despite this, SAC-
SCB-08-150 (washed until neutral pH) exhibited higher sulfonic
acid activity (7.49 mmol/g$h) as compared to that of the SAC-SCB
reported in the study of Savaliya et al. [23] (6.92 mmol/g$h),
which was observed at a relatively higher reaction time and tem-
perature of 11 h and 65
C, respectively.
With regards to catalyst synthesis, the peanut shell-derived
catalyst had the advantage of requiring the lowest temperature of
85
C, while the catalyst derived from X. sorbifolia bunge hulls
required the least amount of preparation time. Meanwhile, SAC-
SCB-08-150 have the advantage over the SCB-derived and the
catalyst synthesized from red liquor solids with reference to both
synthesis time and temperature.
In view of catalyst reusability, the peanut shell-derived catalyst
offered the highest stability, being able to retain 97% of its original
performance even at the 6th cycle of reusing the catalyst. Although
SAC-SCB-08-150 exhibited lower performance, it had a relatively
higher retention (78%) as compared to the catalysts derived from
red liquor solids and X. sorbifolia, bunge hulls, which retained 2.35
and ~70% retention of initial performance, respectively. Further-
more, it should be noted that the stability test of SAC-SCB-08-150
was conducted at 24-h esterification cycles, which is higher than
all of the listed catalysts.
Overall, based on the results from this study, the catalyst pre-
pared from low-value biomass, sugarcane bagasse, possessed good
potential for biodiesel production, mainly owing to its good sta-
bility and relatively low synthesis requirements. Despite showing
relatively lower catalytic performance as compared to most of the
synthesized catalysts such as those form Jatropha curcas shells, the
local availability of sugarcane bagasse provides a practical advan-
tage. Thus, solid acid catalyst derived from sugarcane bagasse
would be more practical for biodiesel production in the local
context.
4. Conclusions
In this study, solid acid catalyst derived from sugarcane bagasse
(SAC-SCB) was prepared through simultaneous carbonization-
sulfonation (SCS). In general, increasing the SCS temperature from
150 to 250
C resulted in a decrease in the catalytic performance. In
522 K.P. Flores et al. / Renewable Energy 130 (2019) 510e523

Table 3
Biomass-derived solid acid catalysts synthesized through simultaneous carbonization-sulfonation.

Catalyst Source SCSc T (
C)/t ECd T (
C)/t Substrate and Catalyst Alcohol Cycles/Washing XFFA (%)g ACi ASO3Hj Ref
(h) (h) Loading

Sugarcane bagasse rSO3Ha: 0.90 racidb: 180/10 65/11 Soapstock oil w/we: 0.05 Methanol n/nf: 4/Methylene 97.2 6.26 6.92 [23]
1.9 15 dichloride (84.3)h
Red Liquor Solids rSO3H: 1.15 racid: 1.52 200/12 65/4 Oleic acid w/w: 0.05 Methanol n/n: 3/Conc. H2SO4 85 (<2) 15.04 13.11 [32]
55
Bunge hulls (X. sorbifolia) rSO3H: 0.86 150/1 70/5 Soybean soapstock w/w: Methanol n/n: 4/n-Butanol 97.2 9.83 11.26 [33]
racid: 1.71 0.07 9 (~67.8)
Peanut Shell rSO3H: 2.13 racid: 3.53 85/3 85/3 Oleic acid w/w: 0.04 Methanol n/n: 6/- 98 (>95) 28.9 13.63 [34]
10
Distillers' Grain rSO3H: 0.89 racid: 1.89 20/1.4 117/n.s. Acetic acid w/w: 0.02 n-Butanol n/n: 5/Ethanol 97.5 e e [24]
1.5 (50.7)
Wheat Husk rSO3H: 0.30 racid: 0.76 90/1.5 65/3.5 Rice Bran Oil Fatty Acid w/w: Methanol n/n: e 81.3 () e e [35]
0.08 20
Coconut meal rSO3H: 0.28 racid: 3.38 100/1 65e70/8 Waste palm oil w/w: 0.05 Methanol n/n: 4/n-Hexane 92.7 1.55 3.48 [36]
12 (>80)
Sugarcane bagasse rSO3H: 0.59 racid: 150/8 45 ± 5/24 Oleic acid w/w: 0.10 Methanol n/n: 5/n-Hexane 85.1 1.26 2.14 This
0.79 (soxhlet)k 20 (66.6) study
Sugarcane bagasse rSO3H: 0.70 racid: 150/8 45 ± 5/6 Oleic acid w/w: 0.10 Methanol n/n: No Washing 89.1 5.26 7.49
1.12 20
a
eSO3H density as mmol eSO3H per g catalyst.
b
Total acid density as mmol acid/g catalyst.
c
Simultaneous carbonization and sulfonation temperature and time.
d
Esterification temperature and time.
e
Catalyst loading as g catalyst per g oil/substrate.
f
Alcohol to oil ratio as mol alcohol per mol oil.
g
Percent FFA conversion.
h
FFA conversion after several cycles of use.
i
Catalytic activity as mmol FAME per g catalyst per hour.
j
Sulfonic acid activity as mmol FAME per mmol SO3H per hour.
k
Catalyst is exhaustively washed using Soxhlet apparatus.

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