Effects of adsorbed phase on diffusion of subcritical hydrocarbons in activated carbon at low pressures

Diffusions of free and adsorbed molecules of subcritical hydrocarbons in activated carbon were investigated to study the influence of adsorbed molecules on both diffusion processes at low pressures. A collision reflection factor, defined as the fraction of molecules undergoing collision to the solid surface over reflection from the surface, is incorporated into Knudsen diffusivity and surface diffusivity in meso/macropores. Since the porous structure of activated carbon is bimodal in nature, the diffusion of adsorbed molecules is contributed by that of weakly adsorbed molecules on the meso/macropore surfaces and that of strongly adsorbed molecules in the small confinement of micropores. The mobility of adsorbed molecules on the meso/macropore surface is characterized by the surface diffusivity D-mu 2, while that in the micropore is characterized by D-mu 1. In our study with subcritical hydrocarbons, we have found that the former increases almost linearly with pressure, while the latter exhibits a sharp increase at a very low-pressure region and then decreases beyond a critical pressure. This critical pressure is identified as a pressure at which the micropores are saturated.

Preparation and anode property of Pt-CeO2 electrodes supported on carbon black for direct methanol fuel cell applications

A platinum (Pt) on pure ceria (CeO2) supported by carbon black (CB) anode was synthesized using a combined process of precipitation and coimpregnation methods. The electrochemical activity of methanol oxidation reaction on synthesized Pt-CeO2/CB anodes was investigated by cyclic voltammetry and chronoamperometry experimentation. To improve the anode property on Pt-CeO2/CB, the influence of particle morphology and particle size on anode properties was examined. The morphology and particle size of the pure CeO2 particles could be controlled by changing the preparation conditions. The anode properties (i.e., peak current density and onset potential for methanol oxidation) were improved by using nanosize CeO2 particles. This indicates that a larger surface area and higher activity on the surface of CeO2 improve the anode properties. The influence of particle morphology of CeO2 on anode properties was not very large. The onset potential for methanol oxidation reaction on Pt-CeO2/CB, which consisted of CeO2 with a high surface area, was shifted to a lower potential compared with that on the anodes, which consisted of CeO2 with a low surface area. The onset potential on Pt-CeO2/CB at 60 degrees C became similar to that on the commercially available Pt-Ru/carbon anode. We suggest that the rate-determining steps of the methanol oxidation reaction on Pt-CeO2/CB and commercially available Pt-Ru/carbon anodes are different, which accounts for the difference in performance. In the reaction mechanism on Pt-CeO2/CB, we conclude that the released oxygen species from the surface of CeO2 particles contribute to oxidation of adsorbed CO species on the Pt surface. This suggests that the anode performance of the Pt-CeO2/CB anode would lead to improvements in the operation of direct methanol fuel cells at 80 degrees C by the enhancement of diffusion of oxygen species created from the surface of nanosized CeO2 particles. Therefore, we conclude that fabrication of nanosized CeO2 with a high surface area is a key factor for development of a high-quality Pt-CeO2/CB anode in direct methanol fuel cells.

On the equilibrium and dynamic behavior of alcohol vapors in activated carbon

As alcohol molecules such as methanol and ethanol have both polar and non-polar groups, their adsorption behavior is governed by the contributions of dispersion interaction (alkyl group) and hydrogen bonding (OH group). In this paper, the adsorption behavior of alcohol molecules and its effect on transport processes are elucidated. From the total permeability (B-T) of alcohol molecules in activated carbon, an adsorption mechanism is proposed, describing well the experimental data, by taking combination effects of clustering, entering micropores, layering and pore filling processes. Unlike the case of non-polar compounds, it was found that at low pressures there are two rises in the BT of alcohol molecules in activated carbon. The first rise is due to the major contribution of surface diffusion to the transport (which is the case of non-polar molecules) and the second one may be associated with cluster formation at the edge of micropores and entering micropores when the clusters are sufficiently large enough to induce a dispersive energy. In addition the clusters formed may enhance surface diffusion at low pressures and hinder gas phase diffusion and flow in meso/macropores. (c) 2006 Elsevier Ltd. All fights reserved.

An investigation of thin amorphous carbon-based sputtered coatings for MEMS and micro-engineering applications

The work presented in this thesis describes an investigation into the production and properties of thin amorphous C films, with and without Cr doping, as a low wear / friction coating applicable to MEMS and other micro- and nano-engineering applications. Firstly, an assessment was made of the available testing techniques. Secondly, the optimised test methods were applied to a series of sputtered films of thickness 10 - 2000 nm in order to: (i) investigate the effect of thickness on the properties of coatingslcoating process (ii) investigate fundamental tribology at the nano-scale and (iii) provide a starting point for nanotribological coating optimisation at ultra low thickness. The use of XPS was investigated for the determination of Sp3/Sp2 carbon bonding. Under C 1s peak analysis, significant errors were identified and this was attributed to the absence of sufficient instrument resolution to guide the component peak structure (even with a high resolution instrument). A simple peak width analysis and correlation work with C KLL D value confirmed the errors. The use of XPS for Sp3/Sp2 was therefore limited to initial tentative estimations. Nanoindentation was shown to provide consistent hardness and reduced modulus results with depth (to < 7nm) when replicate data was suitably statistically processed. No significant pile-up or cracking of the films was identified under nanoindentation. Nanowear experimentation by multiple nanoscratching provided some useful information, however the conditions of test were very different to those expect for MEMS and micro- / nano-engineering systems. A novel 'sample oscillated nanoindentation' system was developed for testing nanowear under more relevant conditions. The films were produced in an industrial production coating line. In order to maximise the available information and to take account of uncontrolled process variation a statistical design of experiment procedure was used to investigate the effect of four key process control parameters. Cr doping was the most significant control parameter at all thicknesses tested and produced a softening effect and thus increased nanowear. Substrate bias voltage was also a significant parameter and produced hardening and a wear reducing effect at all thicknesses tested. The use of a Cr adhesion layer produced beneficial results at 150 nm thickness, but was ineffective at 50 nm. Argon flow to the coating chamber produced a complex effect. All effects reduced significantly with reducing film thickness. Classic fretting wear was produced at low amplitude under nanowear testing. Reciprocating sliding was produced at higher amplitude which generated three body abrasive wear and this was generally consistent with the Archard model. Specific wear rates were very low (typically 10-16 - 10-18 m3N-1m-1). Wear rates reduced exponentially with reduced film thickness and below (approx.) 20 nm, thickness was identified as the most important control of wear.

The molecular design of a new solvent for the absorption of carbon dioxide

Gas absorption, the removal of one or more constitutents from a gas mixture, is widely used in chemical processes. In many gas absorption processes, the gas mixture is already at high pressure and in recent years organic solvents have been developed for the process of physical absorption at high pressure followed by low pressure regeneration of the solvent and recovery of the absorbed gases. Until now the discovery of new solvents has usually been by expensive and time consuming trial and error laboratory tests. This work describes a new approach, whereby a solvent is selected from considerations of its molecular structure by applying recently published methods of predicting gas solubility from the molecular groups which make up the solvent molecule. The removal of the acid gases of carbon dioxide and hydrogen sulfide from methane or hydrogen was used as a commercially important example. After a preliminary assessment to identify promising moecular groups, more than eighty new solvent molecules were designed and evaluated by predicting gas solubility. The other important physical properties were also predicted by appropriate theoretical procedures, and a commercially promising new solvent was chosen to have a high solubility for acid gases, a low solubility for methane and hydrogen, a low vapour pressure, and a low viscosity. The solvent chosen, of molecular structure Ch3-COCH2-CH2-CO-CH3, was tested in the laboratory and shown to have physical properties, except for vapour pressures, close to those predicted. That is gas solubilities were within 10% but lower than predicted. Viscosity within 10% but higher than predicted and a vapour pressure significantly lower than predicted. A computer program was written to predict gas solubility in the new solvent at the high pressures (25 bar) used in practice. This is based on the group contribution method of Skold Jorgensen (1984). Before using this with the new solvent, Acetonyl acetone, the method was show to be sufficiently accurate by comparing predicted values of gas solubility with experimental solubilities from the literature for 14 systems up to 50 bar. A test of the commercial potential of the new solvent was made by means of two design studies which compared the size of plant and approximate relative costs of absorbing acid gases by means of the new solvent with other commonly used solvents. These were refrigerated methanol(Rectisol process) and Dimethyl Ether or Polyethylene Glycol(Selexol process). Both studies showed in terms of capital and operating cost some significant advantage for plant designed for the new solvent process.

A new role for Low German? Language insertion as bilingual practice in the process of language shift

This article analyses language insertion as a bilingual communicative practice, applying a functional, speaker-focused approach to the study of sociolinguistics and language contact. The article is based on a study of contact phenomena in a formerly diglossic region in Northern Germany, where the previously spoken language – Low German – is in the process of being replaced by the dominant standard variety, German. It examines regional publications in order to establish the linguistic techniques by which Low German elements are incorporated into the Standard German texts and the communicative purposes that they serve. The paper concludes that in the process of language shift an emblematic repertoire from Low German is created which can be applied into the dominant contact language, German, for specific communicative purposes.

Low severity Fischer-Tropsch synthesis for the production of synthetic hydrocarbon fuels

Currently, the main source for the production of liquid transportation fuels is petroleum, the continued use of which faces many challenges including depleting oil reserves, significant oil price rises, and environmental concerns over global warming which is widely believed to be due to fossil fuel derived CO2 emissions and other greenhouse gases. In this respect, lignocellulosic or plant biomass is a particularly interesting resource as it is the only renewable source of organic carbon that can be converted into liquid transportation fuels. The gasification of biomass produces syngas which can then be converted into synthetic liquid hydrocarbon fuels by means of the Fischer-Tropsch (FT) synthesis. This process has been widely considered as an attractive option for producing clean liquid hydrocarbon fuels from biomass that have been identified as promising alternatives to conventional fossil fuels like diesel and kerosene. The resulting product composition in FT synthesis is influenced by the type of catalyst and the reaction conditions that are used in the process. One of the issues facing this conversion process is the development of a technology that can be scaled down to match the scattered nature of biomass resources, including lower operating pressures, without compromising liquid composition. The primary aims of this work were to experimentally explore FT synthesis at low pressures for the purpose of process down-scaling and cost reduction, and to investigate the potential for obtaining an intermediate FT synthetic crude liquid product that can be integrated into existing refineries under the range of process conditions employed. Two different fixed-bed micro-reactors were used for FT synthesis; a 2cm3 reactor at the University of Rio de Janeiro (UFRJ) and a 20cm3 reactor at Aston University. The experimental work firstly involved the selection of a suitable catalyst from three that were available. Secondly, a parameter study was carried out on the 20cm3 reactor using the selected catalyst to investigate the influence of reactor temperature, reactor pressure, space velocity, the H2/CO molar ratio in the feed syngas and catalyst loading on the reaction performance measured as CO conversion, catalyst stability, product distribution, product yields and liquid hydrocarbon product composition. From this parameter study a set of preferred operating conditions was identified for low pressure FT synthesis. The three catalysts were characterized using BET, XRD, TPR and SEM. The catalyst selected was an unpromoted Co/Al2O3 catalyst. FT synthesis runs on the 20cm3 reactor at Aston were conducted for 48 hours. Permanent gases and light hydrocarbons (C1-C5) were analysed in an online GC-TCD/FID at hourly intervals. The liquid hydrocarbons collected were analyzed offline using GC-MS for determination of fuel composition. The parameter study showed that CO conversion and liquid hydrocarbon yields increase with increasing reactor pressure up to around 8 bar, above which the effect of pressure is small. The parameters that had the most significant influence on CO conversion, product selectivity and liquid hydrocarbon yields were reactor temperature and catalyst loading. The preferred reaction conditions identified for this research were: T = 230ºC, P = 10 bar, H2/CO = 2.0, WHSV = 2.2 h-1, and catalyst loading = 2.0g. Operation in the low range of pressures studied resulted in low CO conversions and liquid hydrocarbon yields, indicating that low pressure BTL-FT operation may not be industrially viable as the trade off in lower CO conversions and once-through liquid hydrocarbon product yields has to be carefully weighed against the potential cost savings resulting from process operation at lower pressures.

Effect of preparation conditions on the formation of the active phase of carbon fiber catalytic systems for the low-temperature oxidation of carbon monoxide

We studied the effects of the composition of impregnating solution and heat treatment conditions on the activity of catalytic systems for the low-temperature oxidation of CO obtained by the impregnation of Busofit carbon-fiber cloth with aqueous solutions of palladium, copper, and iron salts. The formation of an active phase in the synthesized catalysts at different stages of their preparation was examined with the use of differential thermal and thermogravimetric analyses, X-ray diffraction analysis, X-ray photoelectron spectroscopy, and elemental spectral analysis. The catalytic system prepared by the impregnation of electrochemically treated Busofit with the solutions of PdCl, FeCl, CuBr, and Cu(NO ) and activated under optimum conditions ensured 100% CO conversion under a respiratory regime at both low (0.03%) and high (0.5%) carbon monoxide contents of air. It was found that the activation of a catalytic system at elevated temperatures (170-180°C) leads to the conversion of Pd(II) into Pd(I), which was predominantly localized in a near-surface layer. The promoting action of copper nitrate consists in the formation of a crystalline phase of the rhombic atacamite CuCl(OH). The catalyst surface is finally formed under the conditions of a catalytic reaction, when a joint Pd(I)-Cu(I) active site is formed. © 2014 Pleiades Publishing, Ltd.

Experiments on the generation of activated carbon from biomass

Activated carbon is generated from various waste biomass sources like rice straw, wheat straw, wheat straw pellets, olive stones, pistachios shells, walnut shells, beech wood and hardcoal. After drying the biomass is pyrolysed in the temperature range of 500-600 °C at low heating rates of 10 K/min. The activation of the chars is performed as steam activation at temperatures between 800 °C and 900 °C. Both the pyrolysis and activation experiments were run in lab-scale facilities. It is shown that nut shells provide high active surfaces of 1000-1300 m/g whereas the active surface of straw matters does hardly exceed 800 m/g which might be a result of the high ash content of the straws and the slightly higher carbon content of the nut shells. The active surface is detected by BET method. Besides the testing of a many types of biomass for the suitability as base material in the activated carbon production process, the experiments allow for the determination of production parameters like heating rate and pyrolysis temperature, activation time and temperature as well as steam flux which are necessary for the scale up of the process chain. © 2006 Elsevier B.V. All rights reserved.

Catalytic systems based on carbon supports for the low-temperature oxidation of carbon monoxide

Catalytic systems containing palladium, copper, and iron compounds on carbon supports-kernel activated carbon and fibrous carbon materials (Karbopon and Busofit)-for the low-temperature oxidation of CO were synthesized. The effects of the nature of the support, the concentration and composition of the active component, and the conditions of preparation on the efficiency of the catalytic system were studied. The catalytic system based on Karbopon exhibited the highest activity: the conversion of carbon monoxide was 90% at room temperature and a reaction mixture (0.03% CO in air) space velocity of 10 000 h. It was found that the metals occurred in oxidized states in the course of operation: palladium mainly occurred as Pd, whereas copper and iron occurred as Cu and Fe, respectively. © 2008 MAIK Nauka.

Catalytic systems based on carbon fiber materials for the low-temperature oxidation of carbon monoxide

New heterogenized catalytic systems for the low-temperature oxidation of CO were synthesized by supporting solutions of Pd, Cu, and Fe salts on carbon fibrous materials (carbopon and busofit). The carbon supports were studied by elemental analysis, SEM, TGA, and TPD. The effects of the nature of the support, the concentration and composition of the active component, and the conditions of preparation on the efficiency of the catalytic system were studied. It was ascertained that attenuation of hydrophilic properties of the support led to the decrease in system activity. The investigation of the catalysts by XPS showed that sample treatment in the reaction medium results in redistribution of the components of the active phase in the near-surface layer of the catalyst. The catalytic system based on carbon fibrous material carbopon prepared by supporting active components (Pd, Cu, and Fe salts) in three stages with intermediate activation in the reaction medium ensures 95% conversion of CO under respiratory conditions, and is promising for the design of the main element of breathing masks on its basis.