Chapter 5

Chapter 5

4B – Demonstrating photocatalytic esterification as

a potential strategy to improve the properties of
feedstock oil derived from dairy waste scum for
biodiesel production
Abstract

The availability of quality feedstock for biodiesel production is challenging; and therefore,
techniques to improve the quality of feedstock are highly desired, as they could be utilized
to modify any feedstock and enhance the biodiesel production. Dairy waste scum oil
(DWSO) is recently known to be a valuable feedstock for producing biodiesel. However,
DWSO needs to go through an esterification process to reduce its high free fatty acid (FFA)
content. To do this, herein, we have treated the DWSO using photocatalytic tin oxide (SnO 2)
particles under UV light irradiation and reduced the FFA content significantly compared to
the conventional cumbersome acid-mediated esterification process. The synthesized catalyst
is characterized for its structural, morphological, optical and surface properties using various
characterization techniques. Parameters such as catalysts dosage, methanol to oil ratio,
reaction time, and temperature involved in the photo-assisted esterification processes are
optimized, and a mechanism for the photocatalytic esterification reaction is also proposed.
Importantly, SnO2 particles also showed excellent reusability in the photo-assisted
esterification process. Overall, the physiochemical and fuel properties of the photo-esterified
DWSO-derived biodiesel are found to be improved compared to the biodiesel synthesized
via conventional acid-esterified oil.
Keywords: Biodiesel; Feedstock; Free fatty acids; Esterification; Transesterification;
Photocatalysis.

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5.1. Introduction

Biodiesel is a renewable resource-derived fuel and can be a potential substitute for fossil
fuels. However, the availability of ‘quality’ feedstock is challenging, and the price of such
quality feedstock has a greater impact on the overall cost of biodiesel production [1, 2].
Enormous research on finding quality and cheaper alternative feedstock is underway at
many levels. One of them is the use of waste oils, which can reduce the overall production
cost and also improve the yield of biodiesel, showing prospects of long-term viability as a
quality feedstock [3]. These waste oils include used cooking oil and brown grease (collected
from waste water treatment plants), which typically contain more than 15% free fatty acid
(FFA) contents [4-6]. On the other hand, the homogeneous catalysts namely KOH and
NaOH are largely used in biodiesel production[7], but they are not often effectively suitable
for reducing FFA in feedstock, leading to saponification reactions rather than biodiesel
formation [8, 9]. Therefore, a pre-treatment step (i.e., esterification process) is commonly
performed to reduce the FFA content of the oil using the homogeneous acid catalysts such as
H2SO4 and HCl [10]. However, this process requires high pressure (~1.7 to 2 bar),
temperature (> 100 oC), higher methanol to oil molar ratios, strong acids, and longer reaction
times due to its slower reaction rate [11, 12]. Also, it is essential to use expensive and
sophisticated equipment to accelerate the reaction and mitigate other associated issues such
as corrosion, stability, etc. [13, 14]. In this direction, the supercritical transesterification and
enzyme catalyzed processes have been reported as novel one-step techniques to make
biodiesel from high FFA oils. However, supercritical processes also require high
temperatures (~300-400 oC), higher methanol to oil ratio (~40:1), and high pressure (> 100
bar) to produce biodiesel [15]. Similarly, enzyme catalyzed processes require longer reaction
time (above 10 h), and its reusability is also not possible. Hence, it is crucial to develop cost-
effective processes for converting of high FFA waste oils to biodiesel [16].
The production of biodiesel by catalytic esterification or transesterification using
heterogeneous catalysts is a very active area of research. Therefore, many heterogeneous
catalysts have been developed for biodiesel production using high FFA oils through
different methods. Recently, cation exchange resin (CER) was used in the esterification of
high FFA oleic acid and achieved around 91.63% oleic acid conversion by adopting the
Taguchi algorithm. The catalyst showed high activity over six consecutive catalytic cycles,
indicating its satisfactory catalytic stability [17].

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The PEG/MgO/ZSM-5@Fe3O4 magnetic catalyst was synthesized using polyethylene glycol

(PEG) as a mediator and was used in microwave-assisted biodiesel [Link] PEG
content beneficial to the catalyst's higher basicity, larger pore size, and greater surface area
resulting in a 95.8% biodiesel yield [18]. Furthermore, a fixed-bed coupled pervaporation
(PV) technology was utilized in esterification reaction of oleic acid (OA) and achieved a
99.32% conversion yield at optimum conditions using response surface methodology. The
conversion rate of OA increased by 12.69% compared to the esterification reaction without
PV, and the cation exchange resin used in the fixed bed showed greater reusability [19].
Similarly, solid acid catalyst Zr4+-CER was used in the esterification reaction. The
esterification of tall oil fatty acids (TOFA) with ethanol dehydration was studied by fixed-
bed coupled PV and achieved around 99.51% conversion. After six esterification cycles, the
TOFA conversion of the catalyst reached around 90.03%, indicating that the catalyst had
high stability [20]. In addition, MgO/ZSM-5 catalysts [21] and mixed metal oxide of CaO-
Al2O3 [22] were used as potential catalysts in biodiesel production.
In recent times, photocatalysts have gained more importance in the esterification of
oils under light radiations, and this motivated us to envision that this technique can evolve a
potential method to reduce FFA content in the feedstock. Eventually, it can be designated as
a feedstock modification technique. A sustainable method for producing biodiesel that uses
renewable resources and has less of an impact on the environment is photocatalytic
esterification. With this process, fatty acids and triglycerides are converted into biodiesel
more quickly by using photocatalysts in mild esterification reactions [23]. Photocatalysis is
mainly mediated through reduction-oxidation reactions, initiated by excited electron-hole
pairs when light of suitable wavelength/energy [24-26] is irradiated on the photocatalyst.
Also, this process can be conducted at atmospheric pressure and room temperature using
direct sunlight or other artificial light sources. It can hence be a viable technique to reduce
FFA in the feedstock and can be reused for several cycles as well, eventually reducing the
overall cost of biodiesel production [27-29].
Currently, very limited heterogeneous photocatalysts have been reported for the
esterification of FFA to produce biodiesel. The ZnO/SiO 2 heterogeneous photocatalyst
showed high activity in the esterification of FFA with methanol under UV irradiation, and
the catalyst’s activity remained unchanged after being used 10 times [30]. Furthermore, the
Cr/SiO2 photocatalyst calcined between 700-1000 oC showed greater photocatalytic activity
in the esterification of high FFA oil. The coexistence of Cr 6+ and Cr3+ moieties in the

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photocatalyst facilitated a wide range absorption of light energies and made it extremely

efficient for photocatalytic esterification of FFAs with methanol [31]. In 2021, Guo et al.
[32] prepared La3+/ZnO-TiO2 photocatalyst for the esterification of FFA with waste cooking
oil and reported around 96.14% FFA conversion at 4 wt.% catalyst dosage, 12:1 methanol to
oil ratio, 3 h UV irradiation at 35 oC temperature. This catalyst also showed good reusability
up to 5 cycles with an FFA conversion of 87%. Similarly, a TiO 2-based composite with
graphitic carbon [33] [34] and CuO/ZnO composites have also been reported for
photocatalytic esterification reactions [35]. These reports demonstrated that the
photocatalytic esterification process is efficient, with high selectivity and reduced energy
consumption compared to traditional methods. Photocatalytic esterification shows promise
for sustainable biodiesel production, contributing to the development of greener and more
efficient processes in the renewable energy sector.
In this context, herein, SnO2 has been used as a potential photocatalyst for photo-
assisted esterification reactions. SnO2 possesses a band gap energy of ~3.6 eV with
excitation binding energy of 130 eV [36]. The UV light absorption property of this material
is found to be promising and similar to that of TiO 2, where SnO2 also has outstanding
electrical, optical, mechanical, and photocatalytic properties [37]. In this direction, this study
demonstrates the synthesis of highly active, stable, and recyclable tin oxide (SnO 2)
photocatalyst through solution combustion route and their photocatalytic esterification
reaction towards the degradation of FFA in the dairy waste scum-derived oil (DWSO) to
produce biodiesel. The properties of the prepared photocatalyst are characterized to
understand their various physiochemical properties. Then, a conventional transesterification
reaction using KOH catalyst is performed to produce high-quality biodiesel from the
obtained photocatalysis-assisted FFA-degraded DWSO feedstock. Parametric studies have
also been conducted to understand the influence of various parameters in the photocatalysis-
assisted FFA degradation in the DWSO feedstock.

5.2. Experimental
5.2.1 Materials
The dairy waste scum is collected from Karnataka Milk Federation (KMF), Tumakuru Milk
Union (TMU), Mallasandra, Karnataka, India. The collected dairy waste scum was heated to
100 oC to convert it into a liquid form. Then, the unwanted materials and semi-solid particles
present in the liquid were filtered and centrifuged to obtain pure dairy waste scum oil
(DWSO). The fatty acid composition of DWSO includes myristic acid (32.60%), capric acid

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(1.60), lauric acid (3.39%), stearic acid (5%), pentadecyclic acid (1.20%), palmitic acid

(13.56%), elaidic acid (11.42%), oleic acid (29.61%), and oleic acid (29.61%) [38]. The
chemicals such as tin chloride, urea, calcium oxide, and methanol used in this study were
purchased from Fisher Scientifics, Mumbai, India.

5.2.2. Synthesis of SnO2

In the process of combustion synthesis, 2 g of SnCl 2.2H2O was added to 20 mL of distilled
water to form a transparent solution. A magnetic stirrer was used to enhance reactivity and
homogeneity of the mixture and mixed for 30 min. While stirring, 2 mL of HNO 3 was added
dropwise to form the tin nitrate solution, acting as an oxidizer. Subsequently, 4 g of urea and
3.3 g of CTAB were added to the solution and stirred for 30 min. The resulting solution was
then transferred into a crucible and heated in a muffle furnace at 650 ˚C for 2 h for
calcination, yielding the final product as depicted in Fig. 1. Based on the reactants, the
formation of Sn(OH)₂ and its transformation to SnO 2 during the solution combustion
process can be represented as given in Eq. (1)-(3).
SnCl2 + 2HNO3 → Sn(NO3)2 + 2HCl (Eq. 1)
Sn(NO3)2 + 2CO(NH2)2 → Sn(OH)2 + 2NH4NO3 + CO2 (Eq. 2)
2Sn(OH)2 → SnO2 + 2H2O (Eq. 3)

Figure 5.1. Schematic representation of the synthesis of SnO2 via solution combustion
method.

5.3. Characterizations
The phase identification of SnO2 was conducted using Rigaku Ultima IV X-ray diffraction
(XRD) analysis with Cu-Kα (1.5418 Å) radiation. Morphology analysis of the sample was
carried out using field emission scanning electron microscopy (FE-SEM) with a JEOL JSM-
7100F instrument. Optical absorption properties of the prepared SnO 2 were determined
using a UV-Vis-spectrometer (Shimadzu UV-1800), and Tauc’s plot was used to estimate
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the band gap energy.

Specific surface area of the samples was estimated using the Brunner-Emmer-Teller (BET)
with as Smart Instruments, SMART SORB 92/93, SS 93/11/11-12 instrument, based on the
obtained N2 adsorption and desorption isotherms. FTIR analysis of the samples was
conducted using a Brucker Alpha–T FTIR spectrometer.

5.4. Determination of FFA in DWSO

Estimating the free fatty acid (FFA) content in the oil is crucial as it can lead to soap
formation instead of biodiesel [39]. To determine the FFA content of dairy waste scum oil
(DWSO), the acid value of DWSO was initially assessed. In this procedure, 10 g of DWSO
was added to 50 mL of isopropyl alcohol in a conical flask and gently heated to
approximately 35°C while shaking. The solution was then titrated using a phenolphthalein
indicator with 0.1 N KOH, and the appearance of a light pink color indicated the endpoint.
The acid value of DWSO was calculated using Eq. 4, the % of FFA in the feedstock was
estimated using Eq. 5, and the % FFA degradation was calculated using Eq. 6.
V x N x 56.1
Acid value (KOH g-1) ¿ (Eq. 4)
W
Acid value
%FFA ¿ x 100 (Eq. 5)
2
Initial FFA −Final FFA
FFA degradation (%) ¿ X 100 (Eq. 6)
Initial FFA
Here, N, V and W represent the normality of KOH, volume of alkali added (in mL), and
weight of the oil sample (in g), respectively. The constant 56.1 represents the equivalent
mass of KOH.

5.5. Photocatalysis-assisted feedstock modification through esterification reaction

In this procedure, 100 g of DWSO feedstock was taken in a three-neck flask equipped with a
reflux condenser, thermometer, and a magnetic condenser. Different oil to methanol molar
ratios (ranging from 1:6 to 1:14) and SnO2 (2.5 to 5 wt.%) were added and stirred at ~35 oC.
The setup was enclosed in a closed black box with a 30 W ultraviolet (UV) light (~254 nm,
0.5 mW/cm2). The reaction proceeded for up to 4 h at a constant stirring speed of 400 rpm.
After the reaction, the resulting mixture was filtered through a separating funnel, yielding
two layers: an upper layer containing methanol and water, and a lower layer consisting of
catalyst, unreacted triglycerides, and methyl ester. The lower layer, containing the catalyst,
was separated. Methanol was collected through distillation, and the water was removed by
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heating the reaction mixture in a hot-air oven at 100 °C.

This resulting esterified DWSO, obtained through photocatalysis, was then sued for
biodiesel production, as discussed in the following section.

5.6. Transesterification of DWSO catalyzed by KOH

The transesterification was conducted after the esterification of DWSO (with acid value less
than 2% or FFA less than 4%). The esterified DWSO was taken in a three-neck flask with a
condenser and placed on magnetic stirrer, and the fixed transesterification reaction
parameters such as 4.5:1 molar ratio of methanol to oil, 75 minutes reaction time, 1.20 wt%
KOH, 62 oC temperature and 650 rpm were selected based on our previous work [40]. After
the completion of reaction, the formed biodiesel and glycerin were separated. The excess
methanol was recollected from the reaction mixture through distillation, and the resulting
biodiesel was treated with water to eliminate the soap and other residues, and then heated at
100 oC to eliminate the water molecules present in the biodiesel. The biodiesel yield was
calculated using Eq. 7.
Mass of biodiesel produced
Biodiesel yield (%) = X 100 (Eq. 7)
Mass of oil taken

5.7. Results and discussion

5.7.1 Characterizations of the synthesized SnO2
5.7.2 Structural studies
The XRD pattern of the synthesized SnO 2 is presented in Figure 5.2(a). The obtained XRD
pattern matched with the JCPDS card No. 41-1445, which indicates that the obtained tin
oxide is crystalized into a tetragonal rutile phase of SnO2. The observed shift in the XRD
peaks with respect to the standard could be attributed to the presence of strain in the system
due to the smaller crystallite size of the particles, which can also be correlated with the
observed peak broadening in the XRD peaks. Accordingly, the average crystallite size of the
synthesized SnO2 estimated using Scherrer’s formula [41] is found to be ~9.63 nm, which is
in agreement with the values reported by Kumar et al.[42]. Clear and distinct peaks indicate
good crystallinity, and the absence of any other peaks suggests that the prepared SnO 2 is free
from impurities and secondary phases. The Williamson and Hall (W-H) plot was obtained to
understand the association between grain size and micro-strain [35] in the system. The
obtained plot, as given in Figure 5.2(b), shows a low value of 1.98 × 10 -2 corresponding to a

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compressive micro-strain in the system with a respective crystallite size of around 10.6 nm,
consistent with the crystallite size estimated using the Scherrer's formula.

A similar observation was reported by Abdel-latief et al [43], where they reported the
synthesis of SnO2 via the hydrothermal route in the presence of cationic surfactant CTAB.
Consequently, a crystallite size of around 2.54 and 2.12 nm was estimated through the
Scherrer and Williamson-Hall plot, respectively. Furthermore, the micro-strain reported was
0.041. In another study, Amruta et al., [44] used the W-H equation to determine the lattice
parameters, strain, and effective particle size of SnO 2 nanoparticles synthesized through the
co-precipitation method. They reported that intercept of the slop for pure tin oxide sample
exhibits the mean particle size and the micro strain in the systems.

(a) (b)

Figure 5.2. (a) XRD pattern and (b) W-H plot of the synthesized SnO2 particles.
The FTIR spectrum of the synthesized SnO 2 NPs (Figure 5.3) displays bands at 542
and 660 cm-1 corresponding to the stretching and bending vibrations of Sn-O and O-Sn-O,
respectively. The presence of bands at these frequencies indicates that the synthesized SnO 2
is free from defects such as tin and oxygen vacancies. This ensures that the obtained SnO 2 is
stable in terms of its structure and chemical composition, which can ultimately support
durable catalytic activity during successive reactions. The bands at 1425 and 1097 cm -1 can
be assigned to stretching O-H and C-H bonds, respectively. Typically, the bands in the range
of 3200-3500 cm-1 are associated with O-H bending, indicating the presence of OH groups
on the SnO2 surface [45, 46]. However, in the current study, the band related to OH group is
not observed. This absence could be due to combustion and subsequent annealing processes
that removed the hydroxyl group and water molecules from the catalyst surface.

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Figure 5.3. FTIR spectrum of the synthesized SnO2 system.

5.7.3. SEM, EDX and TEM analysis

The morphological features and elemental analysis of SnO 2 particles are presented in Figure
5.4 (a-c). The obtained SEM and TEM images obtained show irregularly shaped micron-
sized particles with rough surface along with uneven distribution. The abrupt and
uncontrolled exothermic reactions during the combustion process leads to the formation of
particles with uneven distributions since there is no strict control over the size and shape of
the particles. However, due to the nucleation and subsequent particle growth occurring
rapidly during the combustion process, the particles tend be highly crystalline and robust in
nature, as observed from their structural analysis using XRD and IR techniques.
This a robust formation of particles also ensures the proper chemical composition of sample,
as observed in the EDS spectrum shown in Figure 5.4 (d). The presence of respective
elements such as Sn and O, along with their estimated atomic percentages (78.8% (Sn) and
21.2% (O)) (Figure 5.4 (d)), suggested that the formed particles are stoichiometric SnO 2
without any impurities and secondary phases.

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(a) (b)

50 µm 10 µm

(c) (d)

Figure 5.4. (a-b) SEM images at different scales, (c) TEM image and (d) EDS elemental
spectrum of the synthesized SnO2 particles.

5.7.4. BET surface property analysis

The specific surface area and pore size distribution of the synthesized SnO 2 were determined

using BET N2 gas adsorption-desorption analysis, and the obtained isotherm and pore-size

distribution curves are shown in Figure 5.5 (a)-(b), respectively. The observed isotherm

indicates the existence of type IV hysteresis, suggesting the mesoporous nature of the

particles. Furthermore, the obtained Barrette-Joynere-Halenda (BJH) plot indicates that the

particles possess a multimodal pore structure with pore size ranging from 2 to 16 nm.

The surface area of SnO2 is estimated to be around 23.45 m 2 g-1, which is relatively low due

to their larger particle size [38, 47]. Accordingly, the formation mechanism of mesoporous

SnO2 during calcination is schematically shown in Figure 5.6. This signifies that the
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particles can establish a smooth adsorption-desorption process on their surface, which is

essential for the robust catalytic reactions with prolonged stability and activity.

Fig. 5.5. (a) BET N2 adsorption-desorption isotherm and (b) BJH pore size distribution plot

of the synthesized SnO2 particles.

Fig. 5.6. Formation mechanism of mesoporous structures in the synthesized SnO2 particles.

5.7.5 Optical analysis

The UV-visible absorption spectrum and Tauc’s plot for the band gap estimation of the
synthesized SnO2 particles are displayed in Figure 5.7(a)-(b), respectively. An absorption
maximum is observed around 313 nm, indicating the typical UV-light driven properties of
the SnO2 particles. However, the spectrum extends across the visible light region up to 700
nm, suggesting that the SnO2 is active over a broad range of solar spectrum, which is
consistent with previous literature [48]. The observed visible light activity of SnO 2 could be
originated due to the induced strain in the material owing to their smaller crystallites, which
gives rise to
the localized active optical transitions in the system. The optical bandgap energy of SnO 2 is
calculated using Tauc’s plot as shown in Figure 5.7(b) and found to be ~3.42 eV, which is
less than the band gap energy of the typical bulk-SnO 2 (3.6 eV). This decreased bandgap
energy could be attributed to the disorder-induced modification in the direct-bandgap
structure and anisotropic nano-crystallite size of the synthesized SnO2 particles [49, 50].

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(a) (b)

3.42 eV

Figure 5.7. (a) UV-Visible absorption spectrum and (b) Tauc’s plot of the synthesized SnO 2

particles.

5.8 Photocatalytic esterification-mediated degradation of FFA in feedstock: Effect of

reaction parameters
As discussed, the feedstock modification (i.e., the degradation of free fatty acid in the
obtained dairy waste-scum derived oil) was carried out through photocatalytic esterification
using the developed SnO2 particles under UV light irradiation. This investigation includes a
parametric study, where key parameters such as methanol-to-oil ratio, catalyst dosage, and
UV irradiation time are varied. These results are presented in the following sections.

5.8.1 Effect of methanol/oil ratio and catalyst dosage

The photocatalytic efficiency of SnO2 particles in degrading free fatty acids (FFA) was
studied by varying the methanol-to-oil (M/O) ratios from 6:1 to 14:1, while keeping the
other parameters constant at 100 mL of oil, 3.5 wt% of catalyst, 3 h of UV irradiation. The
results are presented in Figure 5.8(a).

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 Chapter 5

(a) (b)

Figure 5.8. Parametric studies showing the (a) methanol-to-oil ratio and (b) catalyst
concentration dependent FFA degradation efficiency of the synthesized photocatalyst under
UV irradiation.
The FFA conversion rate increases with increasing M/O ratio, reaching a maximum
value of ~94.4% (1.2% FFA) at 12:1. However, beyond this molar ration, the conversion
rate decreases, which may be due to the reversible esterification reactions. Here, increasing
the M/O ratio improves reactant concentration, leading to faster reactions and higher
conversion rate [51, 52]. However, excessively high methanol volumes inhibit the reaction
in the positive direction, resulting decreased conversion rates. Therefore, the optimal M/O
molar ratio is determined to be 12:1.
Similarly, by increasing the dosage of SnO 2 particles from 2.5 to 4 wt% (as shown in
Figure 5.8 (b)), while keeping the other parameters constant at 100 mL of oil, 12:1 M/O
ratio, 3 h of UV irradiation, the FFA degradation increases from around 57.1 (9.3% FFA) to
96.1% (0.81% FFA). However, with a further increase to 5 wt%, the FFA degradation
decreases to 77.8% (4.8% FFA). It is known that the surface-active sites play crucial role in
effective catalytic reactions over heterogeneous catalysts. Accordingly, the observed
decrease in FAA degradation at higher catalyst concentrations may be attributed to the
inhibition of active sites due to increased particle-particle interactions rather than particle-
reactant interactions in the
reaction medium. Also, photocatalytic reactions largely depend on effective redox reactions
mediated by radicals produced by photo-excited carriers. Their formation and transfer to
reactant molecules may be limited by particle agglomeration via particle-particle

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interactions [53, 54]. Therefore, 4 wt% of catalyst was determined as the optimized
concentration for this reaction. Further, the catalytic activity of SnO 2 (5 wt%) was conducted
without UV irradiation, resulting in around 63% degradation of FFA.

5.8.2 Effect of UV irradiation time

The impact of UV irradiation time on FFA degradation efficiency of SnO 2 was studied by
varying the irradiation time from 1 to 5 h, maintaining other parameters constant at 100 mL
of oil, a 12:1 M/O ratio, and 4 wt% of photocatalyst. In Figure 5.9(a), it is evident that
without UV irradiation, photocatalytic esterification of FFA at 35°C does not occur, with
FFA conversion remaining nearly zero even after a three-hour reaction without illumination.
The FFA degradation shows an increasing trend with irradiation time up to 3.5 h, reaching
around 96.3% (0.8% FFA), but it starts to decline with further increases in irradiation time
up to 5 h.

During photocatalytic reactions, activating the photocatalyst is crucial, and this activation is
time-dependent, closely linked to the response of the surface-active sites. The participation
of these sites increases with irradiation time from 1 to 3 h, peaking at 3.5 hours. Beyond this,
additional irradiation time does not enhance reactions as all surface-active sites are already
engaged, leading to a saturation point in FFA degradation beyond 3.5 h of irradiation.
Moreover, a conventional esterification reaction conducted at 65 °C also resulted in FFA
degradation, reaching a maximum of approximately 74.6% (5.5% FFA) after 5 h, as shown
in Figure 5.9(b). This highlights the effectiveness of the prepared SnO 2 photocatalyst under
UV irradiation and its potential as a heterogeneous catalyst for reducing FFA.

(a) (b)

Figure 5.9. FFA degradation over SnO2 photocatalyst (a) with and without UV light
irradiation and (b) without light irradiation under heating at 65 °C.

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5.8.3 Effect of reaction time
The effect of reaction time on FFA degradation was investigated by varying the reaction
time from 2 to 4.5 h while maintaining other reaction conditions at 4 wt% catalyst loading,
3.5 h UV irradiation, and 12:1 methanol/oil ratio. The increase in FFA degradation was
observed with longer reaction times, as shown in Figure 5.10. Degradation of FFA
increased and reached 94.7% at 3.5 h, with no further increase in degradation observed with
longer reaction time. This could be due to the balance between reverse and forwards
reactions [55, 56]. Therefore, the optimum reaction time was determined to be 3.5 h.

Figure 5.10 Effect of reaction time on FFA degradation by the synthesized SnO 2

photocatalyst

5.9 Photo-esterification mechanism of SnO2 in FFA degradation

Photo-esterification for FFA degradation is mediated via the active radicals generated by the

reaction of excited charge carriers with the surrounding molecules. In a typical reaction,

upon the incident photons, the electrons are excited to the conduction band (CB) and holes

are generated in the valence band (VB) [Eq. (8)]. The electrons (e ̄) react with carboxylic

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 Chapter 5
molecules (ROOH) and form their corresponding anions (RCOO • ̄) [Eq. (9)], while the holes

(h+) react with methanol (CH3OH) and produce anionic CH3O ̄ radicals and protons (H+)

[Eq. (10)]. Then, these formed RCOO • ̄ species react with CH3OH and produce RHCOO•

[Eq. (11)], which further react with CH 3O• radicals and H+, forming the methyl ester

(RCOOCH3) and water (H2O) as shown in Eq. (12). The similar mechanism is demonstrated

in Cr/SiO2 [31] and La3+/ZnO-TiO2 [32] photocatalysts in esterification. The overall

mechanism is depicted in Figure 5.11(a)-(b).

SnO2 + hν  SnO2 (e + h+) (Eq. 8)

SnO2 + (e-CB) + ROOHads  SnO2 + RCOO. (Eq. 9)

SnO2 (h+VB) + CH3OH  SnO2 + [Link] + H+ (Eq. 10)

RCOO. + CH3OH  RHCOO. + CH3O. (Eq. 11)

RHCOO. + CH3O. + H+  RCOOCH3 + H2O (Eq. 12)

RCOOH RCOO.

UV irradiation e- e - e-
CB

SnO2
photocatalyst

VB

h+ h+ h+

CH30H CH30-

Figure 5.11. (a) Mechanism of photocatalytic esterification over SnO 2 and (b) reaction steps

in FFA degradation.

5.10 Conventional esterification of DWSO using H 2SO4 and reusability of SnO2

photocatalyst

For comparison, the esterification reaction was conducted using the homogeneous acid

catalyst H2SO4. The reaction parameters were selected according to the literature [10]. The

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obtained results (Figure 5.12(a)) showed that at the end of 1 st (1 h) and 4th cycle (1 h), the

FFA content is decreased to ~16.25% (i.e. 25.34% degradation of FFA) and ~1.6% (92.62%

degradation of FFA), respectively, from the initial FFA content of 21.7% (i.e. 100% FAA).

It should be noted that the FFA content is decreased to ~1.02% (96.31% degradation of

FFA) in the first step (i.e., 3.5 h) of the photocatalytic reaction itself under the optimized

conditions of 100 mL of oil, M/O ratio 12:1, 4 wt% catalyst, and 3.5 h of UV irradiation.

Whilst, it took 4 repeated processes to decrease the FFA content to ~1.6% in the

conventional acid-based homogeneous catalytic process. Moreover, in each step, the

obtained H2SO4-treated feedstock should be thoroughly washed several times using water in

order to avoid the sulfur residues in the final biodiesel, which otherwise will impair the

quality of biodiesel.

It is evident that the conventional acid-based homogeneous catalytic esterification

process can be relatively far expensive, time-consuming, and can adversely affect the quality

of biodiesel compared to the photocatalyst-assisted esterification process. Importantly, one

of the key advantages of heterogenous catalysts is their reusability. Accordingly, the
synthesized SnO2 photocatalyst was reused up to 5 cycles for FFA degradation, and the
obtained results are shown in Figure 5.12(b). Under the optimized conditions, the FFA
degradation efficiency of the photocatalyst remained consistent up to 3 cycles with an
average of ~90.5% degradation efficiency. However, it started decreasing to 86 and 84% in
4th and 5th cycle, respectively. Even though the catalyst was washed with n-hexane and dried
at 80 °C before starting the next cycle, complete regeneration of catalyst is difficult during
the recycles. This observed decreased efficiency of the photocatalyst with cycles could be
attributed to the catalyst loss, strong interaction of triglycerides and by-products formed
during the esterification reaction with the surface of photocatalyst, significantly affect the
reactive sites thus poisoning the catalyst surface.
Furthermore, the recovered SnO2 photocatalyst was characterized using XRD and SEM
techniques. As depicted in Figure 5.12(c), the crystalline phase and structure of the
recovered photocatalyst remained unaltered compared to the fresh photocatalyst. Similarly,
the SEM image of the recycled photocatalyst (Fig. 12(d)) shows irregularly shaped micron-
sized particles with a relatively rough surface and uneven distribution of particles,
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 Chapter 5
emphasizing their morphology and particulate structure are relatively stable compared to the
fresh SnO2 photocatalyst. However, the observed slight decrease in catalytic activity can be
attributed to the deposition of organic materials on the catalyst surface, leading to the
suppression of active sites on the surface of the photocatalyst.

Figure 5.12. (a) FFA degradation of feedstock oil using the conventional homogenous acid-

based catalyst (H2SO4), (b) reusable efficiency of the photocatalyst toward FFA degradation,
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 Chapter 5
(c) XRD and (d) SEM image of the recovered SnO2 photocatalyst.

5.11 Kinetic study

Typically, a pseudo-first-order kinetic model is utilized to describe the kinetics of

heterogeneously catalyzed esterification when the mole ratio of methanol to oil exceeds 5

[57]. To investigate the reaction kinetics of the SnO 2 photocatalyst in the esterification

process, experiments were performed under optimized conditions. The kinetic equation for

the esterification reaction can be expressed as shown in Eq. 13.

RCOOH + CH3OH ↔ RCOOCH3 + H2O (Eq. 12)

The apparent reaction rate for the esterification reaction is given by Eq. 14.

−d C FFA
=k 1 ,est C FFA Cmethanol (Eq. 14)
dt

Where k1,est is the kinetic constant, C represents the concentration, and t represents the time.

[C FFA ( 1−x ) ] (Eq. 15)

−d =k 1 ,est C FFA (1−x )C methanol
dt

On cancelling the terms in Eq. 15, the following simplified differential Eq. 16 can be
obtained.
dx
=k 1 , est C methanol (1−x) (Eq. 16)
dt
The concentration of the methanol is unchanged in the esterification reaction, and
therefore, the Cmethanol is known and the Eq. 17 is an analytical equation, which is obtained by
solving the differential equation of Eq 16.
−ln(1−x )=k 1 , est Cmethanol t (Eq. 17)
Since the molar ratio of methanol to oil exceeds 5 (i.e., 12:1), it can be assumed to
follow a pseudo-first-order reaction kinetic given the fixed concentration of catalyst. A plot
was created for –ln(1-x) vs ‘t’ at various reaction temperatures using the 4 wt.% catalyst.
Figure 5.13(a) shows the plot of –ln(1-x) vs ‘t’, where the slope of the linear plot curve is
utilized to determine the rate constant (k). The rate constant was determined to be 0.00296 k
(min-1), 0.00305 k (min-1), 0.00314 k (min-1), and 0.00325 k (min-1) at different temperatures
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 Chapter 5
of 35 oC, 45 oC, 55 oC, and 65 oC, respectively.
The activation energy can be calculated by using the Arrhenius equation as given in Eq. 18.

K= Aexp
[ ]
−Ea
RT
(Eq. 18)

By performing the logarithm of Eq. 18 on both sides, Eq. 19 can be obtained as,
−Ea
lnK = +lnA (Eq. 19)
RT
The activation energy (Ea) can be determined by plotting lnK against 1/T, as shown
in Figure 5.13(b). Based on this plot, the activation energy for the SnO 2 photocatalyst was
found to be ~33.82 kJ/mol for catalyzing the esterification of feedstock oil. This indicates
that the SnO2 photocatalyst relatively requires relatively lower activation energy for the
esterification, enabling the degradation of FFA content in the feedstock oil under mild
reaction conditions.

(a) (b)

igure 5.13. (a) –ln(1-x) vs time at different temperatures and (b) Arrhenius plot of lnK vs

1/T.

5.12 Synthesis of biodiesel

The FFA-reduced esterified oil obtained through (i) photocatalysis-assisted and (ii)

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 Chapter 5
conventional acid-based homogeneous catalysis-assisted process was further utilized to
produce biodiesel via conventional homogeneous transesterification using KOH, as
described in section 2.4.2. At the end of the reaction, biodiesel yields of around 94.6 and
93.7% were achieved using the esterified oil from photocatalysis and conventional catalysis
process, respectively. It is important to note that the biodiesel yield of 93.7% corresponds to
the oil obtained after the 4th round of esterification via the conventional homogeneous
catalysis process, while the yield of 94.6% is achieved using the esterified oil obtained in a
single step photo-esterification reaction. Consequently, this photo-esterified-oil derived
biodiesel was further taken for its structural and physiochemical analysis using various
technique as discussed in the following sections.

5.13 Characterization of the biodiesel produced

The FTIR spectra of DWSO (oil) and DSME (biodiesel) are displayed in Figure 5.14. The

peaks at 3256, 2359, and 1914 cm -1 indicate the presence of alcohol, alkyne, and aromatic

compound, respectively in the esterified oil (DWSO). Conversely, the observed peak shift

from 1700 to 1740 cm-1, as well as the disappearance of the C-O stretch corresponding to

DWSO at 1700 cm-1 in the spectrum of DSME, clearly indicates the effective conversion of

oil into biodiesel.

The absence of carboxylic acid peaks between 2500-3300 cm -1 represents the absence of

moisture in the obtained biodiesel (DSME) [58, 59].

Figure 5.14. FTIR spectra of the photo-esterified dairy waste scum oil and its methyl ester.
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 Chapter 5

5.14 Physicochemical properties of biodiesel

Various physicochemical features associated with fuel properties of the biodiesel produced
from photo- and conventional-esterified oil are analyzed and provided in Table 1 in
comparison with the ASTM standards. Notably, density and kinematic viscosity are
important fuel properties, where lower density and viscosity of biodiesel improve spray
atomization and flow ability in diesel engines [60, 61]. Accordingly, the density and
viscosity of biodiesel synthesized from photo- and conventional esterified feedstock were
found to be comparable with respect to the ASTM standards. The copper corrosion of
biodiesel synthesized from both photo- and conventionally esterified feedstock was found to
be 1a, indicating that the fuel is less corrosive. The calorific value of the biodiesel produced
from photo- and conventionally esterified feedstock is found to be relatively similar,
showing the good combustibility of the fuel. In addition, the cloud (28 oC) and pour point
(21 oC) of DWSO are greater due to the presence of saturated fatty acids in it [62]. After the
transesterification of photo- and conventional esterified feedstock, the cloud (7 oC) and pour
point (3 oC) are reduced, and these results are similar in both photo- and conventionally
esterified feedstock biodiesel. The acid value of photo- and conventional esterified feedstock
biodiesel was determined to be ~0.09 mg KOH/g and ~0.11 mg KOH/g, respectively, which
lies within the limit of the ASTM standard of 0.5 mg KOH/g.

The flash point of biodiesel produced from photo-esterified feedstock (144 oC) was found to
be higher compared to the biodiesel produced from conventionally esterified feedstock (138
o
C). This decreased reduced flashpoint temperature can be attributed to the high quantity of
methanol used in the conventional esterification process to reduce FFA [63]. However,
properties of both the biodiesels are in the range of ASTM standards, which essentially
means that they are safe for storage and transportation. The carbon residue of photo-
esterified feedstock biodiesel was found to be less compared to conventionally esterified-
feedstock biodiesel and within the limits of ASTM standards, suggesting the effective
burning of the fuel without making any deposits in the engine [64]. The sulfur content in
conventionally esterified feedstock biodiesel (0.051% m/m) is higher compared to the
photo-esterified feedstock biodiesel (0.018% m/m). This is because a large quantity of
sulfuric acid was used in the esterification reaction to reduce FFA in the DWSO. This
indicates that photo-esterified biodiesel is less corrosive in nature and hence it can be safely
stored. The acid value of photo-esterified feedstock biodiesel (0.09 mg KOH/g) is lower
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 Chapter 5
than the conventionally esterified feedstock (0.11 mg KOH/g). The higher acid value of the
biodiesel results in the corrosion of fuel injectors in the diesel engines [65]. Overall, the fuel
properties of biodiesel from photo-esterified feedstock, such as viscosity, flash point, sulfur
content, ash content, and acid value, are superior to those of conventionally esterified
feedstock.
Table 1. Physicochemical properties of photo-esterified oil (DWSO) and the derived

biodiesel.

Nd = Not determined, DWSO = dairy waste scum oil, FAME = Fatty acid methyl ester

5.15 Conclusion

In this study, tin oxide (SnO2) particles were synthesized via solution combustion method
and employed as a photocatalyst to degrade free fatty acid (FFA) in diary waste scum-
derived oil (DWSO), rendering it as a suitable high-quality feedstock for biodiesel
production through conventional homogeneous catalytic transesterification. The developed
SnO2 particle exhibited a wide band gap energy, indicating their UV light driven
photocatalytic properties. Through parametric studies by varying the catalyst concentration,
methanol-to-oil ratio, light irradiation time, and reaction time an optimized condition of
12:1, 4 wt%, 3.5 h, and 3.5 h respectively was determined. This condition resulted in the
degradation of around 96.31% of FFA, leading to a final FFA concentration of 0.8% in the
treated DWSO, compared to ~21.7% in the untreated DWSO. In contrast, the conventional
acid-treatment process using H2SO4 as an acid catalyst degraded around 92.62% of FFA but
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 Chapter 5
required for consecutive esterification processes. Furthermore, the stability of SnO 2 allows
for its recyclable usage in FFA degradation in DWSO, maintaining over 80% efficiency up
to 4 cycles. Finally, the biodiesel produced using the SnO 2 photocatalysts-treated DWSO
met ASTM 6751 standards with improved physiochemical and fuel properties. This study
underscores that compared to the conventional acid-assisted esterification process; the
photocatalytic esterification can be an effective alternative for degrading FFA in feedstock
oil. It offers advantages such as reduced process time, cost-effectiveness, and scalability for
large-scale biodiesel production

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