Commercial catalysts screening for liquid phase nitrobenzene hydrogenation

• Commercial catalysts screening for aniline production.
• Study of the operating conditions influence in nitrobenzene hydrogenation.
• Pd-based catalysts present higher activity.
• No major differences in the morphological and textural properties of fresh and used catalysts.

In this work, a series of commercially available materials was screened for the catalytic hydrogenation of nitrobenzene (NB). The materials revealed different performances, particularly different activities in what concerns the NB conversion, and notably diverse selectivities towards the industrially desired reaction product, aniline (ANL). The catalysts’ active phases are based on Pd and Ni (respectively groups I and II), namely 1 wt.% Pd/Al2O3 (catalyst I.1), 0.3 wt.% Pd/Al2O3 (catalyst I.2), 0.3 wt.% Pd/Al2O3 (catalyst I.3), and 50 wt.% NiO/(Al2O3 + SiO2) (catalyst II.1). The fresh and used materials were characterized by several physical-chemical techniques, specifically scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), nitrogen adsorption (with BET surface area determination), X-ray diffraction (XRD), H2 temperature-programmed reduction (TPR), inductively coupled plasma mass spectrometry (ICP-MS) and elemental (CHNS) analysis. It was shown that the catalysts are stable in the conditions studied and no deactivation was found. The characterization results allowed explaining the catalytic behavior of the tested materials. In particular, catalyst I.1 was found to be the less active, probably due to its much lower BET surface area (and larger Pd particle size). On the other hand, catalyst I.2 was the more active, which was well correlated to the smaller average particle size (along with narrower Pd particle size distribution) and smaller pellet size, although the active metal content is low. Finally, it was observed that catalyst II.1 is the most selective towards light by-products (benzene (Bz), cyclohexylamine (CHA), cyclohexanol (CHOL) and cyclohexanone (CHONA)), probably due to its lower pore size dimensions.

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