Introduction

Biodiesel, commonly in the form of fatty acid methyl ester (FAME), is a renewable fuel derived
from vegetable oil or animal fat. Compared to petroleum-based diesel, biodiesel has fewer emissions of
carbon monoxide, particulate matter, and unburned hydrocarbon (Zhang, Dub, McLean, & Kates, 2003).
Because of these advantages, biodiesel production is extensively studied for the past years. However, the
major problem of biodiesel is its high price due to the raw material cost which corresponds to about 70%
of the overall investment in production (Zhou, Niu, & Li, 2016). In the Philippines, major biodiesel
producers use coconut oil as feedstock to produce coco-methyl ester (CME). The production of CME thus
competes with the demand for coconut oil in the food industry. Because of these considerations, cheaper
raw material alternatives, such as waste cooking oil (WCO), are being explored.

Utilization of WCO as feedstock for biodiesel production would require a pretreatment step before
transesterification reaction because of its high free fatty acid (FFA) and moisture content . The presence of
high FFA and moisture content in the transesterification reaction would lead to the formation of soap which
is undesirable. Lepper and Friesenhagen (Henry, 1986) recommended reducing the FFA content via an
esterification reaction wherein FFAs are converted to alkyl esters using an acid catalyst . Unlike base
catalysts, acid catalysts will not react with FFA to form soap. However, reactions employing homogeneous
acid catalysts, such as H2SO4, present inherent challenges in the separation of the catalyst, and purification
of the product.

In view of the catalyst separation and reuse, the use of solid acid catalysts would be advantageous.
Studies on solid acid catalysts prepared from agricultural residues have been reported in literature. Ground
bamboo (Zhou et al., 2016), corn straw (Liu, Li, Li, Shi, & Wang, 2013), peanut hulls (Kastner et al., 2012)
and coffee residue (Ngaosuwan, Goodwin, & Prasertdham, 2016) were carbonized and functionalized with
SO3H groups through sulfonation to produce biomass-derived solid acid catalyst (SAC) that can be used
in the esterification of FFA.

Cacao shell is one of the agricultural waste generated from chocolate production. In the Philippines,
about 3,000 metric tons of cacao shells are produced anually. Valorization of cacao shell as activated carbon
were studied by Ahmad et al. (Ahmad, Mohd, Wan, Azmier, & Radzi, 2011, 2012, 2013) and Theivarasu
et al. (Theivarasu, Mylsamy, & Sivakumar, 2011) for the adsorption of dye, methylene blue and 4-
nitrophenol. However, no studies are available about the utilization of cacao shells as SAC. Cacao shell has
high fixed carbon content of about 23.8% which are comparable to the fixed carbon content of other
agricultural wastes utilized for the synthesis of SAC such as ground bamboo, corn straw, peanut hulls and
coffee residue which are 19.6%, 19.3%, 21.1% and 17.0% respectively (Jenkins & Ebeling, 1985). Fixed
carbon is used as a basis for comparison of different biomass because it is essentially what remains after
carbonization. Thus, having comparable fixed carbon, cacao shells can be a potential raw material for the
synthesis of SAC. Utilization of cacao shells as SAC for the esterification of FFA would not only address
environmental problems regarding their disposal but also targets the issue regarding the use of WCO as
feedstock for biodiesel production.

Solid Acid Catalyst derived from biomass can be produced by carbonization, then followed by
sulfonation. During carbonization, volatile matter and other components of the material are released and
polycylic aromatic hyrdocarbon sheets are formed. The carbonized biomass is then functionalized by
sulfonation wherein the sulfonic groups attach to the polycyclic aromatic hydrocarbon sheets. Factors such
as carbonization temperature, carbonization time, sulfonation temperature, and sulfonation time affect the
performance and the textural properties of the synthesized SAC.

Zhou, et al. (2016) studied the effect of the preparation conditions on the catalytic activity of a
bamboo-derived SAC. In this study, bamboo was carbonized at varying temperature and time (300 to 500
C; 0.5 to 5 h). The carbonized bamboo was then sulfonated at 75 to 135 C for 1 to 5 h. Esterification of
oleic acid with methanol was carried out to determine the catalytic activity of the bamboo-derived SAC.
From the SAC with the highest catalytic activity, optimum preparation conditions was determined at
carbonization temperature of 350 C for 2 h and sulfonation temperature of 105 C for 2 h. From the
results obtained, it was observed that increasing the carbonization temperature above 350 C would result
to inefficient attachment of sulfonic groups. This is attributed to the rigid carbon structure formed at higher
carbonization temperatures. Increasing sulfonation temperature decreased the total acid density of the SAC
due to sulfone side reactions that inhibit attachment of sulfonic groups to the carbon sheet. For the effect of
carbonization time and sulfonation time, it was reported that it had no significant effect on the catalytic
activity of the bamboo-derived SAC.

Liu, et al. (2013) studied the effect of carbonization temperature and time on the total acid density
of the corn straw-derived SAC. In this study, corn straw was carbonized at 250 to 500 C for 0.5 to 3 h.
Sulfonation conditions were set at 80 C and 4 h. Highest total acid density was obtained at carbonization
temperature of 300 C and carbonization time of 1 h. Further increase in the carbonization conditions
resulted in a decline in the total acid density. The result were similar to the study of Zhou, et al. where
further increasing carbonization temperature beyond optimum condition decreased the total acid density.
The SAC with the highest total acid density had the highest catalytic activity.

Kastner, et al. (2012) synthesized SAC from peanut hulls for the esterification of palmitic acid with
methanol and studied the effect of sulfionation on the properties of the SAC produced. SAC were
synthesized by the carbonization of peanut hulls at 400C for an hour followed by sulfonation at 100 C
for 12 to 18 h. From the results obtained, it was found out that after sulfonation, there was an increase in
the total acid density of the SAC which indicates the attachment of sulfonic groups on the carbonized peanut
hulls. This also indicates that at low carbonization temperatures, carbonized peanut hulls can be easily
functionalized. Also, there was an increase in pore volume and surface area of the carbonized peanut hulls
after sulfonation, which suggests the activation of the carbon.

Ngaosuwan, et al. (2016) studied the effect of sulfonation temperature on the SAC derived from
coffee residue. Carbonization temperature and time were set at 600 C and 4 h respectively. Sulfonation
temperature was varied at 140 to 200 C while sulfonation time was set to 18 h. Catalytic activity of the
coffe residue-derived SAC was determined by carrying out esterification of caprylic acid with methanol .
From the results, the highest catalytic activity was prepared at sulfonation temperature of 200 C.
Ngaosuwan, et al. (2016) explained that SO3H density decreased due to oxiation side reaction leaching to
the formation of sulfone. This was similar to the explanation of Zhou, et al. (2016).

The preparation conditions used in this study is based from the biomass-derived SAC studies. The
effective carbonizaation temperature for the biomass-derived SAC ranges from 300 to 400 C and
carbonixation time of 1 to 5 h. In this study, carbonization temperature of 350 C and carbonization time
of 1 h is used, similar to the carbonization conditions used by Wang, et al .(2015) since it had the closest
fixed carbon content to the cacao shells. The effect of sulfonation conditions at carbonization temperatures
of 300-400 C has not been thoroughly studied. For the sulfonation temperatuers, it was observed that
biomass-derived SAC yield high catalytic activities at sulfonation temperature range of 80 to 150 C. With
these findings, sulfonation temperature and sulfonation time were set at a range of 80 to 120 C and 4 to 8
h repectively.

After synthesis of the SAC, the perfomnace of the catalyst is determined in the esterification
process. Catlystic activity of the catalyst is also measured. Catalytic activity is quantified by the amount of
fatty acid alkyl ester (FAAE) produced per mass of catalyst per unit time (Hara et al., 2004; Lou, Guo,
Chen, Zong, & Wu, 2012; Nakajima & Hara, 2007). Other studies measure perfomance of SAC in terms of
conversion or ester yield over a certain reaction period at specified esterification conditions (Siril, Davison,
Randhawa, & Brown, 2007; Zeng, Zhang, Chen, Liu, & Wang, 2016). Thus, catalytic activity is affected
by esterification reasction parameters such as catalyst loading, solvent-to-oil ratio (SOR), esterification
temperature and esterification time.

Catalyst loading is the amount of SAC per weight of oil used in the reaction which is expressed as
weight percent. Increasing catalyst loading hastens reaction because of the increase in acid sites . Futher
increasing the catalyst loading would result to crowdiing which leads to lesser contact between reactants,
thus decreasing catalytic activity. Catalyst loading used in biomass-derived SAC studies ranges from 0.005
to 0.1 w/w (Kastner et al., 2012; Liu et al., 2013; Ngaosuwan et al., 2016; Zhou et al., 2016). In this study,
catalyst loading of 0.05 w/w was used following the studies of Ngaosuwan, et al. ( 2016) and Kastner, et
al. (2012).

Solvent-to-oil ratio is the amount of solvent used for esterification of a certain amount of oil . It is
commonly expressed as weight solvent per weight oil (w/w) or mole solvent per mole oil (n/n) . Solvent
used for this study was methanol, which was similar to the solvent used by the studies by Wang, et al .
(2015), Liu, et al. (2013), Ngaosuwan, et al. ( 2016) and Kastner, et al. (2012). Increasing amount of alcohol
would favor forward reaction, which is the formation of FAAE. However, increasing the amount of alcohol
in the medium would also lead to dilution, thus reducing accessibility of FFA to the active sites of the
catalyst. SOR used in biomass-derived SAC studies ranges from 1:1 to 20:1(n/n). In this study, SOR of 7:1
(n/n) was used following the study of Liu, et al. (2013) and Zhou, et al. (2016).

Esterification temperature and time also affect the eserification reaction. An increase in the reaction
temperature would favor production of FAAE. However, taking to account alcohol present in the medium,
higher esterification temperatures would evaporate the low-boiling point alcohol resulting to reduction of
the amount of reactant. In effect, a decrease in FAAE production is obtained (Zhou et al., 2016). Also,
longer esterification time would increase the production of FAAE, up to a certain extent. Since the reaction
is reversible, prolonging reaction would not increase FAAE production further because the reaction could
reach equlibrium where rate of forward and backward reaction is equal. Eserification temperature and time
used in biomass-derived SAC studies ranges from 58 to 90 C and 1 to 4 h respectively. In this study,
eserification temperature and time of 60 C and 1 h was used.

In this work, a novel biomass-derived SAC for the methylation of oleic acid was prepared through
sulfonation of carbonized cacao shells. Specifically, the effects of the sulfonation temperature and time on
the catalytic activity, total acid site and sulfur content of the cacao shell-derived solid acid catalyst were
studied. The catalytic activity of the solid acid catalysts were evaluated through measurements done with
the esterification of oleic acid with methanol. Reusability study of the catalyst that obtained the highest
catalytic activity was also investigated. The data obtained from this study can serve as basis for assessing
the industrial potential of cacao shell solid acid catalyst (CS-SAC) for the esterification of FFA in WCO.
Why pursue this study

Please elaborate or expand your discussions. You may go as long as 3 to 4 pages for the introduction.

Provide the reader a good back ground as to why cacao shell was chosen as the catalyst support. What really is the
active catalyst. What was the hypothesis and framework of why and how you believe this work is essential and
would work based on scientific reasoning and backed with previous results and theories established in the literature.

Why cacao shelli

What has been done, result of rel liit

Research gap

Why select this conditions

Goal of the research