Journal of Oleo Science

Copyright ©2017 by Japan Oil Chemists’ Society

doi : 10.5650/jos.ess17026
J. Oleo Sci. 66, (9) 1029-1039 (2017)

Catalytic Ethanol Dehydration to Ethylene over

Nanocrystalline χ- and γ-Al2O3 Catalysts
Jakrapan Janlamool and Bunjerd Jongsomjit＊
Center of Excellence on Catalysis and Catalytic Reaction Engineering, Department of Chemical Engineering, Faculty of Engineering,
Chulalongkorn University, Bangkok 10330, THAILAND

Abstract: The study is aimed to investigate the combination of nanocrystalline γ- and χ- alumina that
displays the attractive chemical and physical properties for the catalytic dehydration of ethanol. The
correlation between the acid density and ethanol conversion was observed. The high acid density apparently
results in high catalytic activity, especially for the equally mixed γ- and χ- phase alumina (G50C50). In order
to obtain a better understanding on how different catalysts would affect the ethylene yield, one of the most
powerful techniques such as X-ray photoelectron spectroscopy (XPS) was performed. Hence, the different O
1s surface atoms can be identified and divided into three types including lattice oxygen (O, 530.7 eV),
surface hydroxyl (OH, 532.1 eV) and lattice water (H2O, 532.9 eV). It was remarkably found that the large
amount of O 1s surface atoms in lattice water can result in increased ethylene yield. In summary, the
appearance of metastable χ-alumina structure exhibited better catalytic activity and ethylene yield than γ-
alumina. Thus, the introduction of metastable χ- alumina structure into γ- alumina enhanced catalytic
activity and ethylene yield. As the result, it was found that the G50C50 catalyst exhibits the ethylene yield
(80%) at the lowest reaction temperature ca. 250℃ among other catalysts.

Key words: ethanol dehydration, XPS analysis, solvothermal method, mixed phase alumina

1 Introduction character2, 3）. However, the relationship between catalytic

At present, ethylene as one of the most important
olefins, is increasingly attracting more attention. It has
been used as the major feedstock in many petrochemical
industries. In general, ethylene is mainly produced by
thermal cracking of naphtha. Many efforts have been done
to explore an alternative route to produce ethylene from
other carbon resources using cleaner technology. The
biomass is considered as one of the most important renew-
able energy resources. The fermentation of biomass is
famous as one of the most powerful technologies that can
be applied to produce bio-ethanol. It has been well known
that the advantage of renewable biomass is that the
biomass can be converted to green bio-ethanol. The use of
bio-ethanol to ethylene has greater development potential
and broad application prospects. Ethanol can be dehydrat-
ed through intramolecular route to produce ethylene or via
intermolecular pathway to obtain diethyl ether（DEE）1）.
Many studies have been investigated on the correlation
between the catalyst properties and catalytic performances
in ethanol dehydration. The catalytic ethanol dehydration
has been well known that using solid catalysts with acidic
activity and the characteristic of acid type, which is evalu-
ated by NH3-TPD, is unclear. Nowadays, the most widely
used catalyst in this application is still γ-Al2O31, 4）.Although,
some other catalysts such as zeolite5, 6）, heteropolyacid7）,
transition metal oxides8）, acid carbon9）and montmorillonite
clays10）are also investigated.
Recently, the advanced solid materials have been attrac-
tive due to their structures that are organized into na-
noscale. The nanoscale HZSM-5 zeolite catalyst exhibits
better catalytic stability and selectivity for ethylene during
ethanol dehydration than microscale HZSM-5 zeolite cata-
lyst11）. Moreover, the activated alumina-based catalyst has
good stability, and the purity of produced ethylene product
based on such a catalyst is also high. However, the concen-
tration of raw material of ethanol should not be too low, or
it can make the ethanol dehydration reaction, which re-
quires higher temperature and lower space velocity, that in
turn leads to higher energy consumption. In addition, the
nanocrystalline γ-Al2O3 has been well known as a bifunc-
tional oxide comprising acidic and basic sites12）. It is the
most widely used inert carrier for metal catalysts in hetero-

＊
Correspondence to: Bunjerd Jongsomjit, Center of Excellence on Catalysis and Catalytic Reaction Engineering, Department of
Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok 10330, THAILAND
E-mail: bunjerd.j@chula.ac.th
Accepted April 11, 2017 (received for review February 2, 2017)
Journal of Oleo Science ISSN 1345-8957 print / ISSN 1347-3352 online
http://www.jstage.jst.go.jp/browse/jos/  http://mc.manusriptcentral.com/jjocs

1029
 J. Janlamool and B. Jongsomjit
geneous catalysis because of its fine particle size, high
surface area, surface catalytic activity, high mechanical re-
sistance, excellent thermal stability, and wide range of
chemical, physical, and catalytic properties13−15）. Several
studies attempt to synthesize alumina that has uniform
mesoporous distribution. Besides, the surface area and
pore structure also play important roles in the catalytic ac-
tivity. The nanocrystalline Al2O3 has been generally synthe-
sized by the sol-gel16）, precipitation17）, flame spray pyroly-
sis 18）and solvothermal 13−15）methods. The solvothermal
synthesis attracts the most attention because this applica-
tion gives products with small uniform morphology, homo-
geneous chemical composition, and narrow size distribu-
tion19）.
The nanocrystalline Al 2 O 3 having mixed γ- and
χ-crystalline phases, which is prepared from the thermal
decomposition of aluminium isopropoxide（AIP）in organic
solvent exhibits high thermal stability. The nanocrystalline
χ-Al2O3 is one of the metastable polymorphs based on the
hexagonal close packing（hcp）of the oxygen atom20）. The
previous studies show that highly stable nanocrystalline
Al2O3 with mixed γ- and χ-crystalline phases prepared by
the solvothermal method resulted in interesting outcomes.
It can be employed as catalyst supports in many catalytic
reactions such as CO oxidation21）, and propane oxidation22）.
The goal of this research was to present the outstanding
properties of the nanocrystalline alumina comprising of
mixed γ- and χ-crystalline phases for catalytic behaviors via
vapor phase ethanol dehydration. The mixed γ- and
χ-crystalline phase alumina was prepared using the solvo-
thermal method. The results obtained from catalytic be-
haviors are used to evaluate the role of the different char-
acteristics on the overall reaction activity and product
selectivity.
2 Experimental
2.1 Materials
Chemicals as follows were used; aluminium isopropoxide
98％（Aldrich）, methanol（commercial grad）, 1-butanol
（Fischer scientific）, toluene（ Fischer scientific）, and
99.9％ ethanol（VWRPROLABO） .
Table 1　Detail of different alumina catalysts and nomenclatures.
Phase % Dissolved solvent (ml)
Catalysts
χ- phases γ- phases Toluene
G100 0 100 0 100
G70C30 30 70 30
G50C50 50 50 50
C100 100 0 100
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J. Oleo Sci. 66, (9) 1029-1039 (2017)
2.2 Nanocrystalline aluminapreparation
Nanocrystalline alumina having different chi and gamma
phases（ Table 1）were prepared by the solvothermal
method according to the procedure described by Meephoka
et al.21）. 25 g of aluminium isopropoxide（AIP, 25g）was dis-
solved in 100 ml with different ratios of mixed solvent
（butanol and toluene as shown in Table 1）in a test tube.
The autoclave was purged with nitrogen after that it was
heated up to the desired temperature（300℃）at the rate of
2.5℃ min−1 and the temperature was held for 2 h. The
precipitated powder was collected after the autoclave had
been cooled to room temperature. The white powder was
repeatedly washed with methanol and dried at room tem-
perature. The synthesized alumina was subsequently cal-
cined with a heating rate of 10℃/min at the temperature
raised to 600℃ and held on that temperature for 6 h using
an air flow rate of 100 Ml/min. The obtained alumina cata-
lysts consisting of single γ-phase, 30％, 50％ χ-phase and
single χ-phase are denoted as G100, G70C30, G50C50 and
C100, respectively as confirmed by the XRD measurement.
2.3 Catalyst characterization and reaction test
The prepared alumina catalysts were characterized by
several techniques as follows;
2.3.1 Surface area and porosity
N 2 physisorption（N 2 adsorption at −196℃ in a Mi-
cromeritics ASPS 2020）was performed to determine
surface areas, pore size and adsorption isotherm of the dif-
ferent alumina catalysts.
2.3.2 X-ray diffraction（XRD）
XRD was used to determine the phase composition of
the different mixed phase alumina using Bruker D8
Advance X-ray diffractometer with Cu-Kα radiation（λ＝
1.54056 Å）with Ni filter in the 2θ range of 20-80 degrees
with resolution of 0.04°.
2.3.3 Scanning electron microscopy（SEM）and dispersive
X-ray spectroscopy（EDX）
SEM（JEOL mode JSM-5800LV）and EDX （Link Isis Series
300） were used to determine the morphology and elemental
distribution of the catalyst particles. The morphology of
alumina samples was observed using JEOL-JEM 200CX
transmission electron microscope operated at 100 kV.
the gap between the test
tube and autoclave wall (ml)
1-Butanol Toluene 1-Butanol
0 30
70 9 21
50 15 15
0 30 0
 Catalytic Ethanol Dehydration to Ethylene over Nanocrystalline χ- and γ-Al2O3 Catalysts
2.3.4 Ammonia temperature programmed desorption（NH3-
TPD）
The acidity of alumina was investigated by temperature
programmed desorption of ammonia using a Micromeritics
Chemisorp 2750 with a computer. First, 0.10 g of the
alumina sample was placed in a glass tube and pretreated
at 500℃ with flowing of helium for 1 h. Then, the sample
was saturated with 15％ NH3 in He at room temperature.
After saturation, the physisorbed ammonia was desorbed
in a He flow for 3 h. Then, the sample was heated from 30
to 500℃ with a heating rate of 10℃/min. The effluent
amount of ammonia was measured via TCD signal as a
function of time.
2.3.5 X-ray photoelectron spectroscopy （XPS）
The XPS analysis was performed originally using an
AMICUS spectrometer equipped with a Mg Kα X-ray radia-
tion. For a typical analysis, the source was operated at
voltage of 15 kV and current of 12 mA. The pressure in the
analysis chamber was less than 10−5 Pa.
Ethanol dehydration was performed to determine the
overall activity and desired product yield of the catalysts.
Typically, 0.05 g of catalyst was packed in the middle of the
glass microreactor. The catalyst sample was pre-treated in
situ in flowing Ar（50 mL/min）at 200℃ for 1 h prior to
ethanol dehydration. Ethanol was introduced into the
reactor by bubbling Ar as a carrier gas through the satura-
tor, while the temperature was kept at 45℃ to maintain the
partial pressure and hence the composition of the feed. A
flow rate of Ar was kept at 50 mL/min with WHSV of 8.4
［g Ethanol ×（g cat ×h）−1 ］. The reaction temperature was
ranged between 200 to 400℃ at atmospheric pressure. The
product gas samples were analyzed by gas chromatography
［Flame ionization detector（FID） , where the DB-5 capillary
column was used for separation of ethanol（C 2H 5OH）,
ethylene（C2H4）, diethyl ether（C2H5OC2H5）, and acetalde-
hyde （C2H4O）］.
3 Results and discussion
3.1 Characteristics
The physical properties of the catalysts were obtained
from the N2 physisorption and XRD data. The compositions
of γ- and χ-phases of nanocrystalline alumina were pro-
duced depending on the different types and amounts of
solvents, such as 1-butanol and toluene employed during
the synthesis. In fact, the mixed γ- and χ-phases of nano-
crystalline alumina was controllably obtained by mixing
solvents between 1-butanol and toluene with desirable
composition as shown in Table 1. The phase identification
of all catalysts was carried out on the basis of data obtained
from XRD measurement as shown in Fig. 1. The G100 cata-
lyst, exhibits the diffraction peak at 32 37, 39, 45, 61 and
66°as proven that G100 catalyst is the single γ-phase.
J. Oleo Sci. 66, (9) 1029-1039 (2017)
Fig. 1　XRD patterns of all prepared catalysts.
Moreover, with the use of mixed solvent between toluene
and 1-butanol, the characteristic diffraction peak of
χ-phase nanocrystalline alumina was remarkably appeared
at 43°. Certainly, the higher intensity of peak area at 43°
can be attributed to the increase of χ-phase present in the
catalysts. In addition, the γ- and χ-phase compositions of
alumina catalysts were determined by the area of charac-
teristic peak at 43°from the calibration curve obtaining
from the XRD patterns of the physical mixture between
single γ- and χ-phase with different contents according to
Meephoka et al.21）
The effect of phase composition on the pore size and
pore size distribution of catalysts measured by the nitrogen
adsorption-desorption is shown in Figs. 2a and 2b. The
isotherms of all catalysts are in the classical shape of the
typical Type IV isotherms that refer to mesoporous materi-
als as described by the IUPAC. As seen in Fig. 2a, the iso-
therms of the G70C30, G50C50, and C100 catalysts reveal
the H1 hysteresis loops occurred at a relative pressure
range（P/P0） of 0.55 – 0.95. The H1 hysteresis loop is often
associated with porous materials indicating a broad pore
size distribution with a uniform cylindrical-like pore. In the
contrary, the isotherm of G100 catalyst was quite different
indicating that the H3 hysteresis loop does not exhibit any
limiting adsorption at high relative pressure. This behavior
can be for instance caused by the existence of non-rigid
aggregation of wrinkled sheet-like particles or agglomera-
tion of slit-shaped pores. The pore size distribution present
here confirms isotherm assertion and mesoporous struc-
ture for all prepared catalysts as seen in Fig. 2b. The struc-
tural parameters of all alumina catalysts derived from these
isotherms are summarized in Table 2. The BET surface
area of the catalysts decreased from 257 to136 m2/g with
the larger quantity of χ-phase being present from 0 to
100％, whereas the average pore diameter was rather
similar for the different catalysts.
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 J. Janlamool and B. Jongsomjit

(a) (a)

(b) (b)

Fig. 2　N2 physisorption profiles of all prepared catalysts (c)

（a）adsorption-desorption isotherm and（b）pore
size distribution profiles.

Table 2　B ET surface area, pore volume and pore

diameter of all prepared catalysts.
ABET Vp DBJH
Catalysts
(m2/g) (cm3/g) (nm)
G100 257 0.84 8.27
G70C30 254 0.87 8.19
G50C50 168 0.37 5.46
C100 137 0.55 10.42

The SEM images of prepared catalysts containing the
single γ-phase（ G100）, the mixed-phase（ G50C50）and
χ-phase（C100）are shown in Figs. 3a-3c, respectively. It
can be observed that the catalyst particles are the second-
ary agglomerated catalyst particles of the prepared single
γ-phase and single χ-phase alumina resulting in the pres-
ence of large micron sized granules.
It is well known that the acidity on the surface of
alumina catalysts importantly influences on their catalytic
properties. The acidity and acid strength were investigated
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J. Oleo Sci. 66, (9) 1029-1039 (2017)
Fig. 3　SEM micrographs of prepared pure γ- phase and
χ-phase alumina catalysts（a）G100,（b）G50C50,
（c）C100.
using the temperature-programmed desorption of NH 3
（NH 3-TPD）. The bimodal desorption peaks obviously
reveal that the catalyst samples occupy a heterogeneous
distribution of two different strength types of acid sites.
Two distinguish desorption peaks are according to the
temperature range between 40 to 250 and 250 to 500℃ as
 Catalytic Ethanol Dehydration to Ethylene over Nanocrystalline χ- and γ-Al2O3 Catalysts

acid sites determined either per mass of catalysts or per

Fig. 4　NH3-TPD profiles of all prepared catalysts.
seen in Fig. 4. This can be generally assigned to the overlap
of two desorption steps of weak acid sites and moderate to
strong acid sites. The weak acid sites are probably defined
as Lewis acid site on aluminum oxide at lower tempera-
ture1）. It was found that the fraction of weak acid sites for
all catalysts was ranged between 22.5 to 36.4％. On the
contrary, the moderate to strong mode of interaction is
perhaps defined as the Brønsted acid sites at higher tem-
perature1）. However, the identity of acid type, which was
evaluated by NH3-TPD, was unclear. The total amount of
surface area is practically equal for all catalysts as given in
Table 3. The total acid sites for all catalysts were ranged
from 804 to 1,332 μmol NH 3/g. It can be observed that
mainly the acid sites distribution was consistent upon the
moderate to strong acid sites. In addition, if the NH3 de-
sorption data are expressed in per unit surface area, the
density of surface acid sites for all alumina catalysts will
approximately range between 4.4 to 7.7 μmol NH3/m2. The
G70C30 catalyst exhibited the highest concentration of the
acid sites at 1,332 μmol NH3/g, while the G50C50 catalyst
displayed the highest acid density on the surface of the
catalyst at 7.7 μmol NH3/m2. This crucial characteristic will
be used to explain the catalytic behaviors for all catalysts
during ethanol dehydration reaction.
3.2 Ethanol dehydration reaction
In order to determine the catalytic behaviors of all pre-
pared catalysts, the conversion of ethanol and the yield of
products such as ethylene, diethyl ether and acetaldehyde
as a function of temperature were investigated in vapor
phase ethanol dehydration. The experiment was performed
with the same catalyst weight. The dehydration activity is
already significant at ca. 200℃ and total at 400℃ as dis-
played in Table 4. Typically, ethanol conversion increases
as the reaction temperature is raised. The obtained cata-
lytic activity for all catalysts can be achieved completely
for ethanol conversion at 300℃. The resulting conversions

Table 3　NH3 TPD analysis of all prepared catalysts.

Acidity (µmol NH3/g) Acid site density (µmol NH3/m2)
Catalysts Moderate to Total acid Moderate to
Weak Weak Total
Strong site Strong
G100 393.82 743.17 1136.99 1.53 2.89 4.42
G70C30 533.08 799.31 1332.39 2.09 3.15 5.24
G50C50 356.53 936.36 1292.89 2.12 5.58 7.70
C100 180.80 623.22 804.02 1.32 4.55 5.87

Table 4　Conversion and reaction rate of ethanol dehydration for all prepared catalysts.
Rate of ethanol consumption
Ethanol Conversion (%)
Temperature (℃) (gethanol×(gcat×h)–1)
G100 G70C30 G50C50 C100 G100 G70C30 G50C50 C100
200 29.3 43.4 47.0 40.0 2.5 3.7 3.9 3.4
225 50.4 54.2 68.2 67.0 4.2 4.6 5.7 5.6
250 70.7 72.6 87.3 83.7 5.9 6.1 7.3 7.0
275 86.6 86.5 97.2 95.1 7.3 7.3 8.2 8.0
300 97.0 96.2 100.0 99.5 8.2 8.1 8.4 8.4
350 100.0 100.0 100.0 100.0 8.4 8.4 8.4 8.4
400 100.0 100.0 100.0 100.0 8.4 8.4 8.4 8.4

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J. Oleo Sci. 66, (9) 1029-1039 (2017)
 J. Janlamool and B. Jongsomjit
were ranged between 96.2 to 100％ in accordance with the
−1
ethanol consumption rate of 8.1 to 8.4 （gEthanol×（gcat×h） ） ,
respectively. The catalytic activity decreased in the order:
G50C50＞C100＞G70C30＞G100 during the reaction tem-
perature around 200 to 300℃. Moreover, it can be observed
that the catalytic activity of the mixed of γ- and χ-alumina
（G70C30 and G50C50）and single χ-phase alumina（C100）
exhibited remarkably higher catalytic conversion than the
single γ-phase alumina （G100） at the temperature of 200℃.
During the reaction temperature between 225 to 275℃, it
was attractively observed that G50C50 and C100 still
present distinctly high catalytic conversion, whereas
G70C30 was not significantly different in the catalytic ac-
tivity with G100. In a number of researches, they were ob-
served that the acidity over solid catalysts predominantly
plays an important role on alcoholic dehydration. The
presence of strong acid sites on alumina catalysts increases
the alcoholic conversion14, 23, 24）. The result indicated that
the dehydration activity was independent of the amount of
acid sites on the catalyst. Evidently, this is consequence of
an effect of phase composition on alumina catalysts as
being observed from the result that C100 exhibits higher
catalytic activity thanG100 in spite of its lower acidity.
Moreover, the effect of different morphologies on the phys-
icochemical, surface and catalytic properties of γ-alumina
was also explained25）. Interestingly, this catalytic observa-
tion displayed the ethanol conversions and reaction rate
（μmol NH3/m2）
related to the acid density10） as mentioned in
Table 3. The obtained highest activity of G50C50 was in ac-
cordance with the largest total acid density （7.7 μmol NH3/
m2）, while the lowest activity of G100 was corresponding
to the least total acid density（4.4 μmol NH3/m2）. The im-
portant factor is difficult to understand, while the mecha-
nistic detail of ethylene formation remains unclear. In a
number of experiments, it was demonstrated that the eth-
Scheme 1　The conceptual pathway for ethanol conversion.
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J. Oleo Sci. 66, (9) 1029-1039 (2017)
ylene and diethyl ether formation depends on acidity. The
catalytic process may occur via two reaction pathways.
One possible pathway includes diethyl ether acts as a reac-
tion intermediate, which is subsequently decomposed to
ethylene and ethanol26, 27）as seen in Scheme 1. A bimolecu-
lar nucleophilic substitution mechanism is preferred with
two adjacent ethanol molecules which probably co-adsorb
on two nearby neighboring sites and react to form an
ethanol dimeric species（diethyl ether） at low temperature.
The shorter distances between two nearby neighboring
acid sites（high acid density）probably lead to rapidly react
to form diethyl ether as seen in Scheme 1. This rationale
can be used to clarify the fact that why diethyl ether selec-
tivity is dominant at low temperature5, 10）.
Ethanol conversion can be catalyzed by acidic or basic
site, therefore the yield of desired products can be easily
related to the characteristics of the surface. Besides, the
measurement of elemental composition on the catalyst
surface such as XPS is famous as one of the most powerful
techniques that can be also applied to obtain the informa-
tion of the oxidation state and chemical environment of the
elements on the surface of the catalyst. The XPS analysis,
that has the depth of ca. 10 Å, convinces the external
surface elemental concentrations influencing on the cata-
lytic activity. The XPS data for all alumina catalysts are
given in Table 5. The Al 2p and O 1s peaks were detected
at the binding energy between 74.10 to 75.05 eV and
531.00 to 531.95 eV, respectively. As seen from XPS
results, the atomic ratio of Al 2p over O 1s is slightly lower
than the expected composition of Al2O3, which has the
value of 0.67. It was observed that the atomic ratios of Al
2p over O 1s were ranged from 0.478 to 0.530. Moreover,
this ratio slightly decreased with increasing the quantity of
χ-phase. This reason becomes apparent from the possessed
defect spinel lattices, which are slightly tetragonal distort-
 Catalytic Ethanol Dehydration to Ethylene over Nanocrystalline χ- and γ-Al2O3 Catalysts

Table 5　XPS analysis of all prepared catalysts.

Atomic Atomic O 1s peak area fraction O 1s atomic concentration
BE for Al BE for O
Catalysts concentration (%) ratio (%O 1s) (%)
2p(eV) 1s(eV)
Al 2p O 1s Al/O H 2O OH O H 2O OH O
G100 74.10 531.00 34.61 65.39 0.530 0.023 0.203 0.774 1.52 13.28 50.59
G70C30 74.30 531.70 34.37 65.63 0.524 0.146 0.477 0.378 9.56 31.29 24.79
G50C50 75.05 531.95 32.95 67.05 0.491 0.226 0.518 0.256 15.14 34.74 17.17
C100 74.90 531.80 32.36 67.64 0.478 0.205 0.457 0.338 13.86 30.93 22.85

Scheme 2　The conceptual pathway for acid site formation on alumina surface by dehydroxylation process1）.

ed that can be pronounced for γ-alumina25）. Hexagonal
χ-alumina seems to possess a layer structure. The arrange-
ment of anions inherited from gibbsite, whereas the alumi-
num cations occupy octahedral sites within the hexagonal
oxygen layer28）.
In principle, the transition alumina generally from alumi-
num monohydroxide and trihydroxide. As the dehydration
process of transition alumina in air takes place, the loss of
water by desorption of physisorbed water or by condensa-
tion of hydroxyl group occurs. The dehydroxylation condi-
tion predominantly presents that the condensation of two
nearby surface hydroxyls forms water molecule on the
surface during the formation of alumina catalysts as seen
in Scheme 21）.
As mentioned above, the O 1s spectra show the presence
of three different oxygen species. The spectra analysis of
XPS core level spectra focusing on O 1s was used to identi-
fy the oxygen species on the surface of all alumina catalysts
as seen in Figs. 5a-5d. The deconvolution of the O 1s
spectra, separated and fitted into three signals can be gen-
erally attributed to the different species of atomic oxygen
such as H 2O, OH and O on the surface. Normally, the
crystal structure of corundum has lattice oxygen（O）,
which is in the form of aluminium oxide in accordance with
binding energy of 530.7 eV 29）. Besides, the corundum
structure of alumina contains O 1s peak including surface
hydroxyl（OH）and lattice water（ H 2O）corresponded to
532.1 and 532.9 eV, respectively. The atomic concentra-
tions of each O 1s species for all catalysts were fitted and
determined as mentioned in Table 5. This result presents
J. Oleo Sci. 66, (9) 1029-1039 (2017)
that the G100 catalyst exhibited the highest area fraction
of the lattice oxygen about 77.4％ from the total atomic
oxygen, while the G50C50 catalyst displayed the maximum
value of the lattice water ca. 22.6％ from the total atomic
oxygen.
The alumina catalysts predominantly lead to the forma-
tion of ethylene and diethyl ether either with minor
amount of acetaldehyde for ethanol dehydration. The
process involves the unimolecular dehydration of ethanol
leading to ethylene formation, while the bimolecular reac-
tion produces diethyl ether. The yield towards ethylene in-
creased with rising reaction temperature, while the yield
towards diethyl ether apparently decreased（Table 6）. At
low temperature, ethanol dehydration is predominantly a
bimolecular reaction whilst the unimolecular reaction route
prevails at high temperature30）. On the contrary, the mech-
anism of ethylene formation has been expected from the
decomposition of diethyl ether at higher temperature31, 32）.
The yield towards ethylene reaches around 88.4 to 97.9％
at 300℃. The obtained yield of ethylene for all catalysts
was approximately completed at the reaction temperature
range between 300 to 350℃. It decreased in the following
order: G50C50＞C100＞G70C30＞G100 as observed at the
reaction temperature between 200 to 300℃. This result
can likely be illustrated as the dehydration of ethanol to
ethylene corresponded to the amount of lattice water
（Brønsted acid）on the surface, which was evaluated from
the O 1s core level spectra as shown in Table 5. The H2O
fraction decreased in the following order: G50C50 （22.6％）
＞ C100（20.5％）＞ G70C30（14.6％）＞ G100（2.3％）. The
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 J. Janlamool and B. Jongsomjit

(a) (c)

(b) (d)

Fig. 5　XPS analysis for O 1s spectra of all prepared catalysts（a）G100,（b）G70C30,（c）G50C50,（d）

C100.

Table 6　Yield to ethylene, diethyl ether and acetaldehyde of ethanol dehydration for all prepared catalysts.
Temperature Ethylene yield (%) Diethyl ether yield (%) Acetaldehyde yield (%)
(℃) G100 G70C30 G50C50 C100 G100 G70C30 G50C50 C100 G100 G70C30 G50C50 C100
200 7.18 18.86 25.12 19.61 18.26 22.94 20.29 19.04 3.86 1.60 1.60 1.35
225 26.50 40.22 54.52 51.71 19.08 11.46 11.48 12.46 4.82 2.53 2.20 2.83
250 54.04 62.52 78.12 75.85 10.28 6.13 5.66 3.83 6.38 3.95 3.52 4.03
275 75.71 78.72 91.08 89.85 2.67 2.66 0.73 0.74 8.22 5.11 5.39 4.51
300 88.35 91.24 97.92 95.93 0.71 0.46 0.00 0.05 7.94 4.50 2.08 3.52
350 97.99 99.09 99.50 98.72 0.00 0.00 0.00 0.00 2.01 0.91 0.50 1.28
400 99.55 99.58 99.71 99.61 0.00 0.00 0.00 0.00 0.45 0.42 0.29 0.39

predominant concentration of lattice water on the surface
of G50C50 was received while the highest efficient yield of
ethylene was detected. This relation is in good agreement
with the Brønsted acid, that being active sites as the direct
conversion of ethanol into ethylene via elimination reac-
tion8）. Recently, the appearance of lattice water in hydrated
AgPW salts plays important role in generation of protons,
which needed for an acidic type reaction 33）. Moreover, a
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J. Oleo Sci. 66, (9) 1029-1039 (2017)
moderate surface acid site of ZSM-5 seems to be suitable
for bioethanol to ethylene reaction34）. In addition, C100 has
a higher yield of ethylene than that of G100. This attractive
observation is an effect of phase composition on alumina
catalysts. Moreover, the possible pathway including diethyl
ether formation and decomposition leads to ethylene pro-
duction as mentioned before. The higher efficiency of
diethyl ether formation probably took place to higher eth-
 Catalytic Ethanol Dehydration to Ethylene over Nanocrystalline χ- and γ-Al2O3 Catalysts
ylene formation rate.
The formation of diethyl ether begins around 18.3 to
22.9％ at 200℃（Table 6）. The obtained yield of diethyl
ether for all catalysts was absolutely disappeared at the re-
action temperature of 300℃. It decreased in the following
order: G100＞G70C30＞C100＞G50C50during the reaction
temperature between 200 to 300℃. The yield of diethyl
ether is disproportional to the yield of ethylene. The
highest ethylene yield of G50C50 was obtained, while the
lowest efficient yield of diethyl ether was found. The for-
mation towards acetaldehyde can be observed at the reac-
tion temperature around 200 to 350℃. It decreased in the
following order: G100＞G70C30＞C100＞G50C50. More-
over, the yield of acetaldehyde from the mixed phase of γ-
and χ-alumina（G70C30 and G50C50）and single χ-phases
alumina（C100） remarkably displayed the low yield at 1.6％,
while the single γ-phase alumina（G100）exhibited 3.9％ at
the reaction temperature of 200℃. This evidence can be
alternatively used to suggest that the appearance of
χ-phases promoted the inhibition of dehydrogenation reac-
tion. Nevertheless, the suitable temperature of the acetal-
dehyde formation was seen around 275℃. The basic cata-
lysts are responsible for the dehydrogenation of ethanol to
produce acetaldehyde35）.
It should be noted that the appearance of metastable
χ-alumina structure based on hexagonal close packing
（hcp）exhibited better catalytic activity and ethylene yield
than γ-alumina with the cubic close packing（ ccp）.
However, to compare the performance for ethylene pro-
duction, the ethylene yield at 80％ is considered for this
framework alumina catalyst. Thus, the plot of ethylene
yield as a function of temperature was shown in Fig. 6. For
the reaction temperature at 200℃, the ethylene yield of
G50C50 is 3.5, 2.7 and 2.6 times higher than that of G100,
C100 and G70C30, respectively. In addition, the tempera-
ture at which ethylene yield reaches at 80％ is designated
as T80. The obtained T of G50C50, C100, G70C30 and G100
catalysts is 252, 257, 277 and 284℃, respectively. It indi-
cated that the G50C50 distinctly exhibits the best perfor-
mance in ethylene production, even at the reaction tem-
perature lower than 300℃.
4 Conclusion
In summary, the combination of nanocrystalline γ- and
χ-alumina can be attractively used for catalytic dehydra-
tion of ethanol with distinct chemical and physical proper-
ties from single γ- and χ-phase alumina. The correlation
between ethanol conversion and acid density of the cata-
lysts suggested that the possible pathway includes diethyl
ether as a reaction intermediate, which is continually de-
composed to ethylene at low temperature. The relationship
between ethylene yield and H2O on surface as observed
J. Oleo Sci. 66, (9) 1029-1039 (2017)
Fig. 6　Ethylene yield of all prepared alumina catalysts.
from XPS analysis is crucial. The effect of phase composi-
tion and crystallographic orientation on alumina displays
the distinct activity of acid site. The appearance of meta-
stable χ-alumina structure based on hexagonal close
packing（hcp）exhibits better catalytic conversion and eth-
ylene yield than γ-alumina based on cubic close packing
（ccp）, in spite of its lower acidity. The resulting catalytic
activity in ethanol dehydration was dependent on the
sample acidity. This behavior can be explained by the com-
bination of samples acid density and surface adsorbed
water. This work highlights on both adsorbed water and
acid density that must be considered in the evaluation of
the overall activity of the catalysts.
Acknowledgement
The authors thank the Royal Golden Jubilee Ph.D. schol-
arship from the Thailand Research Fund, Grant for Inter-
national Research Integration: Chula Research Scholar,
Ratchadaphiseksomphot Endowment Fund, Grant for Re-
search: Government Budget, Chulalongkorn University
（2017）, and the National Research Council of Thailand
（NRCT） for the financial support of this project.
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