Tapered element oscillating microbalance (TEOM) studies of isobutane,n‐butane and propane sorption in β‐ and Y‐zeolites

A TEOM is used to elucidate the adsorption/desorption characteristics of alkylation reactants on USY‐ and β‐zeolites. Equilibrium adsorption isotherms were obtained on USY‐ and β‐zeolites using n‐butane, isobutane and propane as proxy reactant molecules (T = 303–398 K, adsorbate partial pressure 0–1.2 bar). Analysis of the transient adsorption/desorption profiles of these molecules from either a bed of the zeolite or pelletized particles of the crystals (with mean size < 1 μm) demonstrate that diffusion in the secondary meso‐/macroporous structure formed in the packing or the pellets controls the overall sorption rates. The experimental adsorption/desorption profiles from the pelletized zeolites were regressed with available mathematical models to obtain effective meso‐/macropore diffusivities for reactant molecules, and nearly perfect fits of the experimental and the modeled profiles. Taking into account the dead volume in the system, a criterion for reliable measurements of either micropore or mesopore diffusivities by the TEOM technique is derived. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Modeling of key reaction pathways: Zeolite catalyzed alkylation processes

A six lump kinetic model that considers the key reactions for the zeolite catalyzed alkylation process is presented. The influence of different reactions and rate limiting steps on reactor performance is examined by coupling an appropriate reactor model that accounts for different back-mixing on reactor scale, with a zeolite particle model which accounts for the diffusion inside the zeolite pore, the alkylation reaction, and zeolite deactivation. Model predictions are compared with experimental results and lead to conclusions that hydride transfer and oligomerization reactions are the key kinetic steps affecting the overall performance of zeolite catalyzed alkylation processes. It is suggested that higher alkylate yield and longer zeolite activity are achieved by increasing the intrinsic hydride transfer rate and the ratio of feed isobutane to n-butene (P/O) concentration. For a given P/O feed ratio, achieving close to plug flow for isobutane and high back-mixing for n-butene further enhances local P/O ratio and yield. Furthermore, optimal zeolite catalyst design should consider the egg shell type of Brønsted acid site distribution and a lower silicon to alumina (Si/Al) ratio.     

Effective parameter estimation within a multi-dimensional population balance model framework

This study considers optimization problems with multi-dimensional population balance models embedded. The objective function is formulated as a least-squares problem, minimizing the difference between target data and simulated model output and the goal is to find model parameter values that best fit the data. Results show that derivative-free methods, such as the Nelder–Mead simplex method, fail to converge to an optimal solution. A similar result was obtained with gradient-based methods such as BFGS, quasi-Newton, Newton, Gauss–Newton, Levenberg–Marquardt and SQP, and with a stochastic genetic algorithm. It was hypothesized that three main issues could contribute to these convergence failures: (1) gradients were calculated based on finite differences, and as a result of improper step size determination, the numerical error could be prohibitive resulting in inaccurate derivative information, (2) the parameters may not be identifiable and (3) numerical instability could occur during the course of optimization. To circumvent these issues, this work addresses the calculation of derivative information based on automatic differentiation and sensitivity analysis to ensure increased accuracy. Issues such as parameter identifiability are also dealt with by analyzing an accurate Fisher information matrix. Given the computational burden in calculating accurate Jacobians and Hessians, compounded by the potential nonsmoothness introduced into the objective function as a result of granule nucleation, other optimization strategies may be warranted and this work addresses those accordingly. Overall, by systematically assessing the problem formulation and mechanisms, the results show that substantial improvements in convergence can be achieved by utilizing appropriate optimization techniques, thus leading to more successful and optimal parameter estimation.     

Effect of imbibed moisture on monotonic and low-velocity impact behavior of injection over-molded short/continuous fiber reinforced polypropylene composites

Design of automotive components with over-molded short/continuous fiber reinforced thermoplastic composites necessitates understanding of their behavior under extreme outdoor conditions. The short, quasi-isotropic and over-molded short/continuous glass fiber reinforced polypropylene (PP) composite specimens were prepared as per standard and immersed in water until equilibration to study their relative moisture absorption characteristics and consequent mechanical behavior. As the absorbed moisture mostly occupied the interface between fiber and matrix in laminated composite inserts and moisture absorption of short fiber composite core is insignificant, the moisture absorption of over-molded composites is just above 50% of that of laminated composites. The flexural, interlaminar shear and impact behavior of equilibrated composites is primarily governed by the quantum of imbibed moisture of composite materials. Optical analysis of failed moisture equilibrated over-molded specimens showed a marginal delamination between plies of the inserts without any perceptible damage within the short fiber composite similar to dry as molded specimens.     

Thermal stability of CeO<Subscript>2</Subscript>/ZrO<Subscript>2</Subscript> multilayer thin films prepared by pulsed laser deposition

Multilayers of CeO₂/ZrO₂ thin films were deposited on Si (100) substrates using pulsed laser deposition at an optimized oxygen partial pressure of 3×10⁻² mbar and at room temperature. The CeO₂ layer thickness was 10 nm, while the ZrO₂ layer thickness was varied as 10, 20 and 30 nm. CeO₂ and ZrO₂ layers were deposited alternately to obtain 25 bilayers. High temperature x-ray diffraction (HTXRD) results showed that the multilayer films had cubic ceria and tetragonal ZrO₂. Thermal expansion coefficients were calculated for CeO₂ and t-ZrO₂ and found to increase with the decrease of ZrO₂ layer thickness. The cross sectional transmission electron microscopy (XTEM) of CeO₂/ZrO₂ multilayer also indicated that ceria was found to be in cubic phase while zirconia contained predominantly tetragonal phase along with cubic phase in thermally annealed specimen.     

Palladium‐nanoparticle intercalated vermiculite for selective hydrogenation of α,β‐unsaturated aldehydes

Palladium nanoparticles were generated in the interlamellar region of swelling 2:1 type vermiculite clay using an adsorption excess isotherm. An adsorption excess isotherm was constructed for vermiculite after exchanging the exchangeable Na⁺ ions in the interlamellar region using a binary liquid mixture (ethanol:toluene). Based on adsorption excess isotherm, 1% w/w palladium was intercalated into the interlamellar space of vermiculite. The Pd‐intercalated vermiculite was characterized by X‐ray diffraction, transmission electron microscopy and atomic absorption spectroscopy. The 1% w/w Pd‐intercalated vermiculite was tested for its catalytic activity towards selective hydrogenation reactions involving some α,β‐unsaturated carbonyl compounds using a pulse reactor and its catalytic activity was compared with commercial 1% Pd/C. The intercalated catalyst was found to be very selective towards the desired product of unsaturated alcohols. Copyright © 2007 Society of Chemical Industry     

The iterative contribution and relevance of modelling to UK energy policy

This paper discusses the iterative provision of modelling insights on long-term decarbonisation scenarios for UK energy policy makers. A multi-year model construction process of the UK MARKAL-Macro-hybrid energy-economic model, and four subsequent major policy analyses illustrates the scope of this interaction. The initial set of modelling runs focused on the technical feasibility of long-term 60% carbon dioxide (CO₂) reduction scenarios, the role of key technologies, and the underlying uncertainties. Furthermore subsequent modelling studies were aimed to generate insights on more stringent targets, and on issues and uncertainties that may make targets harder to achieve. Hence, this paper analyses the large number of long-term UK CO₂ reduction scenarios through a clustering approach on target stringency and barriers to implementation. Robust findings and key uncertainties are highlighted, including the critical role of the power sector, trade-offs between resources, sectors, key energy technologies and behavioural responses, and the increasing level and spread of CO₂ marginal prices and GDP impacts. The relevance and use of modelling insights to the UK energy policy process is shown in the continuation of the energy modelling–policy interface. This constitutes both ongoing model development, and nuanced scenario analysis designed to further explore key uncertainties in evolving policy issues.     

Modularization of a Large-Scale Business Application: A Case Study

Large software systems, developed over several years, are the backbone of industries such as banking, retail, transportation, and telecommunications. With multiple bug fixes and feature enhancements, these systems gradually deviate from the intended architecture and deteriorate into unmanageable monoliths. This article presents a case study of a banking application besot with such problems and the modularization approach that the company adopted as a solution. It also highlights benefits unearthed as a result of this reengineering exercise.     

Lattice dynamics of colloidal crystals during photopolymerization of acrylic monomer matrix

The photoinitiated bulk polymerization process, which has been used recently in the manufacture of solid optical diffraction filters, is examined to understand the dynamics of both the crystalline colloidal arrays (CCA) and the host monomer species. Our analysis indicates that volume shrinkage of the monomer, changes in the dielectric properties of the monomer, and inhomogeneities of polymerization reaction rate across the dispersion during the polymerization process, are the major contributors for observed lattice compression and lattice disorder of the CCA of silica spheres in polymerized acrylic/methacrylic ester films. The effect of orientation of photocell with respect to the radiation source on Bragg diffraction of CCA indicated the presence of convective stirring in the thin fluid system during the photopolymerization that deleteriously affects the periodic array structures. To devise reproducible and more efficient optical filters, experimental methods to minimize or eliminate convective instabilities in monomeric dispersions during polymerization are suggested. © 1998 Chapman & Hall