Hydrogenation of p-Chloronitrobenzene on Nanosized Modified NiMoB Catalysts

NiMoB alloy catalyst has been reported to be a good catalyst for the hydrogenation of p-chloronitrobenzene to p-chloroaniline. The objective of this study was to investigate the effect of additives (Pd, La, Fe and Co) on the catalytic properties of NiMoB in the hydrogenation of p-chloronitrobenzene. The catalysts were prepared by chemical reduction method using sodium borohydride as the reducing agent. The molar ratios of Ni/Mo/B/additives in the starting materials were 0.4/1/3/0.1. The catalysts were characterized by inductively coupled plasma-mass spectrometry, X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. The catalysts were tested for liquid-phase hydrogenation of p-chloronitrobenzene at 1.2?MPa H₂ pressure and 333–353?K. Adding additives decreased the particle size of modified-NiMoB catalyst, suppressed the growth of the crystalline structure of NiMoB and helped the NiMoB nanocluster maintain its amorphous state. The reaction activity is in the order of the following: Pd-NiMoB?>?La-NiMoB?>?Co-NiMoB?>?NiMoB?>?Fe-NiMoB. Pd itself is the active metal for hydrogenation, but NiPd bimetallic alloy was too active resulting in low selectivity of chloroaniline. The other additives were in the form of hydroxide and acted as a spacer to prevent NiMoB catalysts from sintering and aggregation.