The Modification of Diphenyl Sulfide to Pd/C Catalyst and Its Application in Selective Hydrogenation of p-Chloronitrobenzene

doi:10.1016/j.cjche.2014.08.007

Abstract

Abstract: In this study, diphenyl sulfide (Ph₂S) was employed to prepare a series of Ph₂S-modified Pd/C catalysts (Pd-Ph₂S/C). Catalyst characterization carried out by Brunner-Emmet-Teller (BET), energy dispersive spectrometer (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and CO chemisorption uptakemeasurements suggested a chemical interaction between Ph₂S and Pd. The ligand was preferably absorbed on the active site of Pd metal but after increasing the amount of Ph₂S, the adsorption of Ph₂S on Pd metal tended to be saturated and the excess of Ph₂S partially adsorbed on the activated carbon. A part of Pd atoms without adsorbing any Ph₂S still existed, even for the saturated Pd-Ph₂S/C catalyst. The Pd-Ph₂S/C catalysts exhibited a good selectivity of p-chloroaniline (p-CAN) in the hydrogenation of p-chloronitrobenzene (p-CNB). However, the chemisorption between Ph₂S and Pdwas not so strong that part of Ph₂Swas leached fromPd-Ph₂S/C catalyst during the hydrogenation,which caused the decline of the selectivity of p-CAN over the used Pd-Ph₂S/C catalyst. Resulfidation of the used Pd-Ph₂S/C catalystwas effective to resume its stability, and the regenerated Pd-Ph₂S/C catalyst could be reused for at least ten runs with a stable catalytic performance.

Key words: Diphenyl sulfide, Modification, p-Chloronitrobenzene, Pd/C, Selective hydrogenation, Stability

摘要： In this study, diphenyl sulfide (Ph₂S) was employed to prepare a series of Ph₂S-modified Pd/C catalysts (Pd-Ph₂S/C). Catalyst characterization carried out by Brunner-Emmet-Teller (BET), energy dispersive spectrometer (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and CO chemisorption uptakemeasurements suggested a chemical interaction between Ph₂S and Pd. The ligand was preferably absorbed on the active site of Pd metal but after increasing the amount of Ph₂S, the adsorption of Ph₂S on Pd metal tended to be saturated and the excess of Ph₂S partially adsorbed on the activated carbon. A part of Pd atoms without adsorbing any Ph₂S still existed, even for the saturated Pd-Ph₂S/C catalyst. The Pd-Ph₂S/C catalysts exhibited a good selectivity of p-chloroaniline (p-CAN) in the hydrogenation of p-chloronitrobenzene (p-CNB). However, the chemisorption between Ph₂S and Pdwas not so strong that part of Ph₂Swas leached fromPd-Ph₂S/C catalyst during the hydrogenation,which caused the decline of the selectivity of p-CAN over the used Pd-Ph₂S/C catalyst. Resulfidation of the used Pd-Ph₂S/C catalystwas effective to resume its stability, and the regenerated Pd-Ph₂S/C catalyst could be reused for at least ten runs with a stable catalytic performance.

关键词: Diphenyl sulfide, Modification, p-Chloronitrobenzene, Pd/C, Selective hydrogenation, Stability

Qunfeng Zhang, Chang Su, Jie Cen, Feng Feng, Lei Ma, Chunshan Lu, Xiaonian Li. The Modification of Diphenyl Sulfide to Pd/C Catalyst and Its Application in Selective Hydrogenation of p-Chloronitrobenzene[J]. , 2014, 22(10): 1111-1116.

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