Renewable Energy 138 (2019) 161e173

Contents lists available at ScienceDirect

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

Catalytic hydrodeoxygenation of jojoba oil to the green-fuel

application on Ni-MoS/Mesoporous zirconia-silica catalysts
Arumugam Ramesh, Perumal Tamizhdurai, Kannan Shanthi*
Department of Chemistry, Anna University, Chennai, 600 025, Tamilnadu, India

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

Article history: Zirconia modified mesoporous silica such as Zr-SBA-15, Zr-KIT-6, Zr-SiO2, and Zr-FSM-16 with Si/Zr ¼ 10
Received 9 August 2018 ratio over Ni-MoS catalysts were prepared under the hydrothermal condition and compared with Ni-
Received in revised form MoS/Zr-Al (10). The prepared materials were characterized by various techniques like X-ray diffraction
28 November 2018
analysis (XRD), N2-sorption studies, diffuse reflectance measurementeUV-Vis spectrophotometers (DR-
Accepted 18 January 2019
UV-vis), NH3-temperature-programmed desorption (NH3-TPD)/H2-Temperature programmed reduction
Available online 26 January 2019
(H2-TPR), Laser-Raman, high resolution transmission electron microscopy (HRTEM) and fourier-
transform infrared spectroscopy (FT-IR) techniques. The activity of materials was investigated in
Keywords:
Mesoporous
hydrodeoxygenation (HDO) of jojoba oil to produce long-chain hydrocarbons at 225e375  C under 10
Zirconia-silica e40 bar H2 pressure in a stainless steel fixed bed reactor. Among the catalysts tested, Ni-MoS/Zr-K (10)
Hydrodeoxygenation exhibited the highest catalytic activity of 90% conversion and 79% yield of C18eC22 hydrocarbon. The
Jojoba oil structure-activity relationships and product distributions were also discussed in detail.
Green fuel © 2019 Published by Elsevier Ltd.
Catalyst

1. Introduction cosmetics, pharmaceuticals and lubricants. The jojoba oils have

Biomass has a great attention across the globe and it can be
utilized as a feed stock for sustainable energy production [1,2].
Biofuels are more advantageous over fossil fuels since it can be
produced domestically and also they produce less greenhouse gas
emission, and increase national energy security [3]. Bio-oil sources
such as jojoba, jatropha, watermelon, agriculture by-products have
high energy density, high amount bio-oil production, cost effective,
easy to cultivate, etc., [4]. The common name of jojoba has been
growth in several countries such as USA, Latin America, South Af-
rica and many other countries. In current decades jojoba oil has
more needed essential Egyptian products of fuel alternative sources
[5]. The jojoba seeds nuts are 1e2 cm long with red-brown color
and the liquid is golden took by cool pressing or solvent extraction
methods [6]. Jojoba oil containing seeds of oils level between 45
and 55 wt% it is more advantage of fuel productions. The jojoba has
becomes entirely different to other vegetable oils because of unique
chemical properties such as long chain ester, fatty acids and no
glycerides [5]. The fatty acid composition of jojoba wax esters pri-
marily consists of eicosenoic, erucic, and oleic acids. Jojoba oil and
followed by other processes it can be used in different fields such as
* Corresponding author.
E-mail address: shanthiramesh@annauniv.edu (K. Shanthi).
been a direct usage of fuels due to low viscosity as compared to
vegetable 10e20 times higher. Hence, other vegetable oils are high
viscosity to reduce various steps involved likes dilution, pyrolysis,
micro-emulsification, catalytic cracking and transesterification [7].
Another important parameter is blended with other mineral diesel
to produce numerous operating issues such as poor atomization,
carbon deposits due to incomplete combustion and so on [8].
The non-edible oils (jojoba oil) contain long hydrocarbon chain
length (C 18e22) and high oxygen content. The oxygen content
affects fuel properties like chemical instability, poor heating com-
bustion, high pH, corrosiveness, immiscibility, thermal instability.
Further, these non-edible oils tend to polymerize during storage
[5,9,10]. Hence, it is necessary to upgrade non-edible oils to in-
crease the fuel properties by removing the oxygen content from
bio-oils. Especially, catalytic reaction pathways are emerging route
because of more suitable for direct hydrocarbon fuel production [1].
Numerous research works have been reported about bio-oil up-
gradation via catalytic transformation to produce biofuel by
reducing/removing the amount of oxygen by H2O [9]. Generally,
hydrodeoxygenation (HDO) reactions satisfies the industrial, global
requirements and also to find an alternative pollution-free fuel [10].
Usually, the industrial hydrotreatment has been used the noble
metal catalysts likes Pt, Pd, Ru NieRe and PteRe for these materials
are excellent activity towards the production of hydrocarbon fuel or
biofuel [11e15]. However, the noble metal catalysts reactions are

https://doi.org/10.1016/j.renene.2019.01.076
0960-1481/© 2019 Published by Elsevier Ltd.
162 A. Ramesh et al. / Renewable Energy 138 (2019) 161e173
required at high-pressure, high cost and inadequate reserves
further limits its application on larger scale industrial processes
[16,17]. To overcome these problems, the transition metals based
materials such as Ni, Co, Mo and W have been used which are active
metal catalysts as well as promoters for HDO reaction to minimize
the coke deposition [18e20]. Even though Ni-Mo catalysts over
Al2O3, MgO, ZrO2, and TiO2 supports has been studied towards HDO
of lignin, such supports are still need the development because
textural property and stability [21,22]. Recently, ordered meso-
porous silica supports have been commonly used for Ni-Mo catalyst
with enriched textural properties and activity [23]. Various ordered
mesoporous supports likes MCM-41, HMS, SBA-15, SBA-16, and KIT-
6 have been widely used in HDO reaction [24e26]. These materials
are enhancing the textural properties with neutral form of sup-
ports. However, the HDO reaction required for acidity in term of
Lewis and Bronsted acid sites (soild acid catalysts). Introduction of
zirconium was extra frame work of silica it can create the Hþ.
Hence, the synthesis of zirconium-silica with Si/Zr 10 ratio was
increasing the acidity of supports by one-pot synthesis, this ma-
terial has been reported that increasing the dispersion as well as
the activity of active metals [27,28].
Ni-Mo oxide catalysts over different supports have been studied
[19,22,26]. Metal oxide catalysts are not stable for industrial aspects
and due to low thermal stability [29]. However, the developments
of high stable industrial catalysts were also prepared materials and
also improve the production of biofuel is a major challenges [27].
Hence, various forms of sulfide Ni-Mo catalysts were prepared likes
sequential impregnation, pore-filing impregnation, impregnation,
and conventional sulfiding method these methods are not able to
complete sulfidation process because the materials are a required
at high calcination temperature of 550  C [30e32]. This method of
preparation is not effective for the industrial requirement and also
lacking the sulfidation [33]. However, another preparation method
some of the sulfiding source with post sulfidation in presence of
hydrogen gas and used source as following carbon disulphide,
dimethyl disulphide and diphenyl polysulfide (cost effective) at
high temperature required (400  C). These methods have some
environmental issues likes’ unreacted sulfur, and limited catalytic
active sites [30]. These types of catalysts preparation were not
suitable for industrials aspect. Even though, low-level sulfur
(10e100 ppm) content demonstrates superior activity in biofuel
production. However, the sulfur leaching in small concentration (in
ppm level) into bio-fuel products are creates some problems such
as fuel contamination, environmental, human health issue and air
pollution as major part [34]. In order to overcome these problems,
for the low-cost sulfidation agent and less harmful source for
thiourea has been used to prepare the catalysts [35].
In this present work, the catalytic hydrotreating of jojoba oil has
been carried out using Ni-MoS catalysts supported with different
mesoporous materials such as SBA-15, KIT-6, SiO2, FSM-16 and g-
Al2O3. Further, acid functionalities of mesoporous silica enhanced
the amount of acid sites using zirconyl oxy-chloride octa-hydrate as
a Zr source. Ni-MoS material preparation is challenging one with
complete sulfiding source. Ni-MoS catalyst was prepared by hy-
drothermal condition using thiourea as a low-cost sulfiding source
and less toxic. The prepared catalysts were investigated at different
temperature HDO of jojoba oil to liquid hydrocarbon with high
pressure fixed bed vapour phase reactor; reaction conditions and
the structural-activity relationship of the catalysts were also dis-
cussed in details.
2. Materials
Zirconyl oxy-chloride octa-hydrate, tetraethylorthosilicate
(TEOS), Pluronic P123 (EO20PO70EO20, Mw ¼ 5800) were acquired
from Sigma Aldrich. Cetyltrimethyl ammonium bromide (CTAB),
ammonium heptamolybdate, kanemite, nickel nitrate hexa-
hydrate, and decalin were purchased from Sigma Alrich. Hydro-
chloric acid 35e38% was purchased from S. D chemicals, India.
Jojoba oil was purchased from local make (only for research pur-
pose). Polyethylene glycol Mw-4000 (PEG) was purchased from
Molychem, India. All the procured chemicals were used as received
without any further purification.
2.1. Synthesis of mesoporous supports (FSM-16, SBA-15 and KIT-6)
Mesoporous FSM-16, SBA-15 and KIT-6 supports were prepared
by following methods. FSM-16 was prepared using CTAB as a sur-
factant and kanemite (NaHSi2O5$3H2O) as a silica source. Kanemite
with Si/Zr ¼ 10 ratio using zirconyl chloride octa-hydrate as a zir-
conia source was prepared one pot addition of according to a
procedure reported elsewhere by Michalik-Zym et al. [36]. KIT-6
with Si/Zr ¼ 10 ratio using zirconyl chloride octa-hydrate was pre-
pared by following the procedure reported [37]. SBA-15 with Si/
Zr ¼ 10 ratio using zirconyl chloride octa-hydrate as a zirconia
source synthesized were reported elsewhere [38]. The obtained
products were filtered and washed, dried and calcined at 550  C for
6 h. The final products are denoted as Zr-K (10), Zr-S (10) and Zr-F
(10).
2.2. Synthesis of mesoporous zirconia-silicates (Zr-SiO2 (10))
Mesoporous zirconia-silicates were synthesized using CTAB as
structure directing agent and PEG-4000 as particle size regulator
respectively [39]. After the addition of homogenous solution of
surfactant, calculated amounts of zirconyl chloride and TEOS were
added with Si/Zr ¼ 10 ratio using zirconyl oxy-chloride octa-hy-
drate as zirconium source at room temperature (RT). The pH of the
reaction mixture was maintained at 9.0 using 25% liquid ammonia.
After gel formation the solution was stirred for 2 days at RT. The
solid mass obtained was filtered off and dried at 100  C followed by
calcination at 550  C. The final product is denoted as Zr-SiO2 (10).
2.3. Synthesis of Ni-MoS/Zr-Silica mesoporous support
Ni-MoS impregnated over different acid supports such as Zr-K
(10), Zr-S (10), Zr-SiO2 (10), Zr-F (10) and commercial Zr-Al (10)
respectively by hydrothermal method. Ni-MoS were prepared us-
ing thiourea used as a sulfur source in which S/Mo and Ni/Mo ratios
of 0.25 were fixed. The metal precursors and thiourea were dis-
solved in distilled deionized water and the final solution was
transferred to 100 ml autoclave under the hydrothermal condition
at 180  C for 24 h. The catalysts were labeled as Ni-MoS/Zr-K (10),
Ni-MoS/Zr-S (10), Ni-MoS/Zr-SiO2 (10), Ni-MoS/Zr-F (10) and Ni-
MoS/Zr-Al (10). All the catalysts were pre-reduced at 400  C for
3 h under the H2 gas atmosphere at a flow rate of 50 cm3/min.
2.4. Materials characterization
All the catalysts were characterized by various techniques such
as XRD, N2-sorption studies, DR UV-vis, NH3TPD/H2-TPR, and FT-IR
respectively. XRD was analyzed by Brucker D8 diffractometer at a
2q value of 0.5e5 as a low angle and 10e80 as a high angle with a
step scan of 0.2 deg min1 using Kl radiation (l ¼ 1.548 Å). N2-
sorption study was carried out using QUADRASORB SI automatic
analyzer at was done at low boiling point of 196  C for liquid ni-
trogen temperature and the sample prepared by degassing under
N2 atmosphere at 300  C for 3 h. DR UV-Vis spectra of the samples
were recorded (200e800 nm) using Shimadzu UV-2450 spectro-
photometer equipped with diffuse reflection attachment and BaSO4
 A. Ramesh et al. / Renewable Energy 138 (2019) 161e173 163

was used as a reference. H2-TPR and NH3-TPD studies were carried several months) was used as a liquid feed. Both temperature and
out using QUADRASORB SI with sample preparation 0.030 g were pressure were monitored by the pneumatic control panel. The
taken to analysis along with the mixture gas of 5%H2/95%Ar and 10% catalysts were pelletized & packed (15 mm inner diameter and
NH3/90%He respectively. FT-IR spectrum was recorded using Per- 380 mm in length) inside the bed and along with glass beads
kinElmer Spectrum (FT-IR C101375). The prepared sample was (3.5 mm) and silica wool to maintain the temperature throughout
mixed with KBr and to make a thin pellet for FT-IR spectra. the reactor. The liquid feed vaporization ensures adequate reaching
the catalyst bed.
Jojoba oil conversion (X) and selectivity (Si) were calculated
2.5. Catalytic activity and reactor setup
using the following the equations
All Ni-MoS/Zr-K (10), Ni-MoS/Zr-S (10), Ni-MoS/Zr-SiO2 (10), Ni-
X ¼ (mole of Jojoba) in  (mole of Jojoba) out / (mole of Jojoba)
MoS/Zr-F (10) and Ni-MoS/Zr-Al (10) catalysts were screened for
HDO of jojoba oil by tuning various reaction parameters such as in  100% (1)
temperature (225e375  C), pressure (10e40 bar H2 pressure) and
Si ¼ (moles of product i) / (the sum of moles of products)  100%(2)
WHSV. The product was collected at one-hour time interval and
analyzed using GC (Shimadzu-GC-17A with DB-5 column). For each
The specific reaction rate (SRR) was calculated by the formula.
run, all the catalysts were activated under nitrogen atmosphere at
400  C for 3 h under 4 bar followed by ultra-high pure hydrogen gas
SRR ¼ F0X/w (3)
for 4 h.
Vapour phase HDO of jojoba was carried out in a stainless steel
where, F0 ¼ Flow rate of jojoba oil (mol g1 s1) X ¼ Jojoba oil
fixed bed flow reactor (100 bar) which is purchased from Amar
conversion (%) and w ¼ weight of the catalyst (g).
Equipment (India) Pvt. Ltd, Mumbai, India. The schematic diagram
The Turnover frequency (TOF) was calculated using the
(Scheme 1) shows the high pressure fixed bed flow reactor setup. A
following equation
single feed to reactor system with three gas lines was connected to
one liquid line (HPLC pump). In this work, high pure hydrogen, and
TOF (s1) ¼ (SRR, mol g1 s1)/ (quantity of sites) (4)
the nitrogen were used as a gas feed and jojoba in decalin (HDO of
jojoba oil in decalin solvent have been used, the decalin as a solvent
where, quantity of active sites is calculated from H2 chemisorption
because of certain advantage likes high boiling at 190  C when
(mmol g1).
compare to other solvents. It is high stability under the reaction
condition and can be separated easily by distillation at particular
temperature. Decalin is a cyclic compound without further hydro- 3. Results and discussion
genation and cracking not yet formed under assayed reaction
condition. Directly usage of jojoba oil on the catalysts surface active 3.1. XRD pattern
sites gets coke/carbon deposition on several days, even it will be
dissolving in decalin solvent the catalysts stability with stands up to A low angle XRD pattern of the calcined materials namely Ni-

Scheme 1. The schematic diagram of vapour phase high pressure fixed bed continuous flow reactor system.
164 A. Ramesh et al. / Renewable Energy 138 (2019) 161e173

MoS/Zr-S (10), Ni-MoS/Zr-K (10), Ni-MoS/Zr-SiO2 (10) and Ni-MoS/

Zr-F (10) were shown in Fig. 1. Fig. 1, it has been observed a sharp
intense peak consists of three diffraction peaks at a 2q values of
1.0 , 1.71, and 1.99o corresponding to (1 0 0), (1 1 0) and (2 0 0)
reflections with P6mm hexagonal symmetry. The ordered meso-
porous nature of Zr-S (10) retained even though high loading of Zr
content with Si/Zr ¼ 10 ratio [37]. Fig. 1 shows three types of
diffraction peaks, the sharp intense peak and two small peaks at a
2q value of 1.11, 1.25 and 2.0 corresponding to (211), (220), and
(332) planes with a cubic space group of Ia3d symmetry confirms
the ordered mesoporous nature of Zr-K (10) [38]. Fig. 1 shows the
broad diffraction peaks of mesoporous zirconium-silicate at 2q
values of 1.72 and 2.2 planes corresponding to 100 reflections
with long-range ordered hexagonal symmetry of Zr-SiO2 (10) [39].
Finally, Zr-F (10) catalyst shows two planes corresponds to 2q value
of 2.3 and 4.0 respective of (100), and (200) reflections of hex-
agonal symmetry. In addition, (110) and (210) two planes which are
saturated due to heavy loading of Zr incorporated over FSM-16 (10)
[36].
High angle XRD pattern of Ni-MoS over various supports such as
Zr-S (10), Zr-K (10), Zr-SiO2 (10), Zr-F (10) and Zr-Al (10) was
recorded. All the catalysts show diffraction peaks at a 2q region of
Fig. 2. High angle XRD pattern of catalysts.
23.5 found to be a centre point corresponds to amorphous nature
of supports (Fig. 2). Fig. 2 illustrates that NiSx/MoS (x ¼ 2 and 4)
was impregnated over Zr-S (10) support by hydrothermal method. 3.2. Textural properties
The XRD peaks at a 2q ¼ 14.01, 33.52 , 39.8 , and 59.75 corre-
spond to (002), (100), (103), and (110) reflections respectively due N2 adsorption-desorption isotherm of mesoporous Zr-S (10), Zr-
to tiny crystallite plane formation of MoS2 [40]. The diffraction K (10), Zr-SiO2 (10), Zr-F (10) and Zr-Al (10) supports were shown in
peaks at 2q ¼ 44 and 53.2 are assigned to (220) and (311) crys- Fig. S1. The mesoporous Zr-S (10), Zr-K (10), Zr-SiO2 (10) supports
talline planes of cubic form of NiS2 [41]. In addition, the diffraction shows type-IV isotherm and Zr-F (10) supports shows type II
plane showed a peak at 2q ¼ 38.02 due to the formation of Ni-MoS, isotherm. Furthermore, the sharp nitrogen uptake was measured at
however, there are no additional peaks found which indicates that the relative pressure of P/P0 ¼ 0.5e0.8 with H1 type hysteresis loop
the active metals were finely dispersed over Zr-S (10) [42]. Fig. 2 for Zr-S (10), Zr-SiO2 (10), and Zr-F (10). However, the Zr-K (10)
illustrates that NiSx/MoS active metals over different supports possesses the sharp inflection nitrogen uptake and measured at a
namely Zr-K (10), Zr-SiO2 (10), and Zr-F (10) formed the crystalline relative pressure of P/P0 ¼ 0.7e0.98. Even though all the prepared
plane at the same peak position. Fig. 2 shows three diffraction supports possess different isotherms, they retained the meso-
peaks at 2q ¼ 36.4 , 45.3 , and 66.4 which confirms the presence porous ordered nature. Among the different synthesized meso-
of g-Al2O3. Further, Zr incorporation into g-Al2O3 exhibited new porous supports, Zr-SiO2 (10) support possess the high surface area
diffraction peaks at 2q region of 18.2 , and 24.2 which confirms the (720 m2 g1) and pore volume (0.81 cm3 g1) [36e38]. The surface
formation of Zr-Al (10) [43]. area and pore volume of the supports were found to be decreasing
in the following order Zr-SiO2(10) > Zr-K (10) > Zr-SiO2 (10) > Zr-F
(10) > Zr-Al (10) and the pore size of the support were found to be
decreasing in the order of Zr-K (10) > Zr-S (10) > Zr-SiO2 (10) > Zr-F
(10) >Zr-Al (10) (Table 1).
After the impregnation of Ni-MoS over different supports, the
textural properties such as surface area pore volume and pore size
decreased due to the blockage of pores as shown in Table 1 and N2
values are shifted to the higher region this may be pore blockage or
diminished is seen in Fig. 3 [30]. The pore diameter of Ni-MoS/Zr-S
(10), Ni-MoS/Zr-K (10), Ni-MoS/Zr-SiO2 (10), and Ni-MoS/Zr-F (10)
were found to be 15.3, 18.9, 15.9 and 13.5 nm respectively [41]. In
addition to that, the unit cell parameter and the wall thickness were
calculated by XRD and BET results reveal that the unit cell param-
eter gradually increases which may be due to the impregnation of
Ni-MoS species over different mesoporous zirconia-silica supports
Ni-MoS/Zr-S (10), Ni-MoS/Zr-K (10), Ni-MoS/Zr-SiO2 (10), and Ni-
MoS/Zr-F (10) which further evidenced from Table 1 [44].

3.3. DR Uv Vis spectrophotometer

The DRS-UV-Visible spectrum of Ni-MoS catalysts over different

supports such as Zr-S (10), Zr-K (10), Zr-SiO2 (10), Zr-F (10) and Zr-Al
(10) with Si/Zr (10) were analyzed and the coordination of active
Fig. 1. Low angle XRD pattern. metals and interaction between supports are shown in Fig. 4.
 A. Ramesh et al. / Renewable Energy 138 (2019) 161e173 165

Table 1
Textural properties of support & catalysts and % coke formation of spent catalysts: Ni-MoS/Zr-S (10), Ni-MoS/Zr-K (10), Ni-MoS/Zr-SiO2 (10), Ni-MoS/Zr-F (10) and Ni-MoS/Zr-Al
(10).

S.No Samples SaBET Vbt dc BJH ao d (nm)e Dispersion f

Number of Active sites SRR  105 TOF  103s1
(m2/g) (cm3/g) (nm) (nm)d (%) (sites/g cat)  106 (mol g1 s1)

1 Zr-S (10) 580 0.62 15.5 9.42 6.08 n.d n.d n.d n.d
2 Zr-K (10) 555 0.59 18.1 8.61 9.49 n.d n.d n.d n.d
3 Zr-SiO2 (10) 720 0.81 14.9 5.37 9.53 n.d n.d n.d n.d
4 Zr-F (10) 535 0.55 13.4 4.09 9.31 n.d n.d n.d n.d
5 Ni-MoS/Zr-S (10) 375 0.42 14.1 9.38 4.72 32 11.2 7.85 7.01
6 Ni-MoS/Zr-K (10) 360 0.44 15.8 8.56 7.24 30 10.5 10.09 9.61
7 Ni-MoS/Zr- 480 0.71 13.8 5.30 8.50 35 11.55 8.86 7.67
SiO2(10)
8 Ni-MoS/Zr-F (10) 365 0.45 12.9 4.01 8.89 34 11.9 7.26 6.12
9 Ni-MoS/Zr-Al (10) e e e e e 33 11.55 6.61 5.73
a, b & c
Surface area, Pore volume & Pore diameter (Dp) (desorption branch by BJH method) obtained from N2 physisorption study, results d & f Unit cell parameter(ao) of the
support and catalyst size obtained from the position of d100 plane low angle and high angle, ePore wall thickness (d) obtained from unit cell parameter and pore diame-
ter(d ¼ ao-Dp), n.d. ¼ not determined, reaction conditions: 7% of jojoba oil, WHSV 1 h1, reaction time: 5 h, H2 flow rate ¼ 3600 ml/h, temperature 350  C, pressure 30 bar,
f
number of active sites, calculated by H2 chemisorption.

Fig. 3. (a) N2-Sorption studies and (b) Pore size distribution of catalysts.

presence of Mo in Td coordination. In the third absorption band at

330 nm region corresponds to Mo present in both Td and octahe-
dral (Oh) environment. The absorption band at 320 nm region is
due to Ni-MoS [Ni (Oh) and Mo (Oh)] species present in all the
supported catalysts except Zr-S (10) and Zr-F (10) [45]. However,
the absorption band at 600e720 nm regions confirms there was no
formation of Ni-O [46]. In addition, among the different supports
Zr-SiO2 (10) showed new absorbance band at 325e375 nm regions
due to the strong interaction of Ni-MoS over Zr-SiO2 (10).
The absorption edge energy (Eg) is calculated using DRS-UV-
visible spectrum. In an earlier report [44], the Mo edge energy
(Eg) calculation was made for the supports such as Ni-MoS/Zr-S
(10), Ni-MoS/Zr-K (10), Ni-MoS/Zr-SiO2 (10), and Ni-MoS/Zr-F (10)
(Table 2) and the Eg value of (4.87 eV) of MoNi/Zr-SiO2 (10) was
found to be high [44].
The Eg value follows the order of Ni-MoS/Zr-SiO2 (10) > Ni-MoS/
Zr-S (10) > Ni-MoS/Zr-K (10) > Ni-MoS/Zr-F (10) > Mo-Ni/Zr-Al (10)
respectively. The calculated Eg value of Ni-MoS/Zr-Al (10) is the
Fig. 4. DRS-UV Visible spectrum. lowest due to the formation of bulk crystalline Mo oxide specie.

3.4. NH3-Temperature Programmed Desorption

Initially, three types of absorption band were absorbed and the first
absorption band at 211 nm region is due to the formation of MoS2 NH3-TPD analysis was carried out to measure the type and
[44]. The second absorption band appeared at 260 nm evidence the amount of acid sites exist on the catalysts. Fig. 5 represents NH3-
166 A. Ramesh et al. / Renewable Energy 138 (2019) 161e173

Table 2
Acid site distribution, H2 consumption and edge energies of catalysts such as Ni-MoS/Zr-S (10), Ni-MoS/Zr-K (10), Ni-MoS/Zr-SiO2 (10), Ni-MoS/Zr-F (10) and Ni-MoS/Zr-Al (10).
a b c
S.No Catalysts Reduction Volume of H2 Acidity (mmol NH3/g cat) Total Acidity Edge Energy
Temperature (oC) consumption (mmol/g)a (mmol NH3/g cat)b (Eg) eV
Weak Acid sites M and S acid sites

1 Ni-MoS/Zr-S (10) 174, 349, 505 155 0.7 0.8 1.5 4.86
2 Ni-MoS/Zr-K(10) 177, 309, 349 180 0.5 2.2 2.7 4.83
3 Ni-MoS/Zr-SiO2 (10) 170, 318, 522 165 0.4 1.2 1.6 4.87
4 Ni-MoS/Zr-F (10) 217, 520 120 0.19 0.45 0.64 4.85
5 Ni-MoS/Zr-Al (10) 301, 501, 687 95 0.15 0.5 0.65 4.85
a
H2 Temperature Programme Reduction.
b
NH3-Temperature Programme Desorption.
c
Calculated from UV-Vis DRS spectra, S ¼ strong acid site, and M ¼ moderate acid sites.

Fig. 5. NH3-TPD profile of catalysts.

TPD acidity profile of the prepared catalysts. In general, NH3
desorption peaks between 100 and 225  C, 250e450  C and above
450  C are referred to as weak acid sites, moderate, and strong acid
sites respectively [44]. All the catalysts possess weak, moderate and
strong acid sites in the temperature range of 100e600  C. The total
acidity of Ni-MoS supported on mesoporous supports in the order
of Ni-MoS/Zr-K (10) > Ni-MoS/Zr-S (10) > Ni-MoS/Zr-SiO2 (10) > Ni-
MoS/Zr-F (10) > Ni-MoS/Zr-Al (10). All the materials exhibited the
total amount of acidic sites of 0.65e2.7 mmol g1 with larger
amount of moderate acid sites with desorption peaks around
250e450  C. The moderate and strong acidity is found to be
2.7 mmol g1 for Ni-MoS/Zr-K (10) [30,44]. NH3-TPD profile of Ni-
MoS over different supports shows two types of acid sites and the
strength of acidic sites depends on the supports. Table 2 summa-
rizes the total acidities measured for different sites with zirconia-
silicate. It has been inferred that the acidity data of the moderate
and strong acid sites of supported catalyst is in the order of Ni-MoS/
Zr-K (10) >Ni-MoS/Zr-SiO2 (10) > Ni-MoS/Zr-S (10) >Ni-MoS/Zr-F
(10) > Ni-MoS/Zr-Al (10) respectively.
3.5. Pyridine FT-IR analysis
Different types of acidic strength (Lewis or Bronsted) were
investigated for various supported catalysts by pyridine FT-IR and
the data are shown in Fig. 6. It has been observed that FT-IR bands
at 1540 cm1 and 1450 cm1 corresponds to Bronsted (B) acid sites
and Lewis (L) acid sites respectively [47]. Py-FT-IR absorbed the
band of all the supported catalysts such as Ni-MoS/Zr-S (10), Ni-
MoS/Zr-K (10), Ni-MoS/Zr-SiO2 (10), Ni-MoS/Zr-F (10), and Ni-
Fig. 6. Pyridine-IR Spectrum of a) Ni-MoS/Zr-S (10), b) Ni-MoS/Zr-K (10), c) Ni-MoS/Zr-
SiO2 (10), d) Ni-MoS/Zr-F (10), and e) Ni-MoS/Zr-Al (10) catalysts.
MoS/Zr-Al (10) is shown in Fig. 6. All the prepared catalysts show
an absorption band at 1449 cm1, 1490 cm1, 1600-1630 cm1 and
1645 cm1. The sharp absorbed peak at 1449 cm1 and weak peaks
at 1600-1630 cm1 are assigned to Lewis acid site whereas, the
peak at 1490 cm1 is due to pyridine adsorbed on both L and B type
acid sites. The broad peak at 1645 cm1 corresponds to Bronsted
acidic sites [47,48]. However, the Py-FT-IR results reveal that the
catalysts have both types of acid sites (L þ B). Py-FT-IR acidic profile
of Ni-MoS/Zr-S (10), Ni-MoS/Zr-K (10), Ni-MoS/Zr-SiO2 (10), and Ni-
MoS/Zr-F (10) catalysts displayed all the above mentioned acidic
sites. Among the different supported system, the Ni-MoS/Zr-K (10)
had higher acidic nature. Zr-Al (10) supported catalysts showed
adsorption peaks at 1600-1650 cm1 corresponds to both L þ B
sites. Apart from this, there is no specific adsorption peaks due to
support. The Bronsted acidic sites are in the order of Ni-MoS/Zr-K
(10) > Ni-MoS/Zr-S (10) > Ni-MoS/Zr-F (10) > Ni-MoS/Zr-SiO2
(10) > Ni-MoS/Zr-Al (10).
Different types of acidic strength (Lewis or Bronsted) were
investigated for variously supported catalysts by pyridine FT-IR and
the data are shown in Fig. 6. It has been observed that the FT-IR
bands at 1540 cm1 and 1450 cm1 corresponds to Bronsted (B)
acid sites and Lewis (L) acid sites respectively [47]. Py-FTIR absor-
bed the band of all the supported catalysts such as Ni-MoS/Zr-S
(10), Ni-MoS/Zr-K (10), Ni-MoS/Zr-SiO2 (10), Ni-MoS/Zr-F (10),
and Ni-MoS/Zr-Al (10) is as shown in Fig. 6. All the prepared cata-
lysts show an absorption band at 1449 cm1, 1490 cm1, 1600-
1630 cm1 and 1645 cm1. The sharp absorbed peak at 1449 cm1
 A. Ramesh et al. / Renewable Energy 138 (2019) 161e173
and weak peaks at 1600-1630 cm1 are assigned to Lewis acid site
whereas, the peak at 1490 cm1 is due to pyridine adsorbed on both
L and B type acid sites. The broad peak at 1645 cm1 corresponds to
Bronsted acidic sites [48,49]. However, the Py-FT-IR results reveal
that the catalysts have both types of acid sites (L þ B). Py-FT-IR
acidic profile of Ni-MoS/Zr-S (10), Ni-MoS/Zr-K (10), Ni-MoS/Zr-
SiO2 (10), and Ni-MoS/Zr-F (10) catalysts displayed all the above
mentioned acidic sites. Among the different supported system, the
Ni-MoS/Zr-K (10) has higher acidic nature. Zr-Al (10) supported
catalysts showed adsorption peaks at 1600-1650 cm1 corresponds
to both L þ B sites. In another side, there is no adsorption peaks due
to support. The Bronsted acidic sites are in the order of Ni-MoS/Zr-K
(10) > Ni-MoS/Zr-S (10) > Ni-MoS/Zr-F (10) > Ni-MoS/Zr-SiO2
(10) > Ni-MoS/Zr-Al (10).
3.6. H2-TPR profiles
H2-TPR profiles of Ni-MoS/Zr-S (10), Ni-MoS/Zr-K (10), Ni-MoS/
Zr-SiO2 (10), Ni-MoS/Zr-F (10) and Ni-MoS/Zr-Al (10) catalysts are
shown in Fig. 7. The preparation method, metal precursor, type of
support and the nature of sulfiding agents have altered the
reduction of catalyst behaviour. H2-TPR profile of Ni-MoS/Zr-S (10)
catalyst displayed three types of reduction peaks at 174, 349, and
505  C corresponds to NiS4 in Ni-MoS phase and other reduction
peaks at 349  C is due to Ni-MoS phase. The reduction peaks of Ni-
MoS2 is related to the reduction of Mo6þ to Mo4þ whereas the
reduction peak at 505  C is ascribed to the reduction of Mo4þ to Mo0
and also promotes the NiS4 at a low temperature of 349  C [44]. The
reduction behaviour of Ni-MoS has been observed at moderate
temperature of 350  C when compared to other previous methods
such as temperature programme reduction, impregnation, pre and
post sulfiding methods [30]. The above-mentioned methods
showed the reduction peaks of Ni-MoS active metals and supports
interaction at beyond 500  C [50].
In these studies, the support and active metal were prepared by
hydrothermal condition (180  C) and the variation may be due to
the nature of sulfiding agent thiourea. The huge variation due to
complete sulfide form, with low-temperature reduction behaviour
was achieved [51]. Ni-MoS/Zr-K (10) showed three types of
reduction peaks at 177, 309 and 436  C correspond to different Ni-
MoS species over Zr-K (10). The reduction peak observed at 177  C is
Fig. 7. H2-TPR profiles of a) Ni-MoS/Zr-S (10), b) Ni-MoS/Zr-K (10), c) Ni-MoS/Zr-SiO2
(10), d) Ni-MoS/Zr-F (10), and e) Ni-MoS/Zr-Al (10) catalysts.
167
attributed to the reduction of NiS4 in Ni-MoS. The low temperature
reduction peak at 309  C due to the reduction behaviour of Mo6þ to
Mo4þ [44], whereas the reduction peak observed at 436  C is
ascribed to the reduction of Mo4þ to Mo0 [30].
Ni-MoS over Zr-SiO2 and Zr-F (10) showed similar kind of
reduction peaks. Mo6þ to Mo4þ and Mo4þ to Mo0 states were
overlapped in both supporting materials which are shown in Fig. 7.
Finally, Ni-MoS/Zr-Al (10) catalysts showed the high-temperature
peak beyond 500  C due to the reduction of Mo6þ to Mo4þ and
the reduction peak at 687  C is assigned to Mo4þ to Mo0 reduction.
This result strongly suggests that the metal and support interaction
plays an important role in hydrotreating reaction [33]. The
hydrogen consumption values are given in Table 2.
3.7. HR-TEM images
HR-TEM images of Ni-MoS/Zr-K (10) catalyst are shown in Fig. 8.
The image seems to be ordered nature of Zr-K (10) support as
shown in Fig. 8a and b. Even after the deposition of Ni-MoS species
over Zr-K (10) support, the mesoporous order of the support has
been retained under hydrothermal condition. The dark patches
confirm the dispersion of Ni-MoS species over the support. Hence,
it can be concluded that the preparation condition of the catalyst
did not affect the morphology of the support and the catalyst.
3.8. Catalytic activity of hydrogenation of jojoba oil using Ni-MoS
supported catalyst
3.8.1. Effect of reaction temperature
Effect of temperature on hydrodeoxygenation of jojoba oil over
Ni-MoS supported catalyst is displayed in Fig. 9 (a). HDO reaction
involves the treatment of jojoba oil to hydrocarbon fuel at
225e375  C and at constant pressure of 30 bar (435 psig) H2 pres-
sure. The conversion of jojoba oil over Ni-MoS/Zr-S (10), Ni-MoS/Zr-
K (10), Ni-MoS/Zr-SiO2 (10), Ni-MoS/Zr-F (10) and Ni-MoS/Zr-Al
(10) catalysts were measured to be 40, 50, 42, 35, and 30%. It has
been observed that the increase in temperature up to 350  C
resulted in increase of hydrocarbon conversion. At 350  C, the
conversion of the catalysts was evaluated to be 70, 90, 79, 65 and
59%. Further, increase in temperature beyond 350  C, there was a
slight decrease in conversion which may be probably due to coke
formation on the surface of the catalysts. The conversion values are
shown in Fig. 9 (a). Among the catalysts, Ni-MoS/Zr-K (10) catalyst
showed the maximum conversion towards hydrocarbon (>90%).
The high amount of hydrocarbon selectivity was given in Fig. S2.
Hence, 350  C had been chosen as an optimum temperature for
further studies.
HDO of jojoba oil was monitored using Ni-MoS/Zr-S (10), Ni-
MoS/Zr-K (10), Ni-MoS/Zr-SiO2 (10), Ni-MoS/Zr-F (10) and Ni-
MoS/Zr-Al (10) to find turn over frequency (TOF) at a temperature
of 225  C. The hydrocarbon TOF was found to be 4.0, 5.3, 4.1, 3.3, and
2.9  103 s1 for Ni-MoS/Zr-S (10), Ni-MoS/Zr-K (10), Ni-MoS/Zr-
SiO2 (10), Ni-MoS/Zr-F (10) and Ni-MoS/Zr-Al (10) catalysts
respectively. Further, the increase in temperature up to 350  C, the
TOF values is greatly increased to 7.1, 9.61, 7.7, 6.1 and 5.73  103
s1. Beyond 350  C, a slight decrease in TOF was observed because
of coking/carbon deposition over the catalysts. The optimum re-
action parameter is 30 bar pressure at 350  C and the data are given
in Fig. 9 (b).
3.8.2. Effect of reaction H2 pressure
The effect of H2 pressure on hydrodeoxygenation of jojoba oil
was studied for all the catalysts and the results are shown in Fig. 9
(c). Initially, the reaction was carried out at constant 350  C by
varying the H2 pressure. Initially, 10 bar H2 pressure the conversion
168 A. Ramesh et al. / Renewable Energy 138 (2019) 161e173

Fig. 8. HR-TEM images of a & b) Zr-K (10) supports and c & d) Ni-MoS/Zr-K (10) catalysts.

Fig. 9. a) Effect of Temperature, HDO of Jojoba oil for conversion at constant pressure 30 bar, (b) Effect of Temperature, HDO of Jojoba oil for TOF at constant temperature 350  C,
30 bar H2 pressure, c) Effect of Pressure, HDO of Jojoba oil for conversion at 350  C temperature, and (d) Effect of Pressure, HDO of Jojoba oil for TOF at constant temperature
350  C, 30 bar H2 pressure. Reaction condition 7% of Jojoba oil, WHSV ¼ 1.5 h1, reaction time 8 h, H2 flow rate ¼ 3600 ml/h.

of jojoba oil to hydrocarbon over the different catalysts Ni-MoS/Zr-S Ni-MoS/Zr-Al (10) was calculated to be 35, 42.3, 49, 39 and 29%
(10), Ni-MoS/Zr-K (10), Ni-MoS/Zr-SiO2 (10), Ni-MoS/Zr-F (10) and respectively.
 A. Ramesh et al. / Renewable Energy 138 (2019) 161e173
The effect of H2 pressure on hydrodeoxygenation of jojoba oil
was studied for all the catalysts and the results are shown in Fig. 9
(c). The overall reactions were carried out at constant temperature
of 350  C with different H2 pressure. Initially, 10 bar H2 pressure
was maintained and the conversion of jojoba oil to hydrocarbon
over different catalysts such as Ni-MoS/Zr-S (10), Ni-MoS/Zr-K (10),
Ni-MoS/Zr-SiO2 (10), Ni-MoS/Zr-F (10) and Ni-MoS/Zr-Al (10) were
calculated to be 35, 42.3, 49, 39, and 29% respectively. Upon
increasing the pressure up to 30 bar, the maximum conversion of
70, 90, 79, 65, and 59 were observed. Further increase in H2 pres-
sure (under 40 bar), the conversion was slightly decreased due to
flocking of the reactant molecules on the surface of the catalysts.
This resulted in the decrease of reactant contact time over the
catalysts. Ni-MoS/Zr-K (10) showed the maximum jojoba oil con-
version of >90% compared to other catalysts.
Hence, 30 bar H2 pressure was chosen as optimum pressure
condition for further studies. The activity of catalysts had been
tested in terms of TOF. The activity was also increased at a pressure
of 30 H2 beyond that the activity was slightly decreased which may
be due to the crowding of the reactant molecules over the active
sites on the surface of the catalysts. The less contact time between
active sites and reactants is also one of the major reasons for the
drop in activity of the catalysts which is clearly seen in Fig. 9 (d).
3.8.3. Effect of WHSV
Effect of WHSV was investigated using Ni-MoS/Zr-K (10) catalyst
in HDO of jojoba oil at constant pressure of 30 bar H2 pressure,
temperature of 350  C and WHSV of 0.5e2.5 h1 range as shown in
Fig. 10 (a). With increase in space velocity, the conversion was
decreased from 93% (0.5 h1) to 58% (2.5 h1). The selectivity is
decreased from 3, 30, 25, and 42 to 6, 25, 35, and 33% for < C16, C17,
C18 and C22 respectively. The effect of WHSV was found to be 1.5
h1 and the higher conversion (90%) and selectivity (6, 28, 24, and
42%) were achieved. On the other hand, increase in the WHSV up to
2.5 h1 decreased the selectivity of < C16, C17, C18 and C22 carbon
chain length (6, 25, 35, and 33%) due to inaccessibility of surface
molecules and the interaction was very less. The stearic hindrance
of molecules and the contact time between reactant and active sites
of the catalysts were also decreased the selectivity. The selectivity is
greatly increased only towards C18 and C22, because of less se-
lective on C22 and the surface active sites are shown in Fig. 10 (a).
Fig. 10. (a) Effect of WHSV, Conversion and selectivity of hydrocarbon at 350  C temperature, 30 bar H2 pressure, and b)Time on stream, Conversion and selectivity of hydrocarbon
at 350  C temperature, 30 bar H2 pressure, Reactant conditions; 7% jojoba oil, WHSV ¼ 1.5 h1, Reaction time 8 h, H2 flow rate ¼ 3600 ml/h.
169
3.8.4. Time on stream (TOS)
Fig. 10 (b) shows the effect of time-on-stream of Ni-MoS/Zr-K
(10) catalyst in jojoba oil conversion and the selectivity product
over 36 h. From Fig. 10 (b), the selected product in-
cludes < C16eC22, within first hour, jojoba oil over Ni-MoS/Zr-K
(10) catalyst was (with the selectivity) around 77% and the same
way the selectivity for < C16, C17, C18 and C22 are 7, 32, 23 and 38
respectively. The activity of the catalyst was increased with increase
in time and reached the maximum activity in sixth hour with the
conversion greater than >93%. But the change in hydrocarbon
selectivity was found to be 10, 28, 22, and 40% for < C16, C17, C18
and C22 respectively. After 8th h, the conversion and selectivity
were found to be slightly changed with time on stream and reached
the steady state after 8th h.
3.9. comparative catalytic activity of supported system
The prepared Ni-MoS catalysts supported on various zirconia-
silicates such as Zr-S (10), Zr-K (10), Zr-SiO2 (10), Zr-F (10), and
Zr-Al (10) are screened for hydrodeoxygenation of jojoba oil at
constant temperature of 350  C and 30 bar H2 pressure as seen in
Fig. 11. Effect of support was investigated in terms of specific re-
action rate (SRR) and TOF of HDO of jojoba oil is given in Fig. 11
[36,53]. Among different supported catalysts, the higher SRR
value and TOF of 10.09  105 (mol g1 s1) and 9.61  103 s1 was
observed for Ni-MoS/Zr-K (10) catalyst. This result shows that Ni-
MoS/Zr-K (10) catalyst had low reduction behaviour. This may be
due to the strong interaction of metal and support.
It can be concluded that there is strong interaction between
active metals and supports which is confirmed by H2-TPR and NH3-
TPD profiles. Zr-Al (10) supported Ni-MoS catalysts were found to
be very low in activity and the SRR and TOF value were found to be
6.61  105 mol g1 s1 and 5.73  103 s1 which may be due to
the unavailability of activity sites over the catalyst and the least
interaction of the support & active metal. Among all the catalysts,
Ni-MoS/Zr-K (10) exhibited the highest catalytic activity, whereas
Ni-MoS/Zr-Al (10) catalyst exhibited the lowest activity.
Ni-MoS/Zr-K (10) catalyst showed high hydrogen consumption
values (180 mmol g1) when compared to supported catalyst. NH3-
TPD results show that the moderate and strong acid sites were
present in Ni-MoS/Zr-K (10) was found to be higher (2.7 mmol NH3
170 A. Ramesh et al. / Renewable Energy 138 (2019) 161e173
Fig. 11. Effect of Supports, A) Ni-MoS/Zr-S (10), B) Ni-MoS/Zr-K (10), C) Ni-MoS/Zr-
SiO2 (10), D) Ni-MoS/Zr-F (10), and E) Ni-MoS/Zr-Al (10), Conversion and yield of
C18 þ C22 hydrocarbon at 350  C temperature, 30 bar H2 pressure, reactant: 7% jojoba
oil, WHSV ¼ 1.5 h1, Reaction time: 8 h; H2 flow rate ¼ 3600 ml/h.
g1 cat) which are responsible for hydrodeoxygenation of jojoba oil.
The catalytic activity was found to be in the order of Ni-MoS/Zr-K
(10) > Ni-MoS/Zr-SiO2 (10) > Ni-MoS/Zr-S (10) > Ni-MoS/Zr-F
(10) > Ni-MoS/Zr-Al (10).
3.10. Molecular weight distribution of jojoba oil
Jojoba oil was analyzed by gel permeation chromatography
(GPC). Before start up the reaction, the reactants were tested in
GPC. The results showed that two types of peaks are present at the
retention time of 8.9, and 9.2 min corresponds to average molecular
weight of 1358 and 522 respectively with high intensity as shown
in Fig. S3. After, the catalytic transformation at 275  C showed the
GPC peak at 9.19 min retention time corresponds to the average
molecular weight of 865. The peak at 8.9 min retention time was
completely shifted to 9.2 min with less intensity. It indicates that
the long chain de-polymerization was occurred. Furthermore,
change in molecule weight is confirmed by GPC results. This result
clearly shows that GPC peaks continuously shifted towards the
lower molecular weight region as the reaction time increased with
temperature and pressure. On increasing the temperature to
350  C, GPC peaks shifted to higher retention time corresponds to
the formation of long chain hydrocarbon as shown in Fig. S3. On
increasing to 375  C, the retention time increased with reduction in
the intensity due to more amount of low cracked product forma-
tion. The decarboxylation and de-carbonylation reaction took place
at higher temperature.
3.11. Proposed mechanism of jojoba oil
The preparation of sulphide Ni-Mo bimetals over different
mesoporous supports were carried out for HDO of jojoba and the
reaction takes place through several pathways. The possible reac-
tion mechanism is shown in Fig. 12. Jojoba oil was examined to
determine the percentage yield of hydrocarbon which is shown in
Fig. 12. The main goal for HDO reaction is to minimize the O/C ratio
at the same time to increase the H/C ratio [51]. HDO of jojoba oil
followed hydrodeoxygenation and decarboxylation mechanism to
form long chain hydrocarbons. In the first step, the hydrogenation
of jojoba oil took place followed by the formation of free fatty acid.
In the next step, long chain free fatty acids were transformed into
long-chain hydrocarbon. Based on GC data, three routes are
possible namely decarbonylation, decarboxylation and deoxygen-
ation. In decarboxylation and decarbonylation the products with
one carbon atom less were formed. But in the case of deoxygen-
ation same numbers of carbon atoms were present. This indicates
that the later was atom efficient reaction.
The decarbonylation involves the production of alcohol where
as the decarboxylation and deoxygenation produced alkenes and
alkanes. These reactions involved the cleavage of CeO and C]O
bonds of oil molecules in presence of low in-situ hydrogen. The
hydrocarbons involving more selective products in presence of Ni-
MoS due to the strong acidity of supports. As a result of this strong
acidity, C]O, C]C bonds get hydrogenated and CeC bonds were
broken to produce hydrocarbons. The CeO bond cleavage was
occurred by dehydrogenation in presence of surface-adsorbed
species. The surface active sites (Ni-MoS) and acid sites (Zr-K
(10)) of the catalyst were responsible for dehydration as seen in
Fig. 9 [51,52]. Furthermore, a small amount of cracking product and
isomerised products were included in the hydrocarbon conversion
and selectivity in Fig. S2. HDO reaction mechanism is shown in
Fig. 12. The conversion and selectivity of hydrocarbon products
depends on the temperature, pressure and the acidity of catalysts.
Hence, different nature of supports could establish the interaction
with active metal which plays a crucial role in biofuel production.
These products have improved fuel properties when compared to
conventional petroleum-based fuel.
3.12. Mass transfer considerations
Mass transfer consideration of catalytic treatment of biofuel
analysis involves various steps. Mass transfer limitation depends
upon the parameters such as diffusion of H2 gas (ultra-pure) in
liquid, transfer of gaseous reactants, transfer of liquid reactants on
the surface of active sites (Ni-MoS) and acid supports, intra particle
diffusion on the catalyst surface, internal as well as external
diffusion which were also affects the activity and product distri-
bution. The Specific reaction rate (SRR) generally determines the
reaction parameters. The kinetic parameter confirms that the mass
transfer limitation present or absent, in this step mainly focused to
eliminate mass transfer resistances which is previously reported by
Ancheyta et al. [52].
Some of the parameters influence the external diffusion con-
siderations. These parameters affect the reaction condition
constantly to find the diffusion at 350  C, H2 Pressure 30 bar, and
WHSV 1.5 h1 in presence of all the catalysts. However, catalyst
weight is constant and the jojoba oil flow rate was varied from 2 to
6 g and 0.1e0.3 ml min1. The corresponding results were present
in Table 3 [53]. When the jojoba oil flow increased from 0.1 to
0.3 ml min1 at a constant WHSV, the hydrocarbon conversion was
not decreased. This data concludes that the absence of external
mass transfer resistance. Furthermore, to avoid internal mass
transfer resistance, the catalysts were crushed into smaller size. To
investigate the pore diffusion resistance, another test was per-
formed using two different catalyst pellet size ranges (0.5e1 mm
and 3e4 mm). The other parameters were fixed as same (350  C; H2
Pressure 30 bar; and WHSV 1.5 h1) for all the prepared catalysts.
We have observed that similar kinds of results are appeared; and
the SRR values are shown in Table 3. However, the calculated value
evidences that the internal diffusion were not affected the reaction
condition.
4. Conclusion
A series of Ni-MoS catalyst over various mesoporous supports
 A. Ramesh et al. / Renewable Energy 138 (2019) 161e173 171

Fig. 12. Possible reaction mechanism of Jojoba oil to hydrocarbon fuel.

Table 3
Mass transfer considerations of Ni-MoS/Zr-S (10), Ni-MoS/Zr-K (10), Ni-MoS/Zr-SiO2 (10), Ni-MoS/Zr-F (10) and Ni-MoS/Zr-Al (10) catalysts.

S.N Catalysts Catalysts weight (g) Jojoba oil flow rate (ml) (SRR)  105 (mol g1 s1) Catalysts size (mm) (SRR)  105 (mol g1 s1)

1 Ni-MoS/Zr-S (10) 2 0.1 7.85 0.5e1 8.18

4 0.2 8.0 3e4 7.62
6 0.3 7.96
2 Ni-MoS/Zr-K (10) 2 0.1 10.09 0.5e1 10.4
4 0.2 10.15 3e4 9.87
6 0.3 9.98
3 Ni-MoS/Zr-SiO2 (10) 2 0.1 8.86 0.5e1 9.20
4 0.2 8.98 3e4 8.64
6 0.3 8.64
4 Ni-MoS/Zr-F (10) 2 0.1 7.26 0.5e1 7.41
4 0.2 7.63 3e4 7.07
6 0.3 7.52
5 Ni-MoS/Zr-Al (10) 2 0.1 6.61 0.5e1 6.96
4 0.2 6.73 3e4 6.73
6 0.3 6.96

Reaction parameters at 350  C; 7% jojoba oil in decalin, H2 Pressure 30 bar; and WHSV 1.5 h1, H2 flow rate ¼ 3600 ml/h.

such as Zr-SBA-15 (10), Zr-KIT-6 (10), Zr-SiO2 (10), Zr-FSM-16 (10)
and Zr-Al (10) were prepared and used in HDO of Jojoba oil in a
vapour phase fixed bed reactor. The catalytic activity of superior
catalyst was investigated based on SRR, TOF, conversion, stability
and selectivity. Remarkable changes (Improved textural properties
support) are observed due to the acid supports which influenced
the HDO reaction. However, Ni-MoS/Zr-K (10) catalyst showed su-
perior activity which is correlated with the physicochemical
properties. It has been inferred that the results of Ni-MoS/Zr-K (10)
catalysts shows the highest conversion (>90%) and selectivity of 18,
42, 33.8, and 6.2% for < C16, C17, C18, C22 respectively. The catalytic
activity in hydrodeoxygenation of jojoba oil follows the order of Ni-
MoS/Zr-K (10) >Ni-MoS/Zr-SiO2 (10) Ni-MoS/Zr-S (10) >Ni-MoS/Zr-
F (10) >Ni-MoS/Zr-Al (10). In addition, the mass transfer limitations
for all the synthesized catalysts were also investigated and the
results conclude that both internal and external mass
172 A. Ramesh et al. / Renewable Energy 138 (2019) 161e173
considerations are absent. Ni-MoS catalyst on different supports
under hydro processing conditions was successfully carried out. In
addition, effects of various parameters such as temperature, pres-
sure, WHSV, time on stream were also studied for Ni-MoS/Zr-K (10)
catalyst. The parameters are correlated with the physicochemical
techniques.
Acknowledgements
The authors are grateful for the financial support provided by
Defence Research and Development Organization (DRDO), New
Delhi, India the project sanction no. EPIR/ER/1203047/M/01/1535,
dt. 16.05.2014. Authors are thankful to DRDO.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.renene.2019.01.076.
References
[1] Juben N. Chheda, George W. Huber, James A. Dumesic, Liquid-phase catalytic
processing of biomass-derived oxygenated hydrocarbons to fuels and chem-
icals, Angew. Chem. Int. Ed. 46 (38) (2007) 7164e7183.
[2] Pandiyan Arjun, Surender Singh, Anil Kumar Singh, Technological in-
terventions for utilization of crop residues and weedy biomass for second
generation bio-ethanol production, Renew. Energy 132 (2019) 723e741.
[3] S. Gopinath, P. Vinoth Kumar, P. Sahaya Murphin Kumar, KA Yasar Arafath,
S. Sivanesan, P. Baskaralingam, Cs-tungstosilicic acid/Zr-KIT-6 for esterifica-
tion of oleic acid and transesterification of non-edible oils for green diesel
production, Fuel 234 (2018) 824e835.
[4] W.M.J. Achten, Louis Verchot, Ywe Jan Franken, Erik Mathijs, Virendra
Pal Singh, Raf Aerts, Bart Muys, Jatropha bio-diesel production and use,
Biomass Bioenergy 32 (12) (2008) 1063e1084.
[5] Hoda Shafaghat, Ji Man Kim, In-Gu Lee, Jungho Jae, Sang-Chul Jung, Young-
Kwon Park, Catalytic hydrodeoxygenation of crude bio-oil in supercritical
methanol using supported nickel catalysts, Renew. Energy (2018) 1e8.
[6] S.P. Sing, D. Sing, Biodiesel production through the use of different sources
and characterization of oils and their esters as the substitute of diesel: a re-
view, Renew. Sustain. Energy Rev. 14 (2010) 200e216.
[7] M.K. Abu-Arabi, M.A. Allawzi, H.S. Al-Zoubi, A. Tamimi, Extraction of jojoba oil
by pressing and leaching, Chem. Eng. J. 76 (2000) 61e65.
[8] Ekin Kıpçak, Mesut Akgün, Biofuel production from olive mill wastewater
through its Ni/Al2O3 and Ru/Al2O3 catalyzed supercritical water gasification,
Renew. Energy 124 (2018) 155e164.
[9] Shima Ahmadi, Ehsan Reyhanitash, Zhongshun Yuan, Sohrab Rohani, Chunbao
Charles Xu, Upgrading of fast pyrolysis oil via catalytic hydrodeoxygenation:
effects of type of solvents, Renew. Energy 114 (2017) 376e382.
[10] Arwa Sandouqa, Zayed Al-Hamamre, Energy analysis of biodiesel production
from jojoba seed oil, Renew. Energy 130 (2019) 831e842.
[11] Qi-Neng Xia, Cuan Qian, Xiao-Hui Liu, Xue-Qing Gong, Guan-Zhong Lu, Yan-
Qin Wang, Pd/NbOPO4 multifunctional catalyst for the direct production of
liquid alkanes from aldol adducts of furans, Angew. Chem. Int. Ed. 53 (37)
(2014) 9755e9760.
[12] Afsanehsadat Larimi, Farhad Khorasheh, Renewable hydrogen production by
ethylene glycol steam reforming over Al2O3 supported Ni-Pt bimetallic nano-
catalysts, Renew. Energy 128 (2018) 188e199.
[13] Meng-Yuan Chen, Yao-Bing Huang, Huan Pang, Xin-Xin Liu, Yao Fu, Hydro-
deoxygenation of lignin-derived phenols into alkanes over carbon nanotube
supported Ru catalysts in biphasic systems, Green Chem. 17 (3) (2015)
1710e1717.
[14] P. Tamizhdurai, P. Santhana Krishnan, A. Ramesh, K. Shanthi, Isomerization of
hydrocarbons over Pt supported on micro-mesoporous ZSM-5, Polyhedron
154 (2018) 314e324.
[15] Pornlada Daorattanachai, Weerawan Laosiripojana, Apirat Laobuthee,
Navadol Laosiripojana, Type of contribution: Research article catalytic activity
of sewage sludge char supported Re-Ni bimetallic catalyst toward cracking/
reforming of biomass tar, Renew. Energy 121 (2018) 644e651.
[16] Alexey V. Kirilin, Anton V. Tokarev, Elena V. Murzina, Leonid M. Kustov, Jyri-
Pekka Mikkola, Dmitry Yu Murzin, Reaction products and transformations of
intermediates in the aqueous-phase reforming of sorbitol, ChemSusChem 3
(6) (2010) 708e718.
[17] Lungang Chen, Yulei Zhu, Hongyan Zheng, Chenghua Zhang, Bin Zhang,
Yongwang Li, Aqueous-phase hydrodeoxygenation of carboxylic acids to al-
cohols or alkanes over supported Ru catalysts, J. Mol. Catal. Chem. 351 (2011)
217e227.
[18] A.A. Taromi, S. Kaliaguine, Hydrodeoxygenation of triglycerides over reduced
mesostructured Ni/g-alumina catalysts prepared via one-pot sol-gel route for
green diesel production, Appl. Catal. Gen. 558 (2018) 140e149.
[19] Ahmed E. Awadallah, Ateyya A. Aboul-Enein, Ahmed K. Aboul-Gheit, Various
nickel doping in commercial NieMo/Al2O3 as catalysts for natural gas
decomposition to COx-free hydrogen production, Renew. Energy 57 (2013)
671e678.
[20] Thiago LR. Hewer, Adriana GF Souza, Karina TC. Roseno, Paulo F. Moreira,
Bonfim Rodrigo, Rita MB Alves, Martin Schmal, Influence of acid sites on the
hydrodeoxygenation of anisole with metal supported on SBA-15 and SAPO-
11, Renew. Energy 119 (2018) 615e624.
[21] T.M.H. Dabros, A. Gaur, D.G. Pintos, P. Sprenger, M. Høj, T.W. Hansen, F. Studt,
J. Gabrielsen, J.D. Grunwaldt, A.D. Jensen, Influence of H2O and H2S on the
composition, activity, and stability of sulfided Mo, CoMo, and NiMo supported
on MgAl2O4 for hydrodeoxygenation of ethylene glycol, Appl. Catal. Gen. 551
(2018) 106e121.
[22] O.Y. Gutierrez, S. Singh, E. Schachtl, J. Kim, E. Kondratieva, J. Hein, J.A. Lercher,
Effects of the support on the performance and promotion of (Ni) MoS2 cata-
lysts for simultaneous hydrodenitrogenation and hydrodesulfurization, ACS
Catal. 4 (5) (2014) 1487e1499.
[23] G. Deepa, A.V. Ajgaonkar, K. Shanthi, S. Sivasanker, Hydrodemetallation and
hydrogenation activity of NieMo (S) supported on porous materials: In-
vestigations using model compounds, Adv. Porous Mater. 4 (2) (2016)
144e149.
[24] P. Tamizhdurai, Subramanian Sakthinathan, P. Santhana Krishnan, A. Ramesh,
V.L. Mangesh, A. Abilarasu, S. Narayanan, K. Shanthi, Te-Wei Chiu, Catalytic
activity of ratio-dependent SBA-15 supported zirconia catalysts for highly
selective oxidation of benzyl alcohol to benzaldehyde and environmental
pollutant heavy metal ions detection, J. Mol. Struct. 1176 (2019) 650e661.
[25] K. Chandra Mouli, Kapil Soni, Ajay Dalai, John Adjaye, Effect of pore diameter
of NieMo/Al-SBA-15 catalysts on the hydrotreating of heavy gas oil, Appl.
Catal. Gen. 404 (1e2) (2011) 21e29.
[26] K. Soni, B.S. Rana, A.K. Sinha, A. Bhaumik, M. Nandi, M. Kumar, G.M. Dhar, 3-D
ordered mesoporous KIT-6 support for effective hydrodesulfurization cata-
lysts, Appl. Catal. B Environ. 90 (1e2) (2009) 55e63.
[27] E.I. Muresan, D. Lutic, M. Dobrota, A. Coroaba, F. Doroftei, M. Pinteala,
Multimodal porous zirconium silicate macrospheres: Synthesis, character-
ization and application as catalyst in the ring opening reaction of epichloro-
hydrin with acrylic acid, Appl. Catal. Gen. 556 (2018) 29e40.
[28] Taotao Qiang, Jing Zhao, Ji Li, Direct synthesis of homogeneous Zr-doped SBA-
15 mesoporous silica via masking zirconium sulfate, Microporous Mesoporous
Mater. 257 (2018) 162e174.
[29] Prachee Misra, Sandeep Badoga, Ajay K. Dalai, John Adjaye, Enhancement of
sulfur and nitrogen removal from heavy gas oil by using polymeric adsorbent
followed by hydrotreatment, Fuel 226 (2018) 127e136.
[30] C. Suresh, D. Santhanaraj, M. Gurulakshmi, G. Deepa, M. Selvaraj, N.R. Sasi
Rekha, K. Shanthi, MoeNi/Al-SBA-15 (sulfide) catalysts for hydro-
denitrogenation: Effect of Si/Al ratio on catalytic activity, ACS Catal. 2 (1)
(2011) 127e134.
[31] Nasser H. Shalaby, Samia A. Hanafi, Salah A. Hassan, Mamdouh S. Elmelawy,
Can mesoporous TiO2-Al2O3-supported Ni-MoS OR CoMoS effectively perform
in ultra-deep desulfurization of gas oil? Petrol. Chem. 58 (5) (2018) 387e394.
[32] Amir Atabak Asadi, Seyed Mahdi Alavi, Sayed Javid Royaee, Mansour Bazmi,
Ultra-deep hydrodesulfurization of feedstock containing cracked gasoil
through NiMo/g-Al2O3 catalyst pore size optimization, Energy Fuels 32 (2018)
2203e2212.
[33] Marimuthu Selvaraj, Shanthi Kannan, Rajamanickam Maheswari,
Anand Ramanathan, Hydrodeoxygenation of guaiacol over MoO3-NiO/meso-
porous silicates: Effect of incorporated heteroatom, Energy Fuels 28 (4) (2014)
2598e2607.
[34] Carlos E. Scott, M. Josefina Perez-Zurita, Lante A. Carbognani, Hebert Molero,
Gerardo Vitale, He ctor J. Guzma
n, Pedro Pereira-Almao, Preparation of Ni-MoS
nanoparticles for hydrotreating, Catal. Today 250 (2015) 21e27.
[35] A.V. Mozhaev, P.A. Nikulshin, Al A. Pimerzin, K.I. Maslakov, A.A. Pimerzin,
Investigation of co-promotion effect in NiCoMoS/Al2O3 catalysts based on
Co2Mo10-heteropolyacid and nickel citrate, Catal. Today 271 (2016) 80e90.
[36] Guodong Jiang, Shijun Liao, Jian Qifei, Synthesis of Zr-FSM-16 mesoporous
zeolite and its catalytic performance for hydroxylation of benzene, Chin. J.
Catal. 2 (2005) 007.
[37] Li Fuxiang, Feng Yu, Yongli Li, Ruifeng Li, Kechang Xie, Direct synthesis of Zr-
SBA-15 mesoporous molecular sieves with high zirconium loading: charac-
terization and catalytic performance after sulfated, Microporous Mesoporous
Mater. 101 (1e2) (2007) 250e255.
[38] Anand Ramanathan, Bala Subramaniam, Rajamanickam Maheswari,
Ulf Hanefeld, Synthesis and characterization of Zirconium incorporated ultra
large pore mesoporous silicate, ZreKIT-6, Microporous Mesoporous Mater.
167 (2013) 207e212.
[39] Shang-Ru Zhai, Chang-Sik Ha, Structural control of mesoporous aluminosili-
cate nanoparticles in a binary surfactant system assisted by hydrolysis and
ordered assembly, Microporous Mesoporous Mater. 102 (1e3) (2007)
212e222.
[40] Shima Ahmadi, Ehsan Reyhanitash, Zhongshun Yuan, Sohrab Rohani, Chunbao
Charles Xu, Upgrading of fast pyrolysis oil via catalytic hydrodeoxygenation:
Effects of type of solvents, Renew. Energy 114 (2017) 376e382.
[41] Shi-Liu Yang, Hong-Bin Yao, Min-Rui Gao, Shu-Hong Yu, Monodisperse cubic
pyrite NiS2 dodecahedrons and microspheres synthesized by a solvothermal
process in a mixed solvent: Thermal stability and magnetic properties,
 A. Ramesh et al. / Renewable Energy 138 (2019) 161e173
CrystEngComm 11 (7) (2009) 1383e1390.
[42] Sandeep Badoga, Arvind Ganesan, Ajay K. Dalai, Shri Chand, Effect of synthesis
technique on the activity of CoNiMo tri-metallic catalyst for hydrotreating of
heavy gas oil, Catal. Today 291 (2017) 160e171.
[43] Chidchon Sararuk, Dan Yang, Guoliang Zhang, Chunshan Li, Suojiang Zhang,
A simple strategy to synthesize and characterization of zirconium modified
PCs/geAl2O3, Chin. J. Chem. Eng. 26 (2018) 1209e1212.
[44] P. Santhana Krishnan, R. Ramya, S. Umasankar, K. Shanthi, Promotional effect
of Ni2P on mixed and separated phase MoS2/Al-SBA-15 (10) catalyst for
hydrodenitrogenation of ortho-Propylaniline, Microporous Mesoporous
Mater. 242 (2017) 208e220.
[45] Dengqian Zhang, Aijun Duan, Zhen Zhao, Guofu Wan, Zhenyong Gao,
Guiyuan Jiang, Kebin Chi, H. Keng, Chuang, Preparation, characterization and
hydrotreating performances of ZrO2eAl2O3-supported NiMo catalysts, Catal.
Today 149 (1e2) (2010) 62e68.
[46] Jie Li, Yuanhang Ren, Bin Yue, Heyong He, Ni/Al2O3 catalysts derived from
spinel NiAl2O4 for low-temperature hydrogenation of maleic anhydride to
succinic anhydride, Chin. J. Catal. 38 (7) (2017) 1166e1173.
[47] Baker Rhimi, Mourad Mhamdi, Venkata Narayana Kalevaru, Andreas Martin,
Synergy between vanadium and molybdenum in bimetallic ZSM-5 supported
catalysts for ethylene ammoxidation, RSC Adv. 6 (70) (2016) 65866e65878.
[48] A. Hess, E. Kemnitz, A. Lippitz, W.E.S. Unger, D.H. Menz, ESCA, XRD, and IR
173
characterization of aluminum oxide, hydroxyfluoride, and fluoride surfaces in
correlation with their catalytic activity in heterogeneous halogen exchange
reactions, J. Catal. 148 (1) (1994) 270e280.
[49] Huan Liu, Changlong Yin, Xuehui Li, Yongming Chai, Yanpeng Li,
Chenguang Liu, Effect of NiMo phases on the hydrodesulfurization activities of
dibenzothiophene, Catal. Today 282 (2017) 222e229.
[50] Xi-long Wang, Zhen Zhao, Zhen-tao Chen, Jian-mei Li, Ai-jun Duan, Chun-
ming Xu, Dao-wei Gao, Zheng-kai Cao, Peng Zheng, Ji-yuan Fan, Effect of
synthesis temperature on structure-activity-relationship over NiMo/g-Al2O3
catalysts for the hydrodesulfurization of DBT and 4, 6-DMDBT, Fuel Process.
Technol. 161 (2017) 52e61.
[51] Wenwu Zhou, Qing Zhang, Yasong Zhou, Wei Qiang, Lin Du, Sijia Ding,
Shujiao Jiang, Yanan Zhang, Effects of Ga-and P-modified USY-based NiMoS
catalysts on ultra-deep hydrodesulfurization for FCC diesels, Catal. Today 305
(2018) 171e181.
[52] J. Ancheyta, G. Marroquin, M.J. Angeles, M.J. Macias, I. Pitault, M. Forissier,
R.D. Morales, Some experimental observations of mass transfer limitations in
a trickle-bed hydrotreating pilot reactor, Energy Fuels 16 (2002) 1059e1067.
[53] Shailesh J. Patil, Prakash D. Vaidya, Production of hydrotreated jatropha oil
using CoeMo and NieMo catalysts and its blending with petroleum diesel,
Energy Fuels 32 (2) (2018) 1812e1821.