Catalytic activities and coking characteristics of oxides-supported Ni catalysts for CH4 reforming with carbon dioxide

Catalytic activities and deactivation characteristics of oxides-supported nickel catalysts for the reaction of methane reforming with carbon dioxide were investigated. The dynamic carbon deposition on various nickel catalysts was also studied by a thermogravimetric method. Among the catalysts prepared, Ni/La2O3, Ni/alpha-Al2O3, Ni/SiO2, and Ni/CeO2 showed very high CH4 and CO2 conversions and moderate deactivation whereas Ni/MgO and Ni/TiO2 had lower conversions when the Ni reduction was conducted at 500 degrees C. When Ni/MgO catalyst was reduced at 800 degrees C, it exhibited not only comparable conversions of CH4 and CO2 with other active catalysts but also much longer period of stability without deactivation. The amount of carbon deposited in Ni-based catalysts varied depending on the nature of support and followed the order of Ni/La2O3 > Ni/alpha-Al2O3 > Ni/SiO2 > Ni/MgO > Ni/CeO2 at 700 degrees C. The carbons formed on the catalyst surface showed different structural and chemical properties, and these in turn affected the catalytic activity of the catalysts.

Capillary coexistence and criticality in mesopores: Modification of the Kelvin theory

The classical model of capillary equilibrium in cylindrical pores is modified here by the introduction of molecular concepts and the solid fluid interaction potential. The new approach accurately predicts capillary coexistence and criticality, with results quantitatively matching those from density functional theory for nitrogen adsorption, while also predicting condensation pressures in agreement with reported experimental findings for MCM-41. The larger critical pore size for nitrogen adsorption in these materials, however, suggests a modification of the potential function parameters, evaluated here from data for hydroxylated silica.

Effects of acidic treatments on the pore and surface properties of Ni catalyst supported on activated carbon

Activated carbon as catalyst support was treated with HCl, HNO3, and HF and the effects of acid treatments on the properties of the activated carbon support were studied by N-2 adsorption, mass titration, temperature-programmed desorption (TPD), and X-ray photoelectron spectrometry (XPS). Ni catalysts supported on untreated and treated activated carbons were prepared, characterized and tested for the reforming reaction of methane with carbon dioxide. It is found that acid treatment significantly changed the surface chemical properties and pore structure of the activated carbon. The surface area and pore volume of the carbon supports are generally enhanced upon acid treatment due to the removal of impurities present in the carbon. The adsorption capacity of Ni2+ on the carbon supports is also increased, and the increase can be closely correlated with the surface acidity. The impregnation of nickel salts decreases the surface area and pore volume of carbon supports both in micropores and mesopores. Acid treatment results in a more homogeneous distribution of the nickel salt in carbon. When the impregnated carbons are heated in inert atmosphere, there exists a redox reaction between nickel oxide and the carbon. Catalytic activity tests for methane reforming with carbon dioxide show that the activity of nickel catalysts based on the acid-treated carbon supports is closely related with the surface characteristics of catalysts. (C) 1998 Elsevier Science Ltd. All rights reserved.

Structure of Caribbean ciguatoxin isolated from Caranx latus

Caribbean ciguatoxins (C-CTXs) are responsible for the widespread occurrence of ciguatera in the Caribbean Sea. The structure and configuration of C-CTX-1 (1), the major ciguatoxin isolated from the horse-eye jack (Caranx latus), has been determined from DQF-COSY, E-COSY, TOCSY, NOESY, POESY, ge-HSQC. and HMQC experiments performed at 750 MHz and 500 MHz on a 0.13 pmol sample. C-CTX-1 ([M + H](+) m/z 1141.6 Da, molecular formula C62H92O19) has a ciguatoxin/breveroxin ladder structure comprising 14 trans-fused, ether-linked rings (7/6/6/7/8/9/7/6/8/6/7/6/7/6) assembled fi um 6 protonated fragments. The relative stereochemistry and ring configuration of 1 was determined from an analysis of coupling constant and NOE data. Like ciguatoxins in the Pacific Ocean (P-CTX), C-CTX-1 possesses a flexible nine-membered ring which may be a conserved feature among ciguatoxins. However, C-CTX-1 has a longer contiguous carbon backbone (57 vs 55 carbons for P-CTX-1), one extra ring, and a hemiketal in ring N but no spiroketal as found in P-CTX. C-CTX-1 possesses a primary hydroxyl which may allow selective derivatization. A minor analogue, C-CTX-2, was also isolated from fish and assigned the structure 56 epi-C-CTX-1 (2). since it slowly rearranged to C-CTX-1 in solution. Given the structural similarities between Caribbean and Pacific ciguatoxins, we propose that C-CTX-1 and C-CTX-2 arise from a Caribbean strain of the benthic dinoflagellate, Gambierdiscus toxicus.

Adsorption of binary hydrocarbon mixtures in carbon slit pores: A density functional theory study

Adsorption of binary hydrocarbon mixtures involving methane in carbon slit pores is theoretically studied here from the viewpoints of separation and of the effect of impurities on methane storage. It is seen that even small amounts of ethane, propane, or butane can significantly reduce the methane capacity of carbons. Optimal pore sizes and pressures, depending on impurity concentration, are noted in the present work, suggesting that careful adsorbent and process design can lead to enhanced separation. These results are consistent with earlier literature studies for the infinite dilution limit. For methane storage applications a carbon micropore width of 11.4 Angstrom (based on distance between centers of carbon atoms on opposing walls) is found to be the most suitable from the point of view of lower impurity uptake during high-pressure adsorption and greater impurity retention during low-pressure delivery. The results also theoretically confirm unusual recently reported observations of enhanced methane adsorption in the presence of a small amount of heavier hydrocarbon impurity.

VOC removal: Comparison of MCM-41 with hydrophobic zeolites and activated carbon

The recently discovered mesoporous molecular sieve MCM-41 was tested as an adsorbent for VOC removal. Its adsorption/desorption properties were evaluated and compared with other hydrophobic zeolites (silicalite-1 and zeolite Y) and a commercial activated carbon, BPL. The adsorption isotherms of some typical VOCs (benzene, carbon tetrachloride, and n-hexane) on MCM-41 are of type IV according to the IUPAC classification, drastically different from the other microporous adsorbents, indicating that VOCs, in the gas phase, have to be at high partial pressures in order to make the most of the new mesoporous material as an adsorbent for VOC removal. However, a proper modification of the pore openings of MCM-41 can change the isotherm types from type IV to type I without remarkable loss of the accessible pare volumes and, therefore, significantly enhance the adsorption performance at low partial pressures. Adsorption isotherms of water on these adsorbents are all of type V, demonstrating that they possess a similar hydrophobicity. Desorption of VOCs from MCM-41 could be achieved at lower temperatures (50-60 degrees C), while this had to be conducted at higher temperatures (100-120 degrees C) for microporous adsorbents, zeolites, and activated carbons.

Adsorption characteristics of phenolic compounds onto coal-reject-derived adsorbents

Carbonaceous adsorbents were prepared by heat treatment of coal reject at 600 degrees C, after chemical treatment in HNO3, H2SO4, and NaOH at 25 and 75 degrees C. Pore structure characterization and the phenol adsorption capacities of the adsorbents showed that nitric acid pretreatment significantly enhanced the surface properties, consequently the adsorption capacities of the adsorbents. A number of samples were subsequently prepared by carbonizing coal reject at 600 degrees C, after pretreatment in HNO3 under various conditions. The acid concentration, residence time, and reaction temperature were varied to obtain adsorbents with various pore structures. The adsorption capacities of the derived adsorbents for phenol, p-nitrophenol, and benzene were measured to gain further insights into the pore structure evolution. Adsorption isotherms of phenol, p-nitrophenol, and p-chlorophenol on the best adsorbent prepared were determined and correlated with theoretical isotherm equations, such as the Langmuir, Freundlich, and Redlich-Peterson equations.

A comparative study of N2O conversion to N-2 over Co/AC and Cu/AC catalysts

Catalytic conversion of N2O to N-2 over Cu- and Co-impregnated activated carbon catalysts (Cu/AC and Co/AC) was investigated. Catalytic activity measurements were carried out in a fixed-bed flow reactor at atmospheric pressure. The catalysts were characterized by N-2 adsorption, X-ray diffraction (XRD) and thermogravimetric analysis (TGA). This study aimed to provide insights into the following aspects: the metal dispersion, changes in pore structure, influence of catalyst loading on reaction, and reaction mechanism. Increasing loading of Co or Cu led to decreasing dispersion, but 20 wt % loading was an upper limit for optimal activities in both cases, with too high loading causing sintering of metal. Co exhibited a relatively better dispersion than Cu. Impregnation of metal led to a large decrease in surface area and pore volume, especially for 30 wt % of loading. 20 wt % of loading has proved to be the optimum for both Cu and Co, which shows the highest activity. Both N2O-Co/AC and -Cu/AC reactions are based upon a redox mechanism, but the former is limited by the oxygen transfer from catalysts to carbon, while N2O chemisorption on the surface of Cu catalyst controls the latter. The removal of oxygen from cobalt promotes the activity of Co/AC, but it is beneficial for Cu/AC to keep plenty of oxygen to maintain the intermediate oxidation of copper-Cu1+. The different nature of the two catalysts and their catalytic reaction mechanisms are closely related to their different electronegativities.

Carbon structure and porosity of carbonaceous adsorbents in relation to their adsorption properties

A number of carbonaceous adsorbents were prepared by carbonisation at 600 degrees C following acidic oxidation under various conditions. Effects of the chemical nature of the precursor, such as the ratio of aromatic to aliphatic carbons and oxygen content, on the chemical and structural characteristics of the resultant chars were investigated using C-13 NMR and Raman spectroscopy, respectively. The C-13 NMR spectral parameters of the coal samples show that as the severity of oxidation conditions increased, the ratio of aromatic to aliphatic carbons increased. Furthermore, it was also found that the amount of disorganised carbon affects both the pore structure and the adsorption properties of carbonaceous adsorbents. It is demonstrated that higher amount of the disorganised carbon indicates smaller micropore size. (C) 1999 Elsevier Science Ltd. All rights reserved.

The effect of solidification rate on the structure of magnesium-aluminium eutectic grains

A magnesium-aluminium alloy of eutectic composition was solidified under two different cooling conditions, producing a low and a high growth rate of the eutectic solid-liquid interface. The high growth rate specimen contained smaller eutectic grains and cells, with a smaller interphase spacing compared with the low growth rate specimen. The high growth rate specimen also contained some primary Mg17Al12 dendrites, suggesting that the coupled zone is skewed towards the Mg phase with increased undercooling, A lamellar eutectic morphology was observed in the low growth rate specimen, while the morphology was fibrous in the high growth rate specimen.

Atoms in an amplitude-modulated standing wave - dynamics and pathways to quantum chaos

Cold rubidium atoms are subjected to an amplitude-modulated far-detuned standing wave of light to form a quantum-driven pendulum. Here we discuss the dynamics of these atoms. Phase space resonances and chaotic transients of the system exhibit dynamics which can be useful in many atom optics applications as they can be utilized as means for phase space state preparation. We explain the occurrence of distinct peaks in the atomic momentum distribution, analyse them in detail and give evidence for the importance of the system for quantum chaos and decoherence studies.

Determination of activation energy distributions for chemisorption of oxygen on carbon: an improved approach

The present paper proposes an approach to obtaining the activation energy distribution for chemisorption of oxygen onto carbon surfaces, while simultaneously allowing for the activation energy dependence of the pre-exponential factor of the rate constant. Prior studies in this area have considered this factor to be uniform, thereby biasing estimated distributions. The results show that the derived activation energy distribution is not sensitive to the chemisorption mechanism because of the step function like property of the coverage. The activation energy distribution is essentially uniform for some carbons, and has two or possibly more discrete stages, suggestive of at least two types of sites, each with its own uniform distribution. The pre-exponential factors of the reactions are determined directly from the experimental data, and are found not to be constant as assumed in earlier work, but correlated with the activation energy. The latter results empirically follow an exponential function, supporting some earlier statistical and experimental work. The activation energy distribution obtained in the present paper permits improved correlation of chemisorption data in comparison to earlier studies. (C) 2000 Elsevier Science Ltd. All rights reserved.

Dendrite coherency of Al-Si-Cu alloys

The dendrite coherency point of Al-Si-Cu alloys was determined by thermal analysis and rheological measurement methods by performing parallel measurements at two cooling rates for aluminum alloys across a wide range of silicon and copper contents. Contrary to previous findings, the two methods yield significantly different values for the fraction solid at the dendrite coherency point. This disparity is greatest for alloys of low solute concentration. The results from this study also contradict previously reported tl ends in the effect of cooling rate on the dendritic coherency point. Consideration of the results shows that thermal analysis is not a valid technique for the measurement of coherency. Analysis of the results from rheological testing indicates that silicon concentration has a dominant effect on grain size and dendritic morphology, independent of cooling rate and copper content, and thus is the factor that determines the fraction solid at dendrite coherency for Al-Si-Cu alloys.

Opposite roles of O-2 in NO- and N2O-carbon reactions: An ab initio study

Previous experimental studies showed that the presence of O-2 greatly enhances NO-carbon reaction while it depresses N2O-carbon reaction on carbon surfaces. A popular explanation for the rate increase is that the addition of O-2 results in a large number of reactive carbon-oxygen complexes, and decomposition of these complexes produces many more active sites. The explanation for the latter is that excess O-2 simply blocks the active sites, thus reducing the rate of N2O-carbon reaction. The contradiction is that O-2 can also occupy active sites in NO-carbon reaction and produce active sites in N2O-carbon reduction. By using ab initio calculation, we find that the opposite roles of O-2 are caused by the different manners of N2O and NO adsorption on the carbon surface. In the presence of excess O-2, most Of the active sites are occupied by oxygen groups. In the competition for the remaining active sites, NO is more likely to chemisorb in the form of NO2 and NO chemisorption is mon thermodynamically favorable than O-2 chemisorption. By contrast, the presence of excess O-2 makes N2O chemisorption much less thermally stable either on the consecutive edge sites or edge sites isolated by semiquinone oxygen. A detailed analysis and discussion of the reaction mechanism of N-2 formation from NO- and N2O-carbon reaction in the presence of O-2 is presented in this paper.

Dynamics of trapped Bose-Einstein condensates: Beyond the mean-field

Since dilute Bose gas condensates were first experimentally produced, the Gross-Pitaevskii equation has been successfully used as a descriptive tool. As a mean-field equation, it cannot by definition predict anything about the many-body quantum statistics of condensate. We show here that there are a class of dynamical systems where it cannot even make successful predictions about the mean-field behavior, starting with the process of evaporative cooling by which condensates are formed. Among others are parametric processes, such as photoassociation and dissociation of atomic and molecular condensates.