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Article history:
Received 18 July 2015
Received in revised form 29 October 2015
Accepted 30 October 2015
Available online 4 November 2015
Keywords:
Eley-Rideal mechanism
DRIFTS
Sonochemical synthesis
Bimetallic catalysts
a b s t r a c t
Platinum group materials (Pt, Ru, Rh) are highly active materials for reforming. In the present study,
bimetallic Pt and Ru substituted TiO2 catalysts were synthesized by sonochemical method. The bimetallic 2% Pt 2% Ru/TiO2 showed high surface area of 66 m2 /g compared with the other catalysts. The prepared
catalysts were characterized by XRD, XPS, TEM, TPR and BET. Dry reforming, partial oxidation and combined reforming (CR) with CO2 were studied on these materials. Synthesized catalysts were found to be
highly active for dry reforming reaction. 26% and 95% of methane conversions were obtained with Ru
substituted TiO2 (4% Ru/TiO2 ) at 400 C and at 700 C. The H2 /CO ratio was close to unity with both Pt
and Ru substituted catalysts after 650 C. The apparent activation energies found to be 51 and 56 kJ mol1
with respect to methane for 4% Ru/TiO2 and 4% Pt/TiO2 , respectively. High oxygen storage capacity of 4%
Pt/TiO2 further showed the good activity for dry reforming. The bimetallic catalyst 2% Pt 2% Ru/TiO2 sintered under time on stream condition and also resulted in the formation of amorphous carbon on to the
surface of catalysts, which made them an inactive catalyst for reforming process. The surface intermediates during these reactions were found by in situ FTIR at different temperatures for reforming processes.
The peaks corresponding to CO2 adsorption were not observed in case of 4% Ru/TiO2 and 2% Pt 2% Ru/TiO2
for dry reforming and this indicates the Eley-Rideal mechanism on both catalysts. A kinetic model was
developed by considering CH4 dissociation as rate determining step (RDS) and the model was validated
to the obtained experimental data.
2015 Elsevier B.V. All rights reserved.
1. Introduction
Abundant resources of methane from natural wet lands, fermentation, biomass, fossil fuels and agriculture would be useful
for exploiting the syngas production [1]. FischerTropsch synthesis (FTS) for the production of liquid fuels production, ammonia
and methanol industries utilizes syngas as a feed stock [2,3]. Syngas can be produced by processes like steam reforming (SR), dry
reforming (DR), autothermal reforming (ATR), combined reforming
(CR) and partial oxidation (PO). The product H2 /CO ratio depends
on the reaction process and conditions used. For the production of
oxygenated compounds and for liquid hydrocarbons by FT process,
the H2 /CO ratio of syngas must be close to unity [4], which can be
achieved by dry reforming.
Both steam and dry reforming reactions are highly endothermic, whereas partial oxidation is exothermic. High temperatures
are required for both steam and dry reforming to achieve maximum
CH4 and CO2 conversions. The economics of the overall process can
be minimized by combining one of the reforming reactions with
partial oxidation of methane [5]. This process is called autother-
103
*
4% Pt/TiO2 After reaction
20
30
40
50
60
Diffraction angle, 2
70
80
Fig. 1. X-ray diffraction pattern of Pt, Ru catalysts on TiO2 supports (*anatase phase
TiO2 ).
CH4 dissociation or CO2 dissociation on support as a rate determining step (RDS) [27,28]. The reaction pathway of reforming on the
catalyst surface depends on the surface acidity and/or basicity. If
the support possesses Lewis acidity, CO2 can adsorb on the surface
of the support and dissociate. In case of basic support, carbonates
and bicarbonates play a role in the CO and H2 formation [29]. PGM
catalysts enhance the transport of hydrogen and oxygen between
the precious metal and support by spillover mechanism. This metal
support interaction is important to achieve higher rates and low
coke formation on the catalyst. Despite this, strong metal support
interactions at higher temperatures can reduce the catalytic activity
due to loss of active sites [30].
In the present study, monometallic and bimetallic Pt, Ru catalysts with TiO2 supports were synthesized by sonochemical
synthesis. These catalysts were employed for dry reforming, partial oxidation and dry autothermal reforming reactions for the rst
time with these catalysts based on this particular synthesis route.
The mechanisms of all these reactions were proposed according to
the information obtained from in situ FTIR or DRIFTS. The kinetics
of dry reforming was studied further due to the catalytic activity
towards this reaction. Eley-Rideal mechanism was proposed for
dry reforming reaction on these materials as per the information
collected from DRIFTS study. All catalysts were characterized with
XRD, XPS, TEM before and after the reaction and the chemical stability was studied. The amount of coke deposition was determined
by using high pressure thermogravimetric analysis after stability
studies.
2. Experimental
2.1. Catalyst synthesis
Sonochemical synthesis is one of the well employed techniques to synthesize metal oxides of homogeneous size distribution
Fig. 2. TEM images of fresh catalysts (a), (b) 4%Pt/TiO2 , (c), (d) 2%Pt 2%Ru/TiO2 and
(e), (f) 4%Ru/TiO2 .
Table 1
Amounts of precursors required for the bimetallic Pt, Ru TiO2 catalysts synthesis for 5 ml of titanium iso-propoxide.
Catalyst
4% Pt/TiO2
3% Pt 1% Ru/TiO2
2% Pt 2% Ru/TiO2
1% Pt 3% Ru/TiO2
4% Ru/TiO2
0
0.0356
0.0712
0.1069
0.1425
0.2815
0.2111
0.1407
0.0704
0
10
43
66
13
22
104
Fig. 3. TEM images of spent catalysts (a), (b) 4%Pt/TiO2 , (c), (d) 2%Pt 2%Ru/TiO2 and (e), (f) 4%Ru/TiO2 after reaction 20 h time on stream condition.
both ame ionized detector (FID) and thermal conductivity detector (TCD) was used to analyze CO, CO2 , CH4 and H2 concentrations
at the reactor outlet.
2.4. H2 TPR study
Temperature programmed reduction (TPR) with H2 was performed with 10 mg of catalyst, loaded in a quartz reactor. The
experiments were done under the ow rate of 30 ml/min of 5% H2
gas mixture diluted with Ar (Chemix gases, India) in temperature
range of 50600 C with a rate of 10 C/min. Hydrogen consumption during the reduction was analyzed with thermal conductivity
detector connected to outlet stream. The temperatures were controlled by using a PID controller (Culture instruments, India) during
the experiments.
2.5. In situ FTIR (DRIFTS) analysis
Fourier transform infrared spectroscopy (FTIR, Perkin Elmer)
machine was connected to Praying mantis system which contains
a high temperature reaction chamber. The reaction chamber was
lled with a catalyst and FTIR spectra were collected at different temperatures (30 C, 300 C, 450 C and 600 C, respectively).
At each temperature the background was collected with 32 scans
and 4 cm1 resolution with nitrogen purging. For each reaction, IR
spectra were collected after 30 min of the respective composition
of gas ow depending upon the process (CR/PO/DRM). After nishing the study at a particular temperature, the reaction chamber
(b)
(a)
2
2% Pt 2% Ru/TiO
4% Pt/TiO
4% Ru/TiO
279
200
400
600
800
282
1000
Pt
Ti
4+
Pt
70
455
291
4+
Ti
288
(d)
(c)
285
Binding energy, eV
Binding energy, eV
450
105
460
72
74
465
76
78
80
82
84
Binding energy, eV
Binding energy, eV
(e)
Pt
66
68
70
72
74
4+
4+
76
78
80
82
84
Binding energy, eV
Fig. 4. (a) Wide spectra of 4%Pt/TiO2 , 2%Pt 2%Ru/TiO2 and 4%Ru/TiO2 , (b) Core level Ru3d spectra for 4%Ru/TiO2 , (c) Core level Ti2p spectra for 4%Ru/TiO2 , (d) Core level
Pt4f spectra (after reaction) in 4%Pt/TiO2 , 2%Pt 2%Ru/TiO2 , (e) Core level Pt4f spectra (before reaction) in 4%Pt/TiO2 , 2%Pt 2%Ru/TiO2 .
3.0x10
2.5x10
2.0x10
1.5x10
(a)
C o ncentrati o n, ppm
C o ncentratio n, ppm
106
CH 4
1.0x10
CO 2
H2
5.0x10
CO
3.0x10
2.5x10
2.0x10
(b)
CH 4
CO 2
1.5x10
1.0x10
5.0x10
0.0
H2
CO
0.0
300
400
500
600
700
800
900
300
C o ncentrati o n, ppm
Temperature, C
2.5x10
2.0x10
1.5x10
1.0x10
400
500
600
700
800
900
Temperature, C
(c)
CH 4
CO 2
H2
5.0x10
CO
0.0
300
400
500
600
700
800
900
Temperature, C
Fig. 5. CR reaction with (a) 4%Pt/TiO2 , (b) 2%Pt 2%Ru/TiO2 and (c) 4%Ru/TiO2 .
Eapp,CH4 , kJ mol1
Eapp,CO2 , kJ mol1
4% Pt/TiO2
2% Pt 2% Ru /TiO2
4% Ru/TiO2
56.5 4.2
17.4 0.6
50.8 3.8
49.8 2.0
36.8 2.0
48.3 4.4
2.5x10
(a)
2.0x10
(b)
CH 4
1.5x10
CH 4
H2
1.0x10
5.0x10
C o ncentrati o n, ppm
CO 2
H2
CO
1.0x10
5.0x10
0.0
0.0
400
500
600
700
o
800
900
300
Temperature, C
400
500
600
Temperature, C
C o ncentratio n, ppm
C o ncentrati o n, ppm
2.0x10
CO 2
CO
1.5x10
107
3.0x10
2.5x10
2.0x10
1.5x10
1.0x10
5.0x10
(c)
CH 4
CO 2
H2
CO
0.0
300
400
500
600
700
800
900
Temperature, C
Fig. 6. POM reaction with (a) 4%Pt/TiO2 , (b) 2%Pt 2%Ru/TiO2 and (c) 4%Ru/TiO2 .
700
800
900
3.5x10
3.0x10
2.5x10
2.0x10
1.5x10
1.0x10
(a)
CH 4
2.5x10
2.0x10
1.5x10
1.0x10
H2
CO
CH 4
CO 2
H2
CO
5.0x10
5.0x10
(b)
CO 2
C o ncentrati o n, ppm
C o ncentrati o n, ppm
108
0.0
0.0
300
400
500
600
700
800
300
400
500
C o ncentrati o n, ppm
Temperature, C
600
700
800
900
Temperature, C
3.5x10
3.0x10
2.5x10
2.0x10
1.5x10
1.0x10
CO 2
5.0x10
CO
(c)
CH 4
H2
0.0
300
400
500
60o0
700
800
Temperature, C
Fig. 7. DRM reaction with (a) 4%Pt/TiO2 , (b) 2%Pt 2%Ru/TiO2 and (c) 4%Ru/TiO2 .
centration at outlet of the reactor. Fig. 8(a) and (b) shows the
methane and CO2 conversion variation with temperature. Clearly
from these gures, 4% Ru/TiO2 and 4% Pt/TiO2 have shown better
performance compared with the bimetallic catalysts. 4%Ru/TiO2
has shown methane conversion as high as 98% and CO2 conversion of 95% at 800 C, whereas 4%Pt/TiO2 has shown 92% and 93%
CH4 and CO2 conversions. All these conversions are found to be
lower than equilibrium values at various temperatures denoted
by a dotted line in Fig. 8. Among all the catalysts, 2%Pt 2%Ru/TiO2
has shown very poor activity for the reforming reaction. All the
materials started showing activity from 400 C (other than 3%Pt
1%Ru/TiO2 ). With 2%Pt 2%Ru/TiO2 , the CO2 and CH4 conversions
reduced to 4% and again increased to higher conversion. This is
due to the coke formation during reaction and sintering of active
metal on the support as shown in Fig. 3. 2%Pt 2%Ru/TiO2 showed
37%CH4 conversion even at 900 C, so this bimetallic catalyst can
be considered to be ineffective for dry reforming reaction. With
3%Pt 1%Ru/TiO2 the DRM reaction started at 600 C, which is higher
compared with the other materials. At 900 C, CH4 and CO2 conversions reached 72% and 83%. Among all bimetallic catalysts, 1%Pt
3%Ru/TiO2 showed higher CH4 and CO2 conversions due to high Ru
content. With this material CH4 and CO2 conversions reached 83%
and 91% at 800 C. In all cases, at temperatures >700 C, CH4 and CO2
conversions are comparable, which indicates that the contribution
of reverse water gas shift (RWGS) reaction is negligible.
109
Fig. 8. (a) Variation of methane conversion (XCH4 ) with temperature, (b) Variation of carbon dioxide conversion (XCO2 ) with temperature, (c) H2 /CO molar ratio variation for
dry reforming reaction with temperature with bimetallic catalysts.
-7
(b)
-8.0
0.35
-8.5
-8
C O 2 co nv ersi o n, X CO
0.3
0.40
(a)
ln(rate), (rate in mol/(g-s))
0.4
110
-9
-10
1.2
0.2
1.3
1.4
-1
1000/T (K )
1.5
400 C
o
450 C
o
500 C
o
550 C
0.1
0.30
-9.0
0.25
-9.5
1.2
0.20
1.3
1.4
-1
1000/T (K )
1.5
400 C
o
450 C
o
500 C
o
550 C
0.15
0.10
0.05
0.00
0.0
200
400
600
800
-0.05
-200
1000
200
400
0.25
0.35
2
-8
-9
C O 2 co nv ersi o n, X CO
0.30
0.35
0.40
-10
0.20
1.2
1.3
1.4
-1
1000/T (K )
o
1.5
400 C
o
450 C
o
500 C
o
550 C
0.15
0.10
0.30
0.25
200
400
600
800
W/FCH (g-s/mol)
1000
1200
1.2
1.3
1.4
-1
1000/T (K )
1.5
400 C
o
450 C
o
500 C
o
550 C
-200
1400
200
400
W/F
0.25
0.16
2
-8.8
C O 2 co nv ersi o n, X CO
0.20
-8.6
-9.0
0.15
-9.2
0.10
1.3
1.4
-1
1000/T (K )
o
1.5
400 C
o
450 C
o
500 C
0.05
CO 2
800
1000
1200
1400
1600
1200
1400
1600
(g-s/mol)
-9.0
-9.5
-10.0
0.12
-10.5
1.2
1.3
1.4
-1
1000/T (K )
o
1.5
200
400
400 C
o
450 C
o
500 C
o
550 C
0.08
0.04
0.00
0.00
-200
600
(f)
ln(rate), (rate in mol/(g-s))
0.20
(e)
1600
-9.5
0.10
0.00
1400
-9.0
0.15
0.00
1200
-8.5
0.20
0.05
1000
(g-s/mol)
-8.0
-10.0
0.05
800
CO 2
(d)
ln(rate), (rate in mol/(g-s))
(c)
0.40
600
W/F
W/FCH (g-s/mol)
200
400
600
800
1000
1200
1400
1600
-200
W/F
W/FCH (g-s/mol)
4
600
CO 2
800
1000
(g-s/mol)
Fig. 9. Arrhenius plot for (a), (b) 4%Ru/TiO2 , (c), (d) 4%Pt/TiO2 , (e), (f) 2%Pt 2%Ru/TiO2 .
M + CH4 M CH4
k1,b
k2
M CH4 M C + 2H2
(1)
(2)
M C + CO2 + M 2M CO
(3)
k3,b
k4,f
2M CO 2M + 2CO
k2 K1 K3 K4 PCH4 PCO2
1 + K1 PCH4 K3 K4 PCO2 + K3
(5)
2
K4 PCO + PCO
TCD Signal, mV
4% Ru/TiO2
(4)
k4,b
rate =
111
2% Pt 2% Ru/TiO2
Ru/TiO2 does not result in any CO adsorption peak at any temperature. For dry reforming, Eley-Rideal mechanism without CO
adsorption on support is as follows,
k5,f
M C + CO2 M + 2CO
4% Pt/TiO2
100
(6)
k5,b
where, k2 = A2 exp
E
2
RT
and Ki =
(7)
ki,f
ki,b
= Ai exp
Hi
RT
500
600
.
The kinetic parameters were found by using nonlinear regression and listed in Table 3. The initial guesses were taken from the
literature [44]. Fig. 14 shows the kinetic model that ts the variation
of rate with partial pressure of CH4 .
(b)
(a)
3095
2953
3017
2186
2186
1341
3095
1267
2311
2358
1267
2311
2358
1341
600 C
Transmi ttance
600 C
1299
2109
1299
2109
2953
3017
Transmi ttance
400
k2 K1 K5 PCH4 PCO2
2
1 + K1 PCH4 K5 PCO2 + PCO
300
Temperature, C
200
450 C
300 C
450 C
300 C
2065
o
30 C
3500
3000
2500
2000
Wavenumber, cm
1500
-1
1000
4000
3500
3000
2500
1299
2953
3017
2175
1267
2311
3095
2358
1341
600 C
450 C
o
300 C
30 C
4000
3500
3000
2000
Wavenumber, cm
(c)
Transmi ttance
4000
30 C
2500
2000
Wavenumber, cm
-1
1500
Fig. 11. DRIFTS for CR with (a) 4%Pt/TiO2 , (b) 2%Pt 2%Ru/TiO2 , (c) 4%Ru/TiO2 .
1000
-1
1500
1000
112
(a)
1267
2311
2358
1299
2953
3017
2186
3095
3095
600 C
o
450 C
o
300 C
1267
2311
2358
600 C
1341
Transmi ttance
Transmi ttance
(b)
1299
2109
2953
3017
1341
450 C
300 C
30 C
4000
3500
30 C
3000
2500
2000
Wavenumber, cm
1500
1000
4000
-1
3500
3000
2500
2000
Wavenumber, cm
-1
1500
1000
(c)
1267
1341
600 C
Transmi ttance
1299
2311
2358
2953
3017
3095
450 C
300 C
30 C
4000
3500
3000
2500
2000
Wavenumber, cm
-1
1500
1000
Fig. 12. DRIFTS for POM with (a) 4%Pt/TiO2 , (b) 2%Pt 2%Ru/TiO2 , (c) 4%Ru/TiO2 .
Table 3
Kinetic parameters of 4% Ru/TiO2 and 4% Pt/TiO2 .
Parameter
k2
K1
K3
K4 K5
4% Ru/TiO2
(1.216 0.11) 10 exp 1518112
RT
4
(2.279 0.210) 10 exp 75416
RT
74318
5
10
(0.442 0.03) 10
exp
RT
4% Pt/TiO2
10
(6.724 0.21) 10 exp
4
(2.465 0.33) 10
exp
1691105
RT
65613
(0.338 0.041) 10
exp
RT
193237
RT
113
(b)
(a)
2298
2298
3013
3013
2385
2385
600 C
Transmi ttance
Transmi ttance
600 C
o
450 C
300 C
450 C
300 C
2058
o
30 C
30 C
3095 2950
3095 2950
1349
1303
1349
1303
4000
3500
3000
2500
2000
Wavenumber, cm
1500
-1
4000
1000
3500
3000
2500
2000
Wavenumber, cm
1500
1000
-1
(c)
2298
3013
2385
2108
2179
Transmi ttance
600 C
3095 2950
o
450 C
300 C
o
1349
1303
30 C
4000
3500
3000
2500
2000
Wavenumber, cm
1500
1000
-1
Fig. 13. DRIFTS for DRM with (a) 4%Pt/TiO2 , (b) 2%Pt 2%Ru/TiO2 , (c) 4%Ru/TiO2 .
500
(a)
400
300
300
200
673 K
723 K
773 K
823 K
200
400
(b)
673 K
723 K
773 K
823 K
100
100
0
0
Fig. 14. Rate variation with partial pressure of methane (a) 4% Ru/TiO2 and (b) 4% Pt/TiO2 .
4. Conclusions
In the present study, Pt and Ru catalysts with TiO2 were prepared
by using sonochemical synthesis. The materials were characterized by XRD and combination of anatase and rutile phases was
observed. The bimetallic Pt and Ru doped TiO2 has higher surface
area among all composites. These materials are employed for all
dry reforming, partial oxidation and autothermal reforming and
combined dry autothermal reforming. 4%Ru/TiO2 and 4%Pt/TiO2
has shown favorable hydrogen conversions for all reactions. But
higher conversions and close to equal H2 /CO ratio were observed
in case of dry reforming for 4%Ru/TiO2 and 4%Pt/TiO2 . All bimetal-
114
80
70
% Conversion
60
50
40
30
20
10
0
0
10
12
14
16
18
20
Time on stream, h
Fig. 15. Stability of 4% Ru/TiO2 , 2%Pt 2% Ru/TiO2 and 4% Pt/TiO2 at 923 K.
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