Andrew P. E. York

Brief Overview of the Partial Oxidation of Methane to Synthesis Gas

A review of the main developments in the partial oxidation of methane to synthesis gas since the first paper in 1929 to the present day is given. The reaction is discussed from the view of the thermodynamics; the main catalysts studied for the reaction are summarised, and the reaction mechanism is discussed. The review is not comprehensive, but it is designed to provide a general background to the most important developments in the field.

A study of carbon deposition on catalysts during the partial oxidation of methane to synthesis gas

The deposition of carbon on catalysts during the partial oxidation of methane to synthesis gas has been investigated and it has been found that the relative rate of carbon deposition follows the order Ni>Pd>Rh>Ir. Methane decomposition was found to be the principal route for carbon formation over a supported nickel catalyst, and electron micrographs showed that both “whisker” and “encapsulate” forms of carbon are present on the catalyst. Negligible carbon deposition occurred on iridium catalysts, even after 200 h.

Methane Oxyforming for Synthesis Gas Production

This article is concerned with the reforming of methane to synthesis gas; a review of the steam reforming Rxn is presented, and the dry reforming and partial oxidation Rxns introduced. Collectively, these processes are known as “oxyforming.” A background to oxyforming, industrial practice, and some of the most important latest developments will be presented, along with a section on the uses of synthesis gas. The current understanding of the Rxn mechanisms for the three processes and the problem of deactivation by carbon deposition will be discussed in detail. Finally, the economics of synfuel production will be addressed and compared with the production of other fuels, and the future directions and outlook for oxyforming will be forwarded. This article should allow the reader to make comparisons between these three important industrial reactions.

The size distribution, imaging and obstructing properties of C60 and higher fullerenes formed within arc-grown single walled carbon nanotubes

Abstract The relative size distributions of molecules of C60 and higher fullerenes observed in single walled carbon nanotubes (SWNTs) produced by arc vaporization of carbon in the presence of a mixed Ni/Y catalyst are described. The experimental and calculated imaging properties of the fullerenes, which were observed in ca. 5–10% of SWNTs, are also described. The in situ e-beam irradiation in a 300 kV field emission gun transmission electron microscope causes rapid coalescence of the fullerenes within the SWNTs. The incorporated fullerenes also directly impede crystal growth in SWNTs when their cavities are filled by the liquid phase capillary method.

Two layer 4:4 co-ordinated KI crystals grown within single walled carbon nanotubes

The formation of ‘all surface’ 4:4 co-ordinated KI crystals within 1.4 nm diameter single walled carbon nanotubes (SWNT) is reported. KI was inserted into the SWNTs by a capillary method [J. Sloan, D.M. Wright, H.G. Woo, S. Bailey, G. Brown, A.P.E. York, K.S. Coleman, J.L. Hutchison, M.L.H. Green, J. Chem. Soc. Chem. Commun. (1999) 699], whereby the nanotubes were combined intimately with the molten halide. The crystals grew withh 001 i (relative to bulk KI) parallel to the tubule axes and were continuous tetragonally distorted bilayer crystals composed of alternating columns of K‐I and I‐K pairs when viewed along h 100 i. ” 2000 Elsevier Science B.V. All rights reserved.

Surface WO4 tetrahedron: the essence of the oxidative coupling of methane over M-W-Mn/SiO2 catalysts

Abstract A series of MWMn/SiO2 catalysts (M = Li, Na, K, Ba, Ca, Fe, Co, Ni, and Al) have been prepared and their catalytic performance for the oxidative coupling of methane (OCM) was evaluated in a continuous-flow microreactor. The structural properties of the catalysts have been studied using X-ray photoelectron spectroscopy (XPS), laser Raman spectroscopy (LRS), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). In the trimetallic catalysts studied, there was evidence for WO4 tetrahedron on the surface in the Li, Na, and KWMn/SiO2 catalysts, which is mainly present in the subsurface of the BaWMn/SiO2 catalyst. It appears that the WO4 has a strong interaction with the α-cristobalite support and is stabilized in the Na and KWMn/SiO2 catalysts. However, the WO4 species appear to be less stable in Li or BaWMn/SiO2 catalysts, in which the support turns into quartz SiO2 or amorphous SiO2. The WO4 tetrahedron on the catalyst surface appears to play an essential role in achieving high CH4 conversion and high C2 hydrocarbon selectivity in the OCM reaction. Calculations suggest that the WO4 tetrahedron interacts with the CH4, giving suitable geometry and energy matching with CH4, and this may account for the high OCM activities.

Capillarity and silver nanowire formation observed in single walled carbon nanotubes

Single walled carbon nanotubes (SWNTs) exhibit similar capillarity properties to those exhibited by multiple walled carbon nanotubes (MWNTs); SWNTs, previously filled in low yield (ca. 2%) by solution chemistry techniques, can be filled in high yield (up to ca. 50%) by the liquid phase method; compositions from the KCl–UCl4 and AgCl–AgBr systems were used to fill SWNTs without causing them significant chemical or thermal damage; in the case of the latter, exposure to light or an electron beam resulted in the partial photolytic reduction of SWNT incorporated silver halides to continuous metallic silver ‘nanowires’ within the capillaries.

Effect of carburising agent on the structure of molybdenum carbides

Molybdenum carbides have been prepared by the temperature programmed reaction method using mixtures of hydrogen and methane, hydrogen and ethane, and hydrogen and butane, and characterised with X-ray diffraction, transmission electron microscopy, 13C solid state NMR and EXAFS spectroscopy. The results show that the choice of hydrocarbon used to synthesise molybdenum carbide significantly affects the structure and texture of the resultant materials. Increasing the chain length of the carburising agent reduces the particle size and the temperature for complete phase transformation from molybdenum oxide to carbide is lowered. Carburising with a mixture of hydrogen and methane gives rise to hexagonal closed packed (hcp) carbide, while when using butane as the carbon source, molybdenum oxide is mainly reduced to face centred cubic (fcc) carbide. However, using ethane as the carbon source, the resultant carbide has a mixed phase composition with the hcp phase predominant. The molybdenum carbide prepared with ethane as the carbon source has the roughest surface and highest hydrogen adsorption capacity, while that prepared with butane has a very condensed surface. There is a substantial difference in the molybdenum co-ordination environments present among the carbides prepared with different carburising agents.

Oxidative dehydrogenation of ethane over La1−xSrxFeO3−δ perovskite oxides

Catalysts of the composition La1−xSrxFeO3−δ, 0⩽x ⩽1, have been tested for the oxidative dehydrogenation of ethane in the temperature range 300–800°C. The catalyst is active above 400°C, giving a maximum yield of 37% ethylene at 650°C. Above 650°C, synthesis gas was formed together with methane, suggesting that the reforming reaction and thermal cracking of ethane took place. The catalytic data are compared to conductivity measurements on the same material, and a good correlation between the activity and p-type conductivity has been found. In the phase diagram for the system LaFeO3-SrFeO3−δ, a phase separation to two types of (La, Sr)FeO3−δ perovskites was observed in the La/Sr binary composition in the temperature range below 800°C. The phase separation can elucidate the dependency of the catalytic activity on its p-type conductivity.

Study on the mechanism of partial oxidation of methane to synthesis gas over molybdenum carbide catalyst

The performance of molybdenum carbide catalyst for partial oxidation of methane to syngas has been evaluated in a micro-reactor under various conditions. The molybdenum carbide catalyst is stable in methane partial oxidation to syngas at high reaction temperatures, high pressures and with a low space velocity of reactants. Pre-treatment has a significant effect on the catalyst activity and selectivity. The reaction mechanism over molybdenum carbide has been studied using 13C isotope exchange and in situ laser Raman. It is seen that the carbon in the lattice of the molybdenum carbide takes an active part in the reaction. The deactivation of molybdenum carbide catalyst results from the oxidation of the catalyst surface.