Renewable Energy 152 (2020) 320e330

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

Direct sulfonation of cacao shell to synthesize a solid acid catalyst for

the esterification of oleic acid with methanol
Czarina M. Mendaros a, Alchris W. Go b, *, Winston Jose T. Nietes a,
Babe Eden Joy O. Gollem a, Luis K. Cabatingan a, **
a
Department of Chemical Engineering, University of San Carlos, Talamban, Cebu City, 6000, Philippines
b
Graduate Institute of Applied Science and Technology, National Taiwan University of Science and Technology, Keelung Road, Taipei City, 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 (SAC) was synthesized via direct treatment of cacao shells (CS) with concentrated
Received 11 July 2019 sulfuric acid at varying temperature (80, 100, 120
C) and time (4, 6, 8 h) settings. The synthesized
Received in revised form catalysts were found to have sulfonic acid density ranging from 0.6326 to 0.8500 mmol SO3H/g dry CS-
6 December 2019
SAC and total acid density from 6.0509 to 7.1165 mmol Hþ/g dry CS-SAC. The catalytic activity is
Accepted 15 January 2020
Available online 20 January 2020
dependent on the sulfonic acid density of the catalyst. Catalyst synthesized at 120
C for 6 h showed the
highest sulfonic acid density (0.85 mmol SO3H/g catalyst) corresponding to highest catalytic activity
(5.73 mmol OA converted/mmol SO3H$h) and a conversion of ~39% after a fixed reaction time of 4 h and
Keywords:
Acid density
carried out at 65
C. Conversions of up to 76% could be achieved after 24 h. The catalyst was reused for 4
Cacao shell cycles and was able to retain 78% of its catalytic activity from the 2nd to the 4th cycle. Direct sulfonation
Direct sulfonation may be an alternative to conventional synthesis process.
Esterification © 2020 Elsevier Ltd. All rights reserved.
Solid acid catalyst

1. Introduction leading to its deactivation and difficulty in product separation. Pre-

Biodiesel is a series of mono-alkyl esters of long-chain fatty
acids commonly produced via transesterification of refined oils
using a base catalyst [1e3] and it is used as an alternative to petro-
diesel. Biodiesel production via base-catalyzed transesterification
have been studied in much detail in the past year including detailed
investigation on mass transfer limitations of the pseudo-
homogeneous reaction involved [4], reactor configuration [5] and
scaling up from laboratory experiments to industrial scale [6].
However, biodiesel is more expensive than petro-diesel owing to
the feedstock used, which accounts for 70e90% of the total pro-
duction cost [7]. As a way of addressing this problem, low-quality
oils such as waste cooking oil (WCO) are considered. The main
bottleneck with the use of low-quality oils is its high free fatty acid
(FFA) content (0.5e20 %w/w), which exceeds the limit (<0.5 %w/w
of the oil) [7e9] when using base catalyst. High FFA content results
in the consumption of the base catalyst due to saponification,
* Corresponding author.
** Corresponding author.
E-mail addresses: awgo@mail.ntust.edu.tw (A.W. Go), lkcabatingan@usc.edu.ph
(L.K. Cabatingan).
treatment via esterification using acid catalyst, commonly sulfuric
acid (H2SO4), is required to reduce the FFA content to below 0.5 %w/
w prior to base-catalyzed transesterification [10]. Unfortunately,
the use of mineral acids like H2SO4 have its drawbacks, which
includes corrosion and generation of by products during neutrali-
zation [6]. For ease of handling of the acid during and after the
pre-treatment step, solid acid catalysts (SACs) are considered as
alternatives to homogeneous liquid acid catalysts. Solid acid cata-
lysts can be prepared by attaching active functional groups to a
solid support via physical or chemical method forming active sites
which catalyzes the desired reaction. Solid acid catalysts can be
zeolite-non-renewable polymeric- or renewable carbon-based [11].
Addressing the drawbacks of zeolite- and non-renewable poly-
meric-based SACs owing to their non-renewable nature are carbon-
based SACs derived from renewable sources whose supports are
sourced from widely available renewable materials and allow for
covalent bonding of acid functional groups to the carbon support
[12,13].
Carbon-based SACs are synthesized by subjecting the carbona-
ceous material to pyrolysis to produce the carbon (catalyst support)
which is then subjected to sulfonation for the attachment of the
active sites. Materials that have been studied as sources of carbon
supports for SACs include: refined carbohydrates (glucose, sucrose

https://doi.org/10.1016/j.renene.2020.01.066
0960-1481/© 2020 Elsevier Ltd. All rights reserved.
 C.M. Mendaros et al. / Renewable Energy 152 (2020) 320e330
and starch) [14e16]; lignocellulosic biomass such as peanut hull
[17], wood [17] and Terminalia catappa [18]; agricultural and agro-
industrial biomass residues such as sugarcane bagasse [19], spent
coffee residue [20], wood chip [17] and coconut shell [21]. Refined
carbohydrates are derived from a parent biomass, requiring pre-
treatment and purification steps adding to the total cost of cata-
lyst synthesis. While lignocellulosic biomass are widely available,
these are utilized for several other applications (e.g. food, agricul-
ture, energy), thus, competing with different industries. As an
alternative, agricultural and agro-industrial biomass residues are
looked into. Synthesis of carbon-based SAC can be done by a two-
step carbonization-sulfonation process or by direct sulfonation.
Carbonization is a thermal decomposition technique, conducted at
a temperature range of 300e600
C for 0.5e4 h [20,22e25]. This is
done to break the chemical bonds of the material, rearranging its
molecules to form a highly cross-linked, multi-ringed aromatic
structure where functional groups, namely, carboxylic acid
(eCOOH) and phenolic (eOH) are produced, then sulfonic (eSO3H)
acid is easily attached via sulfonation using concentrated sulfuric
acid (H2SO4) as an activating agent [17]. Direct sulfonation is done
at a temperature range of 20e180
C for 1e10 h wherein simulta-
neous carbonization and sulfonation happens, using H2SO4 which
acts as a dehydrating and sulfonating agent [26e30]. This requires
lesser energy compared to that of the two-step carbonization-sul-
fonation process considering that both employs similar conditions
during sulfonation but direct sulfonation avoids the need to carry
out carbonization as a pretreatment process.
Cacao shell is an example of an agro-industrial biomass residue
generated from cocoa bean processing for chocolate production. In
the Philippines, ~7000 metric tons (MT) of cacao shells are gener-
ated annually [31]. Due to its high carbon content (~50 %w/w),
researches conducted using cacao shell involved conversion to
activated carbon which were then used as adsorbent [32e34]. An
important factor to consider in assessing the potential of a material
as solid acid catalyst support is its fixed carbon (FC) content. This
component is the remaining carbon of the material after carbon-
ization. Cacao shells have a fixed carbon content of ~24.46 %w/w
[22], which is comparable to other residues (11.71e35.2 %w/w)
used as raw material for synthesis of solid acid catalysts [35e43]. A
study on the synthesis of solid acid catalyst from cacao shell using
two-step carbonization-sulfonation has been done by Bureros et al.
[22], with resulting catalysts that are comparable with other
carbon-based SACs in terms of performance and reusability. Syn-
thesis of CS-SAC via direct sulfonation was carried out in this study
to determine whether this method will lead to similar performance
as the CS-SAC synthesized using two-step carbonization-sulfona-
tion. This study aimed in particular to investigate the effects of
direct sulfonation temperature (80e120
C) and time (4e6 h) on
the catalyst yield, sulfur content ratios, acid densities and catalytic
activity of the CS-SAC. Acid densities of the spent catalysts were
determined to assess the stability of the synthesized catalysts. The
reusability of the CS-SAC with the highest observed catalytic ac-
tivity was also studied.
2. Materials and methods
Cacao shells were sourced from Catmon, Cebu, Philippines from
a small-scale cacao bean processor to produce chocolate tablets
known locally as tablea. Chemical reagents as supplied by (a)
Scharlau (Spain) brand: ethanol (99.8 %v⁄v), methanol (99.8 %v⁄v),
n-hexane (96 %v⁄v), magnesium oxide (99.9 %w⁄w), silver nitrate,
phenolphthalein indicator (98 %v⁄v), sodium chloride (99.9%w/w),
anhydrous sodium carbonate (99.8 %w⁄w), sodium hydroxide pel-
lets (97 %w⁄w); (b) Merck (Germany) brand: sulfuric acid (98 %v⁄v),
potassium hydroxide (85 %w⁄w); (c) Ajax (Australia) brand:
321
hydrochloric acid (36 %w⁄w), barium chloride dehydrate (99 %w⁄w),
oleic acid (99 %w⁄w), and potassium hydrogen phthalate
(99.8e110.2 %w/w).
2.1. Collection and storage of cacao shell
Three batches of cacao shells as received were sorted and
representative samples were analyzed for moisture content.
Because the moisture content for all batches were found to be less
than 10 %w/w, the shells were directly milled using a Wiley mill
(Model 4, Thomas Scientific, USA) fitted with 2000 mm aperture
screen. The milled cacao shells were then stored in tightly sealed
plastic containers until further use.
2.2. Characterization of cacao shell
Milled cacao shells were subjected to sieve analysis for deter-
mination of the average particle size. The procedure for proximate
analysis of cacao shells was adopted from ASTM method D1762-84
(Reapproved 2007) [44] for chemical analysis of wood charcoal.
Milled cacao shells were characterized for its total sulfur content,
total acid density (rTAD ), carboxylic acid (rCOOH ) and phenolic acid
(rOH ) density. Total sulfur content analysis was done through the
Eschka method, as described in ASTM D3177-02 [45]. Sulfonic acid
density (rSO3H ) was then estimated from the total sulfur content.
Total acid density was determined by back-titration method as
described by the study of Goertzen et al. [46,47]. The strong acid
density (rSAD ) by acid-base titration using the procedure adopted
from the study of Wang et al. [48], after allowing the exchange of
hydronium ions with 2 N NaCl solution. The phenolic (eOH), and
carboxylic acid (eCOOH) density were determined by difference of
the other know acid density determined. The same procedures
were adopted in the characterization of the produced CS-SAC.
2.3. Simultaneous carbonization-sulfonation of dried cacao shells
The simultaneous carbonization-sulfonation of cacao shells was
carried out based from the studies by Dholakiya et al. [26] and
Flores et al. [49]. Each experimental run was carried out in dupli-
cates. The synthesis was done in a Kjeldhal digester (DK-8S Heating
Digester, VELP 241 Scientifica). Approximately 3.5 g of powdered
cacao shells was weighed and transferred into a Kjeldhal digestion
tube and was mixed with the sulfonating agent, 70 mL of 98%v/v
H2SO4, ensuring that the sample was fully immersed to promote
homogeneity. Eight tubes containing the cacao shell-acid mixture
were mounted in the digester and heated at a rate of 10
C/min to
the desired synthesis temperature (80
C, 100
C, 120
C), then was
maintained for a particular time (4 h, 6 h, 8 h). After simultaneous
carbonization and sulfonation, the resulting mixture was cooled to
room temperature. The contents of the tubes were transferred into
a 3-L beaker immersed in a water bath. The reaction mixture was
diluted with 1 L of distilled water and filtered to recover the solids.
To remove the unbound acids, the solids were continuously washed
with hot distilled water (90
C) and recovered via centrifugation
until the pH of the washing solution was near the pH of the distilled
water used for washing. Three to four drops of 0.48 M BaCl2 was
added to the washing solution to qualitatively test the presence of
sulfate ions (eSO24 ).
The obtained solids were partially dried in an oven set at 80
C
approximately 10 h, to ease the later handling of the solids. A
determined amount of the incompletely dried solids were added in
a pre-weighed improvised extraction thimble (Whatman No. 42).
To leach out the remaining loosely bound sulfate ions, the catalyst
was further washed with distilled water in a Soxhlet extractor
under continuous reflux (~100
C) for 12 h. The catalyst contained
322 C.M. Mendaros et al. / Renewable Energy 152 (2020) 320e330

in the improvised thimbles were then dried in an oven maintained titration, C A (mol/L) is the concentration of the titrant (NaOH so-
at 80
C until constant weight. The catalyst yield (YieldCSSAC ) or lution), msample (g) is the mass of the oil sample, and MM OA
the amount of CS-SAC produced per unit mass of cacao shell (CS) (282.5 g/mol) is the molar mass of OA. The OA conversion (xFFA )
was determined using Equation (1), was then calculated using Equation (3),
P   w C  
mCSSAC; total ðmtþSAC  mt Þ g CS  SAC OA0  C OA1 g oleic acid reacted
YieldCSSAC ¼ ¼ ¼ X OA ¼ ¼ (3)
mCS ð1  MÞ mCS ð1  MÞ g dry CS w C OA0 g initial oleic acid
(1)
where C OA0 and C OA1 are the acid values of the oil before and after
where mCSSAC; total (g) and mCS (g) are the total mass of the catalyst the methylation reaction, respectively.
obtained and the milled cacao shell used during synthesis, respec- The catalytic activity over a specified reaction time of 4 h was
tively, while M is the moisture content of the cacao shell used. then calculated using Equation (4) to Equation (6).
Moreover, mtþSAC and mt are the mass of the extraction thimbles " #
containing SC-SAC after the last drying process and the mass of the xFFA mOA mmolFFAconverted
catalyticactivity;A¼ MM ¼
g catalyst ,h
1000 mCSSAC t
thimble, respectively. The catalyst prepared under the same condi- OA

tion were accumulated and stored in a small airtight plastic

container for subsequent analysis and assay of acid density and
catalytic activity. The synthesized cacao shell-solid acid catalysts (CS-
SAC) were then designated as CS-SAC-TTT-t, to indicate the sulfo-
nation temperature (T) and time (t). As an example, CS-SAC-120-6 is
used to designate the catalyst synthesized at 120
C for 6 h.
2.4. Determination of catalytic activity
Esterification of oleic acid (OA) with methanol catalyzed using
the synthesized CS-SAC was done to determine the activity of the
catalyst. Approximately 42.86 g of OA was weighed in a 250-mL
screw capped flask. Using a graduated cylinder, 55.40 mL of
methanol was measured and added in the flask containing the OA.
This is equivalent to a methanol-to-OA molar ratio of 7:1. The flask
containing the mixture was closed then loaded to the incubator
shaker (Model-G25, New Brunswick Scientific Co. Inc, USA) set at
65
C and 200 rpm. Upon reaching the set temperature of the
system, the shaker was turned off and 3 g of the catalyst was loaded
to the flask. The reaction was allowed to proceed for 4 h. To stop the
reaction, the flasks were quenched in a cooling bath. The reaction
mixture was filtered using a Whatman No. 2 filter paper and
washed with methanol to recover the spent catalyst.
To recover the oil, the mixture obtained after esterification was
separated into two phases. Approximately 50 mL of n-hexane and
20 mL of 5 %w/w NaCl was then added to the reaction mixture in a
separatory funnel. The funnel containing the mixture was swirled
and allowed to settle until two distinct layers were formed. The
bottom layer was discarded and further washing with 5 %w/w NaCl,
of the remaining mixture in the funnel was done until the pH of the
bottom layer was close to neutral. The resulting oil-hexane mixture
after washing was weighed. Approximately 10 g aliquot was taken
from the oil-phase of the obtained mixture after washing and
placed in a pre-weighed evaporating dish. The samples were
heated in the oven at 65
C for 2 h to remove the n-hexane in the
mixture, then allowed to cool and weighed. Further heating and
weighing was done until less than 0.01 g difference of the samples
was obtained.
About 0.5 g of oil sample was weighed in a 125-mL Erlenmeyer
flask. A known volume (25 mL) of neutralized ethanol was trans-
ferred to the flask with the aid of a volumetric pipette. The oil-
ethanol mixture was then added with 3 drops of phenolphthalein
indicator and titrated against standardized 0.075 M ethanolic NaOH
solution until the endpoint. The OA content (C OA ) of the oil was
then determined using Equation (2).
 
V A  C A  MM OA g OA
C OA ¼ ¼ (2)
msample g oil sample
where V A (L) is the volume of the NaOH solution used in the
(4)
 
A mmol FFA converted
sulfonic acid activity; ASO3 H ¼ ¼
rSAD mmol  SO3 H ,h
(5)
 
A mmol FFA converted
total acid activity; AH þ ¼ ¼ (6)
rTAD mmol H þ ,h
2.5. Reusability of SC-SAC
Eight sets of reactant mixtures were loaded in the incubator
shaker to undergo esterification for 24 h to ensure that recycling or
reuse was done at the highest possible conversion within a
reasonable time. The catalyst with the highest catalytic activity was
used to catalyze the reaction. The same procedure was done for the
recovery of oil and spent catalyst as described previously. The
recovered catalysts were pooled then used for the next cycle. To
ensure sufficient amount of catalyst, two sets of reactant mixtures
were reduced for every succeeding cycle. The excess spent catalysts
were analyzed for its acid density. Percent reduction (% reduction)
of the catalytic activity with respect to the first cycle was deter-
mined using Equation (7),
Ancycle
% reduction ¼  100 % (7)
A1cycle
where Ancycle is the catalytic activity of the nth cycle and A1cycle is
the catalytic activity of the first cycle.
3. Results and discussion
The acquired raw cacao shells were milled and characterized in
terms of particle size, proximate components and acid site den-
sities. The milled cacao shells used in this study after milling had a
mean particle size of 93.15 ± 2.27 mm. The proximate composition
(7.40 ± 0.12 %Moisture, 66.78 ± 0.68 %VCM, 23.73 ± 0.56 %FC and
9.50 ± 0.31 %Ash on dry basis (db) of the cacao shells used in this
study is close to the range of values reported in literature
(9.09e9.45 %Moisture, 67.95e69.28 %VCM, 23.80e24.46 %FC, and
2.05e8.25 %Ash) for cacao shells [22,33,50].
In the synthesis of solid acid catalyst from biomass, an impor-
tant consideration is the fixed carbon (FC) content because it allows
the estimation of the amount of catalyst that can be produced. The
FC content of the cacao shell used in this study is close to that of
coconut shell (24.40 %w/w) [51], and within the range of values
(9.53e35.2 %w/w) of FC contents of the other biomass residues that
 C.M. Mendaros et al. / Renewable Energy 152 (2020) 320e330
were studied as raw material for the synthesis of solid acid catalysts
[35e43]. The sulfur content (0.13 ± 0.01 %w/w, db) of the milled CS
used in this study are the same with the values reported by Bureros
et al. [22], which was previously reported to be 0.13 ± 0.01 %w/w.
The presence of sulfur in the biomass indicates that part of the
sulfur making up the total sulfonic group in the synthesized solid
acid catalyst is to be accounted as originally present in the biomass.
Apart from the fixed carbon and sulfur contents, carbon-based
solid acid catalysts are routinely characterized for its acid den-
sities as these quantities affects their catalytic activity in the
esterification of oils. These acid sites, namely the sites containing
the phenolic (eOH), carboxylic (-COOH) and sulfonic (-SO3H)
functional groups, are thought to be formed from the partial
carbonization of the biomass and the oxidation of aliphatic groups
during the roasting of the cacao beans [52]. Total acid density is the
sum of the three acid sites mentioned. The total acid density
(0.6976 mmol Hþ/g dry CS) of the raw CS used in this study is
considerably smaller in contrast to the value reported by Bureros
et al. [22], which is 3.23 mmol Hþ/g dry CS and much lower when
compared to CS-SAC from a two-step synthesis process, which had
4.56 mmol Hþ/g dry CS-SAC and 1.48 mmol SO3H/g dry CS-SAC.
Discrepancies in the raw CS may be attributed to the difference in
origin of the raw material and the manner by which the cacao shells
were roasted. Corresponding acid densities of the raw CS in this
study are considerably low, thus, needing a sulfonation step to in-
crease the sulfur content as well as the acid densities of the
biomass.
3.1. Effect of sulfonation temperature and time on catalyst yield and
extent of sulfonation
The highest catalyst yield of ~0.73 g CS-SAC/g dry CS is obtained
after direct sulfonation at 80
C and 4 h, while the lowest yield of
~0.56 g CS-SAC/g dry CS at 120
C and 8 h. There is a decrease in the
catalyst yield as sulfonation temperature is increased from 80
C to
100
C, but further increase in the temperature to 120
C, leads to
no significant change in the catalyst yield. At a sulfonation time of
6 h, an 11% decrease is observed from 80
C to 100
C and further
increasing the temperature to 120
C only leads to a 5% decrease in
the catalyst yield. At 8 h, an increase in temperature from 80
C to
100
C then to 120
C both resulted to a 5% decrease in the catalyst
yield. Based on the results obtained, sulfonation temperature has a
significant effect (p ¼ 0.0164) on the catalyst yield, while sulfona-
tion time does not have influence (p ¼ 0.1565).
Fig. 1. Sulfur content ratio (extent of sulfonation) of CS-SAC after direct sulfonation at various temperature and time.
323
In comparison to the study done by Bureros et al. [22], which
employed two-step carbonization-sulfonation to synthesize CS-
SAC-120-6, the catalyst yield obtained in this study is ~40%
higher. This is owing to the omission of the separate carbonization
step, where the greatest loss in mass is usually observed. With the
higher catalyst yield, direct sulfonation may be a more favorable
and cost-effective synthesis method because of the reduced pro-
cessing step, and is a less energy intensive process. However,
further studies may have to be conducted to reduce the required
sulfuric acid during direct sulfonation as it would require 27e35 mL
of sulfuric acid for each gram of catalyst produced as compared to
the conventional 2-step process, where 25 mL per gram of catalyst
are required.
Aside from the catalyst yield, the extent of sulfonation (quan-
tified as the ratio of the sulfur content of the catalyst and the raw
cacao shells) is an important parameter in evaluating the effec-
tiveness of the synthesis step. The extent of successful incorpora-
tion of the eSO3H to the biomass as a function of sulfonation
temperature and time is depicted in Fig. 1.
The sulfur content ratio pertains to the number of times the
sulfur content of cacao shell is increased by thermochemical
treatment, in this case, direct sulfonation. Relative to the sulfur
content (0.13 %w/w) of raw cacao shell, as much as 21 fold increase
in the sulfur content is obtained after direct sulfonation using
H2SO4. This is proof of the successful incorporation of the sulfonic
acid groups onto the surface of the carbon support during sulfo-
nation. Analysis of variance indicated that within the set sulfona-
tion temperature and time investigated, no significant difference
(p ¼ 0.06 and p ¼ 0.23, respectively) on the resulting sulfur content
ratio of the CS-SAC produced was observed. This is in agreement
with the findings of the work done by Bureros et al. [22] wherein
there is no significant difference on the total amount of sulfur
attached to the CS-SAC after sulfonation, considering that both
studies have the same sulfonation temperature and time ranges.
The CS-SAC synthesized at various synthesis temperature (80, 100,
120
C) and time (4, 6, 8 h) has an average sulfur content ratio of
19.85.
3.2. Characteristics of CS-SAC as a function of sulfonation
temperature and time
As mentioned in the previous section, fixed carbon content is an
important characteristic of a material to determine its potential as a
raw material to serve as catalyst support. Proximate analysis was
324 C.M. Mendaros et al. / Renewable Energy 152 (2020) 320e330
Fig. 2. Proximate contents of CS-SAC synthesized at varying sulfonation temperature (80, 100, 120
C) and time (4, 6, 8 h) at a sulfuric acid-to-cacao shell ratio of 20.00 mL/g.
done on the catalysts synthesized at various direct sulfonation
temperature and time. Moisture content of the synthesized CS-
SACs is at ~0.09 ± 0.04 g moisture/g dry CS-SAC. As could be
observed from the results presented in Fig. 2, the volatile matter of
the CS-SACs is at ~0.50 g VM/g dry CS-SAC excluding the CS-SAC-
080-4 (VM ¼ 0.5350 g VM/g dry CS-SAC). Apart from the CS-SAC-
080-6 with an ash content of 0.0462, the rest of the CS-SACs
compose of ~0.01 g ash/g dry CS-SAC. As the CS was subjected to
sulfonation, the FC content of the catalyst increased. This supports
the idea that during carbonization and sulfonation, the decrease in
mass of the synthesized catalyst was due to the removal of some of
the volatile components and partial dissolution of the ash leaving
behind volatiles which would require higher temperatures to
volatilize and acid insoluble ashes. The CS-SAC-120-6 had the
highest fixed carbon content (49.83%) which is close to the results
reported in the studies of Ahmad et al. (~43.2%) [53] and Bureros
et al. (49.91%) [22].
Solid acid catalysts are assessed for its activity and stability. As
mentioned previously, the presence of the eSO3H groups as well as
the weak carboxylic (eCOOH) and phenolic acid groups (eOH) on
the synthesized catalysts were determined since catalytic activity
are often associated with acid density [54]. Morphological changes,
volatilization, oxidation, thermal decomposition and degradation
of the biomass occur during simultaneous carbonization and sul-
fonation, which influences the incorporation of the acid site [49].
The determined acid densities for the synthesized catalyst are
shown in Fig. 3. During catalyst synthesis, partial carbonization of
the biomass leads to depolymerization and formation of small
polycyclic aromatic carbon sheets with phenolic groups. Sulfona-
tion with H2SO4 takes place wherein sulfonic acid is covalently
bonded to the polycyclic aromatic carbon sheets as evidenced by
the increase in the sulfur content of the carbonaceous material after
synthesis [13]. In view of the effects of synthesis condition on the
sulfonic acid density (Fig. 3a) increase in temperature from 80 to
120
C and synthesis time of 4e8 h are found to have insignificant
influence as have been previously discussed in view of the sulfur
content ratio. This is consistent with the finding of Kumar et al. [29]
wherein the direct sulfonation time of over 1.5 h in the synthesis of
wheat husked-derived SAC did not result in significant increase of
the sulfonic acid sites. The highest sulfonic acid density obtained
with CS-SAC-120-6 with 0.85 mmol SO3H/g dry CS-SAC.
After the sulfonation process, other acid sites were also
observed apart from the sulfonic sites. Density of carboxylic acid
sites (eCOOH) of the synthesized catalysts increased when the
temperature was increased from 80
C to 120
C. High phenolic
hydroxyl functional groups were also noted from the synthesized
catalyst with values ranging from 4.8111 to 5.6708 mmol Hþ/g dry
CS-SAC. These could have resulted owing to the breakdown or
hydrolysis of the lignin network and carbohydrates. However, in
view of the total acid density no significant difference (p ¼ 0.10)
could be observed among the CS-SAC synthesized at the tempera-
tures and time investigated. Nevertheless, relatively higher total
acid densities (6.8291e7.1165 mmol Hþ/g dry CS-SAC) were ob-
tained with CS-SAC-120. These findings are comparable to that of
Suganuma et al. [55] who determine a phenolic acid density of
5.6 mmol Hþ/g catalyst and a total acid density of 7.5 mmol Hþ/g
catalyst from a cellulose-derived solid acid catalyst.
3.3. Catalytic activity of synthesize CS-SAC
Among the three acid moieties, eSO3H is the main functional
group in a SAC responsible in catalyzing the desired reaction. In
Fig. 4a are shown the catalytic activities of the synthesized CS-SACs.
A positive correlation (r ¼ 0.6899) was observed between the sul-
fonic acid density and amount of OA converted. The highest sulfonic
acid activity was ~5.73 mmol OA converted/mmol SO3H$h using the
CS-SAC-12-6, which also has the highest sulfonic acid density.
Other functional groups (eCOOH and eOH) help improve the
catalyst performance. However, no strong correlation could be
observed between the weak functional groups, eCOOH (r ¼ 0.1614)
and eOH (r ¼ 0.0775), and the amount of OA converted.
In view of conversion during the esterification of OA with
methanol, using CS-SAC-80, the OA conversion was observed to be
around ~0.32e0.33 g OA converted/g initial OA. Consequently, with
CS-SAC-100 the conversion was around ~0.26e~0.30 g OA con-
verted/g initial OA. The low OA conversion despite the high total
acid density of the catalyst can be attributed to the significant
amount of weak acid densities attached to the catalyst which is
estimated to be around 4.3780e7.7633 mmol Hþ/g dry CS-SAC. The
presence of the eOH and eCOOH functional groups in over-
abundance can attract water molecules (inherent or reaction by-
product), which could lead to the formation of a water layer on
the surface of the catalyst. The presence of such water layer has
previously been found to decrease the accessibility of the FFA [25]
or may have induced and favored the reverse reaction. At a fixed
reaction time of 4 h, the highest OA conversion was recorded to be
about ~0.39 g OA converted/g initial OA for CS-SAC-120-6.
 C.M. Mendaros et al. / Renewable Energy 152 (2020) 320e330 325

Fig. 3. (a) Sulfonic, (b) Carboxylic, (c) Phenolic, and (d) Total acid density of CS-SAC synthesized under various temperature and time (temperature: 80, 100, 120
C; time: 4, 6, 8 h).

Fig. 4. Effect of sulfonation temperature (80, 100, 120
C) and time (4, 6, 8 h) at a sulfuric acid-to-cacao shell ratio of 20 mL/g on the activity of CS-SAC and percent OA conversion.

3.4. Characteristics of spent catalysts as a function of sulfonation
temperature and time
It can be inferred from the results presented so far that the
catalytic activity of CS-SAC is highly attributed to its sulfonic acid
functional groups [29,56]. Though conversion and catalytic activity
are response parameters to consider in assessing the performance
of the catalyst, the stability of the catalyst must also be considered.
The spent catalysts were characterized for its sulfonic acid density
after its use in the esterification of OA. The results are presented in
Fig. 5.
The stability of the catalyst is as important as its activity since it
determines the length of time the catalyst can be used at its
designed activity before subjected to regeneration or substitution.
It can be observed that the sulfonic acid density of all the CS-SAC
decreased after their use in catalyzing an esterification reaction.
The decrease in sulfonic acid density may be attributed to the
leaching of the components part of the solid matrix where the
active sites are attached. After the esterification reaction, washing
the catalyst with methanol might have further removed the com-
ponents of the catalyst matrix where eSO3H groups are attached. In
a study by Mo et al. [57], deactivation of sulfonated glucose-based
326 C.M. Mendaros et al. / Renewable Energy 152 (2020) 320e330
solid acid catalyst is attributed to the leaching of sulfonic acid
groups due to washing with methanol. The high polarity and hy-
drophilic characteristics of methanol entails great affinity to the
loosely bound sulfonic groups and stabilized by hydrogen bonding
or dissolving non-water soluble components of the matrix where
the active sites are attached. Thus, the type of solvent used in
catalyst washing has an influence on the decrease in active sites.
Leaching of sulfonic acid can also be caused by the changes in
morphology of the catalyst. During the esterification reaction, the
catalyst might have partially collapsed along with the attached
sulfonic groups due to continuous shaking of the reaction mixture
[58]. For sulfonated solid acid catalysts, leaching of sulfonic acid
groups results to poor catalytic activity and stability making it
uneconomical to use in biodiesel production.
It can be observed that although catalysts synthesized at
different temperatures with the same reaction time have compa-
rable sulfonic acid densities, reduction of sulfonic acid density in-
creases as the temperature is lowered. For instance, the percent
reduction of sulfonic acid density of CS-SAC-080-6 is 39.31% while
for the CS-SAC-120-6 only has 5.99%. At lower synthesis tempera-
ture, soft aggregate which are mainly small polycyclic aromatic
carbon moieties with sulfonic groups are produced, these are easily
removed or leached from the solid matrix when used as catalyst
during esterification reactions [59]. Among the catalysts, CS-SAC-
120-6 had the highest initial acid density (0.85 mmol SO3H/g CS)
and the least sulfonic acid reduction (5.99%) suggesting that it has
the most stable sulfonic acid groups. Influence of sulfonation
temperature was not significant (p ¼ 0.2268) when compared to
time (p ¼ 0.0584), however, interaction between the temperature
and time was significantly (p < 0.0001) affected the stability of the
sulfonic acid sites of the synthesized CS-SACs.
Fig. 5. Sulfonic acid density (a) and weak acid density (b) of CS-SAC synthesized under various temperature and time (temperature: 80, 100, 120
C; time: 4, 6, 8 h) and sulfonic acid
density (c) and weak acid density (d) of spent CS-SAC recovered after esterification.
For weak acid density (Fig. 5b), it decreased after esterification.
It can be observed that the decrease in eSO3H functional groups
(Fig. 5a and c) is greater than the reduction in weak acid density
with the greatest recorded to be only about 32% (Fig. 5b and d)
relative to that of sulfonic acid density which is estimated to be
about 84%. These data suggest that more eSO3H were removed
from the catalyst surface during the esterification reaction than the
other functional groups (eCOOH and eOH). The catalyst CS-SAC-
120-6 exhibited the least reduction in total acid density with only
a ~2.4% decrease. In terms of weak acid density, CS-SAC-120-6 and
CS-SAC-120-8 have small decrease after esterification reaction with
percent reduction in the range of 1.8e2.0%. Both the sulfonation
temperature and time have significant effect (p ¼ < 0.0001) on the
total and weak acid density retained in the spent CS-SACs.
3.5. Reusability of SC-SAC
The CS-SAC-120-6 showed the highest catalytic activity and
better retention of sulfonic sites, thus, it is used for subsequent
reusability test. To assess the stability of the CS-SAC, OA conversion
was determined over four cycles. As shown in Fig. 6a, a decrease of
the OA conversion from ~0.77 to 0.60 was obtained after 4 cycles.
On first cycle of using the recovered catalyst, a decrease of ~10.6% in
the OA conversion was observed. The second reuse (cycle 2)
resulted to another ~10.5% decrease in activity relative to the fresh
catalyst, which corresponds to an overall decrease in activity by
~21%. Beyond the second cycle, the OA conversion stabilized at 0.60.
Since the functional groups attached in the catalyst support is
responsible for catalyzing the reaction, analysis of the acid density
was also done after every cycle. Although eSO3H is the main
functional group involved, eCOOH and e OH groups also influence
 C.M. Mendaros et al. / Renewable Energy 152 (2020) 320e330
Fig. 6. Reusability study of CS-SAC sulfonated at 120
C for 6 h (Esterification conditions: T ¼ 65
C, t ¼ 24 h, catalyst loading ¼ 7 %w/w of OA, MOR 7:1).
the catalysis process within the reaction, thus, changes in the total
acid density after each cycle was investigated. As can be observed
from Fig. 6b the total acid density decreased during the first two
cycles and maintained at ~6.50 mmol Hþ/gcatalyst$h on the suc-
ceeding cycles. From this, it can be said that the decrease in OA
conversion may be attributed to the decrease in the acid densities
caused by the leaching of the functional groups which are
responsible for catalyzing the reaction.
In this study, ~78% of the catalytic performance was retained
after four cycles, higher than the values reported by Bureros et al.
[22], where ~52% of the catalytic performance was retained after
the same amount of cycles. Higher stability may be due to incor-
poration of exhaustive washing with water using a sohxlet
extractor for 12 h right after catalyst synthesis. The exhaustive
washing step ensures removing majority of the loosely bound
active cites [49], which may have resulted in the lesser decrease in
the total acid density. For instance, the CS-SAC synthesized via
direct sulfonation only has an 18% decrease on the total acid density
when compared to the CS-SAC synthesized via two-step carbon-
ization-sulfonation that were not exhaustively washed prior to its
use, which had a decrease of 38% [22].
3.6. Comparison of CS-SAC with other carbon-based solid acid
catalyst
In Table 1 are reported results of different agricultural residues
used as a carbon precursor in the synthesis of solid acid catalyst for
the esterification of OA with methanol which serves as a compar-
ison with the results of this study. Among the carbon-based solid
acid catalyst employed in the esterification of OA, SAC derived from
the de-oiled Jatropha curcas seed cake waste exhibits the highest
catalytic activity, based on the amount of catalyst and sulfonic acid
sites. The peanut shell-derived SAC has the highest catalytic activity
of all the SAC synthesized via direct sulfonation. The high catalytic
activity from the result of both studies may be attributed to the
higher esterification temperature (80e85
C) employed. Moreover,
the high catalytic activity of peanut shell-derived SAC, although
synthesized at the lowest synthesis temperature (85
C) and
shortest time (3 h), is mainly due to its relatively higher sulfonic
acid density. Comparing sugarcane bagasse (SCB)-derived SAC
synthesized via direct sulfonaiton with the CS-SAC in this study,
although esterification with SCB-SAC had higher catalyst loading
(10.0 %w/w) and the same reaction time (24 h), the OA conversion
327
as well as the catalytic activity of the CS-SAC is comparable to that
of SCB-SAC.
With regards catalyst reusability, the SCB-SAC prepared via two-
step synthesis offered the highest stability which retained ~90% of
its original performance after 8 cycles of use. This was followed by
the catalyst synthesized from peanut shell, being able to retain 95%
of its initial performance after 6 cycles. Comparing SCB-SAC and CS-
SAC wherein both catalysts are synthesized through direct sulfo-
nation, it is noted that both exhibit the same degree of stability
which retained 78% of their original performance after 4 cycles of
use without regeneration. The CS-SAC prepared through direct
sulfonation has higher retention (78%) than the CS-SAC prepared
via two-step synthesis (52%) considering that both are being reused
for 4 cycles and each cycle is being run for 24 h. Despite having
lower catalytic activity compared to other biomass-derived SAC
through direct sulfonation, solid acid catalyst derived from cacao
shell has comparable stability. Considering that direct sulfonation
has lesser synthesis time and energy requirement than the two-
step synthesis, CS-SAC synthesized via direct sulfonation may be
more practical to adopt for industrial use, for geographical locations
where these are abundant.
4. Conclusions
Synthesis of the cacao shell-derived solid acid catalyst was done
via direct sulfonation. Sulfonation temperature and time have
minimal influence on the sulfonic sites and catalytic activity of
fresh catalyst but greatly influences the stability and retention of
active sites. The presence of sulfonic groups is positively correlated
with the catalytic activity exhibited during esterification. Catalyst
synthesized at 120
C for 6 h showed highest sulfonic acid sites
(0.85 mmol SO3H/g dry CS-SAC) and highest catalytic activity
(~5.8 mmol OA converted/mmol SO3H$h). The highest OA conver-
sion achieved during esterification at 65
C for 24 h with a
methanol-to-oil mole ratio of 7:1 and a catalyst loading of 7% w/w
of OA was 0.77. After the 3rd use only 78% of the catalytic activity
and 82% of the acid density were retained, but remained the same
thereafter, implying good stability of the catalyst. Among the
different acid moieties present in the catalyst, sulfonic acid greatly
influences the activity of the catalyst. The intermediate washing
steps right after sulfonation process affects the acid density and
improves stability of the synthesized catalyst.
 328
Table 1
Carbon-based solid acid catalyst synthesized using two-step carbonization-sulfonation or direct sulfonation for the esterification of oleic acid.

Biomass Method of Synthesis Synthesis Conditions Acid CLa (%w/w) MORb (n:n) ECc Catalytic Activity Washing Recycles Activity Retention XFFA Ref
T (
C)/t(h) Density (Fresh Catalyst)

rHh rSO3Hi T (
C) t(h) Acj A Hk ASO3Hl R nm R %n Fresho Recycledp

Sugarcane bagasse Two-step Tcd/tce: 375/0.5 3.69 1.06 5.0 10:1 80 5 12.88 3.49 12.15 n-hexane 8 90 0.91 0.81 [59]

C.M. Mendaros et al. / Renewable Energy 152 (2020) 320e330

Tsf/tsg: 150/15
Direct sulfonation Tsf/tsg: 150/8 0.79 0.59 10.0 20:1 45 24 1.26 1.59 2.14 n-hexane 4 78 0.85 0.66 [49]
Corn straw Two-step Tcd/tce: 350/1 2.64 2.44 7.0 7:1 60 4 12.39 4.69 5.08 Methanol e e 0.98 e [24]
Tsf/tsg: 80/4
de-oiled Jatropha curcas Two-step Tcd/tce: 350/5 e 2.00 0.5 1:1 80 2 339.82 e 169.91 Methanol 4 97 0.96 0.95 [60]
seed cake waste Tsf/tsg: 100/8
Peanut shell Direct sulfonation Tsd/tse: 85/3 3.53 2.13 4.0 10:1 85 3 28.91 8.19 13.57 e 6 95 0.98 0.95 [27]
Cacao shell Two-step Tcd/tce: 387/1 4.56 1.48 5.0 7:1 42 24 12.74 2.79 8.61 Methanol 4 52 0.93 0.48 [22]
Tsf/tsg: 120/6
Cacao shell Direct sulfonation Tsf/tsg: 120/6 7.12 0.85 7.0 7:1 65 4 4.93 0.69 5.80 e - - 0.39 e This study
Cacao shell Direct sulfonation Tsf/tsg: 120/6 7.12 0.85 7.0 7:1 65 24 2.27 0.32 2.67 Methanol 4 78 0.77 0.60 This study
a
Catalyst loading based on weight of OA.
b
Methanol-to-OA ratio.
c
Esterification conditions.
d
Carbonization temperature.
e
Carbonization time.
f
Sulfonation temperature.
g
Sulfonation time.
h
total acid density (mmol Hþ/gcatalyst).
i
sulfonic acid density (mmol SO3H/gcatalyst).
j
catalytic activity (mmol FFA reacted/gcatalyst∙h).
k
catalytic activity (mmol FFA reacted/mmol Hþ∙h).
l
catalytic activity (mmol FFA reacted/mmol SO3H∙ ∙h).
m
number of cycles the catalyst was used in the reusability test.
n
percent of the initial catalytic activity retained on the last cycle of the reusability test.
o
fractional FFA conversion of fresh catalyst.
p
OA conversion after several cycles of use.
 C.M. Mendaros et al. / Renewable Energy 152 (2020) 320e330
Credit author statement
Czarina M. Mendaros: Conceptualization, Formal analysis,
Investigation, Data Curation, Writing - Original Draft.
Alchris W. Go: Conceptualization, Formal analysis, Methodol-
ogy, Visualization, Supervision, Writing - Review & Editing.
Winston Jose T. Nietes: Conceptualization, Formal analysis,
Investigation.
Babe Eden Joy O. Gollem: Conceptualization, Investigation,
Visualization.
Luis K. Cabatingan: Conceptualization, Data Curation, Supervi-
sion, Writing - Review & Editing.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
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