A comparison of cesium-containing heteropolyacid and sulfated zirconia catalysts for isomerization of light alkanes

The heteropolyacid H3PW12O40 and its cesium salts CsxH3-xPW12O40 (x = 1, 2, 2.5, 3) were synthesized, characterized and tested as catalysts for hydrocarbon reactions. All samples were characterized by a variety of techniques including elemental analysis, X-ray diffraction, dinitrogen adsorption, thermal gravimetric analysis and ammonia sorption. Results from these methods confirmed that pure cesium salts were prepared without significant contamination by amorphous oxide phases. Incorporation of cesium into the heteropolyacid decreased the acidic protons available for catalysis, increased the specific surface area, and increased the thermal stability. The heteropolyacids were tested as catalysts for butane skeletal isomerization, pentane skeletal isomerization and 1-butene double bond isomerization. For comparison, the activity of sulfated zirconia, a well-studied strong acid catalyst, was also evaluated for the three probe reactions. On a per gram basis, the Cs2HPW12O40 sample was the most active heteropolyacid, presumably due to its high surface area. This sample was more active than sulfated zirconia for pentane skeletal isomerization and 1-butene double bond isomerization. However, sulfated zirconia was more effective for butane skeletal isomerization. Since the pentane and 1-butene reactions were monomolecular in nature, whereas butane isomerization was bimolecular, restrictions inside the micropores of the heteropolyacid may inhibit the formation of long chain intermediates. Interestingly, trace butenes were required to initiate butane isomerization reactions on sulfated zirconia whereas heteropolyacids catalyzed the reaction in the absence of butenes.