Research Article 590

Zongwei Zhang1,2
Hydroconversion of Waste Cooking Oil into
Qingfa Wang1,*
Hao Chen1 Bio-Jet Fuel over a Hierarchical NiMo/
Xiangwen Zhang1
USY@Al-SBA-15 Zeolite
The direct conversion of waste cooking oil (WCO) into bio-jet fuel was investi-
gated over a core-shell hierarchical USY@Al-SBA-15 zeolite-supported NiMo cat-
alyst. The core-shell structure showed better acid and pore size distributions. The
synergetic effect of the core-shell micropore and mesopore structure significantly
contributed to enhancing the selectivity for the jet fuel (C9–15 hydrocarbons) from
9.3 % over NiMo/USY up to 35.7 % over NiMo/USY@Al-SBA-15, with high isom-
erization (iso-/n-paraffins ratio = 2.7) and moderate aromatic fraction (18.7 %).
The decarboxylation reaction was selectively enhanced. Optimal selectivity for jet
fuel (39.7 %) was obtained at 380 C and a high H2/oil ratio would decrease the
yield of jet fuel. This catalyst showed excellent stability for the hydroconversion of
WCO to hydrocarbons.

Keywords: Biofuel, Core-shell hierarchical zeolite, Hydrodeoxygenation, Waste cooking oil

Received: October 30, 2016; revised: July 12, 2017; accepted: December 15, 2017
Supporting Information
available online DOI: 10.1002/ceat.201600601

1 Introduction two-step process and a one-pot process to synthesize bio-jet

The aviation industry has come under the public spotlight due
to the carbon emissions and their contribution to climate
change. Moreover, the industry’s reliance on a single product
has also raised concerns over future supply security and opera-
tional cost [1]. These factors have led to the development of
renewable and clean fuels produced from alternative sources
[1–4]. Research on the conversion of biomass-based resources
to biofuels is of current interest [4–7]. The main concern is the
production of bio-jet fuel from renewable resources with a rela-
tively low greenhouse gas life cycle and with sustainability at an
affordable price [4, 8]. Several routes based on hydrotreatment
of vegetable oil have been pursued to produce aviation biofuels
from biomass feedstock. Among these routes, two-step process-
es are industrially available. For example, the UOP Renewable
Jet Fuel ProcessTM, the Nesto Oil NEXBTL process, and Haldor
Topsoe’s HydroFlexTM technology were developed to convert
vegetable oil (jatropha oil, palm oil, non-edible animal fats and
oils, etc.) into green jet fuel based on commercially available
Ni-based catalysts [9, 10]. Recently, many works have been per-
formed to develop a one-step process to prepare bio-jet fuel
–
from lipids. Verma et al. [11] investigated the bio-jet fuel produc-
tion from jatropha oil by a single-step route using hierarchical
ZSM-5-supported NiMo or NiW catalysts. High yields of jet-
range (C9–C15) hydrocarbons with excellent isomerization selec-
tivity (40–45 % with i/n = 2–6 and 40–50 % with i/n = 3–13 over
NiW and NiMo catalysts, respectively) were obtained. The
product distribution (jet fuel with the desired aromatics, diesel
and gasoline) was tailored by the sulfided NiMo and NiW cata-
lysts supported on hierarchical mesoporous SAPO-11 [12]. A
fuel from castor oil were compared using NiP/SAPO-11 and
Ni-Ag/SAPO-11 catalysts [13]. Similar conversion of castor oil
into bio-jet fuel was achieved by a bifunctional catalyst,
Ni/MCM-41-APETS-USY, in a one-pot process.
Waste cooking oil (WCO) is also composed of triglycerides
and long-chain carbon fatty acids. Compared with vegetable
oils, WCO is two to three times cheaper than virgin vegetable
oils [14] and has become a promising feedstock in biodiesel
production [7, 15, 16]. However, few works have been per-
formed producing renewable jet fuel from WCO in a single-
step process. Recently, only Li et al. [17] investigated the influ-
ence of three types of zeolites (Meso-Y, SAPO-34, and HY) on
the conversion of WCO to bio-jet fuel. Hence, research for a
new approach to produce jet fuel from WCO is significant for
both academic research and industrial application.
Hierarchical zeolite played a significant role in the one-step
process to prepare bio-jet fuel from vegetable oils [11–13, 17].
The synergetic functions from different pore channels in the
hierarchical material were crucial for the selectivity of the jet
1
Zongwei Zhang, Dr. Qingfa Wang, Dr. Hao Chen, Prof. Xiangwen
Zhang
qfwang@tju.edu.cn
Tianjin University, School of Chemical Engineering and Technology,
Key Laboratory of Green Chemical Technology of the Ministry of
Education, Tianjin 300072, China.
2
Zongwei Zhang
Civil Aviation University of China, Airport Department, Tianjin
300300, China.

Chem. Eng. Technol. 2018, 41, No. 3, 590–597 ª 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
 Research Article
fuel in the conversion of lipids. Therefore, it was very impor-
tant to develop a hierarchical catalyst with the appropriate
structure for one-pot synthesis of renewable jet fuel from vege-
table oils and/or WCO. Herein, we designed and synthesized a
core-shell hierarchical USY@Al-SBA-15 zeolite. The direct
hydroconversion of WCO to renewable jet fuel was investi-
gated over the USY@Al-SBA-15-supported Ni and Mo catalyst.
The effects of the temperature, pressure, and hydrogen-to-oil
(H2/oil) ratio on the hydrodeoxygenation (HDO) and hydro-
cracking of WCO were evaluated. The reaction pathways over
the different zeolites were discussed and the stability of the cat-
alyst was also evaluated.
2 Experimental
2.1 Catalyst Preparation and Characterizations
For a detailed description of the catalyst preparation and its
characterization, please refer to the Supporting Information.
2.2 Hydrotreatment of WCO
The hydroconversion of WCO was conducted in a fixed-bed
flow reactor (1.2 cm i.d. and 45 cm in length). The reaction
temperature was controlled by three thermocouples on the
reactor wall and monitored with a thermocouple in the catalyst
bed. To achieve a sufficient catalyst bed length in the reactor,
8 g of catalyst was loaded and fixed by SiC. A solution of
20 wt % WCO in cyclohexane was used as feedstock and sup-
plied at a flow rate of 0.8 mL min–1 with a high-pressure pump.
All catalysts were presulfided in situ at 320 C and 3.0 MPa for
4 h, using 3.0 wt % CS2 in cyclohexane.
The products were collected after the reaction reached equi-
librium and separated into the gas and liquid fractions in a sep-
arator. The gaseous products were analyzed by an Agilent 3000
gas chromatograph equipped with three columns (molecular
sieve, plot U, and alumina) and thermal conductivity detectors.
The organic liquid products (OLP) were qualitatively
determined with an Agilent 6890 gas chromato-
graph/5975N mass spectrometer. A gas chromato-
graph (Bruker 456 GC) equipped with a flame ion-
ization detector (FID) and a commercial column
(ZB-5 HT; 60 m ·0.25 mm · 0.25 mm) was used to
quantitatively analyze the hydrocarbons in the
OLP.
3 Results and Discussion
3.1 Texture Structures of USY@Al-SBA-15
After being coated with SBA-15, the USY zeolite
surface became rough and the core-shell particles
grew larger, on average (Supporting Information
Fig. S1). Moreover, highly ordered stripe-like meso-
porous channels with a pore diameter of 5 nm and Figure 1. (a) Low-angle and (b) wide-angle XRD patterns of USY and
a wall thickness of about 6 nm were coated on the USY@Al-SBA-15.
Chem. Eng. Technol. 2018, 41, No. 3, 590–597 ª 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
591
surface of the USY core. This indicated that the core-shell
USY@AlSBA-15 structure had formed. The X-ray diffraction
(XRD) pattern of the USY@Al-SBA-15 sample (Fig. 1) dis-
played the characteristic diffraction peaks of USY in the range
between 5 and 30 and of SBA-15 at 0.95, which further con-
firmed the coexistence of mesoporous SBA-15 and micropo-
rous USY in the USY@Al-SBA-15 sample.
The pore size distribution of the USY@Al-SBA-15 zeolite
also showed the behavior of the coexistence of micropores and
mesopores, i.e. type IV isotherms with remarkable hysteresis
loops at P/P0 = 0.5–0.85 (Fig. S2). The pore diameter of the
USY@Al-SBA-15 sample was ~5.3 nm, which was consistent
with the transmission electron microscopy (TEM) results. The
specific Brunauer-Emmett-Teller (BET) surface area and the
total pore volume of the USY@Al-SBA-15 catalyst were
612 m2g–1 and 0.5 cm3g–1, respectively. However, 57 %
(349 m2g–1) of the surface area and 76 % (0.38 cm3g–1) of the
pore volume stemmed from the external surface and the meso-
pore volume, respectively, indicating the accessible micro-/
mesoporous core-shell structures [18]. The mesopore volume
of the USY@Al-SBA-15 sample had increased to about 4.5
times that of the USY zeolite. However, they had approximately
equal BET surface areas (658 m2g–1 for USY and 612 m2g–1 for
USY@Al-SBA-15). This indicated that the Al-SBA-15 shell
layer was crystalline and that shell formation did not result in
appreciable pore blockage.
3.2 Surface Acidity
Compared to USY, USY@Al-SBA-15 showed a relative weak
O–H stretching absorbance peak at 3600 cm–1 (Fig. S3), indicat-
ing that the surface acidity of USY was covered by mesoporous
Al-SBA-15 [19]. The concentrations and strengths of the acid
sites in different samples were further investigated by pyrolysis
infrared (Py-IR) spectroscopy and NH3-temperature pro-
grammed desorption (TPD) (Fig. 2). The concentrations and
strengths of the acid sites were calculated according to the de-
sorbed NH3 amount. As shown in Tab. 1, the USY zeolite
showed a high Brønsted/Lewis (B/L) ratio (1.6) and medium/
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 Research Article 592

Figure 2. (a) Py-IR spectra and (b) NH3-TPD profiles of USY, Al-SBA-15, and USY@Al-SBA-15.

strong acidity, indicating that USY was dominated by Brønsted

acidity and medium/strong acidity. After coating with SBA-15,
the number of acid sites decreased significantly and the B/L
ratio decreased almost by half because of the selective coverage
and the conversion of the framework aluminum (FAl, associ-
ated with B acidity) into extraframework aluminum (EFAl,
associated with L acidity) during the preparation process
[20, 21]. Al-SBA-15 showed the lowest acidity with a high B/L
ratio. These results indicated that the core-shell structure sig-
nificantly tuned the distribution of Brønsted and Lewis acid
sites (B/L ratio from 1.6–1.7 to 0.97) as well as the medium/
strong acidity distribution by suppressing the core acidity, sug-
gesting a synergy between the microporous and the mesopo-
rous architecture.

3.3 Reduction Behavior

The H2-temperature programmed reduction (TPR) results for
different catalysts are shown in Fig. 3. The NiMo/USY cata-
lyst showed three principal reduction peaks at 505, 572, and
744 C, which were associated with the reduction of Mo6+ to
Mo4+ of the polymeric octahedral Mo species, Ni2+ species
reduction, and tetrahedrally coordinated Mo species reduc-
tion in the zeolite cavities, respectively [22, 23]. The NiMo/
USY@Al-SBA-15 catalyst showed similar reduction behavior.
Figure 3. TPR profiles for NiMo catalysts supported on USY,
Al-SBA-15, and USY@Al-SBA-15.
But all the peaks shifted to lower temperature and the inten-
sity decreased, indicating that the interactions between the
metal species and the supports weakened [24]. As for NiMo/
Al-SBA-15, the reduction peak temperature further de-
creased. A much weaker metal-support interaction was ob-
tained due to the low acidity.

Table 1. Acidic properties of USY, USY@SBA-15, and USY@Al-SBA-15, determined by Py-IR spec- 3.4 Influence of the Support
troscopy and NH3-TPD.
on the Hydroconversion
Samples Acidity by typea) [mmol g–1] Acidity by strengthb) [mmol g–1] of WCO
Brønsted Lewis B/L Weak Medium Strong The hydroconversion of WCO over
USY 1792 1120 1.60 158 530 598 the series of catalysts was investi-
gated. The conversions of the
Al-SBA-15 250 149 1.70 59 196 168 WCO were approximately 100 % at
USY@Al-SBA-15 878 903 0.97 99 286 249 the given conditions. As shown in
Fig. 4, the OLP yields for NiMo/
a)
Determined by Py-IR spectroscopy; b)determined by NH3-TPD. USY@Al-SBA-15 increased up to

Chem. Eng. Technol. 2018, 41, No. 3, 590–597 ª 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
 Research Article
Figure 4. (a) Hydrocarbon distributions and (b) reaction pathways over NiMo/USY, NiMo/Al-SBA-15, and NiMo/USY@Al-SBA-15.
83.3 %. Generally, the triglycerides converted into alkanes
through three reaction pathways: HDO, decarbonylation
(DCO), and decarboxylation (DCO2). The C18 and C17 hydro-
carbons originated from oleic acid (OA) or linoleic acid (LA)
by the HDO and DCO/DCO2 reactions, respectively, and the
C16 and C15 hydrocarbons came from palmitic acid (PA) by the
same ways. In our previous work, it was observed that the C16
and C15 hydrocarbons also could be produced from OA or LA
by a/b-C scission reactions [25]. So the selectivity for DCOx/
HDO could be identified by the C17/C18 ratio. Moreover, the
DCO2 or DCO could be further distinguished by the CO2/CO
ratio since the methanation reaction and water-gas shift reac-
tion were much slower and could be ignored under the experi-
mental conditions [26]. For the NiMo/USY catalyst, the ratio of
C17/C18 hydrocarbons was 1.6 and the CO2/CO ratio was 0.17
(Fig. 4 b). This meant that DCOx, especially the DCO reaction,
were the main reaction pathways. As for NiMo/Al-SBA-15, the
ratio of C17/C18 hydrocarbons dramatically decreased to 0.7,
indicating that the HDO reaction dominated the deoxygena-
tion process. Meanwhile the NiMo/USY@Al-SBA-15 catalyst
showed a much higher ratio of C17/C18 hydrocarbons (1.84)
and the lowest CO2/CO ratio (0.1). The DCO reaction was
preferentially carried out over the NiMo/USY@Al-SBA-15 cat-
alyst, indicating a much more economic process to produce
hydrocarbons due to less hydrogen consumption. Recent
research found that the reaction pathways mainly depended on
the metal phase [27]. Our previous work revealed that the met-
al phase could be tailored by the support and that high-valence
active metal favored the DCOx reactions [28]. High acidity
would generate much more high-valence-state metal active
sites due to the strong support-metal interaction, which
favored the DCOx reactions [26, 28, 29]. From Tab. 1, it could
be observed that the acid density decreased gradually in the
order of USY, USY@Al-BA-15, and Al-BA-15 zeolites. Conse-
quently, the active sites for DCOx decreased successively over
these catalysts. Therefore, the NiMo/Al-SBA-15 catalyst
showed the lowest ratio of C17/C18 hydrocarbon (0.7). Al-
though the acid density of the NiMo/USY catalyst was higher
than that of the NiMo/USY@Al-SBA-15 catalyst, a low C17/C18
ratio was obtained for the NiMo/USY catalyst. This could be
attributed to more accessible active sites for the DCOx reac-
tions provided by the core-shell USY@Al-SBA-15 structure.
The CO2/CO ratio varied from 0.10 to 0.17, indicating that the
Chem. Eng. Technol. 2018, 41, No. 3, 590–597 ª 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
593
DCO reaction dominated the DCOx process. The strong metal-
support interaction would generate more active metal sites in
higher valence state, which would favor the DCO2 reaction. So
a high CO2/CO ratio for the NiMo/USY catalyst and a low one
for the NiMo/Al-SBA-15 catalyst were obtained. Although the
NiMo/USY@Al-SBA-15 catalyst had a medium acidity, it
showed a better selectivity for the DCO reaction. It might be
reasoned that more active metal was deposited in the meso-
pores for the NiMo/USY@Al-SBA-15 catalyst compared to
NiMo/USY. Moreover, the density of the medium/strong acid
sites, especially the medium acid sites, in USY@Al-SBA-15 was
enhanced (see Tab. 1) due to the contribution of the surface
medium/strong acid sites from the core USY exposed in the
mesopores. Therefore, more active sites for the DCO reaction
were formed.
A different distribution of alkanes was also obtained by the se-
lective hydrocracking. The medium and strong Brønsted acidity
of the catalyst played a very important role in the cracking activ-
ity of paraffins [29]. As for the USY zeolite, the medium/strong
acidity and the B/L ratio were very high (see Tab. 1). So the gaso-
line fraction dominated the products for the NiMo/USY catalyst.
The Al-SBA-15 zeolite had the lowest medium/strong acidity so
that the deep cracking to C4–8 hydrocarbons was significantly
inhibited (only 44.2 %) for the NiMo/Al-SBA-15 catalyst. Mean-
while the selectivity for jet fuel increased from 9.3 % to 22.6 %
due to the high mesopore content. This indicated that the meso-
pore structure and its acidity were essential for jet fuel produc-
tion. As for the core-shell USY@Al-SBA-15, its medium/strong
acidity was about 1.5 times that of the mesoporous Al-SBA-15
zeolite and less than that of USY. But the selectivity for C4–8
hydrocarbons further decreased to 41.3 % and the selectivity for
C9–15 hydrocarbons significantly increased up to 35.7 %. These
results indicate that the core-shell USY@Al-SBA-15 catalyst
could significantly enhance the selective cracking for jet-range
hydrocarbons by tailoring the acidity distribution in the meso-
pores.
As a petroleum-based jet fuel surrogate, the fuels from bio-
mass such as vegetable oils are expected to have a similar hy-
drocarbon distribution. Tab. 2 shows the product distribution
of C9–15 hydrocarbons (jet fuel fraction) over different catalysts.
The mesoporous NiMo/Al-SBA-15 catalyst had a high selectiv-
ity for the paraffin fraction (96.1 %) with a low iso-/n-paraffins
ratio (i/n = 1.2). An aromatic fraction of 3.5 % and few cyclo-
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 Research Article 594

Table 2. Hydrocarbon class composition in jet-range hydrocarbons. tivity, due to the enhancement of the
cracking at high temperature. The
Catalysts i/n C9–15 hydrocarbons [wt %] selectivity for jet fuel increased and
Paraffins Cycloparaffins Aromatics then decreased, with a maximum at
380 C, but the C17/C18 ratio showed
NiMo/USY 1.8 68.8 1.4 29.8 the smallest value (1.2) at 380 C.
NiMo/Al-SBA-15 1.2 96.1 0.4 3.5 The HDO was competitive with
DCO/DCO2 (exothermic reaction
NiMo/USY@Al-SBA-15 2.7 79.4 1.9 18.7 versus endothermic reactions). So a
JP-8 fuel a)
2.0 57.2 24.1 13.5 maximum reaction temperature of
380 C was reached for the hydro-
–1
Reaction conditions: 3 MPa, 380 C, and 500 mL mL (H2/oil). i/n is calculated based on the con- conversion of WCO on the NiMo/
tents of iso-paraffins to n-paraffins in the C9–15 hydrocarbons; a)data from [30]. USY@Al-SBA-15 catalysts.

paraffins were found. However, for the microporous NiMo/
USY catalyst, the selectivity for aromatics increased up to
29.8 %, and 68.8 % paraffins with i/n = 1.8 and 1.4 % cyclic
compounds were obtained. As for the hierarchical core-shell
NiMo/USY@Al-SBA-15 catalyst, the expected fuel with 79.4 %
paraffins (i/n = 2.7), 18.7 % aromatics, and 1.9 % cyclic com-
pounds was achieved, which was similar to the commercial JP-
8 fuel and met the requirements of the ASTM D7566 standard
specifications for aviation turbine fuel containing synthesized
hydrocarbons (Tab. 2). The activity of isomerization of paraffin
and aromatization from vegetable oil mainly depends on the
distribution of Lewis and Brønsted acid sites [31, 32]. The
NiMo/USY@Al-SBA-15 catalyst showed high isomerization
activity, indicating that the core-shell USY@Al-SBA-15 struc-
ture could tailor the distribution of Lewis and Brønsted acid
sites to achieve a better catalytic activity.
3.5 Effect of the Temperature on the Conversion
of WCO
The effect of the temperature on the HDO and hydrocracking
performance over the NiMo/USY@Al-SBA-15 catalyst is shown
in Fig. 5. The conversion of WCO was also approximately 100 %
at 350–400 C. The selectivity for diesel products (C16–18 hydro-
carbons) dramatically decreased with increasing gasoline selec-
3.6 Effect of the H2/Oil Ratio on the Conversion
of WCO
A series of H2/oil ratios from 250 to 750 mL mL–1 were also in-
vestigated in this work. Approximately 100 % conversions of
WCO were obtained under these conditions. The yields of OLP
were almost the same (82.3–83.9 %). As shown in Fig. 6, the
selectivity for jet fuel decreased with an optimum value
(39.7 %) at an H2/oil ratio of 250 mL mL–1. Meanwhile, the
selectivity for the gasoline fraction increased obviously with a
gradual decrease of the diesel selectivity. A high H2/oil ratio did
not favor the formation of jet fuel. This was partially attributed
to the diffusion restraint of reactant and intermediates due to
the increase of the hydrogen partial pressure with increasing
H2/oil ratio. The C17/C18 hydrocarbons ratio showed the same
variation with the jet fuel selectivity as the H2/oil ratio in-
creased (Fig. 6 b), indicating that a high H2/oil ratio was prone
to the HDO reaction. The likely reason was that the HDO reac-
tion needed higher adsorbed hydrogen in contrast to the DCO/
DCO2 reactions. So the C17/C18 ratio decreased significantly at
high H2/oil ratio. And a high H2/oil ratio favored the selectivity
for DCO, resulting in the sharp increase of the CO2/CO ratio.

Figure 5. Effect of the hydrotreatment temperature on the conversion of WCO and the product distribution.

Chem. Eng. Technol. 2018, 41, No. 3, 590–597 ª 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
 Research Article 595

Figure 6. Effect of the H2/oil ratio on (a) the product distribution and (b) the reaction pathways.

3.7 Stability of the Core-Shell

NiMo/USY@Al-SBA-15 catalyst

This core-shell NiMo/USY@Al-SBA-15 catalyst also showed

excellent stability in converting WCO into fuel-like hydro-
carbons. As shown in Fig. 7, the NiMo/USY@Al-SBA-15
catalyst showed high cracking activity in the initial 4 h and then
became stable. The product distribution showed almost no
change after 14 h. But over the NiMo/USY, the cracking activity
decreased gradually with an increased selectivity for jet- and
diesel-range hydrocarbons even after 7 h (Fig. S5). This was
probably due to the coverage of some strong acid sites by crack-
ing cokes. The used catalysts after the stability experiments were
further analyzed by thermogravimetric analysis (TGA). The
fresh NiMo/USY@Al-SBA-15 and NiMo/USY catalysts showed
Figure 7. The hydroconversion of WCO and the product distri-
a significant mass loss only between 30 and 220 C (Fig. 8 and
bution versus time on stream.
Fig. S6), which was attributed to water desorption. But for the
used NoMo/USY, four mass loss stages (Fig. S6) occurred at
around 100, 300, 470, and 570 C, which corresponded to the The second weight loss at around 470 C was assigned to the
loss of adsorbed water, the soft coke, hard coke, and graphitiza- coke removal. It could be found that the soft coke disappeared
tion, respectively [17]. For the used NiMo/USY@Al-SBA-15 cat- over the core-shell NiMo/USY@Al-SBA-15 sample. Moreover,
alyst, only two obvious weight losses could be observed (Fig. 8). the quantities of cokes for the used NiMo/USY@Al-SBA-15 cat-
The first weight loss at around 100 C was the water desorption. alyst also decreased, much in contrast to the used NoMo/USY

Figure 8. TG-DTG profiles of (a) fresh and (b) used NiMo/USY@Al-SBA-15.

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 Research Article 596

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