Elsevier

Catalysis Communications

Volume 9, Issue 1, January 2008, Pages 106-110
Catalysis Communications

Effectiveness of the template-ion exchange method for appearance of catalytic activity of Ni–MCM-41 for the ethene to propene reaction

https://doi.org/10.1016/j.catcom.2007.05.032Get rights and content

Abstract

The template-ion exchange (TIE) method, an equilibrium adsorption (EA) of nickel ammine complex, and a conventional impregnation (IMP) method were applied to prepare nickel ion-loaded mesoporous silica MCM-41 and silica gel and their catalytic activity was examined for the newly developed ethene to propene (ETP) reaction. When we employed TIE as the preparation method and MCM-41 as the support, the most active and stable catalyst could be prepared. The local structures of the nickel species supported on the TIE and EA samples were very similar to that of layered nickel silicate, while those on the IMP-catalysts were the same as that of NiO particles.

Introduction

The one-path conversion of ethene to propene (ETP) on nickel ion-loaded MCM-41 (Ni–M41) catalysts was very recently found by the authors [1]. The ETP reaction is believed to become very important because demands for propene and its derivatives are rapidly increasing in recent years though current petrochemical industry has been based on ethene. Iwamoto and Kosugi reported that the ETP reaction could be catalyzed only on Ni–M41s prepared by the template-ion exchange (TIE) method [2], [3] while Ni–M41s prepared by the conventional impregnation (IMP) method were inert [1]. As has already been suggested, the catalysis on Ni–M41 is entirely different from the ETP reaction reported on supported metathesis catalysts [4], [5] or acidic zeolites [6]. The activity of the former was so low that the reaction could be observed only in a closed recirculation system. The selective propene formation on zeolites is widely reported to result from the oligomerization/decomposition of lower olefins and the subsequent shape selectivity. This activity greatly differs from the catalysis on Ni–M41 because of little possibility of the shape selective reaction in the wide pores of M41. The origin of the high catalytic activity of Ni–M41 and the reaction mechanism therefore would be the new targets to be studied. We found here that the preparation methods of Ni-catalysts, especially the loading method of nickel ion, significantly affect the ETP activity, which is useful to shed light on the active sites and the reaction mechanism.

Section snippets

Experimental section

The mesoporous silica MCM-41 was prepared by the reported method [7]. The M41 obtained was washed with deionized water and dried at 353 K for 1 h before further treatment. The as-synthesized M41 (as-M41) underwent the template-ion exchange (TIE) treatment [3] with an aqueous solution of nickel nitrate to prepare the nickel ion-loaded MCM-41 (Ni–M41 5.0–5.5 wt%). The initial and final pHs of the solution were 10.2 and 7.4, respectively. An equilibrium adsorption (EA) of [Ni(NH3)x]2+ was applied to

Results and discussion

The hexagonal structures of the prepared M41 samples were confirmed by the appearance of 2θ = 2.580°, 4.476°, and 5.124° peaks in the XRD patterns, corresponding to (1 0 0), (1 1 0), and (2 0 0), respectively [12]. The pore diameters and surface areas were ca. 2.24 nm and 820–960 m2 g−1, which were approximately the same as those reported previously [1]. The following results and discussion will be described on the premise of no essential difference in the pore structures among the M41 samples employed

Acknowledgements

This work was supported by the Grand-in-Aids from the Ministry of Education, Culture, Sports, Science and Technology of Japan and CREST of JST.

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