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Abstract <p>Nickel, cobalt, molybdenum, tungsten, and iron phosphides were prepared in situ from oil-soluble precursors and red phosphorus in the presence of a chlorinated substrate, 1,4-dichlorobenzene. Their catalytic activity was studied in competing processes of the hydrogenolysis of model feedstock containing a chlorinated derivative (1,4-dichlorobenzene) and heteroatomic compounds (benzothiophene, guaiacol, terephthalic acid, quinoline). Analysis of the phase composition of the catalysts by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) confirmed the formation of the phases of the metal phosphides, chlorides, and phosphates. The activity of the phosphides in the 1,4-dichlorobenzene hydrodechlorination increases in the order Mo &lt; Fe &lt; W &lt; Co &lt; Ni, and that in the joint process of 1,4-dichlorobenzene hydrodechlorination and benzothiophene hydrodesulfurization, in the order Co &lt; W &lt; Fe ≈ Ni &lt; Mo. In the hydrodechlorination of 1,4-dichlorobenzene in a mixture with guaiacol, the activity of all the phosphides except iron phosphide decreases as compared to the 1,4-dichlorobenzene hydrodechlorination in the single-component system. Iron phosphide shows promise as a protective bed catalyst in the hydrotreating of polymer waste pyrolysis products, and nickel phosphide, as a catalyst for the hydrotreating of products formed by pyrolysis of polyvinyl chloride in polymer waste mixtures.</p>

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Catalytic Properties of Unsupported Catalysts Based on Transition Metal Phosphides in Hydrotreating of Pyrolysis Products of Chlorinated Polymer Wastes

  • 期刊论文

  • 发表日期：

    2025年3月1日

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  • E. G. Dzhabarov,
  • N. N. Petrukhina,
  • E. M. Zakharyan

摘要

Abstract

Nickel, cobalt, molybdenum, tungsten, and iron phosphides were prepared in situ from oil-soluble precursors and red phosphorus in the presence of a chlorinated substrate, 1,4-dichlorobenzene. Their catalytic activity was studied in competing processes of the hydrogenolysis of model feedstock containing a chlorinated derivative (1,4-dichlorobenzene) and heteroatomic compounds (benzothiophene, guaiacol, terephthalic acid, quinoline). Analysis of the phase composition of the catalysts by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) confirmed the formation of the phases of the metal phosphides, chlorides, and phosphates. The activity of the phosphides in the 1,4-dichlorobenzene hydrodechlorination increases in the order Mo < Fe < W < Co < Ni, and that in the joint process of 1,4-dichlorobenzene hydrodechlorination and benzothiophene hydrodesulfurization, in the order Co < W < Fe ≈ Ni < Mo. In the hydrodechlorination of 1,4-dichlorobenzene in a mixture with guaiacol, the activity of all the phosphides except iron phosphide decreases as compared to the 1,4-dichlorobenzene hydrodechlorination in the single-component system. Iron phosphide shows promise as a protective bed catalyst in the hydrotreating of polymer waste pyrolysis products, and nickel phosphide, as a catalyst for the hydrotreating of products formed by pyrolysis of polyvinyl chloride in polymer waste mixtures.