Journal of Physics and Chemistry of Solids 73 (2012) 1542–1545

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Journal of Physics and Chemistry of Solids

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Deactivation by coke deposition on the HZSM-5 catalysts

in the methanol-to-hydrocarbon conversion
Ki-Yong Lee, Min-Young Kang, Son-Ki Ihm n
Department of Chemical and Biomolecular Engineering, KAIST, 291 Daehak-ro, Yuseong-gu, Daejeon 305-701, Republic of Korea

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

Available online 11 September 2012 HZSM-5 used to be the main catalyst component for the MTG process of Exxonmobil Co. Catalyst
Keywords: deactivation by coke in methanol-to-hydrocarbon (MTH) over HZSM-5 was studied in a fixed-bed
A. Inorganic compounds reactor by observing the activity and selectivity with time-on-stream at 500 1C and WHSV ¼4.25 h  1.
A. Microporous materials The HZSM-5 with SiO2/Al2O3 ratios of 40 and 280 were synthesized and characterized with XRD,
B. Chemical synthesis N2 adsorption/desorption and NH3-TPD. The used catalysts were investigated by N2 adsorption/desorption,
XRD, elemental analysis (EA) and UV–vis spectroscopy to identify the nature of coke. If the acidity of
HZSM-5 is low (SiO2/Al2O3 ¼ 280), the coke deposited is mainly mono- or bi-aromatic which did not affect
the catalyst activity significantly. On the other hand when the acidity is high (SiO2/Al2O3 ¼ 40), the coke
deposited is polycyclic aromatics with 3 or 4 fused rings which leads to significant deactivation after 24 h.
It is presumed that the coke on the HZSM-5 with low acidity must be located inside the pores and/or in the
framework, since the coke particles without polycyclic aromatics should be small. The deactivation of
HZSM-5 with high acidity is mainly caused by the bulky coke molecules, most probably inducing the
topological blocking of the zeolite pores and channels.
& 2012 Elsevier Ltd. All rights reserved.

1. Introduction in MTH [6,7] and that the deposition of carbonaceous residues on

The methanol-to-hydrocarbon (MTH) process has attracted a
great deal of interest from academic and industrial researchers in
the past few years, since methanol could be simply mass-
produced from natural gas, coal, and biomass. The zeotypes or
acidic zeolites, such as HSAPO-34 and HZSM-5, have been used as
catalysts in the MTH processes [1–3]. The structure of HZSM-5
catalyst having the high coke-resistance contains two perpendi-
cularly intersecting channel systems: the sinusoidal channels
(0.51  0.57 nm) and the straight channels (0.53  0.56 nm). The
free space at the intersections is larger (0.9 nm) and it is believed
that the active sites are located there [4].
During MTH reaction, HZSM-5 catalyst is deactivated by the
buildup of carbonaceous residues (generally termed coke) which
block access of reactant molecules to the active sites [5]. The coke
deposited must be removed by combustion process for the reuse
of catalyst, known as the regeneration. Hence, a large effort has
been devoted to identify the coke formation, location and nature
during methanol conversion on HZSM-5 catalysts. The coke formation
rate is known to be dependent on the reactant composition, reaction
temperature, pore diameter of the zeolite and acid strength [5]. It was
reported that the HZSM-5 with high Si/Al ratio is deactivated slowly
n
Corresponding author. Tel.: þ82 42 350 3915; fax: þ82 42 350 5955.
E-mail address: skihm@kaist.ac.kr (S.-K. Ihm).
HZSM-5 occurs predominantly on its external surface [8–10]. It was
also reported that internal coke formation occurs initially during the
methanol conversion on HZSM-5 [11,12]. Previous studies on coke
formation on HZSM-5 are contradictory, and there is still a contro-
versy. Some reports showed that the catalytic lifetime in MTH is
improved via the generation of secondary mesoporosity within
HZSM-5 [13,14]. Many works were carried out to investigate the
nature of cokes [15,16], and still further works are desirable. In this
work, the role of acidity of HZSM-5 catalyst in the deactivation by
coke deposition during MTH was investigated in terms of the nature
of coke formed.
2. Material and methods
2.1. Preparation of catalysts
The HZSM-5 catalysts were obtained by hydrothermal synthesis
at 170 1C for 3 days in a Teflon-lined autoclave following the
procedures in US Patent 3 702 886 [17]. The molar composition of
the synthesis gel was 0.4Na2O:1SiO2:xAl2O3:0.2 TPABr:38H2O (x¼
40  1, 280  1). The reactants for the synthesis of NaZSM-5 were
colloidal silica sol (Ludox HS-40, Aldrich), aluminum nitrate non-
ahydrate (Junsei Chemical Co., Ltd.), tetrapropylammonium bromide
(TPABr, 98%, Aldrich) and NaOH (Junsei Chemical Co., Ltd.). The
crystalline products were washed and calcined overnight at 550 1C.

0022-3697/$ - see front matter & 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jpcs.2012.09.005
 K.-Y. Lee et al. / Journal of Physics and Chemistry of Solids 73 (2012) 1542–1545 1543

The calcined NaZSM-5 samples were converted to NH4þ forms by

SiO2/Al2O3=40
three times of ion exchanges with 1 M ammonium chloride solution
SiO2/Al2O3=280
and calcined again at 550 1C for conversion to the H þ form.

NH3 desorbed [A.U.]

2.2. Catalysts characterization

Powder X-ray diffraction (XRD) patterns were obtained with

a Rigaku D/MAX-III diffractometer using CuKa radiation (l ¼
1.54173 Å). Data were collected in a continuous scan mode from
51 to 501 of 2y with a 0.011 sampling and 3 1/min scan rate for the
confirmation of crystal structure of the prepared catalysts. BET
surface area and pore volume of the prepared catalysts were
measured by N2 adsorption/desorption using ASAP2010 (Micro-
meritics Inc.). The samples were degassed at 350 1C, and N2
adsorption was carried out at  196 1C. Temperature-programmed
desorption of NH3 (TPD) for the prepared catalysts was carried out
100 200 300 400 500 600
with a conventional flow apparatus (Pulsechemisorb 2705, Micro-
Temperature(°C)
meritics Inc.). 0.05 g of sample was loaded in a U-type tube. Before
adsorption the samples were degassed at 500 1C with He flow of Fig. 1. NH3-TPD profiles of the prepared HZSM-5 catalysts.
20 ml/min for 2 h. After cooling to 100 1C, ammonia was adsorbed
by pulse injection. The temperature of the samples was raised at
the rate of 5 1C/min from 100 1C to 600 1C, and the TCD signal was 100 100
recorded. The coke deposits on the used catalysts were quantified by

elemental analysis using the Flash EA 1112 series of CE Instruments
(Elemental Analyses system, Thermo Finnigan, Italia Flash EA 1112).
The UV–vis spectra of the extracted organic phases were obtained
using a UV–vis spectrophotometer (SHIMADZU UV-2450). In the
first step, the carbonaceous compounds were liberated from the
catalyst by dissolution of the matrix in hydrofluoric acid (Sigma-
Aldrich, 35 wt% solution in water). In the second step, carbon
tetrachloride (Aldrich Chemical Company, Inc., 99þ%) was employed
to extract soluble compounds from the solutions.
2.3. Catalytic activity measurement
The methanol conversion was carried out in a fixed-bed
reactor at 500 1C under atmospheric pressure. Prior to each
reaction, the samples were pretreated in He flow at 550 1C for
2 h and cooled to the reaction temperature. Methanol (Sigma-
Aldrich, Z99.9%) was fed into a reactor by a liquid mass flow
controller (Bronkhorst High-Tech, LIQUID-FLOW series L1) and
the weight hourly space velocity (WHSV) was 4.25 h  1. A homo-
geneous mixture of MeOH (10%) and He (90%) was achieved by
using a pre-heater to vaporize the methanol. All products were
passed through a heated transfer line to a gas chromatograph
with a thermal conductivity detector and a flame ionization
detector (column: HP-PLOT Q, Agilent) in series. After the reac-
tion, the reactor was purged with a He gas flow (50 ml/min) for
3 h at 400 1C to remove organic volatiles.
3. Results and discussion
The HZSM-5 catalysts with SiO2/Al2O3 ratios of 40 and 280 were
prepared and the characteristic of a crystalline MFI structure was
identified from the X-ray diffraction patterns of both catalysts.
The acidity of the prepared catalysts was investigated by NH3-
TPD and the results are shown in Fig. 1. Generally, the NH3-TPD
profile of HZSM-5 zeolite shows two peaks: a low temperature
peak at around 150 1C (weak acid sites) and a high temperature
peak at around 350 1C (strong acid sites). The acidity of the
prepared catalysts increased with increasing Al content (decreas-
ing SiO2/Al2O3 ratio). Since the acid strength is almost the same,
the acidity is comparable to the acid site density in this case.
Methanol conversions and product selectivities for the methanol-
to-hydrocarbon (MTH) reaction over HZSM-5 catalysts with different
Methanol Conversion(%)
80
Product selectivity(%) 90
60
80
C2=~C4= (SiO2/Al2O3=40)
40
C2=~C4= (SiO2/Al2O3=280)
DME (SiO2/Al2O3=40)
20 DME (SiO2/Al2O3=280) 70
Methanol Conversion (SiO2/Al2O3=40)
Methanol Conversion (SiO2/Al2O3=280)
0 0
0 2 8 16 20 24
Time-on-stream(h)
Fig. 2. Methanol conversion and product selectivity in the MTH over HZSM-5
catalysts (SiO2/Al2O3 ¼ 40, 280): WHSV¼ 4.25 h  1, MeOH:He¼ 1:9, and reaction
temperature ¼500 1C.
acidities are presented in Fig. 2. For the HZSM-5 with low acidity
(SiO2/Al2O3 ¼280), methanol conversion was almost 100% and
dimethylether (DME), and intermediate in the MTH reaction, was
not produced during 24 h. The selectivity to light olefins (ethylene,
propylene and butylene) remained at about 80% and catalytic
deactivation was not observed during the reaction. The HZSM-5
with high acidity (SiO2/Al2O3 ¼40), on the other hand, showed that
the catalytic activity decreased after 16 h and that methanol was
mostly dehydrated into DME without further transformation into
hydrocarbons at the time on stream of 24 h although methanol
conversion was 100% and the selectivity to light olefins was more
than 40% during the initial reaction period.
After MTH reaction, the amount of coke deposited on the
catalyst was analyzed using elemental analysis (EA) and listed in
Table 1 together with surface area and pore volume. For the
HZSM-5 with high acidity, the amount of coke formed was 12 wt%
and the surface area and pore volume were significantly
decreased. The decreases in surface area and pore volume could
conceivably be ascribed to coke deposits. In the case of HZSM-5
with low acidity, the amount of coke deposited was 3.3 wt% and
the changes in physical properties were less significant.
To identify the nature of coke formed, the UV–vis absorption
spectra of the organic phase extracted from the HZSM-5 catalysts
used for 24 h in the MTH reaction were obtained and are shown in
Fig. 3. Since the color of a polycyclic aromatic compound varies
1544 K.-Y. Lee et al. / Journal of Physics and Chemistry of Solids 73 (2012) 1542–1545

Table 1 2/Al2O3=40
Physical properties of the fresh and used HZSM-5 catalysts and coke contents
of used catalysts.
SiO2/Al2O3=280 a b
SiO2/ State Surface Pore Carbon

Intensity [A.U.]
Al2O3 area volume (wt%)
(m2/g) (cm3/g) b

Intensity [A.U.]
40 Fresh 449 0.24 –
Useda 20 0.02 12.0b

280 Fresh 472 0.24 –

Useda 346 0.20 3.3b
22 23 24 25 22 23 24 25
a
Reaction condition: WHSV¼4.25 h  1, MeOH:He ¼1:9, TOS ¼24 h, and reac- 2θ 2θ
SiO2/Al2O3=40
tion temperature ¼500 1C.
b
From the elemental analysis. a

5
SiO2/Al2O3=40 10 20 30 40 50
SiO2/Al2O3=280
2θ
4
Fig. 4. XRD patterns of the used HZSM-5 catalysts: (a) SiO2/Al2O3 ¼40 and
(b) SiO2/Al2O3 ¼ 280 (WHSV¼4.25 h  1, MeOH:He¼ 1:9, TOS ¼24 h, and reaction
Absorbance

3 temperature¼ 500 1C).

The effect of this transformation is to alter the relative peak

2 positions and intensities in the XRD patterns [7].
1 over HZSM-5 with high acidity (SiO2/Al2O3 ¼40) were carried out
0 time-on-stream are shown in Fig. 5 with methanol conversion
200 250 300 350 400 450 500
Wavelength (nm)
Fig. 3. UV–vis absorption spectra of the organic phase extracted from the HZSM-5
used for 24 h in the MTH reaction: WHSV¼ 4.25 h  1, MeOH:He¼ 1:9, TOS ¼24 h,
and reaction temperature ¼ 500 1C.
with the number of aromatic rings fused, the UV–vis adsorption
spectra of the extracted organic phases make it possible to
identify the basic structures of polycyclic aromatic compounds
occluded in the pores and intersections [18]. The spectrum of the
organic phase extracted from the HZSM-5 with low acidity
showed a narrow peak over 260–280 nm and two shoulder peaks
over 280–300 nm. The absorption of the organic phases extracted
from the HZSM-5 with high acidity appeared at 260–300 nm,
being similar to that of the low acidity HZSM-5, but appreciable
absorption was still observed even over 350–420 nm. Benzene
and naphthalene showed their absorption peaks over 260–
300 nm. Absorption peak of anthracene and phenanthrene com-
posed of three fused benzene rings appear over 300–400 nm,
while those of pyrene composed of four benzene fused rings
appear above 400 nm [19]. From the UV–vis adsorption spectra,
the coke deposited on HZSM-5 with low acidity is mainly mono-
or bi-aromatic. On the other hand, the coke deposited on the
HZSM-5 with high acidity is polycyclic aromatic with 3 or 4 fused
rings which leads to significant deactivation after 24 h.
The XRD patterns of used HZSM-5 catalysts are shown in Fig. 4.
There was no difference in XRD patterns between fresh and used
HZSM-5 catalysts with SiO2/Al2O3 ratio of 280. However, the XRD
spectrum of used HZSM-5 catalyst with SiO2/Al2O3 ratio of 40
changed slightly at 2y E23–241 compared with fresh catalyst.
It can be suggested that the HZSM-5 catalyst with SiO2/Al2O3 ratio
of 40 undergoes a displacive transformation from monoclinic
to orthorhombic due to the internal coke after MTH reaction.
To elucidate the influence of the coke deposition with time-on-
stream on physical properties of the catalysts, the MTH reactions
under the same reaction conditions for 2, 8, 16 and 20 h at 500 1C.
The pore volumes and coke contents of the used HZSM-5 with
and DME selectivity. The pore volume of the HZSM-5 decreased
with reaction time (coke content). The pore volume of the HZSM-5
used for 2, 8, 16 and 20 h was 0.15, 0.14, 0.05 and 0.03 cm3/g,
respectively. The coke content of the HZSM-5 with the time on
stream of 2, 8, 16 and 20 h was 1.7, 4.8, 9.8 and 11.2 wt%,
respectively. In spite of a large decrease in the pore volume, the
catalytic activity of HZSM-5 did not change significantly until coke
level of the catalyst was up to 9.8 wt%. The catalytic activity started
to decrease after 16 h and the increase in the coke formed turned
into a gradual decline. Methanol conversion and DME selectivity
were about 90% and 20% respectively at the time on stream of 20 h.
The UV–vis absorption spectra of the organic phase extracted
from the high acidic HZSM-5 (SiO2/Al2O3 ¼40) used for 2, 8, 16
and 20 h in the MTH reaction are shown in Fig. 6. The spectrum of
the organic phase extracted from the HZSM-5 used for 2 h
showed a narrow peak over 260–280 nm and two shoulder peaks
over 280–300 nm without any absorption peak at longer wave-
lengths at which the coke formed is mainly mono- or bi-aromatic.
The additional absorption of the organic phase extracted from the
HZSM-5 used for 8 h appeared over 350–420 nm at which the
coke formed is polycyclic aromatic with 3 or 4 fused rings. During
this period (from 2 to 8 h), part of the coke formed must be in the
channel intersections not only because the sizes of polycyclic
aromatics are greater than those of the apertures of the channels
of HZSM-5 but also because most of the soluble coke molecules
are too volatile and too weakly basic to be located on the outer
surface. This is quite obvious since pyrene have a boiling point
below the reaction temperature (the boiling point of naphthalene,
anthracene and pyrene is 218, 340 and 404 1C, respectively).
The spectrum of the organic phase extracted from the HZSM-5
used for 16 h showed the absorption peak over 350–420 nm more
clearly; increasing the intensity of the peak over 350–420 nm
increased the level of coke formed in the channel intersections.
The intensity of absorption peak was not increased significantly
 K.-Y. Lee et al. / Journal of Physics and Chemistry of Solids 73 (2012) 1542–1545 1545

12 100
0.25 100
Coke content
10 Pore volume of the catalyst
Methanol conversion 80

Methanol Conversion(%)
0.20 DME selectivity

Pore volume(cm3/g)
90

Coke content(wt%)

DME selectivity(%)
8
0.15 60
6
80
0.10 40
4

0.05 70 20
2

0.00 0 0 0
0 2 8 16 20 24
Time-on-stream (h)

Fig. 5. Methanol conversion, DME selectivity, coke content and pore volume of the HZSM-5 catalyst (SiO2/Al2O3 ¼ 40) in the MTH reaction with time-on-stream:
WHSV¼ 4.25 h  1, MeOH:He¼ 1:9, and reaction temperature ¼500 1C.

5 deactivation after 24 h. It is presumed that the coke on the

HZSM-5 with low acidity must be located inside the pores and/or
TOS: 2h
TOS: 8h in the framework, since the coke particles without polycyclic
4 TOS: 16h aromatics should be small. The deactivation of HZSM-5 with high
TOS: 20h acidity is mainly caused by the bulky coke molecules, most probably
TOS: 24h
inducing the topological blocking of the zeolite pores and channels.
Absorbancce

Acknowledgments
2
This research was supported by The Basic Science Research
Program through the National Research Foundation of Korea
1 (NRF) funded by the Ministry of Education, Science and Technol-
ogy (2012R1A1A2000922).

0
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