Applied Catalysis A, General 547 (2017) 30–36

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Applied Catalysis A, General

journal homepage: www.elsevier.com/locate/apcata

Direct deoxygenation of lignin model compounds into aromatic MARK

hydrocarbons through hydrogen transfer reaction
⁎ ⁎
Tianye Guo, Qineng Xia , Yi Shao, Xiaohui Liu, Yanqin Wang
Shanghai Key Laboratory of Functional Materials Chemistry, Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China
University of Science and Technology, Shanghai, 200237, China

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

Keywords: A new route is reported for the direct deoxygenation of lignin model compounds to aromatic hydrocarbons via
Lignin model compounds the catalytic hydrogen transfer reactions over Ru/Nb2O5-SiO2 catalyst with 2-PrOH as a hydrogen donor. It is
Direct deoxygenation found that Ru/Nb2O5-SiO2 catalyst is active for the hydrodeoxygenation of p-cresol with 98.5% conversion and
Aromatic hydrocarbons 84.0% yield of toluene at 230 °C, owing to the significant promotion effect of NbOx species on CeO bond
Ru/Nb2O5-SiO2 catalyst
cleavage and the proper transfer hydrogenation activity of Ru. Furthermore, Ru/Nb2O5-SiO2 catalyst also shows
Catalytic hydrogen transfer
excellent performances in the transfer hydrodeoxygenation of various lignin model compounds such as 2-
methoxy-4-methyl phenol, benzyl phenyl ether (α-O-4 model compound), 2-(2-methoxyphenyl)oxy-1-phe-
nethanol (β-O-4 model compound) and even the real lignin extracted from birch, into aromatic hydrocarbons
with 2-PrOH as the hydrogen donor. The reaction pathway studies of these model compounds demonstrate that
the direct deoxygenation (DDO) is the main reaction route over Ru/Nb2O5-SiO2 catalyst in the presence of 2-
PrOH. Here, using 2-PrOH as a hydrogen source is found to be more selective to aromatic hydrocarbons than
using molecular hydrogen. This work provides a new way for the high selective production of aromatic hy-
drocarbons from renewable lignin via the catalytic hydrogen transfer reactions.

1. Introduction commonly applied for the hydrodeoxygenation of substituted phenols

Plant-derived lignocellulosic biomass is considered as an important
alternative source to fossil reserves for the production of fuels and
chemicals, hence it is necessary to develop economic and efficient
processes for large-scale transformation of lignocellulosic biomass into
chemicals and fuels [1,2]. Lignin, a three-dimensional biological
polymer composed of three primary units: syringyl (S), guaiacyl (G),
and p-hydroxyphenyl (H), via CeO and CeC linkages, is the only large-
volume renewable feedstock for aromatic compounds, making up
25–35% carbon content of woody biomass [3–5]. Aromatic hydro-
carbons are high-grade fuel additives for jet fuels because of its high
volume energy density and other excellent performances, for example,
ensure the shrinkage of aged elastomer seals to prevent fuel leakage
[6]. Therefore, it is of high interest and attraction to selective and ef-
ficient production of aromatic hydrocarbons from lignin.
For lignin-to-hydrocarbon processes, the current researches mostly
focused on the catalytic hydrodeoxygenation of lignin model com-
pounds (such as functionalized phenols), considering the robust and
complex structure of lignin. Among these, conventional hydro-
desulfurization catalysts (e.g., sulfided NiMo and CoMo catalysts) were
[7], and their catalytic performances can be greatly enhanced when
these catalysts were exfoliated to few-layer or monolayer [8,9]. Re-
cently, significant efforts have been made to develop hydro-
deoxygenation processes of phenols over supported metal (Pd, Pt and
Ni) catalysts, which have a relatively higher activity and stability than
sulfided catalysts [10–13]. However, in most recent studies, the main
products were aromatic ring hydrogenated products (cyclohexanes)
with additional consumption of H2. Considering that the aromatic hy-
drocarbons have unique combustion properties, preserving the aro-
matic rings while selectively cleaving the CeO bonds is of crucial im-
portance. However, it is a highly challenging task because the CeO
bond in aryl ethers is strong, especially for the CeO bond in phenol
(414 kJ/mol) [14]. Therefore, competition reactions exist between the
hydrogenolysis of CeO bonds and the hydrogenation of the aromatic
rings during lignin hydrodeoxygenation.
Normally, aromatic hydrocarbons can be achieved from phenols by
two parallel routes: one is, via the hydrogenation (HYD) pathway to
cyclohexanol, then through tandem dehydration to cyclohexene and
dehydrogenation to benzene; another is the direct deoxygenation
(DDO) to benzene, as shown in Scheme 1. For example, Zhao et al. [15]

⁎
Corresponding authors.
E-mail addresses: xiaqineng159@163.com (Q. Xia), wangyanqin@ecust.edu.cn (Y. Wang).

http://dx.doi.org/10.1016/j.apcata.2017.07.050
Received 11 April 2017; Received in revised form 28 July 2017; Accepted 31 July 2017
Available online 01 August 2017
0926-860X/ © 2017 Elsevier B.V. All rights reserved.
T. Guo et al.
used Ru/sulfate zirconia as catalyst and found phenol and substituted
phenols can be converted to desired aromatic hydrocarbons in water
through the HYD pathway at 240 °C in the presence of low pressurized
H2 (0.2-0.8 MPa). While in vapor-phase hydrodeoxygenation, Wang
et al. [16] found that over Pd/Fe2O3 catalyst, high selectivity to toluene
can be obtained from m-cresol via the DDO route (CeO cleavage
without saturation of aromatic ring). Austin et al. [17] also reported
that the DDO reaction of phenol could be achieved over Ru/TiO2 cat-
alyst under 0.5 MPa H2. However, the reaction conditions for above
DDO route were hash (300 °C), resulting in a high energy consumption.
Rinaldi et al. [18] found that the aromatic hydrocarbons can be
achieved via the HYD pathway over Raney Ni combined with β-zeolite
catalyst by catalytic transfer hydrogenation with 2-PrOH as a hydrogen
source. Catalytic transfer hydrogenation reactions are considered to be
more promising than using molecular H2 for safety reasons. Further-
more, biomass-derived alcohols [19,20] (EtOH, 2-PrOH, 1-BuOH) can
be used as sustainable hydrogen sources and provide low content hy-
drogenation environment to reserve the unsaturated structure of aro-
matic compounds in the lignin.
To the best of our knowledge, there is no report on the production of
aromatic hydrocarbons from lignin or its model compounds by catalytic
transfer hydrodeoxygenation via DDO route. In our previous study, we
found that NbOx species can promote the cleavage of CeO bond sig-
nificantly, especially for the CeO bond in tetrahydrofuran ring during
the production of liquid alkanes from furfural-derived aldol adducts,
sorbitol and raw biomass over Pd- or Pt-loaded NbOPO4 catalysts
[21–23]. More interestingly, a simple Pd/Nb2O5-SiO2 catalyst showed
an excellent activity and stability for the hydrodeoxygenation of pal-
mitic acid with almost no decrease in hexadecane yield (94–95.0%) in a
150 h time-on-stream test due to the significant promotion effect of
NbOx species on CeO bond cleavage [24]. Herein, we report a novel
catalytic system for the selective conversion of lignin model compounds
(i.e., 2-methoxy-4-methyl phenol, benzyl phenyl ether, 2-(2-methox-
yphenyl)oxy-1-phenethanol) and real lignin extracted from birch to
aromatic hydrocarbons, by catalytic transfer hydrodeoxygenation with
2-PrOH as a hydrogen source over a Ru/Nb2O5-SiO2 catalyst. The re-
action pathway studies reveal that the DDO route is the main reaction
route, owing to the promotion effect of NbOx species on CeO bond
cleavage.
31
Applied Catalysis A, General 547 (2017) 30–36
Scheme 1. The reaction pathway for the con-
version of p-cresol.
2. Experimental
2.1. Materials
RuCl3∙3H2O, Pd(NO3)2∙xH2O and Pt(NO3)2∙xH2O solution were
purchased from Heraeus Materials Technology Shanghai Co., Ltd. H-
Beta zeolite and ZSM-5 were purchased from the Catalyst Plant of
Nankai University. γ-Al2O3 was purchased from BASF Chemical Co.
Ltd., TiO2 was purchased from Aladdin Co. Ltd. Nb2O5 was synthesized
according to literature [23]. Active carbon was purchased from SCM
Industrial Chemical Co. Ltd., p-Cresol, toluene, ethylcyclohexane, cy-
clohexane, 2-methoxy-4-methyl phenol were purchased from J & K Co.
Ltd., methylcyclohexanol, propylbenzene, ethylbenzene, propylcyclo-
hexane, methylcyclohexanone were purchased from TCl. Methylcyclo-
hexane was purchased from Macklin. Benzyl phenyl ether (α-O-4) were
purchased from Alfa Aesar Chemicals Co. Ltd., 2-(2-methoxyphenyl)
oxy-1-phenethanol (β-O-4) was prepared according to literature [25].
Birch wood was purchased from local manufactory (ca. 40 mesh), and
dried at 100 °C for 5 h before use. All other chemicals were purchased
from Sinopharm Chemical Reagent Co. Ltd. and used without pur-
ification.
2.2. Catalyst preparation
Nb2O5-SiO2 composite was synthesized by a sol-gel method ac-
cording to literature [24], unless otherwise specified, the Nb2O5 content
in Nb2O5-SiO2 was 10 wt% in all cases. The preparion of SiO2 was si-
milar to that of Nb2O5-SiO2 without the addition of niobium tartrate.
The Ru/Nb2O5-SiO2 catalysts and other Ru-loaded catalysts were pre-
pared by the incipient wetness impregnation method using a calculated
amount of RuCl3∙xH2O. After impregnation, the obtained catalysts were
dried at 50 °C overnight, followed by reduction at 400 °C under flowing
10 vol% H2/Ar for 4 h and then purged with N2 for 2 h until room
temperature. Supported Pd, Pt catalysts were prepared with the similar
method to the case of Ru/Nb2O5-SiO2, but the reduction temperature
was 300 °C. Other Ru-based catalysts with various supports were pre-
pared in the same way to the case of Ru/Nb2O5-SiO2. The metal load-
ings of catalysts were 5 wt%, unless specifically noted.
T. Guo et al.
2.3. Characterizations
The N2 adsorption–desorption isotherms were measured at 77 K by
using a NOVA 4200e analyzer (Quantachrome Co. Ltd). The BET
method was used to calculate the specific surface area.
Actual content of Ru, Pt, and Pd in loaded catalysts were determined
on the inductively coupled plasma-atomic emission spectroscopy (ICP,
TJA IRIS 1000).
The dispersions of Ru, Pt and Pd were calculated on the basis of CO
adsorption using chemical adsorption equipment (Micromeritics, Model
AutoChem II 2920) and performed using the same procedure as in lit-
erature [26].
2.4. Catalytic reactions and products analysis
The reactions for the hydrogenation of model compounds were
performed in a 50 mL stainless-steel autoclave. A typical experiment
was carried out as follows: p-cresol (0.2 g), Ru/Nb2O5-SiO2 (5 wt%,
0.1 g), deionized water (14 mL), isopropanol (0.52 g) were charged into
the autoclave. After purging air outside the reactor with N2 by three
times, the reaction was carried out at 230 °C with a magnetic stirring
speed of 700 rpm. After reaction, the reactor was cooled to room
temperature by loading cooling water, the organic products were ex-
tracted using ethyl acetate and analyzed by a GC (Agilent 7890B) and
GC–MS (Agilent 7890A-5975C). The batch hydrodeoxygenation reac-
tions of 2-methoxy-4-methyl phenol, α-O-4 and β-O-4 model com-
pounds were conducted in the same procedure. Tridecane was used as
the internal standard for the quantification of the liquid products. The
lignin is obtained from birch according to the studies of Hu et al. [27].
The retained liquid products were purified with 3% HCl solution for
20 h under stirring at 100 °C to remove residue and hemicellulose re-
sidued. After cooled to room temperature, the mixture was poured into
1 L of ice-cold water with vigorous stirring, causing a brown solid to
precipitate. This lignin was collected by filtration and dried under va-
cuum.
The reaction for the hydrogenation of birch lignin was performed in
a 50 mL stainless-steel autoclave as follows: lignin (0.1 g), Ru/Nb2O5-
SiO2 (5 wt%, 0.2 g), deionized water (14 mL), cyclohexane (5 mL),
isopropanol (1.0 g) were charged into the autoclave. After purging air
outside the reactor with N2 by three times, the reaction was carried out
at 250 °C with a magnetic stirring speed of 700 rpm. After reaction, the
reactor was cooled to room temperature by loading cooling water, the
organic products were extracted using ethyl acetate and analyzed by a
GC (Agilent 7890B) and GC–MS (Agilent 7890A-5975C).
Conversion of p-cresol: moles of p-cresol reacted/moles of p-cresol
input × 100%;
Yield of liquid products = mol of the products/moles of p-cresol
input × 100%.
Selectivity to liquid products = mol of the products/moles of p-
cresol reacted × 100%.
The conversion of 2-methoxy-4-methyl phenol, α-O-4 and β-O-4
model compounds and the yield and selectivity to their liquid products
were calculated in the same way.
Yield of liquid products of lignin = mass of products/mass of lignin
input × 100%.
3. Results and discussion
3.1. p-Cresol hydrodeoxygenation over various catalysts
The hydrodeoxygenation of p-cresol was firstly carried out over
different metal-loaded Nb2O5-SiO2 catalysts in the presence of 2-PrOH,
and the catalytic performances are summarized in Table 1. It should be
noted that almost no product is produced at 230 °C for 20 h over Nb2O5-
SiO2 (Table 1, entry 1), strongly suggesting that the transfer hydro-
deoxygenation cannot happen without the metal sites. After
32
Applied Catalysis A, General 547 (2017) 30–36
introducing noble metal (Ru, Pt and Pd) into the Nb2O5-SiO2 support,
excellent catalytic performances for the hydrodeoxygenation of p-cresol
are achieved under relatively mild conditions (Table 1, entries 2–4).
Especially for Ru/Nb2O5-SiO2 catalyst, p-cresol is selectively hydro-
deoxygenated to toluene with 84.0% yield. The Pt- and Pd-loaded
Nb2O5-SiO2 catalysts (Table 1, entries 2, 3) show similar catalytic ac-
tivities (96.8% and 97.8% conversion, respectively), but the yields of
toluene (56.7% and 78.8%, respectively) are lower than that over Ru/
Nb2O5-SiO2 catalyst (84.0%). On the contrary, the yields of methylcy-
clohexane (18.7% and 10.2%, respectively) are much higher, with a
small amount of methylcyclohexanol and methylcyclohexanone. These
results indicate that the noble metals (Ru, Pt and Pd) play an important
role on the transfer hydrodeoxygenation of p-cresol to toluene and Ru
shows the most suitable transfer hydrogenation activity.
Considering that the supports may also contribute to the catalytic
activity, the catalytic performances of different supports (TiO2, SiO2, H-
Beta) supported Ru catalysts were also investigated. The Ru dispersions
of these catalysts are similar (in the range of 22.6–27.2%), as shown in
Table 2, but their catalytic activities are quite different (Table 1, entries
2, 5–7). In particular, the surface area and metal dispersion of Ru/SiO2
catalyst are similar to those of Ru/Nb2O5-SiO2 (Table 2), but the cat-
alytic activity of the former catalyst is much poorer, with only 11.3%
conversion of p-cresol and 3.8% yield of toluene (Table 1, Entry 5). This
result indicates that surface area and metal dispersion are not the main
factors for the high hydrodeoxygenation activity of Ru/Nb2O5-SiO2
catalyst, but is the significant promotion effect of NbOx species of the
support on CeO bond cleavage, in well accordance with our previous
reports [21–24]. The Ru/TiO2 catalyst, which was reported to have the
unprecedented activity in the vapor-phase hydrodeoxygenation of
phenol[12], was also tested at the same condition (230 °C, 20 h), the
yield of toluene (67.1%) is much higher than those over Ru/SiO2 and
Ru/H-Beta, but still lower than that of Ru/Nb2O5-SiO2, although the
conversion is higher. All these results strongly indicate that NbOx spe-
cies play a vital role on hydrodeoxygenation of p-cresol.
Meanwhile, the influence of Ru loading on the selectivity to toluene
was investigated. The yield of toluene decreases from 85.3 to 75.8%
with the Ru loading decreases from 5 wt% to 1 wt% (Table 1, entries 2,
8 and 9) with full conversion of p-cresol. These results show that the
higher loading of Ru has a positive effect on the yield of toluene due to
the higher reduction degree (Fig. S1, Table S1). However, higher yields
of methyl cyclohexane are obtained over 1% and 3% Ru/Nb2O5-SiO2
catalysts due to the excessive hydrogenation of toluene, indicating 1%
and 3% Ru/Nb2O5-SiO2 catalysts with smaller Ru particle size show
higher hydrogenation activity than the 5%Ru/Nb2O5-SiO2 catalyst.
When the equimolar molecular H2 is used as hydrogen source for
comparison (Table 1, entry 10), the yield of toluene (56.0%) is lower
than that (59.1%) using 2-PrOH as hydrogen source (Table 1, entry 11)
at similar p-cresol conversion, and the yield of methyl cyclohexane is
significantly higher (8.6%) than the latter (2.2%). These results strongly
suggest that using 2-PrOH as the hydrogen source is more selective to
aromatic hydrocarbons than using molecular H2.
In addition, Ru/Nb2O5-SiO2 catalyst shows the excellent recycling
stability for this transfer hydrodeoxygenation reaction. The conversion
of p-cresol and selectivity to toluene remain consistant at 69.5% and
83.8%, respectively, after five successive runs (Fig. 1), and the reduc-
tion degree of Ru/Nb2O5-SiO2 catalyst after reaction still keeps 90.3%
(Table S1). The others products can not be observed by GC–MS, and
belongs to coking. Its amount is estimated from the carbon balance. The
Ru/Nb2O5-SiO2 catalyst was then treated hydrothermally at 230 °C for
20 h and the Ru particle size has no obvious change (Fig. S2). Then Ru/
Nb2O5-SiO2 after hydrothermal treatment catalyst was tested for the
conversion of p-cresol, the result shows (Table S2) that its catalytic
performance remains almost the same after hydrothermal treatment,
indicating its well stability.
T. Guo et al. Applied Catalysis A, General 547 (2017) 30–36

Table 1
The hydrodeoxygenation of p-cresol over various catalystsa.

Entry Catalyst Conv. (%) Yield (%) Carbon balance (%)

toluene methyl cyclohexane methyl cyclohexene methyl cyclohexanol methyl cyclohexanone

1 Nb2O5-SiO2 0 0 0 0 0 0 –
2 Ru/Nb2O5-SiO2 98.5 84.0 4.5 0.5 0 0 90.5
3 Pt/Nb2O5-SiO2 96.8 56.7 18.7 0.1 11.1 3.4 93.2
4 Pd/Nb2O5-SiO2 97.8 78.8 10.2 0.3 2.7 1.0 95.2
5 Ru/SiO2 11.3 3.8 0.5 0.4 1.8 0.6 95.8
6 Ru/H-Beta 29.1 8.5 1.3 0.8 0 0 81.5
7 Ru/TiO2 96.0 67.1 11.1 0.4 0 0 82.6
8b 3%Ru/Nb2O5-SiO2 > 99 78.0 7.9 0.5 0 0 86.4
9c 1%Ru/Nb2O5-SiO2 > 99 75.8 9.3 0.3 0 0 85.4
10d Ru/Nb2O5-SiO2 69.2 56.0 8.6 0.5 0 0 95.9
11e Ru/Nb2O5-SiO2 67.8 59.1 2.2 0.8 0.4 0 94.7

a
Unless otherwise specified, reaction conditions: 0.2 g p-cresol, 0.1 g catalyst, 0.5 g 2-PrOH and 14 mL H2O (ratio of 2-PrOH to p-cresol is 4.6), 230 °C, 20 h. The metal loading is 5 wt
% and the Nb2O5-SiO2 composite contains 10 wt% Nb2O5.
b
The Ru loading of catalyst is 3 wt%.
c
The Ru loading of catalyst is 1 wt%.
d
Reaction condition: 0.2 g p-cresol, 0.1 g catalyst and 14 mL H2O, 0.6 MPa H2, 230 °C, 3 h.
e
Reaction condition: 0.2 g p-cresol, 0.1 g catalyst, 0.5 g 2-PrOH and 14 mL H2O, 230 °C, 6 h.

Table 2 100
Characterization of various catalystsa.
80
Catalyst Dispersion/% Metal element analysis/% SBET/m2g−1

Ru/Nb2O5-SiO2 24.4 3.5 398.9 60

Pt/Nb2O5-SiO2 47.4 5.3 340.9
Sel. to toluene
%
Pd/Nb2O5-SiO2 28.7 4.6 564.0
Ru/SiO2 22.6 3.7 380.5 40 Sel. to methylcyclohexane
Ru/H-Beta 24.7 4.0 377.1 Sel. to methylcyclohexene
Ru/TiO2 27.2 3.0 59.1 Sel. to methylcyclohexanol
20
3wt%Ru/Nb2O5-SiO2 54.3 2.1 414.3 Sel. to methylcyclohexanone
1wt%Ru/Nb2O5-SiO2 73.7 0.9 437.0 8 Conv. of p-cresol
4
a
Unless otherwise specified, the metal loading is 5 wt% and the Nb2O5-SiO2 composite
0
contains 10 wt% Nb2O5.
5 10 15 20
Time (h)
80 Fig. 2. The time courses of hydrodeoxygenation of p-cresol over Ru/Nb2O5-SiO2.
Reaction conditions: 0.2 g p-cresol, 0.1 g Ru/Nb2O5-SiO2, 0.52 g 2-PrOH with 14 mL of
H2O, 230 °C.
60
Conv. of p-cresol
Sel. to methylcyclohexanol
toluene is generated directly from p-cresol (Scheme 2, route 1).
Sel. to methylcyclohexane
40
%

Sel. to toluene Meanwhile, only a small amount of methylcyclohexanone and me-

Sel. to methylcyclohexene thylcyclohexanol (both achieved via the hydrogenation (HYD) of p-
Sel. to methylcyclohexanone cresol) was detected during the reaction, with only 5.2% selectivity to
20 Sel. to others
methylcyclohexane finally (Scheme 2, route 2). These results are totally
different with those from the tandem reactions with concurrent use of
4 Raney Ni and β-zeolite [18], in the latter cyclohexene formed first, then
2
0
dehydrogenated to arenes. Based on the above results, the DDO route
fresh1 cycle 2 cycle 3 cycle 4 cycle 5
(Scheme 2, route 1) is proposed to be the main reaction pathway for the
Run Times transfer oxygen removal from p-cresol over Ru/Nb2O5-SiO2 catalyst.
Fig 1. The stability test of Ru/Nb2O5-SiO2 for the transfer hydrodeoxygenation of p-cresol This represents the first example for the catalytic transfer hydro-
in the presence of 2-PrOH. Reaction conditions: 0.1 g catalyst, 0.2 g p-cresol, 0.52 g 2- deoxygenation of phenols via DDO route. The domination of DDO route
PrOH and 14 mL H2O (molar ratio of 2-PrOH to p-cresol is 4.6), 230 °C, 10 h. in our catalytic system originates from the significant activation of
Caromatic-O bond on NbOx species, thus makes the cleavage of Caromatic-O
3.2. Reaction pathway study of p-cresol hydrodeoxygenation over Ru/ a facile process.
Nb2O5-SiO2 catalyst

There are mainly two reaction pathways reported for the oxygen
removal from phenols (i.e., DDO or HYD route), as shown in Scheme 1.
In order to clarify how the CeO bond was cleaved in the presence of 2-
PrOH over Ru/Nb2O5-SiO2 catalyst, the reaction pathways of the
transfer hydrodeoxygenation of p-cresol was investigated. It can be seen
from Fig. 2 that the selectivity to toluene is 86% from the very begin-
ning and throughout the entire reaction, strongly indicating that
3.3. Influence of 2-PrOH dosage and reaction temperature on the
hydrodeoxygenation of p-cresol to toluene
Besides proper transfer hydrogenation activity of Ru and promotion
effect of NbOx species, the dosage of 2-PrOH and reaction temperature
are also the key factors to high yield of toluene. It is known that the
stoichiometric molar ratio of 2-PrOH to p-cresol for hydro-
deoxygenantion of p-cresol to toluene is 1, but more 2-PrOH is needed

33
T. Guo et al. Applied Catalysis A, General 547 (2017) 30–36

OH O
O H2O
OH

OH

O OH methyl methyl methyl

OH cyclohexanol cyclohexene cyclohexane
Ru
Route 2
Route 1
toluene p-cresol
O
OH

methyl toluene
cyclohexanone
Scheme 2. Reaction sequence on hydrodeoxygenation of p-cresol to toluene on catalysts using water as solvents.

to reach a high toluene yield. methylcyclohexane (16.2% selectivity), with the remarkable decrease
When the molar ratio of 2-PrOH to p-cresol increases from 2.3 to of toluene selectivity from 85.3% to 72.9%, owing to the over hydro-
4.6, the conversion of p-cresol boosts from 69.5 to 98.5%, while the genation of toluene. These results indicate that the dosage of 2-PrOH
selectivity to toluene remians almost constant, ranging from 86.7% to should be in a proper range for achieving high yield and avoiding the
85.3%, as shown in Fig. 3a. However, further increasing the molar ratio over hydrogenation of benzene ring.
of 2-PrOH to p-cresol from 4.6 to 9.2 leads to a large amount of The influence of the reaction temperature on p-cresol conversion
and toluene selectivity was also investigated and the results are shown
in Fig. 3b. At relatively low temperature (190 °C), the selectivity to
(a) methylcyclohexanone (an intermediate in HYD route, 7.3% selectivity)
100 is significantly higher than that obtained at higher temperatures, in-
dicating the obvious co-existence of both reaction routes (DDO and
80 HYD routes) at low temperature. When the reaction temperature is
raised to 210 °C, the DDO reaction dominates as the major route (72.2%
Conv. of p-cresol
60 Sel. to methylcyclohexane
selectivity to toluene) and HYD reaction occurs as a tiny part, sug-
gesting that high temperature benefits the direct cleavage of CeO bond
%

Sel. to methylcyclohexanol
Sel. to methylcyclohexene of p-cresol to toluene. To verify this, reactions at higher tempertures
40 Sel. to methylcyclohexanone (230 and 250 °C) were also tested. The selectivity to toluene increases
Sel. to toluene further to 85.5% and 86.4% with an obvious decrease of methycyclo-
20 hexane selectivity (4.6% and 2.6%, respectively). This result confirms
that high temperature has a positive effect on the direct deoxygenation
of p-cresol to toluene.
0
2.3 4.6 9.2
The molar ratio of 2-PrOH to p-cresol 3.4. The hydrodeoxygenation of 2-methoxy-4-methyl phenol over Ru/
Nb2O5-SiO2 catalyst
(b)100
The high performance of the Ru/Nb2O5-SiO2 catalyst in the direct
80 cleavage of CeO bond of p-cresol to toluene opens up the possibility of
using more complex lignin-derived compound, such as 2-methoxy-4-
60 methyl phenol, which represents the main abundant phenolic monomer
Conv. of p-cresol
from lignin depolymerization [28–30], possesses more types of CeO
Sel. to methylcyclohexane
bonds than p-cresol: CeOAr, Caromatic-OMe and Caromatic-OH with the
%

40 Sel. to methylcyclohexanol
Sel. to methylcyclohexene bond energies about 247, 356 and 414 kJ/mol, respectively [14]. The
Sel. to methylcyclohexanone possible reaction networks for 2-methoxy-4-methyl phenol conversion
20 Sel. to toluene are summarized and drawn in Scheme 3. Route 1 shows the cleavage of
10 the Caromatic-OH bond, which results in the formation of methylanisole,
5 route 2 shows the cleavage of the Caromatic-OMe bond with p-cresol
0 formed, route 3 shows the cleavage of the CeOAr bond and results in
190 210 o 230 250 the formation of (methyl)catechol [31–34].
T/ C The time course of the conversion of 2-methoxy-4-methyl phenol
Fig. 3. (a) Influence of 2-PrOH dosage on the conversion of p-cresol; Reaction conditions: catalyzed by Ru/Nb2O5-SiO2 is shown in Fig. 4. The selectivity to p-
0.2 g p-cresol, 0.1 g Ru/Nb2O5-SiO2, 0.52 g 2-PrOH with 14 mL of H2O, 230 °C, 20 h; (b) cresol initially accumulates to 44.3% at 4 h and then decreases to
Influence of the reaction temperature on the conversion of p-cresol. Reaction conditions: 22.0% at full conversion, indicating that the 2-methoxy-4-methyl
0.2 g p-cresol, 0.1 g Ru/Nb2O5-SiO2, 0.52 g 2-PrOH with 14 mL of H2O, 170–250 °C, 20 h.
phenol is initially demethoxylated rapidly to p-cresol through the

34
T. Guo et al. Applied Catalysis A, General 547 (2017) 30–36

Scheme 3. The feasible reaction networks of 2-methoxy-4-methyl hydrodeoxygenation.

100 lower with 84.3% selectivity to toluene.

80 These results suggest that the synergistic effect between Ru metal
and NbOx species enables the direct cleavage of Caromatic-O bonds (the
60 firmest bond) on either 2-methoxy-4-methyl phenol or p-cresol mole-
40 cule. Thus, the main reaction pathway for the transfer hydro-
20 deoxygenation of 2-methoxy-4-methyl phenol in the presence of 2-
%

Conv. of 2-methoxy-4-methyl-phenol
Sel. to methylcyclohexane
8 two steps, demethoxylation (DMO) and DDO (Scheme 4), and any other
Sel. to toluene
6 Sel. to methyanisole
Sel. to p-cresol
4
Sel. to methycyclohexene
2 3.5. Selective hydrodeoxygenation of lignin-derived aryl ethers over Ru/
0 Nb2O5-SiO2 catalyst
4 8 12 16 20 24
Time (h)
Fig. 4. The time courses of hydrodeoxygenation of 2-methoxy-4-methyl phenol over Ru/
Nb2O5-SiO2 catalyst. Reaction conditions: 0.2 g 2-methoxy-4-methyl phenol, 0.1 g cata-
lyst, 0.52 g 2-PrOH and 14 mL H2O, 230 °C. The hollow symbol: 0.80 g 2-PrOH was used.
cleavage of Caromatic-OMe bond (Scheme 3, route 2). Meanwhile, only
trace amount of methylanisole (2.8% selectivity, an intermediate from
route 1) was detected, with no methylcatechol observed in our case.
This initial product distribution indicates that the breakage of Caromatic-
OMe bond is the easiest and first step for transfer hydrodeoxygenation
of 2-methoxy-4-methyl phenol, owing to the significant Caromatic-O bond
activation on NbOx species. Further extending the reaction time, the
selectivity to toluene increases from 46.8% to 73.4% at the expense of
p-cresol, suggesting that p-cresol is converted to toluene via the direct
cleavage of Caromatic-OH bond. However, the selectivity to p-cresol re-
mains almost constant after 16 h at 21.4%, owing to the insufficiency of
2-PrOH dosage. Therefore, another experiment with higher 2-PrOH
dosage (hollow symbol in Fig. 4) was also carried out at 230 °C for 20 h,
and the amount of oxygen-containing intermediates is significantly
PrOH over Ru/Nb2O5-SiO2 can be proposed in a very simple way via
complex reaction routes, such as routes 1 and 3 in Scheme 3 can be
technically ignored.
Based on the above findings, the designed catalytic system was
applied to hydrodeoxygenate the lignin-derived representative phenolic
dimers, such as benzyl phenyl ether (α-O-4 model compound) and 2-(2-
methoxyphenyl)oxy-1-phenethanol (β-O-4 model compound). The α-O-
4 model compound is selectively hydrodeoxygenated to benzene and
toluene with yields exceeding 92.0% and 82.0% (calculated respec-
tively from their corresponding parts), respectively, over Ru/Nb2O5-
SiO2 in water at 230 °C (Fig. 5). The oxygen removal follows a similar
mechanism to that of 2-methoxy-4-methyl phenol conversion (Scheme
3), that is via the direct cleavage of CeO ether bond to produce arenes,
rather than via sequential hydrogenation, dehydration and dehy-
drogenation reactions (Fig. S3A). In the conversion of β-O-4 model
compound which is more closer to the chemical structure of lignin,
85.0% yield of benzene and 90.4% yield of ethylbenzene are obtained
(calculated respectively from their corresponding parts), suggesting
that the more complex substituted syringols can also be converted to
aromatic hydrocarbons directly by the transfer hydrodeoxygenation
reactions using 2-PrOH as the hydrogen source (Fig. S3B).
Inspired by the results obtained from the transfer hydro-
deoxygenation reactions of lignin model compounds, we applied this

Scheme 4. Principal reaction network occurring on Ru/

Nb2O5-SiO2 catalyst for 2-methoxy-4- methyl hydro-
deoxygenation.

35
T. Guo et al.
catalyst to the conversion of real lignin extracted from birch wood. It is
found that Ru/Nb2O5-SiO2 catalyst is also active for the transfer hy-
drodeoxygenation of organosolv lignin in the presence of 2-PrOH, and
the yield of arenes is 19.8 wt% in total, including toluene (1.8 wt%),
ethylbenzene (8.0 wt%), propyl benzene (5.0 wt%) and arene dimers
(3.8 wt%). In addition, 1.2 wt% yield of cycloalkanes is also obtained
(Table S3), and the corresponding carbon yield of C7 ∼ C9 hydro-
carbons is 55.8% (Fig. S4). This result indicates the efficiency and ap-
plicability of this approach for lignin utilization.
4. Conclusions
In summary, we have demonstrated an efficient conversion of lignin
model compounds and real lignin extracted from birch wood to aro-
matic hydrocarbons through catalytic transfer hydrodeoxygenation,
using 2-PrOH as the hydrogen source. Ru/Nb2O5-SiO2 catalyst catalyzes
the selective and direct cleavage of the Caromatic-O bond on phenolic
monomers and dimers and the use of 2-PrOH as the hydrogen source
further limits the over hydrogenation of benzene-ring. Therefore, high
yield of aromatic hydrocarbons is achieved through DDO route.
Reaction pathway studies of p-cresol over Ru/Nb2O5-SiO2 provide
strong evidences pointing to the direct cleavage of Caromatic−O bond
(DDO route) rather than mechanisms via sequential hydrogenation-
dehydration-dehydrogenation steps (HYD route). For the transfer hy-
drodeoxygenation of 2-methoxy-4-methyl phenol, the direct cleavage of
the Caromatic-O is also prefered over Ru/Nb2O5-SiO2 catalyst with high
yield of toluene. Further works on more complex lignin model com-
pounds (α-O-4 and β-O-4 dimers) and birch-extracted organosolv lignin
also give excellent yields of aromatic hydrocarbons. These results de-
monstrate that Ru/Nb2O5-SiO2 catalyst is an excellent transfer hydro-
deoxygenation catalyst in the conversion of lignin-derived compounds
to aromatic hydrocarbons, owing to the synergistic effect between NbOx
species and Ru particle. This catalytic approach provides a novel and
efficient route for lignin valorization via catalytic transfer hydro-
dexoygenation.
Acknowledgements
This work was supported financially by the NSFC of China (No.
91545103, 21603072 and 21403065) and the Science and Technology
Commission of Shanghai Municipality (10dz2220500).
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Applied Catalysis A, General 547 (2017) 30–36
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