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Ultrasonics Sonochemistry 33 (2016) 150163

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Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultson

CO2-enhanced dehydrogenation of ethane over sonochemically


synthesized Cr/clinoptilolite-ZrO2 nanocatalyst: Effects of ultrasound
irradiation and ZrO2 loading on catalytic activity and stability
Farhad Rahmani, Mohammad Haghighi , Salar Mahboob
Chemical Engineering Faculty, Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz, Iran
Reactor and Catalysis Research Center (RCRC), Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz, Iran

a r t i c l e

i n f o

Article history:
Received 26 February 2016
Received in revised form 28 April 2016
Accepted 29 April 2016
Available online 29 April 2016
Keywords:
Cr/Clinoptilolite-ZrO2
Ultrasound
C2H6/CO2 oxidative dehydrogenation
Ethane
Ethylene

a b s t r a c t
CO2-enhanced oxidative dehydrogenation of ethane was investigated over sonochemically synthesized
Cr/clinoptilolite-ZrO2 nanocatalyst with the aim of assessing the effect of composite support and ultrasonic irradiation on the nanocatalyst reactivity and stability. To this aim, ZrO2 promoted clinoptilolite
supports varying in zirconia content (0, 25, 50 wt%) were synthesized by hydrothermally precipitation
method and impregnated with chromium nitrate under ultrasound irradiation. The samples were characterized by XRD, FESEM, EDX, TEM, ICP, BET, FTIR, TPR-H2 and TPD-NH3 techniques. The characterization
results indicated that ultrasound irradiation could not only reduce the formation of Cr2O3 and decrease
submicron particle size of chromium oxide to nanometer scale, but also promote the distribution of
metallic particles and strengthen the chromium-support interaction. As a result, utilizing ultrasound irradiation in the synthesis of Cr/Clinoptilolite helped to maintain a high and stable catalytic activity. These
features were more prominent in the presence of zirconia. It was found that the metal oxide nanoparticles with about 48 nm are dispersed uniformly on the surface of composite support containing 25 wt%
ZrO2 (CLT-Z25). Moreover, the addition of ZrO2 resulted in the formation of new strong acid sites and a
significant modification in the reducibility of chromium species, which alongside homogenous and small
Cr nanoparticles account for the superior catalytic performance of ZrO2 containing samples. However,
excessive loading of ZrO2 (50 wt%) severely covered the surface of clinoptilolite, afforded the aggregations
of metallic particles and thereupon, weakened the contact between clinoptilolite and ZrO2, which
together with more acid strength seriously resulted in the deactivation of catalyst. In spite of superior
initial activity of ZrO2-rich sample among the catalysts tested, ultrasonic synthesized Cr/CLT-Z25
nanocatalyst showed the best catalytic performance after 5 h-catalytic reaction.
2016 Elsevier B.V. All rights reserved.

1. Introduction
Exploitation of CO2 as a soft oxidant for the ethane oxidative
dehydrogenation process has received enormous interest recently
owing to important environmental and technological features such
as CO2 utilization and abatement, suppressing the formation of CO2
greenhouse gas as a by-product and minimizing the deep oxidation
and the hot spot phenomenon on the catalyst surface [13].
Despite intense research activity through the last decades, the
industrial implementation of such a process is not yet achieved
[46]. The main obstacle is the low olefin yield, still well below
Corresponding author at: Reactor and Catalysis Research Center, Sahand
University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz, Iran.
E-mail address: haghighi@sut.ac.ir (M. Haghighi).
URL: http://rcrc.sut.ac.ir (M. Haghighi).
http://dx.doi.org/10.1016/j.ultsonch.2016.04.034
1350-4177/ 2016 Elsevier B.V. All rights reserved.

that obtained by the currently applied processes. Thus, the development of a suitable catalyst able to efficiently convert ethane to
ethylene is still important challenge. In attempts to improve the
ethylene yield; many catalysts have been studied in the literature.
Among these, supported chromium oxide catalysts are the most
promising [711]. It has been established that an apt dispersion
of the active phase over the support represents a key factor to
obtain an active catalyst [9,12]. Uniform dispersion of CrOX species
provides more high-valent and reducible chromium species which
are believed to be the active sites or the precursors of the active
sites [9,12]. Accordingly, catalytic performance of chromiumbased catalysts depends strongly on the support and deposition
method.
The deposition method of the active chromium phase strongly
affects the nature and abundance of CrOX species. The wet impregnation method is very often used for the deposition of CrOX species

F. Rahmani et al. / Ultrasonics Sonochemistry 33 (2016) 150163

over support [2,7,8,10,13]. However, this method very often results


in low dispersion of metal species due to the small impetus of
transmitting mass in the preparation process [14] and also, broad
distribution of Cr species containing the CrOX units with a low
degree of dispersion or bulk oxide [13]. Moreover, the impregnation method sometimes leads to the channels blockage by the formation of bulk metal oxide clusters [13,15], especially in the case
of micropore materials. The application of ultrasound irradiation
as auxiliary means in metal deposition during the wet impregnation process has attracted many attentions in the past few years
[14,1619]. Ultrasound has proven to be a very useful and interesting tool to prepare novel supported nanocatalysts [18]. Ultrasound
method enhances the dispersal of the active species on the surface
of support and makes uniform nanoscale component in the structure, thus promoting the catalytic performance in a variety of catalytic systems [14,16,18,20]. In addition, the use of ultrasound
technique during the impregnation process can significantly
shorten the catalyst preparation period [2123]. The beneficial
effects of ultrasound in the preparation of heterogeneous catalysts
rely on the acoustic cavitation [18,24,25]. Oscillating bubbles
formed by ultrasonic waves tend to collapse preferentially near
the solid surfaces and collapsing bubbles generate shockwaves
and high velocity solvent microjets [16,18,26] which will drive
the formed clusters/nanoparticles in solution to the support surface and immobilize them before they are severely aggregated in
solution [16,27]. These microjets and shock waves can inhibit the
agglomeration of metal particles on the surface, making the fine
active metal species more dispersed over the surface. The acoustic
cavitation can also avoid excess concentration within the solution
and provide a uniform environment for the nucleation and growth
of metal particles, resulting in formation of uniform nanoparticles
in size. The presence of noble gases dissolved like Ar significantly
affects the cavitational intensity. Dissolved gases act as nucleation
sites for cavitation. Therefore, bubbling argon through the mixture
facilitates the production of cavitation bubbles, giving a greater
cavitational effect [18,25]. However, the high energy demand of
ultrasound operation is a commonly cited main obstacle for the
application of this technology [28,29]. To alleviate this problem,
pulsed ultrasound can be used as an effective operational mode
[29]. In pulsed ultrasound, the ultrasonic equipment is run in
repetitive on and off cycles. The energy wasted due to shielding
and scattering effects in continuous mode can be recovered in
the pulsed mode [2830]. The large bubbles and/or cloud of bubbles formed close to the irradiating surface that cause scattering
of ultrasound waves in the continuous mode, would dissolve or
float to the surface during the Off period of pulsed ultrasound operation reducing shieling and scattering [29]. In addition, the pulsed
mode can implement coalescence of small degassing bubbles more
effectively and promote the high amplitude of sound propagation,
which leads to an increased number of bubbles that are effective
for sonochemical reaction [30]. Operating ultrasound on pulsed
mode can also reduce the undesirable temperature rise [29].
Apart from synthesis method, support has a considerable effect
on the catalytic performance [3133]. The support not only affects
on the dispersion of Cr species [12,13,34], but also has influence on
the nature of active sites (i.e. reactivity, acidity, accessibility, etc.)
[13,35]. Regarding the relatively poor hydrothermal and mechanical stability of silica materials [36], attention has been recently
focused on employing zeolites as efficient supports for
chromium-based catalysts in the CO2-assisted dehydrogenation
reaction [2,3639]. In this regard, clinoptilolite was successfully
applied as a support for the CO2 oxidative dehydrogenation process
[39]. Nevertheless, the more ethylene yield is necessary to compete
with the current steam cracking technology. Impregnation method
alongside low surface area prevents dispersion of chromium oxide
species, which leads to further decrease in yield. Modification of

151

support and utilization of a proper deposition method which cause


chromium to be distributed homogeneously at the surface, will
probably promote the catalytic activity. The ZrO2 containing catalysts were reported to display good catalytic properties for oxidative conversion of ethane to ethylene [7,10,40,41]. Zirconia
presents properties that make it interesting for its use as modifiers
of oxidation catalysts. These properties may be the improvement
of metallic dispersion and reducibility, the sintering decrease, the
improvement of thermal stability and the enhancement of oxygen
storage capacity, helping, in this way, promotion of initial activity
and the gasification of carbon formed during the dehydrogenation
[4245]. Considering these aspects, the use of ZrO2 as supports
modifier and sonochemical method seems to be useful in developing Cr/Clinoptilolite catalysts with desirable catalytic performances for the oxidative dehydrogenation of ethane.
Based on review of the literature, the use of ultrasound method
and ZrO2 modifier for the preparation of zeolite-supported Cr catalysts has not been previously studied. Therefore, it is very interesting to sonochemically dispersion of Cr species over ZrO2clinoptilolite composites and study the effect of the catalyst preparation method and zirconia loading on the ODH performance. To
this aim, a series of Cr supported over Clinoptilolite-ZrO2 composites with various ZrO2 content were prepared by ultrasoundassisted impregnation method. The obtained materials were characterized with various physicochemical techniques and examined
their catalytic performance as the catalysts for the ethane dehydrogenation in the presence of CO2. To gain a more detailed insight
into the effect of ultrasonic Cr deposition and ZrO2 loading, Cr supported samples were also synthesized by conventional wet
impregnation method.

2. Materials and methods


2.1. Materials
Clinoptilolite tuffs used as the support were obtained from Mianeh deposit in East Azerbaijan region of Iran. The analytical grade
of chromium nitrate nonahydrate (Cr(NO3)3.9H2O, Aldrich) and zirconyl nitrate hydrate (ZrO(NO3)26H2O, Aldrich) were used as
active phase source and the precursor of zirconia modifier, respectively. Moreover, ammonium hydroxide solution (NH4OH, Aldrich)
was supplied as a precipitating agent.

2.2. Nanocatalysts preparation and procedures


Cr-loaded catalysts containing 5 wt% Cr2O3 were prepared by
impregnating an aqueous solution of Cr(NO3)3.9H2O onto suspended supports under ultrasound irradiation. The experimental
setup used for the ultrasonic dispersion of Cr species over the
clinoptilolite-based composites has been illustrated in Fig. 1. The
precursors solution was sonicated under a flow of Ar at 70 C by
means of SONOPULS HD 3200 sonicator with a frequency of
20 kHz and equipped with an immersion titanium horn
( = 13 mm). The pulsed sonication was performed by applying
pulse ratio (On:Off) of 0.3:0.1 s at an input power of 90 W for an
effective treatment time of 60 min. After drying the samples, the
ultrasonic impregnated samples were calcined at 700 C for 4 h
in a static air atmosphere. The resulting catalysts depending on
the deposition method (impregnation or ultrasound) and the
amount of ZrO2 loading were designated as Cr/CLT(I or U) and
Cr/CLT-Zx(I or U) for the parent and ZrO2 promoted clinoptilolite
supported chromia catalysts, respectively. The term x represents
the nominal weight percentage of ZrO2 in the composite support
(x: 25 and 50).

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F. Rahmani et al. / Ultrasonics Sonochemistry 33 (2016) 150163

Fig. 1. Experimental setup for sonochemically synthesis of Cr/Clinoptilolite-ZrO2 nanocatalysts.

Before impregnation, ZrO2 modified clinoptilolite supports were


prepared by hydrothermally precipitation method. To prepare supports, at first, the chosen clinoptilolite tuff was crushed and sieved,
and the fraction with particle size in the 6473 lm range was
selected. This fraction was washed to remove the water-soluble
residues and other undesirable materials, and dried in an oven at
383 K for 24 h before its use in the catalyst preparation. Then, an
appropriate amount of clinoptilolite was added into the zirconyl
nitrate solution under stirring. The pH of this slurry increased to
be 9 at 50 C by the addition of dilute aqueous ammonia dropwise under vigorous stirring. At this pH, zirconia precipitate is
mainly deposited on the external surface of clinoptilolite. Afterwards, the precipitate was aged in the mother liquor at 50 C for
60 min and then transferred into a Teflon-lined stainless steel
autoclave to age hydrothermally under stirring for 12 h at 110 C.
The well-formed precipitates were filtered and washed with deionized water. After drying at 110 C for 12 h and calcination at
700 C in air for 4 h, the clinoptilolite-ZrO2 composite was prepared. The details of the clinoptilolite-based supports and Cr loading catalysts preparation have been illustrated in Fig. 2.
2.3. Nanocatalysts characterization
X-ray diffraction (XRD) patterns were collected on a D5000 Siemens X-ray diffractometer using Cu Ka radiation (0.154056 nm).
The working voltage and current of the instrument were 30 kV
and 40 mA, respectively. The surface morphology of the nanocatalysts was observed by Field Emission Scanning Electron Microscopy (FESEM) analyzer (HITACHI S-4160). The samples studied
were covered with a thin film of gold (ion sputtering) to improve
conductivity. The surface elemental composition and dispersion
of the synthesized catalysts were analysed by energy dispersive
X-ray (EDX) on MIRAPLMU. To study the particle size and dispersion of the supported species, transmission electron microscopy
(TEM) images were obtained using a Philips CM-200 electron
microscope operated at 150 kV. Samples were ultrasonically dispersed in ethanol and then, the suspension was deposited on a thin
carbon film-coated Cu grid. The BET specific surface area of the
samples was determined by adsorption-desorption of nitrogen at
liquid nitrogen temperature, using a Quantachrome ChemBET
3000 equipment. Before acquiring the adsorption isotherm and
analysis, all samples were degassed at 200 C for 30 min. Inductively coupled plasma optical emission spectroscopy (ICP-OES)

was applied to determine the content of loaded metals in the synthesized catalysts. The measurements were performed with a Varian Vista-PRO CCD Simultaneous ICP-OES instrument. Catalysts
acidity was measured by ammonia temperature programmed desorption (NH3-TPD) using BELCAT analyser equipped with a TCD
detector. For addressing surface functional groups, Fourier Transform Infrared Spectroscopy (FTIR, UNICAM 4600) was done in the
range of 4004000 cm1 wave number. Self-supported wafer containing 10 wt% of KBr was used.
2.4. Nanocatalysts performance test
Fig. 3 depicts the experimental setup for catalytic evaluation of
prepared samples. The catalytic tests were conducted in a fixedbed quartz microreactor placed inside an electrical furnace which
provides the required temperature. The catalyst load was
500 mg, and it was activated in situ at 600 C in an air stream
(15 cm3 min1) for at least 0.5 h prior to the reaction. Catalytic
reactions were carried out at atmospheric pressure and temperature range of 600700 C with a feed flow rate of 50 ml/min under
steady-state conditions. For ethane dehydrogenation in the presence of CO2, the gas reactant contained 10 vol% C2H6, 50 vol%
CO2, and the balance N2 while in the absence of CO2, the feed consisted of 10 vol% C2H6 and the balance N2. The reactants and products were analyzed on-line by a gas chromatograph (GC Chrom,
Teif Gostar Faraz, Iran) equipped with TCD and FID detectors and
a CarboxenTM 1000 column (Agilent Co.). Before analysing, the effluent stream was passed through an ice-cooled trap to condensate
and separate H2O. Blank runs performed under the same conditions excluded the occurrence of thermal dehydrogenation.
The ethane conversion (XC2H6), the yield of ethylene (YC2H4) and
selectivity to ethylene (SC2H4) were calculated as follows:

X C 2 H6 % 100 

F C 2 H6 in  F C2 H6 out
F C 2 H6 in

SC2 H4 % 100 

F C 2 H4
F CH4 F C 2 H4

Y C 2 H4 % 100 

F C 2 H4
F C 2 H6 in

where Fi is the molar flow rate of each component.

(i) Clinoptilolite preparation

F. Rahmani et al. / Ultrasonics Sonochemistry 33 (2016) 150163

153

Clinoptilolite tuffs
Crushing and Sieving (63-74 m)
Washing with de-ionized water
Filtration and drying at 110C for 24 h under air flow
Impregnation route

Sonochemical route

Support: Washed clinoptilolite (CLT)

Zirconium precursor: ZrO(NO3 )2 .6H 2 O

CLT

De-ionized water

Precipitant: NH 4 OH solution (25%)

(ii) Clinoptilolite-ZrO2 Synthesis

Mixing for 0.5 h at 40C while stirring at 500 rpm


Precipitation: Drop-wise addition of NH 4 OH solution to
mixture at 40C under vigorous stirring until pH=9 0.2
Mixing at 40C and pH=9 for 1 h
Hydrothermal aging : in a teflon-lined stainless steel autoclave reactor at 110C for 12 h while stirring at 500 rpm

Filtration and washing with de-ionized water

Drying at 110C for 24 h under air flow


Calcination at 700C for 4 h under air flow
Support: Clinoptilolite-ZrO2 (CLT-Z25, CLT-Z50)

(iii) Addition of Cr

Aqueous solution of Cr(NO 3 )3 .9H2 O (5 wt%)


Impregnation: Dispersion of Cr over support
at 70C while stirring at 300 rpm

Ultrasound: Dispersion of Cr over support


in pulsed condition at 70C and 90W

Drying at 110C for 12 h while mixing

Calcination at 700C for 4 h under air flow


Catalyst shaping:
Cr/Clinoptilolite: Cr/CLT(I), Cr/CLT(U)
Cr/Clinoptilolite-ZrO2 : Cr/CLT-Z25(I), Cr/CLT-Z25(U), Cr/CLT-Z50(U)

Fig. 2. Synthesis steps of nanocatalysts: Cr/CLT(I), Cr/CLT(U), Cr/CLT-Z25(I), Cr/CLT-Z25(U) and Cr/CLT-Z50(U).

3. Results and discussions


3.1. Nanocatalyst characterizations
3.1.1. XRD analysis
The XRD patterns of the synthesized Cr-based catalysts are
shown in Fig. 4. Regarding to the reference patterns, the diffraction
peaks of clinoptilolite and a-Cr2O3 can be detected in the XRD patterns. The diffraction peaks, centered at 2h = 9.8, 11.2, 22.4, 22.7,
26.1, 28.2, 30.0 and 32.0 confirmed the presence of clinoptilolite
(JCPDS 00-025-1349) in monoclinic phase. In addition, the
appeared peaks at 2h = 24.5, 33.6, 36.2, 41.5, 50.2, 54.9 and 63.4
are attributed to a-Cr2O3 (JCPDS 00-006-0504) in rhombohedral
phase. The presence of a-Cr2O3 has a negative effect on the catalytic activity due to the poor accessibility of lattice chromium
entities in the bulk of a-Cr2O3 [9,46,47]. Moreover, crystalline aCr2O3 is highly resistant to oxidant what makes it useless as a catalyst [4648]. A close examination of XRD results indicates that the
relative crystallinity of a-Cr2O3 decreased by employing ultrasound irradiation and/or ZrO2 loading. In comparison to ultrasound
treatment, ZrO2 addition seems to be relatively more efficient.
Regarding to intrinsically low surface area of clinoptilolite and also
decisive role of the support in the dispersion of deposited species,
this superior might be mainly due to much higher surface area of
modifier compared to the support. However, the crystallinity loss
is more prominent when ZrO2 modification and ultrasound

treatment are simultaneously employed. The presence of low


intensity peaks of Cr2O3 in ZrO2 containing catalysts especially
ultrasound synthesized ones suggests that Cr species are welldispersed throughout the support structure. This claim is going
to be supported by the EDX and TEM analysis. The acoustic cavitation phenomenon and also the synergistic effect of ZrO2 modifier
on the surface area and metal-support interaction can be responsible for this finding. Moreover, XRD patterns of zirconia containing
samples show the presence of ZrO2 as indicated by the diffraction
peaks at about 2h = 30.2, 34.6, 35.3, 43.0, 50.3, 50.7, 53.9, 59.4 and
60.2 (JCPDS 01-075-0076). The XRD observation demonstrates
that zirconia exists in a pure tetragonal phase. It is obvious
that by increasing zirconia content, the ZrO2 peaks become intense
and in contrast, the intensity of clinoptilolite peaks diminishes. By
taking the fact into account that for obtaining a high activity, a
high dispersion of Cr species has to be achieved, it is expected
that zirconia containing nanocatalysts especially sonosynthesized ones exhibit satisfying performance for the ethane
oxidative dehydrogenation.
3.1.2. FESEM analysis
The surface morphology of synthesized nanocatalysts was studied by FESEM and the corresponding images are presented in Fig. 5.
It can be observed from these images that the synthesized catalysts
have nanometric particles. Nano particles provide more reactive
and reducible sites and result to a high catalytic performance of

154

F. Rahmani et al. / Ultrasonics Sonochemistry 33 (2016) 150163

PI-04
N2

MFC (04)
PRV-04

V-04

Notations:
C:
Cylinder
GC: Gas Chromatography
GCS: Gas Collector System
MFC: Mass Flow Controller
MFM: Mass Flow Meter

PI-03
N2

MFC (03)
PRV-03

V-03

PI: Pressure Indicator


PRV: Pressure Regulator Valve
R:
Reactor
TIC: Temp. Indicator & Controller
4WV: 4-Way Valve

GCS-01
PI-02
CO2

MFC (02)
PRV-02

Feed to reactor

V-02
Feed
to analyzer

N2

CO2

Vent
C2H6

MFC (01)

N2

4WV-01

Feed

MFM (01)

PI-01

PRV-01

N2

PI-05

4WV-02

V-01

C2H6

Reactor
outlet

Reactor
inlet

Cooler
Ar

Gas mixture
to GC

Air
H2

Electrical heating
furnace with
temperature
controller

Vent

N2

N2

GC-01
CO2

C2H6

Temperature
Controller

Controlled
power supply

GC
Ar

Air

H2

TIC-01
R-01

C-01

C-02

C-03

C-04

C-05 C-06

C-07

Furnace/Reactor

Fig. 3. Experimental setup for testing of catalytic performance of synthesized nanocatalysts used in C2H6/CO2 oxidative dehydrogenation reaction.

the nanocatalyst. The Cr/CLT(I) sample has a dense structure and


the formation of surface agglomerations cover the blade-shaped
structure of clinoptilolite. Some morphological changes, brought
about by employing ultrasound method and ZrO2 addition, are
observed. Nanocatalysts synthesized with ultrasound assisted
impregnation method show more well-defined morphology compared to impregnated sample. FESEM micrographs of the Cr/CLT
(U) sample indicated a decrease in agglomeration size and relatively open morphology compared to the Cr/CLT(I) nanocatalyst.
This observation reflects the remarkable synergetic effect of ultrasound irradiation on the surface morphology. The reason for this
behaviour could be explained by taking acoustic cavitation phenomenon into consideration, which pushed the aggregated particles on the external surface of alumina, penetrated into the pores
of alumina and form very small clusters after the ultrasound treatment, simultaneously hindering the agglomeration of particles on
the support surface [17,19,49]. These features, on the other hand,
are more prominent when appropriate amount of ZrO2 modifier
and ultrasound treatment are simultaneously employed (Cr/CLTZ25(U)). In comparison to Cr/CLT nanocatalysts, no obvious conglutinated particles were observed in the FESEM micrographs of
the Cr/CLT-Z25(U) nanocatalyst and the surface appeared to be
covered with a great deal of small nano scale particles. Moreover,
a uniform distribution of particle size is observed at respective captured images. Distinct surface morphology was also obtained as a
result of increasing ZrO2 content. The ZrO2-rich sample has irregular aggregations of nanoparticles and rough surface and the size of
particles is larger. It seems clinoptilolite was severely covered by
zirconia particles. Obtained results from FESEM images are in good
consistency with corresponding XRD analysis in which zirconia
containing samples especially rich one exhibit less intense peaks
for clinoptilolite phase.

3.1.3. EDX analysis


As well known, the dispersion of chromium species is a crucial
factor affecting the intrinsic activity and stability of Cr-based catalysts in the oxidative dehydrogenation process. To determine the
surface elemental composition and also assess the dispersion of
Cr species in the synthesized samples, the EDX analysis was carried
out. The EDX micrographs including spectrums and dot-mappings
were shown in Fig. 6. The elemental analysis results confirmed the
presence of all elements used in the synthesis of all samples and
absence of any impurities in their structure. This result, together
with the actual and nominal values of Cr and Zr loading given in
Table 1 indicates the accuracy of synthesis procedure. Interestingly, the Cr composition of modified samples obtained by the
EDX spectra is near to the actual Cr content determined by ICP
analysis, indicating ability of the ZrO2 modified supports and ultrasound method to uniformly disperse Cr species. Regarding to XRD
and FESEM findings, a high degree of Cr dispersion was expected
for modified catalysts, especially ultrasound synthesized ZrO2 containing ones. The apt dispersion of chromium in the EDX dotmapping results of modified samples confirms this expectancy.
According to EDX dot-mappings of Zr element, it is apparent that
the clinoptilolite surface in Cr/CLT-Z50(U) is severely covered by
zirconium element, presenting an evidence on the hypothesis
asserted in FESEM results about surface coverage. This feature
which could be partly expected according to low surface area of
clinoptilolite and high amount of ZrO2 loading causes inappropriate contact between deposited metal species and zeolitic support
and thereupon, would weaken the oxygen mobility, resulting in
activity loss. By considering the Marsvan Krevelen mechanism
of ODH reaction and this fact that oxygen mobility may affect
the working regeneration cycles of the catalyst during the reaction,
it can be inferred that oxygen mobility of the catalyst was closely

F. Rahmani et al. / Ultrasonics Sonochemistry 33 (2016) 150163

155

tion of particles on the support surface. These features becomes


more apparently with the existence of zirconia in the support. As
can be seen, the presence of zirconia enhances metal dispersion
effectively, implying that the deposition of ZrO2 over the support
can increase the interactions between chromium and the support,
thus suppressing the migration of metallic particles and decrease
the size of loaded particles. Other reason for the improved dispersion of metallic particles may be attributed to the increased surface
area of the ZrO2-containing supports (Table 1). In this circumstance, the increased surface area may strengthen the metalsupport interaction, which in consequence decreases the degree
of metal sintering during the process of calcination. Accordingly,
it can be concluded that the particles size reduction and metal dispersion ability of ultrasound method can be boosted in the presence of zirconia. The uniformly dispersed metal nanoparticles
with about 48 nm on the surface of composite support CLT-Z25
are observed. However, the slightly aggregation of metallic particles in some regions is found when the content of ZrO2 is excessive
(50 wt%, Fig. 7(d)).

Fig. 4. XRD patterns of synthesized nanocatalysts: (a) Cr/CLT(I), (b)Cr/CLT(U), (c)


Cr/CLT-Z25(I), (d) Cr/CLT-Z25(U) and (e) Cr/CLT-Z50(U).

related to the stability of catalytic activity [50]. Moreover, the comparison between the Zr containing samples reveals that, Cr/CLTZ25(U) enables an extremely uniform dispersion of deposited species on the surface which is going to affect the catalytic process.
3.1.4. TEM analysis
TEM images of the samples are shown in Fig. 7. As impregnation
method is used as the deposition method, the spherical chromium
oxide particles in the submicron scale are obviously observed and
not well distributed. Comparing with this, much smaller and uniform nanoparticles which are in the homogeneous distributed on
the catalyst are observed on the ultrasonic synthesized samples,
demonstrating the remarkable synergetic effect of ultrasound irradiation on the distribution and size of metallic particles. Moreover,
a strong metal-support interaction is observed for the sonochemically synthesized nanocatalysts at respective captured images. The
reason for these observations could be explained by taking acoustic
cavitation phenomenon into consideration, which pushed the
aggregated particles on the external surface of support, penetrated
into the pores of support and form very small clusters after the
ultrasound treatment, simultaneously hindering the agglomera-

3.1.5. BET analysis


Table 1 lists the specific surface area of the synthesized supports and Cr loaded nanocatalysts. As expected, using zirconia to
modify clinoptilolite support significantly increased the low surface area of raw clinoptilolite. The surface area of support plays
an important role in dispersion and concentration of redox chromium species which affect the catalytic activity strongly. As can
be seen, the composite supports possess higher BET surface area
which somehow confirms less formation of a-Cr2O3, as evidenced
by XRD results. The high-surface-area supports provide more
active sites as a consequence of better dispersion of Cr species
which may result in higher catalytic activity. Meanwhile, a
decrease in the total surface area is noticed after chromium loading
on the bare supports. This decrease in surface area is ascribed to
the blockage of some of the support pores by the Cr species.
Despite similar loading of chromium on different supports, the
specific surface area of Cr/CLT(I) is the lowest value which was predictable according to the BET results of supports and the deposition
method employed. The severe blockage of support pores and the
agglomeration of surface particles occur during impregnation process. The sonication can partially solve these problems. Ultrasound
irradiation results in formation of uniform, small and welldispersed particles, as evidenced by EDX, FESEM and TEM micrographs. Furthermore, substrate agglomeration disintegrates under
ultrasound irradiation. These features hinder the pore plugging
as much as possible and lead to higher BET surface area of ultrasound irradiated samples. An increase of the specific surface area
of both Cr/CLT(U) and Cr/CLT-Z25(U) shown in Table 1, presented
evidence on the hypothesis. It is worth noting that the ultrasound
irradiation treatment bring much deserved results when the composite support was employed. The synergistic effect of zirconia on
the surface properties and more importantly, high surface area of
composite supports could be reasonable justification for this
observation.
3.1.6. FTIR analysis
Infrared spectra of the as-synthesized samples in a frequency
range of 4004000 cm1 are shown in Fig. 8. The vibration frequency peaks at 470, 590, 670, 800, 1090, 1640, 2350 and
3450 cm1 can be recognized from absorption spectra of the prepared samples which are the typical vibrations in clinoptilolite
based samples. Based on the literature assignments, the absorption
bands appearing around 470, 590, 670, 800 and 1090 cm1 are
assigned to the characteristic vibration peaks of the aluminosilicates [5155]. In detail, the peak at 470 cm1 can be attributed
to the bending vibration of AlO4 and SiO4. The bands around 670,

156

F. Rahmani et al. / Ultrasonics Sonochemistry 33 (2016) 150163

(a) Cr/CLT(I)

500nm

200nm

(b) Cr/CLT(U)

500nm

200nm

(c) Cr/CLT-Z25(U)

500nm

200nm

(d) Cr/CLT-Z50(U)

500nm

200nm

Fig. 5. FESEM images of synthesized nanocatalysts: (a) Cr/CLT(I), (b)Cr/CLT(U), (c) Cr/CLT-Z25(U) and (d) Cr/CLT-Z50(U).

800, 1090 cm1 are ascribed to the T-O bending in D-5 rings,
asymmetric and symmetric vibrations of T-O-T, respectively [56].
These bands are related to internal linkages in SiO4 or AlO4 of zeolite lattices. Appearance of the main zeolitic vibration in 450
1200 cm1 [56] indicates that the clinoptilolite structure has not
been destroyed and remains intact after modification and Cr
impregnation and thus supporting the XRD results. The recorded
peaks at around 470 and 590 cm1 could be also related to M-O
stretching and Cr-O distortion vibrations, respectively [57], which
have overlaps with zeolitic vibrations. All spectra exhibited a broad

absorption peak at 31003700 cm1 with a maximum around


3450 cm1, which characterizes the stretching vibrations of surface
hydroxyl groups [19,39,51,57]. The bands observed at 1640 cm1
can be assigned to the molecular water bending mode
[19,39,51,57]. It indicates the presence of physically adsorbed
water in samples that occurred during maintenance of synthetic
samples [5860]. The weak peak observed at 2350 cm1 corresponds to the asymmetric stretching frequency [t(CO)] of CO2,
which can be addressed by the adsorption of aerial CO2 over the
course of FTIR analysis [6163].

157

F. Rahmani et al. / Ultrasonics Sonochemistry 33 (2016) 150163

Element
O
Si
Al
Cr
Other Cations

Total

wt. %
46.5
31.8
6.1
7.4
8.3
100

Cr

(a) Cr/CLT(I)

25.0m
keV
Element
O
Si
Al
Cr
Other Cations

Total

wt. %
46.48
34.38
6.84
3.98
8.32
100

Cr

(b) Cr/CLT(U)

25.0m
keV
Element
O
Si
Al
Cr
Other Cations

Zr
Total

wt. %
41.9
25.5
4.4
4.0
5.1
19.1
100

Cr

Zr

(c) Cr/CLT-Z25(I)

25.0m

25.0m

keV
Element
O
Si
Al
Cr
Other Cations

Zr
Total

wt. %
42.72
25.54
4.75
3.62
5.07
18.30
100

Cr

Zr

25.0m

(d) Cr/CLT-Z25(U)

25.0m

25.0m

keV
Element
O
Si
Al
Cr
Other Cations

Zr
Total

wt. %
37.32
16.60
3.67
3.04
5.07
37.27
100

Cr

Zr

(e) Cr/CLT-Z50(U)

25.0m

25.0m

keV
Fig. 6. EDX analysis of synthesized nanocatalysts: (a) Cr/CLT(I), (b) Cr/CLT(U), (c) Cr/CLT-Z25(I), (d) Cr/CLT-Z25(U) and (e) Cr/CLT-Z50(U).

3.1.7. TPR-H2 analysis


It is well known that the ODH of alkanes over supported
transition-metal oxides proceeds via a redox mechanism, in which
the reducibility is a key factor influencing strongly the catalyst per-

formance [2,9,10,12,47]. Shown in Fig. 9 are the TPR-H2 profiles


and H2 consumptions of the impregnation catalyst and ultrasound
irradiated nanocatalysts with different zirconia loading in the temperature range of 100700 C. As can be seen, the impregnation

158

F. Rahmani et al. / Ultrasonics Sonochemistry 33 (2016) 150163

Table 1
BET specific surface area and composition of synthesized samples.
Catalyst

Synthesis Method

Nominal ICP

Nominal ICP

Cr/CLT(I)

Impregnation

3.4

Cr/CLT(U)

Ultrasound

3.4

Cr/CLT-Z25(I)

Hydrothermally
precipitation/
Impregnation
Hydrothermally
precipitation/
Ultrasound
Hydrothermally
precipitation/
Ultrasound

17.5

17.0 3.4

17.5

16.9 3.4

3.4 81.4
(1 1 1)

35.2

34.1 3.4

3.3 109.7
(145)

Cr/CLT-Z25(U)

Cr/CLT-Z50(U)

Zr content
(wt%)

Cr content
(wt%)

SBET
(m2/g)

3.2 13.8
(25.5)a
3.5 17.9
(25.5)
3.5 72.1
(1 1 1)

The values in the brackets correspond to bare supports.

sample presents a single reduction peak, whose maximum is


placed at 487 C while the zirconia promoted nanocatalysts display
an additional reduction band as shoulder (25 wt% ZrO2) or overlapping peak (50 wt% ZrO2) centered within 350360 C. Based on the
literature assignments [2,9,12,38,41], the reduction peaks below
550 C can be ascribed to the reduction process of isolated surface
CrOx species from Cr6+ to Cr3+ and/or Cr2+. The location of the low
temperature maximum coincided well with the reduction maxi-

mum observed for Cr/ZrO2 [41], which are assigned to the reduction of Cr6+ species dispersed on ZrO2 (Cr6+/ZrO2). The high
temperature maximum that is observed for all of the catalysts is
ascribed to the reduction of Cr6+ species directly attached to the
zeolite material (Cr6+/zeolite). Moreover, it is also observed that
the latter reduction peak shifts to a lower temperature on the
zirconia-promoted samples. The reason for this behaviour could
be explained by taking acoustic cavitation phenomenon and synergetic effect of ZrO2 modifier into consideration, which form very
small and well-dispersed loaded metals, simultaneously hindering
the agglomeration of particles on the support surface. From Fig. 9,
it can be found that the H2 consumption of supported chromia
increases with ZrO2 loading. This can be corresponded to less formation of crystal Cr2O3 phase as confirmed by the XRD analysis,
which is more difficult to reduce. In general, the concentration of
reducible Cr species is strongly influenced by chromium dispersion. It is obvious that the fraction of low temperature reduction
peak, attributable to the reduction of Cr6+/ZrO2 species, increases
with increasing ZrO2 loading. This observation further confirms
the presence of at least two types of the Cr6+ species with different
reducibility in the ZrO2 containing samples. The Cr6+/zeolite species are harder to reduce compared to Cr6+/ZrO2 species. At low
ZrO2 loading, the Cr6+ species directly attached to the clinoptilolite
dominate, whereas at higher ZrO2 content, both Cr6+/Clinoptilolite
and Cr6+/ZrO2 species co-exist. Taking into account the H2-TPR
results, it can be concluded that employing both ultrasonic deposition method and composite support results in more reducibility
and consequently, higher catalytic activity.

(b) Cr/CLT(U)

(a) Cr/CLT(I)

514 nm
27.5 nm

333 nm

8.1 nm

50nm

500nm

(c) Cr/CLT-Z25(U)

(d) Cr/CLT-Z50(U)

6.8 nm
7.4 nm
4.1 nm

21.2 nm
50nm

50nm

Fig. 7. TEM images of synthesized nanocatalysts: (a) Cr/CLT(I), (b) Cr/CLT(U), (c) Cr/CLT-Z25(U) and (d) Cr/CLT-Z50(U).

159

800

590
470

1090

1640

2350

3450

F. Rahmani et al. / Ultrasonics Sonochemistry 33 (2016) 150163

Zone-I
(100-410C)

Zone-II
(410-700C)
487C
0.068 mmol H2/g

(a) Cr/CLT(I)
472C

TPR Signal (a.u.)

(a) Cr/CLT(I)

Transmittance (a.u.)

(b) Cr/CLT(U)

0.141 mmol H2/g


356C
0.014 mmol H2/g

(b) Cr/CLT-Z25(U)

(c) Cr/CLT-Z25(I)

464C
360C

0.097 mmol H2/g

0.055 mmol H2/g

(d) Cr/CLT-Z25(U)
(c) Cr/CLT-Z50(U)

(e) Cr/CLT-Z50(U)
100

200

300

400

500

600

700

Temperature (C)
Fig. 9. TPR-H2 analysis of synthesized nanocatalysts: (a) Cr/CLT(I), (b) Cr/CLT-Z25
(U) and (c) Cr/CLT-Z50(U).

4000

3500

3000

2500

2000

1500

1000

Zone-I
(100-550C)

500

Wavenumber (cm-1)
176C

Fig. 8. FTIR spectra of synthesized nanocatalysts: (a) Cr/CLT(I), (b) Cr/CLT(U), (c) Cr/
CLT-Z25(I), (d) Cr/CLT-Z25(U) and (e) Cr/CLT-Z50(U).

1.33 mmol NH3/g

TPD Signal (a.u.)

3.1.8. TPD-NH3 analysis


As well known, catalytic oxydehydrogenation performance is
closely related to the surface acidity of catalyst. In spite of the fact
that acid sites are essentially required for alkane activation and initiate reaction, the presence of strong acid sites would lead to carbon depositions eventually. Fig. 10 illustrates the results of TPDNH3 analysis to reveal the effect of zirconia addition on the acidity
of clinoptilolite supported nanocatalysts. Only an intense and
broad peak extending from 100 C to 550 C with the maximum
at about 176 C is observed over Cr/CLT(I) ascribed to the presence
of the weak to moderate acid sites while the promoted samples
display another peak in a higher temperature range (550900 C)
associated with the strong acid sites. From the TPD-NH3 results,
it can be inferred that the ZrO2 loading over clinoptilolite induces
new strong acid sites and decrease mainly the weak acid sites in
the zeolite. In a comparison, a distinct decrease of ammonia desorption at low temperature zone and an increase of ammonia desorption at high temperature zone were observed over ZrO2
containing nanocatalysts with increasing the zirconia content. This
somehow reflects the coverage of clinoptilolite surface by zirconia
addition which is in consistent with XRD, FESEM, BET and EDX
results. Nonetheless, the total amount of acid sites decreases with
raising the ZrO2 content. In addition, it is also observed that the
ammonia desorption maxima shifts to higher temperatures with
zirconia loading, which is more evident for the ZrO2-rich sample.
Considering the above, it can be expected that employing compos-

Zone-II
(550-900C)

180C
(a) Cr/CLT(I)

0.691 mmol NH3/g

0.138 mmol NH3/g


677C
183C

(b) Cr/CLT-Z25(U)

0.527 mmol NH3/g

0.181 mmol NH3/g


710C
(c) Cr/CLT-Z50(U)
100

200

300

400

500

600

700

800

900

Temperature (C)
Fig. 10. TPD-NH3 analysis of synthesized nanocatalysts: (a) Cr/CLT(I), (b) Cr/CLT(U),
(c) Cr/CLT-Z25(U) and (d) Cr/CLT-Z50(U).

ite support containing 50 wt% zirconia results less stable catalyst


compared with other ones.

160

F. Rahmani et al. / Ultrasonics Sonochemistry 33 (2016) 150163

3.2. Catalytic performance toward C2H6/CO2 oxidative


dehydrogenation
3.2.1. Effect of ultrasound irradiation and ZrO2 loading
The variation of catalytic activity of the prepared nanocatalysts
in terms of ethane conversion and ethylene yield with the ODH
reaction is depicted in Fig. 11. The ethane conversion and ethylene
yield increase with the rise of the reaction temperature, reflecting
the endothermic feature of this reaction. From this variation, it can
be inferred that the oxidation catalysts in the presence of CO2 are
more active at higher temperatures, suggesting that temperature
of 700 C is beneficial for the ethylene production. In addition,
the ethane conversion and the ethylene yield are close to each
other in whole temperature range, indicating the high selectivity
of ethylene. This can be attributed to the mild oxidant applied
and partly, favourable acidity behaviour of zeolitic support. It is
obvious that ultrasound irradiation and ZrO2 loading exert a
remarkable impact on the catalytic performance of the nanocatalysts. The variation in the ODE activity of the chromia-based catalysts is mainly corresponded to the difference in their Cr
dispersion, reducibility and acidity property. As well known, the
presence of reducible Cr(VI) and acid sites on the calcined samples
are crucial for the dehydrogenation reaction. As might be expected
from less formation of a-Cr2O3 and appearance of strong acid sites
in the zirconia containing samples, ZrO2 modification has greater
impact on the catalytic activity of Cr/CLT(I) than ultrasound treatment. It should be noted that the presence of strong acid sites in
the zirconia containing nanocatalysts helps the achievement of
higher ethane conversion in spite of a slight decrease in ethylene
selectivity. The eminent results in activity test was found as both
the ZrO2 modification and ultrasound irradiation were employed
in the preparation of Cr-based catalysts. Over all the examined
temperatures, the ultrasound prepared ZrO2 containing samples
especially the rich one exhibit better catalytic activity for the
60

C2H6 Conversion (%)

50

80

Cr/CLT(U)
70

Cr/CLT-Z25(I)

40

Cr/CLT-Z25(U)

60

Cr/CLT-Z50(U)

50

Equilibrium

40

30
20

(a)

30
20

10

Equilibrium Conversion (%)

90
C2H6/CO2/N2 = 10/50/40
GHSV = 6000 h-1

Cr/CLT(I)

10

600

625

650

675

oxidative dehydrogenation of ethane in the presence of CO2 as


expected. The Cr/CLT-Z25(U) and Cr/CLT-Z50(U) nanocatalysts displayed ethylene yields of 47.9 and 40.7% at 700 C, respectively,
whereas in the case of Cr/CLT(I), only an ethylene yield of 30.5%
was obtained.
3.2.2. Effect of CO2 addition on catalytic performance
The catalytic performance of the Cr/CLT-Z25(U) sample in the
ethane dehydrogenation process in the presence and absence of
CO2 at different temperatures is depicted in Fig. 12. As can be seen,
the initial activity increases with increase in temperature irrespective of the presence or absence of oxidizing agent in the reaction. In
addition, it is observed that the presence of CO2 markedly promoted the dehydrogenation of ethane over the nanocatalyst. In
the presence of CO2, ethylene is simultaneously obtained by dehydrogenation (DH) and oxidative dehydrogenation (ODH) pathways
[47,64]. The ODH reaction over Cr-based catalysts is believed to
proceed via a Mars-Van Krevelen (redox type) mechanism, in
which adsorbed ethane reacts with lattice oxygen atoms to produce ethylene along with water in initial step and Cr3+ species
resulted from the reduction of Cr6+ species by ethane, were reoxidized by surface oxygen species arisen from dissociated CO2
in a separate step [47,64]. These cyclic reduction and reoxidation proceed simultaneously to remove produced H2 as thermodynamically stable H2O which promotes the equilibrium conversion for the ODH with CO2. In addition, this direct oxidative
pathway is less endothermic compared to non-oxidative one,
reflecting more advantage of kinetics at a certain temperature.

3C2 H6 2CrO3 $ 3C2 H4 Cr2 O3 3H2 O

Cr2 O3 3CO2 $ 3CO 2CrO3

Another possibility is the reverse water-gas shift reaction


(RWGS) coupled with the direct dehydrogenation that operates
under CO2 atmosphere, which shifts the equilibrium of ethane
dehydrogenation towards the products by consuming H2 [2,65].
Generally, in the absence of CO2, a direct dehydrogenation takes
place which is thermodynamically limited making it impossible
to achieve acceptable yields at low temperatures.

C2 H6 $ C2 H4 H2

H2 CO2 $ CO H2 O

Considering the above, it seems that CO2 can participate in


direct oxidation of ethane to ethylene via the donation of oxygen
species and/or in the removal of H2 in the RWGS reaction. Therefore, the roles of CO2 in the dehydrogenation of ethane under a

700

Temperature (C)
45

50

C2H4 Yield (%)

40
35
30
25
20

C2H6/CO2/N2 = 10/50/40
GHSV = 6000 h-1

Cr/CLT(I)

C2H6 Conversion (%) (Without CO2)

40
C2H6 Conversion (%) (With CO2)

Cr/CLT(U)

Conversion/Yield (%)

45

Cr/CLT-Z25(I)
Cr/CLT-Z25(U)
Cr/CLT-Z50(U)

(b)

15
10

35
30
25
20

C2H4 Yield (%) (Without CO2)


C2H4 Yield (%) (With CO2)
Cr/CLT-Z25(U)
C2H6/N2 = 10/90 (without CO2)
C2H6/CO2/N2 = 10/50/40 (with CO2)
GHSV = 6000 h-1

15
10
5

0
600

625

650

675

700

Temperature (C)
Fig. 11. Effect of ultrasound irradiation and ZrO2 loading on catalytic performance
of synthesized nanocatalysts: (a) C2H6 conversion and (b) C2H4 yield.

600

650

700

Temperature (C)
Fig. 12. Effect of CO2 addition and temperature on C2H6 conversion and C2H4 yield
over Cr/CLT-Z25(U) nanocatalysts.

F. Rahmani et al. / Ultrasonics Sonochemistry 33 (2016) 150163

CO2 atmosphere would be considered either as lattice oxygen supplier to maintain the Cr species at higher valence state and help
redox cycle proceed or as hydrogen consumer in RWGS reaction.
Another role of CO2 in the dehydrogenation of ethane might be
the assistant in the rapid desorption of product (ethylene) from
the surface of the catalyst which seems to be necessary for obtaining high dehydrogenation activity and anticoking [65]. Accordingly, the promoting effect of CO2 on the dehydrogenation of
ethane is mainly attributed to weak oxidative properties of CO2,
which alleviates the thermodynamic equilibrium restriction of
ethane dehydrogenation process.
3.2.3. Time on stream performance
To examine the stability of the Cr-containing catalysts, the
oxidative dehydrogenation reaction was run continuously for 5 h
and the results are shown in Fig. 13. Both the ethane conversion
and ethylene yield over the Cr/CLT(I) catalyst drops gradually with
the time-on-stream. The unfavourable behaviour can be removed
by ZrO2 modification of support and/or applying ultrasound irradiation during impregnation process. The Cr/CLT(U), Cr/CLT-Z25(I)
and Cr/CLT-Z25(U) catalysts are relatively stable; the ethylene
yield and ethane conversion over these catalysts are maintained
at about initial values without any obvious deactivation over the
5 h. It is reasonable to attribute this finding to superior metalsupport interaction and uniform dispersion of metal species, in
accordance with TEM and EDX images. The deposition of redox
Cr species in close contact with the support helps to increase oxygen mobility and accelerates the reduction-oxidation cycle, alleviating the deactivation caused by reduced redox sites. Besides, this
fact that the nanocatalyst prepared by ultrasonic impregnation
contains more active sites or that some of the chromium may be

60

(a)
C2H6 Conversion (%)

50
40

30
Cr/CLT(I)

20

Cr/CLT(U)
Cr/CLT-Z25(I)

10

C2H6/CO2/N2 = 10/50/40
T = 700C
GHSV = 6000 h-1

Cr/CLT-Z25(U)

Cr/CLT-Z50(U)
0

30

60

90

120

150

180

210

240

270

300

Time on stream (min)


50

(b)

C2H4 Yield (%)

40

30

20

Cr/CLT(I)
Cr/CLT(U)
Cr/CLT-Z25(I)

10

C2H6/CO2/N2 = 10/50/40
T = 700C
GHSV = 6000 h-1

Cr/CLT-Z25(U)
Cr/CLT-Z50(U)
0

30

60

90

120

150

180

210

240

270

300

Time on stream (min)


Fig. 13. Time on stream behaviour of synthesized nanocatalysts: (a) C2H6 conversion and (b) C2H4 yield.

161

forced inside the pores of the support and also improvement of


coke resistance ability by ZrO2 addition in an appropriate content
might be the other reasons. Apart from the above reasons, longterm stability of Cr/CLT-Z25(U) can also be corresponded to the
synergistic effect of presence of ZrO2 modifier and applying ultrasound treatment in the nanocatalyst, which lead to further promoting the structural and surface properties. Nevertheless, the
activity of ZrO2-rich sample drop markedly. This is quite different
from the behaviour of other modified Cr-containing catalysts especially Cr/CLT-Z25(U) one, over which the ethylene yields are
observed to have no considerable changes within 5 h. This severe
loss of activity might be due to relatively weak dispersion of
ZrO2 and inappropriate contact between metal species and zeolitic
support whose surface has been converged by zirconia modifier.
These issues decline anti-coking ability of ZrO2 modifier and prevent the facile oxygen mobility of catalyst which led to stable catalytic activity during the catalytic reaction. Another possibility that
has to be considered for explaining the deactivation is the presence
of more number of stronger acid sites on the catalyst surface,
resulting in more coke formation. Accordingly, both the coke formation and deep reduction of redox species may contribute to
the deactivation of Cr/CLT-Z50(U) nanocatalyst. Ethylene yield
after 5 h-catalytic reaction decreased in the order of Cr/CLT-Z25
(U) > Cr/CLT-Z25(I) > Cr/CLT-Z50(U) > Cr/CLT(U) > Cr/CLT(I).
The
collection of results presented above indicated that the most
promising catalytic performances were obtained with the Cr/CLTZ25(U) nanocatalyst.

4. Conclusions
The characterization results indicated the remarkable synergetic and synergistic effects of ultrasound irradiation and ZrO2
modification on the surface properties and Cr dispersion. Ultrasound irradiation could not only reduce the formation of Cr2O3
and decrease submicron particle size of chromium to nanometer
scale over the catalyst surface, but also improve the dispersion of
loaded chromium and strengthen the chromium-support interaction. As a result, utilizing ultrasound irradiation in the synthesis
of Cr/Clinoptilolite prevented the catalyst deactivation. Based on
the further increase in the surface area and less formation of aCr2O3, the impact of ZrO2 loading was found to be greater than that
of ultrasonic dispersion of Cr species. The synergistic effects of
ultrasound irradiation were more prominent in the presence of zirconia due to an increase in the surface area of support and unique
properties of ZrO2 promoter. The uniformly dispersed metal
nanoparticles with about 48 nm on the surface of composite support containing 25 wt% ZrO2 (CLT-Z25) were obtained. Moreover,
the ZrO2 loading resulted in a significant modification of the surface area and redox properties of the impregnated Cr/Clinoptilolite
catalyst. In addition, the formation of new strong acid sites over
the ZrO2 modified Cr/Clinoptilolite catalysts was also identified.
These findings are responsible for the superior catalytic performance of ZrO2 containing samples, especially ultrasound synthesized ones. However, with the excessive addition of ZrO2
promoter, the agglomerations of metallic particles on the catalyst
and the severe coverage of clinoptilolite surface were observed,
which weakened the contact between clinoptilolite and ZrO2 and
seriously resulted in the deactivation of catalyst. More coke formation as a result of the presence of greater number of stronger acid
sites may be another reason. Therefore, the loss in the activity of
Cr/CLT-Z50(U) nanocatalyst closely related to coke deposition
and deep reduction of redox sites. Among the catalysts tested,
Cr/CLT-Z25(U) nanocatalyst showed the best catalytic performance
at 700 C after 5 h-catalytic reaction, giving 38% ethylene yield.

162

F. Rahmani et al. / Ultrasonics Sonochemistry 33 (2016) 150163

Acknowledgements
The authors gratefully acknowledge Sahand University of Technology for the financial support of the project as well as Iran Nanotechnology Initiative Council for complementary financial
support.
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