Applied Catalysis A: General 304 (2006) 6271 www.elsevier.

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Temperature prole of catalyst bed during oxidative steam reforming of methane over Pt-Ni bimetallic catalysts
Baitao Li a, Shigeru Kado a, Yuya Mukainakano a, Mohammad Nurunnabi a, Toshihiro Miyao b, Shuichi Naito b, Kimio Kunimori a, Keiichi Tomishige a,*
a b

Institute of Materials Science, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8573, Japan Department of Applied Chemistry, Faculty of Engineering, Kanagawa University, 3-27-1, Rokkakubashi, Kanagawa-ku, Yokohama, Kanagawa 221-8686, Japan Received 20 October 2005; received in revised form 30 January 2006; accepted 7 February 2006 Available online 9 March 2006

Abstract The catalyst bed temperature during oxidative reforming of methane (CH4/H2O/O2/Ar = 40/30/20/10) at 1123 K and atmospheric pressure was investigated by infrared thermography over g-Al2O3 supported bimetallic Pt-Ni catalysts prepared by different impregnation methods: coimpregnation and sequential impregnation. The thermographical results clearly demonstrated that the catalyst bed temperature was strongly dependent on the preparation method. The bimetallic catalyst prepared from the sequential impregnation method exhibited much higher resistance to hot spot formation in oxidative reforming of methane. Temperature programmed reduction (TPR) with H2 revealed that the addition of Pt by a sequential impregnation method greatly promoted the reduction of Ni species; furthermore, infrared spectra of CO adsorption suggests that the surface composition of Pt on the catalyst prepared by the sequential method is much higher than that for the catalyst prepared by the coimpregnation method. The surface enrichment of Pt is responsible for the effective overlap between the combustion and reforming zones, and this can enhance the inhibition of hot spot formation. # 2006 Elsevier B.V. All rights reserved.
Keywords: Oxidative steam reforming of methane; Pt; Ni; Bimetallic catalyst; Thermograph; Hot spot

1. Introduction In recent years, there has been much interest in the production of hydrogen for highly efcient generation of electricity using fuel cells, where one of the candidates for the hydrogen source is the natural gas composed mainly of methane [1]. At the same time, much attention has been paid to the production of synthesis gas by natural gas reforming which is related to gas to liquid (GTL) technology [2,3]. Steam reforming of methane (Eq. (1)) and other light hydrocarbons is the primary and most important commercial method of synthesis gas production [35]. Because of its endothermic nature, external energy cost is necessary. CH4 H2 O ! CO 3H2
 DH298 K 206 kJ=mol

In the conventional process, the heat is supplied from the outside the reactor wall by methane combustion, which makes the efciency of the production process inuenced by the heat supplying method. On the other hand, it is well-known that an internal heat supply is more energy-efcient than an external heat supplying system. A famous internal heat supplying system for natural gas reforming is the autothermal reforming process (called ATR), which has been developed by Haldor Topsoe [6,7]. The ATR process consists of the non-catalytic partial oxidation (Eq. (2)), combustion of methane (Eq. (3)), and catalytic reforming of methane (Eq. (1)). CH4 1 2O2 ! CO 2H2
 DH298 K 36 kJ=mol  DH298 K 803 kJ=mol

(2) (3)

(1)

CH4 2O2 ! CO2 2H2 O

* Corresponding author. Tel.: +81 29 853 5030; fax: +81 29 853 5030. E-mail address: tomi@tulip.sannet.ne.jp (K. Tomishige). 0926-860X/$ see front matter # 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.apcata.2006.02.025

One of the important points in ATR is to inhibit the contact of the reforming catalysts with oxygen which causes the sintering of support materials and the aggregation of metal particles. Such results are connected to catalyst deactivation

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and the large temperature gradient in the catalyst bed [8,9]. Catalytic partial oxidation of methane, shown in Eq. (2), has advantages such as mild exothermicity, high conversion, high selectivity, suitable H2/CO ratio and very short residence time [1012]. However, even a low conversion to CO generates a large amount of heat, which leads to the hot spot formation, as reported previously [13,14]. Oxidative steam reforming of methane, which is a combination of a catalytic combustion and/ or partial oxidation reaction with reforming reaction, is an effective and economic internal heat supply process [1517]. Since the combustion reaction proceeds more rapidly than the reforming reaction, in the usual cases it occurs near the catalyst bed inlet where the temperature becomes very high within a very small thickness; especially when Ni catalyst is utilized, it can easily be oxidized in the presence of oxygen and can lose its reforming activity [1820]. On the other hand, in the catalyst bed after oxygen is consumed, Ni species can maintain the metallic state and contribute to the reforming reaction. This will reasonably result in a very large temperature gradient because the exothermic and the endothermic regions are separated [2123]. Recently, our group used an infrared thermograph to monitor the surface temperature and found that Rh and Pt catalysts exhibited atter temperature proles in oxidative steam reforming of methane reaction than Ni and Pd catalysts [24,25]. This phenomenon is due to the overlap of the combustion zone with the reforming zone. In this research, the oxidative steam reforming of methane was investigated by infrared thermography over monometallic Ni and Pt catalysts and over bimetallic Pt-Ni catalysts prepared by two methods: co-impregnation method and sequential impregnation method. Various characterization techniques were applied to determine the surface structures of these catalysts. The relationship between the catalyst structure and the bed temperature is discussed in detail. 2. Experimental 2.1. Catalyst preparation g-Al2O3 support was prepared by calcining commercially available JRC-ALO-1 (Catalysis Society of Japan, SBET = 143 m2/g, grain size of 23 mm) at 1123 K in the air for 3 h. The support thus obtained had a specic surface area of 110 m2/g. Then it was crushed and sieved to particle sizes between 180 and 250 mm before the impregnation with the metal components. Supported monometallic Ni and Pt catalysts were prepared by a wet impregnation method using Ni(NO3)26H2O (Wako Pure Chemical Industries, Ltd., 99.9%) or H2PtCl66H2O (Soekawa Chemical Co., Ltd., 99.9%), respectively. After removal of the solvent by the evaporation at 353 K, the resulting product was dried in an oven at 383 K overnight. Subsequently, the sample was calcined at 773 K in the air for 3 h. Bimetallic Pt-Ni catalysts were prepared by two methods. One is the sequential (two-step) impregnation method. The calcined monometallic nickel catalyst was reduced at 1123 K for 0.5 h under H2 ow, followed by the

impregnation of Pt using the precursor of Pt(C5H7O2)2H2O (Soekawa Chemical Co., Ltd., 99.9%) acetone solution. After the removal of the acetone solvent, the catalyst was dried at 383 K overnight and next calcined in air at 573 K for 3 h. The catalyst thus prepared is denoted as Pt/Ni/Al2O3. The other is the co-impregnation method; here the aqueous solution mixture of Ni(NO3)26H2O and H2PtCl66H2O was used a precursor. After co-impregnation, the calcination procedure was the same as that of monometallic catalyst. This catalyst thus obtained is denoted as Pt + Ni/Al2O3. The value in parentheses represents the weight percent of metallic components in the catalyst. 2.2. Activity test and thermographical observation Methane reforming catalytic reaction was conducted under atmospheric pressure in a continuous xed-bed quartz reactor (i.d. 4 mm). Details are explained in our previous report [26]. Pictures of catalyst granules with 180250 mm diameter in the reactor and one example of a thermographical image are illustrated in Fig. 1. The quartz reactor had an axial thermowell (i.d. 1.5 mm) containing a chromelalumel thermocouple located at the outlet of the catalyst bed that was used for the temperature control. An electronic furnace was connected with this thermo-controller; it had a window (15 mm 18 mm) for the observation of the temperature prole of catalyst granules. The temperature prole was measured with infrared thermograph equipment (TH31, NEC San-ei Instruments Ltd.). As shown in Fig. 1, the radial temperature gradient was rather at in the A cross section, indicating that the gas owing condition is close to the plug ow. Therefore, we only show the temperature prole along the B cross section in Section 3. The catalyst (0.08 g) was reduced in the hydrogen ow (30 ml/min, 100% H2) at 1123 K for 0.5 h in the reactor prior to every activity test. After the reduction, the feed gases with partial pressure ratio CH4/H2O/ O2/Ar = 40/30/20/10 were introduced to the catalyst bed at various contact times W/F (W (g) = catalyst weight, F (mol/ h) = total ow rate of gases). CH4, O2, Ar and H2 (Takachiho Trading Co., Ltd.) were research grade and they were used without further purication. Steam was obtained by vaporizing distilled water supplied by a feeding pump (MT2111, Moleh Ltd.). An iced water trap was located at the reactor exit to remove the steam contained in the efuent gas. The efuent gas was collected from the sampling port using a micro-syringe and then analyzed by gas chromatography (Shimadzu GC-14A). This instrument was equipped with a ame ionization detector (FID) and a thermal conductivity detector (TCD). The concentrations of CO, CO2 and CH4 were determined on an FID-GC equipped with a methanator, using a stainless steel column packed with Gaskuropack 54; the concentration of H2 was determined by TCD-GC using a stainless steel column packed with molecular sieve 13X. The activity test of methane combustion was performed using air containing 2% CH4 as the reactant gas (W/F = 0.40 g h/mol) with 0.09 g catalyst. The measurement was carried out from 523 to 1123 K at the temperature intervals of 50 K. The analysis method was the same as that described above.

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Fig. 1. Picture of catalyst granules in the quartz glass tube (a) before reaction and (b) one example of thermographical image.

2.3. Catalyst characterization The surface area of the catalysts was determined by the BET method using a Gemini (Micromeritics) instrument. Powder X-ray diffraction (XRD) patterns of the reduced samples (H2 ow, 1123 K, 0.5 h) were collected on a Philips Xpert diffraction-meter using Cu Ka (l = 0.154 nm) generated at 40 kV and 20 mA. Scanning was conducted over the range of 2u = 5758. Transmission electron microscope (TEM, JEM2010) measurements were collected over the reduced catalyst (H2 ow, 1123 K, 0.5 h). Samples were dispersed in 2-propanol by supersonic waves and put on Cu grids for the TEM observations under atmosphere. Temperature programmed reduction (TPR) measurements were conducted in a xed bed quartz reactor containing 0.01 g of sample at a heating rate of 10 K/min, from room temperature to 1273 K, in 5% hydrogen diluted in argon (30 ml/min) as a reducing gas. Water produced during the reduction was removed using a cold trap with frozen acetone (about 173 K). The TPR prole was monitored continuously with an on-line TCD-GC. H2 consumption was estimated from the integrated peak area of the reduction proles. Infrared (IR) spectra of CO adsorption on the catalysts were measured at room temperature with an FT-IR spectrometer (Nicolet, Magna-IR 550 spectrometer) in transmission mode using a quartz glass IR cell with CaF2 windows connected to a vacuum-closed circulating system. Fresh catalyst was reduced in hydrogen ow ex situ at 1073 K for 0.5 h. Then the reduced sample was pressed into a disk (20 mm ) at a weight of about 0.12 g. After reduction in situ at 773 K for 1 h, CO (0.1 kPa)

was exposed to the catalyst at room temperature and IR spectra were recorded at room temperature under vacuum. 3. Results and discussion 3.1. Catalytic performance and catalyst bed temperature prole over monometallic Ni and Pt catalysts in oxidative steam reforming of methane Oxidative steam reforming of methane was conducted under the condition of CH4/H2O/O2/Ar = 40/30/20/10 which corresponds to the combination of the combustion gas (CH4/O2 = 10/ 20) and the steam reforming gas (CH4/H2O = 30/30). In this part, we examine the catalytic performance and the bed temperature prole over Ni/Al2O3 and Pt/Al2O3 with various metal loading amounts. The catalytic performance details in terms of the methane conversion, H2/CO ratio and CO selectivity over Ni/Al2O3 are listed in Table 1 and the
Table 1 Catalytic performance over nickel catalysts with different loading amounts Catalyst Ni (2.6) W/F (g h/mol) 0.07 0.12 0.24 0.80 0.12 0.12 CH4 conversion (%) >99.9 >99.9 >99.9 >99.9 94 67 H2/CO 2.7 2.7 2.7 2.6 2.9 2.3 CO selectivity (%) 82 82 83 86 78 76

Ni (0.9) Ni (0.3)

Reaction conditions: CH4/H2O/O2/Ar = 40/30/20/10; temperature 1123 K; total pressure 0.1 MPa; catalyst weight 0.08 g; H2 pretreatment at 1123 K.

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Fig. 2. Temperature proles of the catalyst bed in oxidative steam reforming of methane over monometallic Ni catalysts measured by using IR thermography. (A) W/F dependence over Ni (2.6) catalyst: W/F (g h/mol) = 0.07 (bold solid line), 0.12 (dotted line), 0.24 (thin solid line), 0.80 (broken line). (B) Ni loading amount dependence at W/F = 0.12 g h/mol: Ni (0.3) (dotted line), Ni (0.9) (thin solid line), Ni (2.6) (bold solid line). Reaction conditions: CH4/H2O/O2/ Ar = 40/30/20/10; temperature 1123 K; total pressure 0.1 MPa; catalyst weight 0.08 g; H2 pretreatment at 1123 K.

temperature proles along the catalyst bed are shown in Fig. 2. From the comparison at W/F = 0.12 g h/mol, one can clearly observe that methane conversion decreased with decreasing the loading amount of Ni. Especially, Ni (2.6) showed high methane conversion even at low W/F, for example 0.07 g h/ mol, where the reaction almost reached the equilibrium. Fig. 2(A) shows the effect of W/F on the catalyst bed temperature prole over Ni (2.6). At W/F = 0.07 g h/mol, the exothermic prole near the catalyst bed inlet was present and the maximum reached about 1323 K; the temperature decreased steeply after the maximum. This behavior in the temperature prole was observed in oxidative reforming of methane, which corresponds to the combination of the exothermic reactions, such as methane combustion and partial oxidation of methane, with the endothermic reaction, such as steam and dry reforming of methane [25,26]. The exothermic reaction zone is usually located near the catalyst bed inlet, which is due to the rates of the exothermic reactions being higher than those of the endothermic reactions. The temperature decrease after the maximum is assigned to the endothermic reaction. It can be found that the maximum decreased with increasing in W/F and with decreasing the total ow rate of

reactant gases. At W/F = 0.24 g h/mol, the exothermic prole was observed only at the half part near the inlet, while the endothermic prole was found at the half part near the outlet. This prole clearly indicates that the exothermic and endothermic zones exist separately. Furthermore, at W/ F = 0.80 g h/mol, almost no exothermic zone was observed, which means that the heat produced by the oxidation of methane near the catalyst bed inlet can be applied to the endothermic reaction directly, suggesting that the endothermic zone can effectively overlap the exothermic zone. The W/F dependence of the catalyst bed temperature revealed that hot spot can easily form at higher ow rate condition (low W/F ). Fig. 2(B) shows the effect of the loading amount of Ni on the temperature prole at W/F = 0.12 g h/mol. In addition, the catalyst performance details of various Ni catalysts are also listed in Table 1. Methane conversion decreased with decreasing Ni loading amount. The temperature peak near the catalyst bed inlet over Ni (2.6) was higher than that over Ni (0.9), and the declination after the maximum over the former was more dramatic than that of the latter. These can be reected by the methane combustion activity of Ni (2.6) being higher than that of Ni (0.9) [26]. Furthermore, the peak of Ni (0.3) was close to that of Ni (0.9) and the temperature after the peak was higher than that of Ni (0.9), which is corresponding to its lower reforming activity; these behaviors are also observed in methane conversion, as listed in Table 1. It is important to nd that the maximum temperature in the catalyst bed cannot be decreased even if the loading amount of Ni is lowered. This result demonstrates that the monometallic Ni is not suitable to the oxidative steam reforming of methane because of its facility to form hot spots, which agrees with our previous reports [26]. Catalytic performance over monometallic Pt catalysts is presented in Table 2. At W/F = 0.12 g h/mol methane conversion increased with increasing loading amount; over Pt (0.1) catalyst, it slightly increased with the increasing W/F. The results of catalyst bed temperature prole over Pt catalyst are shown in Fig. 3. Over Pt (0.1), one can clearly observe that the maximum temperature increased with decreasing W/F, and that such behavior was similar to that over nickel catalysts. Fig. 3(B) shows the effect of loading amount of Pt on the catalyst bed temperature prole at W/F = 0.12 g h/mol; the temperature peak decreased with increasing Pt loading amount. If one compares Fig. 2(B) with Fig. 3(B), one will nd that the peak over Ni catalysts cannot be decreased by changing the amount
Table 2 Catalytic performance over platinum catalysts with different loading amounts Catalyst Pt (0.9) Pt (0.2) Pt (0.1) W/F (g h/mol) 0.12 0.12 0.07 0.12 0.24 0.80 0.12 CH4 conversion (%) >99.9 99 90 91 92 96 84 H2/CO 2.5 2.6 2.3 2.4 2.4 2.7 2.0 CO selectivity (%) 80 83 90 88 87 85 92

Pt (0.03)

Reaction conditions are the same as those in Table 1.

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Fig. 4. Methane conversion as a function of reaction temperature in the methane combustion. Reaction conditions: CH4/air = 2/98, W/F = 0.40 g h/ mol, total pressure 0.1 MPa, catalyst weight 0.09 g, H2 pretreatment 1123 K. (*) Pt (0.1); (~) Pt (0.9); (*) Ni (2.6).

afnity [27] maintains the metallic state even in the presence of gas phase oxygen. The stable metal state enables the overlap between two reaction zones over the Pt catalysts. However, in fact, higher resistance to hot spot formation needs a sufcient loading amount of Pt, as shown in Fig. 3(B). 3.2. Catalytic performance and catalyst bed temperature prole over Pt-Ni bimetallic catalysts Because of the high cost and limited availability of platinum, it is important to develop a catalyst with high resistance to hot spot formation that uses only a slight amount of platinum. Here, we investigated the additive effect of a small amount of Pt to Ni catalysts on the temperature prole during the oxidative steam reforming of methane. Two preparation methods for Pt-Ni bimetallic catalysts were developed: coimpregnation method (denoted as Pt + Ni) and sequential impregnation method (Pt/Ni). Table 3 summarizes the catalytic performance over two bimetallic catalysts. It was found that both of two catalysts showed very high methane conversion and H2/CO ratio where the reactions almost reached the equilibrium level; however, the bed temperature proles were quite different. Fig. 5(A) presents the results over Pt (0.1) + Ni (2.6) catalyst prepared by the co-impregnation method. The temperature maximum was located near the catalyst bed inlet
Table 3 Catalytic performance over Pt-Ni bimetallic catalysts prepared by different methods Catalyst Pt (0.1) + Ni (2.6) W/F (g h/mol) 0.07 0.12 0.24 0.80 0.07 0.12 0.24 0.80 CH4 conversion (%) >99.9 >99.9 >99.9 >99.9 >99.9 >99.9 >99.9 >99.9 H2/CO 2.7 2.7 2.7 2.8 2.7 2.8 2.7 2.7 CO selectivity (%) 82 81 82 82 82 81 81 82

Fig. 3. Temperature proles of the catalyst bed in oxidative steam reforming of methane over monometallic Pt catalysts measured by using IR thermography. (A) W/F dependence over Pt (0.1) catalyst: W/F (g h/mol) = 0.07 (bold solid line), 0.12 (dotted line), 0.24 (thin solid line), 0.80 (broken line). (B) Pt loading amount dependence at W/F = 0.12 g h/mol: Pt (0.03) (thin solid line), Pt (0.1) (bold solid line), Pt (0.2) (broken line), Pt (0.9) (dotted line). Reaction conditions are the same as those in Fig. 2.

of Ni loaded; in the case of Pt, however, the peak can be decreased by increasing the loading amount of Pt. Furthermore, the temperature on Pt catalyst was usually lower than that on Ni catalyst. If one considers Pt (0.9) and Ni (0.3) catalysts with the identical mole-based loading (4.5 105 mol/g-catalyst), one nds that the Pt catalyst exhibited much lower bed temperature that the Ni catalyst. These results indicate that Pt catalysts have high reforming activity and high resistance to the hot spot formation. Next, we evaluated the combustion activity over the Ni and Pt catalysts (Fig. 4). It is clear that Pt catalysts have higher combustion activity than Ni catalysts considering the differences of loading amount. Pt catalysts showed a low temperature prole in oxidative reforming of methane in spite of their high combustion activity. This behavior can be explained by the overlap between exothermic and endothermic reaction zones, which is related to the oxygen afnity [27] of the metal species. Ni species with higher oxygen afnity are easily oxidized in the presence of gas phase oxygen and thus, lose their reforming activity [28] and mainly show the combustion activity, although the activity was not so high. Therefore, the effective overlap between exothermic and endothermic zones is difcult. In contrast, Pt with lower oxygen

Pt (0.1)/Ni (2.6)

Reaction conditions are the same as those in Table 1.

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Fig. 5. Temperature proles of the catalyst bed in oxidative steam reforming of methane over bimetallic catalysts prepared by (A) co-impregnation method Pt (0.1) + Ni (2.6) and (B) sequential impregnation method Ni Pt (0.1)/Ni (2.6) measured by using IR thermograph. W/F (g h/mol) = 0.07 (bold solid line), 0.12 (dotted line), 0.24 (thin solid line), 0.80 (broken line). Reaction conditions are the same as shown in Fig. 2.

and it increased with decreasing W/F. A comparison between Ni (2.6) (Fig. 2(A)) and Pt (0.1) + Ni (2.6) (Fig. 5(A)) shows that the temperature maximum decreased by about 20 K with the addition of Pt by co-impregnation method; however, the effect was small. On the other hand, the additive effect of Pt during the sequential impregnation method was found to be much more remarkable. Fig. 5(B) shows the result of the Pt (0.1)/Ni (2.6) catalyst. No obvious exothermic peak was found at W/F = 0.24 g h/mol. The temperature maximum was about 80 K lower than that over Ni (2.6) at W/F = 0.07 g h/mol. These results strongly conrmed that the additive effect of platinum by the sequential impregnation method was much more effective than that by the co-impregnation method in terms of the inhibition of hot spot formation. It should be noted that the catalyst bed temperature of Pt (0.1)/Ni (2.6) was lower than that of the individual monometallic catalysts, Pt (0.1) and Ni (2.6), which proved the existence of a synergetic effect between Pt and Ni species. Similar behavior was observed in the case of oxidative CO2 reforming of methane [21,23]. Furthermore, this synergetic effect is strongly dependent on the preparation methods and the interaction between Pt and Ni species, which will be discussed later based on the characterization results. Next, we investigated the effect of Ni loading amount over Pt/Ni bimetallic catalyst prepared by the sequential impregTable 4 Catalytic performance over Pt-Ni bimetallic catalysts with different nickel loading amounts prepared by sequential impregnation method Catalyst Pt (0.1)/Ni (0.9) W/F (g h/mol) 0.07 0.12 0.24 0.80 0.07 0.12 0.24 0.80 CH4 conversion (%) >99.9 >99.9 >99.9 >99.9 >99.9 >99.9 >99.9 >99.9 H2/CO 2.7 2.7 2.7 2.6 2.6 2.6 2.6 2.6 CO selectivity (%) 82 82 83 85 81 81 81 83

nation method. The catalytic performance (Table 4) remained high even over Pt (0.1)/Ni (0.3), higher than that over the individual monometallic catalysts, Ni (0.3) and Pt (0.1) as presented in Tables 1 and 2, respectively. The catalyst bed temperature proles for Pt (0.1)/Ni (0.9) and Pt (0.1)/Ni (0.3) catalysts are shown in Fig. 6. A comparison between Fig. 5(B) and Fig. 6 shows that the catalyst bed temperature decreased

Pt (0.1)/Ni (0.3)

Reaction conditions are the same as those in Table 1.

Fig. 6. Temperature proles of the catalyst bed in oxidative steam reforming of methane over bimetallic catalysts with different nickel loading amounts prepared by sequential impregnation method. (A) Pt (0.1)/Ni (0.9), (B) Pt (0.1)/Ni (0.3). W/F (g h/mol) = 0.07 (bold solid line), 0.12 (dotted line), 0.24 (thin solid line), 0.80 (broken line). Reaction conditions are the same as those in Fig. 2.

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Table 5 Catalyst properties of monometallic and bimetallic catalysts Catalyst BET surface areaa (m2/g-catalyst) Particle size of Nia (nm) XRD d Pt (0.1) Ni (2.6) Pt (0.1) + Ni (2.6) Pt (0.1)/Ni (2.6)
a b

Metal dispersionb (%)

Reduction degreec (%)

TEMe 4.8 0.4 4.5 0.4 5.0 0.4 19 17 20 102 96 104

109 104 101 104

5.2 0.6 5.6 0.6 4.8 0.6

Reduced in H2 ow at 1123 K, 0.5 h. Determined by XRD results [34]. c Determined from TPR results. d Evaluated by Ni(2 0 0) at 51.88 [32]. Calculated from Scherrer equation, using the half-width at half-height of the peak [33]. P P e Calculated according to Ref. [34]. Mean diameter ds ni di3 = ni di2 , in which ni is the number of particles having a characteristic diameter di (within a given diameter range).

signicantly with decreasing Ni loading amount. An important and meaningful temperature prole was observed over Pt (0.1)/ Ni (0.3), which gave a comparable temperature prole to that of Pt (0.2) (Fig. 3(B)) at W/F = 0.12 g h/mol. This tendency suggests that bimetallic catalyst with lower nickel loading prepared by sequential method is a good substitute for a Pt catalyst with higher metal component content.

4. Catalysts characterization BET surface area, metal dispersion, and particle size are compiled in Table 5. The BET surface areas of the catalysts after reduction pretreatment were slightly lower than that of the support material after the pre-calcination; this decrease during the catalyst preparation and pretreatment procedure is thought

Fig. 7. (A) XRD patterns of various catalysts reduced in H2 ow, 1123 K, 0.5 h. (a) Pt (0.1); (b) Ni (2.6); (c) Pt (0.1) + Ni (2.6); (d) Pt (0.1)/Ni (2.6). (*) g-Al2O3; (&) Ni. (B) TEM images of various catalysts reduced in H2 ow, 1123 K, 0.5 h. (a) Ni (2.6); (b) Pt (0.1) + Ni (2.6); (c) Pt (0.1)/Ni (2.6).

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to be due to the moderate sintering of g-Al2O3. The XRD patterns of the reduced catalysts (Fig. 7(A)) shows the presence of the diffraction peaks assigned to g-Al2O3 with a strong intensity; no peak assigned to a-Al2O3 was found. Over all catalysts, no peak that could be assigned to Pt metal was observed. Over Ni-containing catalyst, the characteristic peak assigned to Ni metal (2u = 44.58) [2931] was overlapped by that of g-Al2O3; therefore, the second strongest peak at 51.88 was applied to estimate the particle size of Ni phase. It was found that the peaks at 51.88 were rather broad, suggesting that the Ni metal phase is highly dispersed. In the case of Pt-Ni bimetallic catalysts, one would expect that the diffraction angle should be shifted by alloy formation. However, it is difcult to distinguish the peak shift by XRD data because of the low and broad peak intensity of Ni phase and the low concentration of Pt in Ni phase. The results of the size of Ni metal phase estimated by XRD peak broadening are listed in Table 5. The particle size had no signicant difference among the three Ni-containing catalysts. In order to estimate the particle size of metal phase more precisely, we measured the TEM images over reduced catalysts (Fig. 7(B)). The average particle sizes of three catalysts are also listed in Table 5 and the results are in good agreement with those by XRD. The characterization results obtained by XRD and TEM indicate that the effect of particle size is not an important factor in determining the bed temperature prole in oxidative steam reforming of methane. Therefore, we think that the surface temperature can be reected by the surface properties of the catalysts, for example, the reduction degree or the surface composition. To conrm this hypothesis and to obtain more information on the catalyst surface, we conducted temperature programmed reduction and IR spectra of CO adsorption. TPR were performed to evaluate the catalyst reducibility. Fig. 8(a) shows the TPR prole of the calcined Ni (2.6). The consumption of H2 was observed in the temperature range 700 1200 K and the reduction degree of Ni reached almost 100% (Table 5). This H2 consumption peak is assigned to the reduction of highly dispersed NiO that strongly interacted with the Al2O3 surface [35]. On the other hand, in the case of Pt (0.1) + Ni (2.6), the reduction peak started at about 40 K lower than Ni (2.6), suggesting that the addition of Pt promoted the NiO reduction, as was observed in the previous report [3638]. Fig. 8(c) shows the TPR prole of Pt (0.1)/Ni (2.6); an impressive sharp peak at 560 K was found [30,39], which is quite different from the case of Fig. 8(a). The evident temperature shift is considered to be due to the different Ni species on the bimetallic and monometallic Ni catalysts. It should be noted that in a sequential impregnation method, Ni catalyst was reduced before the Pt impregnation; during the preparation procedure, the structure of Ni may be changed drastically. Therefore, as a reference we measured TPR of Ni (2.6) calcined at 573 K after the reduction at 1123 K. Here, the calcination temperature (573 K) was adjusted to the preparation condition of Pt (0.1)/Ni (2.6). Fig. 8(d) presented a strong peak at 620 K, 60 K higher than that in Fig. 8(c). TPR proles conrmed that the additive effect of Pt during the sequential method is more remarkable than that in the case of co-

Fig. 8. Temperature-programmed reduction proles for fresh catalysts: (a) Ni (2.6); (b) Pt (0.1) + Ni (2.6); (c) Pt (0.1)/Ni (2.6); (d) Ni (2.6)-calcined at 573 K again after reduction at 1123 K.

impregnation, and that the reduction peak shift to the lower temperature in Pt (0.1)/Ni (2.6) originated from the sequentially impregnated platinum. It is known that Pt-Ni alloy exists in the supported Pt-Ni bimetallic catalysts [4042]. The difference in the temperature prole during oxidative steam reforming of methane can be caused by the surface structure and composition of Pt-Ni alloy particles. In order to evaluate these surface properties of alloy particles, we measured FT-IR spectra of CO adsorption. Over Ni (2.6) catalyst (Fig. 9(a)), the band at 2070 cm1 is attributed to the multi-carbonyl species typical of well-dispersed Ni0 [43], while the band at 2048 cm1 is due to the linearly adsorbed CO

Fig. 9. IR spectra of CO adsorption on various catalysts at room temperature: (a) Ni (2.6); (b) Pt (0.1) + Ni (2.6); (c) Pt (0.1)/Ni (2.6); (d) Pt (0.1).

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[43,44]. The band at the lower frequency, i.e., 1930 cm1, is assigned to the bridged adsorbed CO [45]. For the monometallic platinum catalyst (Fig. 9(d)), only one band was observed at 2070 cm1; this is assigned to linear CO [4648]. We found that the band of the linear CO on Pt has almost the same position as that of multi-carbonyl species of Ni. Therefore, the relative intensity of the band was taken into account for the peak assignment in the bimetal catalysts. In the case of Pt (0.1) + Ni (2.6) catalyst (Fig. 9(b)), two broad bands at 2070 and 2048 cm1 were observed at the same intensity, which was similar to the spectrum of Ni (2.6). On the other hand, over Pt (0.1)/Ni (2.6) catalyst (Fig. 9(c)), the intensity of the 2070 cm1 band was much higher than that of the 2048 cm1 band, suggesting that a signicant amount of Pt atoms are located on the catalyst prepared by the sequential impregnation method. The similarity of Pt (0.1) + Ni (2.6) and Ni (2.6) indicates that the ratio of Pt on the surface in Pt (0.1) + Ni (2.6) is much lower than that in Pt (0.1)/Ni (2.6). This means that the sequential impregnation method is more effective than the co-impregnation method in terms of the surface modication, even with a small amount of Pt. A surface segregation phenomenon of Pt atoms was often found in Pt-Ni alloy [4951]. However, this effect is not so signicant on the catalyst prepared by the co-impregnation method, due to the very low composition of Pt to Ni (molar ratio Pt/Ni = 1/100). In contrast, the surface concentration of Pt is enhanced by the sequential impregnation method, although the average composition of Pt to Ni was just the same as that for the co-impregnation method. The effect of preparation methods can be explained on the basis of the TPR proles. From the TPR prole of Pt (0.1) + Ni (2.6) (Fig. 8(b)), one can deduce that Ni interacted with Al2O3 support surface and that the Ni species is reduced slowly even in the presence of Pt. Since the reducibility of Pt is high, Ni species is gradually reduced after the reduction of Pt, suggesting that Pt species can be covered with reduced Ni species. This would induce the low composition of surface Pt. In contrast, the TPR prole of Ni species without Pt (Fig. 8(d)) gave a sharp peak at much lower temperature than that of Ni (2.6), suggesting that NiO formed on the surface and that the interaction between NiO species and the support surface was rather weak. The sharp peak at much lower temperature in Pt (0.1)/Ni (2.6) (Fig. 8(c)) showed that the introduction of Pt promoted the reduction of this NiO species, and that NiO particles were reduced directly to Ni metal particles, thus inhibiting the mixing of Pt with Ni species and leading to the high surface composition of Pt. Further investigations are necessary for the structural analysis of the Pt-Ni bimetallic catalysts; however, we can conclude that the addition of Pt to Ni/Al2O3 catalysts by the sequential impregnation method is very effective for the inhibition of the hot spot formation in oxidative reforming of methane and that the preparation methodology ensured the surface enrichment of Pt. 5. Conclusions (1) In the oxidative steam reforming of methane (CH4/H2O/O2/ Ar = 40/30/20/10), Ni catalysts showed the presence of an

exothermic reaction at the catalyst bed inlet; the endothermic reaction zone and the exothermic zone are present separately, exhibiting a large temperature gradient in the catalyst bed. The maximum of the bed temperature cannot be decreased by the decrease of Ni loading amount. (2) Monometallic Pt catalyst gave a much smaller temperature gradient than Ni catalysts, attributable to the overlap between the endothermic and exothermic reaction zones. The inhibition of hot spots is dependent on the loading amount of Pt, and the catalyst with a small amount of Pt did not have a signicant effect. (3) The addition of small amount of Pt to Ni/Al2O3 was effective for the inhibition of hot spot formation. The two bimetallic Pt-Ni catalysts investigated showed different temperature proles. The effect of adding small amounts of Pt to Ni/Al2O3 was strongly dependent on the preparation method and the addition by a sequential impregnation method had a more remarkable effect than that by a coimpregnation method. (4) Characterizations of monometallic and bimetallic catalysts by means of XRD, TEM, TPR and FT-IR of CO adsorption suggest that the introduction of Pt by a sequential impregnation leads to the efcient surface modication even with a small amount of Pt, showing the high Pt surface composition. Acknowledgement This study was supported by the Industrial Technology Research Grant Program (05A43002C) from the New Energy and Industrial Technology Development Organization (NEDO) of Japan. References
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