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Vance, Brandon C.

Publications and source records attributed to Vance, Brandon C..

5 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Plastic-waste hydrogenolysis over two-dimensional MXene-supported ruthenium catalysts with tunable interlayer spacing

The hydrogenolysis of plastics is limited by active-site inaccessibility and inefficient mass transport of bulky polymer chains. To overcome these challenges, this work developed two-dimensional MXene-supported Ru (Ru@MXene) catalysts. Lyophilization of a solution containing dispersed MXene sheets and Ru precursors enabled the confinement of Ru species within the MXene interlayers, which act as pillars to expand the interlayer spacing. Building on this, a silica-pillared MXene-supported Ru (Ru@P-MXene) with even larger interlayer spacing exhibited a reaction rate of 914.9 g C5–C35 g Ru –1 h –1 for the hydrogenolysis of low-density polyethylene (LDPE) into valuable liquid chemicals (e.g., C 5 –C 35 ). A comparison of product yields between Ru@P-MXene and Ru@MXene suggests that elongated Ru particles confined within the MXene support expose their side facets for the reaction. In conclusion, this work demonstrates a new application of MXene in thermochemical catalysis, offering a solution to the challenges of active-site accessibility, mass transport, and reaction confinement in chemical plastic upcycling.

2D materials↗
DOE OSTI2024

Catalytic Deconstruction of Ethylene Vinyl Acetate Copolymer and Polyethylene Mixtures via Hydroconversion: Challenges and Solutions

We explore hydrogenolysis over ruthenium supported on zirconia (Ru/ZrO 2 ) and hydrocracking over platinum (Pt) supported on zeolites as an effective end-of-life strategy for ethylene vinyl acetate (EVA)–a widely used performance heat sealant in hard-to-recycle multilayer packaging. For Ru/ZrO 2 hydrogenolysis, EVA reacts slower than low-density polyethylene (LDPE) and the catalyst deactivates due to carbonaceous deposits originating from polyenes generated in situ during EVA thermal degradation. High H 2 pressures and temperatures can overcome catalyst deactivation; however, CH 4 yields are excessive due to cascade hydrogenolysis stemming from strong C=C/metal interactions. Polyene hydrogenation allows chains anchored by C=C to desorb from Ru, shifting product selectivity from CH 4 to higher-value liquids. Hydrogenolysis of mixed EVA and linear low-density polyethylene (LLDPE), mirroring typical frozen food packaging formulations, results in comparable catalyst activity and CH 4 yield as the pure EVA resin. For Pt/zeolite hydrocracking, pure EVA and EVA:LLDPE mixtures are deconstructed to propane or light naphtha with minimal CH 4 production. Among catalysts tested, Pt/HY gives the highest liquid productivity (g C5+products /g cat ·h). Furthermore, these findings showcase the recalcitrant nature of EVA and its associated mixtures for Ru/ZrO 2 hydrogenolysis, highlighting that hydrocracking catalysts may be superior for complex packaging waste.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Polystyrene Hydrogenolysis to High-Quality Lubricants Using Ni/SiO 2

Pyrolytic and light-activated oxidation processes are leading technologies for utilizing polystyrene (PS) wastes. These approaches exhibit poor selectivities, use complex reactors, and require solvents. Hydrogenolysis is effective for deconstructing polyolefins, but its application to PS feedstocks has been limited. Herein, we demonstrate Ni/SiO 2 catalysts to facilitate PS (M w ≈ 97 kDa) hydrogenolysis to produce lubricant base oils possessing group IV properties, achieving maximum yields of 70% within 6 h at 300 °C and 70 bar of H 2 . Gas, liquid, and oil product yields are stable across reaction conditions, whereas hydrogenation of the PS aromaticity and reduction of the molecular weight benefit from higher temperatures and H 2 pressures. Time-dependent experiments underscore the importance of elevated H 2 pressure, revealing that PS hydrogenolysis occurs sequentially, with aromatic ring hydrogenation preceding degradation of the C–C backbone. Kinetic measurements with 1,2-diphenylethane as a probe molecule demonstrate that ring hydrogenation pis 3 orders of magnitude faster than internal C–C bond cleavage over Ni/SiO 2 . Ni/SiO 2 proves to be effective in the hydrogenolysis of heavier PS polymers and rigid commercial PS products. Conversely, flexibility and foam PS feeds result in Ni/SiO 2 deactivation, attributed to performance additives. Unlike polyolefins, the process produces very little methane and other light hydrocarbons. Furthermore, these findings expand the applicability of hydrogenolysis to PS feedstocks, offering a versatile solution and broadening the range of high-value products from PS to include lubricant base oils.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Unlocking naphtha from polyolefins using Ni-based hydrocracking catalysts

Naphtha (C 5 -C 12 alkanes) is a platform feedstock in the petroleum industry and an ideal target for reutilizing plastic waste at scale. Hydrocracking has emerged as a promising technology for deconstructing polyolefins to naphtha. However, contemporary catalysts rely on Pt to achieve high rates, while earth-abundant metals (EAM) perform poorly. Herein, we develop high-performance Ni/BEA catalysts for polyolefin hydrocracking, achieving complete low-density polyethylene (LDPE) deconstruction with 80 % maximum naphtha yield within 12 h at 250 °C, 60 bar H 2 , and a catalyst-to-polymer ratio of 1:100. These catalysts are versatile, accommodating virgin resins and commercial polymer products, and are directly reusable and regenerable. Comparative analysis highlights that 5Ni/BEA(25) exhibits the highest naphtha productivity of 11.4 $\huge{(}$$\frac{g_{Naphtha}}{g_{cat}{•h}}$$\huge{)}$, surpassing previously reported Pt- and EAM-based catalysts by 2.5–6.2x. Technoeconomic and life-cycle analyses reveal naphtha from LDPE hydrocracking is economically and environmentally competitive to fossil-fuel-derived naphtha. In conclusion, these advancements pave the way for the industrial implementation of earth-abundant Ni-based catalysts in polyolefin hydrocracking, followed by retrofitting steam crackers to address plastics waste at scale.

Circular Economy↗