Review

Cite This: Ind. Eng. Chem. Res. 2018, 57, 1768−1789 pubs.acs.org/IECR

Progress in Nonoxidative Dehydroaromatization of Methane in the

Last 6 Years
Kaidi Sun,† Daniel M. Ginosar,‡ Ting He,‡ Yulong Zhang,× Maohong Fan,*,†,§,∥,⊥
and Ruiping Chen*,†,#
†
Department of Chemical Engineering, University of Wyoming, Laramie, Wyoming 82072, United States
‡
Idaho National Laboratory, Idaho Falls, Idaho 83402, United States
§
Department of Petroleum Engineering, University of Wyoming, Laramie, Wyoming 82072, United States
∥
School of Energy Resources, University of Wyoming, Laramie, Wyoming 82071, United States
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⊥
School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332, United States
#
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences,
Fuzhou 350002, China
×
Chemistry & Physics Center, National Institute of Clean-and-Low-Carbon Energy, P.O. Box 001 Shenhua NICE, Beijing 102211,
Downloaded via TU DELFT on December 19, 2019 at 04:02:56 (UTC).

China
*
S Supporting Information

ABSTRACT: Revolutionary shale gas production has resulted in

increasing interest in the use of methane for producing various
types of high-value chemicals and among them is aromatics via
methane dehydroaromatization (MDA). Progresses achieved in the
area of MDA during the last 6 years are significant. However, a
review in this area is lacking. This review is designed to fill the gap.
The review not only discusses he development of MDA catalysts,
including conventional molybdenum (Mo)-based catalyst and non-
Mo-based catalysts and novel catalysts. Also, the insights for the
associated reaction mechanisms and catalyst regeneration methods
and applications of various types of reactors are provided.

1. INTRODUCTION (SiO2), Fe©SiO2, was synthesized and proved to have a high

Methane is a very abundant resource around the globe. An
effective process of converting lower price methane to higher
value products is required.1−7 Since 1993,8 nonoxidative
methane aromatization to produce benzene over molybdenum
loaded catalysts have been widely studied. The work showed
high selectivity for the formation of aromatic hydrocarbons as
follows:
6CH4 → C6H6 + 9H 2
Thermodynamic calculations demonstrated that the possible
direct nonoxidative conversion rate of CH4 to aromatics to be
about 14% at 973 K.9 The main goal of the recent research is to
develop new catalysts for improved performance and inhibiting
excessive coke formation. Among the development of catalysts
for MDA, the metal/zeolite system has attracted much
attention due to their structure and acidic sites for the catalytic
properties of the bifunctional systems. To achieve high
methane conversion and product selectivity, various methods
were applied to modify the supports, Mo and/or other metals
loaded on zeolites catalysts were suggested, and catalyst
regeneration methods for the MDA reaction were devel-
oped.10−18 A novel catalyst with iron (Fe) on silicon dioxide
methane conversion ratio as well as good selectivity to
aromatics.19 Uniquely, neither coke nor carbon dioxide
(CO2) was detected during the reaction running over the
Fe©SiO2 catalyst, despite the relatively high reaction temper-
ature. Semiconductor material gallium nitride (GaN) was first
discovered to show the photocatalytic performance of methane
conversion to benzene at low temperature and thermal catalytic
activity of methane aromatization at high temperature.20 Several
possible MDA mechanisms have been proposed in the past few
years, including an elementary step based kinetic model and a
microscopically reversible 54-step detailed reaction mecha-
nism21 model over Mo-based zeolite catalysts.15 Fixed bed
reactors were applied by most researchers for the MDA
reaction; however, in order to overcome thermodynamic
limitation and rapid decreasing activity attributed to the
accumulation of coke on external surface of the zeolite, several
researchers have explored fluidized reactor22 and membrane
Received: November 14, 2017
Revised: January 21, 2018
Accepted: January 23, 2018
Published: January 23, 2018

© 2018 American Chemical Society 1768 DOI: 10.1021/acs.iecr.7b04707

Ind. Eng. Chem. Res. 2018, 57, 1768−1789
Industrial & Engineering Chemistry Research Review

Figure 1. (A) The CH4 conversions over catalysts. (B) Yields of total aromatics of catalysts. Reaction conditions: T = 993 K, P = 1 atm, and GHSV =
1500 h−1.38 Reproduced with permission from ref 38. Copyright 2013 Elsevier.

reactor.23,24 This review focuses on the development and shell would severely inhibite Mo species to migrate into the
regeneration of catalysts, recently raised reaction mechanisms, zeolite channels.
and utilization of new types of reactors. Liu’s group39 impregnated Mo into multilamellar support
materials MFI (zeolite structure code) to synthesize meso-/
2. DEVELOPMENT OF CATALYSTS FOR MDA microporous zeolite catalysts (4.7 wt % Mo, Si/Al = 30) and
systematically investigated the textural and acidity properties of
2.1. Modification of Molybdenum Loaded Catalysts. the catalysts. Figures 2 and 3 showed the catalytic performances
Since the first effective catalyst (Mo/HZSM-5) for MDA
reaction was found in the last century,8 molybdenum-based
ZSM-5 zeolites have been extensively investigated by industry
and academia. It was suggested that ZSM-5 zeolite was one of
the most suitable supports, and molybdenum was the proper
metal component.25 A variety of synthesis techniques and
promoters were applied to improve the overall catalytic
performance in conventional fixed-bed reactors.26−30 Various
catalysts have been developed through modification of the
structural feature of the zeolite supports,31−33 adjusting metal
species and acidity with the intention of enhancing the catalytic
activity, stability, and selectivity to aromatics.34−36
2.1.1. Modification and Optimizing Mo/ZSM-5 Catalysts.
To achieve high conversion with minimum coke formation,
some authors assessed the influence of catalytic supports in
molybdenum loaded ZSM-5 zeolites for methane aromatization
reaction. Extensive studies are reviewed and discussed below.
Modification methods for Mo/HZSM-5 and catalytic perform-
ances were summarized and included in Table S1.
Recently, a novel Mo/HZSM-5 catalyst with a capsule
Figure 2. Catalytic performance of catalysts. Reaction conditions: T =
structure was developed and evaluated.37 Activated carbon was 983 K, P = 1 atm, and GHSV = 1600 h−1.39 Reproduced with
used as the hard template to synthesize the ZSM-5 zeolite permission from ref 39. Copyright 2014 Elsevier.
through the method of self-assembly combined hydrothermal
crystallization. Catalytic performances especially benene
formation and stability were significantly improved. These and the textural properties of Mo/MFI and Mo/lamellar MFI.
improvements could attribute to accelerated mass-transfer rate The results demonstrated that Mo loaded lamellar supported
that induced by the hollow structure of this new kind of catalysts showed higher methane conversion, aromatic
HZSM-5 zeolite. production, and coke formation than those of Mo loaded
Besides developing the hollow ZSM-5 zeolite with capsule microporous MFI (crystal size of 1.4 μm named as Mo/MFI-
structure, ZSM-5 with multilamellar structure was also 1.4 and crystal size of 0.2 μm noted as Mo/MFI-0.2). These
synthesized and evaluated. Jin et al.38 synthesized an MFI- results could be due to the presence of mesopores in zeolites.
type zeolite, HZ5@S1, with different core/shell ratios. These With the presence of these mesopores, the reactants could
supports were used to prepare corresponding Mo/HZ5@S1 access active sites easier and the products could diffuse faster.
catalysts (6 wt % Mo, Si/Al = 15) via impregnated incipient Further, because of the outstanding catalytic performance
wetness. The catalysts showed high aromatic selectivity as well achieved over Mo/lamellar MFI catalyst in MDA reaction,
as the stability (shown in Figure 1). Experimental results Liu’s40 group applied dual template synthesis strategy in the
revealed that catalytic performance was related to the ratio of preparation of lamellar MFI zeolite The spatial distribution of
core/shell, which is because the overgrowth of the Silicalite-1 tunable meso-/microporosity and the catalytic performance of
1769 DOI: 10.1021/acs.iecr.7b04707
Ind. Eng. Chem. Res. 2018, 57, 1768−1789
Industrial & Engineering Chemistry Research Review

exhibited similar CH4 conversion rates but showed better

stabilities and aromatics yields than the conventional ZSM-5
catalyst in the evaluation tests. The excellent catalytic
performance achieved by this Mo/ZSM-5 catalyst (mesopo-
rous) could be because of the formation of secondary
mesoporous systems in the zeolite. It might make the reactants
more accessible to active sites during the reaction and allow
large molecule products to diffuse from microporous channels.
Cui and co-workers42,31 used several HZSM-5 zeolites with
various average particle sizes, from 4.0, 1.9, 1.0, 0.5, and 0.2 μm
on highly crystalline parent HZSM-5 (Si/Al = 20) to prepare 5
wt % Mo/HZSM-5 catalysts and carried out MDA reactions on
these catalysts at 1073 K with different space velocities.
Characterizations of the catalysts with different particle size
supports were reported in Table 2. The NH3-TPD (ammonia-

Table 2. Characterizations of the Catalysts31 a

micropore total pore coke relative
particle size of surface area volume amount acidity
HZSM-5 (μm) (m2/g)b (cm3/g)c (wt %)d (%)e
4.0 462 0.14 6.2 58
1.9 350 0.10 5.4 45
1.0 300 0.09 6.6 40
Figure 3. Scanning electron microscopy (SEM) images of MFI-1.4 0.5 277 0.10 5.8 34
(a), MFI-0.2 (b), and lamellar MFI (c).39 Reproduced with permission 0.2 236 0.10 7.0 25
from ref 39. Copyright 2014 Elsevier. a
Reproduced with permission from ref 31. Copyright 2011 Elsevier.
b
Estimated by the Brunauer−Emmett−Teller (BET) method in the
the catalysts were investigated. Experiment results indicated range up to P/P0 = 0.2 by Ar adsorption (87 K). cEstimated in the
that the external surface area of the zeolite directly influences range up to P/P0 = 0.8 by Ar adsorption (87 K). dDetermined by
thermal gravimetric analysis (TGA) for the spent catalyst samples
the formation of external and internal coke on the catalyst. from the tests at 10 000 mL/h/g and 1073K. eEstimated based on the
Moreover, it was suggested that synthesis dual template could NH3-TPD results.
optimize the ratio of meso-/microporosity, which would result
in better catalyst performance. temperature-programmed desorption) measurements (shown
A new 3 wt % Mo/HZSM-5-BP (BP, model of carbon in Figure 4) showed that both Brønsted acidity and crystallinity
template, Si/Al = 26) catalyst was evaluated and compared to a
reference Mo/HZSM-5 catalyst.33 This new catalyst was
comprised of carbon-templated nanoparticles zeolites with
intracrystalline mesopores. Better resistance to carbonaceous
deposition on the catalyst could be concluded from its
performance, which was due to the existence of the
intracrystalline mesopores which act as a trap for carbon
deposition. This allowed a larger amount of carbon deposition
to be formed in the 10-ring channels structure. Liu et al.41
added two kinds of carbon as meso-templates in the synthesis
gel, then burned away the carbon templates to generate
mesoporous ZSM-5 for preparing Mo modified mesoporous Figure 4. (a) NH3-TPD results of used zeolites and (b) NH3-TPD
catalysts. Reaction results are summarized in Table 1. Catalytic results of 5% Mo/HZSM-5 catalysts.31 Reproduced with permission
performances of Mo modified mesoporous ZSM-5 catalysts from ref 31. Copyright 2011 Elsevier.

Table 1. Reaction Results of Methane Aromatization41 a

selectivity (%)
catalysts reaction time (min) conversion of CH4 (%) C6H6 C7H8 C10H8 coke aromatics yields (%)
Mo-ZSM-5-C 60 9.8 45 1.8 12 41 5.8
300 6.7 44 2.2 6 47 3.5
Mo-ZSM-5-M 60 9.8 48 1.5 15 35 6.4
300 7.3 57 3.0 9 31 5.0
Mo-ZSM-5-S 60 9.7 50 1.8 14 34 6.4
300 7.4 57 3.0 8 32 5.2

a
Reproduced with permission from ref 41. Copyright 2012 Elsevier. Reaction conditions: 1 atm, T = 973 K, GHSV = 1500 h−1. Catalyst synthesized
from a conventional ZSM-5 zeolite was noted as Mo-ZSM-5-C. The sample prepared from CMK-3 was denoted as Mo-ZSM-5-S. The sample
prepared from C-MCM-44 was denoted as Mo-ZSM-5-M.

1770 DOI: 10.1021/acs.iecr.7b04707

Ind. Eng. Chem. Res. 2018, 57, 1768−1789
Industrial & Engineering Chemistry Research Review

of catalysts became lower with the decreasing of average
particle size, which led to their lower activities. Catalytic
performance indicated that the catalyst with an average size of
1.9 μm achieved higher outlet benzene concentrations and
showed little reduction under the space velocities of 5 000−
20 000 mL/g h. These results could be due to the zeolites with
smaller particle sizes made it easier for the formed C6H6 to
migrate out of the zeolite channels. Experiments also confirmed
that instead of external surface of zeolite, the formation of C6H6
under high space velocities took place in the channels of zeolite.
Velebna and co-workers9 loaded molybdenum into the
parent ZSM-5 zeolite via different methods: wet impregnation
(WIM), wet impregnation with treatment of ultrasonic (US),
wet impregnation with treatment in a rotavapor (RV), wet
impregnation combined with microwave irradiations (MW),
and mechanical mixing (MM). SEM images of the parent ZSM-
5 zeolite and all prepared catalyst samples are showed in Figure
5. Catalyst characteristics are listed in Table 3. Catalytic
They drew a conclusion from the performances of these
catalysts that proper crystal size as well as mesoporous
characteristic resulted in high aromatics selectivity and better
stability for MDA reaction. Tempelman and co-workers44
introduced mesoporosity and silylation onto the HZSM-5 for
the preparation of molybdenum loaded (4 wt % Mo, Si/Al =
20) catalysts. The catalysts were prepared by physical mixing
method with MoO3 or prepared by impregnation method with
a solution of (NH3)6Mo7O24·4H2O. The results demonstrated
that mesoporosity did not improve catalytic performance of
Mo/HZSM-5, but the silylation modified catalyst showed
improved benzene selectivity. This may be because silylation
could help the dispersion of Mo species, which could lead to
higher CH4 conversion rates as well as lower carbon deposition.
Kan et al.45 loaded three types of molybdenum oxide to
modify commercial ZSM-5 zeolites (Si/Al = 25) with different
molybdenum weight (2−8 wt % Mo) for investigating catalytic
performances in methane nonoxidative aromatization reaction.
The catalytic performances comparison of catalysts carried out
under the same experimental conditions was shown in Figure 6.

Figure 5. SEM pictures of zeolites.9 Reproduced with permission from

ref 9. Copyright 2015 Elsevier.

Table 3. Characteristics of Catalyst Samples9 a

Mo SBET Vmicro acidity Bronsted
catalyst (wt %) (m2/g) (cm3/g) (mmol/g) acid sites
ZSM-5 343 0.138 1.06 0.99 Figure 6. Catalytic performance over different catalysts in MDA.
Mo/ZSM-5 4.61 308 0.104 0.79 0.75 Reaction conditions: P = 1 atm, T = 773 K, and GHSV = 1500 h−1.
(RV)
Catalyst prepared by physically mixing HZSM-5 and commercial
Mo/ZSM-5 4.65 302 0.108 0.86 0.79 MoO3 was abbreviated as 6Mo(C)-ZSM-5. The samples synthesized
(US)
from micron MoO3 and nano MoO3 were named as 6Mo(I)-ZSM-5
Mo/ZSM-5 4.67 301 0.100 0.82 0.78
(MW) and Mo(II)-ZSM-5, respectively.45 Reproduced with permission from
Mo/ZSM-5 4.64 336 0.134 0.95 0.91
ref 45. Copyright 2015 Royal Society of Chemistry.
(WIM)
Mo/ZSM-5 4.68 323 0.140 1.03 0.96
(MM) Results indicated that nano MoO3 loaded ZSM-5 catalyst
a
Reproduced with permission from ref 9. Copyright 2015 Elsevier. achieved higher aromatics yield (9.5%), CH4 conversion rate
(14.1%), and better catalytic stability than those of micron
MoO3 modified ZSM-5 zeolites. Those results could be due to
performances and the physicochemical characteristics of the MoO3 particles with smaller sizes could easily sublimate and
catalysts showed that the catalyst prepared with microwaves migrate in the channels of ZSM-5. These Mo species then
exhibited the highest CH4 conversion rate. The catalyst interacted with Brønsted acid sites and form Mo−O−Al
prepared with the assistance of mechanical mixing showed species. This resulted in more actives sites for methane
the lowest activity for methane aromatization reaction. That activation. In this case, better catalytic performance was
result could be due to the intrusion of molybdenum species achieved.
into zeolite pores and their association with the Brønsted acid Kucherov46 loaded Mo on ZSM-5 to prepare Mo/ZSM-5 (4
sites. wt % Mo, Si/Al = 30) by mechanical mixing method. The
Xu et al.43 added triethoxyphenylsilane for the modification catalysts then treated with the aqueous solution of NaOH and
of ZSM-5 zeolites and synthesized several Mo-based zeolite then dealuminated with Al(NO3)3 solutions to modify the
catalysts by mixing molybdenum trioxide (MoO3) and HZSM- support materials for mesoporous structure formation. Catalytic
5 with a MoO3 content of 6 wt % that was then calcined in air. studies indicated that catalysts prepared from zeolites etched
1771 DOI: 10.1021/acs.iecr.7b04707
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Industrial & Engineering Chemistry Research Review

with sodium hydroxide solutions increased the methane in shapes. Mo/ITQ-13 showed lower activity and stability
conversion at the initial moment of operation and the total compared to Mo/HZSM-5, but it is better in selectivity to
yield of aromatic hydrocarbons in the MDA reaction but with benzene. These results could be attributed to the unique three-
no notable increase in the selectivity to aromatics. This might dimensional structure in ITQ-13 supports constructed via 9-
be due to the high acidity of the zeolite after reducing the SiO2/ membered-ring (4.0 Å × 4.9 Å), straight 10-member-ring (4.7
Al2O3 module. Catalytic performances also revealed that an Å × 5.1 Å), and sinusoidal 10-member-ring (4.8 Å × 5.7 Å)
increase of the alkali concentration at the stage of etching the down the a, b, and c axes. This structure favored coke formation
initial zeolites was meaningless. This would lower the catalyst during reaction.
activity sharply, resulting in low yield and selectivity to Kan and his co-workers49,50 synthesized a series of Mo
aromatics and rapid catalyst coking. modified catalysts using a new support material, IM-5, and
Zhao and Wang47 applied the steam-treatment method to MoO3 loading for the nonoxidative MDA reaction. Reaction
modify the HZSM-5 zeolite and Mo/HZSM-5 catalyst (6 wt % results for different catalysts at 60 min are shown in Table 4.
Mo, Si/Al = 25) during catalyst preparation. The catalytic
performance of Mo/HZSM-5 with different steaming treat- Table 4. Numerical Reaction Results on the Methane
ments suggested that steaming at 813 K for 1 h was most Aromatization Reactions of Different Catalysts at 60
effective on reducing the deactivation rate of the catalysts. min49,50 a
Hydrofluoric acid (HF) has also been used to pretreat the
selectivity %
HZSM-5 support zeolite. Mo was then loaded to prepare the
Mo/HZSM-5 (HF) (6 wt % Mo, Si/Al = 25) catalyst.48 catalystb
conversion
of CH4, % benzene toluene naphthalene
yields of
coke %
Catalytic performances displayed that the hydrofluorinated
2Mo-IM-5(50) 7.3 34.7 1.4 12.2 3.849
Mo/HZSM-5 catalyst had better coke tolerance than untreated
4Mo-IM-5(50) 10.2 36.2 1.1 13.7 5.049
Mo/HZSM-5 but exhibited lower activity for aromatics
6Mo-IM-5(50) 11.5 39.3 1.3 14.6 5.249
formation. This result could be attributed to the HF treatment
8Mo-IM-5(50) 12.5 32.3 1.2 15.3 6.449
that both strength and amount of Brønsted acid sites were
6Mo-IM-5(40) 11.5 35.7 1.4 15.9 5.449
decreased.
6Mo-IM-5(60) 10.2 39.9 1.4 14.7 4.549
All the modification methods for Mo/HZSM-5 and catalytic
Mo-IM-5-R 11.7 74.2 3.2 22.6 5.550
performances for modified catalysts were summarized and
Mo-IM-5-S 9.6 66.0 2.1 31.9 4.950
included in Table S1. Most of these modification methods have
Mo-IM-5-R(i) 12.4 73.4 1.6 25 6.050
a promotion effect on methane conversion and benzene a
selectivity. These methods include zeolite structure reconstruc- Reproduced with permission from ref 49. Copyright 2011, Elsevier.
Reproduced with permission from ref 50. Copyright 2013 Springer
tion, catalyst particle size adjustment, molybdenum loading Nature. Reaction conditions: P = 1 atm, T = 973 K, GHSV = 1500 h−1.
methods adjustment, acidity adjustment, and steam treatment. b
Mo-IM-5-R synthesized under rotating condition, Mo-IM-5-S
However, modifying Mo/HZSM-5 by HF treatment could synthesized under static condition, and Mo-IM-5-R(i) prepared by
decrease methane conversion and selectivity to benzene. the impregnation method with Si/Al = 50 and 6 wt % MoO3 loading.
2.1.2. Modification and Optimizing Mo Loaded Catalysts 2Mo-IM-5(50) prepared with IM-5 support having Si/Al ratios = 50
Supported by Other Framework Materials. To improve the and 2 wt % MoO3 loading. 4Mo-IM-5(50) with Si/Al = 50 and 4 wt %
activities, selectivities, and stabilities of the catalysts, a good deal MoO3 loading, 6Mo-IM-5(50) with Si/Al = 50 and 6 wt % MoO3
of research was achieved concentrating on synthesizing new loading, 8Mo-IM-5(50) with Si/Al = 50 and 8 wt % MoO3 loading,
support materials, which were modified with Mo to prepare 6Mo-IM-5(40) with Si/Al = 40 and 6 wt % MoO3 loading, and 6Mo-
IM-5(60) with Si/Al = 60 and 6 wt % MoO3 loading.
catalysts for the MDA reaction. Mo loaded catalysts that
supported by other framework materials are summarized.
The catalytic performance of Mo/IM-5 catalyst achieved better
Catalytic performances of these catalysts are compared to
CH4 conversion rate (shown in Figure 8), benzene selectivity
conventional Mo/HZSM-5 catalyst. These contents are (shown in Figure 9), and better stability than that of Mo/ZSM-
summarized in Table S2.
A new high-silica ITQ-13 zeolite was developed, modified
with Mo, and tested in MDA.32 Its catalytic performances were
compared with Mo/HZSM-5. The structures of ZSM-5 and
ITQ-13 are shown in Figure 7, which clearly shows differences

Figure 8. CH4 conversion over Mo-ZSM-5 (■) and Mo-IM-5 (●)

without considering coke. Reaction conditions: P = 1 atm, T = 973 K,
Figure 7. SEM images of (a) ITQ-13 and (b) ZSM-5.32 Reproduced GHSV = 1500 h−1.49 Reproduced with permission from ref 49.
with permission from ref 32. Copyright 2009 Springer Nature. Copyright 2011 Elsevier.

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molecular sieves with different contents of phenyltriethox-

ysilane (PTEOS) introduced as a mesoporous maker.52
Conclusions of catalytic performances (shown in Figure 11)

Figure 9. C6H6 selectivity (■) and C10H8 selectivity (●) over Mo-
ZSM-5 (open symbols) and Mo-IM-5 (filled symbols) without
considering coke. Reaction conditions: P = 1 atm, T = 973 K,
GHSV = 1500 h−1.50 Reproduced with permission from ref 50.
Copyright 2013 Springer Nature.

5, which could be because of its unique 10-member-ring

channel structure and its three-dimensional cavities. It was
concluded that the most suitable catalyst was Mo/IM-5 (Si/Al
= 50) with 6−8 wt % MoO3 loading. The best results were Figure 11. Methane conversion, aromatization yield, benzene yield,
obtained at 1 atm with a temperature range of 973−1023 K. On and naphthalene yield over different catalysts. Reaction conditions: P =
the basis of those preliminary results, they developed synthesis 1 atm, T = 973 K, and GHSV = 1500 h−1.52 Reproduced with
methods for the Mo/IM-5 catalysts preparation. Catalytic permission from ref 52. Copyright 2014 Royal Society of Chemistry.
performances of Mo/IM-5-R catalyst exhibited better CH4
conversion rate and higher benzene selectivity than that of revealed that Mo/TNU-9-20 (6 wt % Mo, Si/Al = 25) showed
Mo/IM-5-S catalyst. The experiment results also revealed that better conversion of methane (14.9%), yield of aromatics
when compared to catalyst synthesized by the impregnation (9.9%), and catalytic stability than those of Mo/TNU-9
method, the physical mixing method prepared catalysts had (microporous) catalyst. This could be due to the formation
better stability and lower initial activity. They also investigated of secondary mesoporous systems in the zeolite.
and suggested that acidity, textural properties, as well as the Liu’s group39 impregnated Mo into multilamellar support
dispersion of Mo species could be the key factors which material MWW (zeolite structure code) to synthesize meso-/
considerably influence the catalytic performance and lead to microporous zeolite catalysts (4.7 wt % Mo, Si/Al = 30). The
different CH4 conversion rate, benzene selectivity, and stability textural and acidity properties of these catalysts were studied.
of the catalysts. The catalytic performances and the textural properties of Mo/
Kan and his co-workers, Liu et al.51 also prepared a new MWW and Mo/lamellar MWW are presented in Figures 12
support material TNU-9 (TNU, framework type) and and 13. It was shown that Mo/lamellar MWW catalysts
synthesized Mo-modified catalysts (SEM images shown in
Figure 10) for the MDA reaction. The catalytic performance of
Mo/TNU-9 exhibited higher CH4 conversion rate, higher C6H6
selectivity as well as better carbon resistance ability than that of
Mo/ZSM-5. This could be due to its 3D 10 member ring (MR)
structure as well as the existence of large 12MR cavities. In
further research, they also carried out hydrothermal reaction
methods to prepare several micromesoporous TNU-9-x

Figure 10. SEM images of TNU-9 support (a) and ZSM-5 zeolite Figure 12. Catalytic performance of catalysts. Reaction conditions: T
(b).51 Reproduced with permission from ref 51. Copyright 2011 = 983 K, P = 1 atm, and GHSV = 1600 h−1.39 Reproduced with
Elsevier. permission from ref 39. Copyright 2014 Elsevier.

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Ind. Eng. Chem. Res. 2018, 57, 1768−1789
Industrial & Engineering Chemistry Research
Figure 13. SEM images of MWW (a) and lamellar MWW (b).39
Reproduced with permission from ref 39. Copyright 2014 Elsevier.
exhibited higher methane conversion, lower benzene and
toluene selectivity, and higher naphthalene selectivity than
those of Mo loaded microporous MWW. These results could
be due to the presence of mesopores in zeolites. The reactants
could access active sites easier, and the products could diffuse
faster.
Yang and co-workers53 used carbon particles and fluoride
ions to prepare hierarchical MCM-22 zeolite aggregates
(MCM-22-FC) for Mo loaded catalysts (6 wt % Mo, Si/Al =
15) by a one-pot hydrothermal synthesis. They found that the
Mo/MCM-22-FC catalyst exhibited improved stability, aro-
matic selectivity, and benzene yield in the MDA reaction. This
result could be due to intergrown and stacked thin MCM-22
lamellas and mesopores and micropores constructed in the
hierarchical MCM-22-FC aggregate zeolite, which led to a
reduction in carbonaceous deposits and improving aromatic
selectivity. The addition of fluoride ions reinforced the acidic
strength, and more active centers in the Mo/MCM-22-FC
catalyst were formed. This was important for improved catalytic
performance and controlling carbonaceous deposits. Tempel-
man et al.54 prepared nanocrystalline MCM-22 zeolite. During
zeolite preparation, organosilane was applied as a crystal
inhibitor, which led to a higher accessibility to active sites for
reactants and better catalytic performance.
Yin et al.55 prepared nanosized MCM-22 zeolites with a
crystal size of about 40 nm by combined in situ crystallization
and self-assembly. The catalytic activity of Mo/MCM-22-NZ (6
wt % Mo, Si/Al = 15) performed with considerably more
stability and had higher methane conversion and benzene yield
in comparison with microsized Mo/MCM-22. This was
thought to be because of the addition of cationic polymer
that avoided the synthesis colloids self-aggregation and
intergrowth, which lowered the tendency to form coke. Hu
and co-workers56 aimed at a simple method to prepare Mo/
HMCM-22 by modifying commercial HMCM-22 zeolites with
nano size MoO3. Catalytic performances demonstrated that the
nano-MoO3 modified HMCM-22 zeolites (6 wt % Mo, Si/Al =
25) had better stability and higher CH4 conversion and yield to
aromatics than commercial MoO3 modified HMCM-22
zeolites. The better catalytic performance may because nano
size MoO3 was easily sublimated and formed molybdenum
species at the atomic or molecular level and then interacted
with Brønsted acid sites.
Large-pore zeolites like SBA-15 and zeolite beta are also
identified as promising supports in catalyst preparation because
of their high surface areas.57,58 These large-pore zeolites lack
the unique 10MR structure, which provides shape selectivity to
aromatics in MDA reaction.38 In this case these large-pore
zeolites are not currently applied in the MDA reaction.
1774
Review
However, large-pore zeolites such as zeolite beta can be
applied in coaromatization of methane and propane.58 For
coaromatization of methane and propane, Luzgin et al.58 used
tetraethylammonium hydroxide as a template to synthesize
zeolite beta (H-BEA) to prepare molybdenum-containing
zeolite catalyst (2.6 wt % Mo, Mo/H-BEA). Both gas
chromatography−mass spectrometry (GC−MS) and solid-
state nuclear magnetic resonance (NMR) spectroscopy were
applied to analyze the pathway (shown in Figure 14) of the
reaction. The results revealed that Mo-n-propyl species could
probably be the intermediates of propane aromatization and
were detected in the coaromatization reaction.
Figure 14. Possible pathway for CH4 and C3H8 coaromatization.58
Reproduced with permission from ref 58. Copyright 2013 American
Chemical Society.
The catalytic performances of methane conversion, aromatic
selectivity, and coke yield collected for various catalysts with
different supports at 60 min are summarized in Table 5. The
results demonstrate that most of the Mo loaded catalysts
prepared form newly developed supports and showed higher
methane conversion than Mo modified conventional ZSM-5
zeolite support catalyst. Catalysts synthesized of TNU-9
supports with different content of PTEOS (phenyltriethox-
ysilane) showed the highest methane conversion or benzene
selectivity, which might be due to the 3D 10MR channel
structure within the hierarchical pore materials. All Mo loaded
catalysts that supported by other framework materials discussed
in this section are listed in Table S2. Catalytic performances of
these catalysts are also summarized. Besides ZSM-5 zeolite,
other supporting materials such as TNU-9, IM-5, and MCM-22
(nanosized) are promising candidates as catalyst supporting
materials in MDA research.
2.1.3. Modification of Molybdenum Loaded Catalysts by
Introducing Other Metal Elements. Early research showed that
Mo/HZSM-5 catalyst was the most suitable catalyst for
methane conversion to aromatics. A number of investigations
of MDA over the past few years have been carried out focusing
on improving the catalytic activity and stability as well as
selectivity to aromatics of catalysts by introducing other metals
to the Mo loaded zeolite for catalyst preparation.
Xu and co-workers59 doped several metal species (0.5 wt %
M, M = Pd, Ru, Zn, Cu, Co, Fe, Mn, and Cr) on 5 wt % Mo/
HZSM-5 (Si/Al = 15) catalyst by the coimpregnation method.
The effects of these metals on the catalytic performance of Mo/
HZSM-5 catalyst were investaged. Catalytic performances
indicated that only Fe had a promotion effect on activity and
stability due to the generation of carbon nanotubes induced by
iron species. Table 6 shows the coke amount in all the spent
catalysts. In further investigations, temperature-programmed
oxidation (TPO), TGA, SEM, and BET were applied to study
the promotion mechanism of the iron additive.60 It was
suggested that the promotional effect of iron species is
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Industrial & Engineering Chemistry Research Review

Table 5. Catalytic Performances in the Methane Aromatization Reaction of Various Catalysts at 60 mina
selectivity (%)
catalyst conversion of methane (%) benzene toluene naphthalene yields of aromatics (%) yields of coke (%) refs
Mo/ZSM-5 9.5 67.4 2.4 30.2 5.6 49/51
Mo/ITQ-13 ∼3 ∼2.6 32
Mo/IM-5-R 11.7 74.2 3.2 22.6 6.2 5.5 50
Mo/TNU-9 11.3 81.2 2.2 16.6 6.2 51
Mo/TNU-9-20b 14.9 38.9 1.7 25.9 9.9 5.0 52
Mo(N)-MCM-22c 13.1 61.1 3.1 4.2 8.9 4.1 56
Mo/HZ5@S1d 8.6 63.1 16.9 7.6 11.3e 38
a
Reaction conditions: P = 1 atm, T = 973 K, GHSV = 1500 h−1. bData collected at 80 min cData collected at 130 min dData collected at 20 h. eIt was
the yield of nonaromatics for the reaction running 20 h.

Table 6. Comparison of Coke Amount in Spent Catalysts60 a

0.5% M−5% Mo/HZSM-5
catalyst 5% Mo/HZSM-5 Fe Cu Cr Co Ru Pd Zn Mn
time on stream (min) 200 225 185 165 185 185 185 155 185
coke amount (wt %)b 10.3 12.9 9.6 10.2 10.6 9.4 12.2 11.9 12.5
a
Reproduced with permission from ref 60. Copyright 2011 Elsevier. bDetermined by TGA.

attributed to carbon nanotubes induced by iron species. These
carbon nanotubes could suppress the formation of surface coke
that can be removed at low temperature. This remarkably
improved the catalytic activity, stability, and CH4 conversion.
From Xu’s research,59 Cu and Zn did not show a promotion
effect on the Mo/HZSM-5 catalyst. However, a different story
was found when a higher content of Cu and Zn was loaded on
the Mo/HZSM-5 catalyst. In the research, Cu and Zn were
applied to substitute half of Mo content in Mo/HZSM-5
catalyst (6 wt % Mo, Si/Al = 25).35 The performances of these
catalysts suggested that the extra metal (Cu or Zn) decreased
the catalytic activity but enhanced yield and selectivity to C6H6
compared to the Mo/HZSM-5. The relationship between
benzene yield and time on stream (TOS) and that between
selectivity and TOS are shown in Figure 15.
Figure 15. Results of (a) C6H6 yield and (b) selectivity of catalysts.
Reaction conditions: P = 1 atm, T = 973 K, GHSV = 1500 h−1.35
Reproduced with permission from ref 35. Copyright 2011 Elsevier.
Rodrigues et al. introduced niobium (Nb) carbide to
molybdenum loaded HMCM-22 zeolite for the methane
dehydro-aromatization reaction.61 The catalytic behavior of
niobium containing catalyst showed lower activity and coke
deposition than conventional Mo/MCM-22 catalyst. Benzene
was the major product observed for conventional Mo
containing zeolite, but naphthalene was predominant for the
Nb loaded sample.
1775
Scurrell and co-workers62 doped platinum (Pt) and/or tin
(Sn) on Mo/HZSM-5 zeolite catalyst (2 wt % Mo, Si/Al = 70)
for methane aromatization reaction using incipient wetness
coimpregnation method. Catalytic results of Pt−Mo/HZSM-5
catalyst (0.5 wt % Pt) showed an increase of methane
conversion from 4% to 7% and a 50% reduction of coke
deposition with a 65% aromatics selectivity. However, the
increase in the tin loading (0.05−0.2 wt %) resulted in a
decrease in methane conversion (7.2−4.3%). However,
selectivity to aromatics reached 64−83%, and benzene
selectivity was ∼55% when the loading of tin was at 0.1 wt
%. Moreover, the coke deposit reduced from 30% to 15% at
0.05 wt % of Sn. Furthermore, they synthesized platinum and
tin species modified Mo/HZSM-5 zeolite catalysts for MDA.29
It was concluded that the catalytic performances of catalysts
with additional tin led to lower methane conversion but higher
aromatic products selectivity. Co-impregnation prepared tin−
platinum catalyst and sequentially impregnation prepared
platinum/tin catalyst exhibited higher selectivity to aromatic
and lower selectivity to carbon deposition than sequentially
impregnated tin/platinum catalyst, which could be due to the
better platinum dispersion within the zeolite. The order of
platinum and tin species impregnated sequentially might also
affect the structural and electronic properties of platinum in
Mo/HZSM-5, where the availability of platinum sites could
affect the coke deposition in the methane aromatization
reaction. Table 7 showed the conversion and selectivity of
those catalysts.
Fila et al.63 introduced various amounts of transition metals
(Co, Mn, and Ce) into Mo/ZSM-5 (4 wt % Mo, Si/Al = 30)
and optimized the content of these metals. Experimental results
(shown in Figure 16) indicated that Co modified Mo/ZSM-5
(0.8 wt % Co) was optimal for benzene selectivity. Moreover,
Co−Mo/ZSM-5 achieved better stability during reaction
compared to Mo/ZSM-5, Mn−Mo/ZSM-5, as well as Ce−
Mo/ZSM-5. Also, Ce-doped catalyst had higher selectivity to
toluene at elevated pressures.
Abdelsayed64 introduced Fe and/or Zn to modify conven-
tional Mo loaded HZSM-5 zeolites (4 wt % Mo, Si/Al = 55)
using impregnation method. They investigated catalytic
behaviors of these catalysts in MDA reaction. The experimental
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Industrial & Engineering Chemistry Research
Table 7. Conversion and Selectivity of Catalysts Prepared in Different Methods29 a
selectivity (%)
catalystsb conversion (%) C2s benzene
Pt−Sn 5.5 5.7 70.3
Pt/Mo 7.9 6.3 51.7
Sn/Pt 6.4 8.8 48.8
Pt/Sn 4.9 6.1 65.4
a
Reproduced with permission from ref 29. Copyright 2015 Elsevier. Reaction conditions: P = 1 atm, T = 973 K, space velocity = 1620 h−1, TOS =
305 min. bThe Pt−Sn catalyst was prepared by coimpregnation method. The Pt/Mo, Sn/Pt, and Pt/Sn catalysts were prepared by sequential
impregnation with different orders of metal addition.
Figure 16. CH4 conversion (a) and molar fraction of C6H6 (b) over
catalysts. Reaction conditions: P = 150 kPa, T = 973 K, GHSV = 1500
h−1.63 Reproduced with permission from ref 63. Copyright 2015
Elsevier.
data demonstrated that Fe−Mo/HZSM-5 displayed high
stability and selectivity to aromatics. An addition of Zn slightly
improved the C6H6 formation rate. However, the presence of
both iron and zinc resulted in a significant decrease in CH4
conversion and C6H6 selectivity.
Awadallah et al.30 examined the impact of group VIII metals
(3 wt % Fe, Co and Ni) on Mo/HZSM-5 (3 wt % Mo, Si/Al =
25) in MDA reactions. These catalysts were prepared using
mechanical mixing method. The results (shown in Figure 17)
Figure 17. Total aromatics (a) and benzene selectivity (b) vs TOS
over different catalysts. Reaction conditions: P = 1 atm, T = 973 K,
GHSV = 1500 h−1.30 Reproduced with permission from ref 30.
Copyright 2012 Elsevier.
suggested that the bimetallic catalysts showed faster decom-
position of methane to carbon and hydrogen and lower
aromatization activity when compared to that of monometallic
6 wt %Mo/HZSM-5. This may be due to the mechanical
mixing method which kept the zeolite pores free of metal
incorporation, and reduced interaction between acid site and
metal species.
Sun et al.65 introduced Fe nanoparticles to Mo/HZSM-5
zeolites (5 wt % Mo, Si/Al = 30) by the mechanical mixing
method. The results showed that an addition of nanosized Fe
could enhance the catalytic stability and increase production
rate of aromatics in the MDA reaction. It was also revealed that
carbon nanotubes were found on spent Mo/HZSM-5 catalyst
Review
toluene naphthalene yield of aromatics (%) yield of coke (%)
5.5 0.0 4.2 1.0
12.2 4.2 5.4 2.0
8.3 4.2 3.9 1.9
9.1 6.2 3.6 0.9
even without the existence of nano Fe. In addition, it was also
concluded that Fe can promote the formation process of
carbon nanotubes and a certain amount of carbon nanotubes
could enhance benzene yield and catalytic stability.
Cheung et al.66 prepared several Zn-based (1−2 wt % Zn)
catalysts by coimpregnation with Mo (2 wt % Mo) and/or Ga
(1 wt % Ga) over HZSM-5 (Si/Al = 25) zeolite. The evaluation
tests were carried out under atmospheric pressure and
supersonic jet expansion. Catalytic activities (shown in Figure
18) indicated that an addition of Mo significantly increased
Figure 18. CH4 conversion and selectivity to aromatics over the
catalysts. Reaction conditions: P = 1 atm, T = 973 K, GHSV = 1680
h−1.66 Reproduced with permission from ref 66. Copyright 2011
American Chemical Society.
methane conversion and aromatic selectivity under atmospheric
pressure. However, Zn/HZSM-5 showed the highest catalytic
performance under supersonic jet expansion condition. Two
zinc species, H3C-OZn+ and HZnO−, were detected on spent
Zn/HZSM-5 catalyst. They also prepared Mo (1 wt % Mo), Ga
(1 wt % Ga), and/or Zn (2 wt % Zn) modified HZSM-5 (Si/Al
= 25) catalysts and investigated their catalytic activities on
coconversion of methane and propane to aromatics.67 The
reactions were carried out under supersonic jet expansion
conditions at 673 K. C6H6, C7H8, C2H4, C9H8, C10H8, and
C11H10 were detected from the obtained products by a time-of-
flight mass spectrometer. It was indicated that CH4 was
activated and converted on Lewis acid sites, and the carbon
atom from CH4 entered the methyl group of toluene and
methylnaphthalene.
Martinez et al.68 partially exchanged H+ in HZSM-5 with
alkali (Na+, Cs+) and alkaline-earth (Ca+, Mg+) cations to
modulate both strength and density of Brønsted acid sites.
Coke-forming tendency and stability of Mo/ZSM-5 catalyst
were also studied. They reported that partial exchange H+ with
Na+ and Cs+ could reduce the density of Brønsted acid sites.
Catalyst with a Na/Al atomic ratio of 0.1 exhibited lower coke
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Industrial & Engineering Chemistry Research
formation and higher C6H6 selectivity compared to Mo/
HZSM-5. However, catalysts exchanged with Ca+ and Mg+
cations did not show an enhanced stability.
Zhang69 investigated the effect of indium (In) on Mo/
HZSM-5 in MDA. In−Mo/ZSM-5 was synthesized using the
impregnation method. It was concluded that an addition of
indium could decrease methane conversion. However, an
addition of 1 wt % indium can reduce coke selectivity to 50%
that of Mo/ZSM-5. The results also showed that selectivity to
C2 hydrocarbons and C6H6 over In−Mo/ZSM-5 remains the
same level to that of Mo/ZSM-5.
All the above-mentioned metal elements and their promotion
effect are included and summarized in Table S3. From this
table, the effect of a certain metal element varies with its
addition amount are noticeable. Take Fe as an example, when
0.3 or 0.5 wt % addition of Fe was added to Mo/HZSM-5, the
catalyst showed higher CH4 conversion rate and C 6H6
selectivity than non-Fe added catalyst. However, selectivity to
benzene dropped when Fe content was raised to 3 wt %. In this
case, different contents of metal should be added and tested to
determine whether this metal has a promotion effect in the
MDA reaction.
2.2. Development of Non-Mo Loaded Catalysts. To
improve catalytic performance and coke resistance ability,
several researchers focused on modifying the zeolite supports,
adding promoters, periodic methane/H2 switching treatment,
and shifting the reaction equilibrium by using membrane
reactors to remove hydrogen from the reaction et al.
Nevertheless, many researchers also developed new catalysts
without Mo species loaded in order to find a more robust
catalyst.
2.2.1. Zeolite Based Non-Mo Loaded Catalysts. Abdelsayed
and co-workers70 loaded different amount of Zn (1−8 wt %
Zn) over HZSM-5 (Si/Al = 55) to prepare catalysts by
incipient wetness impregnation method. Catalytic perform-
ances of MDA reaction (shown in Figure 19) exhibited obvious
Figure 19. CH4 conversion (a) and C6H6 yield (b) over Zn loaded
catalysts. Reaction conditions: 1 atm, T = 973 K, GHSV = 3000 h−1.70
Reproduced with permission from ref 70. Copyright 2015 Elsevier.
low stability (less than 12 h), methane conversion (less than
2%), and benzene yield. This poor catalytic activity was due to
coke formation during reaction. The results also showed that
two kinds of Zn species, ZnO and [Zn(OH)]+, were presented
during the reaction. The ZnO particles were loosely bound and
easily reduced. Another Zn species, the anchored [Zn(OH)]+,
acted as a strong Lewis acid and is responsible for CH4
activation.
Shan et al.71 applied a series of rare earth metal species (0.1
wt % Eu, Dy, La, Pr, Ce, Gd, Nd, Tb, Sm, and Ho) to modify
Zn-based HZSM-5 zeolites (1.35 wt % Zn, Si/Al = 32) by
conventional incipient wetness impregnation method. A
1777
Review
mixture of methane and ethylene was used as a reactant gas
to produce aromatics. Evaluation tests were carried out at low
temperatures (723−823 K). The results (shown in Table S4)
demonstrated that catalysts modified by rare-earth metal
species exhibited high methane conversion and aromatic yields,
especially the methane conversion reached 37.3% over Gd−
Zn/HZSM-5.
Stepanov and co-workers72 applied both X-ray photoelectron
spectroscopy (XPS) and magic angle spinning (MAS) NMR in
the research of methane−ethylene aromatization. The state of
indium and quantity of Brønsted acid sites in In/HZSM-5
catalyst were investigated in the research. They demonstrated
the possible pathway of methane transformation to surface
species (shown in Figure 20). Isolated In+ or InO+ was the
Figure 20. Possible pathway of methane transformation to surface
species.72 Reproduced with permission from ref 72. Copyright 2014
American Chemical Society.
main state of In in the catalyst. In+ZO− species was formed
after the zeolite was reduced by hydrogen, and InO+ZO−
species was formed by oxidative treatment. Methane was
exclusively activated on the InO+ZO− sites to form oxyindium-
methyl species and Brønsted acid sites, followed by the
formation of oxyindium-methoxy, C2H4, formate, and acetalde-
hyde.
Zn-ZSM-11 (Si/Al = 17) catalysts were prepared for the
coconversion of methane (C1) and ethane (C2) to higher
hydrocarbons.73 Experiment design-response surface method-
ology (RSM) was applied to study reaction parameters. These
parameters include reaction temperature, C1 molar fraction,
and zinc-loading factors. The optimal reaction parameters were
decided based on C1 conversion and the yields of aromatics.
The results obtained by RSM achieved a C1 conversion of 48.6
mol % C and aromatic yields of 47.2 mol % C. This optimal
result led to the best operation conditions: XC1 should be
located between 0.2 and 0.4, reaction temperature scope is
823−853 K, and Zn2+/Zn2+H = 0.86.
Gao et al.74 applied spectroscopies and computational
method to study the structure of Cr species and anchoring
sites (shown in Figure 21) on Cr/HZSM-5 catalysts in MDA
reaction. Some catalysts were prepared by loading Cr species
(from 0.5 to 2.6 wt %) over HZSM-5 (Si/Al = 15), and others
were prepared by loading 1 wt % Cr on different HZSM-5
zeolites (Si/Al = 15, 25, 40, and 140). Density functional theory
calculation and multiple spectroscopic techniques were applied
to characterize the Cr-oxide structures and anchoring sites in
the catalysts. Spectroscopic techniques include ultraviolet
visible spectroscopy, infrared spectroscopy (IR), and Raman
spectroscopy with online mass spectrometry. Cr/ZSM-5
showed lower methane conversion and benzene yield but
higher stability than that of Mo/ZSM-5. The results also
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Industrial & Engineering Chemistry Research
Figure 21. Raman spectra of catalyst and anchoring sites of Cr
species.74 Reproduced with permission from ref 74. Copyright 2015
American Chemical Society.
indicated that isolated Cr(VI) dioxo and Cr(III) mono-oxo
structure on framework could migrate between framework Al
anchoring sites and external surface Si sites at 773 K in the
absence of oxygen. This study is helpful in understanding the
mechanism of methane aromatization reaction over Cr/ZSM-5.
Tshabalala et al.75 prepared Mn/HZSM-5 (2 wt % Mn), W−
Mn/HZSM-5 (0.5−1.5 wt % W, 2 wt % Mn), Pt−W−Mn/
HZSM-5 (Pt 0.5 wt % Pt, 1.5 wt % W, 2 wt % Mn), and Ru−
W−Mn/HZSM-5 (0.5 wt % Ru, 1.5 wt % W, 2 wt % Mn)
catalysts by a sequential impregnation method. Catalysts were
evaluated in a fixed-bed reactor at 1073 K. It was concluded
that adding tungsten to Mn/HZSM-5 decreased methane
conversion but increased catalyst stability. Further, an addition
of platinum or ruthenium to W−Mn/HZSM-5 increased
selectivity to aromatics. Thus, the addition of a noble metal
improved the yield of aromatics and lowered the yield of coke.
Catalysts with both Pt and Sn nanoparticles loaded on
HZSM-5 zeolite were first synthesized and studied by Gerceker
et al.76 Among all samples tested in this research, PtSn (1:2)/
ZSM-50 showed the highest yield of aromatics. The total
production rate of aromatics was comparable to that of Mo/
HZSM-5.
Ag−Ga/ZSM-5 catalyst was recently synthesized and
evaluated by He for coaromatization of CH4 and C3H6.27
The reaction could happen at a low temperature of 673 K. The
hydrogen from CH4 occupied aromatic hydrogen sites in the
product of benzene and other aromatics, which has been
verified by 1H, 2D, and 13C NMR tests. Compared to methane
aromatization reaction, coaromatization of propylene and
methane has a more extensive product distribution. The liquid
products include C6H6, C7H8, and C8−C12 aromatics. C8
aromatics shows highest selectivity. However, benzene is not
the major product and shows a relatively low component
distribution among all aromatic products.
Fe/zeolite catalysts were proved as promising catalysts for
MDA process.77 Recently, increasing research has been
focusing on Fe loaded zeolite catalysts. Lai et al.77 prepared
Fe-HZSM-5 through three synthetic methods, which include
core−shell synthesis, isomorphous substitution, and wet ion
exchange. They studied the inference of the synthetic methods
on the distribution of Fe species. The results showed that coke
deposition reduced with an increase of Fe dispersion. Tan78
also investigated catalytic performance of 2−6 wt % Fe/HZSM-
5 or 2−6 wt % Fe/HMCM-22 catalysts in a fixed bed flow
quartz reactor. Three reaction periods were found through the
reaction, including oxidization, decomposition, and aromatiza-
tion of CH4. The results of X-ray diffraction (XRD) and XPS
indicated that the metallic iron was formed in the
decomposition period. Iron carbide was formed in the
aromatization period. The results also exhibited that carburized
1778
Review
iron was the active phase for the conversion of CH4 to C2
hydrocarbons as well as aromatics.
2.2.2. Novel Catalysts. Two kinds of novel catalysts were
developed for MDA reaction and drew lots of attention
recently. These catalysts are Fe©SiO219 and GaN nano-
particles/nanowires.79 These two kinds of novel catalysts are
discussed thoroughly in the following paragraphs.
Fe©SiO2 was obtained by the following procedure. Ferrous
metasilicate was fused with SiO2 from commercial quartz at
1973K in air atmosphere. The obtained material was then
leached with aqueous HNO3 and dried at 353 K. Fe©SiO2 was
obtained and © represented a lattice-confined single Fe sites
embedded in a silica matrix in the catalyst.19 Fe©SiO2 contains
0.5 wt % of Fe and its BET surface area is smaller than 1 m2/g.
The transmission electron microscopy (TEM) result of fresh
Fe©SiO2 catalyst indicated that iron oxide nanoparticles (3−4
nm) were distributed homogeneously throughout the SiO2
matrix. The scanning transmission electron microscopy-high-
angle annular dark-field (STEM-HAADF) image of the spent
catalyst is shown in Figure 22. It was revealed that the iron
Figure 22. STEM-HAADF image of spent catalyst (0.5% Fe©SiO2).19
Reproduced with permission from ref 19. Copyright 2014 The
American Association for the Advancement of Science.
oxide species were embedded within the silica matrix by
bonding with C and Si atoms. This result was also confirmed by
density functional theory (DFT) calculations
Online vacuum ultraviolet-soft photoionization-molecular-
beam mass spectrometry (VUV-SPI-MBMS) was employed to
investigate the reaction mechanism. Methyl radicals (•CH3)
were clearly observed at 1193 K in the reaction. Signals for
ethylene, propyne, propylene, benzene, toluene, and naph-
thalene were verified as well. A mechanism was hypothesized
based on these results. •CH3 was generated in the beginning of
the reaction. C2H6 was then formed by combining two •CH3
through an exothermic process. Then C2H6 was dehydro-
genated to give H atoms and C2H4. The •C2H3 radical,
resulting from abstraction of H from C2H4, tended to react with
other C2H4 molecules. This process would have led to the
formation of benzene by further dehydrogenation and
cyclization. Since naphthalene is a more thermodynamically
stable product, benzene could also be dehydrogenated readily
by •H to form naphthalene.
Fe©SiO2 catalyst showed excellent stability, methane
conversion, and aromatic selectively in MDA reaction. Neither
coking nor deactivation was happened in a test lasting for 60 h.
Conversion rate of methane kept around 32% during a long test
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Industrial & Engineering Chemistry Research Review

at 1293 K and exceeded 48.1% at 1363 K. Only ethylene

(selectivity, 52.7%), benzene (selectivity, 21.5%), and naph-
thalene (selectivity, 25.8%) were produced, and selectivity to all
the products was kept >99% throughout the reaction. The
selectivity to ethylene on catalyst Fe©SiO2 is much higher than
that of conventional Mo/HZSM-5, which is lower than 10%.80
All these new findings provide new chances for MDA
fundamental research.
GaN nanowires/nanoparticles catalysts are another series of
novel catalysts. Conversion of CH4 to benzene by photo-
catalysts over Si-GaN nanowires under ultraviolet (UV)
illumination was reported for the first time.20 Plasma-assisted
molecular beam epitaxy (MBE) was used to prepare GaN
nanowires under nitrogen rich conditions. However, synthesis Figure 23. Schematic diagram for methane C−H bond polarization on
of nanostructured GaN catalysts requires a special technique, the surface of the GaN m-plane.20 Reproduced with permission from
which is molecular beam epitaxy under high temperatures ref 20. Copyright 2014 American Chemical Society.
(1073−1273K). It was the first time that GaN has a wurtzite
crystal structure and was discovered to have thermal catalytic
activity to convert light alkanes to benzene.79
Photocatalytic performance evaluation tests of Si-doped GaN
nanowires were conducted in an airtight quartz reactor at 278 K
under UV irradiation. It was revealed that the methane
conversion rate was proportional to the square of light
intensity. The quantum efficiency was increased linearly as a
function of light intensity. Minimum photon energy needed to
drive methane aromatization reaction over GaN can be
provided by UV light with a wavelength of 360 nm. The
reactor was vacuumed first, and pure methane was then
introduced. Experimental results indicated that the selectivity to
benzene achieved 96.5%. The GaN materials also demonstrated
highly stable. No noticeable deactivation showed after several
reaction cycles, and only a small amount of carbon deposits
(polyaromatic and graphitic species) were found on the surface
of GaN nanowires after a long reaction time. These carbon Figure 24. TEM image (a), schematic structure (b), and high-
resolution TEM images (c and d) of GaN nanoparticles.79 Reproduced
deposits could be completely stripped by the oxygen plasma
with permission from ref 79. Copyright 2014 John Wiley and Sons.
treatment. GaN also exhibited superior stability, reactivity, and
high selectivity to benzene at an elevated temperature. In a 4-h
reaction at 723 K, the maximum methane conversion was Further optimization of the MDA reaction over novel catalysts
0.56% and benzene selectivity was 89.8%. No noticeable are in progress to achieve higher CH4 conversion, C6H6
deactivation was detected after 10 repeated catalytic runs were selectivity, and minimizing carbon deposits.
performed over the GaN catalyst. The results also indicated 2.3. Reaction Mechanism. Several parts are included in
that the conversion of methane would be enhanced from 0.56% this section, including characterization methods that used to
to 0.9% when the reaction temperature was increased from 723 study the reaction mechanism and catalyst deactivation
to 823 K. The selectivity to C6H6 would decrease from 89.9% mechanism.
to 80%, because further dehydrogenation of C6H6 would form 2.3.1. Characterization Methods and Reaction Mecha-
polycyclic aromatics as well as coke. nism. Various of characterization methods and tools have been
Mechanism (shown in Figure 2320) was proposed and applied to investigate MDA reaction mechanism. Diffuse
calculated using DFT theory.79 Under UV irradiation, the reflectance infrared spectroscopy (DRIRS), XPS, and electron
adsorbed methane and GaN lattice (consists of Ga3+ and N3−) spin resonance (ESR) spectroscopy were applied to investigate
turned into CH3− and H+. The photo generated electron from the state of molybdenum in Mo/HZSM-5 (4 wt %, Si/Al = 30)
GaN semiconductor migrated to the surface. An electron catalyst for methane aromatization reaction.81 Results assumed
reduced the proton into a H atom, then, two H atoms that two oxidation states of Mo (6+ and 5+) existed in catalysts.
combined to release H2 gas. On the other hand, the photo Existence of (MoO2)2+ and (Mo2O5)2+ intermediates was also
generated hole would oxidize CH3− to form a methyl radical. possible.
Then, ethane was formed by the C−C coupling reaction. The NMR and electron paramagnetic resonance (EPR) were
dehydrogenation of ethane could produce ethylene. Benzene applied to study the location of Mo5+ in the Mo/HZSM-5
could be formed from ethylene through the cyclization and during reaction.82 The results suggested that Mo5+ existed in
dehydrogenation processes. the form of aluminum molybdate phase. However, another
The GaN nanoparticles possessed a regular wurtzite crystal interesting viewpoint was first raised by Kosinov et al.83 They
structure. This structure could be revealed by their electron claimed that MDA reaction is happened in a monofunctional
diffraction patterns and enlarged TEM images (shown in Figure manner on conventional Mo loaded zeolite based catalysts. Mo
24). The morphology of these powders was not quite uniform, carbide species are the active sites for CH4 conversion in the
and the BET surface area of the GaN powders was 6.73 m2/g. MDA reaction. The specific 10MR structure of ZSM-5 provides
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Figure 25. Evolution of Mo species during MDA reaction.87 Reproduced with permission from ref 87. Copyright 2016 John Wiley and Sons.
shape selectivity to the aromatics. The Brønsted acid sites only
have the function to disperse Mo species into the micropores.
Ultrahigh field 95Mo NMR spectroscopy was also applied to
identify the active center for MDA reaction.84 The results
obtained from ultrahigh field 95Mo NMR spectroscopy showed
that neither bulk nor small crystallites of MoO3 are the main
Mo species during the reaction. It was concluded that the active
centers for MDA reaction are the carburized molybdenum
species that derived from the exchanged Mo species.
To investigate the functions of Mo carbide nanoparticles, IR
vibrational spectra and DFT calculations were conducted.85,86
The IR spectroscopic results demonstrated that Mo oxide
species mainly anchored on Al sites in the framework and partly
anchored on the Si sites on the external surface of the zeolite.
Results of DFT calculations suggested that Mo carbide species
prefer to bind within two molybdenum atoms. Moreover, Mo
carbide nanoparticles (C/Mo > 1.5) were more stable on
external Si sites. This is the reason why these Mo carbide
nanoparticles were tending to migrate from pores to the zeolite
external surface. The possible reaction mechanism was also
obtained by present periodic DFT calculations, which was
concisely described as CH4 → C2H6 → C2H4 → C6H8→
C6H6.86
Operando time-resolved combined XRD and high energy
resolution fluorescence detection X-ray absorption near-edge
spectroscopy (HERFD-XANES) were used in the research.
These techniques were applied under operando conditions to
investigate the nature of the Mo species in the zeolite. The
results are demonstrated in Figure 25. Along with the result
from X-ray emission spectroscopy (XES), indicating that
isolated Mo-oxo species were converted by CH4 into
metastable MoCxOy species. These Mo-oxo species were
responsible for the formation of C2Hx/C3Hx. Then MoC3
started to form during further carburization, and its presence
coincides with benzene formation. The possible reasons for the
decrease in catalytic performance were also revealed by
fluorescence-lifetime imaging microscopy. The main reason
was that MoC3 was sintered and large hydrocarbons were
accumulated on the external surface of the catalyst.87
Different atmospheres (artificial air, He, CH4/He mixture)
were applied during the activation period of MDA. The effect
of different atmospheres on Mo/ZSM was studied.88 Catalyst
carburized in CH4 showed higher selectivity to aromatics, and a
lower deactivation rate phase was formed during heating in
methane. Then less Mo oxide species could have migrated in
the micropores to make the Brønsted acid sites inaccessible.
Gao et al.89 applied the density functional theory calculation
and multiple spectroscopic techniques to determine the
anchoring sites and identity Mo species in the catalysts for
the methane aromatization reaction. Computational results and
experiment observations (Figure 26) indicated that the Mo
oxide initially exhibited as a single Mo atom, which would then
agglomerate and form carbided Mo nanoparticles. Gas phase
oxygen treatment was also employed to adjust the distribution
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Figure 26. Operando Raman spectra for Mo/ZSM-5: (A) fresh
catalyst, (B) catalyst during reaction, and (C) catalyst after
regeneration.89 Reproduced with permission from ref 89. Copyright
2015 The American Association for the Advancement of Science.
of Mo nanostructures and restore catalytic ability. The
investigation proposed that catalytic performance of the
regenerated catalyst could be improved and higher than the
fresh catalyst by repeat regeneration cycles.
Several detailed reaction mechanisms for MDA reaction have
also been raised in the past several years. In 2012, an
elementary step based kinetic model of MDA mechanism over
Mo-based zeolite catalysts had been constructed (shown in
Figure 27):15 CH4 was first dimerized into ethane on
molybdenum sites, and then ethane was generated into C6H6
on acid sites. The mechanism includes several steps:
chemisorption, desorption, oligomerization, β-scission, hydride
transfer, protolytic dehydrogenation and hydrogenation,
protolysis, alkylation, and dealkylation of C7H8 and C10H8.
From the observed results, differences in catalytic performances
between Mo/MCM-22 and Mo/HZSM-5 were noticed. It was
assumed that these differences mainly resulted from topological
effects instead of differences in acidity. After a few years in
2015, based on this mechanism, Karakaya et al.18 developed an
improved chemical kinetics reaction mechanism. Four methane
activation reactions on Mo2C sites and reactions of hydrogen
and ethylene happened on Brønsted acid sites (46 reaction
steps) were included in this mechanism. In 2016, this same
group21 further modified this mechanism. They developed and
validated a microscopically reversible 54-step detailed reaction
mechanism for MDA chemistry through the measured packed-
bed performance. This detailed mechanism satisfies entropic
and enthalpic consistency.
2.3.2. Catalyst Deactivation Mechanism. TGA, XPS, and
TPO were applied to explore the pathway of coke formation on
the catalyst.90 There are three deactivation stages during the
reaction. These stages are the first 10 min, 10−100 min, and
100−160 min of reaction. In the second stage, the selectivity to
benzene remained high and constant, then decreased rapidly in
the last stage. Coke formation in the third stage was observably
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Figure 27. Reaction mechanism for MDA over Mo/HMCM-22.15 Reproduced with permission from ref 15. Copyright 2012 Elsevier.
higher than the second stage, resulting from the formation of
C2H4 in the narrowed zeolite channels and cracked to coke.
Three layers of Mo/HZSM-5 catalyst were loaded in a fixed
bed reactor to investigate the coking pathway for MDA
reaction.91 The reaction was carried out at 1073 K, and an
additional H2 feed was induced in the system to restrain coke
formation. The results obtained from TPO, XPS, and Raman
tests confirmed that two kinds of coke were formed during the
reaction. They are aromatic-type coke and graphite-like C. An
additional H2 feed effectively suppressed the formation of
aromatic-type coke. Three possible coke formation pathways
were proposed and shown in Figure 28. The coke formation on
Figure 28. Schematic diagram of proposed coking pathways.91
Reproduced with permission from ref 91. Copyright 2015 Elsevier.
the three layers was nonuniform, and C2H4 was the main coke
source. The cracking of C2H4 (shown as route ②) was
confirmed as the dominant pathway for coke formation. The
results also confirmed that cracking or/and polycondensation
of the formed aromatics (shown as route ③) was not the major
route for coke formation. The authors further proposed that it
is possible that the free radical chain reactions (shown as route
①) could contribute to coke formation. However, further
research needs to be done to confirm this assumption.
UV Raman spectroscopy, TGA, STEM-HAADF, and TEM
were applied to study the deactivation effect on Mo/HZSM-5
and silylated Mo/HZSM-5 in the MDA reaction.92 Catalytic
results demonstrated that carbonaceous layer formed on the
zeolite surface caused the deactivation of catalysts. The
carbonaceous layer was formed by polyaromatic hydrocarbons.
In addition, the carbonaceous layer would decrease the
accessibility of the Brønsted acid sites. This may have resulted
in the decrease of methane conversion rates and shifted the
selectivity from C6H6 to olefinic intermediates. Moreover,
silylation treatment would led to lower coke formation rate at
the external surface of the catalyst and slowed down the
deactivation rate.
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2.4. Catalyst Regeneration. Severe carbon deposition on
catalyst is the major defects in MDA reaction. Researchers have
developed several approaches to extend catalyst life. Treating a
spent catalyst under oxidative atmosphere at a higher
temperature is the most conventional way to regenerate a
coked catalyst. Some other researchers proposed to use H2 to
remove the deposited coke. This method has been demon-
strated to be effective. The catalyst can maintain a high activity
under periodic CH4−H2 switching operation modes.93
2.4.1. Catalyst Regeneration under Oxidative Atmosphere.
Martinez and co-workers94 proposed an effective procedure to
prolong the lifespan of Mo/ZSM-5 catalyst. For this procedure,
they combined reaction period and regeneration period (10 or
21 vol % of O2 in N2) in a continuous cyclic mode. Figure 29
Figure 29. Methane conversion (A) and selectivity to aromatics (B)
for Mo/ZSM-5 vs TOS for six reaction−regeneration cycles.94
Reproduced with permission from ref 94. Copyright 2015 Royal
Society of Chemistry.
showed CH4 conversion and selectivity to aromatics with
generation steps. This procedure could increase the benzene
yield and selectivity. For instance, the yield of benzene could
increase from 33 g/h kgcat (for a single 18 h test) to 97 g/h kgcat
in a reaction with 12 cycles.
Kosinov95 raised a novel isothermal (973 K) reaction−air
regeneration protocol. Research of Mo/HZSM-5 catalyst
regeneration at high reaction temperature by air has been
reported. Structure and textural stability of Mo/HZSM-5 (Mo
1−8 wt %) in air at elevated temperatures (773−973 K) was
studied. The results showed that Mo/HZSM-5 with a low Mo
loading (Mo 1−2% wt %) exhibited high oxidative stability.
This feature makes low Mo loading catalysts suitable candidates
for this novel catalyst regeneration method. Further, optimized
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Figure 30. Time-dependence of CH4 conversion (a), aromatics formation rates (b), and benzene selectivity (c) obtained over catalysts at 1073 K
and GHSV = 10000 h−1 under periodic CH4−H2 switching modes.97 Reproduced with permission from ref 97. Copyright 2014 Royal Society of
Chemistry.

Figure 31. Stability test (1000 h, CH4/H2 switch mode, 1099−1073 K) of Mo/HZSM-5 catalyst in MDA reaction (1) CH4 conversion, (2) C6H6
yield, (3) aromatic yield, (4) C2H4 selectivity, (5) C6H6 selectivity, (6) C10H8 selectivity, (7) coke selectivity.102 Reproduced with permission from
ref 102. Copyright 2015 Elsevier.

Mo/HZSM-5 catalyst can retain more than 50% of its initial
activity after 100 reaction−regeneration cycles, which is as long
as 1 week on stream.
Kosinov and coauthors proposed a catalyst regeneration
method, which periodically supplies short pulses of O2 to
oxidize coke formed on Mo/HZSM-5 catalyst.96 By optimizing
the frequency of oxygen pulse, the benzene yield was 2 times
higher compared to the control test without oxygen pulse in
methane feed. The coke formation rate was also decreased four
times compared to the control test. The results further
demonstrated that O2 mainly reacts with molybdenum carbide
species and does not cause framework damage and loss of
molybdenum.
2.4.2. Catalyst Regeneration under CH4−H2 Switch
Operation Mode. Zhang and co-workers investigated the effect
of periodic CH4−H2 switch operation mode in the MDA
reaction. Their research was conducted on various catalysts and
in different kinds of reactors.91,97−101 In 2011, Zhang et al.
carried out a research100 to study catalytic behaviors of
regeneration (CH4−H2 switch) cycles over Mo/HZSM-5
catalyst (5 wt % Mo, Si/Al = 30) in a two-bed circulating
fluidized bed system. The reaction occurred at 1073 K with
space velocities of 21 080 and 40 000 mL/g h. The results
revealed that more than 50 wt % of the coke formed in the
initial 2 min of the reaction. The results also indicated that 20
1782
min of H2 exposures should be necessary to eliminate most
coke formed during the 5−10 min methane exposure.
In 2012, binder-added and binder-free Mo/HZSM-5 catalysts
were prepared.99 These catalysts were tested under a CH4−H2
switch mode at 1073 K and 10 000 mL/g h. The results
indicated that binder added Mo/HZSM-5 showed higher
mechanical strength. However, it could also lead to an obvious
decrease in C6H6 selectivity. This could be because that
addition of binder accelerated the polyaromatization of
aromatics to coke on the surface of the catalyst.
Later in 2013, they prepared a series of Fe−Mo/HZSM-5
(0.1−2.0 wt % Fe, 5 wt % Mo) with a coimpregnated
modification method. Three kinds of HZSM-5 zeolites with
different sizes were applied.98 Catalytic evaluation tests were
carried out in a CH4−H2 switch mode. It was suggested that 0.5
wt % Fe−5 wt % Mo/HZSM-5 (nanosized HZSM-5) showed
better activity and stability. They also studied the effect of
different CH4/ H2 regeneration cycle periods: 5 min CH4−5
min H2, 5 min CH4−10 min H2, and 5 min CH4−20 min H2.97
Experimental data (shown in Figure 30) revealed that Fe
species could remarkably increase catalyst stability under a 5
min CH4−20 min H2 regeneration cycle. Moreover, results
indicated that the reactivation of Fe nanoparticles required at
least 20 min H2 exposure to eliminate most of the coke on the
catalyst surface formed during a 5 min CH4 exposure.
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In the same year, binder-free spherical-shaped, 17 wt %
binder-added cylinder-shaped and self-prepared Mo/HZSM-5
catalysts (6 wt % Mo, Si/Al = 15) were prepared. Catalysts
were evaluated in fixed-bed and fluidized bed reactors. The
reactions were carried out at 1073−1173 K with the space
velocity of 10 000 mL/g h under CH4−H2 switch regeneration
mode.101 For reactions conducted in the fixed bed reactor,
indiciating that both binder-free spherical-shaped catalyst and
self-prepared Mo/HZSM-5 exhibited good catalytic perform-
ance.
Bao and co-workers102 also applied the periodic switch
procedure of CH4 (15 min, 1500 mL/g h) and H2 (45 min,
2400 mL/g h) in the stability test for MDA catalyst at 1033−
1073 K (shown in Figure 31). Molybdenum modified
nanosized HZSM-5 zeolite (5.5 wt % Mo, Si/Al = 20) was
used in this research. The catalyst showed long-term stability
and higher CH4 conversion (16%) and aromatic yield
(exceeded 10%) during a 1000 h reaction. The results showed
that treating the catalyst with periodic hydrogen input could
suppress coke formation effectively by eliminating the aromatic-
type coke.
Recently, Song et al.93 studied the deactivation mechanism
for Mo/ZSM-5 catalyst in the MDA process. The periodic
switch mode of CH4 (5 min)−H2 (5 min) were carried out
under 1073 K and a space velocity of 12 000 mL/g h. Besides
the already known conclusion that the periodic mode of CH4−
H2 could significantly improve the catalyst stability and lifespan,
coke accumulation and deactivation behavior were also studied.
Two stages of deactivation were revealed, and the low-
temperature burning coke was confirmed as the major type
of coke during the reaction and located in the channel of
zeolite. Another kind of coke, graphite-like C was confirmed
accumulated on the external surface and channel openings of
the zeolite.
2.4.3. Catalyst Regeneration with H2 Cofed Method.
Besides using CH4−H2 switching operation modes to
regenerate catalysts, H2 cofed in the MDA reaction is also an
effective way to suppress coke formation. Zhang91 synthesized a
Mo/HZSM-5 micro zeolite catalyst by the wet impregnation
method. Three layers of catalyst were packed in a fixed-bed
reactor. TG and TPO techniques were applied to investigate
the distribution of coke formation in the reaction with H2 cofed
with CH4. Experimental data indicated that the coke
distribution in the catalyst layers was nonuniform. The coke
content in the inlet layer was higher than in the outlet layer. An
increase of H2 concentration in the feed could suppress the
aromatic coke formation as well as reduce the formation rate of
graphite-like C. Catalytic performances also revealed that the
outlet layer of catalyst showed the highest aromatic
concentration. Increasing the height of catalysts in the reactor
from the first layer to the third layers would result in an evident
decrease in the C2H4 concentration. More results demonstrated
that the intermediate C2H4 could be the main coke source
during the reaction. Most of the C2H4 consumed was converted
to coke instead of aromatics.
3. OTHER REACTORS APPLIED IN MDA REACTION
Most of the research focuses on the fixed bed reactor in the
MDA reaction. However, the process conducted by the fixed
bed reactor met two obstacles that challenge its industrial
application. First, per-pass conversion rate of CH4 was limited
by thermodynamics. Second, the activity of the catalyst
decreased rapidly due to the accumulation of coke.23 In this
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case, other kinds of reactors, including fluidized bed reactor and
membrane reactor started to be applied in MDA research in
order to overcome these barriers.
Although fixed bed reactor shows disadvantages in industrial
utilization, it is still the most widely applied reactor for MDA
studies. Thermodynamic limitation could be improved by the
method that couples MDA with chemical looping. On the basis
of recent research, H2 could be separated from the products by
regeneration on the Fe3O4/FeO redox pair. As a result, the
yield of aromatics was significantly increased compared to the
current single-pass reaction.103 In this section, other kinds of
reactors including the fluidized bed reactor, plasma reactor, as
well as membrane reactor applied in the MDA reaction are
discussed.
3.1. Fluidized Bed Reactor and Plasma Reactor
Applied in MDA Reaction. Because of rapid deactivation of
catalysts caused by coke formation, some researchers believed
that MDA reaction should be conducted under continuous
catalyst regeneration mode. In this case, the fluidized bed
reactor was introduced in the research.22,104
Xu et al.22 applied a circulating fluidized bed reactor (CFBR)
system (shown in Figure 32) and fluidizable Mo/HZSM-5
Figure 32. Schematic diagram of CFBR: (1) reactor and (2) catalyst
regenerator.22 Reproduced with permission from ref 22. Copyright
2017 Elsevier.
catalyst in the research. This CFBR system allows easy and
continuous regeneration of catalyst in the reaction. This system
has proven to maintain a 4-day test with little fragmentation on
the catalyst. The same research group also applied the CFBR
system to study stability of Mo/HZSM-5 catalyst under CH4−
H2 mode.100 The catalytic performances of the catalyst in this
fluidized bed system were discussed and included in section
2.4.2. In other research, a triple-bed CFBR system (shown in
Figure 33) was proposed to achieve two goals, which are
continuous regeneration of Mo/HZSM-5 and converting
methane to benzene.
Since the C−H bond in the CH4 molecule could be broken
by high energy free electrons, the plasma reactor has been
attracted more attention in the past few years in MDA research.
A packed bed dielectric barrier discharge (DBD) plasma−
catalyst hybrid system was applied by Park to test the Mo/
HZSM-5 catalyst in the MDA reaction.105 The results revealed
that CH4 could be activated by plasma at 773 K, which is much
lower than the conventional reaction temperature (973 K). For
the MDA reaction conducted in the DBD plasma−catalyst
hybrid system at 773 K, the methane conversion rate was 4.9%
and the benzene selectivity was 8.7%. Both methane conversion
rate and selectivity to benzene obtained by the DBD plasma−
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Figure 33. Schematic diagram of a triple-bed CFBR system: (1) CH4

converter and (2−3) catalyst regenerator.100 Reproduced with
permission from ref 100. Copyright 2011 Elsevier.

catalyst hybrid system were lower compared to results obtained

by the fixed bed reactor (methane conversion, 7.8%; benzene
selectivity, 53.9%). A two-stage PFC (plasma-followed-by-
catalyst) reactor was also used to study the MDA process.106
Ni/HZSM-5 catalyst was evaluated in this plasma reactor at 623
K under atmospheric pressure. In the first stage, CH4 was
converted to C2H2 by plasma. C2H2 was then trimerized on Ni/
HZSM-5 in the second stage. Selectivity to aromatics could
achieve 47% over 1 wt % Ni/HZSM-5 catalyst, and CH4
conversion was about 35%. This study showed a promising
opportunity to overcome the thermodynamic barrier in the
MDA reaction by utilizing plasma technology.
3.2. Membrane Reactor Applied in MDA Reaction. Per-
pass conversion is limited by thermodynamics, and conversion
of CH4 is a major obstacle in the MDA process. To overcome
this limit, it is necessary to selectively remove H2 in products
from the reactor during reaction. Both experimental and
simulation studies have been conducted by several
groups.23,24,107,108
A current controlled co-ionic membrane reactor integrated
with an electrochemical BaZrO3-based membrane (shown in
Figure 34) was applied to remove coproduct H2 during the
reaction.23 This membrane exhibits oxide ion and proton
conductivity, and better catalyst stability and higher aromatic
yield were achieved. The promotion effects were due to the
removal of H2 and injection of oxide ions along the whole
reactor. This co-ionic reactor also showed high carbon
efficiencies (80%), thus improved the viability of the
technoeconomic process. In the co-ionic membrane reactor,
the coke content in spent Mo/MCM-22 catalyst at TOS = 45 h
was about 0.5 gcoke/gcatalyst. The coke deposition is much lower
than that of the fixed bed reactor, which is about 0.9 gcoke/
gcatalyst.
Xue et al.109 developed a dense ceramic hydrogen-permeable
membrane reactor (shown in Figure 35) to study MDA
performance. The 6 wt % Mo/HZSM-5 catalyst was coated
around outside of the fiber membrane. The fiber membrane
(La5.5W0.6Mo0.4O11.25−δ, LWM0.4) served to remove H2 to the
core side of the fiber. H2 was swept away by CO2 or Ar flowing
in the interior of the reactor. The results showed that 40−60%
of the H2 were extracted during reaction. The yield of aromatics
could be increased at the beginning of the reaction by ∼50−
70% when compared to reaction conducted in the fixed-bed
reactor. However, because of the removal of hydrogen, 10%
more coke was formed than the fixed-bed reactor.
1784
Figure 34. Current controlled co-ionic membrane reactor. 23
Reproduced with permission from ref 23. Copyright 2016 The
American Association for the Advancement of Science.
Figure 35. Schematic diagram of membrane reactor.109 Reproduced
with permission from ref 109. Copyright 2016 American Chemical
Society.
The hydrogen-permselective palladium membrane reactor
(shown in Figure 36) was developed and applied in MDA
research.110 The inner tube of the reactor was the retentate
side, and the feed gas flowed through it. The outer tube of this
reactor was the permeate side, and Ar sweep gas was used to
recover hydrogen permeated through the membrane. At TOS =
15 h, the yield of benzene obtained by membrane reactor
(2.05%) was much higher than that of the fixed bed reactor
(0.57%). Furthermore, the selectivity to naphthalene was also
significantly suppressed in the membrane reactor compared to
the results obtained by using fixed bed reactor (from 13.4% to
3.0%). During the reaction, an additional amount of H2 was
generated in the retentate side of the reactor. In this case, coke
accumulated on the catalysts was inhibited.
Besides the Mo/HZSM-5 catalyst, Fe©SiO219 catalyst
developed by Bao and coauthors was tested in the hydrogen-
permeable tubular membrane reactor (shown in Figure 37) for
the first time. 111 The hydrogen-permeable membrane
(SrCe0.7Zr0.2Eu0.1O3‑δ) was supported on the surface of the
SrCe0.8Zr0.2O3‑δ tube. The results showed that removing H2
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Industrial & Engineering Chemistry Research
Figure 36. Membrane and catalyst testing system (GC, gas
chromatograph; MFC, mass flow controller; PCV, pressure control
valve; PT, pressure transducer; TC, thermocouple).110 Reproduced
with permission from ref 110. Copyright 2015 Royal Society of
Chemistry.
from nonoxidative methane conversion reaction could result in
a remarkable improvement in CH4 conversion. During the
reaction, a 30% methane conversion rate was achieved, and the
reaction showed 99% selectivity to C2 , benzene, and
naphthalene.
Removal of hydrogen by a hydrogen permeable membrane
could result in accelerated coking on a catalyst, and a well
distributed and continuously feed of oxygen could lead to a
better coking resistance ability of the catalyst.112,113 In this case,
an oxygen-permeable membrane reactor (Figure 38) was
suggested for the MDA reaction.113 The material of the oxygen
transporting membrane is Ba0.5Sr0.5Co0.8Fe0.2O3‑δ (BSCF)
perovskite. Higher yield of aromatics (after 200 min, 30%
higher) were obtained in the membrane reactor than that of a
fixed-bed reactor. Besides higher yield of aromatics, catalyst was
more durable in the membrane reactor. The selectivity to coke
in the fixed-bed reactor was higher than 60%. However, in the
membrane reactor, it was only around 10%.
Figure 37. H2 permeable tubular membrane reactor and experimental setup for nonoxidative CH4 conversion reaction. (A) As-prepared
SrCe0.8Zr0.2O3‑δ membrane tube, (B) SEM image showing the cross-sectional image of membrane tube reactor comprised of SrCe0.7Zr0.2Eu0.1O3‑δ
thin film on the porous SrCe0.8Zr0.2O3‑δ tubular support, and (C) assembly of H2 permeable membrane reactor for nonoxidative CH4 conversion
reaction over the Fe©SiO2 catalyst.111 Reproduced with permission from ref 111. Copyright 2016 John Wiley and Sons.
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Review
Figure 38. MDA in a fixed bed reactor and a membrane reactor.113
Reproduced with permission from ref 113. Copyright 2013 John Wiley
and Sons.
Besides experimental research, the simulation study was also
carried out. Corredor et al.107 published a simulation study of
the MDA reaction in a plug-flow isothermal membrane reactor
model. This simulation was conducted by Aspen Plus using a
CAPE-OPEN to CAPE-OPEN simulator. Kee et al.108
computationally simulated the MDA process that carried out
in H2 removal membrane-coupled packed-bed reactors. The
influence of operating conditions including H2 removal and
operating pressure were studied. The simulation results showed
that, when the pressure increases, the CH4 conversion rate and
C6H6 selectivity decrease and the production rate of C6H6
increases. The research also revealed that when membrane was
coupled with the packed bed reactor, the conversion rate of
methane significantly increased. However, selectivity to
benzene decreased since a higher yield of other undesired
aromatics formed during the reaction.
4. CONCLUSIONS
In the MDA reaction, catalytic performance of Mo-based
catalysts are influenced by several factors. These factors include
the state of the Mo species and structure and acidity of zeolite
supports. The main drawback of Mo-based catalysts was the
severe coke and/or polyaromatics formed on the catalysts.
Coke deposition could block zeolite channels and lead to the
relatively low stability. Since the structure of HZSM-5 zeolite
played a shape-selective role to aromatics, the Mo-based zeolite
catalyst system is still considered as one of the most active
catalysts in MDA research so far.
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In the meantime, novel catalysts such as the Fe©SiO2 catalyst
and GaN nanoparticles showed promising activity and excellent
stability. These novel catalysts may lead to a new research
direction of catalyst preparation. Areas for further research
should focus on increasing life-span of catalysts, development of
novel catalysts, in-depth study of the MDA reaction using
fluidized and membrane reactors, and conduct more computa-
tional analysis to guide the development of the reaction
mechanism.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.iecr.7b04707.
Summaries of the catalytic performance of catalysts in the
MDA reaction (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: mfan@uwyo.edu. Phone: +1 307 766 5633. Fax: +1
307 766 6777.
*E-mail: rchen@fjirsm.ac.cn. Phone: +86 0591 6317 3012.
ORCID
Maohong Fan: 0000-0003-1334-7292
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors thank Dr. Lucia M. Petkovic for her valuable
comments.
■
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1789 DOI: 10.1021/acs.iecr.7b04707

Ind. Eng. Chem. Res. 2018, 57, 1768−1789