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Researchers develop viable catalysts for reforming of heavy gas oil to hydrogen
14 October 2013
One approach to delivering hydrogen for the stacks in fuel cell vehicles is via the on-board reforming of hydrocarbon fuels; such an approach obviates the need for on-board hydrogen gas storage technology and leverages the existing liquid fuels infrastructure. However, using more refined low-sulfur hydrocarbon fuels can add to the overall cost of the system. Less refined fuels—such as heavy gas oil—would be less expensive; however, the higher levels of sulfur in the fuels could prove problematic for catalysts.
Now, researchers in S. Korean and Japan have synthesized hollow fiber catalysts networked with perovskite nanoparticles for the production of hydrogen from heavy gas oil reforming, some of which showed high efficiency for H2 production with substantial durability under high concentrations of S, N, and aromatic compounds. Their findings are reported in an open access paper in the journal Scientific Reports.
An oil jackpot of up to 233 billion barrels has been discovered in Australia, the new Saudi Arabia, which is foreseeable to extend the practical use of petroleum to about 200 years from 40 years at today’s oil consumption rate. With a rising concern for gradual fossil fuel exhaustion, an efficient use of such oil resources is faced to an imperative emerging issue towards hydrogen economy based on sustainable energy generation. Hydrogen-based fuel cells that can be used for both automotive and stationary applications require a stable source of H2 produced with a high efficiency reforming process.
The use of pure H2 as a fuel in automotive and residential applications faces the costly process of distillation and/or hydro-treatment of naphtha. One approach to overcoming such limitations is the use of direct reforming of gas oil (heavy hydrocarbons) over a heteroatom-resistant catalyst. This process would be profitable because of the infrastructural reasons and the economical price of starting feeds compared with naphtha hydrocarbon fuels.
...in order to be commercially viable, gas oil appears to be an attractive feed for reforming because of its similar molecular structure to conventional diesel and/or liquid hydrocarbons, apart from its higher S content. There are no reports on reforming using gas oil, which is likely due to the rapid deactivation of conventional catalysts by large amounts of S species during the reaction. Hence, the development of a highly active and stable reforming catalyst under high S and N conditions would be desirable in order to apply the reforming process to gas oil.—Jeon et al.
Perovskite catalysts composed of highly reactive metal oxides have been shown to be alternatives to conventional noble metal catalysts for the reforming of hydrocarbons, the authors noted. Perskovite catalysts have a number of advantages, including stability at high temperatures, in redox environments, and in the presence of H2-rich gases. Moreover, perovskites are known to be significantly resistant to deactivation since their chemical binding energy for S is very low.
In their study, the researchers prepared a hollow fibrous perovskite structure composed of nanoparticles network incorporated with Ru and Ni using a novel process by employing activated carbon fiber (ACF) as a sacrificial template.
The hollow fiber had a well-crystallized structure and a high specific surface area of ≈13 m2/g, with an average particle size of ≈50 nm, which is ~3 times larger than that of grains.
The LaCr0.8Ru0.2O3 hollow fibrous architecture had a favorable effect on the capacity to yield H2 directly from heavy gas oil reforming, at 34.6 mol% compared to grain (23.3 mol%) and Pt–GDC (7.7 mol%), with substantial durability even for long-term reactions with high concentrations of S, N, and aromatic compounds.—Jeon et al.
Yukwon Jeon, Dae-Hwan Park, Joo-Il Park, Seong-Ho Yoon, Isao Mochida, Jin-Ho Choy & Yong-Gun Shul (2013) “Hollow Fibers Networked with Perovskite Nanoparticles for H2 Production from Heavy Oil” Scientific Reports 3, Article number: 2902 doi: 10.1038/srep02902
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