Production of Benzoic Acid through

Catalytic Transformation of Renewable

Lignocellulosic Biomass
Cite as: Chin. J. Chem. Phys. 30, 588 (2017); https://doi.org/10.1063/1674-0068/30/cjcp1703047
Submitted: 22 March 2017 . Accepted: 31 May 2017 . Published Online: 22 November 2017

Yi-heng Zhang, Ming-hui Fan, Rui Chang, and Quan-xin Li

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Chin. J. Chem. Phys. 30, 588 (2017); https://doi.org/10.1063/1674-0068/30/cjcp1703047 30, 588

© 2017 Chinese Physical Society.

CHINESE JOURNAL OF CHEMICAL PHYSICS VOLUME 30, NUMBER 5 OCTOBER 27, 2017

ARTICLE
Production of Benzoic Acid through Catalytic Transformation of Renewable
Lignocellulosic Biomass
Yi-heng Zhanga , Ming-hui Fanb , Rui Changa , Quan-xin Lia ∗
a. Department of Chemical Physics, Key Laboratory of Urban Pollutant Conversion, Chinese Academy of
Sciences, Anhui Key Laboratory of Biomass Clean Energy, University of Science and Technology of China,
Hefei 230026, China
b. Anhui Key Laboratory of Tobacco Chemistry, China Tobacco Anhui Industrial, Co., Ltd., Hefei
230088, China

(Dated: Received on March 22, 2017; Accepted on May 31, 2017)

In the present work, we reported a novel route for the conversion of lignocellulosic biomass
(sawdust) to a high-value chemical of benzoic acid under atmospheric pressure. The trans-
formation involved the catalytic pyrolysis of sawdust into aromatics, the decomposition of
heavier alkylaromatics to toluene, and the liquid-phase oxidation of toluene-rich aromatics
to benzoic acid. The production of the desired benzoic acid from the sawdust-derived aro-
matics, with the benzoic acid selectivity of 85.1 C-mol% and nearly complete conversion of
toluene, was achieved using the MnO2 /NHPI catalyst at 100 ◦ C for 5 h. The influence of
adding methanol on the catalytic conversion of sawdust to the core intermediate of toluene
was also investigated in detail.
Key words: Lignocellulosic biomass, Benzoic acid, Catalytic pyrolysis, Dealkylation, Oxi-
dation

I. INTRODUCTION is also formed through the oligomerization of aromat-

Concerns about the steady decline in fossil fuel re-
serves and the growing increase in carbon dioxide emis-
sions have accelerated advances in alternative fuels and
chemicals using biomass feedstocks [1−3]. Lignocellu-
losic biomass, mainly containing cellulose, hemicellu-
lose and lignin, is considered as a promising, renew-
able and vast resource for the production of bio-fuels
as well as bio-chemicals [4−8]. Among various devel-
oped biomass conversion routes, catalytic pyrolysis (or
catalytic fast pyrolysis) could be an effective method
for producing aromatic chemicals from biomass [9, 10].
Especially, catalytic pyrolysis of biomass over zeolites
has been widely investigated, producing a variety of
aromatics such as benzene, toluene, xylenes, alkylben-
zenes, naphthalenes, and indenes [11, 12]. The con-
version of lignocellulosic biomass to aromatics via cat-
alytic pyrolysis mainly involved the formation of oxy-
genated organic compounds by biomass depolymeriza-
tion, followed by the formation of low carbon aromatics
(mainly C6 −C8 monocyclic aromatic hydrocarbons) by
further deoxygenation, catalytic cracking and aromati-
zation when a zeolite catalyst is used [11, 12]. Coke
as well as somewhat amount of polycyclic aromatics
∗ Author to whom correspondence should be addressed. E-mail:
liqx@ustc.edu.cn, Tel.: +86-551-63601118, FAX: +86-551-
63606689
ics during the catalytic pyrolysis of biomass. However,
the transformation of lignocellulosic biomass into the
desired high-value aromatic chemicals (such as benzoic
acid) still remains a problem.
Benzoic acid is an important chemical, widely used
in the production of pharmaceuticals, dye intermedi-
ates, plasticizers, spices, food preservatives and so on
[13, 14]. There are three main industrial production
methods for the synthesis of benzoic acid now, namely,
the liquid-phase air oxidation of toluene, the hydrolysis
of trichlorotoluene and the decarboxylation of phthalic
anhydride [14]. Toluene can be oxidized to several oxy-
genates like benzoic acid, benzaldehyde, and benzyl al-
cohol [15−18], and the yield of a desired product derived
from the oxidation process depends on catalysts, oxidiz-
ers and reaction conditions [16, 19]. For example, the
gas-phase catalytic oxidation of toluene [20, 21] and the
liquid-phase catalytic oxidation of toluene [16−19], have
been developed for producing benzoic acid or benzalde-
hyde. The gas-phase catalytic oxidation of toluene was
usually performed at middle temperature using air or
oxygen as oxidants over transition metal oxide catalysts
(like vanadium oxide, iron oxide and cobalt oxide) or
composite metal oxide catalysts [20−23]. The gas-phase
oxidation process is more favorable for simplifying prod-
uct separation process as compared with liquid-phase
catalytic oxidation process, but has some disadvantages
including lower selectivity of benzoic acid or benzalde-
hyde, and the deactivation of the catalysts [20, 24].

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Chin. J. Chem. Phys., Vol. 30, No. 5 Production of Benzoic Acid through Catalytic Transformation
Alternatively, the liquid-phase catalytic oxidation of
toluene to benzaldehyde and benzoic acid has also at-
tracted much attention [14−16, 19, 25]. Typically, sol-
uble metal salts like cobalt or manganese-based halides
are used as catalysts for the liquid phase oxidation of
toluene, together with the addition of bromide as a cat-
alyst promoter [26, 27]. The bi-metallic catalysts [28],
metal complex catalysts [29], and metal-molecular sieve
composite catalysts [15, 18, 30] have also been investi-
gated for the liquid phase catalytic oxidation of toluene.
Generally, complex products, consisting of benzyl alco-
hol, benzaldehyde, and benzoic acid, are formed from
the liquid phase oxidation of toluene, since the primary
products like benzaldehyde can undergo the second ox-
idation reactions such as the oxidation of benzaldehyde
to benzoic acid. For example, Zhong et al. reported
a maximum toluene conversion of 24.7% with benzoic
acid selectivity of 79.5% and benzaldehyde selectivity
of 8.3% using 6 wt% MnOx /SBA-15 [15]. Sun et al.
found a mixed-node MOF catalyst of Ag-Cu-BTC ex-
hibited a high benzaldehyde selectivity of 90.6% with a
low toluene conversion of 20.1% [31]. Compared with
the gas phase oxidation method, the liquid phase oxi-
dation of toluene can be carried out at lower reaction
temperature with a higher selectivity of benzaldehyde
or benzoic acid. But increasing the desired product
yield still remains a major challenge.
Herein, the production of benzoic acid from ligno-
cellulosic biomass (sawdust) was achieved by a pro-
posed transformation process under atmospheric pres-
sure, giving the high selectivity of the targeted product
(benzoic acid).
II. EXPERIMENTS
A. Material and characterization
Sawdust used in this work mainly consisted of
46.20 wt% carbon, 6.02 wt% hydrogen, 47.30 wt%
oxygen, and 0.48 wt% nitrogen, which was the same
biomass raw material as that reported in our previ-
ous work [11]. Chemical reagents were purchased from
Sinopharm Chemical Reagent Company Ltd. (Shang-
hai, China).
All zeolite catalysts used were obtained from Nankai
University catalyst Co., Ltd. (Tianjin, China), and
treated at 550 ◦ C for 4 h at nitrogen atmosphere.
The Zn-modified HZSM-5 zeolite for the catalytic py-
rolysis of sawdust was prepared by the impregnation
method with the same procedure reported in Ref.[12].
In addition, the catalysts used for the synthesis of ben-
zoic acid, including MnO2 , CoCl2 , MnCl2 , CuCl2 and
the promoter of N-Hydroxyphthalimide (NHPI), were
purchased from Sinopharm Chemical Reagent Com-
pany Limited (Shanghai, China). The composite cat-
alysts (MnO2 /NHPI, CoCl2 /NHPI, MnCl2 /NHPI, and
CuCl2 /NHPI) were prepared by the blend of the tran-
sition metal salt or oxide with NHPI, and dried in a
dry box at 110 ◦ C until the water was completely re-
DOI:10.1063/1674-0068/30/cjcp1703047
589
TABLE I Main properties of the catalysts. Si/Al: the ra-
tio of silicon to aluminum in the zeolites, SBET : Brunauer-
Emmett-Teller surface area in m2 /g) and Vp : pore volume
in cm3 /g.
Catalysts Si/Al SBET Vp Total aciditya
HZSM-5 25 413.2 0.27 580.6
1%Zn/HZSM-5 25 396.1 0.25 549.5
3%Re/HY 5 532.6 0.37 982.8
a
The acid density was estimated by the Gaussian fitting of
NH3 -TPD profiles (µmol (NH3 )/g(catalyst)).
moved. The catalysts were characterized by the induc-
tively coupled plasma and atomic emission spectroscopy
(ICP/AES), the N2 adsorption/desorption and the
ammonia temperature-programmed desorption (NH3 -
TPD) analyses, as the same procedures described in our
previous work [12]. Main properties of the catalysts are
summarized in Table I.
B. Experimental setup and product analysis
The transformation of sawdust into benzoic acid was
carried out by the catalytic pyrolysis of sawdust, the de-
composition of heavier aromatics and the liquid-phase
oxidation of toluene-rich aromatics. The catalytic py-
rolysis of sawdust was performed in the fixed-bed re-
actor installed with a feeder, two condensers and a gas
analyzer [11], and the experimental procedures were the
same as described in our previous work [12]. Typically,
sawdust was mixed with the 1%Zn/HZSM-5 catalyst
(catalyst/sawdust weight ratio of 2). The mixture was
fed into the reactor by the feeder with a feeding rate of
about 6 g sawdust/h. In the case of co-feeding biomass
with methanol, the methanol was synchronously fed by
a multisyringe pump (TS2-60, Baoding longer preci-
sion pump) with a given feeding rate (6 g/h). The
organic liquid products (catalytic pyrolysis oil, CPO)
were collected by the condensers, weighed and analyzed
by a GC-MS mass spectrometer. For the decompo-
sition of heavier aromatics to toluene, CPO was fur-
ther treated in a fixed-bed reactor using the Re/HY
catalyst. Typical reaction condition for this process
was the temperature of 530 ◦ C, the space velocity of
0.5 h−1 , and the methanol content of 30 wt% in the
CPO/methanol mixture. The resulting organic liquid
products (catalytic dealkylation oil, CDO) were ana-
lyzed by a similar procedure mentioned above. Finally,
the oxidation of toluene-rich aromatics (namely CDO)
to benzoic acid was investigated by low-temperature
liquid-phase reactions using the catalysts of MnO2 ,
NHPI, MnO2 /NHPI, CoCl2 /NHPI, MnCl2 /NHPI, and
CuCl2 /NHPI. The oxidation reactions were carried out
in a two neck flask reactor under the following reaction
conditions: the mass ratio of CDO to acetic acid sol-
vent=1:5, the mass ratio of catalyst to CDO=1:10, tem-
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590 Chin. J. Chem. Phys., Vol. 30, No. 5
FIG. 1 Influence of methanol on the catalytic pyrolysis of sawdust into aromatics over 1%Zn/HZSM-5. Reaction conditions:
the weight of catalyst to sawdust of 2 at 450 ◦ C. CPO: catalytic pyrolysis oil. (a) Overall yields, (b) distribution of CPO
derived from the catalytic pyrolysis of sawdust, (c) distribution of gas.
perature at 60−100 ◦ C and time for 1−5 h. The oxy-
gen was used as oxidant with a flow rate of 50 cm3 /min,
controlled by a mass-flow controller. The products were
separated from the catalysts by the filtration method.
The gas, liquid and solid products obtained in each
test were analyzed using a gas chromatograph (GC-
SP6890, Shandong Lunan Co., Ltd., China), GC-
MS (Thermo Trace GC/ISQ MS, USA; FID detector
with a TR-5 capillary column) and the TGA analy-
sis (Q5000IR thermogravimetric analyzer, USA) respec-
tively [11, 32]. The conversion (C), yield (Y ), selec-
tivity (S), and distribution (D) of the products were
calculated based on Eqs.(1)−(4).
Mass of gas, liquid or solid products
Y= ×100% (1)
Mass of feed
Mass of a liquid product
D= ×100% (2)
Total mass of organic liquid
Moles of reactant reacted
C= ×100% (3)
Moles of reactant fed in
Carbon moles in an aromatic product
S= ×100% (4)
Carbon moles in aromatics
III. RESULTS AND DISCUSSION
A. Catalytic pyrolysis of sawdust
Catalyst deactivation caused by the coke deposition
on the catalysts stood as a serious problem for the cat-
alytic pyrolysis of biomass [11]. Here, it was found
that co-feeding sawdust with methanol was able to obvi-
ously decrease the coke formation. As shown in FIG. 1,
the yield of coke from the direct catalytic pyrolysis of
sawdust was 32.8 wt%, and significantly reduced to
18.5 wt% for co-feeding sawdust with methanol (the
mass ratio of 1:1). The CPO yield was also improved
to 23.2 wt% in the presence of methanol. On the other
hand, the addition of methanol into sawdust increased
the contents of toluene and xylenes, accompanied by the
reduction of polycyclic aromatics (like naphthalenes).
Considering the aromatization of methanol [33, 34], the
final distribution of the liquid products obtained from
co-feeding sawdust with methanol was mainly formed
DOI:10.1063/1674-0068/30/cjcp1703047
Yi-heng Zhang et al.
by the catalytic pyrolysis of sawdust and the aromati-
zation of methanol.
The reaction temperature has also strong impact on
the production of aromatics by the catalytic pyrolysis
of the sawdust. As can be seen from FIG. 2, increasing
the temperatures increased the gas yield and decreased
the CPO yield, attributed to the fact that high tem-
peratures enhanced depolymerization and deoxygena-
tion of biomass, as well as increased biomass gasifica-
tion. The downward trend in the coke yield suggests
that high temperatures are not beneficial to the poly-
merization of aromatics. With increasing temperature,
the contents of benzene and toluene increased and the
heavier aromatics decreased due to the decomposition
of the heavier aromatics at higher temperatures. The
total mass percentage of low carbon aromatics reached
about 90.1 wt%, including 23.7 wt% benzene, 37.2 wt%
toluene, and 29.2 wt% xylenes at 550 ◦ C. Small amounts
of polycyclic aromatics (like naphthalene and methyl-
naphthalene) due to the oligomerization reactions of
low carbon aromatics presented a downward trend with
increasing the temperature. Moreover, the gaseous
alkenes and alkanes from the catalytic pyrolysis de-
creased with increasing the temperature, because the
decomposition and aromatization of light alkenes and
alkanes were enhanced at higher temperatures [35, 36].
B. Decomposition of heavier aromatics
For the decomposition of heavier aromatics to
toluene, CPO was further treated using the Re/HY cat-
alyst. As shown in FIG. 3, adding methanol into CPO
effectively changed the distribution of the liquid prod-
ucts (CDO) and inhibited the formation of coke dur-
ing the catalytic treatment process. The liquid prod-
ucts obtained from CPO contained 36.8 wt% benzene,
43.9 wt% toluene, 16.2 wt% xylenes, and the heavier
aromatics of 3.1 wt%. The compositions in the liquid
products derived from the CPO/methanol mixture (ra-
tio of 1:1) became 23.8 wt% benzene, 51.4 wt% toluene,
22.7 wt% xylenes and the heavier aromatics of 2.1 wt%,
mainly caused by the decomposition of heavier aromat-
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FIG. 2 Effect of temperature on the catalytic pyrolysis of sawdust to aromatics over 1%Zn/HZSM-5. Reaction conditions:
the ratio of sawdust to methanol of 1:1 and temperature of 450−550 ◦ C. (a) Overall yields, (b) distribution of CPO derived
from the catalytic pyrolysis of sawdust, (c) distribution of gas.

FIG. 3 Influence of methanol (MeOH) on transformation of CPO to toluene-rich aromatics over the Re/HY catalyst.
Reaction conditions: T =530 ◦ C and WHSV=0.5 h−1 . CPO was obtained by the catalytic pyrolysis of sawdust at 450 ◦ C
with sawdust/methanol of 1:1. CDO: catalytic dealkylation oil. (a) Overall yields, (b) distribution of CDO derived from
the catalytic dealkylation of CPO, (c) distribution of gas.

FIG. 4 Transformation of CPO into toluene-rich aromatics over the Re/HY catalyst. Reaction conditions:
CPO:MeOH=0.7:0.3, T =490−570 ◦ C and WHSV=0.5 h−1 . CPO was obtained by the catalytic pyrolysis of sawdust at
450 ◦ C with sawdust/methanol of 1:1. (a) Overall yields, (b) distribution of CDO derived from the catalytic dealkylation
of CPO, (c) distribution of gas.

ics and the aromatization of methanol. FIG. 4 shows
the effect of temperature on the catalytic treatment pro-
cess. Increasing the reaction temperature significantly
reduced the yield of liquid products due to the increase
in the gas yield by the decomposition of aromatics. For
the liquid distribution, the content of benzene sharply
increased from 19.0 wt% to 72.1 wt% with increasing
the temperature from 490 ◦ C to 570 ◦ C, which clearly
proved that high temperatures increased the decompo-
sition of heavier aromatics. The formation of toluene
presented the maximal value of 51.7 wt% near 510 ◦ C,
caused by the competitive reaction processes between
the decomposition of heavier aromatics (C8 and C8 +
aromatics) and the demethylation of toluene.
C. Oxidation of toluene-rich aromatics
Finally, the synthesis of benzoic acid was performed
by the low-temprature liquid-phase oxidation of the
toluene-rich aromatics (namely CDO) using oxygen as
an oxidant. The different catalysts, including MnO2 ,
NHPI, MnO2 /NHPI, CoCl2 /NHPI, MnCl2 /NHPI and
CuCl2 /NHPI, have been investigated for the oxida-
tion of CDO to benzoic acid. As can be seen from

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TABLE II Production of benzoic acid by the oxidation of sawdust-derived aromatics (CDO) over the different catalysts.
Reaction conditions: CDO:solvent (acetic acid)= 1:5, catalyst:CDO (in mass ratio)=1:10, T =80 ◦ C, t=4 h. CDO contained
46.1 wt% benzene, 45.2 wt% toluene, 6.8 wt% xylenes, 1.9 wt% other aromatics.
MnO2 NHPI MnO2 /NHPI CoCl2 /NHPI MnCl2 /NHPI CuCl2 /NHPI
Conversion/C-mol% Benzene 0.2 1.5 1.0 0.8 0.7 0.5
Toluene 7.8 19.5 87.1 94.5 92.1 51.7
Xylenes 9.7 28.5 94.5 97.2 95.8 75.2
Overall 4.3 11.4 46.3 49.7 48.5 28.7
Selectivity of products/C-mol% Benzoic acid 52.8 27.7 77.7 81.8 78.6 56.0
Benzaldehyde 20.3 34.0 3.9 1.7 2.9 14.6
Benzyl alcohol 1.3 7.1 0.6 0.1 0.6 3.5
Phenol 1.3 5.5 0.7 0.6 0.7 0.5
Catechol 0.1 0.4 0.1 − − 0.1
Toluic acid 14.6 12.5 14.0 13.2 13.4 15.1
Tolualdehyde 2.8 4.2 0.6 0.3 0.2 2.4
Others 6.8 8.6 2.4 2.3 3.6 7.8
Products distribution/wt% Benzoic acid 54.8 29.7 78.5 82.3 79.3 57.8
Benzaldehyde 18.3 31.7 3.4 1.5 2.5 13.1
Benzyl alcohol 1.2 6.7 0.5 0.1 0.5 3.2
Phenol 1.2 5.3 0.6 0.5 0.6 0.5
Catechol 0.1 0.5 0.1 − − 0.1
Toluic acid 14.8 13.1 13.8 13.0 13.2 15.2
Tolualdehyde 2.5 3.9 0.5 0.3 0.2 2.1
Others 7.1 9.1 2.6 2.3 3.7 8.0

FIG. 5 Effect of temperature on the production of benzoic acid by the oxidation of CDO over the MnO2 /NHPI catalyst.
Reaction conditions: catalyst/CDO (in mass ratio)=1:10, T =60−100 ◦ C and t=4 h. CDO contained 46.1 wt% benzene,
45.2 wt% toluene, 6.8 wt% xylenes, 1.9 wt% other aromatics. (a) Conversion of aromatics, (b) selectivity of products,
(c) distribution of products.

Table II, the MnO2 catalyst shows very low oxidation
activities of aromatics. Adding the promoter of N -
hydroxyphthalimide (NHPI) into the reaction system
(MnO2 /NHPI) effectively enhanced the catalytic ac-
tivities for the oxidation of CDO, especially for the
oxidation of toluene and xylenes. The conversion of
toluene reached 87.1 C-mol% under the typical condi-
tion (80 ◦ C, 4 h) using MnO2 /NHPI, and the main
products obtained were benzoic acid and toluic acid
with the selectivity of 77.7 C-mol% and 14.0 C-mol% re-
spectively. NHPI could mainly play a key role as an ini-
tiator or promotor in the oxidation of aromatics, similar
to the previous investigation on the oxidation of alka-
nes [37]. Moreover, the catalysts containing the transi-
tion metal halide such as CoCl2 /NHPI, MnCl2 /NHPI,
and CuCl2 /NHPI also exhibited high activities for the
CDO oxidation. However, these catalysts may be envi-
ronmentally harmful because of halide-containing com-
positions. Accordingly, MnO2 /NHPI was selected for
the production of benzoic acid, which was investigated
in details under different conditions.
FIG. 5 presents the influence of temperature on the
the oxidation of CDO to benzoic acid over the selected
MnO2 /NHPI catalyst. The conversions of toluene and

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FIG. 6 Effect of reaction time on the production of benzoic acid by the oxidation of CDO over the MnO2 /NHPI catalyst.
Reaction conditions: catalyst/CDO (in mass ratio)=1:10, T =100 ◦ C. CDO was the same sample as described in FIG. 5.
(a) Conversion of aromatics, (b) selectivity of products, (c) distribution of products.

FIG. 7 Comparision of the selectivity for the oxidation of different aromatics over the MnO2 /NHPI catalyst. (a) Oxidation
of benzene, (b) oxidation of toluene, and (c) oxidation of xylenes. Reaction conditions: catalyst/reactants (in mass ratio)
of 1:10 at 100 ◦ C for 4 h.

xylenes in CDO are greatly higher than the conver-
sion of benzene, indicating that alkylaromatic com-
pounds have higher reactivity as compared with ben-
zene. With increasing reaction temperature from 60 ◦ C
to 100 ◦ C, the conversion of toluene gradually increases
from 50.2 C-mol% to 97.1 C-mol%, indicating that in-
creasing temperature favors to overcome the activation
energy required for the the oxidation of CDO to ben-
zoic acid, together with increasing the collision proba-
bility. The main products essentially consisted of ben-
zoic acid and smaller amount of other by-products such
as benzaldehyde, benzyl alcohol, tolualdehyde, toluic
acid, and phenols. For the product selectivity, increas-
ing temperature significantly improved the selectivity
of the benzoic acid. Because the oxidation of toluene
in CDO is a consecutive reaction process, the primary
products can generally undergo the second oxidation re-
actions, such as the oxidation of benzaldehyde to ben-
zoic acid and/or the oxidation of benzyl alcohol to ben-
zoic acid. Thus, increasing the reaction temperature
enhanced the deep oxidation of toluene, leading to the
enhancement of the benzoic acid formation at higher
temperatures.
The reaction time also observably influenced the con-
version of the aromatic reactants and the selectivity of
products during the oxidation of CDO (FIG. 6). The
conversion of all aromatics presented a rising tendency
as increasing the reaction time. Nearly all of toluene
was converted into benzoic acid after the oxidation at
100 ◦ C for 5 h. The selectivity of benzoic acid increased
with increasing reaction time, along with the decrease
in other products. The benzoic acid selectivity reached
a maximum value of 85.1% at 100 ◦ C for 5 h. Ob-
viously, increasing reaction time enhanced the second
oxidation reactions of toluene and improved the selec-
tivity of the desired benzoic acid. In addition, it was
noticed that the toluene conversion was more sensitive
to reaction time, as compared with benzene or xylenes.
The dependence of the benzene conversion on reaction
time was weak due to the low oxidation reactivity of
benzene. Considering that the content of xylenes in
CDO was much lower than that of toluene, the xylenes
conversion rapidly reached saturation.
To further understand the reaction process of the
CDO oxidation, the following comparative experiments
among the oxidation of benzene, toluene and xylenes
were performed (FIG. 7). The oxidation of benzene
presents the lowest conversion compared with that of
toluene or xylenes using the MnO2 /NHPI catalyst un-
der the same condition (100 ◦ C, 4 h). Very low conver-
sion of benzene could be attributed to its high stabil-
ity and low oxidation reactivity when oxygen was used
as the oxidant in the low-temperature liquid-phase ox-
idation process. The oxidation of benzene with oxy-
gen mainly produced phenol (91.2 C-mol%) and cate-
chol (6.3 C-mol%), originating from the primary oxi-
dation of benzene and the secondary oxidation of phe-
nol. For the oxidation of toluene, the products primar-
ily included 0.6 C-mol% benzyl alcohol, 8.1 C-mol%
benzaldehyde, and 88.7 C-mol% benzoic acid, in which
benzoic acid was considered as the secondary oxidation
product of benzyl alcohol and benzaldehyde. Besides,

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594 Chin. J. Chem. Phys., Vol. 30, No. 5
the oxidation of xylenes mainly produced toluic acid
and tolualdehyde, with the selectivity of 71.5 C-mol%
and 26.4 C-mol% respectively. Thus it can be seen that
the oxidation of toluene to form benzoic acid plays a
core role in the oxidation of sawdust-derived aromatics,
attributing to its higher oxidation reactivity as well as
its higher content in CDO. Moreover, the total yield of
benzoic acid under optimized conditions was 207.8 g/kg
sawdust (sawdust/methanol mass ratio of 1:1.2).
IV. CONCLUSION
The transformation of sawdust (a lignocellulosic
biomass) to high-value chemical of benzoic acid was
successfully realized with a controlled reaction path-
way. The production of the core intermediate of toluene
was conducted by the catalytic pyrolysis of sawdust
using the Zn-modified zeolite and the decomposition
of heavier aromatics using the Re/HY zeolite cata-
lyst, the maximal mass percentage of 51.7 wt% toluene
was obtained. Furthermore, the selective synthesis of
benzoic acid by the liquid-phase oxidation of toluene-
rich aromatics from sawdust was achieved using the
MnO2 /NHPI catalyst, leading to the benzoic acid selec-
tivity of 85.1 C-mol% and nearly complete conversion
of toluene under optimized conditions (100 ◦ C and 5 h).
The transformation potentially provides a novel route
for development of green bio-chemicals using biomass.
V. ACKNOWLEDGMENTS
This work was support by the National Natural Key
Basic Program of China (No.2013CB228105), the Pro-
gram for Changjiang Scholars and Innovative Research
Team in University and the Fundamental Research
Funds for the Central Universities (No.wk2060190040).
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⃝2017
c Chinese Physical Society