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Ultrasonics Sonochemistry
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a r t i c l e
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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
151
152
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
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
CLT
De-ionized water
(iii) Addition of Cr
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).
154
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
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.
155
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-
156
(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
157
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).
158
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)
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
Zone-I
(100-410C)
Zone-II
(410-700C)
487C
0.068 mmol H2/g
(a) Cr/CLT(I)
472C
(a) Cr/CLT(I)
Transmittance (a.u.)
(b) Cr/CLT(U)
(b) Cr/CLT-Z25(U)
(c) Cr/CLT-Z25(I)
464C
360C
(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).
Zone-II
(550-900C)
180C
(a) Cr/CLT(I)
(b) Cr/CLT-Z25(U)
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).
160
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
90
C2H6/CO2/N2 = 10/50/40
GHSV = 6000 h-1
Cr/CLT(I)
10
600
625
650
675
C2 H6 $ C2 H4 H2
H2 CO2 $ CO H2 O
700
Temperature (C)
45
50
40
35
30
25
20
C2H6/CO2/N2 = 10/50/40
GHSV = 6000 h-1
Cr/CLT(I)
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
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.
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
(b)
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
161
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
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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