Development of a novel chelation-based recycling strategy for the efficient decontamination of hazardous petroleum refinery spent catalysts.

The conventional hydrometallurgical methods for recycling refinery spent hydroprocessing catalysts are ineffective in simultaneously removing all metals (Ni, V, and Mo) in a single-stage operation. In this study, a novel octadentate chelating agent, diethylenetriaminepentaacetic acid (DTPA-C14H23N3O10), has been proposed for the first time to remove toxic metals (Ni, V, and Mo) in a single stage of operation from an industrial spent atmospheric residue desulfurization (ARDS) catalysts. It was discovered that the efficient formation of metal-DTPA complexes was attained under the optimum experimental conditions (60 °C, stirring - 150 rpm, S/L ration (w/v) of 2.5%, 7.5% DTPA, and medium pH-9) that resulted in the high removal of Mo (83.6%), V (81.3%) and Ni (64.1%) from the spent ARDS catalyst. Kinetic studies suggest that the leaching process followed a semi-empirical Avrami equation (R2 > 0.92), which predicted that the diffusion control reaction controlled the leaching. Species distribution and ecological risk analysis of the remaining metals in the insoluble residue (mostly Al2O3) indicated that the potential bioavailability of the remaining metals (except Ni) was significantly decreased, and residue poses a low ecological and contamination risk (individual contamination factor <1). Furthermore, the textural properties of the residue (BET surface area-103 m2/g and pore volume- 0.49 ml/g) were dramatically improved, suggesting that fresh hydroprocessing catalyst support can be synthesized using the leached residue. Compared to the conventional processes, the proposed chelating process is highly selective, closed-loop, and achieved high metal recovery in a single-stage operation while decreasing the environmental risks of the hazardous spent catalysts.

Feasibility of bioleaching integrated with a chemical oxidation process for improved leaching of valuable metals from refinery spent hydroprocessing catalyst.

Bioleaching is considered an eco-friendly technique for leaching metals from spent hydroprocessing catalysts; however, the low bioleaching yield of some valuable metals (Mo and V) is a severe bottleneck to its successful implementation. The present study reported the potential of an integrated bioleaching-chemical oxidation process in improved leaching of valuable metals (Mo and V) from refinery spent hydroprocessing catalysts. The first stage bioleaching of a spent catalyst (coked/decoked) was conducted using sulfur-oxidizing microbes. The results suggested that after 72 h of bioleaching, 85.7% Ni, 86.9% V, and 72.1% Mo were leached out from the coked spent catalyst. Bioleaching yield in decoked spent catalyst was relatively lower (86.8% Ni, 79.8% V, and 59.8% Mo). The low bioleaching yield in the decoked spent catalyst was attributed to metals' presence in stable fractions (residual + oxidizable). After first stage bioleaching, the integration of a second stage chemical oxidation process (1 M H2O2) drastically improved the leaching of Ni, Mo, and V (94.2-100%) from the coked spent catalyst. The improvement was attributed to the high redox potential (1.77 V) of the H2O2, which led to the transformation of low-valence metal sulfides into high-valence metallic ions more conducive to acidic bioleaching. In the decoked spent catalyst, the increment in the leaching yield after second stage chemical oxidation was marginal (<5%). The results suggested that the integrated bioleaching-chemical oxidation process is an effective method for the complete leaching of valuable metals from the coked spent catalyst.

Epitaxial synthesis of Ni-MoS2/Ti3C2T x MXene heterostructures for hydrodesulfurization.

Hierarchical structures of 2D layered Ti3C2T x MXene hold potential for a range of applications. In this study, catalysts comprising few-layered MoS2 with Ti3C2T x have been formulated for hydrodesulfurization (HDS). The support Ti3C2T x was derived from MAX phases (Ti3AlC2) via a liquid-phase exfoliation process, while MoS2 was obtained from synthesized aqueous ammonium tetrathiomolybdate (ATM). Furthermore, a series of catalysts with different architectures was synthesized by confinement of ATM and/or the promoter Ni in Ti3C2T x at different mole ratios, through a thermal conversion process. The synthesized MoS2/Ti3C2T x and Ni-MoS2/Ti3C2T x catalysts were characterized using X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDS), high-resolution transmission electron microscopy (HRTEM), and temperature-programmed reduction (TPR) measurements. The number of MoS2 layers formed on the Ti3C2T x support was calculated using Raman spectroscopy. The heterostructured few-layered MoS2/Ti3C2T x catalysts were applied in sulfur removal efficiency experiments involving thiophene. The active MoS2 sites confined by the Ti3C2T x enhanced hydrogen activation by proton saturation, and the electron charge stabilized the sulfur atom to facilitate hydrogenation reactions, leading to predominant formation of C4 hydrocarbons. The Ni-MoS2/Ti3C2T x showed the best activity at a promoter molar ratio of 0.3 when compared to the other catalysts. In particular, it is evident from the results that ATM and Ti3C2T x are potential materials for the in situ fabrication of hierarchical few-layered MoS2/Ti3C2T x catalysts for enhancing hydrodesulfurization activity in clean fuel production.