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.

Thermogravimetric analysis of carbon deposition over Ni/gamma-Al2O3 catalysts in carbon dioxide reforming of methane

Carbon formation on Ni/gamma-Al2O3 catalysts and its kinetics during methane reforming with carbon dioxide was studied in the temperature range of 500-700 degrees C using a thermogravimetric analysis technique. The activation energies of methane cracking, carbon gasification in CO2, as well as carbon deposition in CO2-CH4 reforming were obtained. The results show that the activation energy for carbon gasification is larger than that of carbon formation in methane cracking and that the activation energy of coking in CO2-CH4 reforming is also larger than that of methane decomposition to carbon. The dependencies of coking rate on partial pressures of CH4 and CO2 indicate that methane decomposition is the main route for carbon deposition. A mechanism and kinetic model for carbon deposition is proposed.

Thermal diffusion in molecular dynamics simulations of thin film diamond deposition

Molecular dynamics simulations of carbon atom depositions are used to investigate energy diffusion from the impact zone. A modified Stillinger-Weber potential models the carbon interactions for both sp2 and sp3 bonding. Simulations were performed on 50 eV carbon atom depositions onto the (111) surface of a 3.8 x 3.4 x 1.0 nm diamond slab containing 2816 atoms in 11 layers of 256 atoms each. The bottom layer was thermostated to 300 K. At every 100th simulation time step (27 fs), the average local kinetic energy, and hence local temperature, is calculated. To do this the substrate is divided into a set of 15 concentric hemispherical zones, each of thickness one atomic diameter (0.14 nm) and centered on the impact point. A 50-eV incident atom heats the local impact zone above 10 000 K. After the initial large transient (200 fs) the impact zone has cooled below 3000 K, then near 1000 K by 1 ps. Thereafter the temperature profile decays approximately as described by diffusion theory, perturbed by atomic scale fluctuations. A continuum model of classical energy transfer is provided by the traditional thermal diffusion equation. The results show that continuum diffusion theory describes well energy diffusion in low energy atomic deposition processes, at distance and time scales larger than 1.5 nm and 1-2 ps, beyond which the energy decays essentially exponentially. (C) 1998 Published by Elsevier Science S.A. All rights reserved.

Role of CeO2 in Ni/CeO2-Al2O3 catalysts for carbon dioxide reforming of methane

Ni catalysts supported on gamma-Al2O3, CeO2 and CeO2-A1(2)O(3) systems were tested for catalytic CO2 reforming of methane into synthesis gas. Ni/CeO2-Al2O3 catalysts showed much better catalytic performance than either CeO2- or gamma-Al2O3-supported Ni catalysts. CeO2 as a support for Ni catalysts produced a strong metal-support interaction (SMSI), which reduced the catalytic activity and carbon deposition. However, CeO2 had positive effect on catalytic activity, stability, and carbon suppression when used as a promoter in Ni/gamma-Al2O3 catalysts for this reaction. A weight loading of 1-5 wt% CeO2 was found to be the optimum. Ni catalysts with CeO2 promoters reduced the chemical interaction between nickel and support, resulting in an increase in reducibility and stronger dispersion of nickel. The stability and less coking on CeO2-promoted catalysts are attributed to the oxidative properties of CeO2. (C) 1998 Elsevier Science B.V. All rights reserved.

Development of composite adsorbents of carbon and intercalated clay for N2 and O2 adsorption: A preliminary study

Composite adsorbents of carbon and alumina intercalated montmorillonite were prepared and characterized by adsorption of N-2 and O-2 at various temperatures. The effects of pyrolysis, temperature, heating rate, subsequent degassing, and doping of cations and anions were investigated. The adsorption capacities of the composite adsorbents developed at higher temperatures (0 and -79 degrees C) are found to be larger than those of normal alumina pillared clays. The experimental results showed that the framework of these adsorbents is made of alumina particles and clay sheets while the pyrolyzed carbon distributes in the space of interlayers and interpillars. The pores between the carbon particles, clay sheets, and alumina pillars are very narrow with very strong adsorption forces, leading to enhanced adsorption capacities at 0 and -79 degrees C. The composite adsorbents exhibit features similar to those of carbonaceous adsorbents. Their pore structures, adsorption capacities, and selectivities to oxygen can be tailored by a controlled degassing procedure. Meanwhile, ions can be doped into the adsorbents to modify their adsorption properties, as usually observed for oxide adsorbents like zeolite and pillared clays. Such flexibility in pore structure tailoring is a potential advantage of the composite adsorbents developed for their adsorption and separation applications. (C) 1999 Academic Press.

Determination of chemical shielding tensor of an indole carbon and application of tryptophan orientation of a membrane peptide

Using tryptophan C-13-enriched at the C-4 (C epsilon(3)) of the indole, the orientation of the C epsilon(3) chemical shift tensor relative to the C epsilon(3)-H dipolar axis was determined from the C-13 chemical shift/C-13-H-1 dipolar 2D NMR powder pattern. The principal values obtained were 208, 137 and 15 ppm with sigma(33) perpendicular to the indole plane, and sigma(11) (least shielded direction) 5 degrees off the C epsilon(3)-H bond toward C xi(3). The side off the C epsilon(3)-H bond was determined by comparing the reduced chemical shift anisotropies obtained by solid-state NMR and from molecular dynamics calculations of [4-C-13] tryptophans in gramicidin A aligned in phospholipid membranes. (C) 1999 Elsevier Science B.V. All rights reserved.

Flyash as support for Ni catalysts in carbon dioxide reforming of methane

A series of Ni catalysts supported on flyash treated by various chemical methods was tested for carbon dioxide reforming of methane. Ni catalyst on the flyash treated with CaO (Ni/Ash-CaO) shows high conversion and stability, being close to those of the well-reported Ni/Al2O3 and Ni/SiO2 catalysts with conversions approaching thermodynamic equilibrium levels.

A comprehensive study on carbon dioxide reforming of methane over Ni/gamma-Al2O3 catalysts

Carbon dioxide reforming of methane into syngas over Ni/gamma-Al2O3 catalysts was systematically studied. Effects of reaction parameters on catalytic activity and carbon deposition over Ni/gamma-Al2O3 catalysts were investigated. It is found that reduced NiA1204, metal nickel, and active species of carbon deposited were the active sites for this reaction. Carbon deposition on Ni/gamma Al2O3 varied depending on the nickel loading and reaction temperature and is the major cause of catalyst deactivation. Higher nickel loading produced more coke on the catalysts, resulting in rapid deactivation and plugging of the reactor. At 5 wt % Ni/gamma-Al2O3 catalyst exhibited high activity and much lesser magnitude of deactivation in 140 h. Characterization of carbon deposits on the catalyst surface revealed that there are two kinds of carbon species (oxidized and -C-C-) formed during the reaction and they showed different reactivities toward hydrogenation and oxidation. Kinetic studies showed that the activation energy for CO production in this reaction amounted to 80 kJ/mol and the rate of CO production could be described by a Langmuir-Hinshelwood model.

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.

Catalytic conversion to N2O to N2 over potassium catalyst supported on activated carbon

Catalytic conversion of N2O to N-2 With potassium catalysts supported on activated carbon (K/AC) was investigated. Potassium proves to be much more active and stable than either copper or cobalt because potassium possesses strong abilities both for N2O chemisorption and oxygen transfer. Potassium redispersion is found to play a critical role in influencing the catalyst stability. A detailed study of the reaction mechanism was conducted based upon three different catalyst loadings. It was found that during temperature-programmed reaction (TPR), the negative oxygen balance at low temperatures (< 50 degrees C) is due to the oxidation of the external surface of potassium oxide particles, while the bulk oxidation accounts for the oxygen accumulation at higher temperatures (below ca. 270 degrees C). N2O is beneficial for the removal of carbon-oxygen complexes because of the formation of CO2 instead of CO and because of its role in making the chemisorption of produced CO2 on potassium oxide particles less stable. A conceptual three-zone model was proposed to clarify the reaction mechanism over K/AC catalysts. CO2 chemisorption at 250 degrees C proves to be an effective measurement of potassium dispersion. (C) 1999 Academic Press.

The role of carbon surface chemistry in N2O conversion to N2 over Ni catalyst supported on activated carbon

The effect of acidic treatments on N2O reduction over Ni catalysts supported on activated carbon was systematically studied. The catalysts were characterized by N-2 adsorption, mass titration, temperature-programmed desorption (TPD), and X-ray photoelectron spectrometry (XPS). It is found that surface chemistry plays an important role in N2O-carbon reaction catalyzed by Ni catalyst. HNO3 treatment produces more active acidic surface groups such as carboxyl and lactone, resulting in a more uniform catalyst dispersion and higher catalytic activity. However, HCl treatment decreases active acidic groups and increases the inactive groups, playing an opposite role in the catalyst dispersion and catalytic activity. A thorough discussion of the mechanism of the N2O catalytic reduction is made based upon results from isothermal reactions, temperature-programmed reactions (TPR) and characterization of catalysts. The effect of acidic treatment on pore structure is also discussed. (C) 1999 Elsevier Science B.V. All rights reserved.

Implications of specimen preparation and of surface contamination for the measurement of the grain boundary carbon concentration of steels using x-ray microanalysis in an UHVFESTEM

The purpose of the present investigation was to gain an understanding of the nature of the carbon contamination on the surface of standard steel transmission electron spectroscopy (TEM) specimens, the effect of exposure of a clean specimen to normal laboratory air, and the efficacy of plasma-cleaning treatments. This knowledge is a necessary prerequisite to the development of appropriate specimen preparation and/or specimen cleaning methods. X-ray photoelectron spectroscopy in combination with argon ion beam profiling was used to characterize the specimen surfaces of X65 steel and 316 stainless steel. The only clean carbon-free surface obtained was that during argon etching of the sample in the surface analysis chamber. Any exposure of a previously cleaned sample to laboratory air resulted in a rapid carbon (hydrocarbon) contamination of the sample surface and the development of surface oxidation, Plasma cleaning with subsequent exposure of the specimen to the laboratory air also resulted in a carbon-contaminated surface. This suggests that procedures of preparation of TEM specimens of steels outside an ultrahigh vacuum chamber are unlikely to result in the lowering of contamination rates on specimens to levels where measurements for carbon in the grain boundaries are possible. What is needed is a cleaning system as an integral part of the specimen insertion system into the field-emission scanning transmission electron microscope. This cleaning could be carried out by argon ion etching. Copyright (C) 2000 John Wiley & Sons, Ltd.

Effects of acid treatments of carbon on N2O and NO reduction by carbon-supported copper catalysts

The influences of HCl, HNO3 and HF treatments of carbon on N2O and NO reduction with 20 wt% Cu-loaded activated carbon were studied. The order of activity in both N2O and NO is as follows: Cu20/AC-HNO3>Cu20/AC>Cu20/AC-HF>Cu20/AC-HCl. The same sequence was also observed for the amount of CO2 evolved during TPD experiments of supports acid for the catalyst dispersion. On the other hand, N2O exhibited a higher reaction rate than NO and a higher sensitivity to acid treatments, and the presence of gas-phase O-2 had opposite effects in N2O and NO reduction. The key role of carbon surface chemistry is examined to rationalize these findings and the relevant mechanistic and practical implications are discussed. The effects of oxygen surface groups on the pore structure of supports and catalysts are also analyzed, (C) 2000 Elsevier Science Ltd. All rights reserved.