Operation of polymer electrolyte membrane fuel cells with dry feeds: Design and operating strategies

The operation of polymer electrolyte membrane fuel cells (PEMFCs) with dry feeds has been examined with different fuel cell flow channel designs as functions of pressure, temperature and flow rate. Auto-humidified (or self-humidifying) PEMFC operation is improved at higher pressures and low gas velocities where axial dispersion enhances back-mixing of the product water with the dry feed. We demonstrate auto-humidified operation of the channel-less, self-draining fuel cell, based on a stirred tank reactor; data is presented showing auto-humidified operation from 25 to 115 degrees C at 1 and 3 atm. Design and operating requirements are derived for the auto-humidified operation of the channel-less, self-draining fuel cell. The auto-humidified self-draining fuel cell outperforms a fully humidified serpentine flow channel fuel cell at high current densities. The new design offers substantial benefits for simplicity of operation and control including: the ability to self-drain reducing flooding, the ability to uniformly disperse water removing current gradients and the ability to operate on dry feeds eliminating the need for humidifiers. Additionally, the design lends itself well to a modular design concept. (c) 2005 Elsevier B.V. All rights reserved.

Optimum conditions for adsorptive storage

The storage of gases in porous adsorbents, such as activated carbon and carbon nanotubes, is examined here thermodynamically from a systems viewpoint, considering the entire adsorption-desorption cycle. The results provide concrete objective criteria to guide the search for the Holy Grail adsorbent, for which the adsorptive delivery is maximized. It is shown that, for ambient temperature storage of hydrogen and delivery between 30 and 1.5 bar pressure, for the optimum adsorbent the adsorption enthalpy change is 15.1 kJ/mol. For carbons, for which the average enthalpy change is typically 5.8 kJ/mol, an optimum operating temperature of about 115 K is predicted. For methane, an optimum enthalpy change of 18.8 kJ/mol is found, with the optimum temperature for carbons being 254 K. It is also demonstrated that for maximum delivery of the gas the optimum adsorbent must be homogeneous, and that introduction of heterogeneity, such as by ball milling, irradiation, and other means, can only provide small increases in physisorption-related delivery for hydrogen. For methane, heterogeneity is always detrimental, at any value of average adsorption enthalpy change. These results are confirmed with the help of experimental data from the literature, as well as extensive Monte Carlo simulations conducted here using slit pore models of activated carbons as well as atomistic models of carbon nanotubes. The simulations also demonstrate that carbon nanotubes offer little or no advantage over activated carbons in terms of enhanced delivery, when used as storage media for either hydrogen or methane.

Prediction of vapor-moisture equilibriums for a wood-moisture system using a modified UNIQUAC model

A modified UNIQUAC model has been extended to describe and predict the equilibrium relative humidity and moisture content for wood. The method is validated over a range of moisture content from oven-dried state to fiber saturation point, and over a temperature range of 20-70 degrees C. Adjustable parameters and binary interaction parameters of the UNIQUAC model were estimated from experimental data for Caribbean pine and Hoop pine as well as data available in the literature. The two group-interaction parameters for the wood-moisture system were consistent with using function group contributions for H2O, -OH and -CHO. The result reconfirms that the main contributors to water adsorption in cell walls are the hydroxyl groups of the carbohydrates in cellulose and hemicelluloses. This provides some physical insight into the intermolecular force and energy between bound water and the wood material. (c) 2006 Elsevier Ltd. All rights reserved.

Prediction of minimum spouting velocity in two-dimensional flat bottom spouted beds

Spouted beds have been used in industry for operations such as drying, catalytic reactions, and granulation. Conventional cylindrical spouted beds suffer from the disadvantage of scaleup. Two-dimensional beds have been proposed by other authors as a solution for this problem. Minimum spouting velocity has been studied for such two-dimensional beds. A force balance model has been developed to predict the minimum spouting velocity and the maximum pressure drop. Effect of porosity on minimum spouting velocity and maximum pressure drop has been studied using the model. The predictions are in good agreement with the experiments as well as with the experimental results of other investigators.

Reversible active switching of the mechanical properties of a peptide film at a fluid-fluid interface

Designer peptides have recently been developed as building blocks for novel self-assembled materials with stimuli-responsive properties. To date, such materials have been based on self-assembly in bulk aqueous solution or at solid-fluid interfaces. We have designed a 21-residue peptide, AM1, as a stimuli-responsive surfactant that switches molecular architectures at a fluid-fluid interface in response to changes in bulk aqueous solution composition. In the presence of divalent zinc at neutral pH, the peptide forms a mechanically strong 'film state'. In the absence of metal ions or at acid pH, the peptide adsorbs to form a mobile 'detergent state'. The two interfacial states can be actively and reversibly switched. Switching between the two states by a change in pH or the addition of a chelating agent leads to rapid emulsion coalescence or foam collapse. This work introduces a new class of surfactants that offer an environmentally friendly approach to control the stability of interfaces in foams, emulsions and fluid-fluid interfaces more generally.

Scattering and tangential momentum accommodation at a 2D adsorbate-solid interface

We calculate tangential momentum coefficients for the exchange of momentum between molecules in transport and the internal surface of a membrane pore, modelled as a simple atomic structure. We introduce a local specular reflection (LSR) hypothesis, which states that impinging molecules undergo mirror-like reflection in a plane tangent to a surface atom at the point of impact. As a consequence, the components of the velocity, parallel to the direction of flow will (in general) change on impact. The overall effect is a loss of tangential momentum, since more is lost in the upstream direction than is gained in the downstream direction. The loss of tangential momentum is greater when the size ratio of fluid to solid atom is small, allowing more steeply inclined impact planes to become accessible to the fluid phase molecules. (c) 2005 Elsevier B.V. All rights reserved.

Simulation of binary mixture adsorption of methane and CO2 at supercritical conditions in carbons

Knowledge of the adsorption behavior of coal-bed gases, mainly under supercritical high-pressure conditions, is important for optimum design of production processes to recover coal-bed methane and to sequester CO2 in coal-beds. Here, we compare the two most rigorous adsorption methods based on the statistical mechanics approach, which are Density Functional Theory (DFT) and Grand Canonical Monte Carlo (GCMC) simulation, for single and binary mixtures of methane and carbon dioxide in slit-shaped pores ranging from around 0.75 to 7.5 nm in width, for pressure up to 300 bar, and temperature range of 308-348 K, as a preliminary study for the CO2 sequestration problem. For single component adsorption, the isotherms generated by DFT, especially for CO2, do not match well with GCMC calculation, and simulation is subsequently pursued here to investigate the binary mixture adsorption. For binary adsorption, upon increase of pressure, the selectivity of carbon dioxide relative to methane in a binary mixture initially increases to a maximum value, and subsequently drops before attaining a constant value at pressures higher than 300 bar. While the selectivity increases with temperature in the initial pressure-sensitive region, the constant high-pressure value is also temperature independent. Optimum selectivity at any temperature is attained at a pressure of 90-100 bar at low bulk mole fraction of CO2, decreasing to approximately 35 bar at high bulk mole fractions. (c) 2005 American Institute of Chemical Engineers.

Simulation study of methanol and ethanol adsorption on graphitized carbon black

GCMC simulations are applied to the adsorption of sub-critical methanol and ethanol on graphitized carbon black at 300 K. The carbon black was modelled both with and without carbonyl functional groups. Large differences are seen between the amounts adsorbed for different carbonyl configurations at low pressure prior to monolayer coverage. Once a monolayer has been formed on the carbon black, the adsorption behaviour is similar between the model surfaces with and without functional groups. Simulation isotherms for the case of low carbonyl concentrations or no carbonyls are qualitatively similar to the few experimental isotherms available in the literature for methanol and ethanol adsorption on highly graphitized carbon black. Isosteric heats and adsorbed phase heat capacities are shown to be very sensitive to carbonyl configurations. A maximum is observed in the adsorbed phase heat capacity of the alcohols for all simulations but is unrealistically high for the case of a plain graphite surface. The addition of carbonyls to the surface greatly reduces this maximum and approaches experimental data with carbonyl concentration as low as 0.09 carbonyls/nm(2).

Simulations of pendant drop formation of a viscoelastic liquid

A modified Volume-of-Fluid (VOF) numerical method is used to predict the dynamics of a liquid drop of a low viscosity dilute polymer solution, forming in air from a circular nozzle. Viscoelastic effects are represented using an Oldroyd-B model. Predicted drop shapes are compared with experimental observations. The main features, including the timing of the shape evolution and the bead-on-a-string effect, are well reproduced by the simulations. The results confirm published conclusions of the third author, that the deformation is effectively Newtonian until near the time of Newtonian pinch-off and that the elastic stress becomes large in the pinch region due to the higher extensional flow there.

Sustainability metrics for coal power generation in Australia

The basis of this work was to investigate the relative environmental impacts of various power generators knowing that all plants are located in totally different environments and that different receptors will experience different impacts. Based on IChemE sustainability metrics paradigm, we calculated potential environmental indicators (P-EI) that represent the environmental burden of masses of potential pollutants discharged into different receiving media. However, a P-EI may not be of significance, as it may not be expressed at all in different conditions, so to try and include some receiver significance we developed a methodology to take into account some specific environmental indicators (S-EI) that refer to the environmental attributes of a specific site. In this context, we acquired site specific environmental data related to the airsheds and water catchment areas in different locations for a limited number of environmental indicators such as human health (carcinogenic) effects, atmospheric acidification, photochemical (ozone) smog and eutrophication. The S-EI results from this particular analysis show that atmospheric acidification has highest impact value while health risks due to fly ash emissions are considered not to be as significant. This is due to the fact that many coal power plants in Australia are located in low population density air sheds. The contribution of coal power plants to photochemical (ozone) smog and eutrophication were not significant. In this study, we have considered emission related data trends to reflect technology performance (e.g., P-EI indicators) while a real sustainability metric can be associated only with the specific environmental conditions of the relevant sites (e.g., S-EI indicators).

Testing predictions of macroscopic binary diffusion coefficients using lattice models with site heterogeneity

Quantitatively predicting mass transport rates for chemical mixtures in porous materials is important in applications of materials such as adsorbents, membranes, and catalysts. Because directly assessing mixture transport experimentally is challenging, theoretical models that can predict mixture diffusion coefficients using Only single-component information would have many uses. One such model was proposed by Skoulidas, Sholl, and Krishna (Langmuir, 2003, 19, 7977), and applications of this model to a variety of chemical mixtures in nanoporous materials have yielded promising results. In this paper, the accuracy of this model for predicting mixture diffusion coefficients in materials that exhibit a heterogeneous distribution of local binding energies is examined. To examine this issue, single-component and binary mixture diffusion coefficients are computed using kinetic Monte Carlo for a two-dimensional lattice model over a wide range of lattice occupancies and compositions. The approach suggested by Skoulidas, Sholl, and Krishna is found to be accurate in situations where the spatial distribution of binding site energies is relatively homogeneous, but is considerably less accurate for strongly heterogeneous energy distributions.

The economics of inclusion body processing

Many recombinant proteins are often over-expressed in host cells, such as Escherichia coli, and are found as insoluble and inactive protein aggregates known as inclusion bodies (IBs). Recently, a novel process for IB extraction and solubilisation, based on chemical extraction, has been reported. While this method has the potential to radically intensify traditional IB processing, the process economics of the new technique have yet to be reported. This study focuses on the evaluation of process economics for several IB processing schemes based on chemical extraction and/or traditional techniques. Simulations and economic analysis were conducted at various processing conditions using granulocyte macrophage-colony stimulating factor, expressed as IBs in E. coli, as a model protein. In most cases, IB processing schemes based on chemical extraction having a shorter downstream cascade demonstrated a competitive economic edge over the conventional route, validating the new process as an economically more viable alternative for IB processing.

The effect of elasticity on drop creation in T-shaped microchannels

Polymeric microdrops of low viscosity, elastic fluids have been generated in T-shaped microfluidic devices using a cross-flow shear-induced drop generation process. Dilute (c/c* similar to 0.5) aqueous solutions of polyethylene oxide (PEO) of various molecular weights (3 x 10(5) -2 x 10(6) g/mol) were used as the drop phase fluids whilst silicone oils (5 mPa s

The role of carbon in fuel cells

Carbon possesses unique electrical and structural properties that make it an ideal material for use in fuel cell construction. In alkaline, phosphoric acid and proton-exchange membrane fuel cells (PEMFCs), carbon is used in fabricating the bipolar plate and the gas-diffusion layer. It can also act as a support for the active metal in the catalyst layer. Various forms of carbon - from graphite and carbon blacks to composite materials - have been chosen for fuel-cell components. The development of carbon nanotubes and the emergence of nanotechnology in recent years has therefore opened up new avenues of matenials development for the low-temperature fuel cells, particularly the hydrogen PEMFC and the direct methanol PEMFC. Carbon nanotubes and aerogels are also being investigated for use as catalyst support, and this could lead to the production of more stable, high activity catalysts, with low platinum loadings (< 0.1 Mg cm(-2)) and therefore low cost. Carbon can also be used as a fuel in high-temperature fuel cells based on solid oxide, alkaline or molten carbonate technology. In the direct carbon fuel cell (DCFC), the energy of combustion of carbon is converted to electrical power with a thermodynamic efficiency close to 100%. The DCFC could therefore help to extend the use of fossil fuels for power generation as society moves towards a more sustainable energy future. (c) 2006 Elsevier B.V. All rights reserved.

Transport diffusion of gases is rapid in flexible carbon nanotu

Molecular dynamics simulations of rigid, defect-free single-walled carbon nanotubes have previously suggested that the transport diffusivity of gases adsorbed in these materials can be orders of magnitude higher than any other nanoporous material (A. I. Skoulidas et al., Phys. Rev. Lett. 2002, 89, 185901). These simulations must overestimate the molecular diffusion coefficients because they neglect energy exhange between the diffusing molecules and the nanotube. Recently, Jakobtorweihen et al. have reported careful simulations of molecular self-diffusion that allow nanotube flexibility (Phys. Rev. Lett. 2005, 95, 044501). We have used the efficient thermostat developed by Jakobtorweihen et al. to examine the influence of nanotube flexibility on the transport diffusion of CH4 in (20,0) and (15,0) nanotubes. The inclusion of nanotube flexibility reduces the transport diffusion relative to the rigid nanotube by roughly an order of magnitude close to zero pressure, but at pressures above about I bar the transport diffusivities for flexible and rigid nanotubes are very similar, differing by less than a factor or two on average. Hence, the transport diffusivities are still extremely large compared to other known materials when flexibility is taken into account.