Membrane reactors for hydrogenation and dehydrogenation processes based on supported palladium

https://doi.org/10.1016/S1381-1169(01)00149-2Get rights and content

Abstract

Membrane reactors applied to catalytic reactions are currently being studied in many places world-wide. Significant developments in membrane science and the vision of process intensification by multifunctional reactors have stimulated a lot of academic and industrial research, which is impressively demonstrated by more than 100 scientific papers on catalytic membrane reactors being published per year. Palladium as a noble metal with exceptional hydrogen permeation properties and, at the same time, broad applicability as a catalyst, first of all for hydrogenation, is part of many of these developments.

This paper discusses two different membrane reactor concepts which both rely on supported palladium, on the one hand as a permselective membrane material, and on the other hand as base component of a membrane-type hydrogenation catalyst. Dense palladium composite membranes can be used for hydrogen separation from packed-bed catalysts in gas-phase hydrocarbon dehydrogenation reactions. Mesoporous membranes containing dispersed bimetallic Pd/X-clusters can be employed as so-called catalytic diffusers for liquid-phase hydrogenation, e.g. of nitrate and nitrite in water. The principles of both concepts are introduced, recently obtained experimental data are evaluated in connection with literature results, and the perspectives for further development are highlighted.

Section snippets

Membrane reactor concepts

According to the IUPAC definition a membrane reactor is a device that combines a membrane-based separation process with a chemical reaction step in one unit. Various possibilities exist for such a combination. The most widely used concept is the selective removal of products from the reaction zone (cf. Fig. 1a), which is applied first of all to equilibrium limited reactions to increase the yield beyond the corresponding equilibrium value, or, generally speaking, to repress undesired secondary

Membrane reactors based on palladium alloy membranes

It is well established that dense palladium and palladium alloy membranes are permeable for hydrogen only. Two main possibilities arise from this feature to employ these in membrane reactors, namely

  • 1.

    to promote a dehydrogenation reaction by removal of the produced hydrogen from a dehydrogenation catalyst through the membrane, i.e. preventing the establishment of the chemical equilibrium, or

  • 2.

    to carry out a hydrogenation reaction on the palladium surface with supply of hydrogen through the membrane.

Membrane reactors based on porous catalytic membranes with dispersed palladium

Porous membranes with built-in catalytic components are catalytic membranes in the true sense of the word. They can be employed in a reactor in various ways, which may be classified into the following three categories:

  • 1.

    Forced flow of (pre-mixed) reactants through the membrane.

  • 2.

    Co-current or counter-current flow of two reactant streams on opposite sides of the membrane with permeation of all species across the membrane (non-permselective).

  • 3.

    Co-current or counter-current flow of two reactant streams

Critical evaluation and outlook

It has been shown that catalytic membranes with interesting properties can be obtained by introducing palladium and tin in the top layer of asymmetric porous ceramic membranes, preferentially employing macro/mesoporous α-alumina or zirconia as top-layer materials. These membranes can be used as catalytic diffusers for the hydrogenation of nitrate and nitrite in water. The main advantage of the catalytic diffuser, besides the immobilisation of the active phase, is the possibility to supply the

Acknowledgements

The authors thank all partners of the European research project, Prof. G. Strukul, Dr. M. Marella, Dr. P. Ruiz, Dr. F. Luck, Ir. M. van Donk and Prof. G. Centi for the fruitful co-operation and Mrs. M. Schorr and Mr. M. Jusek (DECHEMA e.V.) for EPMA analysis, pulse CO-chemisorption and XRD measurements. Financial support by the Bavarian Catalysis Research Network FORKAT II and by the European Community is gratefully acknowledged.

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