Biomass Conversion and Biorefinery

https://doi.org/10.1007/s13399-022-02769-7

ORIGINAL ARTICLE

Nb2O5 modified ­NiAl2O4 catalysts for hydrodeoxygenation of methyl

palmitate to long‑chain alkane
Jiacheng Wang1 · Xingyong Li1 · Yankun Wu1 · Jinyi Duan1 · Nihong Zhuang1 · Dechao Wang1 · Zhaoxia Zhang2 ·
Yueyuan Ye1 · Shuirong Li1 · Zhifeng Zheng1

Received: 1 March 2022 / Revised: 26 April 2022 / Accepted: 30 April 2022

© The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2022

Abstract
The wide-scale application in the bio-fuel area of fatty acid methyl esters (FAME) has been limited because of its high
oxygen content, awful low temperature flowability, and low heating value. In this work, the hydrodeoxygenation (HDO) of
methyl palmitate as fatty acid methyl ester model compounds for long-chain alkane via N ­ b2O5 modified N ­ iAl2O4 catalysts
was investigated. The effect of Nb/Ni atomic ratio (0.05:0.30), reaction temperature (260–340 ℃), time (2–10 h), and H ­ 2
pressure (1–5 MPa) on the production of long-chain alkane is exhaustively researched. The results show that the products
are mainly pentadecane with a few other alkane hydrocarbons and nickel metal was the main active site. Besides, the added
promoter Nb promoted the dispersion of active metal Nickel, increased the acidity, and thus substantially enhanced the HDO
activity of methyl palmitate. In response to the best conditions (0.3 g catalyst, 3 g methyl palmitate), the methyl palmitate
conversion and pentadecane selectivity over ­Nb2O5-NiAl2O4 with 0.20 Nb/Ni atomic ratio reached 91.14% and 80.07%,
respectively. However, the methyl palmitate conversion and pentadecane selectivity over pure ­NiAl2O4 catalyst were only
62.53% and 74.67%, respectively. Therefore, N­ b2O5-NiAl2O4 catalysts exhibit remarkable catalytic ability for HDO of methyl
palmitate to alkanes. The low cost, easy preparation, high catalytic performance, and recycling stability of N­ b2O5-NiAl2O4
catalyst demonstrate that catalyst ­Nb2O5-NiAl2O4 is a promising effective and efficient catalyst for producing long-chain
alkane from methyl palmitate.

Keywords Hydrodeoxygenation · Methyl palmitate · Long-chain alkane · Nb2O5 · NiAl2O4 spinel catalyst

1 Introduction

Biomass energy is a promising renewable energy, shoulder-

ing the task of filling the growing global energy demand
* Yueyuan Ye and reducing the dependence on limited fossil fuels. Bio-
yyye@xmu.edu.cn
diesel stands out from many energy sources because of its
* Shuirong Li clean, efficient, and easy access to raw materials. The first-
sli@xmu.edu.cn
generation biodiesel, which principally comprises of fatty
* Zhifeng Zheng acid methyl esters (FAME), is the largest and fastest grow-
zhifeng.zheng@xmu.edu.cn
ing category in the petrochemical industry [1, 2]. They are
1
Fujian Provincial Engineering and Research Center basically from the transesterification of triglycerides, mainly
of Clean and High‑Valued Technologies for Biomass, contains vegetable oils and fats, and methanol [3]. However,
Fujian Provincial Industry Technologies Development Base its problems of high oxygen content, low fluidity at low tem-
for New Energy, Xiamen Key Laboratory for High‑Valued
Conversion Technology of Agricultural Biomass, perature, and low calorific value of combustion have not
College of Energy, Xiamen University, Xiamen 361102, been well solved [4]. Fortunately, fatty acids and esters can
People’s Republic of China be converted to long-chain alkane completely by catalyzing
2
National Engineering Laboratory for Green Chemical HDO, where oxygen content can be effectively reduced by
Productions of Alcohols‑Ethers‑Esters, College replacing hydrogen atoms, resulting in the increase of heat-
of Chemistry and Chemical Engineering, Xiamen University, ing value of the obtained biofuels [5–7]. The final product
Xiamen 361005, China

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 Biomass Conversion and Biorefinery

obtained by catalytic hydrodeoxygenation method is also oxides can be effectively promoted by the existing amor-
called the second-generation biodiesel, which is one of the phous ­Nb2O5 species, and thus, the agglomeration of NiO
best substitute green liquid hydrocarbon fuels due to its particles was inhibited. Meanwhile, ­Nb2O5 is a solid acid
long-chain alkyl chemical structure similar to traditional with strong surface acidity, which is rich in Lewis acid and
diesel fuel [8]. Bronsted acid sites [36–38]. Hence, using N ­ b2O5 to modify
Generally, hydrodeoxygenation is dominated by transi- ­NiAl2O4 for HDO of methyl palmitate to long-chain alkane
tion metal sulfide catalysts [9]. However, the use of sulfide might produce a good result. However, ­NiAl2O4 modified
catalysts will lead to sulfur-contaminated products. The non- by ­Nb2O5 as catalyst has not been investigated in previous
sulfide noble metal-based catalysts exhibited good catalytic work.
activity at the required alkanes selectivity, but their high In this paper, a series of ­Nb2O5 modified nickel cata-
cost and rarity are a barrier to the industrial application on lysts were synthesized and applied for the HDO of lipids.
a wide scale [10]. The supported transition metal catalysts Methyl palmitate’s lower melting point (30 ℃) and non-
has attracted considerable attentions in recent years for their corrosiveness to reactor makes it suitable for laboratory
clean, cheap, and efficient catalytic activity [11]. Among studies [39]. Therefore, methyl palmitate was selected as
them, nickel catalysts is one of the most used hydrotreating model compound of FAME to test the catalytic ability of
catalysts, might be attributed to the activity of Ni that was ­Nb2O5-NiAl2O4. The effect of Nb/Ni atomic ratio, reaction
reflected by the affinity of Ni atom for H­ 2 molecules assist- temperature, reaction time, and ­H2 pressure on the HDO
ing hydrogenation [12–15]. The development of Ni catalysts of methyl palmitate was also investigated. The recycle
is thus of consequence to the technological innovation of tests of the optimal N
­ b2O5-NiAl2O4 catalyst were investi-
long-chain alkane. gated under suitable conditions. In addition, ­NiAl2O4 and
Nickel aluminate spinel (­NiAl 2O 4) is considered an Ni-Nb–O catalyst developed by predecessors was used to
excellent transition metal catalyst support for maintaining compare the performance of the optimum ­Nb2O5-NiAl2O4
steady property in severe reaction conditions [16–18]. Even catalyst [33]. Characterization means of ­N2 adsorption–des-
in aqueous-phase reforming of methanol, a reaction with orption, ­H2 temperature-programmed reduction (­ H2-TPR),
a lot of water in the process, ­NiAl2O4 can also maintain ammonia temperature programmed desorption ­(NH3-TPD),
excellent stability [19, 20]. Furthermore, a N ­ iAl2O4 spi- X-ray diffraction (XRD), and X-ray photoelectron spectros-
nel-supported bifunctional catalyst for HDO was developed copy (XPS) were used to observe the characteristics of the
by Zhang [21]. The optimized N ­ iAl2O4 catalyst achieved catalysts.
a 97.8% feed stock conversion and a cycloalkane yield of
83.8% under appropriate technological condition. However,
in the N
­ iAl2O4 catalysts, the agglomeration with wide par- 2 Materials and methods
ticle size distribution of the active metal Ni in the range of
30–70 nm was observed. And partial nickel coverage on 2.1 Materials
the surface and blockage on the pores were also observed
[22]. As Kaewmeesri reported, that compared to the pure All chemicals were used without further pretreatment:
support, the surface area and pore volumes of the Ni loaded Ni(NO 3 ) 2 ·6H 2 O (AR), C
­ 4 H 4 NNbO 9 ·nH 2 O (AR), and
samples decreased [23]. Generally, Ni catalysts are prepared AlOOH·nH2O (AR) were purchased from McLean Bio-
by the impregnation method, which makes no guarantee chemical Technology Co., Ltd. ­HNO3 (AR), octane (GC),
that Ni disperses uniformly on the support. In this way, and methyl palmitate (GC) were purchased from Aladdin
sintering occurs as the reaction proceeds, which will lead Industrial Co. Ltd.
to the deactivation of catalysts over time [24, 25]. All of
these flaws can seriously affect the HDO performance of 2.2 Catalysts preparation
the ­NiAl2O4 catalyst.
Nb-containing compounds, especially niobium oxide, are 2.2.1 Preparation of ­NiAl2O4 and ­Nb2O5‑NiAl2O4 catalysts
diffusedly used for a variety of catalytic conventions due to
its rich acid sites, unsaturated of ­NbOx sites, and excellent Slurry method was used to prepare ­ N iAl 2 O 4 and
activity [26–28]. In recent years, the preparation of HDO ­Nb 2O 5-NiAl 2O 4. Typically, 8 mmol of Ni(NO3) 2·6H 2O
catalysts by using niobium oxide has also been reported was dissolved by 1.2 mL 5 wt% ­HNO3. A suitable mass
frequently [29–32]. For example, Chen et al. developed a of ­C4H4NNbO9·nH2O (0.4–2.4 mol) was then added to
Ni-Nb–O composite HDO catalysts with a satisfactory result the solution for N­ b2O5-NiAl2O4 catalysts which varies
[33]. Moreover, Nb oxides may promote metal dispersion Nb/Ni atomic ratios of 0.05 to 0.30. Then, 20 mmol of
in the catalyst support [34]. Jin et al. [35] reported that the AlOOH·nH2O was added to the above solution and whisked
dispersion of NiO active components in bimetallic Nb-Ni into a paste. The resultant paste was calcined at 600 ℃ for

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Biomass Conversion and Biorefinery

4 h in a static air atmosphere after dehydration at 80 ℃. Ni-Nb-O

­NiAl2O4 and ­Nb2O5-NiAl2O4 catalysts were obtained after
reducing at 500 ℃ in 50 mL/min H ­ 2 for 4 h. The samples
obtained were named as ­NiAl2O4 and xNb (x = 0.05, 0.10,
0.15, 0.20, 0.25, 0.30).
For comparison, ­N b 2 O 5 were obtained by heat- Nb2O5-NiAl2O4
ing ­C4H4NNbO9·nH2O at 600 ℃ for 4 h in a static air
atmosphere.

Intensity (a.u.)
2.2.2 Preparation of Ni‑Nb–O catalyst
Nb2O5
Ni-Nb–O catalyst was synthesized in accordance
with the previous work [33]. Add Ni(NO 3) 2·6H 2O and
­C 4 H 4 NNbO 9 ·nH 2 O with the same stoichiometric ratio
into pure water and mixed for 1 h before evaporating at
NiO
90 ℃. The solid residue was calcining at 400 ℃ for 4 h
after dried at 120 ℃ for 12 h and ground. The result-
ant powder was reduced at 400 ℃ in 50 mL/min ­H 2 for
4 h and passivated by 100 mL/min 0.5 vol% O ­ 2/He gas
mixture for 30 min at room temperature and nominated NiAl2O4
as Ni-Nb–O.

2.3 Catalyst characterization

H2 temperature-programmed reduction (­ H2-TPR) was deter- 100 200 300 400 500 600 700 800
mined by a PCA-1200 chemisorption analyzer with a TCD. Temperature (°C)
The chemical adsorption was from room temperature to 800
℃ and used the 10 vol % ­H2/Ar gas.
Fig. 1  H2-TPR profiles of N
­ b2O5, NiO, N
­ iAl2O4, ­Nb2O5-NiAl2O4,
X-ray diffraction (XRD) patterns were collected on and Ni-Nb–O catalysts
a Rigaku Ultima IV apparatus with Cu Ka radiation
(λ = 0.15406 nm) for 2θ = 10–80°. The Scherrer equation
was used to calculate the Ni average crystalline size of X-ray photoelectron spectroscopy (XPS) was determined
­Nb2O5-NiAl2O4 catalysts. on a Thermo Scientific K-Alpha spectrometer using Al Kα
H2 pulse chemisorption was tested on a PCA-1200 chem- radiation as the monochromatic X-ray source.
isorption analyzer with a TCD. The reduced samples were Transmission electron microscope (TEM) images are
purged with high purity Ar gas at 500 ℃. Then, inject ­H2 collected with a FEI Tecnai G2 F20 to observe the surface
pulses (loop volume of 0.2 mL) for chemisorption at 50 ℃ morphologies of the catalysts.
until the continuous pulse peak remained constant. The Ni
dispersion was calculated assuming H­ ads:Nisurf stoichiometry 2.4 Catalytic activity tests
of 1:1.
The ­N2 adsorption–desorption experiments were car- A 50-mL high-pressure stirred stainless batch reactor was
ried out on a Micromeritics ASAP 2020 adsorption ana- used to perform the HDO of methyl palmitate. Generally,
lyzer. The Brunauer–Emmett–Teller (BET) formula was 0.3 g catalyst, 3 g methyl palmitate, and 15 g n-octane (sol-
used to calculate the specific surface area, and the Barrett- vent) were used. After encapsulation, air was expelled from
Joyner-Halenda (BJH) method from the desorption branch the reactor with ­H2 for three times. Finally, heat the mixture
of the isotherms was used to determine the pore volumes to the required temperature with stirring at 300 rpm. HDO
and pore sizes. was carried out at different reaction temperatures (260–340
NH3 temperature-programmed desorption (­ NH3-TPD) ℃) under different ­H2 pressures (1–5 MPa) and reaction
was determined by PCA-1200 chemisorption analyzer with a times (2–10 h) [40, 41]. Cool the reaction system below
thermal conductivity detector (TCD). The chemical adsorp- 50 ℃ after the reaction finished, and separate the liquid
tion used the 10 vol % ­NH3/He gas and the desorption pro- products with a 0.2 μm organic membrane for subsequent
cedure was from room temperature to 450 ℃. analyses. The filtered products were detected after diluting

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 Biomass Conversion and Biorefinery

with dichloromethane by the Agilent GC–MS instrument column. Finally, quantify the liquid products by the peak
(8890 GC/5977B MSD) equipped with an HP-5MS capillary area normalization method.

area of initial methyl palmitate − area of unreacted methyl palmitate

Conversion (%) = × 100% (1)
area of initial methyl palmitate

area of single products were reduced at 400 ℃, the detection of nickel metal con-
Selectivity(%) = × 100% (2) firms that a small amount of NiO was also produced in the
area of total products
process of synthesis of N ­ iAl2O4. ­Nb2O5 showed obvious
deflection peaks at 2θ = 22.61°, 28.40°, 36.60°, 46.16°,
50.90°, and 55.09°, which exactly correspond to the stand-
3 Results ard ­Nb2O5 phase (JCPDS #71–0336). However, the ­Nb2O5
crystalline phases, which are the thermodynamically sta-
3.1 Catalyst characterization ble state of Nb species, were not distinctly observed on the
­Nb2O5-NiAl2O4 catalysts. It indicates that Nb species are
The redox behaviors of the prepared catalysts were recorded present on the ­NiAl2O4 surfaces in a size that is difficult
by ­H2-TPR profiles, and the results were displayed in Fig. 1. to detect by XRD analysis on account of their well-disper-
It could be distinctly identified that there are two major sions. The amorphous niobium phase is coherent with that
reduction peaks in the ­NiAl2O4 catalysts. Commonly, the reported in Ref. [33, 45] In addition, with the increasing
peak below 500 ℃ is ascribed to the reduction of trace content of Nb, all samples show similar diffraction peaks at
amounts of NiO particles on the surface. The profile of 2θ = 37.03°, 45.04°, and 65.59°, which are consistent with
NiO can also confirm this. On the other hand, ­Ni2+ was the typical structure of ­NiAl2O4 (JCPDS #73–0239). It dem-
reduced to ­Ni0 in the ­NiAl2O4 phase lattice, and that was onstrates that Nb species did not obviously affect the forma-
corresponded to the peak around 780 ℃ [42, 43]. How- tion of the spinel structure of N
­ iAl2O4. And the intensity of
ever, it was mentioned in references that synthesis pure or Ni peaks with high Nb content were lower than that of low
stoichiometric ­NiAl2O4 as traditional pathways is not easy; Nb content. This is because the incorporation of Nb makes
the formation of excess NiO could not be avoided even if the crystalline size of Ni becomes lower, thus improves the
heated to a temperature above 1300 ℃ [24]. Stable typical dispersion of Ni, which favors the HDO performance [33,
spinel structure is easy to form by A ­ l2O3 and NiO in a high 46–48]. The average crystalline sizes of Ni summarized in
temperature environment. In this way, the reduction of NiO Table 1 were calculated by the Scherrer equation. Further-
is inhibited, resulting in the decrease of the intensity and more, the Ni dispersion calculated from ­H2 pulse chemisorp-
range of ­NiAl2O4 reduction peak below 500 ℃ compared tion is broader with the increasing Nb content, which also
with that of NiO [18]. It also proved that N ­ iAl2O4 spinel supports the speculation of XRD results.
constitutes the main body of the catalyst, which is consist- As shown in Fig. 3a, IV-type isotherms with H3-type hys-
ent with the following XRD results. The H ­ 2-TPR profile of teresis loop appear in all the prepared nickel catalysts due to
­Nb2O5 shows that the reduction peaks appeared at about 600 the existence of slit-shaped pores, indicating the presence of
℃ and 680 ℃, perhaps the reduction of N ­ b2O5 to other ­NbOx mesoporous [18, 37]. Figure 3b shows that pore diameter in
species [44]. It is noteworthy that the observed wide peak of the ­Nb2O5-NiAl2O4 primarily centered at 4–5 nm. Hence,
­Nb2O5-NiAl2O4 catalyst at 450–550 ℃ was ascribed to the the addition of Nb species did not affect the mesoporous
reduction peak shift of the highly dispersed NiO. Usually, structure of the catalysts.
the NiO particles strongly interact with the support which Table 1 summarized the BET surface areas ­(SBET), total
will lead to the reduction peak move towards high tempera- pore volumes (­ Vp), and average pore diameter (­ dp) of all
tures [24]. It also proved that the addition of Nb species pro- the nickel catalysts. The average pore diameter of samples
moted dispersion of metal Ni, thus compensates the surface was about the range of 4–6 nm. Interestingly, the ­SBET, ­Vp,
flaw of the spinel catalyst. and ­dp of ­Nb2O5-NiAl2O4 were all larger than those of the
Figure 2 presents the XRD patterns of the ­Nb2O5-NiAl2O4 bare ­NiAl2O4. The decreased crystalline size is further
samples after the reduction by H ­ 2 as well as that of N
­ b 2O 5, confirmed that 0.20 Nb has a much larger ­SBET (160 ­m2/g)
­N iAl 2O 4, and Ni-Nb–O samples. Reflection peaks at than ­NiAl2O4 (117 ­m2/g) (Table 1) [49]. The increase in the
2θ = 44.50° and 51.85° are matched to the (1 1 1) and (2 0 ­SBET of the samples provides a place for more active sites.
0) crystal faces of Ni (JCPDS #87–0712). Since the samples And with the increase of average pore sizes, the diffusion

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Biomass Conversion and Biorefinery

Fig. 2  XRD patterns of

­Nb2O5-NiAl2O4 catalysts with Nb2O5
0.05–0.30 Nb/Ni atomic ratio, Ni-Nb-O Ni
­Nb2O5, ­NiAl2O4, and Ni-Nb–O
NiAl2O4
0.30 Nb

0.25 Nb
0.20 Nb

Intensity (a.u.)
0.15 Nb

0.10 Nb

0.05 Nb

NiAl2O4

Nb2O5

20 30 40 50 60 70
2 (degree)

Table 1  Physicochemical Catalyst SBET ­(m2/g) Vp ­(cm3/g) dp (nm) dNi (nm)a Ni dis- Weak acid Medium Total acid-
properties of Ni/Nb2O5-NiAl2O4 persion sites (a.u.)c acid sites ity (a.u.)c
catalysts (%)b (a.u.)c

NiAl2O4 117 0.15 4.0 15.3 2.5 1.00 1.00 1.00

0.05 Nb 126 0.16 4.2 14.15 6.4 0.95 2.46 1.27
0.10 Nb 127 0.17 4.4 13.81 7.5 1.18 2.17 1.37
0.15 Nb 129 0.17 4.5 12.87 8.1 1.22 2.39 1.40
0.20 Nb 139 0.18 4.8 12.77 9.8 1.46 2.30 1.46
0.25 Nb 145 0.19 5.2 11.54 10.9 1.52 2.23 1.55
0.30 Nb 160 0.20 5.4 11.25 12.5 1.42 3.18 1.72
Ni-Nb–O 34 0.07 12.6 18.30 4.9 - - -
a
Crystalline size of Ni metal, derived from XRD diffraction line which is corresponding to the Ni (1 1 1)
plane at 44.5° by Scherrer equation
b
Calculated from ­H2 pulse chemisorption
c
The amount of acid sites of the samples quantified from peak area normalization

resistance decreases and the reactants can more easily pen- indicating that Ni-Nb–O has small amount of weak acid
etrate into the pore to participate the reaction at the active sites and relatively large amount of medium acid sites while
sites, which would improve the activity of catalyst [50]. ­NiAl2O4 is rich in weak acid sites. The introduction of Nb
Figure 4 shows the acidity of N ­ b2O5-NiAl2O4 catalysts species in N­ b2O5-NiAl2O4 catalysts leads to the increase
by the ­NH3-TPD measurement. The ammonia desorption of acidity of catalyst support [37]. The peak intensity of
peaks of N ­ b2O5-NiAl2O4 are composed of weak (< 220 the sample with Nb species was evidently higher than that
℃) and medium-strength acid sites (220–450 ℃) [24]. As of ­NiAl2O4 support, both for most of the desorption peaks
shown in Fig. 4, a small peak at about 140 ℃ and a relatively of weak and medium acid sites. The amount of acid sites
intense peak at about 365 ℃ were detected for Ni-Nb–O with different strength and total acidity of the samples were
while a strong peak at about 140 ℃ was found for ­NiAl2O4, quantified by peak area normalization, and the results are

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 Biomass Conversion and Biorefinery

(a) (b)
Ni-Nb-O Ni-Nb-O
Quantity Adsorbed (cm3/g STP)

dV/dD Pore Volume (cm3/g·nm)

0.30 Nb
0.30 Nb
0.25 Nb
0.25 Nb
0.20 Nb
0.20 Nb
0.15 Nb
0.15 Nb
0.10 Nb
0.10 Nb
0.05 Nb
0.05 Nb
NiAl2O4 NiAl2O4

0.0 0.2 0.4 0.6 0.8 1.0 4 8 12 16 20 24

Relative Pressure (P/Po) Pore Diameter (nm)

Fig. 3  N2 adsorption–desorption isotherms (a) and pore size distribution curves (b)

The oxidation state and the surface composition of

NiAl2O4
0.05Nb the surface nickel and niobium species of ­NiAl2O4 and
0.10Nb ­Nb2O5-NiAl2O4 catalysts were detected by XPS measure-
0.15Nb
0.20Nb
ment (Fig. 5). The deconvoluted Ni 2p band displayed two
0.25Nb weak peaks at 852.0 and 869.1 eV, indicating the existence
Intensity (a.u.)

0.30Nb of ­Ni0 species [57, 58]. And the existence of N ­ iAl2O4 spe-
Ni-Nb-O
cies will cause two sharp peaks at 855.8 and 873.5 eV on
the spectra, also accompanied by its satellite peaks at 861.7
and 879.7 eV, respectively [59, 60]. Compared with bare
­NiAl2O4, spectra of Ni 2p of N ­ b2O5-NiAl2O4 do not show
significant change, suggesting that the involvement of Nb
species has little influence to the oxidation state of Ni spe-
cies. Figure 5b-4 shows Nb 3d spectra of ­Nb2O5-NiAl2O4
at 200 eV to 216 eV. The Nb 3d spectra contained two
100 200 300 400
peaks, which were deconvoluted to N ­ b5+ (206.5, 209.2 eV)
Temperature (°C) corresponding to 3d 5/2 and 3d 3/2, respectively [61]. No
other oxidation states of Nb species can be detected even
Fig. 4  NH3-TPD profiles of N
­ b2O5-NiAl2O4 catalysts with 0.05–0.30 after hydrogen reduction, which are also well in line with
Nb/Ni atomic, N
­ iAl2O4, and Ni-Nb–O
the ­H2-TPR. Meanwhile, it also suggests that Nb species
exists by this thermodynamically stable state, which is iden-
summarized in Table 1. The acidity of catalysts increased tified with the XRD results [44]. In addition, the peaks of
with the increase of Nb content [51]. The amount of weak O 1 s spectra of ­NiAl2O4 and ­Nb2O5-NiAl2O4 appeared at
acid sites increases with the amount of Nb and reaches a 531.0 eV and 531.3 eV, respectively. The involvement of Nb
maximum value for 0.25 Nb, which shows 1.52 times of resulted in the binding energy of O 1 s shifting toward higher
weak acid sites comparing to that of ­NiAl2O4. For the by 0.3 eV, which was attributed to the strong interaction of
medium acid sites, a significant increase was found for all the highly dispersion of Ni metal with O atom [24].
the sample with Nb when the amount of medium acid sites The micromorphology of the ­NiAl2O4, ­Nb2O5-NiAl2O4,
for ­NiAl2O4 was compared, but little different was found and Ni-Nb–O catalysts was examined through TEM meas-
for most of the samples. Researches have shown that the urement. As shown in Fig. 6, the spherical particles of Ni
enhancement of acidity on supports will affect its catalytic at different magnification for all catalysts can be observed.
performance on HDO reaction directly, and because the sup- Nevertheless, it was visualized that the nickel on ­NiAl2O4
ports’ acidity affected the electronic state of active metal Ni, formed large agglomerates, and it was also composed of
this increased the adsorption rate of reactants and reaction large-sized particle in terms of morphology. By contrast,
rate [52–56]. the nickel particles of N ­ b2O5-NiAl2O4 was much more

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Biomass Conversion and Biorefinery

(a-1) NiAl2O4 Ni 2p (b-1) Nb2O5-NiAl2O4 Ni 2p

Intensity (a.u.)

Intensity (a.u.)
880 875 870 865 860 855 850 845 880 875 870 865 860 855 850 845
Binding Energy (eV) Binding Energy (eV)

(a-2) NiAl2O4 O 1s (b-2) Nb2O5-NiAl2O4 O 1s

Intensity (a.u.)

Intensity (a.u.)

537 534 531 528 537 534 531 528

Binding Energy (eV) Binding Energy (eV)

O 1s
(b-3) Nb2O5-NiAl2O4 survey (b-4) Nb2O5-NiAl2O4 Nb 3d
Intensity (a.u.)

Intensity (a.u.)

Ni 2p

C 1s
Al 2p
Nb 3d

1200 1000 800 600 400 200 0 216 212 208 204 200
Binding Energy (eV) Binding Energy (eV)

Fig. 5  XPS spectra of Ni 2p, Nb 3d, and O 1 s region of N

­ iAl2O4 (a) and N
­ b2O5-NiAl2O4 (b)

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 Biomass Conversion and Biorefinery

Fig. 6  TEM images of N

­ iAl2O4 (a), ­Nb2O5-NiAl2O4 (b), and Ni-Nb–O (c) catalysts

homogeneously dispersed and smaller. This result was con- pentadecane, revealing that the main reaction route of
sistent with those of other catalyst characterizations. methyl palmitate conversion is decarburization which
includes decarboxylation and decarbonylation. On the
3.2 Catalytic activity tests other hand, no hexadecanol can be detected in liquid prod-
ucts. This reveals that the major pathways of HDO over
3.2.1 HDO of methyl palmitate ­NiAl2O4 and N ­ b2O5-NiAl2O4 catalysts are the decarboni-
zation reactions. And methyl heptadecanoate, part of the
HDO of methyl palmitate over prepared catalysts was products, demonstrated the presence of esterification in
evaluated, in which methyl palmitate was selected as the HDO of methyl palmitate.
model compound, and the composition of liquid prod- Ni-Nb–O catalyst developed by predecessors exhibited
ucts was exhibited in Fig. 7. All catalysts showed cata- excellent catalytic activity for producing long-chain alkane.
lytic activity on HDO of methyl palmitate. The conver- Ni-Nb–O catalyst was prepared according to the synthesis
­ iAl2O4,
sion and the selectivity of various products over N method recorded by predecessors’ work. HDO of methyl
­Nb2O5-NiAl2O4 (0.20 Nb/Ni atomic ratio), and Ni-Nb–O palmitate over Ni-Nb–O catalyst was investigated, and the
are demonstrated in Table 2. The conversion of methyl pal- composition of liquid products was demonstrated in Fig. 6.
mitate over N­ iAl2O4 and N ­ b2O5-NiAl2O4 is 62.53% and The conversion of methyl palmitate over Ni-Nb–O catalyst
91.14%, respectively. And, undecane, dodecane, tridecane, reached 95.80%; the selectivity of pentadecane and alkane
tetradecane, pentadecane, and methyl heptadecanoate made is 76.02% and 99.1%, respectively. By contrast, the conver-
up the liquid products. It was obvious that the involve- sion of methyl palmitate over N ­ b2O5-NiAl2O4 is slightly
ment of Nb species significantly increased the conversion lower than that of Ni-Nb–O, but the selectivity of penta-
of methyl palmitate. The selectivity of pentadecane over decane is higher. The reason for the high conversion may
­NiAl2O4 is 74.67% and 80.07% over N ­ b2O5-NiAl2O4. It be that the pore size of Ni-Nb–O catalyst is about 12 nm,
is not hard to see that the largest number of alkanes is which is suitable for FAME large molecules having a better

13
Biomass Conversion and Biorefinery

Fig. 7  Hydrodeoxygenation Heptadecanone Heptadecane Hexadecane Methyl heptadecanoate Methyl palmitate

product compositions of methyl Pentadecane Tetradecane Tridecane Dodecane Undecane
palmitate 100
8.87 9.14

4.2
80 37.47

Conposition (%)
60
72.98

72.83

40 46.69

20
8.19
7.09
5.91
3.61 4.38
3.34
0
NiAl2O4 Nb2O5-NiAl2O4 Ni-Nb-O

Table 2  Conversion (%) and Catalyst Conv. (%) Selectivity (%)

product selectivity (%) of
methyl palmitate C11 C12 C13 C14 C15 C16 C17 C18H36O2 C17H34O

NiAl2O4 62.53 1.66 4.64 5.77 11.34 74.67 - - 1.92 -

Nb2O5-NiAl2O4 91.14 1.10 3.66 4.81 8.99 80.07 - - 1.37 -
Ni-Nb–O 95.80 0.93 2.18 2.79 6.17 76.02 9.54 1.46 - 0.91

access to catalytic sites. It is worth mentioning that the catalysts. The quantitative results of liquid products are
liquid products over Ni-Nb–O catalyst also include hexa- shown in Fig. 8. For the ­NiAl2O4 without Nb species, the
decane, heptadecane, and heptadecanone, which suggest conversion of methyl palmitate is only 62.53%, and penta-
that Ni-Nb–O has different reaction pathway with spinel decane was the major product, which accounted for 80.07%.
catalysts. The reaction pathway of spinel catalyst is sim- With the addition of Nb species, the conversion of methyl
pler, and there are fewer side reactions. Consequently, com- palmitate increased linearly and reached the peak at 93.83%
pared with the Ni-Nb–O catalyst, the catalytic activity of when Nb species content is 0.25. This suggests that niobium
­Nb2O5-NiAl2O4 catalyst is not inferior. On the other side, oxide can efficiently improve the catalytic decarburization
due to the high cost of rare earth metal Nb, part of Nb metal performance of methyl palmitate to produce pentadecane
was replaced by alumina in N ­ b2O5-NiAl2O4, which reduced over ­NiAl2O4. This is because the involvement of Nb makes
the cost of catalyst synthesis. Therefore, N ­ b2O5-NiAl2O4 the dispersion of Ni better and increases the acidity of the
catalyst is a promising green catalyst with low cost and high catalyst, which may provides more active sites of hydrogena-
catalytic performance. tion [33]. While continuing to increase the content of Nb
species to 0.30, the conversion of methyl palmitate almost
3.2.2 HDO of methyl palmitate over ­Nb2O5‑NiAl2O4 remained unchanged. The selectivity of pentadecane showed
catalysts little change and remained at around 80% until the content
of Nb reaches 0.20. When it reached 0.25, the selectivity of
The effects of Nb/Ni atomic ratio on the catalytic activity pentadecane dropped to 60.47% attribute to the occurrence
were investigated for HDO over a series of N
­ b2O5-NiAl2O4 of cracking reaction. This demonstrates that the cracking

13
 Biomass Conversion and Biorefinery

Fig. 8  Effect of Nb/Ni atomic 100

ratio on the N
­ b2O5-NiAl2O4 100
catalyst for hydrodeoxygenation
of methyl palmitate
90 80

80

Conversion (%)
60

Selectivity (%)
70
40
Conversion
60 Pentadecane
Hexadecane
Alkane 20
50

0
40
0 5 10 15 20 25 30
Content of Nb (%)

reaction may be promoted by the modification of niobium detected in the product, which indicates the presence of
oxide solid acid. The different fracture capacities of C–C hydrodeoxygenation reaction. This suggests that complicated
bonds may be ascribed to the acid strength of niobium oxide reactions occurred during the HDO of methyl palmitate over
solid acid, which is confirmed by N ­ H3-TPD results. Acid ­NiAl2O4, and the reactions include decarboxylation/decar-
sites can promote the C–C bond-rupture reaction [51, 56, bonylation, appropriate hydrocracking, esterification, and
62]. Interestingly, a very small amount of hexadecane was hydrodeoxygenation.

Fig. 9  Effect of reaction tem-

perature for the HDO of methyl
palmitate over N­ b2O5-NiAl2O4 100 100
catalyst

90 90
Conversion (%)

Selectivity (%)
80 80

70 Conversion 70
Pentadecane
Alkanes
60 60

50 50
260 280 300 320 340
Temperature (°C)

13
Biomass Conversion and Biorefinery

3.2.3 Reaction temperature The conversion of methyl palmitate is only 56.18% when the
reaction time is only 2 h. The selectivity of alkanes and pen-
Reaction temperature also has a significant influence on the tadecane is 98.08% and 80.98%, respectively. The conver-
conversion and product selectivity. Consequently, the HDO sion continued to increase at the range of 2–6 h. Specifically,
of different reaction time over ­Nb2O5-NiAl2O4 catalyst was the conversion reached to 91.14% and went to a maximum of
investigated and demonstrated in Fig. 9. Based on the liquid 94.05% at reaction time of 8 h. On the other side, the selec-
product results of the above experiments, pentadecane as tivity of pentadecane and alkane decreased as the reaction
a function of reaction temperature was detected. At tem- time was prolonged, which indicated that decarburization
perature of 260 ℃, the conversion of methyl palmitate is was inhibited by the reaction of esterification. Thus, exces-
only 55.68%, and the selectivity of pentadecane is 89.89%. sive reaction time is unnecessary.
When the temperature reaches 300 ℃, the conversion rap-
idly reaches 91.14%, and the selectivity of pentadecane 3.2.5 H2 pressure
is 80.07%. This suggests that the catalytic capacity of the
catalyst is greatly enhanced when the temperature reaches Figure 11 exhibits the remarkable impact of H ­ 2 pressure
300 ℃. As the continued rising of temperature, the conver- on the conversion of methyl palmitate and pentadecane
sion remained stable while the selectivity of pentadecane selectivity. The pressure increased from 1 to 3 MPa, and the
dropped to 75.55%. Similar results were published by the conversion of methyl palmitate substantially increased from
group of Papageridis investigating the HDO of palm oil over 17.82 to 91.14%. Nevertheless, with the further increase of
Ni-supported ­Al2O3 catalysts [60]. The selectivity of penta- pressure, the conversion of methyl palmitate changed little
decane is 90.79% at 260 ℃, and it continued to decline with when pressure exceeds 3 MPa, and methyl palmitate can be
the rising of temperature. The selectivity dropped to 78.55% completely converted at H ­ 2 pressure of 5 MPa. The selec-
at 340 ℃. This could be because the HDO pathway is domi- tivity of pentadecane increased and then mostly held steady
nated by decarburization, and the decarburization reactions as the pressure exceeds 3 MPa. What is noteworthy is that
were inhibited by the high temperature. This finding agrees compared with other reaction conditions, only H ­ 2 pressure
with our observations [63]. affected the selectivity of alkanes. This reveals that the ­H2
pressure has a great influence on the reaction. Insufficient H
­ 2
3.2.4 Reaction time pressure makes it impossible to completely convert methyl
palmitate, but the promotion effect of high ­H2 pressure on
Reaction time is also a pivotal factor affecting conversion the reaction is not obvious.
and product selection. The results are exhibited in Fig. 10.

Fig. 10  Effect of reaction time

on the HDO of methyl palmitate 100 100
over ­Nb2O5-NiAl2O4 catalyst

90 90
Conversion (%)

Selectivity (%)
80 80

70 70
Conversion
Pentadecane
60 Alkanes 60

50 50
2 4 6 8 10

Time (h)

13
 Biomass Conversion and Biorefinery

Fig. 11  Effect of H
­ 2 pressure on 100 100
the HDO of methyl palmitate
over ­Nb2O5-NiAl2O4 catalyst

80 80

Conversion (%)

Selectivity (%)
60
60

Conversion 40
40 Pentadecane
Alkane

20
20

1 2 3 4 5

H2 Pressure (MPa)

Fig. 12  Recycle tests of methyl Methyl palmitate Methyl heptadecanoate Conversion

palmitate over N
­ b2O5-NiAl2O4 Other alkane Pentadecane
catalyst 100 100
Distribution of liquid products (%)

80 80

Conversion (%)
60 60

40 40

20 20

0 0
1st 2nd 3rd 4th 5th 6th
Number of usage

3.2.6 The recycle tests of ­Nb2O5‑NiAl2O4 catalysts same reaction conditions (300 ℃, 6 h, 3 MPa), shown in
Fig. 12. After reaction finished, the catalyst was washed with
To assess the recycling capacity of the ­Nb2O5-NiAl2O4 n-octane for several times to remove the residual material
catalyst, the recycle performance was tested under the from the last reaction after separating from the mixtures.

13
Biomass Conversion and Biorefinery

Then, dry the catalyst in an 80 ℃ vacuum oven for 1 h. As 2. Yee KF, Wu JCS, Lee KT (2011) A green catalyst for biodiesel
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We have successfully conducted hydrodeoxygenation of 7. Liu P, Xu JM, Li J, Zhou MH, Shang SB, Zhao JP, Jiang JC
methyl palmitate as model compound of fatty acid methyl Catalytic hydrotreatment of triglycerides and various renewable
ester over the as-prepared N­ b2O5-NiAl2O4 catalysts to pro- oils into green diesel over metal-organic frameworks derived
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s13399-​021-​01746-w
mote the nickel dispersion and increase the acidity of catalyst 8. Vasquez MC, Silva EE, Castillo EF (2017) Hydrotreatment of veg-
support. The ­Nb2O5-NiAl2O4 catalysts exhibit preeminent etable oils: a review of the technologies and its developments for
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ond-generation biofuel over Pt-Sn/SAPO-11 catalyst. J Anal Appl
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with the Ni-Nb–O catalyst, N ­ b2O5-NiAl2O4 catalyst can 11. Kordulis C, Bourikas K, Gousi M, Kordouli E, Lycourghiotis A
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Author contribution Jiacheng Wang and Yueyuan Ye conceived and 12. Jin W, Pastor-Perez L, Villora-Pico JJ, Pastor-Blas MM, Odriozola
designed of the work. Xingyong Li and Yankun Wu were cooperator in JA, Sepulveda-Escribano A, Reina TR (2021) In-situ HDO of
the experiment. Jinyi Duan and Nihong Zhuang helped to analyze the guaiacol over nitrogen-doped activated carbon supported nickel
datas. Jiacheng Wang wrote the manuscript. Yueyuan Ye, Shuirong Li, nanoparticles. Appl Catal A-Gen 620:ARTN 118033 https://​doi.​
and Zhifeng Zheng ensured funding for project contributed materials, org/​10.​1016/j.​apcata.​2021.​118033
and they are the corresponding authors. Xingyong Li, Shuirong Li, 13. Badoga S, Ganesan A, Dalai AK, Chand S (2017) Effect of syn-
Zhaoxia Zhang, and Yueyuan Ye helped to revise the manuscript. All thesis technique on the activity of CoNiMo tri-metallic catalyst for
authors have read and approved the manuscript. hydrotreating of heavy gas oil. Catal Today 291:160–171. https://​
doi.​org/​10.​1016/j.​cattod.​2017.​01.​005
Funding The work was supported by the National Key Research and 14. Ballesteros-Plata D, Barroso-Martin I, Cervantes JAM, Maciel
Development Project of China (No. 2019YFB1504004). C, Huirache-Acuna R, Rodriguez-Castellon E, Infantes-Molina A
(2021) Bimetallic niobium-based catalysts supported on SBA-15
for hydrodeoxygenation of anisole. Ind Eng Chem Res. https://d​ oi.​
Declarations org/​10.​1021/​acs.​iecr.​1c027​99
15. Chumachenko YA, Buluchevskiy EA, Fedorova ED, Nepomnyash-
Conflict of interest The authors declare no competing interests. chii AA, Gulyaeva TI, Trenikhin MV, Izmailov RR, Mironenko
RM (2021) Hydrodeoxygenation of sorbitol to gasoline-range
hydrocarbons over Pt, Pd, Rh, Ru, Ni catalysts supported on tung-
stated alumina. Biomass Conv Bioref 11(4):1233–1243. https://​
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