Gas-Phase Hydrodechlorination of Chlorobenzene over Alumina-Supported Nickel Catalysts: Effect of Support Structure and Modification with Heteropoly Acid HSiW

The physicochemical and catalytic properties of 6%Ni/Al2O3 catalysts in the gas-phase hydrodechlorination of chlorobenzene (CB) are studied. The catalysts are synthesized by supporting nickel nitrate on two types of alumina—A (synthesized by aluminum isopropoxide hydrolysis) and E (manufactured by Engelhard)—with different morphologies and textures; some of the samples are unmodified, and some are modified by depositing 20% heteropoly acid (HPA) H8Si(W2O7)6 ⋅ nH2O. To prevent the HPA from decomposition, the air calcining and reduction of the modified materials are conducted at relatively low temperatures (250 and 330°C, respectively). To provide an adequate comparison, the catalysts containing no HPA are subjected to a similar treatment. Temperature-programmed reduction (TPR) reveals that air calcining at 250°C does not provide the complete conversion of the original nickel nitrate to oxide; nickel nitrates and hydroxynitrates are present in the catalyst precursors; their content decreases upon modification with the HPA. Differences in the composition and strength of Lewis acid sites on the surface of two types of Al2O3 lead to dissimilar coordination of nitrate and differences in nickel reducibility, as revealed by TPR, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy with CO adsorption, and in situ X-ray photoelectron spectroscopy (XPS). Nickel contained in Ni/Al2O3(E) undergoes reduction somewhat more readily than nickel in Ni/Al2O3(A) does; however, the conditions used in this study provide the reduction of only a small portion of nickel in the two catalysts. According to in situ XPS, TPR, and DRIFT spectroscopy with CO adsorption, the modification of Ni/Al2O3 with the HPA leads to a further change in the acidic properties and the coordination of nickel nitrate during impregnation and an increase in nickel reducibility; it prevents nickel from migration from the surface into the bulk of the sample and leads to the formation of new active sites owing to the strong nickel–tungsten interaction in the HPA. Depending on the nature of the support, modification with the HPA leads to an improvement (Ni/HPA/Al2O3(A)) or deterioration (Ni/HPA/Al2O3(E)) of the catalytic efficiency of the samples. At high temperatures, the benzene selectivity of the HPA-modified catalysts decreases owing to the formation of cyclohexane. The catalyst efficiency increases in the following order: Ni/HPA/Al2O3(E) < Ni/Al2O3(A) < Ni/Al2O3(E) < Ni/HPA/Al2O3(A). The most active catalyst—Ni/HPA/Al2O3(A)—exhibits the highest stability in long-term tests with an increase and subsequent decrease in temperature. The effect of nickel reducibility on the catalyst efficiency in CB hydrodechlorination is more significant than the effect of differences in texture and nickel content.