Steam Reforming of Toluene on Ni/Phyllosilicate: Enhanced Catalytic Activity and Stability
Chun Shen*, Hao Yu, Wuqing Zhou, Shina Ma, Tianwei Tan
Beijing University of Chemical Technology, Chaoyang,
Beijing, PR China
*Corresponding author: Chun Shen, Beijing Key Laboratory of Bioprocess, College of Life Science
and Technology, Beijing University of Chemical Technology, No. 15 of North
Three-Ring East Road, Chaoyang District, Beijing 100029, PR China. Tel: +8618001181869;
Email: shenchun@mail.buct.edu.cn
Received Date: 27 December,
2016; Accepted Date: 12 January;
2017; Published Date: 18 January,
2017
Citation: Shen C, Yu H, Zhou W, Ma S, Tan T (2017) Steam Reforming of Toluene on Ni/Phyllosilicate: Enhanced Catalytic Activity and Stability. J Nanomed Nanosci: JNAN-105. DOI: 10.29011/JNAN-105. 100005
1. Abstract
1.
Introduction
( 1 )
( 2 )
Where X
is the conversion of toluene, nin
is the mole of toluene and is the mole of
unreacted toluene Si is the
selectivity of i.
3.1. Characteristics of Ni-based catalysts
XRD patterns of Ni/SiO2P, Ni/SiO2 and Ni/ZSM-5catalysts are shown as (Figure 2).
Diffraction peaks at 21.6°, 30.2°,
35.6°, 44.0°, 60.4°,
and 71.3° are contributed to the
(111), (110), (220), (222), (121), (130) facets of PS support, respectively [40-41]. Due to the small size and good dispersion of
Ni nanoparticles supported on SiO2 by
the DP method, the peak of Ni was difficult to discern. On the other hand,
diffraction peaks at 44.5°,51.8°, and76.4° appeared in the patterns of Ni/ZSM-5 and Ni/SiO2 are contributed to (111), (200), and (220)
facets of nickel nanoparticles. Diffraction peaks at 21.0°, 26.7°,
36.6°, 39.7° and 50.4°
of Ni/SiO2 are contributed to the
facets of SiO2. The crystal Ni
nanoparticle size of Ni/ZSM-5 and Ni/SiO2
shown in (Table 1) were calculated to be 27 nm
and 25 nm, respectively according to the Scherrer’s equation.
(Figure 3) shows the H2-TPR results of Ni/SiO2P, Ni/SiO2
and Ni/ZSM-5. Ni/ZSM-5 showed two reduction peaks at around 559K and around 573
K, which are attributed to the reduction of NiO.
As for Ni/SiO2,
the main reduction peak around 583K can be ascribed to the reduction of NiO
particles, the peak around 798 K could be assigned to the Ni2+ ions interacting with SiO2. Two reduction peaks could also be observed in
the result of Ni/SiO2P, the small
peak at 561 K could be ascribed to the reduction of NiO particles, while Ni2+ located in phyllosilicates were reduced at
around 823K [42]. The highest main reduction peak of Ni/SiO2P indicated the strongest metal-support
interaction which
would be benefit for the preparation of Ni nanoparticles with small size and
narrow distribution. TEM images of the as-prepared catalysts are shown in (Figure 4).
The perfectly formed structure of PS and mesoporous could be clearly observed. TEM images of Ni nanoparticles supported on PS with Ni content of 17.4 wt.%, 22.4 wt.%, 26.8 wt.%, 31.3 wt.% are shown as (Figure 4(a), 4(b), 4(c), and 4(d)), respectively. And TEM images of Ni/SiO2 and Ni/ZSM-5 catalysts with the Ni content of 24 wt.% are shown as (Figure 4(e) and 4(f)) respectively. The corresponding distribution histograms of Ni nanoparticles are shown as (Figure 4(g), 4(h), 4(i), 4(j), 4(k), 4(l)) respectively. The histograms were derived from corresponding TEM images by more than 100 particles. The mean crystal nickel particle size is calculated using the equation ( where ni is the number of corresponding nickel particles with a diameter of di.). The mean particles size of Ni nanoparticles are3.3nm, 3.6 nm, 4.2 nm and 6.0 nm for catalysts with Ni contents of 17.4 wt.%, 22.4 wt.%, 26.8 wt.%, and 31.3 wt.%, respectively. And the mean diameters of Ni particles supported on SiO2 and ZSM-5 are 23.9 nm and 30.0 nm, respectively. Obviously, as expected, Ni nanoparticles supported on PS exhibited small mean particle size and narrow size distribution which might be of great help for improving the catalytic activity and stability.
With the increase of residence time, the
conversion of toluene increased gradually. The conversion was only 43.8% when
the residence time was 0.1s, and the conversion rapidly increased to 99% when
the residence time increased to 0.37s. Longer residence time means longer
reaction duration, so the conversion would increase as well. TEM image of the
used catalyst is shown as (Figure 5) in the
supporting material. After the catalytic reaction, Ni nanoparticles still
highly dispersed on the surface of PS.
( 3 )
( 4 )
3.4. Effect of Ni content on conversion
Catalytic performances of Ni/SiO2P catalysts with various Ni contents are shown
in (Figure 7).
The conversion of toluene increased from
45% to 78% when the Ni content increased from 21.0 wt.% to 26.8 wt.%. However,
further increase in Ni content resulted in reduction of reaction rate. Catalyst
with the highest Ni content of 31.3 wt.% showed even worse performance than
that of the catalyst with the Ni content of 26.8 wt.%. This may be driven by
two factors: first, with the increase of the loading amount, the Ni particle
size increased to almost 6.0 nm decreasing the catalytic activity (as shown in (Figure 4(d)); second, only the Ni nanoparticles
loaded on the outer part played a role during the reaction.
3.5. Catalysts stability study
The
catalytic stability of our catalysts was studied. The performances of Ni/SiO2P,Ni/SiO2 and Ni/ZSM-5are shown in (Figure 8, 9, and 10), respectively.
As shown
in (Figure 8), the initial toluene conversion
reached 100%, and kept at 90% even after 660 min. The main gas production is H2 with the selectivity of around 60%.
Comparatively, Ni/SiO2 and Ni/ZSM-5
showed much worse stability for the steam reforming of toluene. For Ni/ZSM-5,
the initial conversion was58%, and the conversion is rapidly decreased. And the
conversion of toluene was only 62%, and the conversion decreased to 31% after
660 min using Ni/SiO2 as the
catalyst. Above all, Ni/SiO2P showed
the highest catalytic activity and the best stability. Steam reforming of
toluene has also been investigated in other works. According to Quitetea [43], the conversion of toluene decreased from 78% to
59% after 660 min. Comparisons in catalytic performances with other works are
listed in (Table 2) [27,44,45].
Therefore, the PS supported with Ni nanoparticles showed high catalytic
activity and stability.
4. Conclusion
PS supported with Ni nanoparticles was successfully prepared and acted as a novel heterogeneous catalyst for steam reforming of toluene. Compared with Ni/SiO2 and Ni/ZSM-5, the Ni/SiO2P catalyst prepared in this work showed smaller Ni nanoparticles size and narrower size distribution. The mean Ni nanoparticle size of Ni/SiO2P varied from 3.3 to 6.0nm with the loading amount increased from 17.4 wt.% to 31.3 wt.%. The pore volume, pore size and specific surface area of Ni/SiO2P were 0.92 mL/g, 8.40 nm and 436.0 m2/g, respectively. Effects of residence time, S/C and Ni content on conversion were studied systematically. The conversion increased with the increase of residence time. The increase of S/C could also improve the conversion of toluene. The Ni content was optimized to be 26.8 wt.%. The as-prepared Ni/SiO2P catalysts showed high catalytic activity and stability. The conversion of toluene reached 100% under the reaction conditions (reaction temperature was 923 K; 0.3 g catalyst; S/C was 3; Ni content of 26.8 wt.%; toluene feed rate was 2mL/h). And the conversion of toluene just decreased from 100% to 90% after 660 min.
5. Acknowledgements
We gratefully acknowledge the support of
the National Nature Science Foundation of China (21606008, 21436002), the
National Basic Research Foundation of China (973 program) (2013CB733600), the
Fundamental Research Funds for the Central Universities (ZY1630, JD1617), and
the Fundamental Research Funds for the Central Universities (buctrc201616,
buctrc201617).
Figure 1: N2 Adsorption-Desorption Isotherms and BJH Mesopore
Size Distribution (Inset) of Catalysts with Ni Content Of 26.8 W%; (A): Ni/PS,
(B): Ni/SiO2; (C): Ni/ZSM-5.
Figure 2: XRD Pattern of
Catalysts with Ni Content Of 25 Wt.%; (A): Ni/PS; (B) Ni/SiO2; (C) Ni/ZSM-5.
Figure 3: H2-TPR Results of the As-Prepared Catalysts.
Figure 4(a-l): TEM Images of Catalysts;
(a), (b), (c), and (d): Ni/SiO2P with
Ni Content of 17.4 wt.%, 22.4 wt.%, 26.8 wt.%, 31.3 wt.%; (e): Ni/SiO2 with Ni Content of 26.8%; (f): Ni/ZSM-5 with
Ni Content of 26.8%;(g), (h), (i), (j), (k), and (l): Histograms of Particle
Size Distribution for Ni/SiO2P, Ni/
SiO2, and Ni/ ZSM-5, respectively.
Figure 5: Effect of
Residence Time on Conversion; Reaction Temperature: 923K; 0.3 G Catalyst; Ni Content:
31.6 Wt.%; Toluene Feed Rate: 2ml/H; S/C: 1; The Flow Rate of N2: 30ml/Min.
Figure 6: Effect of S/C on
Conversion; Reaction Temperature: 923K; 0.3 G Catalyst; Ni Content: 31.6 Wt.%;
Toluene Feed Rate: 2ml/H; the Flow Rate of N2:
30ml/Min.
Figure 7: Effect of Ni Content
on Conversion; Reaction Temperature: 923K; 0.3 G Catalyst; S/C: 3; Toluene Feed
Rate: 4ml/H; The Flow Rate of N2:
30ml/Min.
Figure 8: Catalysts Stability
Study on Ni/SiO2P; Reaction
Temperature: 923K; 0.3 G Catalyst; S/C: 3; Ni Content: 26.8 Wt.%; Toluene Feed
Rate: 2ml/H; The Flow Rate of N2:
30ml/Min.
Figure 9: Catalysts Stability
Study on Ni/SiO2; Reaction
Temperature: 923K; 0.3 G Catalyst; S/C: 3; Ni Content: 26.8 Wt.%; Toluene Feed
Rate: 2ml/H; The Flow Rate of N2:
30ml/Min.
Figure 10:
Catalysts Stability Study on Ni/ZSM-5; Reaction Temperature: 923K; 0.3 G
Catalyst; S/C: 3; Ni Content: 26.8 Wt.%; Toluene Feed Rate: 2ml/H; The Flow
Rate of N2: 30ml/Min.
Catalyst |
Ni content (wt.%) |
SAa (m2/g) |
PDb (nm) |
PVc (cm2/g) |
D(Ni)d (nm) |
Ni/SiO2P |
26.8 |
436.00 |
8.40 |
0.92 |
- |
Ni/SiO2 |
26.8 |
409.10 |
3.20 |
0.03 |
25 |
Ni/ZSM-5 |
26.8 |
183.80 |
2.44 |
0.12 |
27 |
a: Specific surface, b: average pore
diameter, c: pore volume, d: Ni nanoparticle size determined from XRD. |
Catalyst |
Ni content (wt.%) |
SAa (m2/g) |
PDb (nm) |
PVc (cm2/g) |
D(Ni)d (nm) |
Ni/SiO2P |
26.8 |
436.00 |
8.40 |
0.92 |
- |
Ni/SiO2 |
26.8 |
409.10 |
3.20 |
0.03 |
25 |
Ni/ZSM-5 |
26.8 |
183.80 |
2.44 |
0.12 |
27 |
a: Specific surface, b: average pore diameter, c: pore volume, d: Ni nanoparticle size determined from XRD. |
Table 1: Structural Properties and Surface Morphology of Catalysts.
s |
Reaction temperature (K) |
Toluene conversion (%) |
TOF×104 (s-1) |
Reference |
Ni/SiO2P Ni/La0.7Sr0.3AlO3−δ Ni/Ce/Mg/olivine Ni-Mn/dolomite |
923 873 1005 1073 |
99 92 93 65 |
17.0 5.8 4.8 1 |
This work [43] [27] [44] |
Table 2: Comparisons in Catalytic Performance with Other Works.
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