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Abstract <p>Using red phosphorus, a series of unsupported nanosized transition-metal phosphides (NiP, MoP, and FeP) were synthesized <i>in situ</i> in the presence of the brominated flame retardant tetrabromobisphenol A (TBBPA). Their catalytic activity was evaluated in the hydroprocessing of model polymer waste mixtures (polystyrene, polyethylene, polypropylene, and polyvinyl chloride) containing 10 wt % TBBPA. Reactions were conducted at 320–380°C, 6 MPa H<sub>2</sub>, with a metal-to-polymer weight ratio of 1 : 80 for 7 h. A comparative investigation of the three phosphides in the hydroprocessing of the polyethylene, polypropylene, and polystyrene mixtures with 10 wt % TBBPA demonstrates that at 320°C, NiP minimized the formation of organobromine intermediates such as 1-(1-methylethylene)-3,5-dibromo-4-hydroxybenzene (6 wt %) and 2,6-dibromophenol (4 wt %), achieving superior debrominating activity. Raising the temperature to 380°C enhanced debromination for all catalysts but reduced styrene selectivity due to aromatic hydrogenation. The optimal temperature for styrene yield was 340°C. Catalyst reuse led to gradual deactivation via the formation of metal bromides and agglomeration of catalyst particles, highlighting the need for effective regeneration methods.</p>

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Hydroprocessing of Tetrabromobisphenol A over Phosphide Catalysts

  • 期刊论文

  • 发表日期：

    2026年3月1日

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  • Eduard G. Dzhabarov,
  • Nikita D. Kashirin,
  • Natalia N. Petrukhina,
  • Elena M. Zakharyan

摘要

Abstract

Using red phosphorus, a series of unsupported nanosized transition-metal phosphides (NiP, MoP, and FeP) were synthesized in situ in the presence of the brominated flame retardant tetrabromobisphenol A (TBBPA). Their catalytic activity was evaluated in the hydroprocessing of model polymer waste mixtures (polystyrene, polyethylene, polypropylene, and polyvinyl chloride) containing 10 wt % TBBPA. Reactions were conducted at 320–380°C, 6 MPa H2, with a metal-to-polymer weight ratio of 1 : 80 for 7 h. A comparative investigation of the three phosphides in the hydroprocessing of the polyethylene, polypropylene, and polystyrene mixtures with 10 wt % TBBPA demonstrates that at 320°C, NiP minimized the formation of organobromine intermediates such as 1-(1-methylethylene)-3,5-dibromo-4-hydroxybenzene (6 wt %) and 2,6-dibromophenol (4 wt %), achieving superior debrominating activity. Raising the temperature to 380°C enhanced debromination for all catalysts but reduced styrene selectivity due to aromatic hydrogenation. The optimal temperature for styrene yield was 340°C. Catalyst reuse led to gradual deactivation via the formation of metal bromides and agglomeration of catalyst particles, highlighting the need for effective regeneration methods.