A novel MINLP-based representation of the original complex model for predicting gasoline emissions

The Environmental Protection Agency (EPA) introduced Reformulated Gasoline (RFG) requirements as a measure to reduce emissions from gasoline-powered vehicles in certain geographic areas. As part of this effort, the EPA developed empirical models for predicting emissions as a function of gasoline properties and established statutory baseline emissions from a representative set of gasolines. All reformulated gasoline requires certification via this model, known as the Complex Model, and all refiners and importers calculate emissions performance reductions from the statutory baseline gasoline. The current representation of the Complex Model is extremely difficult to implement within refinery operations models or to use in combination with models for designer gasoline. RFG and boutique fuels are key driving forces in the North American refining industry.The RFG models introduce increasingly complex constraints with the major limitation that they are implicitly defined through a series of complicated disjunctions assembled by the EPA in the form of spreadsheets. This implicit and cumbersome representation of the emissions predictive models renders rigorous optimization and sensitivity analysis very difficult to address directly. In this paper, we discuss how the federal government requirements for reformulated gasoline can be restated as a set of mixed-integer nonlinear programming (MINLP) constraints with the aid of disjunctive programming techniques. We illustrate the use of this model with two simple example fuel blending problems.     

Pheromone Disruption of Argentine Ant Trail Integrity

Disruption of Argentine ant trail following and reduced ability to forage (measured by bait location success) was achieved after presentation of an oversupply of trail pheromone, (Z)-9-hexadecenal. Experiments tested single pheromone point sources and dispersion of a formulation in small field plots. Ant walking behavior was recorded and digitized by using video tracking, before and after presentation of trail pheromone. Ants showed changes in three parameters within seconds of treatment: (1) Ants on trails normally showed a unimodal frequency distribution of walking track angles, but this pattern disappeared after presentation of the trail pheromone; (2) ants showed initial high trail integrity on a range of untreated substrates from painted walls to wooden or concrete floors, but this was significantly reduced following presentation of a point source of pheromone; (3) the number of ants in the pheromone-treated area increased over time, as recruitment apparently exceeded departures. To test trail disruption in small outdoor plots, the trail pheromone was formulated with carnuba wax-coated quartz laboratory sand (1 g quartz sand/0.2 g wax/1 mg pheromone). The pheromone formulation, with a half-life of 30 h, was applied by rotary spreader at four rates (0, 2.5, 7.5, and 25 mg pheromone/m²) to 1- and 4-m² plots in Volcanoes National Park, Hawaii. Ant counts at bait cards in treated plots were significantly reduced compared to controls on the day of treatment, and there was a significant reduction in ant foraging for 2 days. These results show that trail pheromone disruption of Argentine ants is possible, but a much more durable formulation is needed before nest-level impacts can be expected. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Analysis of Multiphase Flow and Heat Transfer: Pressure Buildup in an Unsaturated Porous Slab Exposed to Hot Gas

This study develops a mathematical model for coupled heat and mass transfer in an unsaturated porous slab exposed to a flowing hot gas. Effects of the initial saturation conditions on associated variables, i.e., total pressure, temperature, moisture content, and multiphase flow, are studied. The Newton-Raphson method based on a finite volume technique is applied. This study emphasizes the influence of initial saturation level and gravitational effect in heat and multiphase flow phenomena associated with this system. Gravity enhances the downward flow of liquid within the porous slab. Pressure buildup occurs near the interface between the wet and the dry zone. However, it appears that the order of magnitude to the total pressure is small. This study explains the fundamental mechanism of multiphase flow that involves heat and mass transfer in a heated unsaturated porous slab.     

Stability of hydrogenated nanodiamonds under extreme ultraviolet irradiation

It is generally accepted that diamond is resistant to a wide spectrum of electromagnetic radiation from the ultraviolet through to the soft X-ray range, which makes it very attractive for the fabrication of diamond-based photodetectors. However the effect of photon radiation on the diamond structure has not yet been examined. In the work presented here, photoelectron spectroscopy has been used to study the graphitization of nanodiamond crystallites exposed to extreme ultraviolet radiation. Under such irradiation, the surface hydrogen groups and graphite species are found to prevent graphitization. The mechanism of radiation-induced nanodiamond graphitization is discussed.     

Studies on adsorption equilibrium of xylenes in AEL framework using biased GCMC and energy minimization

The adsorption of xylene isomers in AlPO₄-11 (AEL network) was investigated using biased grand canonical Monte Carlo (GCMC) simulations. Preferential o-xylene adsorption was predicted by the simulations, in agreement with previously reported experimental data. In AlPO₄-11 the selective adsorption behavior comes from the smaller length of the o-xylene molecule along the crystallographic c-axis compared to p-xylene. This is in contrast to AlPO₄-5 and AlPO₄-8, where the ortho-selectivity is caused by the characteristic face-to-face positioning of o-xylene. Energy minimization studies were also performed in a flexible AlPO₄-11 lattice to study the structural changes upon xylene adsorption. The energy minimization study showed that the AlPO₄-11 crystal distorts upon p- and o-xylene adsorption. The distortion mechanism is related to the strong interaction between xylene methyl groups and the sieve oxygen atoms in the O3 position in the wide region of the pore.     

Molecular weight effect on the obtainment of parallel and perpendicular orientation in thermotropic poly(diethylene glycol <Emphasis Type="Italic">p,p′</Emphasis>-bibenzoate)

Summary The effect of molecular weight on the uniaxial orientation process has been analyzed in two samples of thermotropic poly(diethylene glycol p,p′-bibenzoate), evaluating the influence of that parameter on the type of orientation obtained. Several strain rates and deformation temperatures have been tested in order to map out the conditions for obtaining the two different kinds of orientation. The results show that in the lower molecular weight PDEB sample (M_w=31200) it is rather easy to get exclusively perpendicular “anomalous” orientation, with the molecular axes aligned transversely to the stretching direction. However, it is extremely difficult to obtain 100% parallel “normal” orientation. On the contrary, either type of orientation or a mixture of them can be easily developed for the higher molecular weight PDEB sample (M_w=102900).     

Evaluating the mixing performance of a ribbon blender

This paper investigates the effects of processing and equipment parameters of a ribbon blender (i.e. loading method of lubricant, fill level, blade speed and blade design) on magnesium stearate homogeneity. A core sampling technique is used to obtain at least one hundred samples per sampling event, which are extracted throughout the blender and yield a thorough characterization of the entire bed. The results presented here can be used as a guideline to develop appropriate blending processes and characterization protocols for ribbon blenders.     

DESIGN AND IMPLEMENTATION OF STATE OBSERVERS IN REACTIVE DISTILLATION

This study demonstrates that state observers can be developed and applied to infer the composition profiles of reactive distillation columns from noise-contaminated temperature measurements. The design and implementation of a Kalman filter (KF) and a Luenberger observer (LO) are carried out, and their performances are quantitatively assessed. The reliability, accuracy, and robustness of the two designs method are examined and compared quantitatively. The design and implementation of a Luenberger observer are simpler and easier to carry out than those of a Kalman filter. On the other hand, a Kalman filter is found to be more robust to a noisy measurements, erroneous initial estimates, and model uncertainties. A Luenberger observer could be used for composition estimation of reactive distillation when an ideal model of the system can reasonably approximate the real system; otherwise, a Kalman filter is recommended to be applied in more practical situations.     

X-ray topography studies of dislocations in single crystal CVD diamond

X-ray topography has been used to study single crystal diamond samples homoepitaxially grown by microwave plasma-assisted chemical vapour deposition (CVD) on high pressure high temperature (HPHT) and CVD synthetic diamond substrates. Clusters of dislocations in the CVD diamond layers emanated from points at or near the interface with the substrate. The Burgers vectors of observed dislocations have been determined from sets of {111} projection topographs. Dislocations have line directions close to the [001] growth direction and are either edge or 45° mixed dislocations. Where groups of dislocations originated at isolated points they tended to be of the edge variety. Where the substrate surface was deliberately damaged before growth, two sets of dislocations were observed to have propagated from each line of damage and there was a tendency for dislocations to be of the 45° mixed variety with a component of their Burgers vector parallel to the polishing direction. It is demonstrated that X-ray topography can be used to deduce the growth history of CVD synthetic diamond samples produced in multiple growth stages.