Received: 10 December 2017 Revised: 18 June 2018 Accepted: 20 June 2018

DOI: 10.1002/apj.2228

RESEARCH ARTICLE

Effects of reaction conditions on catalytic hydroconversion

of phenethoxybenzene over bifunctional Ni/Hβ

Xiao Zhou1,2 | Xian‐Yong Wei1 | Yu‐Miao Ma2 | Zhi‐Min Zong1

1
Key Laboratory of Coal Processing and
Abstract
Efficient Utilization, Ministry of
Education, China University of Mining An active Ni/Hβ catalyst was successfully prepared by decomposing nickel car-
and Technology, Xuzhou, China bonyl to dispersed metallic Ni onto Hβ support. Phenethoxybenzene (POB) was
2
Department of Chemical and used as a lignin model compound to evaluate the catalytic activity. The effects
Environmental Engineering, Xinjiang
Institute of Engineering, Urumchi, China of reaction temperature, initial H2 pressure (IHP), and reaction time on the cat-
alytic hydroconversion (CHC) of POB was studied. The results show that Ni/
Correspondence
Hβ effectively catalyzed POB convert to monocyclic cyclanes via direct hydro-
Xian‐Yong Wei, Key Laboratory of Coal
Processing and Efficient Utilization, genation of benzene ring (BR) in POB, the cleavage of C‐O bridged bond
Ministry of Education, China University induced by H+ addition, dehydration, and H− abstraction under higher IHPs.
of Mining and Technology, Xuzhou
221116, Jiangsu, China.
Alternatively, the CHC of POB proceeds preferentially via direct cleavage of
Email: wei_xianyong@163.com C–O bridged bond induced by H+ addition, followed by BR hydrogenation,
dehydration, and H− abstraction under lower IHP. Bicyclic cyclanes were pro-
Funding information
Program of University in Jiangsu Province
duced via rearrangement reactions, which proceed more easily either at higher
for Graduate Student's Innovation in Sci- temperatures or under lower IHPs.
ence Research, Grant/Award Number:
KYLX15_1414; Key Project of Joint Fund KEYWORDS
from National Natural Science Founda-
catalytic mechanism, hydroconversion, nickel, phenethoxybenzene, reaction conditions
tion of China and the Government of
Xinjiang Uygur Autonomous Region,
Grant/Award Number: U1503293

1 | INTRODUCTION fuels can be accomplished by two main routes: fast

Lignin, one of the most abundant organic compounds
on earth,1,2 has traditionally been discarded as waste
material or burned out as low‐grade fuel.3 This is
mainly because the conversion of lignin to high‐grade
fuels is very difficult. Yet, with the increasingly severe
worldwide energy crisis and environmental pollution
problems, more and more attention has been paid to
the conversion of lignin to fuels considering its inherent
structure.4,5 The conversion technologies of lignin to
pyrolysis and catalytic treatments. But the corrosive
nature, high oxygen content, and high viscosity of pyrol-
ysis product limit its direct application as fuel.6 Hence,
catalytic treatments have recently received widespread
attention.6-17 Among them, catalytic hydroconversion
(CHC) of lignin or lignin oligomers is considered to be
the most promising route for producing fuel range
hydrocarbons.6-9
Due to the structural complexity of lignin, dimeric
lignin model compounds representing C–O linkages

NOMENCLATURE: BR, benzene ring; CEOB, (2‐cyclohexylethoxy)benzene; CEOC, (2‐cyclohexylethoxy)cyclohexane; CH, cyclohexane; CHC,
catalytic hydroconversion; CHEB, (2‐cyclohexylethyl)benzene; CHEL, 2‐cyclohexylethanol; CHL, cyclohexanol; COEB, (2‐(cyclohexyloxy)ethyl)
benzene; DCHE, 1,2‐dicyclohexylethane; EB, ethylbenzene; ECH, ethylcyclohexane; GC–MS, gas chromatography/mass spectrometry; IHP, initial
H2 pressure; PEL, 2‐phenylethanol; 2‐PEP, 2‐phenethylphenol; 4‐PEP, 4‐phenethylphenol; POB, phenethoxybenzene; SSA, specific surface area;
TPV, total pore volume

Asia‐Pac J Chem Eng. 2018;13:e2228. wileyonlinelibrary.com/journal/apj © 2018 Curtin University and John Wiley & Sons, Ltd. 1 of 10
https://doi.org/10.1002/apj.2228
2 of 10
in lignin have been studied to investigate the CHC mech-
anism at molecular level.4,18-20 Among various model
compounds, phenethoxybenzene (POB), which repre-
sents β‐O‐4 linkage that is the dominant linkage in lignin,
has been widely used as a lignin model compound for
studying the CHC mechanism.6,21-23 Zhao et al.6,22 found
that the reaction route of POB over Ni/HZSM‐5 or Pd/C
and HZSM‐5 proceeded through metal‐catalyzed C–O
bridged bond cleavage followed by sequential
hydrogenation and dehydration reactions to remove
oxygen atoms in aqueous phase. The results of Chen
et al. showed that the CHC of POB predominantly yielded
cyclohexane (CH) and ethylcyclohexane (ECH) and the
reaction route for the CHC of POB using noble metal
nanoparticles in ionic liquid was not elucidated.21 He
et al. reported aqueous phase CHC of POB over Ni/SiO2
at 120°C under 6 bar H2. They found that the reaction
route of POB proceeded through Ni‐catalyzed C–O
bridged bond cleavage along with subsequent
hydrogenation of the oxygenated intermediates.23 The
researches mentioned above imply that the presence of
both a metal function for hydrogenation and an acid
function for dehydration in bifunctional catalysis is
indispensable for the formation of cyclanes from the
CHC of POB. However, the above CHC processes were
carried out in aqueous phase or ionic liquid, and little
attention has been paid to the CHC of POB in organic
phase. Aqueous‐phase catalytic system is restricted by
the chemical equilibrium of dehydration reaction, and
a high temperature is required for the complete
dehydration.24 The catalytic system in ionic liquid has
disadvantages of tedious extraction operations for product
separation. Whereas, complete dehydration can be
achieved at mild temperature in n‐hexane and n‐hexane
with low boiling point can be easily separated and
recycled from the CHC products by distillation, which
make it a promising organic solvent for the CHC of lig-
nin‐related model compounds.25
Recently, we have reported that benzyloxybenzene
representing α‐O‐4 linkage could be majorly converted
to bicyclic cyclanes in n‐hexane with bifunctional
Ni10%/Hβ via direct cleavage of C–O bridged bond
induced by H+ addition, followed by the attack of
benzylium on two‐ and four‐positions in phenol, hydro-
genation of benzylphenols, dehydration of oxygenated
intermediates, and H− abstraction.26 However, the
mechanism for the CHC of POB has not been
unequivocally established in the presence of Ni/Hβ in
n‐hexane. In the present study, we explore the detailed
mechanism for converting POB to cyclanes over Ni/Hβ
in n‐hexane and investigate the effects of reaction
temperature, initial H2 pressure (IHP), and reaction
time on the CHC of POB.
ZHOU ET AL.
2 | EXPERIMENTAL
2.1 | Materials
Diethyl ether, acetone, and n‐hexane are analytical
reagents and were purchased from Sinopharm Chemical
Reagent Co., Ltd., Shanghai City, China. POB is an
analytical reagent and was purchased from Makclin
Biochemical Co., Ltd., Shanghai City, China. The Hβ
zeolite was purchased from Catalyst Plant of Nankai
University Co., Ltd., Tianjin City, China.
2.2 | Catalyst preparation and
characterizations
The Hβ zeolite was calcined at 550 °C in air for 4 hr prior
to catalyst preparation. Ni20%/Hβ was prepared according
to the methods reported previously.26 The only difference
is that the amount of nickel carbonyl needs to be doubled.
The amount of nickel loaded on the Hβ was measured by
an ICP‐OES Agilent 720. Moreover, the detailed method
for the characterizations of Ni20%/Hβ was described
elsewhere.26
2.3 | Catalytic activity measurements
The microreactor used in this study is a magnetically
stirred autoclave, which was made of stainless steel and
had an effective volume of 60 ml. In a typical run,
0.05 g Ni20%/Hβ was weighted into the reactor, followed
by adding 0.1 g POB or lignin, and then 10 mL n‐hexane
solvent was added. The autoclave was sealed and purged
with hydrogen 3 times before being pressurized with
hydrogen to a desired pressure, that is, IHP between 1
and 6 MPa, at room temperature. Then the autoclave
was placed in a heating furnace, heated to an indicated
temperature (120–280 °C) in 30 min and maintained at
the temperature for a prescribed period of time. Composi-
tions of the products taken out from the autoclave were
determined using an Agilent 7890/5975 gas chromatogra-
phy/mass spectrometry (GC–MS). The quantitative analy-
sis of the products was conducted by an Agilent 7890 gas
chromatography.
3 | R ESULTS A ND DISCUSSION
3.1 | Catalyst characterizations
As displayed in Figure 1 and Table 1, after loading Ni,
part of microchannels was blocked by Ni species. The
result is confirmed by surface physical properties, that
is, the specific surface area of Hβ drops from 534 to
472 m2 g−1 and the total pore volume reduces from 0.45
ZHOU ET AL. 3 of 10

FIGURE 2 X‐ray diffraction patterns of Hβ and Ni20%/Hβ

β TABLE 2 Metallic element contents in Ni20%/Hβ

β Content Content Content

Element (ppmw) Element (ppmw) Element (ppmw)

Al 208,540.0 Ca 825.4 Zn 105.9

Ni 199,740.0 Cr 312.6 Cu 21.4
FIGURE 1 N2 adsorption/desorption isotherms and pore‐size
distributions of Hβ and Ni20%/Hβ Fe 2,694.0 Mn 85.4

to 0.36 cm3 g−1 after loading Ni. Both Hβ and Ni20%/Hβ
exhibit the type‐IV isotherms with type‐H4 hysteresis
loops, suggesting that textural structure of Hβ is largely
retained after the preparation.
As illustrated in Figure 2, compared with Hβ zeolite,
the diffraction peaks at 2θ = 44.5°, 51.8°, and 76.4° can
be assigned to the (111), (200), and (220) planes of
cubic‐phased Ni species, respectively,27 and the peak
intensity of Hβ is slightly reduced in the spectrum of
Ni20%/Hβ, indicating that crystal structure of Hβ is largely
preserved after supporting Ni. The small peak intensity of
Ni suggests a relatively low Ni loading, which is
approximately 20.0 wt% according to the analysis with
inductively coupled plasma‐optical emission spectroscopy
(ICP‐OES) (Table 2). As Figure 3 shows, Ni particles
with average diameter determined as 32.2 nm by
transmission electron microscopy disperse uniformly on
the Hβ.
As Figure 4 exhibits, the existence of Ni in Ni20%/Hβ is
also verified by the analysis with X‐ray photoelectron
spectrum. The peak located at 852.4 eV is attributed to
the binding energy of Ni 2p3/2 in metallic Ni. The second
and third peak centered on 854.4 and 856.0 eV are also
ascribed to Ni 2p3/2 in NiO dispersed on the support
and NiO interacting strongly with the support, respec-
tively. The fourth peak that appears at 861.5 eV is associ-
ated with the satellite peak for NiO.28
As Figure 5 demonstrates, two main NH3 desorption
peaks are at low temperature (centered at 189 °C) and
medium temperature (between 300 and 400 °C) assigning

TABLE 1 Textural properties and acid density of Hβ zeolite and Ni20%/Hβ

Sample SSA (m2/g)a TPV (cm3/g)a Medium acid (mmol/g)b Total acid (mmol/g)b

Hβ (Si/Al = 25) 534 0.45 0.04 0.46

Ni20%/Hβ 472 0.36 0.14 0.35

Note. SSA: specific surface area; TPV: total pore volume.

a
Calculated by Brunauer‐Emmet‐Teller method.
b
Calculated by NH3‐TPD method.
4 of 10
FIGURE 4 X‐ray photoelectron spectrum and fitting curve of Ni
2p3/2 for Ni20%/Hβ
to the weak and medium acid sites, respectively, in the
spectrum of Hβ. Compared with Hβ zeolite, the total acid
amounts decrease from 0.46 to 0.35 mmol/g while the
medium acid amounts increase from 0.04 to 0.14 mmol/g
after supporting Ni (Table 1). The reduction of total acidic
sites is attributed to the plugging of microchannels for
Hβ. Nevertheless, the increased medium acidic sites are
ZHOU ET AL.
FIGURE 3 Transmission electron
microscopic image and Ni particle size
distribution of Ni20%/Hβ
FIGURE 5 NH3 temperature‐programmed desorption profiles for
Hβ and Ni20%/Hβ
possibly ascribe to the acidic [Ni (OH)+] groups over
Ni20%/Hβ.29
3.2 | CHC of POB
POB conversion is only 11.0% over Hβ at 220 °C under
4 MPa IHP for 2 h. Phenol (36.0%), 2‐Phenethylphenol
(2‐PEP; 38.1%), and 4‐phenethylphenol (4‐PEP; 20.2%),
are the main products during this process. According to
the previous study, it is inferred that 2‐PEP and 4‐PEP
are produced by the cleavage of C–O bond in POB
induced by H+ addition to produce 2‐phenyleth‐1‐ylium
and phenol and the attack of 2‐phenyleth‐1‐ylium on 2‐
and 4‐positions in phenol.30 The missing 2‐phenyleth‐1‐
ylium may contribute to the formation of unidentified
products with much higher molecular weights via electro-
philic aromatic substitution of PEPs. Even though consid-
ering the bifunctional catalytic effect between metallic Ni
and acidic Hβ,6 the attack of H+ on oxygen atom only
ZHOU ET AL. 5 of 10

FIGURE 6 CHC of phenethoxybenzene (POB) under different conditions. IHP: initial H2 pressure

leads to the cleavage of a small part of C–O bond in POB
due to the low stability of 2‐phenyleth‐1‐ylium. However,
POB was almost completely converted to CH and ECH
over Ni20%/Hβ under the same condition as mentioned
above. The hydrogenation of benzene ring (BR) in POB
facilitates C–O bond cleavage via the addition to oxygen
atom by H+ to produce phenol/cyclohexanol (CHL)/2‐
phenylethanol (PEL)/2‐cyclohexylethanol (CHEL) and 2‐
cyclohexyleth‐1‐ylium/cyclohex‐1‐ylium, which are more
stable than 2‐phenyleth‐1‐ylium. The inference suggests
that the hydrogenation of BR in POB is a very important
step in the CHC of POB to CH and ECH under higher
IHPs.
As shown in Figure 6, POB conversion monotonously
increases to 96.1% until 220 °C but decreases with raising
temperature further. The decrease in POB conversion at
temperature above 220 °C may be due to the agglomera-
tion of nickel nanoparticles, which inhibits the

SCHEME 1 Possible pathways for CHC of phenethoxybenzene over Ni20%/Hβ in n‐hexane

6 of 10 ZHOU ET AL.

TABLE 3 Proximate and ultimate analyses (wt%) of raw lignin
Proximate analysis Ultimate analysis (daf)
Sample Mad Ad Vdaf C H N Odiff St,d
Lignin 4.0 16.1 46.7 66.8 7.7 0.3 >19.7 6.1
Note. diff: by difference; daf: dry and ash‐free base; Mad: moisture (air dried
base); Ad: ash (dry base,i.e., moisture‐free base); Vdaf: volatile matter (dry
and ash‐free base); St,d: total sulfur (dry base).
hydrogenation of POB to (2‐cyclohexylethoxy) cyclohex-
ane (CEOC), (2‐(cyclohexyloxy)ethyl) benzene (COEB),
and (2‐cyclohexylethoxy) benzene (CEOB). The result
further confirms that the hydrogenation of BR in POB is
a crucially important step in the CHC of POB to CH
and ECH under higher IHP. The trend for the total
selectivity of CH and ECH parallels with that for POB
conversion. CEOC, COEB, and CEOB generated from
the hydrogenation of BR in POB account for a relatively
large proportion in the products at temperature lower
than 200 °C, indicating that the cleavage of C–O bond
in POB hydrogenated products is difficult at lower
temperatures. Thus, it requires higher temperature to
achieve a good performance towards C–O bond cleavage
in POB hydrogenated products. It is noteworthy that the
selectivity of 1,2‐dicyclohexylethane (DCHE) as a bicyclic
cyclane monotonously increases up to 11.4% with
raising temperature, indicating the promotion of acid‐
catalyzed rearrangement of POB at higher temperature,
which products will finally be converted into DCHE
via CHC.
Under the conditions of 220 °C and 2 h, 16.3% of POB
was transformed, and the reaction predominantly yields
2‐PEP (42.8%), ethylbenzene (EB; 26.2%), phenol
(14.4%), CH (10.3%), and (2‐cyclohexylethyl) benzene
(CHEB; 3.4%) under 1 MPa IHP. According to the previ-
ous study,26 the occurrences of above products are attrib-
uted to the cleavage of C–O bond in POB to produce
phenol and 2‐phenyleth‐1‐ylium, whereby 2‐phenyleth‐
1‐ylium continues to be converted to 2‐PEP or EB. It is
noted that phenol is partially converted to CH but EB is
not converted to ECH, which may be related to the
slower hydrogenation rate of BR in EB under 1 MPa
IHP.31 With increasing IHP from 1 to 4 MPa, POB conver-
sion is significantly promoted, and the yields of CH and
ECH increase substantially. Meanwhile, the yields of
phenol and EB decrease monotonously, and the yield of
2‐PEP decreases rapidly and finally disappears. These
results suggest that increasing IHP may have changed

FIGURE 7 Total ion chromatogram of

organic products for CHC of lignin at
240 °C
ZHOU ET AL. 7 of 10

reaction pathway for the CHC of POB and thus POB con-
version is greatly improved. It is noted that CHEB, the
intermediate for the conversion of PEPs to DCHE,
appears in the products from the CHC of POB. As further
increasing IHP from 4 to 6 MPa, little changes are in POB
conversion and the total selectivity of cyclanes.
Over Ni20%/Hβ at 220 °C under 4 MPa IHP, POB con-
version monotonously increases with prolonging reaction
time from 10 to 120 min. As reaction time is extended, the
yields of ECH and CH increase slowly, while those of EB,
CHL, CHEL, PEL, COEB, and CEOB decrease accord-
ingly, indicating that the latter products are converted
into the former two during the CHC. The increase in
the selectivity of DCHE and decrease in that of 2‐PEP
and CHEB suggest the conversion of 2‐PEP and CHEB
to DCHE during the CHC. Interestingly, phenol is not
detected, implying that the hydrogenation rate of BR in
phenol is very fast during the CHC.
3.3 | Mechansim for the CHC of POB
It is reported that C–O bond cleavage, BR hydrogenation,
and H− abstraction proceed over Ni/Hβ.26 Based on the
above results, there are three routes in the overall reac-
tion pathway for the CHC of POB over Ni20%/Hβ. As
Scheme 1 demonstrates, H+ transfers to the oxygen atom
in POB to produce phenol and 2‐phenyleth‐1‐ylium.
Subsequently, the resulting 2‐phenyleth‐1‐ylium abstracts
H− from Ni/Hβ surface to produce EB, and EB is hydro-
genated to ECH. The resulting 2‐phenyleth‐1‐ylium also
attacks two‐ and four‐positions in phenol to produce 2‐
PEP and 4‐PEP and the CHC of PEPs proceeds via hydro-
genation, dehydration, and H− abstraction to produce
DCHE. POB can also be partly hydrogenated to COEB
and CEOB. The oxygen atom in CEOB is attacked by
H+ to form phenol and 2‐cyclohexyleth‐1‐ylium, which
abstracts H− from Ni/Hβ surface to produce ECH. The
oxygen atom in COEB is attacked by H+ to yield CHL
and 2‐phenyleth‐1‐ylium or PEL and cyclohex‐1‐ylium.
The resulting PEL is hydrogenated to CHEL followed
by the dehydration and H− abstraction to yield ECH.
The resulting phenol underwent either dehydroxylation
via H+ addition to hydroxyl to produce benzene‐1‐ylium
followed by H− abstraction and the hydrogenation of
BR or BR hydrogenation to produce CHL followed by
the dehydration along with subsequent H− abstraction
tso produce CH. Moreover, POB can also be completely
hydrogenated to CEOC and then H+ attacks on oxygen
atom in CEOC to produce CHL and 2‐cyclohexyleth‐1‐
ylium or CHEL and cyclohex‐1‐ylium. The resulting
cyclohex‐1‐ylium abstracts H− from Ni/Hβ surface to
produce CH. The resulting CHL and CHEL are
dehydroxylated via H+ addition to hydroxyl followed
by H− abstraction to yield CH and ECH.

TABLE 4 Organic compounds detected in liquid product from CHC of lignin

Peak Compound RC (%) Peak Compound RC (%)

1 2‐methylhexane 6.19 18 1,2‐dimethylcyclohexane 0.78

2 CH 27.78 19 ECH 1.84
3 3‐methylhexane 8.54 20 1,3,5‐trimethylcyclohexane 0.42
4 1,3‐dimethylcyclopentane 1.28 21 m‐xylene 0.69
5 heptane 8.36 22 1,2,4‐trimethylcyclohexane 0.16
6 methylcyclohexane 12.12 23 1‐methyl‐2‐propylcyclopentane 0.36
7 ethylcyclopentane 0.32 24 cis‐1‐ethyl‐4‐methylcyclohexane 0.40
8 1,2,4‐trimethylcyclopentane 0.34 25 trans‐1‐ethyl‐4‐methylcyclohexane 0.44
9 1,2,3‐trimethylcyclopentane 0.40 26 styrene 7.44
10 2,3‐dimethylhexane 0.13 27 2‐butoxyethanol 11.41
11 2‐methylheptane 0.37 28 1‐ethyl‐2‐methylcyclohexane 0.38
12 4‐methylheptane 0.06 29 propylcyclohexane 1.55
13 3‐methylheptane 2.72 30 octahydroindene 0.43
14 1,3‐dimethylcyclohexane 2.60 31 decalin 0.24
15 1‐ethyl‐3‐methylcyclopentane 0.16 32 2‐methyldecalin 0.15
16 octane 1.00 33 dicyclohexylmethane 0.12
17 1,4‐dimethylcyclohexane 0.64 34 DCHE 0.18

Note. RC: relative content.

8 of 10 ZHOU ET AL.

Because hydrogenating BR in POB under lower IHPs 3.5 | Reusability of Ni20%/Hβ for the CHC
is difficult,31 the CHC of POB proceeds preferentially via of POB
direct cleavage of C–O bond in POB to produce phenol
The reusability of Ni20%/Hβ was evaluated via recycling
and EB or 2‐PEP, followed by the hydrogenation of BR
experiments under the optimal conditions. As Figure 8
along with the subsequent dehydration to produce CH
depicts, a gradual decrease is in POB conversion and
and ECH or DCHE under lower IHPs. Alternatively, the
the selectivity of cyclanes with increasing recycle times.
CHC of POB proceeds via direct hydrogenation of BR,
The reason for the above results is the decrease of
the cleavage of C–O bond induced by H+ addition,
catalyst activity, and the aggregation of Ni particles on
dehydration, and H− abstraction to produce CH and
the catalyst surface of third recycle is the main reason
ECH under higher IHPs. The rearrangement of POB to
for the decrease of catalyst activity,32,33 which was
PEPs is promoted at higher temperatures or under lower
confirmed by transmission electron microscopic analysis
IHPs, which should be attributed to the thermal agglom-
(Figure 9). The NH3 desorption peak corresponding to
eration of nickel nanoparticles at higher temperatures or
the slower hydrogenation rate of BR in POB under
lower IHPs.

3.4 | CHC of lignin

Encouraged by the results for the CHC of POB, the CHC of
real lignin was tested over Ni20%/Hβ. The raw lignin was
purchased from Tokyo Chemical Industry, and its
proximate and ultimate analyses are presented in
Table 3. The CHC of lignin was conducted at 240 °C and
4 MPa IHP for 4 h, and the liquid product was analyzed
with GC–MS. As Figure 7 and Table 4 show, the detected
compounds include 53.1% of C6–C13 cyclanes with or
without methyl, ethyl, or propyl groups, as well as 27.4%
of alkanes, along with some arenes (8.1%) and oxygen
containing compounds (11.4%). The result indicates that
lignin could be converted into cyclanes via CHC over
Ni/Hβ. In the future research, we will do further study
on the CHC of lignin over Ni/Hβ.
FIGURE 9 Transmission electron microscopic image of Ni20%/
Hβ after 3‐times recycles

FIGURE 8 Phenethoxybenzene conversion and selectivity of FIGURE 10 NH3 temperature‐programmed desorption profiles
cyclanes over Ni20%/Hβ in 3 recycles for fresh and used Ni20%/Hβ
ZHOU ET AL.
the medium acid sites weakens in the spectrum of
Ni20%/Hβ after 3‐times recycles shown in Figure 10,
which may be due to coke deposition on the surface
of Ni/Hβ. So coke deposition on the surface of catalyst
is also supposed to reduce the activity of Ni/Hβ
relatively.33
4 | CONCLUSION
The CHC of POB to cyclanes has been effectively
achieved over bifunctional Ni20%/Hβ in n‐hexane. Direct
cleavage of C–O bond in POB towards EB and phenol,
which can then undergo BR hydrogenation, dehydration,
and H− abstraction resulting in ECH and CH, preferen-
tially takes place under lower IHP. Direct hydrogenation
of BR in POB towards CEOC, COEB, and CEOB, which
can then undergo C–O bond cleavage, hydrogenation,
dehydration, and H− abstraction resulting in ECH and
CH, is preferred under higher IHP. A lower IHP or higher
temperature is beneficial to the kinetic restriction or
adverse effect on hydrogenation of BR in POB, resulting
in the promotion on the rearrangement of POB. The
resulting hydrocarbons produced from the CHC of lignin
contain 27.4% of alkanes, 53.1% of C6–C13 cyclanes, and
8.1% aromatic molecules, which allows direct blending
into the hydrocarbon fuels.
A C K N O WL E D G M E N T S
This work was subsidized by the Key Project of Joint
Fund from National Natural Science Foundation of
China and the Government of Xinjiang Uygur Autono-
mous Region (Grant U1503293), the Program of Univer-
sity in Jiangsu Province for Graduate Student's
Innovation in Science Research (Grant KYLX15_1414),
and a Project Funded by the Priority Academic Program
Development of Jiangsu Higher Education Institutions.
ORCID
Xiao Zhou http://orcid.org/0000-0002-5586-0871
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How to cite this article: Zhou X, Wei X‐Y, Ma
Y‐M, Zong Z‐M. Effects of reaction conditions on
catalytic hydroconversion of phenethoxybenzene
over bifunctional Ni/Hβ. Asia‐Pac J Chem Eng.
2018;13:e2228. https://doi.org/10.1002/apj.2228