Molecular Catalysis xxx (xxxx) xxxx

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Molecular Catalysis
journal homepage: www.elsevier.com/locate/mcat

Waste cooking oil transformation into third generation green diesel

catalyzed by nickel – Alumina catalysts
Ioannis Nikolopoulosa, George Kogkosa, Eleana Kordoulia, Kyriakos Bourikasb,
Christos Kordulisa,b,c,*, Alexis Lycourghiotisa
a
Department of Chemistry, University of Patras, GR-26504, Patras, Greece
b
Hellenic Open University, Tsamadou 13-15, GR-26222, Patras, Greece
c
Foundation for Research and Technology, Institute of Chemical Engineering Science (FORTH/ICE-HT), Stadiou Str., Platani, P.O. Box 1414, GR-26500, Patras, Greece

A R T I C LE I N FO A B S T R A C T

Keywords: Three nickel-alumina catalysts were prepared with nickel content 60, 80 and 90 wt % (symbols: 60NiAl, 80NiAl,
Green diesel 90NiAl) following a co-precipitation methodology. The catalysts were characterized and evaluated in the se-
Renewable diesel lective deoxygenation of waste cooking oil for the production of third generation green diesel under solvent free
Waste cooking oils conditions.
Biofuels
Metallic Ni, NiO, and NiAl2O4 were detected in the 60NiAl catalyst. NiAl2O4 is hardly detected in the 80NiAl
Nickel catalysts
catalyst but not at all in the 90NiAl catalyst. The extent of reduction of NiO to metallic Ni upon activation is
considerably higher in the 80NiAl and 90NiAl samples with respect to the 60NiAl sample resulting in much
higher active site population. The increase in the nickel content causes a change in the porous structure and a
decrease in the specific surface area. The catalytic performance increases considerably from the 60NiAl catalyst
to the 80NiAl one due to the increase in the active site population. The higher catalytic performance of the
80NiAl catalyst with respect to that of the 90NiAl catalyst, exhibiting almost equal active site population, is due
to convenient porous structure of 80NiAl catalyst, which hinder the insertion of deleterious bulky compounds
present in the waste cooking oil, as well as to its strong acid sites.

1. Introduction
The catalytic transformation of natural triglycerides into C15-C18 n-
alkanes (green diesel) over nickel non-sulphided catalysts supported on
various carriers has gained much interest in the last decade [1–6]. The
domain has been recently reviewed by our group [7]. This transfor-
mation takes place by hydrotreatment in the temperature range
240–360 °C and hydrogen pressure 10–80 bar. The removal of oxygen
without fragmentation of the side chains of triglycerides, selective
deoxygenation (SDO), may proceeds through decarboxylation (deCO2),
decarbonylation-dehydration (deCO–deH2O) and/or dehydration
(deH2O). Following a recently proposed terminology for biodiesel [8],
one can classify green diesel in four generations according to the raw
triglyceride material used (first generation: edible vegetable oils,
second generation: non-edible vegetable oils, third generation: residual
vegetable oils and animal fats, and fourth generation: algal oils). In the
most of studies fresh edible vegetable oils are used as sources of natural
triglycerides. However, the use of such oils compete the production of
foods. Therefore, replacing fresh edible oils by residual materials, like
waste cooking oils (WCO), for producing third generation green diesel is
extremely useful. The exploitation of WCO to produce fuels not only
solves waste problem but also recycles energy [9]. Nowadays, WCO is
readily available in large quantity and presents a cost effective resource
for biofuel production [10]. Nevertheless, studies dealing with the use
of WCO for the production of third generation green diesel are rela-
tively few [7,10–18].
In the last years we have contributed to this domain by developing a
co-precipitation methodology ensuring severe control of the precipita-
tion parameters. Co-precipitation leads to Ni catalysts with high metal
surface area (desired for hydrogen splitting) and less amount of strong
acid sites (desired to avoid extended hydrocracking) [19]. Recently,
Cao et al. [20] following a similar methodology have prepared high Ni-
loading catalysts (50 mol %) with highly dispersed Ni nanoparticles,
which showed excellent catalytic performance in benzonitrile hydro-
genation.
Following co-precipitation we have also succeeded to prepare
nickel-alumina [21] and nickel-zirconia [22] catalysts with high spe-
cific surface area and small supported nickel nanocrystals even for

⁎
Corresponding author at: Department of Chemistry, University of Patras, GR-26504, Patras, Greece.
E-mail address: kordulis@upatras.gr (C. Kordulis).

https://doi.org/10.1016/j.mcat.2019.110697
Received 9 July 2019; Received in revised form 21 October 2019; Accepted 24 October 2019
2468-8231/ © 2019 Elsevier B.V. All rights reserved.

Please cite this article as: Ioannis Nikolopoulos, et al., Molecular Catalysis, https://doi.org/10.1016/j.mcat.2019.110697
I. Nikolopoulos, et al.
catalysts with very high nickel content. Thus, catalysts with very high
active surface have been prepared. These catalysts exhibited high per-
formance, even under solvent free conditions and very high vegetable
oil volume to catalyst mass ratio (100 mL/1 g). The activity was further
increased by applying the co-precipitation methodology for preparing
molybdenum [18,23] and zinc [24] promoted nickel-alumina catalysts.
In almost all cases sunflower oil (SO) has been used as source of natural
triglycerides.
The replacement of the SO by WCO is the main pursuit of the pre-
sent work. Previous catalytic tests had indicated that nickel catalysts
with high nickel content and suitable pore size distribution are required
for obtaining high catalytic performance in the transformation of WCO
into green diesel [22,23]. Therefore, the present study focuses on the
preparation, characterization and evaluation of three nickel-alumina
catalysts with nickel loadings 60, 80 and 90 wt % symbolized by
60NiAl, 80NiAl and 90NiAl, respectively. These catalysts were prepared
using the aforementioned co-precipitation procedure. Moreover, in
order to rationalize the catalytic behavior, important physiochemical
properties of WCO were investigated vis-à-vis to SO.
2. Experimental
The catalysts were prepared by co-precipitation at constant pH from
aqueous solutions containing Al(NO3)3*9H2O, (E. Merck) and Ni
(NO3)2*6H2O (Merck, kGaA). Ammonium hydroxide solution (NH4OH
30%, Carlo Erba Reagents) was used for regulating the pH. Proper
amounts of the above salts were dissolved in distilled water. The so-
lution was fed by a syringe pump to a 500 mL beaker containing 180 mL
of distilled water. The pH was initially adjusted to pH = 8 and main-
tained constant during preparation using a pH-stat (Metrohom-645). A
bare alumina sample was also prepared following the same procedure
without adding nickel nitrate. The solids obtained by filtration were
dried at 110 °C overnight, heated under argon flow (30 mL/min) for
40 min, required for the increase of temperature from room tempera-
ture to 400 °C, and then were reduced at 400 °C for 2.5 h under hy-
drogen flow (30 mL/min). The activated catalysts were characterized
using the following techniques.
Nitrogen adsorption-desorption isotherms were recorded in a
Micromeritics apparatus (Tristar 3000 porosimeter). Specific Surface
Area (SSABET) calculation was based on BET equation using adsorption
data recorded at relative N2 pressure in the range 0.03 < P/P0 < 0.5.
Pore size distribution was determined using the BJH method and the N2
desorption curve.
X-ray powder diffraction (XRD) patterns were recorded in the range
of 10° ≤ 2θ ≤ 80o by a Bucker D8 Advance diffractometer equipped
with nickel-filtered Cu Kα (1.5418 Å) radiation source working at 40 kV
and 20 mA. The step size and the time per step were respectively fixed
at 0.02o and 0.5 s. The mean crystallite size was estimated using
Scherrer’s equation.
Scanning Electron Microscopy-Energy Dispersive Spectrometry
(SEM-EDS) was used for the determination of catalysts percentage
composition in nickel. Scanning Electron Microscope (SEMJEOL
JSM6300) equipped with an Energy Dispersive Spectrometry accessory
has been used working with 20 kV accelerating voltage and 10 nA beam
current. Microanalysis was performed on gold coated samples. The
sample powders were mounted directly on the sample holder.
Transmittance Electron Microscopy (TEM) was used for recording
TEM images of the catalysts in a JEOL JEM-2100 system operated at
200 kV (resolution: point 0.23 nm, lattice 0.14 nm) equipped with an
Erlangshen CCD Camera (Gatan, Model 782 ES500W). The specimens
were prepared by dispersion in water and spread onto a carbon-coated
copper grid (200 meshes).
NH3-TPD experiments were performed in laboratory-constructed
equipment. In a typical experiment, 100 mg of the pre-reduced catalyst
were placed in a quartz micro-reactor and helium was fed (flow rate
30 mL min−1) for 30 min in order to remove any adsorbed species from
2
Molecular Catalysis xxx (xxxx) xxxx
the catalyst surface. Then, a stream of NH3 was fed in the micro-reactor
for 30 min at room temperature and then it was switched to He to re-
move the physically adsorbed ammonia. The temperature was then
increased linearly (10 °C/min) up to 500 °C. The amount of the des-
orbed ammonia was determined by a thermal conductivity detector
(TCD).
CO-chemisorption was performed on the aforementioned labora-
tory-constructed equipment following pulse technique. 100 mg of the
pre-reduced catalyst were placed in the quartz micro-reactor and He
was fed (40 mL min−1) until a constant base line to be obtained. The CO
uptake was measured at 30 °C by successive injection of 0.5 mL of CO
samples (10% v/v in He) via calibrated loop of a six-port valve into He
carrier until saturated peak was detected by TCD in the reactor outlet.
The catalyst surface was washed with He for half an hour and a second
cycle of successive injections was performed. The chemically adsorbed
CO was calculated by subtracting the CO adsorbed during the second
cycle from that of the first one.
Precursor samples (after Ar treatment at 400 °C and before reduc-
tion) were characterized by H2-TPR experiments performed in the same
laboratory-constructed equipment. An amount of sample, 0.04 g, was
placed in the quartz reactor and the reducing gas mixture (H2/Ar: 5/95
v/v) was passed through it for 2 h with a flow rate of 40 mL min−1 at
room temperature. Then the temperature was increased to 1000 °C with
a constant rate of 10 °C min−1. Reduction leads to a decrease of the
hydrogen concentration of the gas mixture, which was detected by the
TCD. The reducing gas mixture was dried in a cold trap (−95 °C) before
reaching the TCD.
The catalysts were evaluated for transformation of WCO to green
diesel under solvent free conditions at 310 °C, 40 bar hydrogen pres-
sure, WCO volume to catalyst mass ratio 100 mL/1 g and various re-
action times up to 9 h. A falling basket batch reactor (300 ml, Autoclave
Engineers), working in a semi-batch mode with hydrogen flow rate
100 mL/min, has been used. The WCO used in this study, was obtained
by a local company, “COLLECTOIL”. It was filtered three times using
cloth filters of different sizes and then it was centrifuged prior to its use.
The analysis of the liquid samples was performed by gas chromato-
graphy and confirmed by gas chromatography-mass spectrometry.
More details concerning preparation, characterization and evaluation of
the catalysts have been reported in references [8,10–13]. SO and WCO
were characterized using TGA, FT-ATR, GC–MS whereas their im-
portant physicochemical properties (acidity, viscosity, iodine number
and water content) have been determined [25].
3. Results and discussion
3.1. Composition and physicochemical properties of WCO
It should be taken into account that the major portion of the WCO,
drawn from the Greek restaurants, is manly produced by cooking SO.
The determination of characteristic parameters has shown that WCO
exhibits higher static and dynamic viscosity (9.89 cSt, 0.088 P) than SO
(7.39 cSt, 0.066 P) as well as lower iodine number than SO (WCO: 67,
SO: 120–134). Both can be attributed to the acidic polymerization of a
small portion of triglycerides upon cooking starting from the double
olefinic C]C bonds of their side chains. The increase in the viscosity
upon cooking can be also partly attributed to the presence of potato
starch or meat proteins in the WCO inserted in the SO upon cooking.
The presence of polymeric compounds, starch and proteins in the WCO
is also investigated by comparing the TGA curves of SO and WCO il-
lustrated in Fig. 1. Inspection of this figure shows that the TGA curves
are almost identical in the range 25–450 °C due to the triglyceride
structure of both raw materials. This is also confirmed by the almost
identical FT-ATR spectra recorded for both of them (Fig. 2). However,
returning to the TGA curves we are observing that the weight of SO
takes a zero value at about 450 °C whereas a small amount of WCO
remains in the range 400–450 °C.
I. Nikolopoulos, et al. Molecular Catalysis xxx (xxxx) xxxx

Fig. 1. TGA curves of SO (red curve) and WCO (black curve). (For interpretation of the references to colour in this figure legend, the reader is referred to the web
version of this article).

This indicates the presence of more difficultly sublimated com-

pounds, much probable polymers, starch and proteins. However, the
weight of WCO takes a zero value after heating the sample at 450 °C for
0.5 h. The determination of characteristic parameters has shown that
WCO exhibits higher acidity expressed in oleic acid (WCO: 0.83%, SO:
0.60%). This can be attributed to the partial dissociation of the natural
triglycerides to fatty acids upon cooking. In fact, small amounts of
stearic acid are identified in the GC chromatograms of the WCO (not
shown here) together with small amounts of mono and di-glycerides
produced by progressive dissociation of a small portion of triglycerides.
The water content of the two feedstocks was also determined and was
found to be different (WCO: 0.14 wt %, SO: 0.04 wt %). In view of the
above one can conclude that besides the differences in acidity and
water content, an important difference between SO and WCO is the
presence of bulky compounds in the latter.

3.2. Solid phases

The compositions of the catalysts determined by EDS are very close

to the nominal ones. The crystal phases of the catalysts studied were Fig. 3. XRD patterns of the activated (reduced) catalysts studied. The symbols
investigated by XRD and electron diffraction whereas the distribution of (#), (*) and (+) denote, respectively NiO, Ni and NiAl2O4.
the solid phases was investigated by TEM. The XRD patterns of the
catalysts studied are illustrated in Fig. 3.
Inspection of the XRD patterns shows the presence of metallic nickel

Fig. 2. FT – ATR spectra of SO (red curve) and

WCO (black curve). The assignments of dif-
ferent of stretching (s), bending (b) and
rocking (r) vibrations of the various groups of
triglycerides have been taken from the litera-
ture [26]. (For interpretation of the references
to colour in this figure legend, the reader is
referred to the web version of this article).

3
I. Nikolopoulos, et al.
Fig. 4. Electron diffraction pattern of the catalyst studied.
[peaks at 2θ: 44.5, 51.8 and 76.3°, JCPDS 04-0850] and nickel oxide
[peaks at 2θ: 43.4, 37.3 and 62.9°, JCPDS 01–1239] on the catalysts
studied. Small amounts of nickel aluminate are detected in the sample
60NiAl [shoulders at 2θ: 45.0 and 65.5, JCPDS 01–1239]. Nickel alu-
minate is very hardly detected, in the 80NiAl catalyst but not in the
90NiAl catalyst. The absence of peaks corresponding to alumina crys-
tals strongly suggests that the alumina formed is amorphous.
Comparison of the height of the peak at 2θ: 44.5° with that at 2θ: 43.4°
shows that the minimum ratio Ni/NiO is obtained in the 60NiAl sample
and the maximum one in the sample 80NiAl. This indicates that in the
latter sample the highest extend of NiO reduction towards the cataly-
tically active metallic nickel is achieved upon activation. The mean
crystal size of the metallic nickel calculated on the base of diffraction
peak at 2θ: 51.8° was found to be equal to 9.6, 11.2 and 10.9 nm for the
60NiAl, 80NiAl and 90NiAl catalysts, respectively.
The XRD results are confirmed by the electron diffraction results.
Thus, the electron diffraction pattern of the sample 60NiAl showed the
presence of Ni, NiO and NiAl2O4 nanocrystals whereas the electron
diffraction patterns of the samples 80NiAl and 90NiAl showed the
presence of only Ni and NiO nanocrystals. A typical electron diffraction
pattern for the most active catalyst, 80NiAl, is illustrated in Fig. 4.
The TEM images recorded for the catalysts studied depict the dis-
tribution of their solid phases at nanoscale. Typical examples are illu-
strated in Fig. 5. The TEM images of the catalyst 60NiAl display two
regions; one with relatively small nickel phase nanoparticles separated
by areas comprised from very small alumina nanoparticles (Fig. 5a) and
another one with relatively big nickel phase nanoparticles separated by
mixed areas comprised from smaller and smaller nickel phase nano-
particles and very small alumina nanoparticles (Fig. 5b). The second
picture predominates in the 80NiAl (Fig. 5c) and 90NiAl catalysts
(Fig. 5d). The separating areas are wider in the 80NiAl catalyst.
3.3. Textural properties and metallic nickel surface
Table 1 compiles important parameters of the catalysts studied
concerning their texture probed by N2 physisorption and metallic area
investigated by pulse CO adsorption experiments.
Inspection of Table 1 shows that although the specific surface area
decreases with nickel content, thanks to the preparation methodology
applied it remains adequately high, even in the catalyst with nickel
content as high as 90 wt %. The relatively high SSABET values are
4
Molecular Catalysis xxx (xxxx) xxxx
compatible to the mesoporous texture of the catalysts inferred by in-
specting Fig. 6.
The change of nickel content is accompanied by considerable
changes in the pore volume distributions. The 60NiAl catalyst exhibits a
double peak centered at 3 and 5 nm and a broad one in the range
12–100 nm. The catalyst 80NiAl exhibits its main peak at about 7 nm
and a smaller size peak in the range 18–100 nm. The no formation of
pores with 3 and 5 nm diameter in the 80NiAl catalyst is reflected in the
decrease of its SSABET whereas the smaller size of the peak in the range
above 10 nm is in accordance with its decreased SPV value (Table1).
Finally, the 90NiAl catalyst exhibits a broad pore volume distribution
with a main maximum in the range 10–20 nm which is extended to
higher than 100 nm justifying both the further decrease in SSABET and
the impressive increase in the value of MPD (Table 1).
It is well known that CO-chemisorption cannot be considered as an
absolute quantification measure of metallic sites. This is mainly caused
by the different ways CO-chemisorption occurs on the various sites. For
Ni catalysts, the CO-chemisorption is affected by the metal content, the
“Ni-support” interaction, the metal particles dispersion, and the pre-
sence of impurities. On the other hand, several possible modes of ad-
sorption such as linear, bridged and carbonyl type adsorption have been
observed [27] and metallic Ni centers can interact with two, even three
CO molecules [28]. However, the low temperature CO-chemisorption
contacted in our case is expected to lead mainly in linear adsorption on
metallic Ni sites. Although, the quantification of chemisorbed CO with
1:1 stoichiometry per surface Ni atom is widely used in the recent lit-
erature for Ni surface area and dispersion determination [29], it is more
realistic to consider the amount of chemisorbed CO (μmol/g catalyst) as
a reliable parameter for comparison [28,30]. In this sense, the CO
chemisorption results (Table 1) clearly show that the surface of metallic
nickel increases with the nickel content. The increase is abrupt when
going from the 60NiAl catalyst to the 80NiAl one. In fact, whereas the
weight ratio in total nickel is equal to 80/60 = 1.33, the corresponding
ratio in the amount of the adsorbed CO is 209/15 = 13.93. This can be
explained considering that a great portion nickel in the 60NiAl catalyst
is present as nickel oxide and nickel aluminate relatively not active in
the CO adsorption. This is not the case for the 80NiAl catalyst where
according to the XRD and electron diffraction results it is obtained the
highest extent of NiO reduction to metallic nickel and where nickel
aluminate is not present. Moreover, combining the XRD, electron dif-
fraction and CO adsorption results we incline to argue that nickel oxide
and nickel aluminate relatively small nanocrystals presumably pre-
dominate in regions of the 60NiAl catalyst pictured in the up- left image
of Fig. 5. The increase in the nickel metallic surface follows the increase
of the nickel content when going from the 80NiAl catalyst to the 90NiAl
one. In fact, the weight ratio in total nickel is equal to 90/80 = 1.12
and the corresponding ratio in the amount of the adsorbed CO is 227/
209 = 1.08. The slightly lower value in the latter ratio could be at-
tributed to the smaller extend of NiO reduction in the 90NiAl catalyst
with respect to the 80NiAl catalyst deduced by XRD.
3.4. Catalysts reducibility and acidity
The XRD, electron diffraction, TEM and CO adsorption findings are
corroborated by the H2-TPR results illustrated in Fig. 7.
Before discussing the H2–TPR curves it is useful to mention that the
reduction time upon activation at 400 °C is much higher (2.5 h) than the
very small reduction time upon the transient H2-TPR procedure. This
allows us to assume that the hydrogen consumption up to roughly
450 °C corresponds to the reduction of NiO nanocrystals to metallic
nickel detected by XRD and electron diffraction in the reduced cata-
lysts. The hydrogen consumption in the range 450–750 °C corresponds
to the reduction of NiO nanocrystals non-reducible upon activation and
thus they are detected by XRD and electron diffraction as nickel oxide.
Finally, the hydrogen consumption in the range 750–800 °C corre-
sponds to the reduction of nickel aluminate [18,31–35]. Let’s
I. Nikolopoulos, et al. Molecular Catalysis xxx (xxxx) xxxx

Fig. 5. Examples of TEM images recorded for the catalysts studied (a: 60NiAl, b: 60NiAl, c: 80NiAl, d: 90NiAl).

Table 1
Textural parameters of the catalysts studied and CO-chemisorption results.
Catalyst SSABET SPV* (cm3 g−1) MPD** (nm) COads*** (μmol/
(m2 g−1) gcat)

60NiAl 273 0.59 6.6 15

80NiAl 116 0.36 8.7 209
90NiAl 89 0.49 16.1 227

* Specific pore volume.

** Mean pore diameter.
*** CO-chemisorption.

Fig. 7. H2-TPR curves of the catalysts studied.

alumina [33,34] and resulting to better dispersed nickel nanocrystals is

Fig. 6. Pore volume distribution of the catalysts studied.
concentrate our attention to the H2-TPR curve of the 60NiAl catalyst.
We are observing a peak at about 350 °C corresponding to quite large
NiO nanocrystals weakly interacted with alumina [31,32] and thus
easily reducible to quite large nickel nanocrystals (low dispersion).
Moreover, the hydrogen consumption in the range 350–450 °C corre-
sponding to smaller NiO nanocrystals moderately interacted with
relatively low compared to the other two samples. In contrast, the hy-
drogen consumption above 450 °C corresponding to NiO nanocrystals
non-reducible upon activation and nickel aluminate [35] is con-
siderably higher compared to those of the other two catalysts. The
above results are in full agreement to the XRD and electron diffraction
results and justify the relatively low metallic nickel surface inferred by
the CO adsorption. The increase in hydrogen consumption in the range
350–450 °C with the nickel content is in line with the increase in the
amount of metallic nickel also inferred by the increase in the magnitude
of the XRD peak at 51.8° and the increase in the CO adsorption. The
decrease in hydrogen consumption in the range 500–750 °C with the
nickel content reflects the decrease in the relative amount of NiO with
respect to metallic nickel. Finally, nickel aluminate, reducible in the
range 750–800 °C is indicated in the 60NiAl catalyst, hardly in the
80NiAl catalyst but not in the 90NiAl one, in agreement to the XRD

5
I. Nikolopoulos, et al.
Fig. 8. NH3-TPD curves of the catalysts studied and the bare alumina (0NiAl).
results.
The acidity of the catalysts was studied by NH3-TPD experiments.
Fig. 8 illustrates the NH3-TPD curves.
Fig. 8 illustrates the NH3-TPD curves of the catalysts studied and the
bare alumina. All the samples exhibit high populations of weak acid
sites (desorption temperature < 300 °C), small populations of sites with
moderate acidity (300 °C < desorption temperature < 450 °C) and few
strong acid sites, only in the sample 80NiAl (desorption tempera-
ture > 450 °C) [36]. We are observing that the bare alumina (0NiAl)
exhibits the highest population of weak acid sites. This population de-
creases with the nickel content following approximately the decrease of
the alumina content and the parallel decrease in the specific surface
area (Table 1). This is an indication that the weak acid sites are mainly
situated on the alumina surface. The observation that the moderately
strong and very strong acid sites appear mainly on the surface of the Ni
catalysts indicates that these are situated on the supported nickel
phases. They could be related to the empty d orbitals of the metallic
nickel and the Ni2+ ions in the supported nickel oxide and nickel alu-
minate which can interact with the lone pair of electrons of ammonia
[37]. Taking into account the XRD results one can attribute the creation
of moderately strong acid sites to all nickel phases while that of the very
few strong acid sites mainly to the metallic Ni. The latter phase was
found to be predominant in the 80NiAl catalyst. We shall return to this
point after the evaluation of the catalysts performance.
3.5. Evaluation of the catalytic performance
Before dealing with the catalytic behavior of the catalysts studied it
is useful reminding the SDO of triglycerides network over nickel non-
sulphided catalysts [7]. It is proceeding through the hydrogenation of
olefinic bonds of the triglycerides followed by the decomposition of the
OCe bonds in the glycerol side and the formation of fatty acids and
propane. The fatty acids are reduced to aldehydes and alcohols. The
aldehydes are decarbonylated resulting to n‐C17 and n‐C15 alkanes and
CO. The alcohols are dehydrated and the produced olefins are hydro-
genated resulting to n‐C18 and n‐C16 alkanes. In parallel, the alcohols
react with the fatty acids producing long chain esters with both hy-
drocarbons parts corresponding to fatty acids of triglycerides. The es-
ters undergo SDO resulting to hydrocarbons. Thus fatty acids and esters
are intermediate products. The CO produced may react with hydrogen
producing methane.
The most important products identified in the liquid phase were
non-reacted triglycerides, long chain esters with both hydrocarbon
parts corresponding to fatty acids of triglycerides, palmitic and stearic
acid (mainly stearic acid) and normal alkanes, n-C15–n-C18, whereas
6
Molecular Catalysis xxx (xxxx) xxxx
Fig. 9. Kinetic curves over the catalyst 80NiAl (310 °C, 40 bar hydrogen pres-
sure, reactant volume to catalyst mass ratio=100 mL/1 g).
CO, propane and methane have been identified in the gas phase. The
above products are expected from the reaction network described just
before. Typical kinetic curves for the catalyst 80NiAl are presented in
Fig. 9. It is seen that the conversion increases considerably even for
reaction time of 1 h indicating that the first steps of the SDO network
(hydrogenation of olefinic bonds of the triglycerides, decomposition of
the O‐C bonds in the glycerol side) are very rapid in agreement to the
literature [7,17,18]. Moreover, the kinetic curves show maxima con-
cerning the acid and esters evolution indicating that these molecules
are actually intermediate ones in agreement to the reaction network.
On the other hand, the evolution of the hydrocarbons, as final products,
follows a rather linear kinetic curve. In almost all cases the amounts of
n-alkanes with even number carbon atoms (principally n-C17) is much
higher than the amounts of the hydrocarbons with odd number of
carbon atoms, indicating that the process proceeds mainly through the
decarbonylation of the intermediate aldehydes which is the case of
nickel metallic catalysts [7]. In conclusion, the replacement of the SO
by WCO does not seem to affect generally the triglyceride SDO network.
The comparative evaluation of the catalysts studied is presented for
the maximum reaction time (Fig. 10). As it is seen complete conversion
of WCO (100%) is achieved under reaction conditions used over all the
catalysts studied. However, the liquid product distribution obtained
depends on the catalyst used.
It is seen that the total amount of the hydrocarbons produced in the
diesel range, the most important evaluation parameter from the cata-
lytic point of view, follows a volcano-like trend maximized over the
80NiAl catalyst. The value obtained over this catalyst, equal to
Fig. 10. Evaluation parameters obtained for the SDO of WCO over the catalysts
studied at reaction time equal to 9 h (310 °C, 40 bar hydrogen pressure, reactant
volume to catalyst mass ratio =100 mL/1 g).
I. Nikolopoulos, et al.
36 ± 2% is quite high taking into account the very high ratio of WCO
volume to catalyst mass adopted in the present work. Moreover, this is
considerably higher than that obtained over the 60NiAl catalyst
(13 ± 2%) and quite higher than that obtained over the 90NiAl cata-
lyst (29 ± 2%). The increase of the catalytic performance from the
60NiAl catalyst to the 80NiAl can be mainly attributed to the increase
in the active site population inferred by the CO adsorption. It is well
known that the reduction of intermediate free fatty acids to the corre-
sponding aldehydes is the rate determining step of the triglycerides SDO
network [7]. This step is catalyzed by active sites situated on the me-
tallic nickel [7]. Thus, the highest green diesel yield achieved over the
80NiAl catalyst is easily explained. In contrast, the change in the active
site population cannot explain the decrease of the catalytic performance
going from the 80NiAl catalyst to the 90NiAl one. Indeed, considering
the chemisorbed CO (Table 1) as a relative measure of metallic nickel
site population one can conclude that active site populations in these
two samples are almost equal. Therefore, two additional observations
should be taken into account in order to explain the achievement of the
maximum catalytic performance over the 80NiAl catalyst. The first
concerns the presence of the very strong acid sites present exclusively in
this catalyst (Fig. 8). These presumably involved in the decomposition
of the bulky compounds being in WCO, mentioned in 3.1 subsection,
which would eventually adsorbed and thus deactivate active sites. The
second observation concerns the catalysts texture. As already men-
tioned, pores of about 7 nm are the predominant ones present in the
80NiAl catalyst. In contrast, pores with sizes extended from 15 up to
higher than 100 nm are present in the 90NiAl catalyst (Fig. 6). One may
assume that the WCO bulky compounds, probably acting as poisons,
cannot easily inserted in the small pores of the 80NiAl catalyst justi-
fying its very high performance in the SDO of WCO.
Closing this section we have to stress that Ni leaching determination
and catalysts reuse experiments are crucial for the application of such
catalysts in real SDO processes of WCO. SEM – EDS experiments per-
formed over fresh and used catalysts proved that the leaching of Ni
phase is not important. This is in agreement with our previous studies
on relevant catalysts [18]. It seems that the co-precipitation metho-
dology used for catalysts preparation results to relatively strong metal-
support interactions [38] preventing Ni leaching, ensuring also good
catalyst stability, as no appreciable aggregation is usually observed in
the spent catalysts [20].
4. Conclusions
Nickel-alumina nanostructured catalysts with nickel content in the
range 60–90 wt % (60NiAl, 80NiAl and 90NiAl) are proved to be active
in the transformation of WCO into green diesel under very high WCO
volume/catalyst mass ratio and solvent free conditions. The catalytic
performance follows a volcano-like trend maximized over the 80NiAl
catalyst. The considerably high catalytic performance obtained over
this catalyst with respect to that of the 60NiAl one is mainly attributed
to its much higher metallic nickel surface compared to the latter cata-
lyst. On the other hand, the higher catalytic performance of the 80NiAl
catalyst with respect to the 90NiAl catalyst, exhibiting somewhat
higher metallic nickel surface, is attributed not only to its convenient
porous structure exhibiting pores with mean diameter about 7 nm,
which hinder the insertion of deleterious bulky compounds present in
the WCO, but also to few but strong acid sites present exclusively in the
80NiAl catalyst, which presumably are involved in the decomposition
of these bulky compounds.
The authors declare the following financial interests/personal re-
lationships which may be considered as potential competing interests:
Molecular Catalysis xxx (xxxx) xxxx
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
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