ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2010, Vol. 84, No. 3, pp. 400–404. © Pleiades Publishing, Ltd., 2010. Original Russian Text © A.I. Pylinina, I.I. Mikhalenko, M.M. Ermilova, N.V. Orekhova, V.I. Pet’kov, 2010, published in Zhurnal Fizicheskoi Khimii, 2010, Vol. 84, No. 3, pp. 465–470. 400 INTRODUCTION Dehydration of the limiting monoatomic alcohols is a route to various olefins. It mostly occurs simulta- neously with dehydrogenation of alcohol and forms aldehydes and ketones along with olefins. The current tendency is to use effective catalytic systems with high activity, selectivity, and stability to deactivation and analyze the elementary stages of surface processes and the nature of active centers [1–4]. The mechanisms of dehydration are best defined for oxide catalysts such as Al 2 O 3 , WO 3 , TiO 2 , etc., as well as aluminum silicates and phosphates [5, 6]. The active sites are Lewis acid centers, but it is not excluded that the final stage of the reaction involves basic centers. The formation of olefins involves surface alkoxides, hydrogen-bonded complexes, and carbe- nium ions, e.g., the + СН 2 –СН(СН 3 )–СН 3 ions formed in dehydration of isobutanol and identified in situ by IR and 13 C NMR spectroscopy. The nature of the active surface of a catalyst (its acidic, basic, or redox properties) can be tested according to the selec- tivity of alcohol decomposition into olefins and carbo- nyl compounds. Of great importance is the acidic and basic bifunctional action. The dependence of the dehydrating ability of oxide catalysts on the number and strength of acid centers appears to be well defined. Dehydration of primary alcohols on acid centers that are stronger than the dehydration sites can lead to migration of the double bond in the olefin. Complex zirconium-containing phosphates from Nasicon (Na-superionic conductor) family were syn- thesized and characterized, and evidence of their cat- alytic activity in reactions with alcohols was given in [7–11]. These systems proved to be selective catalysts of dehydration, possessing important physicochemi- cal properties such as thermal stability combined with a microporous structure with ion conducting channels and offering wide possibilities for varying the compo- sition. Solid electrolytes of this type are open crystal structures containing ZrO 6 octahedra and PO 4 tetrahe- dra, whose voids include conduction ions (compensa- tor ions). From NaZr 2 (PO 4 ) 3 binary phosphate, one can pass to ternary systems by replacing some of the sodium ions in the cation moiety or zirconium ions in the anion framework without changing the type of the crystal lattice. This work is a continuation of our studies of the catalytic properties of Nasicon. The change in the activity and selectivity of the decomposition of butanol-2 on copper-containing sodium–zirconium phosphates and the surface acidity, tested from pyri- dine adsorption after plasmochemical treatment in glow discharge of oxygen, were reported in [12, 13]. The aim of this study was to determine the effect of the sodium to copper ratio (with the same chemical com- position of the anion framework) on the activity and selectivity of the Nasicon catalyst in dehydration of bitanol-1, butanol-2, and isobutanol. EXPERIMENTAL Sodium-copper-zirconium phosphates of the gen- eral formula Na 1  2x Cu x Zr 2 (PO 4 ) 3 (x = 0, 0.15, 0.25, 0.35, 0.5) were prepared by the sol–gel procedure. NaNO 3 , CuCl 2 · 2H 2 O, ZrCl 2 , ZrOCl 2 · 8H 2 O, and H 3 PO 4 of reagent grade were used for the synthesis; the synthetic procedure is described in [7, 9]. The Dehydration of Butanols on Copper-Containing Zirconium Orthophosphates A. I. Pylinina a , I. I. Mikhalenko a , M. M. Ermilova b , N. V. Orekhova b , and V. I. Pet’kov c a Russian University of Peoples’ Friendship, Moscow, 117198 Russia b Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, 119991 Russia c Nizhni Novgorod State University, Nizhni Novgorod, 603600 Russia e-mail: pylinina@list.ru Received March 10, 2009 Abstract—The catalytic properties of ternary zirconium phosphates Na 1–2x Cu x Zr 2 (PO 4 ) 3 in the transfor- mations of butanols were been studied. It was found that the structure of alcohol and the copper content (x = 0, 0.15, 0.25, 0.35) affect the rate and selectivity of dehydration. The activity and selectivity changed as the content of copper that substitutes for sodium ions increased. The general conversion of alcohol and selectivity in dehydration decreased in the series butanol-2 isobutanol butanol-1, due probably to the change in the apparent activation energy of the reaction, depending on the stability of alcohol binding to the surface. DOI: 10.1134/S0036024410030106 CHEMICAL KINETICS AND CATALYSIS