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A near-infrared (NIR) scattering technique is used to measure the wax appearance temperature of several petroleum fluids under nonquiescent conditions. Within the Rayleigh scattering limit, NIR attenuation measurements at a wavelength of 1100 nm can theoretically detect wax crystallites <55 nm in size. In comparison, commonly used cross-polarized microscopy (CPM) observations are limited by a resolution of ∼0.5 μm. The NIR scattering technique readily allows for application of nonquiescent and thermal equilibrium conditions, effectively accelerating the crystal growth process and overcoming subcooling effects. Wax appearance temperature measurements are demonstrated using a waxy crude oil, a waxy gas condensate fluid, and model fluids consisting of macrocrystalline or microcrystalline paraffin wax dissolved in dodecane. Light scattering by wax crystals is evidenced by a baseline elevation in the measured NIR attenuation spectra, with higher shifts observed at lower wavelengths. For opaque crude oils, WAT determination requires delineation of the radiation attenuation originating from the precipitated wax crystals and the mother crude oil. The NIR scattering technique yields WAT values similar to the classical CPM technique. In addition, NIR scattering is shown to be an appropriate technique for measuring the time necessary to melt paraffin wax solids from waxy petroleum fluids at warm temperatures and under nonquiescent processing conditions.

Open filters (with low pressure drop) have potential for energy-efficient reduction of particulate matter (PM) from engines. In the work reported here, the capture efficiency of PM in open substrates has been investigated using PM from a real engine under various flow conditions and sampling settings. The observed capture efficiency (CE) confirmed the expected trends that increased residence time and increased temperature give better CE. However, the volatile content (assumed to be hydrocarbons, HC) can increase the apparent CE due to rapid evaporation and/or shrinkage of the PM. In order to quantify these effects, a conceptual model has been implemented that can be used as an in situ analyzer of the PM properties. The results show how exhaust treatment (heating and/or dilution) changes the characteristics of the PM. These properties affect CE and can be used for subsequent catalyst optimization. In addition, the method developed here was used to analyze nucleation-mode PM from a special fuel injection strategy. The results revealed that these particles were mainly nonvolatiles, demonstrating the usefulness of this characterization methodology. Furthermore, an equation for diffusion losses in the rotary dilutor for the DMS500 is presented.

Cataloged from PDF version of article.To obtain a better understanding of the deactivation of SCR catalysts that may be encountered due to the presence of P-containing impurities in diesel exhausts, the effects induced by P over Cu/BEA NH3-SCR catalysts were studied as functions of the temperature of poisoning and P concentration in the feed. Cu/BEA catalysts with different Cu loadings (4 and 1.3 wt% Cu) were exposed to P by controlled evaporation of H3PO4 in the presence of 8% O-2 and 5% H2O at 573 and 773K. The reaction studies were performed by NH3-storage/TPD, NH3/NO oxidation and standard NH3-SCR. In addition, a combination of several characterisation techniques (ICP-AES, BET surface area, pore size distribution, H-2-TPR and XPS) was applied to provide useful information regarding the mechanism of P deactivation. Pore condensation of H3PO4 in combination with pore blocking was observed. However, the measured overall deactivation was found to occur mostly by chemical deactivation reducing the number of the active Cu species and hence deteriorating the redox properties of the Cu/BEA catalysts. The process of P accumulation on the surface preferentially occurs on the "over exchanged" Cu active sites with the formation of phosphate species. This is likely the reason for the more severe deactivation of the 4% Cu/BEA compared to 1.3% Cu/BEA. Further, the higher NOx reduction performance at 773K of the P-poisoned Cu/BEA catalysts was found to originate from the lower selectivity towards NH3 oxidation, which occurs predominately on the "over-exchanged" sites. (C) 2013 Elsevier B.V. All rights reserved

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The three-way-catalyst (TWC) is an essential part of the exhaust aftertreatment system in spark-ignited powertrains, converting nearly all toxic emissions to harmless gasses. The TWC's conversion efficiency is significantly temperature-dependent, and cold-starts can be the dominating source of emissions for vehicles with frequent start/stops (e.g. hybrid vehicles). In this paper we develop a thermal TWC model and calibrate it with experimental data. Due to the few number of state variables the model is well suited for fast offline simulation as well as subsequent on-line control, for instance using non-linear state-feedback or explicit MPC. Using the model could allow an on-line controller to more optimally adjust the engine ignition timing, the power in an electric catalyst pre-heater, and/or the power split ratio in a hybrid vehicle when the catalyst is not completely hot. The model uses a physics-based approach and resolves both axial and radial temperature gradients, allowing for the thermal transients seen during heat-up to be represented far more accurately than conventional scalar (i.e. lumped-temperature) real-time models. Furthermore, we also use a physics-based chemical kinetics reaction model for computing the exothermic heat of reaction and emission conversion rate which is temperature and residence-time-dependent. We have performed an experimental campaign with a standard spark-ignited engine and a commercial TWC, where we measured steady-state operation and cold-start transient behavior. This experimental data allowed us to tune the model, where we found excellent matching between the measured and modeled tailpipe emissions. Modeling the radial temperature gradient improved the relative accuracy of the conversion efficiency by 15%, and simulations indicate the potential for an absolute improvement by 15 percentage points for some cases. Furthermore, the modeled TWC temperature evolution for a cold-start was typically within ±10°C of the measured temperature (with a maximal deviation of 20°C). The proposed model thus bridges a gap between heuristic models suited for on-line control and accurate models for slower off-line simulation.

The connection cones between an exhaust pipe and an exhaust after-treatment system (EATS) will affect the flow into the first monolith. In this study, a new streamlined connection cone using non-uniform rational B-splines (NURBS) is applied to optimize the flow uniformity inside two different monoliths (a gasoline particulate filter and an un-coated monolith). NURBS and conventional cones were created using 3D printing with two different cone angles. The velocities after the monolith were collected to present the uniformity of the flows under different cones and different velocities. The test results indicate that NURBS cones exhibit better performance. Furthermore, all of the pressure drops of the bench test were measured and compared with those of the conventional cones, demonstrating that the NURBS cones can reduce the pressure drop by up to 12%. The computer fluid dynamics simulations depict detailed changes in the flow before and after entering the monolith. The results show that the NURBS cone avoids the generation of a recirculating zone associated with conventional cones and creates a more uniform flow, which causes a lower pressure drop. Meanwhile, the package structure of the NURBS cone can reduce the space requirements. Finally, the implications of the flow distributions are discussed.