processes

Project Report
Production of Biodiesel from Waste Cooking Oil via
Deoxygenation Using Ni-Mo/Ac Catalyst
Nor Shafinaz Azman 1 , Tengku Sharifah Marliza 1,2, *, Nurul Asikin Mijan 3 , Taufiq Yap Yun Hin 2,4
and Nozieana Khairuddin 1, *

1 Department of Basic Science and Engineering, Faculty of Agriculture and Food Sciences, Universiti Putra
Malaysia Bintulu Sarawak Campus, Bintulu 97008, Malaysia; [email protected]
2 Catalysis Science and Technology Research Centre, Faculty of Science, Universiti Putra Malaysia,
UPM Serdang, Serdang 43300, Malaysia; [email protected]
3 Department of Chemical Sciences, Faculty of Science and Technology, Universiti Kebangsaan Malaysia,
UKM Bangi, Bangi 43600, Malaysia; [email protected]
4 Chancellery Office, Universiti Malaysia Sabah, Kota Kinabalu 88400, Malaysia
* Correspondence: [email protected] (T.S.M.); [email protected] (N.K.); Tel.: +60-86-855-430 (N.K.)

Abstract: Waste cooking oil (WCO) from palm oil is one of the most prospective biodiesel feedstock
when compared to other oil seeds. Thus, WCO has great potential as a green source of diesel fuel
for engines in motor vehicles and machinery. This project aimed to study the potential of three
randomly selected types of WCO, namely; sample A (used 1× once to fry an egg), sample B (used 3–
5× to fry salted fish), and sample C (used repeatedly to fry banana fritter) for the production of
green diesel fuel over Ni-Mo/AC (nickel and molybdenum oxides incorporated with activated
carbon) catalyst through the deoxygenation (DO) process. The prepared catalyst was characterized
through X-ray diffraction (XRD), thermogravimetric analysis (TGA), and field emission scanning





 electron microscopy (FESEM). The DO process was performed at 350 ◦ C to remove oxygen from
the WCO samples. The liquid products were analysed by gas chromatography-mass spectrometer
Citation: Azman, N.S.; Marliza, T.S.;
(GC-MS) and gas chromatography-flame ionization detector (GC-FID), to measure the yields of
Mijan, N.A.; Yun Hin, T.Y.;
Khairuddin, N. Production of
straight-chain hydrocarbons and fractions in the range C8 -C20 . Results showed that the highest
Biodiesel from Waste Cooking Oil via n-(C8 -C20 ) hydrocarbon fractions were produced in the order of sample B (89.93%) > C (88.84%) > A
Deoxygenation Using Ni-Mo/Ac (82.81%).
Catalyst. Processes 2021, 9, 750.
https://dx.doi.org/10.3390/ Keywords: waste cooking oil; green fuel; biodiesel; heterogeneous catalyst; deoxygenation
pr9050750

Received: 12 November 2020

Accepted: 6 December 2020 1. Introduction
Published: 23 April 2021
Current strategies are geared towards a green form of diesel consisting of free-
oxygenated hydrocarbon compounds for future use as a clean-burning fuel. Such fuels
Publisher’s Note: MDPI stays neutral
are characterised by low sulphur and aromatic content, high cetane content, lubricity and
with regard to jurisdictional claims in
regenerability, which can guarantee ~70–90% reduction in GHG emissions (Asikin-Mijan
published maps and institutional affil-
et al., 2016a). Since the substance is not only fungible with crude oil-derived fuels, it also
iations.
has properties similar to alternative biofuels, such as biodiesel or methyl ester fatty acid
(FAME). FAME is an extremely oxygenated compound with various drawbacks, such as
high viscosity, low cloud and pour point properties, along with low heating value and
oxidation stability [1–3]. Green diesel is generally synthesized by the deoxygenation (DO)
Copyright: © 2021 by the authors.
of triglycerides and fatty acid derivatives by decarboxylation or decarbonylation (deCOx),
Licensee MDPI, Basel, Switzerland.
along with the formation of CO2 and CO + H2 O as by-products [4–6]. Green diesel may also
This article is an open access article
be synthesized by the process of hydrodeoxygenation (HDO), during which oxygenated
distributed under the terms and
compounds are extracted in the presence of H2 gas, resulting in the formation of water
conditions of the Creative Commons
(H2 O) as a by-product [7]. However, the process requires a high amount of expensive
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
H2 gas and high reaction pressure [8]. In contrast, the DO procedure is considered to
4.0/).
be more economical, successful and suitable for industrial practices. The process results

Processes 2021, 9, 750. https://doi.org/10.3390/pr9050750 https://www.mdpi.com/journal/processes

Processes 2021, 9, 750 2 of 12

in high-quality green diesel, with similar fuel properties as standard crude oil-derived
diesel [9].
Recently, the DO process was investigated using various catalysts, such as Pd or Pt-
based transition metal oxides consisting of Ni, Co, Zn, Cu, Ga and Ru [2,10–13]. The most
typical transition metal oxides used for DO are Ni, Co, W [14], and Mo, Cu, Fe, and Zn [15],
with Ni showing the highest DO behaviour among the metals. Croker and co-workers
observed that 20 wt. per cent Ni/C yielded higher glycerol tristearate compared to 5 wt.
percent Pd and 1 wt. percent Pt-promoted catalyst [16]. The results are important since
Ni is ~1750 and ~3450 times cheaper than Pd and Pt, respectively. A few studies have
shown that Ni-promoted catalysts exhibited high DO activity through the deCOx pathway
during the DO phase of triglyceride oil and model compounds (palmitic acid methyl group
stearate) for the production of diesel-range hydrocarbons [17]. The efficacy of the DO
reaction mainly includes noble-based catalysts on either Pd or Pt, which result in high
deCOx activity and high hydrocarbon fraction yields. However, the high cost of such cata-
lysts restricts industrial applications. Another downside for large-scale applications is the
complex method of preparing such catalysts. The acid-based catalysts are also vulnerable
to deactivation of the catalytic active sites due to coke formation [18]. The modification of
such catalysts is therefore an essential requirement to enhance stability. Recent studies have
shown that lower coke formation is accomplished by the use of basic metal-catalyst com-
pared to acid metal-catalysts during DO reactions [1,4]. However, despite the existence of
high cracking activity, the fundamental catalyst jointly results in low deCOx activity [4,19].
The acidic-basic properties of disaggregated CaO-La2O3/AC nano-sized carbon-supported
catalysts have been effective in the development of biodiesel [19]. The catalytic properties
of mixed metal oxides are mostly reliant on the microstructure of the nanosized catalyst.
During the nanoparticle stage, the surface-to-volume ratio increases significantly, meaning
that the surface atoms absorb an increasing fraction of the entire particulate volume with
high defective structures. As a consequence, the atoms show interesting new or enhanced
chemical properties. Nanocrystalline NiMoO4, with a particle size of about 20 nm, has been
synthesized [20,21], but no catalytic information has been published in the literature. Fur-
thermore, the development and comprehensive examination of catalysts by researchers for
industrial biodiesel application are yet to be achieved. The high cost of raw materials is a
major obstacle for the commercialization of biodiesel production [22]. Hence, the use of
cheap and renewable feedstocks is crucial to the production of biodiesel. Waste cooking oil
(WCO) is an abundant by-product of daily food preparation [23]. The use of palm oil-based
WCO as feedstock for biodiesel could jointly solve the problems of waste disposal and
dwindling environmental standards in Malaysia.
In the current research, the selective catalytic synthesis of stable mesoporous com-
pounds was investigated through DO, using an acidic bimetallic Ni-Mo/AC OXIDE cata-
lyst. The synthesized catalyst was characterized by XRD, TGA, field emission scanning
electron microscopy (FESEM) and FTIR. The products obtained were subsequently charac-
terized by GC-MS and GC-FID to investigate the effect of the various palm oil-based WCOs.
The selected catalyst for the great performance breakdown of hydrocarbon chains was
synthesized at the recommended ratio of 10%:10%:80%, due to higher AC usage compared
to the acid and basic metal. The paper provides useful information on the evaluation of
WCO from various food types, preparation and frequency of use through DO using a
prepared catalyst.

2. Materials and Methods

2.1. Materials
The AC was purchased from Sigma-Aldrich with the appearance of the 100–400 mesh
as support. The nickel (II) nitrate hexahydrate (Ni (NO3 )2 ·6H2 O) with molecular weight
290.79 g/mol and ammonium molybdate ((NH4 )6 Mo7 ·4H2 O) with molecular weight
1235.86 g/mol were purchased from HmbG Chemicals. The liquid product used was
phosphoric acid (lab-grade standard in 85%) from the Reagent brand. The experimental
Processes 2021, 9, 750 3 of 12

Processes 2020, 8, x FOR PEER REVIEW 3 of 13

palm oil-based WCO feedstock was obtained from a selected café and stall located at
Serdang in Selangor, Malaysia. The three treatments were arranged based on the number of
selected café and stall located at Serdang in Selangor, Malaysia. The three treatments were arranged
uses of the WCO, as shown in Table 1. The oils used for the reactions were applied directly
based on the number of uses of the WCO, as shown in Table 1. The oils used for the reactions were
without any treatment or purification.
applied directly without any treatment or purification.
Table 1. Sample of waste cooking oil and the number of times used before treatment.
Table 1. Sample of waste cooking oil and the number of times used before treatment.
Sample Number of Times Used Types of Usage
Sample Number of Times Used Types of Usage
A 1 time Fried egg
A B 1 time 3–5 times Fried egg
Fried salted fish
B C 3–5 times>5 times Fried salted fish fruit fritter
Fried banana
C >5 times Fried banana fruit fritter
2.2. Catalyst Synthesis
2.2. Catalyst Synthesis
Catalyst preparation for this research was prepared by following the method of Wan
Catalyst Khalit et al. [24]
preparation withresearch
for this minor modification.
was preparedThe reflux apparatus
by following the methodshown of in Figure
Wan 1 was
Khalit et al.set
up in a fume chamber equipped with water flow for the inlet and
[24] with minor modification. The reflux apparatus shown in Figure 1 was set up in a fume chamber an outlet for the excess
distilled water discharged. The heating and stirrer machines were connected with a retort
equipped with water flow for the inlet and an outlet for the excess distilled water discharged. The
stand to hold the reflux condenser upward, together with the temperature detector rod
heating and stirrer machines were connected with a retort stand to hold the reflux condenser upward,
placed inside the stainless-steel basin placed on the heater. The 250 mL round bottom flask
together withwas
the temperature
immersed in detector
paraffin rod placed
liquid inside
to avoid the evaporation
rapid stainless-steel basin
due placed
to the on the
heating heater.
effect. Next,
The 250 mL round bottom
precisely 5 g offlask
the was immersed
AC was weighed in using
paraffin liquidbalance,
a digital to avoidwhile
rapid75 evaporation due to the
mL of phosphoric acid
heating effect.was
Next, precisely
measured 5 g aofmeasuring
using the AC was weighed
cylinder. Bothusing a digital
materials werebalance, while to
transferred 75amL250 of
mL
phosphoric acid wasbottom
round measured using
flask and aameasuring cylinder.
magnetic stirrer was Both materials
placed in thewere
flasktransferred to a 250 a
before connecting
mL round bottom
reflux flask and atomagnetic
condenser the lower stirrer
part. was placed
The hot plateinwas
the then
flasksetbefore
to 150 ◦ C and 500
connecting a rpm
refluxfor
condenser to the lower
12 h. The part. The hotof
purification plate
the was
heatedthen set to 150 using
substances °C andwarm500 rpm for 12water
distilled h. Thewaspurification
done after
adjusting the
of the heated substances solution
using warm to pH 7. water
distilled Next, was
the powder
done after was dried in
adjusting theansolution
oven atto100pH◦7.
C Next,
for 2 h.
the powder wasThedried
AC was then
in an impregnated
oven at 100 °C toforsynthesize
2 h. The AC the was
NiO:then
MoO: AC catalystto
impregnated based on the the
synthesize w/w
NiO: MoO: AC ratio 10%:10%:80%,
catalyst based on the by w/w
constant
ratiostirring for six (6)
10%:10%:80%, by hours.
constant The impregnated
stirring for six (6)metals
hours.on the
The
catalyst support were subsequently desiccated at 100 ◦ C for 24 h. Afterwards, AC doped
impregnated metals on the catalyst support were subsequently desiccated at 100 °C for 24 h.
with the metals was calcined ◦
Afterwards, AC doped with the metals wasunder N2 under
calcined gas flowN2 at
gas700
flowCatfor 4 h.
700 °C for 4 h.

Figure 1. Schematic diagram for catalyst synthesis by wet impregnation method.

2.3. Catalyst Characterization

Figure 1. Schematic diagram for catalyst synthesis by wet impregnation method.
2.3.1. X-ray Diffraction (XRD)
In this study, XRD was utilized to determine the rate of dispersion and the chemical
2.3. Catalyst Characterization
structure of the reformed AC catalyst, before and after the reaction. The XRD inquiry was
carried out(XRD)
2.3.1. X-ray Diffraction on the Shimadzu diffractometer (Model: XRD-6000, Shimadzu Corporation,
Kyoto, Japan).
In this study, XRD was utilized to determine the rate of dispersion and the chemical structure of
the reformed AC catalyst, before and after the reaction. The XRD inquiry was carried out on the
Shimadzu diffractometer (Model: XRD-6000, Shimadzu Corporation, Kyoto, Japan).
Processes 2021, 9, 750 4 of 12

2.3.2. Thermogravimetric Analysis (TGA)

TGA analysis was used to test the stability of the synthesized catalysts. It was also
used to examine the coke deposition on the spent catalysts. Each spent catalyst was heated
at 30 ◦ C/min heating rate under the oxygen gas (O2 ) flow rate of 40 mL/min, from 25 ◦ C
to 900 ◦ C.

2.3.3. Field Emission Scanning Electron Microscopy (FESEM)

The morphological characteristics of the catalyst were investigated by field emission
scanning electron microscopy (Rayny EDX-720; Shimadzu, Kyoto, Japan). The FESEM
images were observed through the LEO 1455 VP electron microscope.

2.3.4. Fourier Transform Infrared (FTIR) Spectroscopy

The FTIR analysis was conducted to analyse the chemical functional groups of the
triolein (feedstock) and deoxygenated materials. During the deoxygenation cycle, the ab-
sorption bands corresponding to the ester, alcohol, carbonyl, glycerides, and carboxylic
groups were recorded. Chemical characterization analysis was done following the method
described by Muhamad et al. (2013) with minor modification. The Perkin–Elmer Spectrum
One FT-IR Spectrometer was used to examine the chemical composition and chemical
bonds present in the prepared films. Before the FTIR analysis, the prepared films were
dried overnight at 40 ◦ C in an oven. Each dried film was then ground into a fine powder.
Next, 4 mg of the ground films were mixed with potassium bromide (KBr) powder in a ratio
of 1:10. The sample pellets were formed under a pressure of 500 kg/cm2 using a hydraulic
press. The prepared samples were then analysed using the Perkin-Elmer Spectrum One
FT-IR Spectrometer at a resolution of 4 cm−1 in the range of 4000–400 cm−1 averaged over
16 scans.

2.4. Catalyst Performance Evaluation

2.4.1. Catalytic Deoxygenation of Waste Cooking Oil (WCO)
The DO of WCO was performed in a 250 mL mechanically stirred, semi-batch reactor,
as shown in Figure 2. For each run, 10 g of WCO and 5 wt.% of the synthesized catalyst
were placed in the reactor, as reported by Wan Khalit et al. [24], who stated that the reactor
must be purged with N2 gas to extract the O2 from the air created during the heating
process, by setting the temperature to 350 ◦ C and run-time of 3 h. The condensed liquid
product was subsequently deoxygenated and stored in the collection vessel placed after the
chiller. After the reaction was completed, the reactor was cooled to an ambient temperature,
while the contents of the vessel collector and round bottom flask were weighed [10]. Lastly,
the products were analysed by gas chromatography-flame ionization detection (GC-FID).
Processes 2020, 8, x FOR PEER REVIEW 5 of 13

Figure 2. Semi-batch schematic

Figure 2. Semi-batchdiagram
schematic and process
diagram setupsetup
and process for deoxygenation
for deoxygenationof
ofwaste cooking
waste cooking oiloil (WCO).
(WCO).

2.4.2. Gas Chromatography-Flame Ionization Detector (GC-FID)

The liquid-based products were examined by GC-FID. Before each test, the sample was
dissolved in the GC standard n-hexane before 1 μL of the sample aliquot was inserted in the GC
column. Simultaneously, the temperature of the injection was fixed at 250 °C, whereas nitrogen was
Processes 2021, 9, 750 5 of 12

2.4.2. Gas Chromatography-Flame Ionization Detector (GC-FID)

The liquid-based products were examined by GC-FID. Before each test, the sample
was dissolved in the GC standard n-hexane before 1 µL of the sample aliquot was inserted
in the GC column. Simultaneously, the temperature of the injection was fixed at 250 ◦ C,
whereas nitrogen was selected as the transport gas. The oven of the GC-FID was set
to 6 min at 40 ◦ C, before ramping to 300 ◦ C at a rate of 7 ◦ C/min for 30 min. The GC-
FID analysis was performed to define the hydrocarbon components from the marketed
saturated versions from C8 -C20 and the commercially unsaturated nonene [5]. The entire
area under the chromatographic peak of each hydrocarbon fraction (% relative abundance)
also termed the total saturated and unsaturated straight-chain hydrocarbons (C8 -C20 )
(n-alkane + n-alkene) fractions, were determined by Equation (1):

Σ Ao + ΣAi
X = × 100% (1)
Σ Az

The term X denotes the saturated and unsaturated straight-chain hydrocarbon frac-
tions (% relative abundance), Ao was determined by the area of the alkene (C8 -C20 ), Ai was
determined by the area of the alkane (C8 -C20 ), and Az was determined by the area of the
total product.

2.4.3. Gas Chromatography-Mass Spectrometer (GC-MS)

GC-MS was employed to evaluate the liquid deoxygenated substances with the sat-
urated and unsaturated hydrocarbon (C8 -C20 ) fractions defined under experimental con-
ditions. Asomaning [25] demonstrated that the identification of the unsaturated hydro-
carbons can be performed by interpreting the GC-MS based data and comparing it to the
National Institute of Standards and Testing Library and Literature data. Asikin-Mijan [26]
reported that the chemical composition of the feedstocks and liquid products of DO were
characterised qualitatively by the GC-MS (Shimadzu QP50550A model) equipped with
a non-polar DB-5HT column (30 m × 0.32 mm × 0.25 µm) through the less split inlet.
The completed examination is significant since the resulting liquid product was then as-
sumed to have functions that are not limited to hydrocarbons. The samples were diluted to
100 mg/L with GC grade n-hexane (purity > 98%), while the compounds were identified
based on a probable match equal to or above 95%. The selectivity of the deoxygenated
products was determined based on Equation (2):

Ax
X = × 100% (2)
Σ Ay

The term X denotes the selectivity (%), Ax was determined by the peak area of the
desired organic compound, and Ay was determined by the peak area of the total organic
compounds.

3. Results and Discussion

3.1. WCO Evaluation as Biodiesel Feedstock
Van et al. highlighted the number of carboxylic acid groups such as fatty acids in a
mixture of chemical compounds [27]. Typically, a fixed amount of a sample is diluted in
an organic solvent (usually isopropanol) and titrated with KOH (potassium hydroxide),
using phenolphthalein as an essential colour indicator. Furthermore, the acid number
measures the acidity of any substance, such as biodiesel. The volume of KOH (in mg)
required to neutralize the acidic constituents is 1 g of the sample. In this study, the three
(3) WCO samples, and the acid values of their liquid oil products are shown in Table 2.
The acidic and FFA values are expressed in Equations (3) and (4):

(Volume of 0.01 M KOH × 0.01 × 56.1)/Weight of oil (g) (3)

Processes 2021, 9, 750 6 of 12

FFA = Acid value/2. (4)

Table 2. Acid values of WCO.

Properties WCO Standard

A: 7.5592
(i) FFA content (%) B: 11.7767 -
C: 14.0520
A: 3.7796
(ii) Acid Value (mg KOH g−1 ) B. 5.8884 ASTM D974
C: 7.026
A: 1.0727 ASTM D6751 (American standard
(iii) Liquid Product (Biodiesel) B: 0.6926 specification). EN14214 (European
C: 1.0595 standard specification)

However, the WCO feedstock was further subjected to chemical property characteri-
zation using GC programs adapted from Wan Khalit et al. [24], due to similarities in the
source and locality obtained, as tabulated in Table 3.

Table 3. Composition of Fatty Acid a .

Fatty Acid Composition a (%)

Myristic acid (C14) 4.5
Palmitic acid (C16) 22.0
Stearic acid (C18:0) 2.1
Oleic acid (C18:1) 48.1
Linoleic acid (C18:2) 7.6
Gadoleic acid (C20:1) 13.0
Others b 2.7
aGC programs: column: zebron ZB5 ms (30 m × 0.25 mm I.D. × 0.25 µm); temperature program: starting from
50 ◦ C and hold for 3 min before heating to 300 ◦ C at 10 ◦ C min−1 . GCMS detector and injector temperature:
250 ◦ C; flow rate: 1 mL min−1 ; carrier gas: helium. b Others = C11 H20 O, C21 H42 O2 Si and C30 H50 , C26 H50 .

3.2. XRD Diffraction

Figure 3 shows the XRD pattern of the analysed Ni-Mo/AC catalyst. There is an
adjacent graph to the XRD peak distance, which is ascribed to the high crystallinity and
clear elements of the mesoporous Ni-Mo/AC structure. Based on the graph, the intense
peaks of MoO2 appeared at 2θ = 26.033◦ , 37.121◦ , 49.498◦ , and 53.888◦ (JCPDS card no:
00-002-0422). However, the NiOOH peaks were located at 2θ = 37.281◦ ) (JCPDS card no:
00-006-0141). Furthermore, the visible peaks of Ni were found at 2θ = 44.349◦ , 51.674◦
(JCPDS card no: 00-001-1272), whereas the NiMoO4 peaks were observed at 2θ = 77.405◦ ,
44.142◦ , 52.488◦ (JCPDS card no: 0120348). The results are in agreement with Wu et al. [28],
who reported that the successful impregnation of NiO and MoO greatly reduced the
amorphous structure of AC. Hence, the overlap of both species in AC ultimately promotes
greater dispersal in the AC-based catalyst.

3.3. Fourier Transform Infrared (FTIR) Spectroscopy

Based on this study, the chemical functional groups of the triglyceride and deoxy-
genated products were studied. The spectra for all the samples in Figure 4 showed an
absorption band detected at 1743 cm−1 (C=O), that is ascribed to the ester groups in glyc-
erides, whereas the band at 1140 cm−1 (C=O) denotes the alcohol group usually attributed
to WCO. The intense peak of the carbonyl (C=O) group and WCO are visible at 1740 cm−1 .
Hence, its presence at 1140 cm−1 indicates the progress of the DO reaction. The breakage
of triglycerides into the fatty acids of the deoxygenated liquid can be observed through the
shift in the C=O (ester) absorption band from 1740 cm−1 to 1700 cm−1 , which is ascribed to
 to the XRD peak distance, which is ascribed to the high crystallinity and clear elements of the
mesoporous Ni-Mo/AC structure. Based on the graph, the intense peaks of MoO2 appeared at 2θ =
26.033°, 37.121°, 49.498°, and 53.888° (JCPDS card no: 00-002-0422). However, the NiOOH peaks were
located at 2θ = 37.281°) (JCPDS card no: 00-006-0141). Furthermore, the visible peaks of Ni were found
Processes 2021, 9, 750
at 2θ = 44.349°, 51.674° (JCPDS card no: 00-001-1272), whereas the NiMoO4 peaks were observed at7 of 12
2θ = 77.405°, 44.142°, 52.488° (JCPDS card no: 0120348). The results are in agreement with Wu et al.
[28], who reported that the successful impregnation of NiO and MoO greatly reduced the amorphous
the intermediate carboxylic acid produced. The reaction phase for DO is also evident in the
structure of AC.loss
Hence, the
of the overlap
C=O of bothband
absorption species
nearin1150
AC cm
ultimately promotes
−1 . According greaterand
to Satyarti dispersal in [29],
Srinivas
the AC-based catalyst. − 1
the typical C-H stretching peaks at 2921 cm are not affected by hydrocarbon formation.

Figure
Processes 2020, Figure
3. XRD
8, x FOR 3. diffraction
PEER XRD diffraction
REVIEW of the of the calcined
calcined NiO-MoO/AC
NiO-MoO/AC catalyst.
catalyst. 8 of 13

3.3. Fourier Transform Infrared (FTIR) Spectroscopy

Based on this study, the chemical functional groups of the triglyceride and deoxygenated
products were studied. The spectra for all the samples in Figure 4 showed an absorption band
detected at 1743 cm−1 (C=O), that is ascribed to the ester groups in glycerides, whereas the band at
1140 cm−1 (C=O) denotes the alcohol group usually attributed to WCO. The intense peak of the
carbonyl (C=O) group and WCO are visible at 1740 cm−1. Hence, its presence at 1140 cm−1 indicates
the progress of the DO reaction. The breakage of triglycerides into the fatty acids of the deoxygenated
liquid can be observed through the shift in the C=O (ester) absorption band from 1740 cm−1 to 1700
cm−1, which is ascribed to the intermediate carboxylic acid produced. The reaction phase for DO is
also evident in the loss of the C=O absorption band near 1150 cm−1. According to Satyarti and Srinivas
[29], the typical C-H stretching peaks at 2921 cm−1 are not affected by hydrocarbon formation.

Figure 4. FTIR spectra of the deoxygenated sample (A–C) liquid product catalysed.
Figure 4. FTIR spectra of the deoxygenated sample (A–C) liquid product catalysed.
3.4. Thermogravimetric Analysis (TGA)
3.4. Thermogravimetric Analysis
The degree (TGA)
of coke formation was investigated by TGA. In this study, the degree of
coke formed on the Ni-Mo/AC catalyst is shown in Figure 5. Based on Figure 5a-(TGA
The degree of coke formation was investigated by TGA. In this study, the degree of coke formed
N2 ), the calcined catalyst is defined by a shorter period or phase of coke formation and
on the Ni-Mo/AC catalyst is shown in Figure 5. Based on Figure 5a-(TGA N2), the calcined catalyst is
temperature range compared to the catalyst before calcination. The formation of coke on
defined bythe a shorter
externalperiod
surfaceorofphase of coke
the catalyst formation
during and temperature
the reaction degraded the range
DOcompared to the
activity. Hence,
catalyst before calcination. The formation of coke on the external surface of the catalyst
the results revealed that the bimetallic Ni-Mo/AC catalyst promotes superior resistance during the
reaction degraded
towards the
cokeDO activity. Hence,
formation. the results
The findings are inrevealed
agreement that theWan
with bimetallic
KhalitNi-Mo/AC catalyst
et al. [24], who re-
promotes superior resistance
ported that the XRDtowards
and TGA coke formation.
confirm Thebimetallic
that the findings are in agreement
Ni-Mo/AC with Wan
has potential Khalit
catalyst
et al. [24], who reported
stability that the XRD
and prospects and TGA
for further confirm at
application that the bimetallic
pilot-scale, due toNi-Mo/AC
its long-lifehas
andpotential
reuse.
Figure and
catalyst stability 5b—(TGA O2 )for
prospects shows thatapplication
further the spent catalyst sampledue
at pilot-scale, A exhibits a decomposition
to its long-life and reuse.
Figure 5b—(TGA O2) shows that the spent catalyst sample A exhibits a decomposition peak in the
range 245 °C to 347 °C. For sample B, the decomposition peak was from 252 °C to 319 °C, whereas
sample C was from 271 °C to 324 °C, which is linked to the combustion of the AC bulk nanorod. In
general, all the spent catalysts showed rapid weight loss due to the decomposition temperature at
700 °C, which indicates the oxidation of coke in air.
 on the Ni-Mo/AC catalyst is shown in Figure 5. Based on Figure 5a-(TGA N2), the calcined catalyst is
defined by a shorter period or phase of coke formation and temperature range compared to the
catalyst before calcination. The formation of coke on the external surface of the catalyst during the
reaction degraded the DO activity. Hence, the results revealed that the bimetallic Ni-Mo/AC catalyst
Processes 2021, 9, 750 promotes superior resistance towards coke formation. The findings are in agreement with Wan 8 ofKhalit
12
et al. [24], who reported that the XRD and TGA confirm that the bimetallic Ni-Mo/AC has potential
catalyst stability and prospects for further application at pilot-scale, due to its long-life and reuse.
Figure
peak 5b—(TGA
in the range 245 ◦ C to 347
O2) shows that◦ the spent
C. For catalyst
sample B, sample A exhibits a decomposition
the decomposition peak was frompeak252 in◦ Cthe
range ◦245 °C to 347 °C. For sample B, the decomposition
◦ ◦ peak was from
to 319 C, whereas sample C was from 271 C to 324 C, which is linked to the combustion 252 °C to 319 °C, whereas
ofsample
the ACC bulk
was from 271 °CIntogeneral,
nanorod. 324 °C, which
all theisspent
linked to the combustion
catalysts of the
showed rapid AC bulk
weight nanorod.
loss due to In
general, all the spent catalysts showed rapid
◦ weight loss due to the decomposition
the decomposition temperature at 700 C, which indicates the oxidation of coke in air. temperature at
700 °C, which indicates the oxidation of coke in air.

Figure 5. TGA profile for (a) before and after catalyst calcination in N2 and (b) spent
Figure 5.sample
catalyst TGA profile
A, B, for (a) before
C using O2 . and after catalyst calcination in N2 and (b) spent catalyst sample
A, B, C using O2.
Processes 2020, 8, x FOR PEER REVIEW 9 of 13
3.5. Field Emission Scanning Electron Microscopy (FESEM)
3.5. Field Emission Scanning Electron
Figure Microscopythe
6a illustrates (FESEM)
FESEM images of the fresh AC and Ni-Mo/AC catalyst at
700 ◦ Cthe
Figure 6a illustrates activation
FESEMtemperature.
images of the Thefresh
images
ACrepresent a significant
and Ni-Mo/AC difference
catalyst at 700between
°C the
fresh AC and Ni-Mo/AC catalyst, which are characterized by smooth surfaces and regular-
activation temperature. The images represent a significant difference between the fresh AC and Ni-
shaped spheres. However, the morphology of the catalyst changed when the fresh AC was
Mo/AC catalyst, which are characterized by smooth surfaces and regular-shaped spheres. However,
doped with the bimetal oxide. Hence, Figure 6b shows rough, aggregate, and irregular
the morphology of the catalyst changed when the fresh AC was doped with the bimetal oxide. Hence,
spherical shapes with particle size > 1 µm. The changes are due to the occurrence of
Figure 6b shows rough, aggregate,
hydrogen and irregular
bond fractures in thespherical shapes
crystalline region with particle
triggered bysize
the >acid
1 μm. The of the
treatment
changes are due to the occurrence of hydrogen bond fractures in the crystalline region triggered
activated charcoal surfaces, which assist in the formation of nanocrystalline fibrous-like by
the acid treatment ofstructures
the activated charcoal [8].
or patterns surfaces, which assist
The addition in the
of the formation
bimetallic of nanocrystalline
phase of Ni-Mo/AC causes
fibrous-like structures
theor patterns [8].ofThe
enlargement addition
particle size,of
asthe bimetallic
expected fromphase of Ni-Mo/AC
the combination ofcauses the metals
interposed
enlargement of particle size, as expected from the combination of interposed metals (NiO +
(NiO + MoO) throughout the synthesis process. Thus, Table 4 below shows the elemental MoO)
composition
throughout the synthesis of the
process. Thus,synthesized catalyst
Table 4 below during
shows thethe experimental
elemental process, of
composition as determined
the
synthesized catalystby EDX.the experimental process, as determined by EDX.
during

Figure 6. Field
Figure emission
6. Field scanning
emission electron
scanning microscopy
electron (FESEM)
microscopy imageimage
(FESEM) of (a) of
fresh AC, (b)
(a) fresh Ni-Mo/AC
AC, catalyst.
(b) Ni-Mo/AC
catalyst.

Table 4. Element composition of the catalyst determined by FESEM-EDX.

Catalyst a Element Composition (%) b

C O Fe Ni
AC 67.91 19.30 - -
Ni-Mo/Ac 62.47 18.76 3.33 15.43
a Theoretical Ni-Mo/AC atomic ratio of catalyst. b Experimental Ni-Mo/AC atomic ratio in synthesized
Processes 2021, 9, 750 9 of 12

Table 4. Element composition of the catalyst determined by FESEM-EDX.

Catalyst a Element Composition (%) b

C O Fe Ni
AC 67.91 19.30 - -
Ni-Mo/Ac 62.47 18.76 3.33 15.43
aTheoretical Ni-Mo/AC atomic ratio of catalyst. b Experimental Ni-Mo/AC atomic ratio in synthesized catalyst
determined by EDX.

3.6. Biodiesel Properties

3.6.1. Gas Chromatography-Flame Ionization Detection
The DO reactivity of WCO over Ni/Mo-AC catalyst is shown in Figure 7a,b. Based
on Figure 7a, sample C shows the highest yield of 31%, followed by sample A (17%) and
sample B (12%). The significant values imply that the catalytic DO reaction was successful.
The dark WCO showed the highest selectivity of DO due to the energetic effect of bimetallic
Ni/Mo on the AC nanorod, which enhanced the properties of the acid-base sites. Figure 7b
shows the comprehensive overview of the distribution of hydrocarbon portions from n(C8 –
C20 ) for the liquid DO products. The WCO consisting of ~45.68% C16 and ~52.34% C18 for
fatty acids is typically converted to hydrocarbon portions comprising nC15 and nC17 by
deCox pathways that are consistent with Bezergianni et al. [30].
Processes 2020, 8, x FOR PEER REVIEW 10 of 13

Figure 7. (a) Hydrocarbon yield %, (b) Distribution of deoxygenation (DO) liquid products of samples A, B, and C using
Figure 7. (a) Hydrocarbon yield %, (b) Distribution of deoxygenation (DO) liquid products of samples
Ni/Mo-AC.
A, B, and C using Ni/Mo-AC.
3.6.2. Gas Chromatography-Mass Spectrometry (GC-MS)
3.6.2. Gas Chromatography-Mass Spectrometry
The comprehensive (GC-MS) of products for all three WCO conditions using the
distribution
Ni-Mo/AC
The comprehensive catalyst
distribution at 350 ◦ Cfor
of products is all
shown
three in
WCOFigure 8. According
conditions using the to Ni-Mo/AC
the GC-MS results,
catalyst at 350 °C is shown in Figure 8. According to the GC-MS results, the arrangementn(C
the arrangement of the highest hydrocarbon fraction produced in the -C20 ) range
of 8the
highest hydrocarbon fraction produced in the n(C8‒C20) range started from sample B (89.93%) >et al. [31]
started from sample B (89.93%) > sample C (88.84%) > sample A (82.81%). Lam
reported that GC-MS analysis allows for easy detection of isomers based on the mass of
sample C (88.84%) > sample A (82.81%). Lam et al. [31] reported that GC-MS analysis allows for easy
the fragmented compound as suggested by the National Institute of Standards. Further-
detection of isomers based on the mass of the fragmented compound as suggested by the National
more, the results of the different range of n(C8 -C20 ) hydrocarbons obtained from both
Institute of Standards. Furthermore, the results of the different range of n(C8‒C20) hydrocarbons
GC-MS and GC-FID confirm that the straight-chained (saturated and unsaturated) hydro-
obtained from both GC-MS
carbons and
were GC-FID
mostly found confirm that the
in the liquid straight-chained
DO product. (saturated
This result and
is in agreement with
unsaturated) hydrocarbons were mostly found in the liquid DO product. This result is in agreement
the finding in Section 3.3. However, a small amount of bulky C21 -C24 hydrocarbons and
with the finding inoxygenated
Section 3.3. However, a(such
intermediates small as amount
aldehydes,of ketones,
bulky Calcohols,
21‒C24 hydrocarbons
and carboxylic andacid) were
oxygenated intermediates (such as aldehydes, ketones, alcohols, and carboxylic acid)
also detected. As reported by Silva [32], WCOs undergo various procedures to achieve were also
detected. As reported by Silva
a perfect [32], WCOs
breakdown undergo various
of triglycerides procedures
into mono-chains to achieve
(free-fatty acid).a Other
perfectproducts
breakdown of triglycerides into mono-chains
include oxygenated (free-fatty acid).
DO intermediates, aldol Other productsketonization
condensation, include oxygenated
and hydrocarbon
deoxygenated
DO intermediates, aldol cyclisation.
condensation, ketonization and hydrocarbon deoxygenated cyclisation.
 unsaturated) hydrocarbons were mostly found in the liquid DO product. This result is in agreement
with the finding in Section 3.3. However, a small amount of bulky C21‒C24 hydrocarbons and
oxygenated intermediates (such as aldehydes, ketones, alcohols, and carboxylic acid) were also
detected. As reported by Silva [32], WCOs undergo various procedures to achieve a perfect
Processes 2021, 9, 750
breakdown of triglycerides into mono-chains (free-fatty acid). Other products include oxygenated
10 of 12
DO intermediates, aldol condensation, ketonization and hydrocarbon deoxygenated cyclisation.

Figure 8. Distribution (%) of DO liquid products from samples A, B and C catalysed by Ni-Mo/AC.
Figure 8. Distribution (%) of DO liquid products from samples A, B and C catalysed by Ni-Mo/AC.
4. Conclusions
4. Conclusions
The remarkable activity of Ni-Mo/AC was due to the energetic effect between the
active acidic
The remarkable promoter
activity (Ni-Mo) was
of Ni-Mo/AC and due
the extensive surfaceeffect
to the energetic area of the ACthe
between support.
active Hence,
acidic
promoter (Ni-Mo) and the extensive surface area of the AC support. Hence, an increase in was
an increase in the penetration of the large WCO triglycerides for the DO reaction the
penetration observed inWCO
of the large this study. The yield
triglycerides of biodiesel
for the DO reactionobtained is influenced
was observed in this by the frequency
study. The yield
of usage and
of biodiesel obtained type of food
is influenced fried
by the with theofpalm
frequency usageoil,
and which
type is
of due
foodto chemical
fried compounds
with the palm oil,
released during the high cooking temperatures. Both samples A and B exhibited high
hydrocarbon fraction yields of 89.93% and 88.84%, respectively, at optimum conditions
within C14 -C18 . In future studies, the authors propose to further investigate the current
bimetallic acid catalyst, using different processes such as the transesterification of WCO to
explore the potential of obtaining higher biodiesel yield and its cost-effectiveness in terms of
catalyst stability and reusability. Other studies will synthesise different bimetallic catalysts
with AC from different waste sources by altering the percentage ratios. The catalysts will
then be examined for reactivity performance using WCO or other fatty acid sources, such as
animal fat from poultry or plants that contains extractable triglyceride.

Author Contributions: N.S.A.: investigation and writing original draft, T.S.M.: Supervision, writing
review and editing, A.-M.N.: Methodology, T.Y.Y.H.: Methodology and resources, N.K.: Funding
acquisition, supervision, writing and review editing. All authors have read and agreed to the
published version of the manuscript.
Funding: This research was funded by Geran Putra-Inisiatif Putra Berkumpulan (Grant number:
9671301) to support the research and development activities at Universiti Putra Malaysia Bintulu
Sarawak Campus, Malaysia.
Data Availability Statement: Data available on request due to ethical restrictions.
Acknowledgments: The authors thank the Department of Basic Science and Engineering, Faculty
of Agriculture and Food Science, University Putra Malaysia, Bintulu Sarawak Campus. Highest
appreciation also goes to PutraCat UPM Serdang for the guidance, facilities, and instruments allowed
for the project analysis to be done smoothly. The authors also thank the Research Management Centre
of Universiti Putra Malaysia (UPM-IPB 9671301) and (Putra-IPM 9559000) for supporting this study.
Conflicts of Interest: The authors declare no conflict of interest.
Processes 2021, 9, 750 11 of 12

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