Fuel 130 (2014) 154–159

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Improving aromatic hydrocarbons yield from coal pyrolysis volatile

products over HZSM-5 and Mo-modified HZSM-5
Guanlong Li, Lunjing Yan, Ruifang Zhao, Fan Li ⇑
State Key Laboratory Breeding Base of Coal Science and Technology Co-founded by Shanxi Province and the Ministry of Science and Technology, Taiyuan University of Technology,
Taiyuan 030024, China

h i g h l i g h t s

 A novel application of Mo/HZSM-5 on improving BTEXN yield was investigated in situ.

 The yield of BTEXN from coal pyrolysis was increased remarkably by HZSM-5 and Mo/HZSM-5.
 The conditions and principle of Mo/HZSM-5 improving BTEXN yield were obtained.

a r t i c l e i n f o a b s t r a c t

Article history: The effect of Mo/HZSM-5 and HZSM-5 on the yield of aromatic hydrocarbons such as BTEXN (benzene,
Received 29 January 2014 toluene, ethylbenzene, xylene, naphthalene) during Pingshuo Coal flash pyrolysis at different tempera-
Received in revised form 9 April 2014 tures was analyzed using Py-GC/MS. It shows that both HZSM-5 and Mo/HZSM-5 can remarkably
Accepted 10 April 2014
increase the yield of BTEXN. HZSM-5 shows the highest catalytic activity at 900 °C, the total BTEXN yield
Available online 26 April 2014
increases from 116 ng/mg at 500 °C to a maximum of 7000 ng/mg at 900 °C, and then decreases with fur-
ther increase of temperature. The maximum yield with HZSM-5 obtained at 900 °C is more than three
Keywords:
times that without HZSM-5. However, Mo/HZSM-5 has the potential to yield more BTEXN, as the maxi-
Coal
Pyrolysis products
mum yield of BTEXN is 7020 ng/mg at 800 °C. The results indicate that Mo has been loaded on the HZSM-
Mo/HZSM-5 5 zeolite as MoO3. As a result, Mo/HZSM-5 can promote the aromatization of olefins and alkanes, dehy-
BTEXN droxylation of phenolic compounds, as well as aromatization of CH4. Thus, Mo/HZSM-5 is more suitable
Py-GC/MS for the catalytic conversion of the gaseous products from coal pyrolysis into BTEXN.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction added directly to coal, or catalytic conversion of coal volatiles over

Benzene, toluene, ethylbenzene, xylene, and naphthalene,
referred to collectively as BTEXN, are currently in widespread use
as industrial chemicals for the production of pesticides, plastic
products and synthetic fibres. However, the traditional way of
extracting BTEXN from petroleum has been called into question
due to the rise of oil price and the shortage of petroleum resources
[1]. A promising alternative is to enrich and extract BTEXN from
coal tar, since there is a substantial amount of coal tar produced
annually in China with the rapid development of coking industry
in recent years [2].
The utilization of catalysts in coal pyrolysis is essential to obtain
a high yield of BTEXN and improve the quality of coal tar, which
can be achieved either by catalytic conversion of coal over catalysts
⇑ Corresponding author. Tel.: +86 351 6018076; fax: +86 351 6010482.
E-mail address: lifan66@hotmail.com (F. Li).
catalysts placed separately from coal. However, the former
approach has a great difficulty in separating the catalysts from
residual chars, thereby making it unsuitable for industrial applica-
tions [3]; whereas the latter approach requires no thermal process-
ing, thereby saving much energy and, more importantly, avoiding
the problem of separating the catalysts from residual chars. Char-
eonpanich et al. [4] demonstrated that the two-stage reaction,
where Millmerran coal was pyrolyzed under high pressure of
hydrogen in the first stage and coal volatiles were hydrocracked
over Ni–Mo–S catalyst in the second stage, could lead to the high-
est BTX yield of 10.4% (daf). Similarly, Nelson and Tyler [5] showed
that gases and tars were produced during the rapid hydropyrolysis
of a subbituminous coal in a fluidized-bed reactor, and passed
through a fixed-bed reactor containing NiMo/c-Al2O3 catalysts,
which resulted in an increase in low-molecular-weight tars, espe-
cially the BTEXN, and a decrease in heteroatoms. Takarada et al. [6]
also found that hydropyrolysis of Taiheiyo coal over CoMo/Al2O3
catalyst in a pressurized powder-particle fluidized bed produced

http://dx.doi.org/10.1016/j.fuel.2014.04.027
0016-2361/Ó 2014 Elsevier Ltd. All rights reserved.

a high yield of hydrocarbon liquid, the main components of which
were light aromatic hydrocarbons such as BTEXN.
HZSM-5 has been shown to have a significant catalytic effect on
the gaseous products from biomass pyrolysis. Adjaye and Bakhshi
[7,8] reported that biomass pyrolysis oil could be upgraded by
HZSM-5 to produce more hydrocarbons, with the yield of aromatic
hydrocarbons being 27 wt% which was more than the aliphatic
hydrocarbons. Bakar and Titiloye [9] studied the effect of HZSM-
5 on the chemical compositions of rice husk bio-oil, and the results
showed that HZSM-5 increased the production of aromatic hydro-
carbons and light phenols. Foster et al. [10] studied the aromatic
yield and distribution from catalytic fast pyrolysis of biomass over
HZSM-5, which showed that the concentration of acid sites inside
HZSM-5 was critical for maximizing aromatic yield. Jin et al. [11]
integrated methane aromatization over Mo/HZSM-5 catalyst with
coal pyrolysis to improve tar yield, some intermediate radicals
were produced during methane aromatization and the free radicals
cracked in coal pyrolysis were stabilized, thus resulting in an
increase in the tar yield, especially the benzene series.
However, as the great majority of these studies have been per-
formed under a pressurized hydrogen atmosphere, the application
is somewhat limited by the high cost of producing hydrogen.
HZSM-5 is known to be an effective catalyst. Although much
research has been conducted on the effect of HZSM-5 on biomass
pyrolysis, its catalytic effect on the volatile products from coal
pyrolysis remains largely unknown, and to our knowledge, there
have been few studies on the distribution of the products before
and after catalysis by on-line analysis. In this study, the release
amount of BTEXN over HZSM-5 and Mo/HZSM-5 was analyzed
online using Py-GC/MS, and the results will provide some useful
insights into the improvement of BTEXN yield from coal volatiles.
2. Experiments
2.1. Coal samples
Pingshuo bituminous coal was used as the feed sample, which
was ground and sieved to give a particle size of 0.15–0.25 mm.
The proximate and ultimate analyses are shown in Table 1.
2.2. Catalyst preparation
HZSM-5 used in this study was purchased from the Catalyst
Plant of Nankai University (Tianjin, China). Prior to the experi-
ments, HZSM-5 zeolite was calcined in air at 550 °C for 5 h to
remove impurities. Mo/HZSM-5 catalyst was prepared by incipient
wetness impregnation with 6 wt% Mo loading in the catalyst.
HZSM-5 was impregnated with aqueous solution of tetrahydrate
heptamolybdate ammonium at room temperature for 16 h, dried
at 50 °C for 5 h and 110 °C for 5 h, and then calcined at 550 °C for
6 h in air.
2.3. Catalysts characterization
X-ray diffraction pattern measured by a Rigaku Miniflex II Dif-
fractometer was used to characterize the crystallinity of the sam-
ples, using Cu Ka1 radiation (k = 0.15406 nm) at 40 kV and
Table 1
Proximate and ultimate analyses of PS bituminous coal.
Proximate analysis wt/% Ultimate analysis wt/% (daf)
Mad Ad Vdaf C H Oa
2.2 18.3 37.2 80.4 5.2 11.9
a
By difference.
G. Li et al. / Fuel 130 (2014) 154–159 155
100 mA over a 2h range from 10° to 50° with a scanning speed of
8°/min and a step size of 0.01°. The total amount of metal incorpo-
rated in the catalyst was quantified by inductively coupled plasma
atomic emission spectroscopy (ICP-AES, Thermo Icap 6300 ICP).
The pore structure of the catalyst was measured using JW-
BK122W Micropore Analyzer (Beijing JWGB Sci.&Tech. Co., Ltd,
China). Prior to the analysis, the samples were degassed by vacuum
at 300 °C for 1 h to remove adsorbed compounds. The specific sur-
face area was calculated by the BET equation, and the micropore
volume by the HK method.
2.4. Experimental instruments and conditions
Coal flash pyrolysis was performed using a CDS Analytical Pyro-
probe 5250. The quartz rod, quartz wool, 1 mg of coal sample,
quartz wool, 0.6 mg of catalyst and quartz wool were in turn
loaded into the quartz tube, as schematically illustrated in Fig. 1.
The HZSM-5 or Mo/HZSM-5 catalyst was placed below the coal
sample and separated by quartz wool, so that the HZSM-5 or
Mo/HZSM-5 catalyst can only act on the volatile products from coal
pyrolysis, without catalytic effect on coal pyrolysis. The tempera-
ture was increased to a predetermined temperature (500 °C,
600 °C, 700 °C, 800 °C, 900 °C, and 1000 °C) at a rate of 10 °C/ms,
and then held at that temperature for 15 s.
The volatile products were analyzed online by GC/MS (Thermo
Scientific Focus GC, Trace DSQ2). The chromatographic separation
was performed using a DB-5MS capillary column (30 m 
0.25 mm  0.25 um), Helium (99.999%) was used as the carrier
gas at a constant flow rate of 1 mL/min and a 1:50 split ratio.
The injector temperature was 250 °C and the oven temperature
was programmed from 50 °C (hold for 3 min) to 300 °C (hold for
1 min) at a heating rate of 3 °C/min. The mass spectrometer was
operated in EI mode at 70 eV, and the ion source temperature
was set to 250 °C.
BTEXN was qualitatively analyzed by the retention time of each
component and the mass spectra in the NIST MS library. After the
retention time was determined, selected ion monitoring mode was
used to obtain a high selectivity and sensibility for BTEXN, and
quantification was made with an external standard method. All
experiments were replicated at least three times to minimize error.
In most cases, the precision of the results, which was expressed as
N S
1.4 1.1
Fig. 1. The placement of catalyst and coal sample in the quartz tube.
156 G. Li et al. / Fuel 130 (2014) 154–159

the relative standard deviation (RSD), was between 3.5% and 10.0%, Table 2
indicating an overall good repeatability. Pore structure analysis of HZSM-5 and Mo/HZSM-5.

Catalyst SBET (m2/g) Micropore volume (cm3/g)

HZSM-5 224 0.103
3. Results and discussion
Mo/HZSM-5 210 0.095

3.1. Characterization of HZSM-5 and Mo/HZSM-5

Fig. 2 shows the XRD patterns of HZSM-5 and Mo/HZSM-5. It is 2750

clear that the characteristic diffraction peaks of HZSM-5 are not 2500 naphthalene
o-xylene
affected by Mo loading, indicating no significant change in the 2250 m/p-xylene
ethylbenzene
crystal structure of HZSM-5 loaded with Mo. The MoO3 character- 2000 toluene

Yield/(ng/mg)
benzene
istic diffraction peaks are observed at 27.3° and 25.7° in the XRD 1750
pattern of Mo/HZSM-5 [12], indicating that the active component 1500
MoO3 has been loaded on the HZSM-5 carrier. The ICP-AES analysis 1250
shows that the content of Mo (5.7%) is slightly lower than the the- 1000
oretical value. 750
Table 2 shows the results of pore structure analysis of HZSM-5 500
and Mo/HZSM-5. The incorporation of Mo into HZSM-5 leads to a 250
decrease in the specific surface area and micropore volume, which 0
is probably due to that Mo can enter into the channel of HZSM-5 500 600 700 800 900 1000
and thus occupy a part of pore volume. T/ (°C)

Fig. 3. Release amount of BTEXN during pyrolysis of PS coal.

3.2. Release amount of BTEXN during coal pyrolysis

We first investigated the release amount of BTEXN during coal
pyrolysis at different temperatures. Fig. 3 shows that BTEXN yield
is as low as 47 ng/mg at 500 °C, and a significant part of it appears
to result from the volatilization of free BTEXN in coal. Moreover,
coal pyrolysis begins to occur at this temperature, and cleavage
of some weak bridge bonds in coal results in the generation of
BTEXN. The total yield of BTEXN increases with increasing temper-
ature and the most dramatic increase is observed in the tempera-
ture range of 700–800 °C, which indicates that violent cracking
reactions occur in PS coal and the cleavage of macromolecular
bridge bonds result in a large amount of BTEXN [13]. The heating
rate of pyrolysis is 10,000 °C/s and far greater than that in the
fixed-bed reactor, thus greatly increasing the initial and active
pyrolysis temperature [14]. After 800 °C, the BTEXN yield contin-
ues to increase with increasing temperature, but with a slower
rate, and reaches a maximum of about 2200 ng/mg at 1000 °C. This
is because that the cracking reaction of PS coal has been largely
completed at 800 °C, and thermal polycondensation reaction
begins to occur.
Fig. 3 also shows that toluene accounts for the largest portion of
the total BTEXN yield, and increases most significantly with
increasing temperature. This is because that a large amount of ben-
zene series with aliphatic side chain is firstly produced, which are
unstable and can be readily decomposed into toluene and hydro-
carbons [15]. After 700 °C, some phenolic compounds such as cre-
sols can react with hydrogen and undergo dehydroxylation [15],
leading to an increase in toluene formation. However, it is noted
that more m/p-xylene is produced than the o-xylene, which may
be ascribed to the fact that the steric hindrance of the two methyls
of o-xylene is larger than that of the m/p-xylene and it trends to
produce more stable m/p-xylene during coal pyrolysis.
3.3. Catalytic effect of HZSM-5 on the volatile products from coal
pyrolysis
BTEXN yield changes significantly when coal volatiles pass
through HZSM-5 catalyst at different temperatures. Fig. 4 shows
that the total BTEXN yield increases from 116 ng/mg at 500 °C to
a maximum of 7000 ng/mg at 900 °C, and then decreases with fur-
ther increase of pyrolysis temperature from 900 °C to 1000 °C. The
maximum yield with HZSM-5 obtained at 900 °C is more than
three times that without HZSM-5. The reduction in BTEXN yield
at 1000 °C is attributed to that HZSM-5 accelerates the polycon-
densation reactions of BTEXN at high temperatures, and eventually
generates large-molecular-weight polycyclic aromatic hydrocarbons.

8000
• ΜοΟ3 naphthalene
7000 o-xylene
m/p-xylene
ethylbenzene
6000 toluene
benzene
Yield/(ng/mg)
Intensity

HZSM-5 5000

4000

3000

Mo/HZSM-5 2000
• •
1000

0
10 15 20 25 30 35 40 45 50 500 600 700 800 900 1000
2θ ( ο) T/ (°C)

Fig. 2. XRD patterns of HZSM-5 and Mo/HZSM-5. Fig. 4. Release amount of BTEXN after HZSM-5 catalysis.
 G. Li et al. / Fuel 130 (2014) 154–159 157

Fig. 4 also shows that the amount of each component of BTEXN 8 before catalysis
increases as the temperature increases from 500 °C to 900 °C, and 8x10 after catalysis
8
then decreases with further increase of temperature to 1000 °C. 7x10
Fig. 5 shows the increment of BTEXN after the catalysis of HZSM- 6x10
8

5. There is a significant increase in benzene, toluene, m/p-xylene,

Peak Aera
8
5x10
and naphthalene; whereas only a slight increase in ethylbenzene
8
and o-xylene. It thus can be concluded that HZSM-5 has a higher 4x10
8
selectivity to benzene, toluene, m/p-xylene and naphthalene, 3x10
which are relatively stable, than ethylbenzene and o-xylene. The 2x10
8

increment of each compound peaks at 900 °C and the total incre- 8

1x10
ment is 5020 ng/mg, indicating that HZSM-5 has the highest cata-
lytic activity at 900 °C. 0

The effect of HZSM-5 on the formation of BTEXN is supposed to
be related to its pore structure and acid sites. HZSM-5 zeolite
framework is composed of two kinds of cross channel systems,
the straight pore channel is elliptic with a long axis of 5.7–5.8 Å
and a short axis of 5.1–5.2 Å [16]. The molecular diameter of
BTEXN is usually smaller than the pore diameter of HZSM-5, which
makes it easier to enter into the HZSM-5 or to be produced in the
HZSM-5 pore [17]. In addition, the acid sites of HZSM-5 also play a
critical role as the concentration of acid sites can affect the gener-
ation of aromatic compounds [10]. As a result, catalytic cracking,
aromatization of olefins and alkanes, and dehydroxylation of phe-
nolic compounds occur as the volatile products from coal pyrolysis
pass through HZSM-5 zeolite, and thus more BTEXN is produced.
First, light olefins such as ethylene and butene produced during
coal flash pyrolysis undergo condensation reactions to form aro-
matic compounds in HZSM-5. Bridgwater [18] has pointed out that
an important step in hydrocarbon reactions in the zeolite channel
is aromatization. Huber and Corma [19] noticed that such aroma-
tization was realized through the Diels–Alder reaction, wherein
light olefins were combined with each other to form cyclic and aro-
matic compounds, as shown following:
Second, alkane compounds also undergo a variety of secondary
reactions, such as catalytic cracking, cyclization and aromatization,
leading to the formation of BTEXN. Fig. 6 shows the change of the
amount of straight-chain hydrocarbons before and after the catal-
ysis at 900 °C. As the sample mass and pyrolysis conditions remain
unchanged before and after the catalysis, we compare the chro-
matographic peak area of the same compound to determine the
heptane octane nonane undecane
paraffin hydrocarbon
Fig. 6. The amount of straight-chain hydrocarbons before and after HZSM-5
catalysis at 900 °C.
change of amount. It shows that the production of straight chain
alkanes is reduced to varying extents, which may be explained
by the fact that light olefins such as C2–C4 olefins are produced
from b-scission and protolysis on the zeolite acid sites at high tem-
peratures [20], which undergo oligomerization reaction to form
C6–C8 olefins on the zeolite Bronsted acid sites and then form aro-
matic precursors, which undergo dehydrogenation reactions to
form benzene, toluene, xylene and naphthalene [21]. Third,
HZSM-5 also has an effect on the phenolic compounds. Fig. 7 shows
the change of amount of phenolic compounds before and after
HZSM-5 catalysis at 900 °C, the major phenolic compounds, such
as phenol, o-cresol, and m/p-cresol, are reduced significantly with
the catalysis of HZSM-5, which is due to the dehydroxylation of
phenolic compounds [22].
It is speculated that the catalytic mechanism of HZSM-5 for the
volatile products of PS coal pyrolysis is as follows: coal pyrolysis is
not violent at a low temperature of 500–600 °C, and some olefins
and alkanes undergo aromatization to form BTEXN due to the acid
catalysis of HZSM-5. As the temperature increases to 700 °C, bridge
bonds in coal begin to fracture and produce a large amount of ole-
fins, alkanes, aromatics with side chains, and phenols. Due to the
special pore structure and acid sides of HZSM-5, olefins and
alkanes undergo aromatization to produce BTEXN; aromatics with
side chains are easily transformed into BTEXN; and dehydroxyla-
tion of phenolic compounds also contributes to the formation of
BTEXN. HZSM-5 shows the highest catalytic activity at 900 °C,
and thus the BTEXN content reaches the maximum at this
temperature.

2200 before catalysis

benzene 6x10 9 after catalysis
2000 toluene
1800 ethylbenzene
5x10 9
m/p-xylene
1600 o-xylene
Yield/(ng/mg)

naphthalene 4x10 9
Peak Aera

1400
1200
1000 3x10 9
800
600 2x10 9
400
1x10 9
200
0 0
-200 phenol o-cresol m,p-cresol
500 600 700 800 900 1000 Phenols
T/ °C
Fig. 7. The amount of phenol components before and after HZSM-5 catalysis at
Fig. 5. Increment of BTEXN after HZSM-5 catalysis. 900 °C.
158
3.4. Catalytic effect of Mo/HZSM-5 on the volatile products from coal
pyrolysis
The catalytic effect of Mo/HZSM-5 on the volatile products from
coal pyrolysis was investigated to further enhance the BTEXN yield.
Fig. 8 shows that the total amount of BTEXN increases as the tem-
perature increases, reaches a maximum of 7020 ng/mg at 800 °C,
and then decreases slightly with further increase of temperature,
indicating that Mo/HZSM-5 has a high catalytic activity even at
high temperatures. As compared with HZSM-5, the temperature
for maximum BTEXN yield is 100 °C lower for Mo/HZSM-5.
Fig. 9(a) shows the increment of BTEXN yield with Mo/HZSM-5
as compared with that without the use of catalyst, which reaches
a maximum of about 5334 ng/mg at 800 °C; and Fig. 9(b) shows
the increment of BTEXN yield with Mo/HZSM-5 as compared with
that with HZSM-5, which indicates that Mo/HZSM-5 is more con-
ducive to the formation of BTEXN at each temperature except
900 °C, with the greatest increment being 2560 ng/mg at 800 °C.
The comparison results in Fig. 9 clearly indicate that the maximum
increment is reached in the temperature range of 700–800 °C, at
which Mo/HZSM-5 has the highest catalytic activity. This is
because that Mo/HZSM-5 plays a role not only in aromatization
of olefins and alkanes and dehydroxylation of phenolic com-
pounds, but also in CH4 aromatization that HZSM-5 does not
[23]. First, Mo/HZSM-5 can promote the aromatization of CH4 pro-
duced due to the violent cracking reaction of coal at 700–800 °C to
form aromatic compounds. Chen et al. [24] argued that CH4 con-
version was catalyzed by the synergistic action of Mo species
inside HZSM-5 channel with the strong acidic sites of HZSM-5 zeo-
lite. In this process, methane is activated to produce CH3 free rad-
icals, which dimerize to form ethylene and ethane, and then
ethylene is aromatized to benzene or naphthalene with the aid of
the protons of HZSM-5 zeolite. The possible reaction schemes are
shown as following:
MoO3
CH4 ƒƒƒƒ! CH3 þ H
MoO3
2CH3 ƒƒƒƒ! C2 H4 þ H2
Hþ
3C2 H4 ƒƒƒƒ! C6 H6 þ 3H2
At 700–800 °C, a large amount of monocyclic and bicyclic aro-
matic radicals are produced due to cleavage of bridge bond and
heterocyclic compounds, these radicals are unstable and thus can
undergo condensation reactions at any moment. However, CH4
generated during coal pyrolysis produces some medium radicals
when catalyzed by Mo/HZSM-5, such as H and CH3, which favors
the formation of BTEXN by combination with monocyclic and
bicyclic aromatic radicals [11]. Thus, as compared with HZSM-5,
8000
benzene
7000 toluene
ethylbenzene
m,p-xylene
6000
o-xylene
Yield (ng/mg)
naphthalene
5000
4000
3000
2000
1000
0
500 600 700 800 900
T/ °C
Fig. 8. Release amount of BTEXN after Mo/HZSM-5 catalysis.
G. Li et al. / Fuel 130 (2014) 154–159
6000
(a)
5000 (b)
4000
Yield/(ng/mg)
3000
2000
1000
0
500 600 700 800 900 1000
T/(°C)
Fig. 9. Increment of BTEXN yield with Mo/HZSM-5 as compared with that without
catalyst (a) and HZSM-5 (b).
Mo/HZSM-5 has the potential to yield more BTEXN. However, after
800 °C, high temperature can accelerate polycondensation reac-
tions of coal, although H2 increase as the products of polyconden-
sation reactions, both CH4 and smaller aromatic fragment decrease
and generate larger molecule polycyclic aromatic hydrocarbon
[15,25], which may cause the site coverage and pore blockage of
Mo/HZSM-5 and lead to the decrease in catalytic activity
[11,20,26]. Thus a temperature higher than 800 °C is not favor to
CH4 reaction and can lead to a slight decrease in the yield of
BTEXN.
4. Conclusions
Both HZSM-5 and Mo/HZSM-5 can remarkably increase the
yield of BTEXN at 500–1000 °C. HZSM-5 shows the highest cata-
lytic activity at 900 °C, at which the total yield of BTEXN is
7000 ng/mg, which is more than three times that without the use
of HZSM-5. However, Mo/HZSM-5 has the potential to yield more
BTEXN, as the maximum yield of BTEXN is 7020 ng/mg at 800 °C.
Therefore, Mo/HZSM-5 is more suitable for the catalytic conversion
of volatile products from coal pyrolysis. This is because that Mo/
HZSM-5 can promote the aromatization of olefins and alkanes,
dehydroxylation of phenolic compounds, as well as the aromatiza-
tion of CH4.
Acknowledgment
The authors gratefully acknowledge the financial support from
the National Natural Science Foundation (21376160) and Interna-
tional Science & Technology Cooperation Program of China
(2013DFG61490).
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