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Jointly published by React KinetCatal Lett. Kluwer Academie Publishers, Dordrecht Vol. 69, No.2, 355-360 and Akaclémiai Kiadé, Budapest (2000) RKCL3602 STEAM REFORMING OF METHANOL OVER Pd-Zn CATALYSTS Nobuhiro Iwasa, Tomoyuki Mayanagi, Satoshi Masuda and Nobutsune ‘Takezawa of Materials Science and Engineering, Graduate School of Enginecring, Hokkaido University, Sapporo, 060-8628, Japan Divi Received September 10, 1999 In revised form January 24, 2000 Accepted January 28, 2000 Abstract Heating the physical mixtures of Pd and Zn selectively yielded PdZn of PdssZns. alloy. These alloys were highly selective for the steam reforming of methanol. Keywords: Steam reforming of methanol, PdZn alloy, PdysZng, alloy INTRODUCTION The catalytic performances of Group 8-10 metals for the steam reforming of methanol, CH,OH + H;0 > CO, + 3Hp, were greatly different from those of copper. Steam reforming occurred selectively over copper catalysts while the decomposition of methanol, CH;OH > CO + 2H;, took place predominantly cover Group 8-10 metal catalysts [1,2] Recently, we have found that Pd/ZnO catalysts exhibit high performance in the conversions of methanol among various supported Pd catalysts [3,4]. The dehydrogenation of methanol to methyl formate, 2CH;OH > HCOOCHs + 2H2 [3], and the steam reforming of methanol occurred selectively [4]. Novel functions of Pd/ZnO were developed by the formation of alloys in a structure of PdZn on ZnO during the course of the reactions or on the previous reduction of the catalysts [5]. (0133-1736/2000/11SS 12.00. © Akadémiai Kind, Budapest All Fights reserved. 356 IWASA ef al: STEAM REFORMING In the present study, the steam reforming of methanol is carried out over Pd- Zn catalysts prepared by heat treatments of Pd and Zn. It is shown that PdZn and PdssZng, alloys exhibit high performance for the steam reforming of methanol. EXPERIMENTAL Pd-Zn catalysts were prepared by the heat treatment of the physical mixtures of Pd and Zn powders at various temperatures in a nitrogen stream ata flow rate of 50 cm¥min. The Pd/Zn molar ratio was varied from 1/1 to 1/8. For comparison, experiments were also conducted over a Ni-Zn or a Fe-Zn catalysts, respectively, prepared from Ni and Zn or Fe and Zn in a similar manner to the preparation of Pd-Zn catalysts. Prior to the reaction, the catalysts were treated in a hydrogen stream (4 vol.% H,) diluted with nitrogen under temperature-programmed conditions at a heating rate of § K/min up to temperatures where the catalysts were previously treated in nitrogen. The steam reforming of methanol was carried out in a conventional flow reactor at 493 K and at atmospheric pressure. Nitrogen was used as a diluent. Space velocity was always kept at 7600 h", Gases in the effluent were analyzed by gas chromatography. The selectivity for the steam reforming was evaluated by the carbon basis. Structures of the catalysts were inspected by X-ray diffraction methods using a JEOL JDX-8020 X-ray diffractometer, using Cu Ka radiation (A = 0.15405 nm). RESULTS AND DISCUSSION Figure | shows XRD patterns for various Pd-Zn catalysts (Pd/Zn molar ratio = 1/1) treated in nitrogen for 3 h at different temperatures along with that for a Pd-Zn catalyst prior to the heat treatment. For Pd-Zn without the heat treatment, a peak ascribed to metallic Pd appear at 2 6 = 40.1" [6] in addition to peaks ascribed to metallic Zn at 2 8 = 36.3", 39,0° and 43,2° [7]. Upon the heat treatment above 493 K, the peaks for metallic Pd and metallic Zn decrease and a new peak for Pds sng, [8] grow at 2 6 = 42.0°. The peak for Pdy.9Zng,; increases up to 523 K and then decreases with increasing temperature. Above 543 K, the peaks ascribed to PdZn [9} are developed. The peak for Pd is practically diminished at 673 K while the peaks for metallic Zn disappear above 573 K. At 673 K, PdZn is selectively produced. Figure 2 illustrates the mole fraction of the products in the effluent against the treatment temperature. The mole fraction of H2 and CO, increases with the temperature up to 623 K and decreases with increasing the temporature while IWASA etal: STEAM REFORMING 337 that of CO decreases monotonically with the increased temperature. The selectivity for the steam reforming increases greatly with the increased temperature, The selectivity exceeds 90% for the catalysts treated at 623 K or 673 K where PdZn alloy is predominantly present. 35 40 45 20 (deg.) Fig. 1. XRD patterns for various Pd-Zin catalysts treated at different temperatures (a) without heat treatment, (b) 493 K, (c) 523 K, (€), $43 K, (¢) 573 K, (1) $93 K, (g) 623 K, and. (h) 673 K. PdiZn molar ratio= 1/. Pd black was kneaded with Zn powder at various Pd/Zn molar ratios and heated at 493 K for 3h, Figure 3 collects XRD spectra after the heat treatment at 493 K. Pd39Zng; alloys are selectively produced irrespective of the molar ratio. With the increasing molar ratio, the peaks for metallic Pd decrease while those for PdsoZng, alloys increase. At the Pd/Zn molar ratio of 1/8, the peaks for metallic Pd are diminished, suggesting that metallic Pd is effectively converted into Pd3 9Zng, alloys. Table 1 lists the catalytic performances of Pd-Zn prepared at 493 K with various Pd/Zn molar ratios along with those of Pd and Zn, High selectivity is 358 IWASA etal: STEAM REFORMING. obtained over the catalysts where Pd3»Zng, alloys predominate. For Pd-Zn with a Pd/Zn molar ratio of 1/8, the selectivity increases to 87.5 %, Over the catalyst with a PdiZn molar ratio of 1/1, where metallic Pd is primarily present, the selectivity decreases to 23.7 %. Over Pd black, methanol was exclusively decomposed to CO and H2. No reaction occurred over metallic Zn alone. Over metallic Pd in the absence or the presence of metallic Zn the selectivity for steam reforming was greatly suppressed unless the alloys were produced. Some experiments were carried out over the Ni-Zn and Fe-Zin catalysts. It was found that NigZny3 or Fe,Zny alloy was selectively produced in the heat treatment of an equimolar mixture of Ni and Zn or Fe and Zn at 623 K for 3 h. Over these Ni- Zn and Fe-Zn alloys no reactions occurred. Among the alloys studied, PdZn and PdsZng: exhibit uniquely high performance for the steam reforming of methanol. 10 5 . g 3 He est g é 3 3 Cor ° ‘0 450 500 550 600 650 700 Treatment temperature (K) Fig. 2, Mole fiaction of the products in the effluent against the treatment temperature TWASA etal: STEAM REFORMING. 359 Tablet Catalytic performance of various composition of Pd-Zn catalysts for steam reforming of methanol Catalyst PwZn Conversion Selectivity molar ratio %) Ca) Pa-zn vl 12.9 23.7 Pad-Zn v4 107 85.7 Pa-Zn 18 485 875 Pd black - 104 0 Zn - 0 - “Catalysts were treated at 493 K for 3h in Nz flow PdssZn61 Kb), 1 35 40 45 28 (deg.) Fig, 3. XRD patterns for Pd-Zn catalysts with various Pd/Zn molar ratios. (a) 1/1, (b) 1/2, (c) 1/4 and (a) 1/8 360 IWASA et af: STEAM REFORMING REFERENCES L K. Takahashi, H. Kobayashi, N. Takezawa: Chem. Lett., 759 (1985). 2 N. Takezawa, N, Iwasa: Catal. Today, 36, 45 (1997). 3. N. Iwasa, O. Yamamoto, T. Akazawa, S. Ohyama, N. Takezawa: J. Chem. Soc. Chem. Commun, 1322 (1991). 4 N. Iwasa, 8. Kudo, H. Takahashi, S.Masuda, N. Takezawa: Catal. Lett, 19, 211 (1993). 5. N, Iwasa, S, Masuda, N. Ogawa, N. Takezawa: Appl. Cazal., 125, 145 (1995). 6. X-ray Powder Data File, ASTM 46-1043. 7. X-ray Powder Data File, ASTM 4-851. 8 X-ray Powder Data File, ASTM 6-630. 9. X-ray Powder Data File, ASTM 6-620.

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