Renewable Energy 197 (2022) 40–49

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

Fe-promoted Ni catalyst with extremely high loading and oxygen vacancy

for lipid deoxygenation into green diesel
Fei Wang a, *, Hui Xu a, Songyin Yu a, Hao Zhu a, Yuchan Du a, Zeng Zhang a, Chaoqun You b,
Xiaoxiang Jiang a, **, Jianchun Jiang b, c
a
School of Energy & Mechanical Engineering, Nanjing Normal University, Nanjing, 210023, PR China
b
Joint Laboratory of Advanced Biomedical Materials (NFU-UGENT), College of Chemical Engineering, Co-Innovation Center of Efficient Processing and Utilization of
Forest Resources, Nanjing Forestry University, Nanjing, 210037, PR China
c
Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Nanjing, 210042, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: The catalytic performance of Ni catalyst in lipid deoxygenation into green diesel is commonly limited by the
Lipid hydrotreatment quantity of accessible active sites, the specific surface area, and the acidity of the catalyst. To cope with these
Second-generation bio-diesel problems, the Fe-promoted Ni catalyst on ZrO2 with 60 wt% Ni loading (60%Ni–Fe/ZrO2) is synthesized by the
Co-precipitation method
co-precipitation method. The deoxygenation of oleic acid over 60%Ni–Fe/ZrO2 catalyst attained 98.7% con­
Hydrocarbons
Hydrotreatment pathway
version and 91.8% alkane yield, much higher than that of 20%Ni–Fe/ZrO2-2 prepared with the impregnation
method (42.8% conversion and 16.2% alkane yield). The kinetics of octadecanol hydrotreatment revealed that
the activation energy over 60%Ni–Fe/ZrO2 was much lower than Ni–Fe/ZrO2-2 (78.48 kJ/mol vs.191.90 kJ/
mol). From the catalyst characterizations, the excellent performance of 60%Ni–Fe/ZrO2 was ascribed to its fine
Ni particles, abundant Ni sites, high surface area, and coordinated acidity. Moreover, the mechanism of lipid
deoxygenation over 60%Ni–Fe/ZrO2 was proposed.

1. Introduction diesel at any proportion [4].

As a kind of liquid fuel, diesel has been playing an important role in
the industrial and transportation sectors. At present, diesel derives pri­
marily from the thermal cracking of crude oil and Fischer-Tropsch
synthesis of CO and H2 [1,2]. The excessive use of nonrenewable
crude oil and coal has led to a severe environmental pollution, therefore,
exploring a green and sustainable resource to produce diesel is a sig­
nificant project worldwide. Cooking oil, inedible vegetable oil, and
microalgae oil are considered promising substitutes for fossil fuels
because they are inedible and productive. These lipid resources can be
converted into fatty acid methyl ester (FAME) via transesterification.
The FAME, namely first-generation bio-diesel can replace partly the
traditional diesel but the percentage of FAME in diesel is very limited
(less than 10 vol%) due to its low poor cold-flow properties and high
oxygenation content [3]. Through deoxygenation (hydrotreatment), the
lipids can be transformed into C15–C18 alkanes, namely
second-generation biodiesel or green diesel, which can replace fossil
During deoxygenation, as the intermediates the fatty acids would
generate hydrocarbons via three possible pathways: decarboxylation
(DCX), decarbonylation (DCN) as well as hydrodeoxygenation (HDO).
The hydrocarbons with the same carbon number as fatty acids are
generated via HDO, while the hydrocarbons with one carbon less are
produced via DCX and DCN [5,6]. The pathways closely depend on the
catalyst kind. By now the noble catalyst (Pd, Pt) and vulcanized mo­
lybdenum catalyst are commonly used for green diesel production [7,8].
Unfortunately, the expensive cost of noble metals and environmental
issues from sulfur agents restrain respectively the development of both
catalysts. The molybdenum carbide was currently applied in lipid
deoxygenation and exhibited decent catalytic performance [9–11].
Whereas, the high temperature (above 700 ◦ C) under H2 during the
carburization process are not beneficial for industrial application.
With cheap cost, sulfur-free, and relatively low reduction tempera­
ture, the Ni catalyst draws lots of attention [12]. However, the poor
dispersion and the agglomeration of Ni metal lead to deficient Ni active

* Corresponding author.
** Corresponding author.
E-mail addresses: feiwang@njnu.edu.cn (F. Wang), 62081@njnu.edu.cn (X. Jiang).

https://doi.org/10.1016/j.renene.2022.07.079
Received 17 February 2022; Received in revised form 27 April 2022; Accepted 14 July 2022
Available online 1 August 2022
0960-1481/© 2022 Published by Elsevier Ltd.
F. Wang et al.
sites, thus limiting the catalytic performance of Ni catalyst [13,14].
Interestingly, the Ni catalyst could be improved by other metals and
supports. The Cu [15,16], Sn [17], Mo [18], Pt [19], and Zn [20] have
been used to promote the activity of Ni catalyst for lipid hydrotreatment.
In our previous study, the NiCu/Al2O3 catalyst was used for green diesel
production. The Cu addition improved the dispersion of Ni sites and
enhanced the electron density of Ni, leading to high catalytic activity in
lipid hydrotreatment [21]. The Al2O3, SiO2, zeolite, and carbon material
are commonly utilized as the supports of Ni catalyst. When ZrO2 was
used as support, the Ni catalyst showed a high catalytic performance due
to its oxygen vacancy [22]. The Ni loading in the catalyst prepared with
the wetness impregnation method is normally less than 25% because
when the Ni loading further increases, the agglomeration of Ni metal
occurs and the extra Ni blocks the pores of catalysts. Therefore,
increasing Ni loading and simultaneously obtaining high dispersion of
the active site and surface area of the catalyst is an effective strategy to
prepare the catalyst with high performance in lipid deoxygenation [23].
Christos et al. [24] prepared the Ni/Al2O3 catalyst with 60 wt% Ni
loading by co-precipitation method and the catalyst exhibited good
performance in sunflower oil hydrotreatment into green diesel. More­
over, the Zn [25] and Mo [18] addition promoted the catalytic perfor­
mance of the co-precipitated Ni/Al2O3 catalyst.
So far, for the co-precipitated Ni catalysts only Al2O3 was used as
support and the promotion metals were very limited (Zn or Mo). Herein,
by co-precipitation method the Ni–Fe/ZrO2 catalyst with extremely high
Ni loading was synthesized to transform lipids into green diesel. The
Ni–Fe interaction was deeply studied, and the equilibrium between Ni
sites and oxygen vacancy was investigated since the increase of Ni
loading resulted in the decrease of ZrO2 content. Moreover, the mech­
anism of lipid deoxygenation and the kinetics of octadecanol hydro­
treatment over Ni–Fe/ZrO2 catalyst were also investigated.
2. Experiment
2.1. Catalyst preparation
Ni–Fe/ZrO2 catalysts with various Ni loading (20, 30, 40, 50, 60, and
70 wt%) were synthesized with the co-precipitation method and the Ni/
Fe ratio was consistently fixed at 4:1. First of all, the Ni(NO3)2⋅6H2O, Fe
(NO3)3⋅9H2O, and Zr(NO3)4⋅5H2O were dissolved in 200 mL of deion­
ized water to get solution A. 150 mL ammonia water with pH 8 was
prepared and denoted as solution B. Then solution A was dropped slowly
into solution B in 2 h, and the pH of the mixture was maintained at 8 by
adding extra ammonia water during the mixing process. After dropping,
the mixture was continuously stirred for 14 h. The solid was collected by
vacuum filtration and washed several times until the pH reached 7. After
that, the solid was dried in the oven at 105 ◦ C for 12 h, followed by
calcination in a furnace at 550 ◦ C for 3 h. Before lipid deoxygenation, the
oxidized catalysts were reduced to obtain x%Ni–Fe/ZrO2 catalyst, in
which the x% meant the Ni loading. In addition, the Ni–Fe on Al2O3,
CeO2, Al2O3–ZrO2 (weight ratio 3:2), and Al2O3–CeO2 (weight ratio 3:2)
with 60 wt% Ni loading were also prepared with the same method.
For comparison, the Ni–Fe/ZrO2 catalyst with 20 wt% Ni and 5 wt%
Fe loading was prepared by the wetness impregnation method. The ZrO2
support was firstly synthesized with the above precipitation method
(specific surface area: 32 m2/g). Afterward, the 2.0 ZrO2, 2.6 g Ni
(NO3)2⋅6H2O, and 1.0 g Fe(NO3)3⋅9H2O were mixed in 12.0 g deionized
water and stirred for 3 h. Then the water was removed by rotary
evaporator and dried in an oven at 105 ◦ C for 12 h. After calcination and
reduction, the 20 wt%Ni-5 wt.%Fe/ZrO2 catalyst was obtained and
labeled as Ni–Fe/ZrO2-2.
2.2. Catalyst characterization
The phase of catalysts was identified by X-ray diffraction (XRD)
patterns on the D/max 2500/PC diffractometer with a Cu-Kα (λ = 1.54
41
Renewable Energy 197 (2022) 40–49
Å) radiation source at 40 kV. The XRD patterns were recorded from
10.0◦ to 90◦ at a scan rate of 10.0◦ /min. The N2 physical sorption was
performed on Quanta NOVA2200e at − 196 ◦ C to detect the textural
properties of catalysts. Before analysis, the samples were degassed at
200 ◦ C for 10 h. Prodigy Plus ICP-OES was used to identify the metal
content in catalysts. Before analysis, the calcined catalysts were firstly
dissolved with HCl and HNO3 solution. X-ray photoelectron spectros­
copy (XPS) was carried out on ESCALAB Xi+ (Thermo Scientific) using
an Al Kα X-ray source. The XPS peaks were fitted by Avantage software.
H2-TPR of catalysts was conducted on the BelCata-II (MicrotracBEL)
to analyze the reduction property of catalysts. About 0.1 g calcined
catalyst precursor was loaded into the reactor and pretreated at 300 ◦ C
for 1 h in the 50 mL/min He. When the temperature was cooled down to
40 ◦ C, the gas was switched to 75 mL/min 10%H2/Ar. After the TCD
signal was stable, the reactor was heated to 800 ◦ C with a rate of 10 ◦ C/
min. The H2 consumption was evaluated by TCD. Before the gas went
through the TCD, the water from catalyst reduction was removed by a
cold trap containing a mixture of dry ice and acetone.
NH3-TPD was conducted on the AutoChem II 2920 (Micromeritics) to
determine the acidity of catalysts. The calcined solid was firstly reduced
in the instrument at 400 ◦ C for 3 h in 60 mL/min 10%H2/Ar, followed by
pretreatment at 450 ◦ C for 30 min in Ar flow. After that, the reactor was
purged with 50 mL/min 4% NH3/He for 1 h, and then swept with 100
mL/min He for 1 h to remove the physically adsorbed NH3. Finally, the
catalyst was heated from 50 to 800 ◦ C, and the TCD was used to detect
the desorbed NH3.
Acetic acid-TPD was also conducted on the AutoChem II 2920
(Micromeritics) coupled with a mass spectrometer (MS, Pfeiffer, Ger­
many) to study the process of organic acid hydrotreatment over cata­
lysts. The calcined solid was firstly reduced in the instrument at 400 ◦ C
for 3 h in 60 mL/min 10%H2/Ar, followed by pretreatment at 450 ◦ C for
30 min in Ar flow. After that, the reactor was cooled down to 50 ◦ C, and
the gas was switched to 10% acetic acid/He for 1 h. And then the He was
used to sweep the acetic acid which was adsorbed physically on the
catalyst for 1 h. Finally, the catalyst was heated from 50 to 800 ◦ C, and
the MS was used to detect the desorbed CH3COOH, CO2, CO, CH4, and
H2.
2.3. Lipid deoxygenation
The lipid deoxygenation was carried out in a 100 mL batch reactor.
Before the deoxygenation reaction, the catalysts were reduced in a tube
furnace under 10%H2/N2 flow at 400 ◦ C for 3 h. Then the catalysts were
passivated under 1%O2/N2 flow for 1 h at ambient temperature to avoid
the acute oxidization of catalyst in the air. After that, 0.25 g catalyst,
20.0 g dodecane, and 2.0 g feedstock were transferred into the batch
reactor and the stirrer was turned on at 500 rpm. The reactor was purged
with H2 three times to sweep away the air and subsequently kept at 2.0
MPa. Then the reactor was heated electrically to the final temperature
and maintained for 3 h. After the reaction, the liquid product was
separated from the catalyst by filtration, and the product absorbed in the
catalyst was rinsed with chloroform. After each reaction, the mass bal­
ance (total mass after reaction/total mass before reaction) was calcu­
lated and it was all above 96%. The vegetable oil (sunflower seed oil),
microalgae oil, oleic acid (89 wt% C18:2 and 11 wt% C16:2), stearic acid
(43 wt% C18:0 and 57 wt% C16:0), and octadecanol were respectively
used as feedstock. The corresponding fatty acids of vegetable oil con­
tained 7.3 wt% C16:1 and 92.7 wt% C18:1. The composition of corre­
sponding fatty acids in microalgae oil was as follows: 41.1 wt% C16: 1,
49.7 wt% C22: 6, 4.2 wt% C14:1, 2.1% C18:1 and 2.9 wt% C20:1.
The composition of the product was identified by GC (Agilent 7890
A) and GC-MS (Agilent 8890-7000D). The capillary chromatographic
column HP-5MS (30 m × 0.25mm × 0.25 μm) was used along with a
temperature program: 50 ◦ C for 2 min; heating to 280 ◦ C with a ramp of
5 ◦ C/min and holding 1 min. The inlet temperature was 260 ◦ C and the
split ratio was 50:1. The temperature of the MS source was set to 260 ◦ C
F. Wang et al. Renewable Energy 197 (2022) 40–49

and the scan range of MSD was 30–500 Da. Neicosane was used as the
internal standard to quantify each composition. Prior to GC and GC-MS
analysis, the product was methylated with TMAH to eliminate uncon­
verted fatty acids and triglycerides. Typically, when the phenolphtha­
lein was used as an indicator, TMAOH solution (25% in methanol) was
dropped into the sample, solved in the mixture of chloroform and
methanol. Based on the GC results, the conversion, yield of products,
HDO/DC, and cracking ratio were respectively calculated by equations
(1)–(4):

Conversion = (CF–CP) / CF × 100% (1)

CP represents the carbon moles of reactant in the product, and CF is

the carbon mole of feedstock, respectively.

Alkane (or fatty alcohols) yield = CA (or CO) / CF × 100% (2)

CA and CO are the carbon mole of alkanes and fatty alcohols in the
product, while CF represents the carbon mole of the initial feedstock.

Light alkane yield (Cracking degree) = C13-14 / CF × 100% (3)

C13-14 is the total carbon moles of light alkanes (carbon numbers 13

and 14), which were produced from the cracking reaction. CF represents
the carbon mole of the initial feedstock. Fig. 1. XRD spectra of various Ni–Fe catalysts.
HDO/DC = (C16 + C18) / (C15 + C17) × 100% (4)
and 60%Ni–Fe/Al2O3, respectively. Notably, the m-ZrO2 (PDF 37–1484)
C15, C16, C17, and C18 are respectively the relative carbon moles of was detected in Ni–Fe/ZrO2-2, while the t-ZrO2 (PDF 34–1084) was
pentadecane, hexadecane, heptadecane, and octodecane in the present in 30%Ni–Fe/ZrO2 and 60%Ni–Fe/ZrO2. The pure ZrO2 support
products. was synthesized by the same method with the 60%Ni–Fe/ZrO2 catalyst,
but its XRD spectrum only showed the m-ZrO2 phase (Fig. S1). This
2.4. Kinetics of octadecanol deoxygenation over Ni–Fe catalysts indicated that the presence of Ni and Fe led to the m-ZrO2 transforming
to t-ZrO2. Based on the diffraction peak at 43.3◦ , NiO crystalline size was
The kinetics of octadecanol deoxygenation over 60%Ni–Fe/ZrO2 and calculated with the Scherrer equation (Table 1). The NiO crystalline size
Ni–Fe/ZrO2-2 catalysts were carried out to analyze the intrinsic activity of 60%Ni–Fe/ZrO2 was only 5.6 nm. In contrast, the Ni–Fe/ZrO2-2
of both catalysts. The elementary reaction from octadecanol to alkane prepared with the wetness impregnation method had a crystalline size of
was the rate-determining step in the lipid deoxygenation, therefore, the 21.1 nm, although its Ni loading was only 20%. This indicated that the
octadecanol was used as the substrate in the kinetics study. Before the co-precipitation method formed the fine NiO crystalline grain. The NiO
kinetics experiment, the diffusion limitation from the particle size of the grain size of 60%Ni–Fe/Al2O3 and 60%Ni–Fe/CeO2 was respectively
catalysts and the agitation speed was verified and the 0.1–0.15 mm 7.7 nm and 6.5 nm. Moreover, the NiO crystalline size of 60%Ni/ZrO2
(particle size of catalyst) and 500 rpm (agitation speed) were adopted. was 14.1 nm, much higher than that of 60%Ni–Fe/ZrO2. It revealed that
The octadecanol deoxygenation over each catalyst was severally con­ the Fe addition promoted the dispersion of Ni and the decrease of NiO
ducted at three reaction temperatures. Each reaction lasted 300 min, grain size.
and the samples were taken per 30 min during the reaction. The con­
version from octadecanol to alkane conformed to the equation (5) of 3.1.2. Nitrogen physical sorption
first-order reaction [26]: The nitrogen physical sorption was used to determine the textural
characters of catalysts. All catalysts exhibited typical Ⅳ isotherm with
ln (1/(1-x)) = kT⋅t (5) an H1 hysteresis loop, which was associated with capillary condensation
in mesopores (Fig. 2) [27]. From Table 1, the surface area and pore
where the x, kT, and the t represent the conversion, reaction rate, and the
volume of 60%Ni–Fe/ZrO2 catalyst were respectively 93.7 m2/g and
reaction time (s), respectively.
0.22 cm3/g, much higher than that of Ni–Fe/ZrO2-2 with 20% Ni
From the Arrhenius equation (6), the activation energy can be
calculated:
Table 1
ln kT = -Ea / (R⋅T) + ln A (6)
The textural properties and NiO crystalline size of catalysts.
where the Ea, T, and A were respectively activation energy, temperature Samples N2 physical sorption NiO crystalline
(K), and the pre-exponential factor. size (nm)
Surface area Pore volume Pore size
(m2/g) (cm3/g) (nm)
3. Results and discussion 60%Ni–Fe/ 144.9 0.26 5.6 7.7
Al2O3
3.1. Catalyst characterization 60%Ni–Fe/CeO2 70.9 0.20 8.4 6.5
60%Ni–Fe/ZrO2 93.7 0.22 7.1 5.6
Ni–Fe/ZrO2-2 23.3 0.07 8.1 21.1
3.1.1. XRD patterns
60%Ni/ZrO2 47.3 0.15 6.3 14.1
The XRD patterns of Ni–Fe catalysts were shown in Fig. 1. All cata­ 15%Fe/ZrO2 99.6 0.16 3.7 -
lysts displayed the typical diffraction peaks at 37.2◦ (111), 43.3◦ (200), 60%Ni–Fe/ 122.8 0.24 5.5 6.5
62.9◦ (220), 75.4◦ (311), and 79.4◦ (222), indexed to the NiO phase Al2O3–ZrO2
(PDF 47–1049) [17]. In addition, the CeO2 (PDF 34–0394) and Al2O3 60%Ni–Fe/ 129.4 0.26 5.9 6.0
Al2O3–CeO2
(PDF 50–1496) were also identified in the spectrum of 60%Ni–Fe/CeO2

42
F. Wang et al.
Fig. 2. Nitrogen sorption isotherms (left) and pore size distribution (right) of catalysts.
loading. This manifested the Ni–Fe/ZrO2 catalyst from the
co-precipitation method has a higher surface area than that from the
impregnation method. In addition, the surface area of 60%Ni/ZrO2 and
15%Fe/ZrO2 were severally 47.3 and 99.6 m2/g, much lower than that
of 60%Ni–Fe/ZrO2, demonstrating the Fe addition increased the surface
areas of catalyst. Moreover, when the Al2O3 acted as support, the surface
area attained the maximum (144.9 m2/g) and the pore size was only 5.6
nm, which was less than 7.1 nm of 60%Ni–Fe/ZrO2.
3.1.3. H2-TPR of catalysts
The H2-TPR of calcined catalysts was conducted to analyze the
reduction property of catalysts, and the corresponding curves were
shown in Fig. 3. The H2-TPR of 60%Ni/ZrO2 and 15%Fe/ZrO2 (Fig. S2)
displayed that the reduction peak of NiO centered at 438 ◦ C, and the iron
oxide had three reduction peaks at 384, 550, and 700 ◦ C. In the H2-TPR
curve of 60%Ni–Fe/ZrO2, a small peak at 350 ◦ C and a strong, board
peak at 500 ◦ C were formed. The former was assigned to the reduction of
Fe2O3 to FeO, while the latter was attributed to the reduction of NiO and
the reduction of FeO to Fe [28]. Among the three supports, the CeO2
supported 60%Ni–Fe had a very similar reduction property with ZrO2, in
contrast, the reduction temperature of 60%Ni–Fe/Al2O3 was the highest
(650 ◦ C). It can be inferred that compared to the Al2O3 support, the CeO2
and ZrO2 facilitated the reduction of nickel oxide and iron oxide. As for
the Ni–Fe/ZrO2-2 catalyst, the reduction peaks were rather lower,
indicating the Ni–Fe/ZrO2 catalyst, prepared by the wetness impreg­
nation method, was easier to be reduced than that prepared with the
co-precipitation method, because of the weak interaction between Ni–Fe
Fig. 3. H2-TPR curves of Ni–Fe catalysts on various supports.
43
Renewable Energy 197 (2022) 40–49
and supports.
3.1.4. NH3-TPD of catalysts
NH3-TPD was conducted to determine the acidity of catalysts and the
curves were shown in Fig. 4, from which the acidity could be divided
into weak acidity (<400 ◦ C, Lewis acidity) and strong acidity (>400 ◦ C,
Brønsted acidity) [29]. The areas of weak acidity and strong acidity were
respectively calculated by integrating the background line between the
curves from 50 to 400 ◦ C and 400–800 ◦ C. Based on the total acidity
amount and the percentages of both acidities, the amounts of weak
acidity and strong acidity were identified, which was displayed in
Table 2. It was worthy to note that a peak of medium acidity at 250 ◦ C
appeared when the ZrO2 was used as the support and the weak acidity
was primary. For the 60%Ni–Fe on three supports, the amount of total
acidity in 60%Ni–Fe/Al2O3 reached up to 6.30 mmolNH3/g, much higher
than that in 60%Ni–Fe/ZrO2 (4.55) and 60%Ni–Fe/CeO2 (3.42). How­
ever, the ratio of weak acidity/strong acidity (W/S ratio) in 60%
Ni–Fe/ZrO2 was 5.5, much higher than the other catalysts (1.9 and 2.8).
Moreover, both values of the total acidity amount and W/S ratio in 60%
Ni–Fe/ZrO2 were much higher than that in the Ni–Fe/ZrO2-2 catalyst
synthesized by the impregnation method.
3.1.5. XPS of catalysts
In the XPS survey spectra (Fig. S3), the Ni, Fe, and the metals of
supports (Zr, Ce, and Al) were present in the corresponding catalysts.
The high-resolution O 1s XPS spectra (Fig. 5) can be fitted into two peaks
at 529.9 eV and 531.8 eV, which were severally due to the lattice oxygen
Fig. 4. NH3-TPD curves of various Ni–Fe catalysts.
F. Wang et al. Renewable Energy 197 (2022) 40–49

Table 2 3.2. Catalytic deoxygenation of lipids

The distribution of various acid sites.
Catalyst Total acidity amount Amount of two W/S 3.2.1. Catalyst preparation method and catalyst support
(mmolNH3/g) acidities ratio The oleic acid deoxygenation over 60%Ni–Fe/ZrO2, 60%Ni–Fe/
(mmolNH3/g) Al2O3, 60%Ni–Fe/CeO2, 60%Ni/ZrO2, and Ni–Fe/ZrO2-2 was per­
Weak Strong formed. The GC spectrum of liquid product from catalytic deoxygen­
Ni–Fe/ZrO2-2 3.14 2.40 0.74 3.2
ation of oleic acid was shown in Fig. S4. The product mainly contained
60%Ni–Fe/ 4.55 3.85 0.70 5.5 alkanes, fatty alcohols (hexadecanol and octadecanol), and fatty acids
ZrO2 (octadecanoic acid, oleic acid, palmitic acid, hexadecenoic acid) which
60%Ni–Fe/ 6.30 4.10 2.21 1.9 were considered unconverted substrates. Among alkanes, the C15, C16,
Al2O3
C17, and C18 were generated from oleic acid hydrotreatment via HDO
60%Ni–Fe/ 3.42 2.51 0.91 2.8
CeO2 and DCX/DCN routes, while the light alkanes with carbon number less
than 15 were originated from the cracking reaction. The catalytic per­
formance over 5 catalysts was displayed in Fig. 7. Under the reaction
(OL) and the defect oxygen (OD) [30,31]. Based on the integral areas of conditions, the deoxygenation of oleic acid over 60%Ni–Fe/ZrO2
the fitted peaks, the percentage was calculated in Table 3. When the
Al2O3 was used as the support, the OD percentage was maximum
(55.5%), demonstrating the defect oxygen was easily formed in Al2O3 Table 3
among the three supports. Compared to 60%Ni–Fe/ZrO2, Ni–Fe/ZrO2-2 The ratio of different states of O and Fe in catalysts.
catalyst had a little more OD. In addition, the peaks of OL and OD shifted Catalyst Ratio of O (%) Ratio of Ni (%)
to 529.5 and 531.2 eV, respectively. In the Ni 2p spectra, the doublet OL OD Ni II Ni III Satellite 1 Satellite 2
peaks at 854.7 and 872.5 eV represented the Ni2+, while the doublet
Ni–Fe/ZrO2-2 64.0 36.0 25 29 43 3
peaks at 856.7 and 873.9 eV revealed the presence of Ni3+ [16,32]. 60%Ni–Fe/ZrO2 70.3 29.7 29 26 39 6
Notably, in the 60%Ni–Fe/ZrO2, the percentage of Ni2+ was higher than 60%Ni–Fe/Al2O3 44.5 55.5 31 25 36 8
Ni3+, however, it was reversed in the Ni–Fe/ZrO2-2. In the Fe 2p spectra, 60%Ni–Fe/CeO2 71.4 28.6 27 29 31 13
the binding energy at 711.8 and 724.7 eV with a satellite peak at 718.7
eV were assigned to Fe3+ [33,34], while the binding energy at 704.2 eV
corresponded to the pre-peak of Fe 2p3/2 [35].

3.1.6. Acetic acid-TPD

The acetic acid-TPD was used to study the hydrotreatment process
over 60%Ni–Fe/ZrO2 and Ni–Fe/ZrO2-2 catalyst, and the curves were
shown in Fig. 6. The MS signals of 43, 44, 28 (deducting the signal from
CO2), 15, and 2 represented respectively the CH3COOH, CO2, CO, CH4,
and H2. Notably, from 50 to 550 ◦ C only very little acetic acid was
desorbed at about 250 ◦ C for both catalysts. This result was different
from the acetic acid-TPD over Cu–Ni alloy catalyst, where the obvious
desorption of acetic acid happened from 100 to 400 ◦ C [36]. It can be
deduced that the acetic acid was easily transformed into other com­
pounds over the Ni–Fe catalysts. For the 60%Ni–Fe/ZrO2 catalyst, when
the temperature reached 220 ◦ C, the CO and CO2 signal became strong
due to the DCN and DCX reaction. The CO2 signal had three peaks at
290, 360, and 420 ◦ C, and but for the CO signal only one broad desorbed
peak from 250 to 380 ◦ C appeared. Meanwhile, a strong H2 signal and a
moderate CH4 signal also came out, which were formed from the com­
bination of H* and CH3* [37,38]. However, in the acetic acid-TPD over
Ni–Fe/ZrO2-2, the peak of CO2 at about 360 ◦ C disappeared, while a
Fig. 6. The MS signal during acetic acid-TPD over 60%Ni–Fe/ZrO2 and Ni–Fe/
strong CO peak at 470 ◦ C emerged, indicating the DCX became weaker
ZrO2-2.
and the DCN route got higher than that over 60%Ni–Fe/ZrO2.

Fig. 5. High-resolution O 1s XPS (left) and Fe 2p (right) of calcined catalysts.

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F. Wang et al. Renewable Energy 197 (2022) 40–49

catalyst attained 98.7% conversion and 91.8% alkane yield (light alkane 3.2.2. Ni content in Ni–Fe/ZrO2 catalysts
yield 2.0%). In addition, the HDO/DC ratio was 0.13, which indicated By using the co-precipitation method, the Ni–Fe/ZrO2 catalysts were
the DCX/DCN was predominant among three hydrotreatment routes. endowed with large Ni loading, high Ni dispersion, and surface area.
The hydrotreatment route depended highly on the catalyst type, among Hence, the Ni loading (from 20 wt% to 70 wt%) of catalysts was
which the Ni catalyst preferred to DCX/DCN pathway [36]. Notably, the investigated in this part. From the XRD patterns (Fig. S3), as the Ni
60%Ni/ZrO2 only got 44.4% conversion and 33.2% alkane yield, man­ content increased, the NiO diffraction peaks became stronger while the
ifesting the Fe promoted greatly the activity of Ni catalyst. However, the peaks of t-ZrO2 varied in the opposite trend. As the Ni loading rose from
improvement of activity was not attributed to the catalytic activity of Fe 20 to 70 wt%, the average particle size of NiO was increased from 4.3 nm
metal because 15%Fe/ZrO2 only got 7.6% conversion of oleic acid to 6.5 nm due to agglomeration of partial Ni (Table 4). Fortunately, even
(Table S1). It can be deduced that the interaction between Fe and Ni though the Ni loading was 70 wt%, the NiO particle size was still much
enhanced the catalytic activity. From the above characterization, the lower than that of Ni–Fe/ZrO2-2 (6.5 nm vs. 21.1 nm). The N2 physical
presence of Fe produced fine NiO particles and enlarged the surface area sorption in Table 4 demonstrated the augment of Ni loading from 20 to
of the catalyst, exposing more Ni sites for the deoxygenation reaction. 50 wt% led to the decrease of surface area from 135.4 to 99.8 m2/g. But
Moreover, the Fe catalyst had a very high hydrogen enrichment capac­ the surface area of the catalyst barely changed with the further increase
ity, and the hydrogen upon the surface was easily dissociated [39]. of Ni loading.
Therefore, the Fe site on 60%Ni–Fe/ZrO2 might influence the catalytic The catalytic deoxygenation of oleic acid as the function of Ni
performance by facilitating the hydrogenation of fatty acid into alde­ loading of Ni–Fe/ZrO2 catalysts was displayed in Fig. 8. It was clear to
hyde/alcohol. The cracking degree over 60%Ni/ZrO2 was 5.1, much find that all catalysts achieved a conversion above 90%, revealing the
higher than 60%Ni–Fe/ZrO2. The strong cracking ability of Ni catalyst in catalysts had a high catalytic activity. As the Ni loading increased from
lipid deoxygenation was found in the previous report [19], and the 20 to 60 wt%, the alkane yield augmented continuously from 36.5% to
excess cracking reaction easily resulted in catalyst deactivation [17]. It 91.8% with the reduction of alcohol yield from 53.9% to 6.9%. How­
was worthy to note that the hydrotreatment of oleic acid over ever, the further increase of Ni loading resulted in the decrease of alkane
NiFe/ZrO2-2 catalyst only obtained 42.8% conversion and 16.2 alkane yield to 20.6%. As the Ni loading rose from 20 to 60 wt%, more Ni sites
yield, much lower than that of 60%Ni–Fe/ZrO2. In addition, the reaction were generated, thus increasing alkane yield. The further increase of Ni
rates of oleic acid deoxygenation over both catalysts were determined at loading led to the Ni agglomeration and fewer Ni sites, which decreased
low conversion, as listed in Table S2. The reaction rate over 60% alkane yield. Moreover, the increase of Ni loading elevated the HDO/DC
Ni–Fe/ZrO2 was greatly higher than the value over NiFe/ZrO2-2 catalyst
(0.0071 vs. 0.0008 mol/(gcat⋅h)), which was closely related to its high
Table 4
surface area, abundant Ni sites, and coordinated acidity.
The textural properties and NiO particle size of catalysts with different Ni
For 60%Ni–Fe on three supports, the catalytic performance was in loading.
the order of ZrO2 > Al2O3> CeO2, in which the conversion and alkane
Samples N2 physical sorption NiO particle
yield over 60%Ni–Fe/Al2O3 were respectively 97.7% and 83.6%. The size (nm)
difference of activity between 60%Ni–Fe/Al2O3 and 60%Ni–Fe/ZrO2 Surface area Pore volume Pore size
(m2/g) (cm3/g) (nm)
can be ascribed to the lower NiO grain size (Table 1) and better reduc­
tion property (Fig. 3) of the later catalyst. Interestingly, the conversion 20%Ni–Fe/ 135.4 0.18 4.6 4.3
over Ni–Fe/CeO2 reached 92.3%, however, the alkane yield was only ZrO2
30%Ni–Fe/ 121.4 0.18 4.9 4.6
19.6% with the alcohol yield of 72.6%. It revealed this catalyst possessed ZrO2
a very high selectivity for intermediate fatty alcohol instead of alkanes 40%Ni–Fe/ 100.4 0.19 5.0 4.7
owing to its pore property and acidity. Moreover, the catalytic activity of ZrO2
60%Ni–Fe on oxide-mixture supports (Al2O3–ZrO2 and Al2O3–CeO2) 50%Ni–Fe/ 99.8 0.20 6.2 5.0
ZrO2
were also tested and both catalysts showed much lower performance
60%Ni–Fe/ 93.7 0.22 7.1 5.6
than 60%Ni–Fe/ZrO2 (Table S3). Herein, the ZrO2 was deemed as the ZrO2
optimal support for 60%Ni–Fe to produce alkanes from deoxygenation 70%Ni–Fe/ 90.1 0.19 7.2 6.5
of oleic acid. ZrO2

Fig. 7. Deoxygenation of oleic acid over 60%Ni–Fe catalysts on various supports

(Reaction condition: temperature 240 ◦ C, initial hydrogen pressure 2.0 MPa, time 3 h).

45
F. Wang et al. Renewable Energy 197 (2022) 40–49

Fig. 8. The effect of Ni loading on catalytic deoxygenation of oleic acid

(Reaction condition: temperature 240 ◦ C, initial hydrogen pressure 2.0 MPa, time 3 h).

ratio, indicating the HDO route was enhanced over larger Ni particles. increased, the conversion kept stable. The increase of reaction temper­
Among 6 catalysts, the cracking degree over 60%Ni–Fe/ZrO2 was min­ ature from 200 to 260 ◦ C greatly improved the alkane yield. At the
imum due to its highest number of Ni sites. temperature of 200 and 220 ◦ C, the alcohol dominated in the products,
revealing that the rate of alcohol formation was higher than that of
3.2.3. Feedstock and deoxygenation conditions alkane formation from alcohol. Moreover, with the rise in temperature,
From the above parts, the 60%Ni–Fe/ZrO2 was considered as the the HDO/DC ratio decreased gradually from 0.32 to 0.10, as evidence of
optimal catalyst for the deoxygenation of oleic acid into green diesel. enhancement of the DCX/DCN pathway. The same phenomenon was
Since the vegetable oil and microalgae oil were two kinds of promising also found in relative studies [5,41]. The influence of initial H2 pressure
feedstocks for green diesel production, the catalytic deoxygenation of on the catalytic performance was shown in Fig. 9 (right). It was worthy
both triglycerides and the intermediates (stearic acid and octadecanol) to note that the conversion was merely zero in the absence of H2, and
was also carried out (Table 5). The deoxygenation of stearic acid ob­ when the H2 pressure was 1.0 MPa the conversion attained 55.8%. With
tained a similar conversion to oleic acid, but the alkane yield was higher the further increase of H2 pressure, the conversion of vegetable oil was
(99.1% vs. 91.8%). During oleic acid hydrotreatment, the first step was greatly elevated to 97.98% at the 3.0 MPa. This indicated that the H2
the hydrogenation of oleic acid into stearic acid, but this step can’t was necessary for the deoxygenation of vegetable oil even though the
explain the higher alkane yield from the hydrogenation of stearic acid DCX/DCN route dominated over 60%Ni–Fe/ZrO2 catalyst.
because the hydrogenation rate was highly rapid. From the previous Based on the above results, the mechanism for triglyceride hydro­
studies, the unsaturated lipid triggered readily the coking reaction that treatment was proposed as displayed in Fig. 10. During the deoxygen­
weakened the catalytic activity [10,40]. However, for the deoxygen­ ation of triglyceride, the first step was the β elimination of triglyceride to
ation of triglyceride (vegetable oil and microalgae), the alcohol yield generate unsaturated fatty acid with a very high reaction rate, followed
was high at the cost of alkane yield. During the hydrotreatment of tri­ by the hydrogenation reaction producing saturated fatty acid. After that,
glyceride, the oleic acid existed as an intermediate, which derived from the saturated fatty acid could be either converted into alkane with one
β elimination of triglyceride, as shown in Fig. 10. This reaction occurred carbon less via the DCX route or transformed into aliphatic aldehyde
rapidly that made merely a little impact on the hydrotreatment [6]. The followed by the DCN route to yield the same alkane. However, the result
low alkane yield in triglyceride deoxygenation was closely related to in Fig. 9 (right) revealed that H2 was necessary for the production of
that the large molecular triglyceride was not easily catalyzed by the alkane, which indicated that herein the pentadecane and heptadecane
active sites in the pores of catalysts because of the steric hindrance. (with one carbon number less than corresponding fatty acids) were
The reaction temperature and initial hydrogen pressure in deoxy­ mainly derived from the DCN, rather than DCX route. This conclusion
genation of vegetable oil over 60%Ni–Fe/ZrO2 were investigated was different from previous reports, where the DCX played a dominating
(Fig. 9). It was obvious that the temperature played an important role in role in heptadecane production during lipid hydrotreatment [42–44].
the reaction. As the temperature rose from 200 to 240 ◦ C, the conversion Sarkar et al. [45] studied the competition of DCX and DCN route of fatty
increased from 10.3 to 98.7%. But when the temperature further acid over Pd catalyst with the DFT, and proved that the initial Cα-H
activation was stronger than the initial OH activation leading to the
preference of DCN over the DCX pathway. Aliphatic alcohol from the
Table 5 hydrogenation of olefin alcohol (tautomer of aliphatic aldehyde) could
The deoxygenation of various feedstocks over 60%Ni–Fe/ZrO2 catalysta.
be transformed into hexadecane and octadecane (with the same carbon
Substrate Conversion Alkane Alcohol Cracking HDO/ number as corresponding fatty acids) via the HDO route. Herein, the
(%) yield (%) yield (%) degree (%) DC
pentadecane and heptadecane from DCN were predominant in alkanes,
Oleic acid 98.7 ± 0.24 91.8 ± 6.9 ± 2.0 ± 0.56 0.13 but the aliphatic alcohol took a high proportion in products at the low
1.83 2.05 ± 0.01 reaction temperatures. It can be inferred that aliphatic alcohol could
Stearic acid 99.1 ± 0.16 99.1 ± 0 0.0 3.4 ± 0.19 0.14
form aliphatic aldehyde through dehydration and then produce alkanes
± 0.01
Octadecanol 100 100 - 2.3 ± 0.02 0.26 via the DCN route.
± 0.02
Vegetable 96.8 ± 0.44 79.2 ± 17.5 ± 3.9 ± 0.16 0.31 3.2.4. Kinetics of octadecanol hydrotreatment over 60%Ni–Fe/ZrO2 and
oil 1.02 1.07 ± 0.02
Ni–Fe/ZrO2-2
Microalgae 92.0 ± 1.64 77.0 ± 14.9 ± 1.2 ± 0.46 0.23
oil 2.60 0.96 ± 0.01 In the kinetics study, the octadecanol hydrotreatment was carried
a
out over 60%Ni–Fe/ZrO2 at 200, 220, and 240 ◦ C, while the reaction
Reaction condition: temperature 240 ◦ C, initial hydrogen pressure 2.0 MPa, over Ni–Fe/ZrO2-2 at 220, 240, and 260 ◦ C to ensure a low conversion.
time 3 h.

46
F. Wang et al. Renewable Energy 197 (2022) 40–49

Fig. 9. The catalytic deoxygenation of vegetable oil as the function of reaction temperature (left) and H2 pressure (right).

Fig. 10. The proposed mechanism for hydrotreatment of triglyceride.

From the first-order reaction equation, the kT over two catalysts at former catalyst had much higher catalytic activity than the latter.
various temperatures was identified, as shown in Fig. 11 (left). Notably, Moreover, as the reaction temperature rose, the k over both catalysts
at 240 ◦ C the k (4.30 × 10− 5 s− 1) over 60%Ni–Fe/ZrO2 was extremely was increased. By using the Arrhenius equation, the activation energy of
higher than that of 60%Ni–Fe/ZrO2-2 (6.35 × 10− 6 s− 1), indicating the octadecanol hydrotreatment over both catalysts was calculated. The

Fig. 11. Reaction rates at different temperatures (left) and Arrhenius plots (right).

47
F. Wang et al.
activation energy over 60%Ni–Fe/ZrO2 and 60%Ni–Fe/ZrO2-2 was
respectively 78.48 and 191.90 kJ/mol. This manifested the energy
barrier for the reaction of octadecanol hydrotreatment over 60%Ni–Fe/
ZrO2 was much lower than 60%Ni–Fe/ZrO2-2. From the above-
mentioned analysis, the reduction of activation energy over 60%
Ni–Fe/ZrO2 was ascribed to the increase of active sites, the improvement
of surface area, optimization of acidity, and the weakening of the DCN
pathway.
4. Conclusion
To improve the catalytic performance of the Ni catalyst in lipid
deoxygenation, the Fe-promoted Ni catalyst with 60 wt% Ni loading
(60%Ni–Fe/ZrO2) was prepared with the co-precipitation method. In the
deoxygenation of oleic acid, the reaction over 60%Ni–Fe/ZrO2 catalyst
reached 98.7% conversion and 91.8% alkane yield, however, the reac­
tion over 20%Ni–Fe/ZrO2-2 prepared with impregnation method only
got 42.8% conversion and 16.2% alkane yield. The activation energy of
octadecanol hydrotreatment over 60%Ni–Fe/ZrO2 catalyst was only
78.48 kJ/mol, much lower than that of 20%Ni–Fe/ZrO2-2 (191.90 kJ/
mol). The characterizations of the catalysts revealed that 60%Ni–Fe/
ZrO2 catalyst obtained smaller Ni particle size, more Ni sites, a higher
surface area of the catalyst, and coordinated acidity compared to the
20%Ni–Fe/ZrO2-2. The acetic acid-TPD indicated the difference in
hydrotreatment route between both catalysts as the HDN route over
20%Ni–Fe/ZrO2-2 was stronger than 60%Ni–Fe/ZrO2.
CRediT authorship contribution statement
Fei Wang: Conceptualization, Methodology, Formal analysis, Vali­
dation, Writing – original draft. Hui Xu: Validation, Methodology,
Formal analysis, Investigation, Writing. Songyin Yu: Formal analysis,
Investigation, Methodology. Hao Zhu: Conceptualization, Methodol­
ogy, Formal analysis. Yuchan Du: Conceptualization, Methodology,
Formal analysis. Zeng Zhang: Conceptualization, Methodology, Formal
analysis. Chaoqun You: Conceptualization, Review. Xiaoxiang Jiang:
Conceptualization, Methodology, Review. Jianchun Jiang: Conceptu­
alization, Methodology, Review.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgment
This work was supported financially by the Natural Science Foun­
dation of Jiangsu Province of China (BK20210566), and the General
Project of Education Department of Jiangsu Province (21KJB480003).
The authors would like to thank Feng Wei from Shiyanjia Lab (www.shiy
anjia.com) for the H2-TPR analysis.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.renene.2022.07.079.
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