Deactivation of Ni-Al-Based Catalysts for Autothermal Reforming of Diesel Surrogate Fuel in the Presence of an Aromatic Hydrocarbon.

Diesel fuel can produce higher concentrations of H2 and CO gases than other types of hydrocarbon fuels via a reforming reaction for solid oxide fuel cells (SOFCs). However, in addition to sulfur compounds and aromatic hydrocarbons in diesel fuel are a major cause of catalyst deactivation. To elucidate the phenomenon of catalyst deactivation in the presence of an aromatic hydrocarbon, dodecane (C12H26) and hexadecane (C16H34) were blended with an aromatic hydrocarbon such as 1-methylnaphthalene (C11H10) to obtain a diesel surrogate fuel. The experiments were performed for autothermal reforming of the diesel surrogate fuel under conditions of S/C = 1.17, O2/C = 0.24, 750°C and GHSV= 12,000 h-1. Three Ni-Al-based catalysts with 10 wt% (N10A), 30 wt% (N30A) and 50 wt% (N50A) of NiO were prepared via the polymer modified incipient method. Whereas all of the Ni-Al-based catalysts were deactivated with increasing reaction time, the catalysts with greater Ni contents tended to maintain their catalytic performance for a longer time. Correlation between the catalytic performances and Ni content were analyzed by temperature-programmed reduction (TPR), Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscope with energy-dispersive X-ray spectroscopy (SEM-EDX), Brunauer-Emmett-Teller(BET) analysis, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Also, we concluded that ethylene (C2H4), which was detected by gas chromatography-mass spectrometry (GC-MS), was the fundamental cause of deactivation of the Ni-Al-based catalysts by accelerating the deposition of wire-type carbon on the catalytic surface.

Improvement of H2S sensing properties of SnO2-based thick film gas sensors promoted with MoO3 and NiO.

The effects of the SnO2 pore size and metal oxide promoters on the sensing properties of SnO2-based thick film gas sensors were investigated to improve the detection of very low H2S concentrations (<1 ppm). SnO2 sensors and SnO2-based thick-film gas sensors promoted with NiO, ZnO, MoO3, CuO or Fe2O3 were prepared, and their sensing properties were examined in a flow system. The SnO2 materials were prepared by calcining SnO2 at 600, 800, 1,000 and 1,200 °C to give materials identified as SnO2(600), SnO2(800), SnO2(1000), and SnO2(1200), respectively. The Sn(12)Mo5Ni3 sensor, which was prepared by physically mixing 5 wt% MoO3 (Mo5), 3 wt% NiO (Ni3) and SnO2(1200) with a large pore size of 312 nm, exhibited a high sensor response of approximately 75% for the detection of 1 ppm H2S at 350 °C with excellent recovery properties. Unlike the SnO2 sensors, its response was maintained during multiple cycles without deactivation. This was attributed to the promoter effect of MoO3. In particular, the Sn(12)Mo5Ni3 sensor developed in this study showed twice the response of the Sn(6)Mo5Ni3 sensor, which was prepared by SnO2(600) with the smaller pore size than SnO2(1200). The excellent sensor response and recovery properties of Sn(12)Mo5Ni3 are believed to be due to the combined promoter effects of MoO3 and NiO and the diffusion effect of H2S as a result of the large pore size of SnO2.

Effects of textural properties on the response of a SnO2-based gas sensor for the detection of chemical warfare agents.

The sensing behavior of SnO(2)-based thick film gas sensors in a flow system in the presence of a very low concentration (ppb level) of chemical agent simulants such as acetonitrile, dipropylene glycol methyl ether (DPGME), dimethyl methylphosphonate (DMMP), and dichloromethane (DCM) was investigated. Commercial SnO(2) [SnO(2)(C)] and nano-SnO(2) prepared by the precipitation method [SnO(2)(P)] were used to prepare the SnO(2) sensor in this study. In the case of DCM and acetonitrile, the SnO(2)(P) sensor showed higher sensor response as compared with the SnO(2)(C) sensors. In the case of DMMP and DPGME, however, the SnO(2)(C) sensor showed higher responses than those of the SnO(2)(P) sensors. In particular, the response of the SnO(2)(P) sensor increased as the calcination temperature increased from 400 °C to 800 °C. These results can be explained by the fact that the response of the SnO(2)-based gas sensor depends on the textural properties of tin oxide and the molecular size of the chemical agent simulant in the detection of the simulant gases (0.1-0.5 ppm).

Improvement of the desulfurization and regeneration properties through the control of pore structures of the Zn-Ti-based H2S removal sorbents.

To improve the sulfur removing capacity of the conventional Zn-Ti-based H2S removal sorbents, a new Zn-Ti based sorbent (ZT-cp) was prepared by the coprecipitation method and tested in a packed bed reactor at middle temperature conditions (H2S absorption at 480 degrees C, regeneration at 580 degrees C). The new Zn-Ti-based sorbent showed excellent sulfur removing capacity without deactivation, even after 10 cycles of absorption and regeneration. The conventional Zn-Ti-based sorbents (ZT-700, ZT-1000), however, that were prepared by physical mixing, were continuously deactivated. In particular, the initial sulfur removing capacity of the ZT-cp sorbent showed a very high absorption value (0.22 g S/g sorbent), which corresponded to 91.6% of theoretical absorption amount. These results can be explained by the difference in physical properties such as pore volume, surface area, and particle size. It was also found that the sulfides formed from the ZT-cp and ZT-1000 sorbents with spinel structure were easily regenerated even at 580 degrees C. Those from the ZT-700 sorbent, with separated ZnO and TiO2 structures, needed a temperature higher than 610 degrees C for regeneration.