Journal of Cleaner Production 274 (2020) 122850

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Renewable diesel via solventless and hydrogen-free catalytic

deoxygenation of palm fatty acid distillate
Khairul Basyar Baharudin a, b, Nurulhuda Abdullah c, Yun Hin Taufiq-Yap d, e,
Darfizzi Derawi a, *
a
Laboratory for Biolubricant, Biofuels and Bioenergy Research, Department of Chemical Sciences, Faculty of Science and Technology, Universiti Kebangsaan
Malaysia, 43600 UKM Bangi, Selangor, Malaysia
b
Faculty of Biotechnology and Biomolecular Science, University Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia
c
Technology & Engineering Division, Malaysian Rubber Board, 47000 Sungai Buloh, Malaysia
d
Catalysis Science and Technology Research Centre (PutraCat), Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia
e
Chancellery Office, Universiti Malaysia Sabah, 88400 Kota Kinabalu, Sabah, Malaysia

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

Article history: This work involved the utilization of a byproduct from the palm oil refining process as reaction feedstock
Received 19 March 2020 in a solventless and hydrogen-free catalytic deoxygenation (DO) over NiOeZnO catalyst in producing
Received in revised form diesel-like hydrocarbons as advanced biofuels. The catalyst supporter was synthesized using copreci-
1 May 2020
pitation methods to form highly crystalline meso-macrostructured ZnO particles. The catalyst support
Accepted 14 June 2020
Available online 16 July 2020
was wet-impregnated with different loadings (wt %) of NiO to prepare the NiOeZnO catalyst. X-ray
diffraction patterns verified the persistence of good crystallinity and phase purity of the support, with
Handling editor: M.T. Moreira fine NiO crystallites of size 14e22 nm. Synthesized NiOeZnO catalysts demonstrated Type IV isotherm
with H3 hysteresis loop with mesoporous-macroporous properties. The Brønsted and Lewis acidic sites
Keywords: of NiOeZnO offer a synergy effect between the active site and catalyst supporter. Both N2 adsorption
NiOeZnO isotherm and electron microscopy analysis revealed the increase of the crystallite size of the catalyst by
Palm fatty acid distillate increase the NiO loadings. The catalytic activity of the NiOeZnO catalyst was tested in a semi-batch
Deoxygenation reactor at 350
C for 2 h in N2 atmospheric. The oxygenated compounds of palm fatty acid distillate
Diesel
(PFAD) have been successfully removed to form linear hydrocarbons as green diesel compounds. The
Palm oil
synergistic effect between NiO and ZnO significantly enhanced the catalytic activity for substrate DO. The
hydrocarbons product yield reached 83.4%, with a diesel range (C11eC17) selectivity of 86.0%. The green
diesel, which contains diesel-range hydrocarbons, is suitable as an alternative fuel product for vehicle
engine usage. It is possible to be upscaled and compatible with the existed petrochemical refinery fa-
cilities. Hence, this is a promising work could be an economic potential and give value added to the palm
oil byproduct sectors.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction pyrolysis (Chang, 2018), and industrial wastes and by-products

The total-dependence on petroleum-based fuel sources is a
significant contributor to environmental pollution and energy se-
curity since the Industrial Revolution era in Britain in the 18th
century (Caineng et al., 2016). In general, second-generation feed-
stock involves usage of non-food resource as feedstock such as
vegetable oil (non-edible oil) (Sawangkeaw and Ngamprasertsith,
2013), biomass (Hachemi et al., 2017), bio-oil from biomass
* Corresponding author.
E-mail address: darfizzi@ukm.edu.my (D. Derawi).
(Sawangkeaw and Ngamprasertsith, 2013). The rivalry between
food and biofuels purposes, also the concern about environmental
harm and food crisis, has gained intention in developing alternative
low-cost feedstock. Biodiesel production from the esterification
reaction of free fatty acids (FFAs) with CH3OH was reported before
(Lee and Wilson, 2015). While, biodiesel has been produced from
Jatropha curcas L. using high-voltage underwater discharges
(Marou
sek et al., 2014). However, the biodiesel product shows poor
thermal and oxidative stability properties rather than commercial
petroleum-diesel (Kordulis et al., 2016). Moreover, fatty acid methyl
ester (FAME) fuel properties are depending on the feedstocks, and a

https://doi.org/10.1016/j.jclepro.2020.122850
0959-6526/© 2020 Elsevier Ltd. All rights reserved.
2 K.B. Baharudin et al. / Journal of Cleaner Production 274 (2020) 122850
high degree of unsaturated fatty acid will affect the poor condition
of the cloud and pour point of resulting biodiesel (Knothe, 2010).
Green diesel, as a second-generation biofuel, offers excellent
potential in this regard (Abdulkareem-Alsultan et al., 2019; Ban ~ os
et al., 2011). The green diesel synthesized from biomass waste-
derived lipid and FFAs is a promising fuel in the transportation
sector. The triglycerides present in fats and non-edible vegetable oil
can serve as an alternative renewable material which can be
deoxygenated at current petroleum refineries (Glisic et al., 2016).
Industrial waste-derived FFAs and lipids such as palm fatty acid
distillate (PFAD) could be a potential renewable feedstock for green
diesel production (Kamaruzaman et al., 2020). PFAD is a low-grade
non-edible byproduct derived from the crude palm oil (CPO)
refining process. Malaysia exported the PFAD with an average Free
On Board (FOB) price of USD 505.7 per metric tonne in 20 years
(Fig. 1) (Palm Oil Analytics 2020). The PFAD contained high frac-
tions of FFAs (81.7%) and glycerides (14.4%), with additional vitamin
E, squalene, sterol, and other volatile substances. Typically, the FFA
fraction in Malaysian PFAD is composed of unsaturated fatty acids
such as oleic acid (36.6%), linoleic acid (9.6%), and linolenic acid
(0.47%); plus, saturated fatty acids such as palmitic acid (47.1%),
stearic acid (4.5%), lauric acid (0.2%), and myristic acid (1.2%). Its
abundant supply, flexibility, low-price, and, most importantly, the
high compositions of FFAs will make it a desirable renewable
feedstock for green diesel production (Abdul Kapor et al., 2017;
Thongkumkoon et al., 2019).
Catalytic technologies play a crucial role in chemical energy and
bioenergy industries. Catalyst design and catalytic process may
influence the cost-effectiveness of a production process. Utilizing
waste resources together with the effective and ‘clean’ catalytic
process would be enough to meet green technology requirements.
So that, a solventless and hydrogen-free catalytic system perhaps
suited with the needs of the green and sustainable catalytic reac-
tion process. Deoxygenation (DO) offers a cleaner catalytic process
compared to the hydrodeoxygenation (HDO) due to its solventless
and H2-free reaction system. Besides, DO uses a lower-energy re-
action rather than HDO because the HDO needs high temperature
to make sure the catalytic reaction moves forward. Moreover, the
HDO reaction is required a high-pressure reactor set up with high
safety measures. In the catalytic DO, all the oxygenated compounds
Fig. 1. Average export FOB prices of PFAD in Malaysia.
are converted to non-oxygenated hydrocarbons fuels with better
thermal stability, through decarboxylation (or decarbonylation)
reactions (Hafriz et al., 2018; Sun et al., 2015; Zdainal Abidin et al.,
2019). The presence of oxygenated compounds in diesel will
decrease the combustion and heating values, poor cold flow
properties, low thermal stability, and engine-compatibility issues
(Jeon et al., 2019).
It should be noted that PFAD has been successfully employed as
a feedstock, which revealed the production of green diesel with
good selectivity by using a range of different active catalysts.
Thongkumkoon and co-workers have reported catalytic activities of
trimetallic ReNiMo sulfide supported on Al2O3 toward the DO of
PFAD that was performed in a fixed-bed reactor under a low H2
pressure atmosphere at 370
C (Thongkumkoon et al., 2019). The
results revealed a high diesel yield (C13eC18) of 72.52% from the
reaction over PFAD feedstock. Nevertheless, continuous sulfidation
(i.e., H2S) is needed to prevent rapid deactivation of metal the
sulfide catalyst which potentially results in sulfur contamination of
alkane product by organosulfur compounds and exposure of the
H2S emission to the environment (Kordulis et al., 2016; Mortensen
et al., 2011). Meanwhile, Asikin Mijan has also reported of H2-free
catalytic DO of PFAD over NiOe5CaO/SiO2eAl2O3 catalysts using
semi-batch reactor under partial vacuum and inert N2 flow at
350
C (Asikin-Mijan et al., 2017b). The result proved selective
decarboxylation pathways by rendering 73% of n-C15 þ n-C17 frac-
tions and a total hydrocarbon fraction of 81%. The DO via decar-
boxylation steps using sustainability and cheaper transition
method oxide (TMO) have been proved effective for the removal of
the oxygenated compound regarding the presence of both basic
and acidic properties (Asikin-Mijan et al., 2017a; Loe et al., 2016).
Both investigations showed the high existence of unsaturated FFA
chains in PFAD, leading to a high degree of coke formation on the
used catalyst.
The efficient catalyst requires direct scission of C]O and CeO as
a predominant reaction in which high cracking product (CeC) will
affect the low selectivity of diesel range hydrocarbon (Jin et al.,
2019). Metal promoters are needed to prepare the active sites on
the catalyst surface (or inside the catalyst pores). Noble metals such
as Pt, Pd, and Rh are undoubtedly highly efficient in the DO reac-
tion. However, those precious metal promoters are very expensive,
 K.B. Baharudin et al. / Journal of Cleaner Production 274 (2020) 122850
and the reaction process itself is not meet the cost-effective criteria
as well as the less ‘available’ they are. While, nickel (Ni) is an
excellent promoter in the DO reaction due to its cost-effectiveness
and higher availability compared with noble metals (Taromi and
Kaliaguine, 2018). Ni supported catalyst was also proven to offer
similar promotional effect as a noble supported catalyst in DO
catalytic activity. Morgan and co-workers have reported the DO
reaction of tristearin over Ni, Pt and Pd supported catalyst.
The result showed the 20 wt% Ni on carbon (C) support affording
similar performance effect with those obtained over 5 wt% Pd/C
and 1 wt% Pt/C catalyst (Morgan et al., 2010). This finding is sup-
ported by an investigation of fuel-like hydrocarbon in tristearin and
stearic acid DO reaction over 20 wt% Ni/C and 5 wt% Pd/C catalyst
(Santillan-jimenez et al., 2013). The cracking of long hydrocarbon
chain by the high acidity of 20 wt% Ni/C affects the lower selectivity
fuel-like hydrocarbon product compared to a 5 wt% Pd/C catalyst.
The high acidity of the catalyst also leads to rapid deactivation of
the 20 wt% Ni/C catalyst. Ni supported catalysts are known to
produce high carbon deposits during hydrocarbon conversion at
the elevated catalyst. Besides, the active metal of Ni easily oxidized
in air, and catalytic activity decreases gradually with the storage
time (Jin et al., 2019). Despite this weakness, a cheaper Ni sup-
ported catalyst still an alternative to an expensive noble supported
catalyst for DO reaction of biomass waste-derived lipid and FFAs in
green diesel production. Nevertheless, the promising Ni supported
catalyst could be improved by synergizing with suitable catalyst
support, as the right synergic effect between those materials will
excite optimum catalytic activity (Kordulis et al., 2016).
In this study, oxygenated compounds of PFAD were converted to
diesel-like hydrocarbons via a solventless and H2-free DO reaction
over synthesized meso-macrostructured NiOeZnO catalyst. Highly
crystalline pure-phase ZnO nanoparticles were synthesized as
catalyst supporter using coprecipitation methods. The NiOeZnO
catalysts were prepared through a wet impregnation process.
Then, the catalytic reaction was performed in a semi-batch reactor
under a N2 atmosphere to produce desired diesel compounds. Re-
action performance was evaluated based on diesel compositions,
product selectivity, as well as the percentage of conversion.
2. Experimental
2.1. Material
The ZnO nanoparticles catalyst support was synthesized by the
coprecipitation method according to our previous study (Baharudin
et al., 2018). Absolute C2H5OH (99.5%) was purchased from Fisher
Scientifics. Ni(NO3)2.6H2O (99%) was purchased from Merck. The
reaction feedstock, PFAD, was gratefully supplied by Sime Darby
Plantation Bhd. and has been used without any pretreatment as
reaction feedstock.
2.2. Preparation of NiOeZnO catalysts
According to the previous study of synthesizing ZnO support
(Baharudin et al., 2018), 0.1 M ZnAc was dissolved in C2H5OH as
solution A. In the meantime, solution B was prepared by 0.5 M
oxalic acid dissolved in a mixed solvent of (CH3)2CHOH:H2O ¼ 1.5:1.
Next, solution B was poured slowly into solution A with constant
stirring in ice bath for 1 h. The uniform white suspensions were
collected by centrifugation dried at 70
C for overnight. The dried
powder was calcined at 400
C for 4 h in a muffle furnace with ramp
rate of 5
C min1.
The NiOeZnO catalysts were prepared through a wet impreg-
nation process using Ni(NO3)2$6H2O as a NiO precursor. The pre-
cursor was dissolved at 5 wt% NiO loading with stirring in 40 ml
3
mixed solvent of C2H5OH: H2O ¼ 1:1. The Zinc oxide powders (1g)
from the coprecipitation method (ZnOeCOP) was continuously
added into the solution and stirred vigorously at 25
C for about 3 h.
Then, the solution was slowly heated and stirred at 80
C until the
light green suspension was almost dried. The resulting material
was dried for 18 h in an electric oven at 80
C. Finally, the dried
sample was ground until a fine powder was obtained, then calcined
in a muffle furnace at a ramp rate of 5
C min1 to 400
C, and held
for 5 h. The above procedure was repeated for 10 and 20 wt% NiO
concentrations.
2.3. Characterization of NiOeZnO nanoparticles
Powdered sample was characterized using a Bruker D8 Advance
diffractometer fitted with a LynxEye X’celerator detector at CuKa
(l ¼ 1.54 Å) for phase confirmation. X-ray diffraction (XRD) pat-
terns were analyzed by wide-angle scans (10
e80
), with a step
size of 0.02
and a scan rate of 1 s. While, the low-angle scanned
between 0.45 and 8
, with a step size of 0.01
and scan rate of 0.6 s.
The volume-averaged crystallite diameters were determined using
the Scherrer equation. Pore properties such as pore size, volume
and surface area were analyzed using a N2 adsorption-desorption
isotherm analysis technique by ASAP 2020 Micromeritics through
the BrunauereEmmetteTeller (BET) and Barrett-Joyner-Halenda
(BJH) algorithms (Kamaruzaman et al., 2020). Elemental composi-
tion analysis was performed through X-ray fluorescence (XRF)
analysis using Bruker S8 Tiger instrument equipped with a rhodium
tube operating at 4 kW.
The acidity of the NiOeZnO catalyst was investigated through
temperature programmed desorption (TPD) analysis with NH3 by
Thermo Finnigan TPD/R/O 1100. About 0.05 g of the catalyst sample
was pre-treated under N2 gas flow for 30 min at 250
C, followed by
NH3 gas for 1 h at ambient temperature. The excess NH3 was sub-
sequently flushed with 20 ml/min of N2 gas flow. The NH3
desorption from the acid sites was detected under He gas flow
(30 ml/min) from 50
C to 900
C. The acidity amount was calcu-
lated based on the NH3 desorption peaks area.
The particle surface morphology was observed by a field emis-
sion scanning electron microscope (FESEM, JEOL model JSM 6700F)
operated at the accelerating voltage of 10 kV. The sample was firstly
mounted on an aluminium stub holder using a double-sided tape,
and then coated with an extremely thin layer of platinum using a
sputter coater under vacuum to eliminate the possibility of electric
charging and thermal loading on the sample during the analysis.
The zeta potential was analyzed on a ZetaPlus instrument (Broo-
khaven 90 Plus) at 25
C. The pH value of the system was adjusted
with 0.1 M H2SO4/KOH and recorded using a calibrated pH meter.
When the particles carry no electrical charge, this pH is called the
zero point of charge (ZPC) or isoelectric point (IEP). The ZPC or IEP
of nanoparticles can be determined from the measured zeta po-
tential as a function of pH. Prior to the test, approximately 0.01 wt%
of NiOeZnO powder catalyst was dispersed in distilled water by
sonication for 10 min. Each experiment was repeated five times to
give an average value of the zeta potential.
2.4. Catalytic deoxygenation of PFAD
The catalytic activity of NiOeZnO catalysts with different
amounts of NiO (5, 10, and 20 wt%) was studied for the solventless
and H2-free DO reaction of PFAD under a N2 gas atmosphere
without any repetition set of experiment. The DO of PFAD was
performed in mechanically stirred semi-batch mode with a 250-ml
three-necked flask reactor system (Fig. 2), which was equipped
with a modified reflux distillation unit and N2 gas flow in a com-
bined system. In the typical procedure, approximately 0.5g of
4 K.B. Baharudin et al. / Journal of Cleaner Production 274 (2020) 122850
Fig. 2. Process flow diagram for DO reaction of PFAD (A: reaction feedstock, B: DO reaction, C: reaction product).
NiOeZnO catalyst powder (5 wt % loading) was added to the PFAD
(10 g) without liquid solvent in a semi-batch reactor. Then, N2 gas
was passed through the reactor system for several minutes to
ensure an inert atmosphere. Under constant stirring and contin-
uous N2 flow of 20 ml/min, the temperature was increased slowly
to the required value of 350
C, and the DO reaction was carried out
for 2 h. N2 carried all the evolved gases/vapours to the cooling
condenser, where the condensable (deoxygenated) products can be
collected in the collector vessel. External circulation of cooling
water kept the condenser temperature below 15
C. After the re-
action was completed, the reactor was cooled to room temperature,
and the N2 flow was stopped. A blank experiment was carried out
without the catalyst under the same reaction condition and pa-
rameters, in order to determine the product distribution during the
thermal decomposition of PFAD.
2.5. Diesel composition analysis
The final liquid phase in the DO fraction products was analyzed
by gas chromatography (GC, Agilent 7890A Series) with flame
ionization detector (FID) equipped with an HP-5 capillary column
(length: 30 m, inner diameter: 0.32 mm, film thickness: 0.25 mm).
Both alkane and alkene standards (C8eC20) and internal standard
(1-bromohexane from Sigma-Aldrich) were used for identification
and quantitative analysis. Prior to the yield analysis, GC-grade n-
hexane (1 ml) was used as solvent to dilute 2 ml deoxygenated
liquid product, and an aliquot of approximately 1 ml was injected
into the GC column. The temperatures of the column inlet and FID
were set to 250
C and 300
C, respectively. The initial oven tem-
perature was set at 40
C, held for 6 min, and then increased to
270
C at a heating rate of 7
C/min.
Catalyst performance in the DO process of PFAD was evaluated
by the total yield percentage of saturated and unsaturated straight-
chain hydrocarbons (X). All experiments were repeated several
times with the same condition to validate the reliability of the
results.
P P
na þ nb
X¼ P  100%
nz
where na ¼ area of alkene (C8eC20), nb ¼ area of alkane (C8eC20),
nz ¼ area of product.
The hydrocarbon selectivity (Y) was calculated by:
Cx
Y¼ P  100% (2)
nx
where Cx ¼ area of desired hydrocarbon fraction, nx ¼ area of total
hydrocarbons.
3. Results and discussion
3.1. Physicochemical properties of the NiOeZnO catalysts
All prepared NiOeZnO catalysts showed good crystallinity and
phase purity according to their XRD patterns (Fig. 3). The effective
impregnation of NiO in the ZnO-COP support can be verified by the
appearance of diffraction peaks at 2q z 37.26
and 43.14
, which
correspond perfectly to the (111) and (200) planes of face-centered
cubic NiO (JCPDS 01-075-0197), respectively (Gbadamasi et al.,
2016). No other peaks of unknown phases were observed within
the detection limits of XRD, indicating that the synthesis condition
could produce NiOeZnO with a relatively pure phase. NiO
impregnation did not alter the hexagonal-wurtzite structure of the
ZnO-COP support, as the XRD diffraction peaks hardly changed
after impregnation. The crystallite sizes of NiO in the NiOeZnO
catalysts were measured according to the Debye-Scherrer method
(Vijayaprasath et al., 2014). The results (Table 1) show that the NiO
crystallite size increases proportionally with the loading of NiO
wt.%. Meanwhile, the crystallite size of the ZnO support demon-
strated a similar trend as the impregnated NiO may promote larger
ZnO crystallite size (Li et al., 2015). Therefore, the NiO particles
were generally aggregates before located on the surface of the
catalyst support (Zulkepli et al., 2018).
According to the previous study (Baharudin et al., 2018), nor-
mally nonporous structure of ZnO now appears as a mesoporous-
macroporous material (Zobir et al., 2010). In Fig. 4, all synthesized
NiOeZnO catalysts demonstrated Type IV isotherm with H3 hys-
teresis loop, similar to the ZnO-COP catalyst support
(1)
(Ramimoghadam et al., 2012). Hence, the structural characteristics
of ZnOeCOP were retained after the impregnation of NiO. As
tabulated in Table 1, ZnOeCOP has the largest specific surface area
 K.B. Baharudin et al. / Journal of Cleaner Production 274 (2020) 122850 5

Fig. 3. XRD patterns show good crystallinity and phase purity on various NiO loadings of NiOeZnO.

Table 1
Physicochemical properties of the synthesized ZnOeCOP catalyst support and NiOeZnO catalyst. NiO crystallite size increases proportionally with the loading of NiO due to its
self-aggregation before the impregnation occurred.

Catalyst Surface area (m2/g) Pore volumea (cm3g1) Average Pore sizea (nm) ZnO Crystallite NiO Crystallite Ni contente (wt.%) Total of acidf (mmol of NH3g1)
Sizec (nm) Sized (nm)

ZnOeCOP 23.0 1.730 68.4 22.7 ± 2.6 e e 33.63

5%NiOeZnO 7.8 0.243 61.8 33.3 ± 5.4 14.5 ± 1.2 6.28 304.28
10%NiOeZnO 7.9 0.304 65.8 41.3 ± 7.9 17.8 ± 1.8 11.75 818.19
20%NiOeZnO 10.9 0.096 27.2 44.4 ± 9.1 20.9 ± 2.4 20.67 195.84

b. BJH desorption average pore diameter.

a
BJH desorption pore volume.
c
Calculated using the Scherrer equation based on the XRD diffraction pattern (31.78
).
d
Calculated using the Scherrer equation based on the XRD diffraction pattern (43.14
).
e
Estimated from the XRF analysis.
f
Acidity was determined by TPD-NH3 analysis.

(23 m2/g), and this value decreases after the impregnation of NiO.
With 20 wt% of NiO, the catalyst surface area dramatically
decreased to 10.9 m2/g, while at 5 and 10 wt% NiO the surface areas
are nearly equal (7.8 and 7.9 m2/g, respectively). The successful
deposition of NiO and particle aggregation during calcination may
have partially blocked some pores or covered the surface of
ZnOeCOP, thereby reducing the surface area (Gancheva et al.,
2016).
As tabulated in Table 1, ZnO support initially has large pore
volume and BET surface area. In comparison, the 20% NiOeZnO
catalyst exhibited a much smaller pore volume of 0.096 cm3/g
and a significant decrease in surface area. The pore volume
reduction is attributed to the presence of NiO in the interparticle
pores of the ZnO support, as proven by the BJH pore size distribu-
tion results in Fig. 5. Only one broad distribution was observed
between 30 and 100 nm with significantly lower intensity, as
compared to the trimodal pore size distribution of the original
catalyst support. The NiO embedded mostly on the surface of ZnO
supports led to the reduced average pore size, especially for 20%
NiOeZnO.
The elemental composition of the NiOeZnO catalysts prepared
with different NiO loadings was investigated using XRF elemental
analysis. In Table 1, the measured NiO wt.% are in good agreement
with the intended loadings (5, 10, and 20 wt%). Hence, the wet
impregnation method could efficiently incorporate a given amount
of NiO impregnated to the catalyst support.
The acidity profile of the catalysts was evaluated by TPD through
NH3 chemisorption, as the area of TPD desorption peak is related to
the total acidity (Table 1 and Fig. 6). Also, the NH3 desorption
temperature depends on the strength of acidic sites in the catalyst.
Typically, the desorption peaks are classified into weak acid
(100e250
C), moderate acid (250e400
C), and high acid strengths
(above 400
C) (Abdul-Kadhim et al., 2017; Zulkepli et al., 2018).
The presence of active NiO particles on the catalyst support
increased the catalyst acidity according to the total amount of NH3
in Table 1. In contrast, the ZnO support demonstrated a little
amount of NH3 desorption with a near absence of acid site, and thus
there is a synergy between the bonded NiO and ZnO support that
enhances the catalyst’s acid profile (Safa Gamal et al., 2019). The
most acidic catalyst is 10% NiOeZnO: its two broad desorption
peaks at around 469
C and 595
C suggest a high amount of
Brønsted and/or Lewis acidic sites (Gwak et al., 2018; Naik and
Fernandes, 1999).
The morphological characteristics of the prepared catalysts are
6 K.B. Baharudin et al. / Journal of Cleaner Production 274 (2020) 122850
Fig. 4. Nitrogen adsorption-desorption isotherms of NiOeZnO catalysts with various
wt.% of NiO. All synthesized NiOeZnO catalysts demonstrated Type IV isotherm with
H3 hysteresis loop.
Fig. 5. Pore size distribution of NiOeZnO catalysts with various wt.% of NiO. The
loadings of NiO on the surface of ZnO supports led to the average pore size reduction.
illustrated in Fig. 7. The NiO impregnation affected the interparticle
pores (mesoporous-macroporous structure) of the catalyst support,
reducing both the pore volume and surface area (Table 1 and Fig. 5).
Furthermore, NiOeZnO catalysts demonstrated an irregular parti-
cle structure, because the NiO particles slightly merged and formed
large secondary or tertiary particles. This observation is most
obvious in the 20% NiOeZnO catalyst.
Zeta potential analysis directly characterizes the colloidal sta-
bility of particles by quantifying their surface charges. Particles
with a zeta potential between 30 and þ 30 mV are considered to
have colloidal stability with a low possibility of agglomeration
(Marsalek, 2014; Yusof et al., 2019). Fig. 8 shows the effect of pH and
also the impregnation of NiO on the zeta potential value. Most
NiOeZnO catalysts were negatively charged over the whole pH
value range examined except for 20% NiOeZnO. The impregnation
of NiO altered the surface charge of ZnO nanoparticles, since there
was a shift in the zeta potential towards positive value at all pH
values. This also proves the presence of synergy between the active
NiO particles and the ZnO-COP support. We have seen that the
loading of NiO decreases the surface area of ZnO while increasing
the crystallite/particle size in the BET and crystallite size results
(Table 1) and the FESEM micrographs (Fig. 7). These factors also
help explain the fact that only 20% NiOeZnO shows an IEP at pH 4.2
while the other catalysts and ZnO-COP support show none. It has
been reported elsewhere (Hammarberg et al., 2009; Tso et al., 2010)
that the IEP of ZnO is in the pH range of 8e9.6, while that of the ZnO
nanoparticles becomes lower as the particle size is reduced.
3.2. Deoxygenation activity of PFAD
Fig. 9 summarizes the catalytic activity of NiOeZnO and the
selectivity range of the deoxygenated liquid product. A range of
saturated and unsaturated straight-chain hydrocarbons was
observed, with more in the diesel range n-(C11eC17) than that in the
gasoline range n-(C8eC10). In contrast, the blank experiments gave
a comparatively low hydrocarbon yield of 22.2%, indicating the
beneficial role of the NiO catalysts. Also, products in the blank
experiment were formed from the thermal cracking of FFAs in PFAD
and are concentrated in the gasoline range (with a selectivity of
around 56.8%), including a high percentage of shorter hydrocarbon
chains especially n-C8 and n-C9 (Figs. 9 and 10).
The commercial NiO material and the ZnO-COP catalyst support
showed similar hydrocarbon yields compared to the blank results,
but the products are much more concentrated in the diesel range.
The 10% NiOeZnO catalyst delivered the highest hydrocarbon yield
of 85.4% in the deoxygenated liquid product but a poor diesel
selectivity (70.8%). This is certainly due to the strongest acidic
characteristics of the catalyst (818.19 mmol of NH3g1), leading to
carbon loss from CeC cracking to form light straight-chain hydro-
carbons. The slightly lower hydrocarbon yield of 83.3% over 20%
NiOeZnO is accompanied by the highest diesel selectivity (86.0%,
compared to 70.8% for 10% NiOeZnO). The 5% NiOeZnO catalyst
also showed good selectivity in the diesel range (83.5%) at the cost
of the lowest hydrocarbon yield (77.8%) due to the low loading of
NiO. The final obtained green diesel product strongly depends on
the capability of the catalyst to efficiently remove oxygen atoms
and reduce carbon loss to avoid the formation of light straight-
hydrocarbon chains.
The product selectivity for n-(C8eC17) in the deoxygenated
liquid product (Fig. 10) illustrates a higher selectivity for n-C15 and
n-C17, which is further verified by the selectivity in the n-(C8eC10),
n-(C11eC14) and n-(C15eC17) fraction ranges in Fig. 11. The large
fractions of C16 (palmitic acid, ~47%) and C18:1 (oleic acid, ~36.6%)
from the FFA components in PFAD play a key role in the final
selectivity of the deoxygenated liquid product. An appropriate
catalytic DO reaction pathway must be maintained to attain high
selectivity in the hydrocarbon product. The high selectivity towards
n-C15 and n-C17 is due to the decarboxylation and decarbonylation
reaction pathways of FFAs in Eqns. (2) and (3), respectively:
RCOOH / CO2 þ RH (2)
RCOOH / CO þ H2O þ RH (3)
The decarboxylation pathway is more favorable. Based on
Fig. 12, the n-C15 liquid deoxygenated product is more than 79%
straight-chain alkanes, and the percentage of alkane decreases with
increasing wt.% of NiO in the catalyst. The hydrocarbon fraction of
 K.B. Baharudin et al. / Journal of Cleaner Production 274 (2020) 122850 7

Fig. 6. TPD-NH3 profiles of ZnOeCOP support and NiOeZnO catalysts with various.
wt.% of NiO. The synergy effect of NiO and ZnO produced Brønsted and/or Lewis acidic sites.

Fig. 7. FESEM micrographs for ZnOeCOP support and NiOeZnO catalysts with different NiO loadings (5, 10, 20 wt%). NiO loading increase the particle size of catalyst.

n-(C8eC16) was mostly affected by further hydrocarbon cracking via RxeRy / Rx ¼ CH þ Ry ¼ CH (4)
CeC scission (Eqn. (4)) from the deoxygenated liquid (n-C15 and n-
C17) and the cracking of long-chain FFAs (C16 and C18) (Eqn. (5)), RxCOOH / Rx-1 H þ RxCOOH (5)
especially during the first hour of the reaction.
The lower n-C17 selectivity (~20%) in the deoxygenated liquid
8 K.B. Baharudin et al. / Journal of Cleaner Production 274 (2020) 122850
Fig. 8. Zeta potential plot for ZnOeCOP support and NiOeZnO catalysts with various
wt.% of NiO. The NiO loadings altered the surface charge of ZnO nanoparticles and
shifted the zeta potential towards positive value at all pH values.
product compared with ~51% of C18 (steric acid, oleic acid, linoleic
acid, and linolenic acid) in the original PFAD feedstock effect from
thus cracking reactions in Eqns. (4) and (5). The DO pathway in
these reaction systems is generally derived from the synergistic
effect between NiO and ZnO, which produced an adequate acid
strength to enhance the DO reaction via decarboxylation, decar-
bonylation, and cracking (Zulkepli et al., 2018).
Table 2 compares the experimental NiOeZnO catalyst with
Fig. 9. Hydrocarbon yield in the deoxygenated liquid product with gasoline n-(C8eC10) and diesel n-(C11eC17) distribution using synthesized NiOeZnO catalysts. The 20%wt of NiO
loading recorded an optimum diesel yield (83%) and selectivity (86%).
related past research that used the DO reaction mode. The results
show that our NiOeZnO catalyst rendered better hydrocarbon yield
and diesel range selectivity compared to the strong acid-base
bifunctional CoeCaO catalyst, the bifunctional NiOe5CaO/SiO2-
$Al2O3 catalyst, and the bimetallic acid-base CaOeLa2O3/activated
carbon (AC) nanosized catalyst. However, its activity is slightly
lower compared to the well-known 10 wt%Ni/hexagonal meso-
porous silica catalyst (HMS) and NiO/SBA-15 catalyst. The selec-
tivity of diesel product for NiOeZnO catalyst is better than NieCo/
SBA-15 catalyst. Based on the comparison, NiOeZnO catalyst shows
promising catalytic activity on removing oxygenated compounds of
PFAD to produce green diesel. Catalytic DO over NiOeZnO recorded
high hydrocarbons yield and good diesel-range selectivity as
compared to previous works. Conversion of non-edible byproduct
into green diesel contributes a positive impact in bioenergy
research and also highly optional for green diesel production (Glisic
et al., 2016). The successful catalytic reaction process is environ-
mentally friendly due to its solventless and H2-free reaction system.
Since the diesel hydrocarbons are non-oxygenated compounds, it
was estimated to give better performance compared to the bio-
diesel, such as heating value, cetane number, calorific value, and
combustion properties (Dahiya, 2015).
The applied catalytic DO flow process, as illustrated in Fig. 2, is
possible to be upscaled and compatible with the current industrial
production technology. It can be applied in the existed petro-
chemical refinery facilities (Kubi
cka et al., 2013). The production
technologies were patented and developed by numerous re-
searchers and companies within the past decades (Glisic et al.,
2016). The reaction process was applied on an industrial scale at
several venues, and generally, all of them are suited for the current
petroleum refineries facilities (Knothe, 2010; Bezergianni and
Dimitriadis, 2013). Glisic et al. (2016) reported that Neste Oil is
producing about 170,000 tonnes/year of green diesel in Finland as
well as a production in Singapore and Rotterdam with 800,000
tonnes/year capacity. Another commercial unit, UOP/Eni Ecofining
is running operation in Italy. While, Diamond Green Diesel installed
 K.B. Baharudin et al. / Journal of Cleaner Production 274 (2020) 122850 9

Fig. 10. Product selectivity of deoxygenated liquid using the synthesized NiOeZnO catalysts revealed that carbon distribution of C15 was the top product composition.

Fig. 11. Comparison of selectivity towards n-(C15eC17), n-(C11eC14), and n-(C8eC10) fractions during the DO reaction of PFAD. The carbon range of C15eC17 was the highest product
composition.

the same facility with a capacity of more than 130 million gallons/
year in Norco, Louisiana. Furthermore, Petrobras/H-BIO was
developed a hydrotreating production line for converting vegetable
oil into green diesel.
Further study is useful to determine the reaction kinetics and
mechanism in green diesel production from PFAD. The possible
assessment of NiO loadings on the hydrocarbon yields and the
selectivity of deoxygenated liquid products. Bifunctional metal-
doped solid acids can be a promising approach to explore the role
of support acidity on the catalyst activity and selectivity. The
tunable acidity of the catalyst can be an added advantage to tune
the reaction pathways and avoid further hydrocarbon cracking via
CeC scission.
4. Conclusions
Cleaner production of diesel-like hydrocarbons has been suc-
cessfully employed. Solventless and H2-free DO offer an environ-
mentally friendly catalytic reaction system in the green diesel
production. Byproduct feedstock used in this work offers a great
advantage to the bioenergy field and can be alternatively in
replacing petroleum-diesel. Moreover, the reactor system in this
10 K.B. Baharudin et al. / Journal of Cleaner Production 274 (2020) 122850

Fig. 12. Comparison of n-alkane and n-alkene hydrocarbon yields within the (a). n-C15 and (b) n-C17 fraction. The major selectivity of products towards alkane formation rather than
alkene.

Table 2
Comparison of TMO-based catalysts in catalytic DO under inert N2 flow with the same reaction mode (decarboxylation/decarbonylation). The present study showed high
hydrocarbons yield and diesel selectivity compared to past studies.

Catalyst Reaction Condition Feeds HC yielda (%) Diesel selectivity (%) Reference
b c

20 wt%NiOeZnO T ¼ 120 min Temp ¼ 350 C PFAD 83 86 Present study
Catalystd ¼ 5%
CoeCaO T ¼ 105 min Temp ¼ 340
C Catalyst ¼ 5% Triolein 56 65 Asikin-Mijan et al. (2017a)
NiOe5CaO/SiOAl2O3 T ¼ 60 min PFAD 81 82 Asikin-Mijan et al. (2017b)
Temp ¼ 50
C Catalyst ¼ 7%
CaOeLa2O3/AC, T ¼ 180 min, Temp ¼ 330
C, catalyst ¼ 3% Waste cooking oil 73 84 Alsultan et al. (2017)
10 wt%Ni/HMS T ¼ 120 min, Temp ¼ 380
C catalyst ¼ 5% Triolein 88 95 Zulkepli et al. (2018)
NieCo/SBA-15 T ¼ 180 min, Temp ¼ 350
C catalyst ¼ 10% PFAD 88 85 Kamaruzaman et al. (2020)
NiO/Al-SBA-15 T ¼ 120 min, Temp ¼ 350
C catalyst ¼ 5% PFAD 86 91 Baharudin et al. (2019)
a
Hydrocarbon yield.
b
Time.
c
Temperature.
d
Catalyst loading.

experiment is compatible with the current industrial production
plant facilities for upscaled production in the industrial sector. The
reaction itself uses non-high-pressure reaction conditions under N2
atmosphere. Hence, this work significantly contributes towards
green and sustainable utilization of a cheap and renewable
byproduct in green diesel production with an average yield of 83%
and diesel selectivity of 86%.
CRediT authorship contribution statement
Khairul Basyar Baharudin: Investigation, Software, Writing -
original draft. Nurulhuda Abdullah: Formal analysis. Yun Hin
Taufiq-Yap: Supervision, Validation. Darfizzi Derawi: Conceptual-
ization, Funding acquisition, Methodology, Supervision, Validation,
Writing - review & editing.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements
The authors are grateful for financial support through the
Newton-Ungku Omar Fund, NA150407 provided by the Royal So-
ciety, UK (60888) and Academy of Science Malaysia/MIGHT (ST-
2016e006). This work was additionally supported by the Universiti
Kebangsaan Malaysia through the Collaborative Matching Fund
(DPK-2017-011). We gratefully acknowledge the research facilities
provided by Aston University, Universiti Kebangsaan Malaysia and
Universiti Putra Malaysia. We would also thank to the Ministry of
Education for the PhD Scholarship provided to Hadiah Latihan
Persekutuan. We would also like to take the opportunity to express
our sincere condolences to the victims of COVID-19 and their
families. Appreciation goes to the frontliners around the world,
especially in Malaysia.
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Nomenclature list
Al2O3: aluminum oxide
C11: undecane (alkane)
C13: tridecane (alkane)
C15: pentadecane (alkane)
C17: heptadecane (alkane)
C2H5OH: ethanol
CaO: calcium oxide
CH3OH: methanol
Co: cobalt
CPO: crude palm oil
DO: deoxygenation
FFAs: free fatty acids
FOB: free on board (price)
H2O: distilled water
H2SO4: sulfuric acid
HDO: hydrodeoxygenation
KOH: potassium hydroxide
La2O3: lanthanum oxide
N2: nitrogen
Ni: nickel
Ni(NO3)2.6H2O: nickel(II) nitrate hexahydrate
NiO: nickel oxide
o
C: degree celcius (temperature unit)
PFAD: palm fatty acid distillate
pH: potential for hydrogen (acidic / basic measurement)
SBA-15: mesoporous silica
USD: US Dollar
ZnO: zinc oxide