Jointly published by Akadmiai Kiad, Budapest and Springer, Dordrecht

React.Kinet.Catal.Lett. Vol. 85, No. 1, 21-27 (2005)

RKCL4574 FORMATION OF FILAMENTOUS CARBON AND HYDROGEN BY METHANE DECOMPOSITION OVER Al2O3-SUPPORTED Ni CATALYSTS Kazuhisa Murataa*, Megumu Inabaa, Masakazu Mikib and Tatsuaki Yamaguchib
a

National Institute of Advanced Industrial Science and Technology (AIST), AIST Tsukuba Central 5, 1-1-1, Higashi, Tsukuba, Ibaraki 305-8565, Japan b Chiba Institute of Technology, 2-17-1, Tsudanuma, Narashino, Chiba 275-0016, Japan Received May 13, 2004 In revised form October 15, 2004 Accepted October 15, 2004

Abstract For methane decomposition, Al2O3supported Ni catalysts were found to be more active and stable than Ni/SiO2 under the conditions employed. The catalyst activities at 823 K were Ni/Ca/Al2O3>Ni/Al2O3> Co/Al2O3>Fe/Al2O3. The carbons formed after 14 h reaction at 823 K were of bent filamentous shape and of graphite-like structure, and metallic Ni particles were located on the tip of the filament, the diameters of which were between 55 and 77 nm. Keywords: Methane decomposition, Al2O3-supported Ni catalyst, graphite-like filamentous carbon

INTRODUCTION Direct catalytic cracking of hydrocarbons is a promising process for hydrogen production from natural gases, because no CO or CO2 are formed. The presence of CO is often undesirable, due to catalyst poisoning in electrocatalytic cells with hydrogen used as fuel [1]. Metal-catalyzed decomposition of methane at moderate temperatures is of most practical importance. Besides hydrogen, filamentous carbon is formed by direct catalytic cracking. It is of interest as a partially and/or fully graphitized carbon material
_________________________ * Corresponding author. E-mail: kazu-murata@aist.go.jp
0133-1736/2005/US$ 20.00. Akadmiai Kiad, Budapest. All rights reserved.

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potentially applicable to various industrial processes. Growth of carbon filaments has been mechanistically investigated [2, 3]. The catalyst is deactivated because of accumulation of carbonaceous deposits [4], but the used catalysts can be easily regenerated by combustion with oxygen or CO2. Since Ni/SiO2 is mostly used for methane decomposition [5,6], our interest was to confirm the performance of Al2O3-supported Ni catalysts and to check the morphologies. Thus, the present work was aimed at investigating the influence of Al2O3 on the ability of Ni catalysts to accumulate carbon and at examining the properties of materials containing carbon, Ni and Al2O3 by SEM, TEM, X-ray diffraction and BET.

EXPERIMENTAL Ni, Co and Fe catalysts supported on Al2O3 were prepared by precipitation of nickel, cobalt and iron nitrates over Al2O3 by K2CO3, followed by filtration and drying at 373 K. Ni/Ca on Al2O3 was prepared by co-precipitation of Ni and Ca nitrates with K2CO3 in the presence of Al2O3. The metals and Ca additive concentrations were 10 wt.% each. The catalyst thus prepared (1 g) was diluted with quartz sand (5 g) and placed in a quartz tube (16 mm id), vertical-type fixed-bed reactor). The catalysts were pretreated in air at 573 K for 3 h, followed by reduction in H2 at 873 K for 3 h. After pretreatment, the premixed gases of CH4 and N2 (CH4/N2 = 1/9, 50 mL min-1) were introduced at atmospheric pressure and the temperature was raised again to the prescribed value (6C/min). The reaction time was 14 h. The CH4 and hydrogen products were analyzed by gas-chromatography (GC) on Porapack Q and MS 5A columns at prescribed time. No organic products were detected. The methane +2 + C) was calculated by the formula: x(%) = (1conversion (CH4 p/p0)x100, where p0 and p denote partial pressures of initially introduced and unreacted methane. The yield of carbon was estimated by weighing the used catalysts. BET surface area of catalysts was measured by nitrogen adsorption at 77 K on a Micromeritics volumetric equipment provided by Shimadzu. XRD measurements were conducted on a Philips PW 1800 X-ray diffractometer at 40 kV and 40 mA. The radiation source was Cu K with a Ni filter. Micrographs were recorded using a Hitachi H-9000 transmission electron microscope and a JSM6300 scanning electron micrograph.

MURATA et al.: METHANE DECOMPOSITION

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50 CH 4 conversion (%)

(a) Ni/SiO2
25

773K 823K 873K 973K

0 0 100 5 10
673K 723K 773K 823K 873K 973K

15

(b)
CH 4 conversion (%)

Ni/Al2O3
50

0 0 100 CH 4 conversion (%) 5 10

723K 773K 823K 873K 973K

15

(c) Ni/Ca/Al2O3

50

0 0 5 10 Time -on-stream (h) 15

Fig. 1. Influence of time-on-stream on methane conversion in methane decomposition. CH4/N2 = 1/9; flow rate, 50 mL min-1; catalyst, 1.0 g; Ni, 10 wt.% and Ca, 10 wt.%

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MURATA et al.: METHANE DECOMPOSITION

Table 1 Summary of filamentous carbons formed by methane decomposition over Al2O3-supported catalysts No. Catalyst T /K a Carbon yieldb (C-mol/ M-mol) 18.4 28.9 43.5 21.6 10.0 19.1 29.6 46.4 17.5 4.8 29.0 46.5 34.2 9.0 0.2 14.9 23.3 30.2 12.9 CNT Diameter (nm) by SEMc 62.5 68.8 69.2 72.5 76.9 55 67.5 72.5 55 34.2 48.3 42.5 48.3 49.2 37.5 BET area /m2/g XRDd Carbon d002 /nm 171.8 133.1 123.1 158.1 113.5 107.0 105.3 126.5 136.2 144.8 178.2 175.9 156.3 104.0 138.8 126.3 154.3 114.3 0.349 0.349 0.347 0.344 0.345 0.346 0.345 0.340 0.344 0.342 0.344 0.349 0.344 0.346 0.348 0.343 0.345 0.343 Lc /nm 7.17 7.65 6.01 5.74 6.04 6.35 4 6.71 8.94 4 4.18 5.71 7.18 5.75 8.21 7.67 d
e

Metal Lc /nm 17.2 24.1 18.2 15.0 21.2 21.2 24.2 12.1 12.1 13.5 17.3

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27
a b

Ni/Al2O3 Ni/Al2O3 Ni/Al2O3 Ni/Al2O3 Ni/Al2O3 h Ni/Al2O3 Ni/Al2O3 h Ni/Al2O3 Ni/Al2O3 h Ni/Al2O3 NiCa/Al2O3 NiCa/Al2O3 NiCa/Al2O3 NiCa/Al2O3 NiCa/Al2O3 NiCa/Al2O3 Co/Al2O3 Co/Al2O3 Co/Al2O3 Co/Al2O3 Co/Al2O3 Fe/Al2O3 Fe/Al2O3 Fe/Al2O3 Fe/Al2O3 Fe/Al2O3 Fe/Al2O3

Red.g 673 723 773 773 823 823 873 873 973 Red. 723 773 823 873 973 Red. 773 823 873 973 Red. 773 823 873 923 973

0.205 0.206 0.206 0.201 0.206 0.199 0.206 0.201 0.205 0.205 0.204 0.204 0.204 0.204 0.207 0.207 0.205 0.205 0.206 0.206 0.206 0.205 0.204 0.204

Reaction conditions: catalyst, 1 g; feed gas, CH4/N2 = 1/9(vol.); 50 mL min-1, reaction time, 14 h. The carbon yield was estimated by weighing used catalyst after 14 h reaction. c CNT denotes carbon nano-tube. d The d and Lc denote for lattice constant and crystallite size, estimated by XRD. e Ni metal: d111, Fe metal: d110, Co metal: d111. f The measurements were carried out at room temperature. g Fresh catalyst which was reduced by H2 at 873 K for 3 h. h In order to remove metal, the used catalyst obtained by CH4 decomposition at prescribed temperature was treated with 12N-HNO3 at 323 K for 6 h

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RESULTS AND DISCUSSION The decomposition of methane occurred at 673-973 K in the presence of these catalysts, and hydrogen and carbon were formed with no other organic products. Figure 1a shows the effect of time-on-stream on the methane conversion at different temperatures over Ni/SiO2 catalyst. At 773 K, the initial methane conversion was 12%, but the conversion dropped to 4% after 14 h. Similar results were obtained at 823 K, where initial conversion was 16%. Higher temperatures such as 873 and 973 K resulted in the low conversion of 4% even at initial stages of the methane decomposition. Figure 1b shows the effect of time-on-stream on the methane conversion over Ni/Al2O3 catalyst. The catalyst activities between 673 and 823 K remained unchanged during 14 h; The methane conversion was 43% (823 K)>30% (773 K)>14% (723 K)> 4%(673 K). On the contrary, at 873 K the initial conversion was 55% during the first 3 h, and then dropped rapidly to 4%, probably due to an aggregation of Ni particles (see Table 1). Also, the conversion was as low as 4% at 973 K over 14 h. The addition of Ca to Ni/Al2O3 led to a slight improvement of the performance of Ni/Al2O3 catalyst, as shown in Fig. 1c. In this case, the methane conversion was 45%(823 K)> 32%(773 K)>16%(723 K). At 873 K, the initial conversion was 61%, but dropped to 7% after 5 h. Also, at 973 K, the conversion of 71% fell to 5% after 1 hour. Thus, Ni/Al2O3 was found to be more effective than Ni/SiO2, under dilute methane (10 vol.%). Methane conversion at 823 K over Al2O3-based catalysts decreased in the order: Ni/Ca/Al2O3 >Ni/Al2O3>Co/Al2O3> Fe/Al2O3. The activity of Fe/Al2O3 decreased more rapidly than those of other catalysts. Table 1 shows the influence of temperature on the yields of carbon formed during 14-reaction. Highest carbon yields of ca. 43-46 C-mol/M-mol were achieved at 823 K over Ni, NiCa and Co/Al2O3 catalysts. On the contrary, the highest carbon yield over Fe/Al2O3 catalyst was obtained at 923 K. Longer reaction time of 44 h resulted in the higher carbon yield of 105. The carbons deposited from CH4 decomposition over Ni/Al2O3 catalyst, reveal an irregular bent filamentous structure, as ascertained by SEM images. Diameters of these filamentous carbons (CNT) at each temperature were in the order: 72.5 nm (823 K)>68.8 nnm (773 K)>62.5 nm (723 K)>55 nm (873 K), as summarized in Table 1. Similarly, CNT diameters of Ni/Ca/Al2O3, Co/Al2O3 and Fe/Al2O3 are summarized in Table 1. Difference in tube diameters is, possibly, associated with metal particle sizes. In fact, high reaction temperature could favor an aggregation of Ni species on contact with methane and result in a growth of carbon tubes with large diameter [7-9]. Figure 2 shows the TEM (HRTEM) micrographs of filamentous carbons obtained in the CH4 decomposition over Ni/Ca/Al2O3 catalysts. All carbons are of tubular-type and bending. Figure 2a shows low magnification images, which

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are analogous to those of SEM pictures. One carbon filament grows from one catalytic particle, while it is located on the tip of filament. The filament diameter corresponds to the size of cubo-octahedral particle (4050 nm) [10] and the filaments originating from both Ni metal are built up by the graphite planes, which are parallel to the filament axis, as shown in Fig. 2b, where high magnification pictures are given.
Graphite layer=0.34nm

32 QP
a) Low magnification image b) High magnification image
Fig. 2. TEM image of Ni/Ca/Al2O3 catalyst obtained by methane decomposition at 823 K for 14 h

The BET surface areas of Ni/Al2O3 and Ni/Ca/Al2O3 slightly decreased with the increase of carbon yield (and tube diameter), as shown in Table 1. On the contrary, for Co/Al2O3 and Fe/Al2O3 catalysts, the areas increased with the increase of the carbon yields. In the XRD pattern of the used Ni/SiO2, no peaks were detected at any conditions. For the Ni/Al2O3 after reduction with hydrogen at 873 K, only a weak peak at 44, which was assigned to Ni metal, was detected, indicating that Ni metal particles are highly dispersed on the Al2O3 surface before decomposition. However, the intensity of XRD pattern of Ni metal at 44 increased with increasing decomposition temperature ranging from 673 to 973 K due to aggregation of Ni, which could be consistent with the changes in d111 and Lc values of Ni metal, as shown in Table 1. No XRD patterns characteristic of graphite-like material at 26 (d002) were detected at 673 K. The intensity of XRD pattern of graphite at 26 increased with increase in the decomposition

MURATA et al.: METHANE DECOMPOSITION

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temperature ranging from 773 to 823 K and then decreased with the temperature increase from 873 to 973 K (Table 1). As shown in Table 1, the d002 values range between 0.349 and 0.345 nm, being higher than for ideal graphite (0.335 nm). The average values of crystallite size (Lc) are 5.74-7.65 nm. Thus, the filamentous carbons obtained over Ni/Al2O3 catalyst would consist of mutually disoriented domains with graphite-like structure. After CH4 decomposition over the Ni/Ca/Al2O3 catalyst, the peak of Ca-containing carbide (Ca4Ni3C5) at 33.5 was detected with the XRD patterns of Ni metal and graphite. The XRD intensity of the carbide increased with increasing decomposition temperature from 773 to 973 K, in a similar manner as the intensity of XRD patterns of Ni metal. XRD patterns of Co/Al2O3 and Fe/Al2O3 also demonstrate metallic Co and Fe species with graphite peaks. All of these data are summarized in Table 1. Thus, graphite-like patterns as well as metallic species were observed for Al2O3supported catalysts, while the XRD pattern of Ni/SiO2 was mostly amorphous. In conclusion, for methane decomposition Al2O3supported Ni catalysts were found to be more active and stable than Ni/SiO2 under the gas conditions of CH4/N2=1/9. The catalyst performances at 823 K followed the order Ni/Ca/Al2O3>Ni/Al2O3>Co/Al2O3>Fe/Al2O3>>Ni/SiO2. Besides H2, carbon materials were formed over these catalyst surfaces. The carbon yield after 14 h reaction at 823 K was 46.4 (mol C/mol Ni) for Ni/Ca/Al2O3, in agreement with that obtained by thermo gravimetric analysis. These carbons were of bent filamentous shape and of graphite-like structure, as confirmed by SEM and TEM pictures. Metallic Ni particles, ascertained by X-ray diffraction, were located on the tip of the filament. The filament diameters, estimated from SEM images, were between 55 and 77 nm, depending on the extent of aggregation of Ni particles. Thus, Al2O3-based catalysts were found to be effective for methane decomposition. REFERENCES
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