Energy Conversion and Management
Energy Conversion and Management
Highlights
At 550 and 600 C, catalyst showed longer activity for the whole test.
At 600 C, a 614.25 gc/gNi of carbon was obtained using 30% Ni/Y zeolite
catalysts.
Produced filamentous carbon has the same diameter as the metallic nickel itself.
VHSV has reverse and non-linear relevancy to the weight of Ni/Y zeolite catalyst.
Abstract
The objective of this paper is to study the influences of different operating
conditions on the hydrogen formation and properties of accumulated carbon
from methane decomposition using zeolite Y supported 15% and 30% Ni,
respectively, at a temperature range between 500 and 650 C in a pilot scale
fixed bed reactor. The temperature ramp was showed a significant impact on
the thermo-catalytic decomposition (TCD) of methane. An optimum temperature
range of 550600 C were required to attain the maximum amount of methane
conversion and revealed that at 550 and 600 C, catalyst showed longer
activity for the whole studied of experimental runs. Additionally, at 550 C, the
methane decomposition is two times longer for 30% Ni/Y zeolite than that for
15% Ni/Y zeolite catalyst, whereas it is almost three times higher at 500 C. A
maximum carbon yield of 614.25 and 157.54 gc/gNi were reported after end of
the complete reaction at 600 C with 30% and 15% Ni/Y zeolite catalyst,
respectively. From BET, TPD, and XRD analysis, we had reported that how the
chemistry between the TCD of methane and metal content of the catalysts
could significantly affect the hydrogen production as well as carbon nano-fibers.
TEM analysis ensured that the produced carbon had fishbone type structures
with a hollow core and grew from crystallites of Ni anchored on the external
surface of the catalysts and irrespective of the metal loadings, the whisker
types of nano filaments were formed as confirmed from FESEM analysis.
Nevertheless, the effect of volume hourly space velocity (VHSV) on the
methane conversion was also investigated and reported that the methane
conversion increased as VHSV and nickel concentration in NiY catalysts
increased. Additionally, the initial methane decomposition rate increases with
VHSV and it has reverse and non-linear relevancy to the weight of Ni/Y zeolite
catalyst.
Keywords
Coproduction;
Hydrogen;
Carbon nanofiber;
Zeolite Y;
Supported Ni;
Methane decomposition
1. Introduction
The idea of co-production of hydrogen and carbon nanomaterials from thermocatalytic decomposition (TCD) of methane has been having a great mettlesome
attention among the Scientists and Engineers around the earth. This is because
it produces environmentally benign hydrogen and carbon nanomaterials that
seem to be a clean, halcyon and officious product in foreseeable
future [1], [2] and [3]. Both of the products are derived from the TCD of
methane, according to the following equation at low temperatures ranging from
400 to 700 C when the process associated with the schemes of metal
catalysts [4]:
equation(1)
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Because of its lower cost selectivity, and much higher active site/carbon
capacities, Ni has been broadly assessed in manufacturing of hydrogen from
methane decomposition as compared with the cobalt or iron [5] and [6].
Regards to catalytic materials, the use of zeolitic materials has of both
fundamental and practical significance due to their well-defined pore
distributions, high surface area and unique catalytic features as compared to
traditional catalyst supported on alumina, silica-alumina, CeO 2, peroviskite,
active carbon, La2O3, and MgO [7]. The Y-zeolite has comparatively larger pores
(Entry aperture of 0.74 nm, and a diameter of 1.3 nm) than the others such as
HZSM-5 (0.510.55 nm; 0.510.55 nm) and zeolite A (0.41 nm 1.1 nm).
Therefore, the introduction of nickel metals into Y zeolites by means of a
suitable method such as impregnation or ion-exchange, etc., would make it
suitable for TCD of methane. However, the research work on Y zeolite
supported Ni catalysts in hydrogen and carbon nanomaterials production from
TCD of methane is still very limited even though a great number of articles have
already been disclosed the application of the metallic nickel catalysts on the
activity of different support materials [2], [6] and [8].
produced carbon and the textural features of the samples used are also
examined for different operating parameters.
2. Experimental Methodology
2.1. Experimental view and operating conditions
Raw methane (99.9995%) purchased from Linde Compressed and nitrogen
(99.999%) served by Air products were utilized in the experiment. The zeolite Y
catalyst (surface area = 650 m2/g, Si/Al = 10) purchased from Tosoh
Corporation, Japan and used it as in the form of impregnation with nickel
metals. The catalysts preparation methods and experimental apparatus used
are described in details elsewhere [3]. In each experimental run, typically 3 g of
Ni/Y zeolite catalyst was loaded into the reactor. Then the reaction started with
the flow of 1 L/min of CH4 over the catalyst bed using 15% and 30% Ni/Y zeolite
catalysts at 500, 550, 600, and 650 C, respectively. Before reaction, the
catalyst is reduced by 20% hydrogen at 600 C (heating ramp was 10 C/min)
in nitrogen for 2 h in order to obtain active metallic state in the catalyst and this
is continued until system reached a set temperature. After that, a 1 L/min of
nitrogen gas was thoroughly flushed for another 1 h within the reactor before
feeding the set CH4 flow rate. The reaction continued until the spontaneous
hydrogen yield below 7%. The percentage of methane conversion calculated
from data obtained from outflow gas that was analyzed by an online gas
analyzer (GA). Using GA, other than hydrogen, no gaseous products detected.
A flow of nitrogen was purged through the reactor to cool down it to ambient
temperature after the reaction, and the total amount of solid carbon measured
by using the following equation:
equation(2)
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In Eq. (2), wtot and wcat represents the total and initial weight of the catalyst after
and before reaction, respectively. This yield was also expressed in the form of
gdep/gNi.
2.2. Characterization techniques
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where 0.9 is the Scherrer constant, is the full width at half maxima (in
radians) of a reflection located at 2.
The morphological structure and the diameter distribution of the catalysts and
carbon nanomaterials were performed on a Field Emission Scanning electron
microscopy, FESEM (QUANTA 450 FEG) and transmission electron
microscopy, TEM (Hitachi HT-7700). Totally, more than 50 carbon nanofibers
(CNFs) was measured on the TEM images, and the result reported as the
arithmetic mean value of the data.
Ru
n
no.
T(
C)
Initia
l
H2a(
%)
Initial
CH4b(
%)
At time = 10 min
AHFR
THF
(mmol/
(mol/g (gcat.
min))
cat)
With 15% Ni-supported Y zeolite catalysts
1
500 19.0 10.52 36.14
4.88
9
2
550 30.2 17.73 59.35
8.56
7
3
600 36.3 22.11 70.21
10.46
2
4
650 41.0 25.76 80.62
12.40
2
With 30% Ni-supported Y zeolite catalysts
5
500 18.0 9.91
39.36
5.36
8
6
550 34.8 20.82 70.41
10.49
5
7
600 48.8 31.57 95.27
15.36
5
8
650 58.5 41.67 116.6
20.22
8
5
At time = 26 min
THF
(mol/g
cat)
AHFR
(mmol/
(gcat.
min))
81.08
4.67
133.3
3
159.3
4
182.9
1
8.19
84.47
4.89
159.2
3
216.3
1
265.8
0
10.10
10.11
11.97
14.82
19.57
ACFR,
(mmol/(gcat
min))
At time = 60 min
AHFR
(mmol/
(gcat.
min))
After end of
complete
reaction
161.5
4
270.7
0
331.5
5
372.3
4
4.17
1.35
7.41
2.06
9.39
2.87
10.82
3.61
172.4
0
324.5
8
449.1
5
557.1
9
4.47
1.79
9.17
2.45
13.66
4.32
18.16
6.01
THF
(mol/g
cat)
The initial hydrogen (%) was derived from the curve fitting of instantaneous hydrogen yield versus
reaction time using a proper nth order polynomial equation with regression coefficients greater
than 0.99 and then substituted of time equal to zero in the right hand side of the curve fitting
equation.
b
The initial methane (%) was calculated exactly as the same method as for initial hydrogen (%)
except, in this case, using the methane conversion against reaction time curve fitting.
Table options
Fig. 1.
Representation of methane conversion as a function of reaction time on stream for (a) 15% Ni/Y
zeolite catalyst, and (b) 30% Ni/Y zeolite catalyst.
Figure options
In accordance with the above results, Inaba et al. [9] has demonstrated that Nisupported on USY zeolite shows the longer activity for more than 6 h among
the others. Very similar results were reported by Ashok et al. [8] who found that
highest activity subjected to 30% Ni/HY catalyst (12 h) and higher activity of
955 molH2/molNi compared to other tested support on HY, USY, SiO2 and SBA-15
at 550 C. With 15% Ni/HY catalysts, they found hydrogen yield of 993
molH2/molNi, whereas 370 molH2/molNi of hydrogen production was noticed for
60% Ni/HY catalysts. Michalkiewicz and Majewska [13] reported about 55% of
hydrogen was produced using the Ni/ZSM-5 (3 0 0) catalysts from methane
decomposition at a temperature range of 650 C and 700 C. The highest
carbon yield was reported to be approximately 32 wt.% at 700 C by using Ni
particle size of about 3060 nm depending on the temperature. In comparison
to these results, ours results is a quite bit lower but our study examined the
temperature range which is much lower than do Michalkiewicz and Majewska
research.
The above discussion established that the carbon deposition is directly related
to the metal content of the catalyst. The highly distribution of nickel species into
the zeolite Y cages and likely more significantly, the synergistic influence
between the microporous surfaces of zeolite Y and metallic nickel were
considered to be the reasons for higher catalytic performance of 30% Ni/Y
zeolite [7]. A greater electron density on the surface of metallic nickel and
increment of the retention capacity of hydrogen in the Ni/Y zeolite catalysts
were caused from the synergistic effects due to it may cover the interactions
between the higher ionic microporous surface of zeolite Y and the nickel
particles. Eventually, a rapid catalytic deactivation of 30% Ni/Y zeolite was
Fig. 2.
Representation of accumulated carbon as a function of reaction time on stream for (a) 15% Ni/Y
zeolite catalyst, and (b) 30% Ni/Y zeolite catalyst.
Figure options
Table 2.
Experimentally observed the behavior of AC with total methane conversion for two types of Ni/Y
zeolite used catalyst.
Run
no.
T(C)
Total
methane
conversion
(mol/gcat)
t = 10 min t = 26 min
With 15% Ni-supported Y zeolite catalysts
1
500
197.08
0.151
0.378
2
550
526.40
0.258
0.652
3
600
586.21
0.323
0.82
4
650
405.47
0.378
0.958
With 30% Ni-supported Y zeolite catalysts
5
500
482.56
0.145
0.37
6
550
1047.30
0.476
0.92
7
600
1242.54
0.484
1.22
8
650
821.67
0.61
1.56
TACa(gdep/gcat)
Mc(%) Mc(gdep/gNi)
After end of
complete reaction
t = 60 min
After end of
complete
reaction
0.80
1.41
1.78
2.08
193.91
1248.97
1083.35
372.39
428
1013
921
684
66.56
157.54
143.23
106.37
0.836
1.80
2.70
3.44
1121.96
4097.12
6651.35
1075.19
923
1567
2629
1534
215.65
366.12
614.25
358.41
The TAC was determined by summing on the total instantaneous solid carbon accumulated per
initial Ni-supported Y zeolite catalyst mass.
Table options
600 C with 30% Ni/Y zeolite catalyst. On the other hand, the highest M c value
for 15% Ni/Y zeolite was 157.54 gc/gNi; which is even lower than from the lower
Mc obtained with 30% Ni/Y zeolite catalyst at 500 C. Evidently, the TCD of
methane over Ni/Y zeolite gave maximum amount of carbon yield in terms of
the quantity of surface nickel at 550 and 600 C. With increase of temperatures,
the carbon yield reached a maximum point and then starts to decrease till the
complete deactivation of the catalyst. Hernadi et al. [18] have reported the
carbon production up to 1.6 gC/gcat for the cracking of an array of organic
reactants over Co and Fe supported silica and zeolite. Park and
Keane [19] have remarked 70 gc/gNi carbon yield after 60 min reaction from the
decomposition of ethylene at 600 C using Ni supported NaY zeolite. Our
carbon yields compare favorably with those generated from methane over
supported Ni-alumina (244 gc/gNi) and from over Ni/Cu/Al (585 gc/gNi) [20].
3.1.2. Effect of VHSV on TCD of methane
Fig. 3 shows the effect of volume hourly space velocity (VHSV) where
percentage of methane conversion is typified as a function of reaction time for
various VHSV, 8.5760 Lgcat1 h1, at 600 C for different values of catalyst
weight (17 g) along with constant methane flow rate of 1 L/min. It can be
apparent from Fig. 3(a) that the deactivation rate of decomposition reaction is
almost half of the Fig. 3(b) for VHSV range between 8.57 and 60 Lgcat1 h1. For
example, at VHSV of 20 Lgcat1 h1, the catalytic activity endures a more than
10 h before falling almost zero with 30% Ni/Y zeolite catalyst, whereas, it was
only more than 5 h for 15% Ni/Y zeolite catalyst.
Fig. 3.
Representation of methane conversion versus reaction time on the stream at different volume
hourly space velocity for (a) 15% Ni/Y zeolite catalyst, and (b) 30% Ni/Y zeolite catalyst.
Figure options
It can be ensured from Fig. 3(a) and (b) that the methane conversion increased
as VHSV and nickel concentration in NiY catalysts increased. The more
insightful observation is reintroduced that, with increasing VHSV, the time
needed for catalyst deactivation gradually increases [20] and [21]. This is
because a lower contact time results from a higher VHSV, the catalyst
deactivation increased as the VHSV increased. The initial hydrogen yield was
65.90% at a low spatial velocity of 8.57 Lgcat1 h1 while its representative stability
time was more than 5 h with 30% nickel concentration in Y zeolite catalyst. As
compared with this result, 15% Ni/Y zeolite catalyst gave initial hydrogen of
50.35%, having stability time more than 2 h at the same spatial velocity of
8.57 Lgcat1 h1. Experimental observation marks that the studied range of VHSV
still figured a high catalytic stability in originating hydrogen production. Using
Ni/Y zeolite catalyst and different VHSV at 600 C, the following Table 3 is
represented an inclusion of experimentally obtained results. From Fig. 3(a) and
(b), it can be visualized that the initial methane conversion was decreased
gradually with increasing VHSV, indicating a continuous diminishing in the
hydrogen yield over the course of the reaction. As a matter fact that the
methane conversion was noticeably increased from 23.10 to 50.40 vol% as with
decreased space velocity from 60 to 8.57 Lgcat1 h1 for 30% Ni/Y zeolite catalyst.
In case of 15% Ni/Y zeolite catalyst, these values increased from 16.65 to
33.92 vol% as shown in Table 3. This carried on to a lower constant hydrogen
yield (below 7%) whilst the complete deactivation of the catalyst.
Table 3.
Summarized experimental results with different VHSV at 600 C using Ni/Y zeolite catalyst.
Initial
TCFR (mmol/(gcat min))
Ru VHSV
H2yie
1
CH (
n
(Lgcat h ld
Ro(mmol/gcat
no. 1)
(%)
%)
min)
At
At
At
time = 10
time = 26
time = 60
min
min
min
With 15% Ni-supported Y zeolite catalysts
1
8.57
50.3
33.92
3.62
22.89
51.52
104.84
5
2
12
46.6
30.31
4.33
25.75
58.27
120.70
9
3
20
36.3
22.11
5.29
31.90
70.78
139.94
2
4
60
28.5
16.65
12.08
73.66
162.70
317.85
3
4
ACFR
(mmol/
(gcatmin))
After end of
complete
reaction
2.59
2.22
2.17
5.66
Ru
n
no.
VHSV
(Lgcat1 h
1
)
Initial
H2yie
ld
(%)
CH (
4
%)
At
time = 10
min
At
time = 26
min
At
time = 60
min
ACFR
(mmol/
(gcatmin))
After end of
complete
reaction
32.56
72.38
144.24
1.97
29.30
66.56
139.13
2.28
35.15
80.22
169.46
2.86
71.23
161.03
334.81
6.91
Ro(mmol/gcat
min)
Table options
It can be clearly obvious from Table 3 that ACFR and initial methane conversion
move in reverse directions. Before catalysts completely deactivated, an
optimum ACFR of 2.86 and 2.17 mmol/(gcat min) can be obtained at space
velocity of 20 Lgcat1 h1 due to a high stability is more pronounced for this
experimental run for 30% and 15% Ni/Y zeolite catalysts, respectively.
Moreover, a higher VHSV, increases the TCFR in the reported results for metal
catalyst is not far away from our observation as reported in Table 3.
Fig. 4 reveals the methane decomposition rate (RD) in (mmol/(gcat min)) as a
function of reaction time for both type of catalyst. The decomposition rate can
be described as the ratio between product of molar flow rates of methane
(mmol/min) and methane fractional decomposition to weight of the Ni/Y zeolite
catalyst [5]. From Fig. 4, it may be inferred that a high initial RD followed by a
dramatic reduction. The initial methane reaction rate (Ro) in (mmol/(gcat min))
was derived from the curve fitting of Fig. 4 using a proper nth order polynomial
equations with regression coefficients greater than 0.99 and then equalizing the
time to zero in the right hand side of the curve fitting equation. From Table
3 and Fig. 5, it can be seen that Ro increases with VHSV and it has a reverse
and non-linear relevancy to the weight of Ni/Y zeolite catalysts. The higher
concentration of nickel in Ni/Y zeolite causes a higher reduction for Ro. On the
other hand, when higher weight of Ni/Y zeolite was used, the yield of hydrogen
was reduced because of the declines of contact time between the reactant
molecule and catalyst, resulting from the increased VHSV. At the same time,
the Ro enhanced due to decreasing the influence of methane pressure drop that
causes from the greater methane decomposition along with dilution by the
formed hydrogen [22]. However, in Fig. 5, the upper curve indicates that 30%
Ni/Y zeolite catalysts was produced maximum amount of hydrogen as well
carbon nanofiber.
Fig. 4.
Representation of methane decomposition rate as a function of time for (a) 15% Ni/Y zeolite
catalyst, and (b) 30% Ni/Y zeolite catalyst.
Figure options
Fig. 5.
Representation of initial methane decomposition versus (a) weight of Ni/Y zeolite, and (b) VHSV
for both 15% and 30% Ni/Y zeolite catalysts at constant methane flow rate of 1 L/min.
Figure options
Total pore
volumee(cm3/
g)
0.388
0.1756
0.272
0.1266
0.237
2.88
9.90
88.71
0.0415
0.274
6.28
17.16
69.09
0.0413
0.209
5.42
19.45
63.43
0.0356
0.201
5.87
21.92
78.50
0.0457
0.242
5.62
17.36
65.35
0.044
0.211
5.39
19.07
55.83
0.0213
0.152
6.06
29.93
61.99
0.0167
0.138
7.49
30.87
52.00
0.0250
0.221
8.55
28.93
Averag
e
particle
size
(nm)
4.73
Micropo
re
volume
(cm3/g)d
0.2684
Pore
size
(nm)
2.45
2
2.45
6
6.76
Represents the total pore volume evaluated from nitrogen uptake at a relative pressure (P/Po) of
N2equal to 0.99.
Table options
It has reported that a fewer quantities of weak acid sites were enwrapped to the
raw Y zeolite [19]. The Na+ ions of the Y zeolite were substituted by Ni2+ ions
mimicked the hydrogen reduction to create Bronsted acid sites (protons)
through the preparation method, resulting in acidity to a greatest extent. It has
suggested that the reduction of nickel species in the impregnated catalyst was
brought to a fewer surface acidity, which in turns fit in reposing the smaller
particles [7]. Actually, the counter diffusion between the cations and protons of
the metal is providing higher numbers of metal ions into the pore mouths;
resulting in form a zerovalent external metal phase followed a reduction. This
type of counter diffusion is significantly accelerated when there is a high
protonic concentration was present in the Y zeolite matrix. The assemblage
process which is known to as responsible to form the particle growth may be
disrupted because of the presence of high volume of cation density in the
diffusion path of Ni content. Thereat, the carbon growths is far more prevailing if
the outer surface areas of Y zeolite are covered by the metal particles and
these sites are exclusively forcible if impregnation processes is employed to
introduce the metal precursor [7]. This phenomenon may be anticipated by
considering the Y zeolite structure. Structurally, zeolite Y has 8 supercages, 8
sodalite cages and 16 hexagonal prism cages per unit cell [23]. It has pore
mouth size of 0.74 nm, and the supercage size has 1.3 nm, suggesting that the
void volume of Y zeolite (0.85 nm3) is big enough to accommodate the
dispersed metallic nickel in the supercages. Nevertheless, the production of
carbon nanomaterials with a diameter below 1.3 is possible if Ni species lodged
in the Y zeolite supercages. Indeed, such type of production is not promising
energetically at all [7].
Table 4 shows that the surface areas subjected to the formation of CNFs are
higher than that of the surface area subjected to the formation of carbon
nanotube, but having a position between the amorphous carbon (surface
area = 670 m2/g) and the graphite (surface area = 7 m2/g) [24]. With the raise of
temperatures ramp from 500 to 600 C, the BET surface area decreased and
afterwards, initiated to increase. The total pore volume and micropore volume
has followed the same trends as BET surface area do until 600 C and then
onset to increase even though a smaller micropore volume was observed in all
Fig. 6.
Representation of NH3-TPD profile for selected sample catalyst.
Figure options
Fig. 7.
Powder XRD patterns of fresh catalyst after calcination and reduction: (A and C) with 15% Ni/Y
zeolite catalyst and (B and D) with 30% Ni/Y zeolite catalyst, respectively. Quadrilateral () and
square () represents Y zeolite phase and NiO phase, respectively.
Figure options
Li et al. [27] have demonstrated that at the low temperature (550 C), the
reduction of catalyst is far from complete. However, after reduction of catalyst,
the intensity of Y and NiO phase is slightly reduced in 30% Ni/Y zeolite (Fig.
7(D)) but significantly reduced in 15% Ni/Y zeolite (Fig. 7(C)). The diffraction
peaks at 2 = 37.44, 43.47, and 63.20 are corresponding to crystalline NiO
phases (ICDS NO: 01-1239) and their interlayer distance are pointed out as
2.40, 2.08, and 1.47 respectively. However, the mean diameter of NiO
crystallites in 30% Ni/Y zeolite was determined of 39.54 nm, while it was 41.69
for 15% Ni/Y zeolite attributing to the larger NiO particles lodged on the zeolite
surface in before reduction. On the other hand, after reduction, the mean
diameter of Ni crystallites was 34.84 nm for 30% Ni/Y zeolite, while it was
36.57 nm for 15% Ni/Y zeolite attributing to the larger Ni particles anchored on
the zeolite surface in after reduction.
At the temperature range of 500650 C, the X-ray diffraction profiles of
deactivated catalysts in presence of 30% and 15% Ni/Y zeolite catalysts are
shown in Fig. 8 and Fig. 9, respectively. As can be seen from Fig. 8 and Fig.
9 that, the broad diffraction peak at 2 = 26.34, 44.83, 54.23, and 77.54 are
characteristic to the graphitic carbon (ICDS NO: 01-0640) and their d values
are defined as 3.38, 2.02, 1.69 and 1.23 , respectively. The presence of
metallic Ni phase (ICDS NO: 04-0850) in the deactivated catalyst gave the
diffraction peak at 2 = 44.5, 51.84, and 76.37 and their corresponding d
values of 2.03, 1.76, and 1.24 , respectively.
Fig. 8.
Powder XRD patterns of used (a) 500 C, (b) 550 C, (c) 600 and (d) 650 C with 30% Ni/Y
zeolite catalysts. Circle (o) and square () represents graphitic carbon phase and metallic Ni
phase, respectively.
Figure options
Fig. 9.
Powder XRD patterns of used (a) 500 C, (b) 550 C, (c) 600 and (d) 650 C with 15% Ni/Y
zeolite catalysts. Circle (o) and square () represents graphitic carbon phase and metallic Ni
phase, respectively.
Figure options
From Fig. 8, it is apparent that, with increasing temperature from 500 to 650 C,
the graphitization intensity enhanced and altered to a higher 2 angle which
indicates a progressive graphitization of the CNFs. For example, the degree of
graphitization in deactivated catalysts increased from 23.25% to 81.40% as
temperature increased from 500 to 600 C and afterwards, slightly reduced
(69.76%) at 650 C for 30% Ni/Y zeolite. One should note that at 600 C, the
degree of graphitization was almost identical to that of natural graphite
(0.335 nm). Of beneficiary feedback from such graphitization is that it can
positively be good for use in composites applications [7]. Table 5 shows the
crystallite sizes of Ni metallic phases for both catalysts from XRD analysis.
Table 5.
Crystallite sizes of deactivated catalysts after TCD of methane from XRD analysis at different
temperatures.
Samples
Ni (1 1 1) (nm)
With 15% Ni-supported Y zeolite
500 C
67.11
550 C
20.97
600 C
83.91
650 C
18.64
Ni (2 0 0) (nm)
Ni (2 2 0) (nm)
57.54
28.77
19.18
28.77
14.10
16.46
16.46
14.10
Samples
Ni (1 1 1) (nm)
With 30% Ni-supported Y zeolite
500 C
83.91
550 C
33.55
600 C
55.92
650 C
27.96
Ni (2 0 0) (nm)
Ni (2 2 0) (nm)
34.53
49.32
28.77
57.54
14.10
49.37
32.92
32.92
Table options
Reported data in Table 5 reflects that at 500 and 550 C, the mean diameter of
metallic Ni crystallites after reaction were 44.18 and 44.08 nm, while it was
39.20 and 39.47 nm, respectively at 600 and 650 C for 30% Ni/Y zeolite.
Conversely, the mean diameter of metallic Ni crystallites in deactivated samples
were 46.25 nm, and 22.06 nm at 500 and 550 C, while it was 39.85 nm, and
20.50 nm at 600 and 650 C, respectively for 15% Ni/Y zeolite catalyst. It can
be observed that the most of the Ni particles of bigger sizes are located on the
zeolite surface especially for 30% Ni/Y zeolite catalyst. Very clearly, as can be
observed that at 600 C, the crystallite size of metallic Ni was almost same for
both used catalyst and a smaller crystallite size of Ni was also appeared
(20.50 nm) among the reported data. Nevertheless, it has suggested that the
beginning of carbon filament growth was utilized diameters of 550 nm of the
Ni metal particles.
3.2.3. FESEM analysis
Fig. 10(a) shows that the particle size of parent Y zeolites has appearance in
two forms, either in single crystallites or in the form of stacked-together small
crystallites form. These small crystallites have an irregular polyhedra structure.
After Ni-impregnation onto the Y zeolite channel, a significant number of
agglomerates, like the one in Fig. 10(b), presented in the zeolite samples, with
mean dimensions of nearly 4.5610.17 m. As can be seen, after nickel
dispersion, the catalyst particles are more uniform and distributed in
homogeneously (Fig. 10b), indicating that the used catalyst preparation
methods in the foregoing experiments are well enough to aggregate the Ni
atoms in the Y zeolite channels or cages. This is indicative that the ligands of
surface hydroxyl groups (SiOH) of nearby crystallites could be broken-down,
resulting in the generation of agglomeration. This agglomeration function is
dependent on the catalyst preparation and subsequent calcination processes.
We can speculate that this type of behavior are only possible when the aperture
diameter of supercage of Y zeolite has much enough larger than the diameter
of metallic nickel ion, which in turns, forms catalyst particles with the same
diameter as that of the cage in zeolite.
Fig. 10.
Representation of SEM morphology of fresh Y zeolite (a), and Ni-supported Y zeolite (b) catalyst,
respectively.
Figure options
Fig. 11 and Fig. 12 are typified with FESEM images along with different
magnification after the complete deactivation of methane at temperatures of
500, 550, 600 and 650 C, respectively using 15% and 30% Ni supported Y
zeolite. As can be seen from Fig. 11 and Fig. 12, that a whisker type of nano
filaments were generated onto the catalyst surface, in regardless of the metal
loadings. Additionally, the lengths and diameter of the formed nano fiber are, of
course, different. The particle size of Ni and the support has significant effect on
the generation of carbon nano fiber (CNF) and the nature of type carbon
produced [8]. FESEM images (Fig. 11) show that the produced CNF had
uniform diameters of about 52.85, 28.41, 45.22, and 30.50 nm, respectively at
temperatures of 500650 C. Moreover, they have no impurities on the
surfaces and curved together. On the other hand, Fig. 12 shows the CNF
formation with a higher metal loading, which yields also a huge quantity of
CNFs, suggesting that a good co-relationship between selectivity and
productivity.
Fig. 11.
Representative FESEM image of TCD methane over 15% Ni/Y zeolite at (a): 500, (b): 550, (c):
600, and (d): 650 C, respectively.
Figure options
Fig. 12.
Representative FESEM image of TCD methane over 30% Ni/Y zeolite at (a): 500, (b): 550, (c):
600, and (d): 650 C, respectively.
Figure options
Generally, CNFs has also uniform diameters of about 51.80, 48.45, 43.71, and
41.84 nm, respectively for all studied temperatures. This result is in line with our
XRD analysis of the spent catalyst that the TCD of methane over metallic nickel
particles has tendency to produce graphitic CNF. Nevertheless, the higher
magnification FESEM images (Fig. 12) reflects that the quality and morphology
of the CNFs produced at higher catalyst density are almost identical to those
produced at the lower one, indicating that without a significant defects in the
quality of CNFs, the productivity shows an incremental pattern. It has reported
that the methane decomposition over Ni supported oxidized diamond produced
a whisker type of CNF, suggesting that the catalyst could be stable for a long
time over the course of reaction stream, resulting in a higher catalytic
activity [28]. On the other hand, a filamentous type of CNF formation is also
possible from the methane decomposition using Ni/SiO 2 and Ni/HY
catalysts [12]. Apart from higher catalytic activities, the accumulated carbon on
Fig. 13.
Representative TEM image of TCD methane over 15% Ni/Y zeolite at 550 C of (a) and (b) and at
600 C of (c), and (d), respectively.
Figure options
also increased. Interestingly, one should note that with temperature increases,
the diameter of CNFs increases for 15% Ni/Y zeolite from 30.76 to 43.58 nm,
but this tendency is completely reverse in 30% Ni/Y zeolite catalyst. The
diameter of the carbon nanomaterials at higher temperatures was smaller, and
after decomposition of methane, the predominant size of nickel particles on the
surface of zeolite Y-supported Ni catalysts was lower. These results are
attributed to the melting temperature of the nickel nanoparticles, which was
linearly reduced and inversely enhanced the diameter. This phenomenon can
be explained by the Lindemann effect [13]: the melting point of a solid material
may be reduced when a nanometer particle size range could be reduced from
the original particle size. Nickel has a melting point of about 1455 C. Upon
heating the nickel nanoparticles at a temperature of 500 C, the softened nickel
nanoparticles may be formed because of the applied temperature, which is
almost one-third of the melting temperature of nickel [13]. This response
indicates that at the highest temperature, the average diameter of carbon
nanomaterials could be lowered. A liquefied nickel form may exist at higher
temperatures and thus cause the deformation of nickel particles. In addition,
melted nickel interacts with carbon. A fraction of liquefied nickel was passed
within the carbon nanomaterials, and the fraction of liquefied nickel particle was
restricted to the external side. Moreover, the reduction temperature does not
affect the diameter of the nickel particle. In the course of methane
decomposition, a miscellaneous trend was observed. Methane decomposition
caused the carbon to accumulate on the surface of zeolite Y-supported nickel
catalysts and to interact with the liquefied nickel. Nickel particle deformation
was noticed as a result of carbonnickel interaction [13]. Nevertheless, Fig.
13(a) and (c) clearly shows that a highly homogeneous crystalline structure with
the graphitic sheets heaped almost collateral to the fiber axis and a hollow
channel obviously observe along the axis of filament, appearing like bamboo at
550600 C [30]. The interaction within the metal-support and metal reactants
are controlled the surface propensity of metal, which is directly related with the
stacking of the graphite layers [31].
It is worthwhile to mention that the tip growths of carbon nano-filament were
observed due to most of the active Ni particles were anchored on top of carbon
nano-filaments. This may be explained from the metal oxides dispersion in the
zeolite channel. On the zeolite Y, the NiO particles have propensity to be more
globular and so, there is a probability to show a weak interaction with the
4. Conclusion
The thermo-catalytic decomposition (TCD) of methane on zeolite Y supported
Ni catalysts were investigated for hydrogen and carbon nanofibers (CNFs)
production at 500, 550, 600, and 650 C using a pilot scale fixed bed reactor.
Experimental investigation had described that the highest initial H 2 and
CH4 have to be found 41.02% and 25.76%, for 15% Ni/Y zeolite catalyst
whereas the value of 58.58% and 41.67% was noted for 30% Ni/Y zeolite
catalyst, respectively at 650 C. The average hydrogen formation rate
increased significantly with increasing temperature but reduced the catalyst
lifetime and the average carbon formation rate also increased as the
temperature rose from 500 to 650 C. Nevertheless, the TCD of methane in
presence of Ni/Y zeolite catalyst required an optimum temperature and in this
case it is ranged from 550 to 600 C. A maximum carbon yield of 614.25 and
157.54 gc/gNi was obtained after end of complete reaction at 600 C with 30 and
15% Ni/Y zeolite catalyst, respectively. The initial methane decomposition rate
increases with VHSV and it has a reverse and non-linear relevancy to the
weight of Ni/Y zeolite catalyst. BET, TPD, and XRD results expressed that how
metallic nickel species were lodged onto the exterior surface of Y zeolite to the
greatest extent using the impregnation system and how it influenced the
catalyst activity of the support materials. The FESEM images gave information
that the produced CNFs are in the form of whisker types, suggesting the
longevity of the catalyst, in regardless of the metal loadings. TEM analysis has
confirmed that the produced CNFs had a fishbone type structures with a hollow
core and the CNFs has identical or very similar as pear-shape of Ni particle,
suggesting the tip growths mechanism of CNFs formation.
Acknowledgment
The authors acknowledge the financial support from the postgraduate
Research Fund (UM.C/HIR/MOHE/ENG/11) University of Malaya, Malaysia.
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