The morphology and crystallography of diesel particulate emissions

The morphology and crystallography of particulate emissions from indirect injection diesel engines has been studied using transmission electron microscopy. Samples were collected in a diluted exhaust stream directly onto amorphous carbon films supported on electron microscope grids. Diesel particles closely resemble carbon blacks and consist of chains or clusters of quasispherical subunits. Diffraction patterns were quantified using a microdensitometer and a graphical background correction. Peak intensity was then normalized to background to eliminate exposure variations. Small clusters were found to be less crystalline than large clusters and the centers of two chain-like particulates were more crystalline than the ends. By analogy with the crystallinity studies of heat treated carbon blacks, these differences were interpreted as differences in the time/temperature histories of the particles.     

Secondary nanoparticle emissions during diesel particulate trap regeneration

Two nanostructured mixed oxide catalysts (the CoCr₂O₄ spinel and the LiCrO₂ delafossite) have been recently developed for diesel soot combustion. The catalysts have been deposited via in situ combustion synthesis over SiC wallflow trap by CTI (Salindres, F). Bench tests proved that, after soot loading, both the developed traps enable a faster and more complete regeneration at 550 °C than the non-catalysed trap. However, a specific study on the particles distribution after the SiC trap, carried out via SMPS analysis, showed that secondary nanoparticles (<20 nm) are emitted during the regeneration promoted by the highly-active CoCr₂O₄ catalytic trap, as opposed to the LiCrO₂-catalysed and the virgin counter parts. This phenomenon has been investigated vs. the regeneration temperature and some sampling conditions so as to draw preliminary indications on the nature of these undesired particles.     

Science and technology of catalytic diesel particulate filters

During the last few decades, concerns have grown on the negative effects that diesel particulate matter has on health. Because of this, particulate emissions were subjected to restrictions and various emission-reduction technologies were developed. It is ironic that some of these technologies led to reductions in the legislated total particulate mass while neglecting the number of particles. Focusing on the mass is not necessarily correct, because it might well be that not the mass but the number of particles and the characteristics of them (size, composition) have a higher impact on health. To eliminate the threat of diesel particulate matter, essentially absolute filtration in combination with the oxidation of all emitted hydrocarbons is what will be required.

After two decades of development, the first filters will soon be introduced on a large scale. Many different problems had to be overcome; it was especially important that the filter was robust and its regeneration was controllable. The key technology to controllable regeneration is oxidation catalysis, which is the main area of focus in this review. Catalytic filter regeneration is very complex, something which is apparent in the main aspects of catalysis (i.e., activity, stability, and selectivity). Complications are that the process conditions can be very transient and that the temperatures are usually low. It is shown that the oxidation catalyst cannot be examined isolated from the total system. Within the margins of size restrictions and an engine's service life, essentially all particulate matter should be trapped, the filter should be regenerated safely, no toxic by-products should be formed, and the catalyst should not alter the filtration characteristics, and vice versa.

The exhaust conditions of passenger cars are not favorable for continuous regeneration strategies, because the best strategy seems to be periodic regeneration with the aid of a catalyst. This concept is not passive, which makes it complex and expensive. The best technology for filter regeneration with trucks and buses seems to be continuous regeneration. Using the NO_x present in the exhaust gas for soot oxidation amounts to a simple and robust concept. A future limitation might be the minimal required NO_x:soot ratio; it is not sure if this will be met in future engines. Alternatively, a low-temperature catalyst may be developed that does not require NO_x. Developing such an advanced catalytic trap will be one of the major challenges of catalytic filter engineering.     

Numerical simulation of soot filtration and combustion within diesel particulate filters

The numerous benefits offered by diesel engines, compared to gasoline ones, are balanced by a drawback of increasing concern, namely soot emissions. Nowadays, soot emissions can be reduced by physically trapping the particles within on-board diesel particulate filters (DPF). The filter gets progressively loaded by filtering the soot laden flue gases, thus causing an increasing pressure drop, until regeneration takes place. The aim of this work is to develop a fully predictive three-dimensional mathematical model able to accurately describe the soot deposition process into the filter, the consequent gradual modification of the properties of the filter itself (i.e. permeability and porosity), the formation of a soot filtration cake, and the final regeneration step. The commercial computational fluid dynamics (CFD) code Fluent 6.2.16, based on a finite-volume numerical scheme, is used to simulate the gas and particulate flow fields in the DPF, whereas particle filtration sub-models and regeneration kinetics are implemented through user-defined-subroutines (UDS).Model predictions highlight uneven soot deposition profiles in the first steps of the filtration process; however, the very high resistance to the gas flow of the readily formed cake layer determines the evolution into an almost constant layer of soot particles. The ignition of the loaded soot was simulated under different operating conditions, and two regeneration strategies were investigated: a “mild regeneration” at low temperature and oxygen concentration, that operated a spatially homogeneous ignition of the deposited soot, and a “fast regeneration”, with an uneven soot combustion along the axial coordinate of the filter, due to strong temperature gradients inside the filter itself. These findings are supported by comparison and validation with experimental data.     

Physical characterization of particulate emissions from diesel engines: a review

Properties of particles emitted from diesel engines and the consequences of these properties for sampling and measuring the particles are reviewed. The influence of aftertreatment devices such as particle traps and catalytic converters on particle properties is demonstrated. Based on the particle properties and results from health effect studies, requirements to metrics, and measurement systems, for example, for type approval testing, are discussed. This discussion is limited to physical properties. Special attention is given to the volatile fraction. We show that care has to be taken when designing the sampling and dilution system, because this step decisively influences what happens with the volatile material, which may remain in the gas phase, condense on solid particles, or form new particles by nucleation. If nucleation occurs, particles formed in the sampling lines may dominate the particle number concentration. A selection of systems for dilution, conditioning and measuring is shown. Systems to determine number, mass, and surface concentrations, size distributions, and carbon concentration are discussed. The discussion is focused on systems developed or adapted recently for the physical characterization of diesel particles.     

Chemical characterization of particulate emissions from diesel engines: A review

This review examines the chemical properties of particulate matter (PM) in diesel vehicle exhaust at a time when emission regulations, diesel technology development, and particle characterization techniques are all undergoing rapid change. The aim is to explore how changes in each of these areas impact the others. Particle composition is of central interest to the practical issues of health effects, climate change, source apportionment, and aerosol modeling. Thus, the emphasis here is to identify the emerging questions and examine how they can be addressed. As regulations drive down the allowed tailpipe emission levels, advances in engine and aftertreatment technology have made it possible to substantially reduce PM emissions. Besides the reduction in level, new technologies such as diesel particulate filters (DPFs) and selective catalytic reduction (SCR) can also affect the physical and chemical properties of PM. This in turn introduces new analytical demands that must address not only the issue of sensitivity, but also of specificity. New methods of aerosol chemical analysis are described that address these needs, improve our understanding of particle composition, and provide critical insight into the current issues surrounding motor vehicle PM emissions and their environmental impact.     

A catalytic diesel particulate filter with a heat recovery function

Based on a folded sheet design, we made and tested a miniature diesel particulate filter (DPF) that can transfer the heat generated by catalytic oxidation in the DPF to its upstream, thus promoting substantial temperature rise at the position where pieces of SiC felt working as PM filters are situated. When 0.6% of H₂, corresponding to 50 K in adiabatic temperature rise, was added to a 43 L/min of exhaust gas, the observed maximum temperature rise at the filter material exceeded 350 K, from which the heat recovery rate was estimated to be more than 86%. The PM filtration rates were 80–90%.     

Oxygenated blend design and its effects on reducing diesel particulate emissions

In order to meet Euro IV emission standards, diesel vehicles are compelled to install exhaust aftertreatment devices, which largely increases the overall cost. This paper explores the possibility to significantly reduce the particulate matter (PM) emissions by new fuel design. Several oxygenated blends were obtained by mixing the biodiesel, ethanol, dimethyl carbonate (DMC), and diesel fuels. The tests were conducted on two heavy-duty diesel engines, both with a high-pressure injection system and a turbocharger. The total PM and its dry soot (DS) and soluble organic fraction (SOF) constituents were analyzed corresponding to their specific fuel physiochemical properties. A blended fuel that contains biodiesel, DMC, and high cetane number diesel fuels was chosen eventually to enable the diesel engines to meet the Euro IV emission regulation. Based on the test results, the basic design principles were derived for the oxygenated blends that not only need the high oxygen content, but also the high cetane number and the low sulfur and low aromatic contents.     

Measurement and prediction of filtration efficiency evolution of soot loaded diesel particulate filters

We here present laboratory based experimental and theoretical methods to characterize the filtration efficiency (FE) behavior of diesel particulate filters (DPFs) exposed to soot laden gas streams. Sensitivity of the FE behavior on filter microstructure and geometry properties have been studied, along with the impact of the hydrodynamic and aerosol flow conditions (flow rate, temperature, aerosol characteristics). Evolution of FE with soot load is reported from clean filter FE to maximum efficiency (100%), as the deposited soot in the filter wall itself acts as the filtering medium. The theoretical model considers different mechanisms (Brownian diffusion, particle interception and inertia) of soot capture and their impact on number based and mass based FE. The predictions from the theoretical model are in good agreement with experimental observations over a broad range of filter microstructure. Sensitivity of FE evolution on bare and coated filters has been reported, along with the impact of ash loading of the filters. Methods presented here are useful in determining the performance of DPFs under well-defined laboratory conditions and their extension to dynamic field conditions. These are also useful in determining filter properties for obtaining high FE and low pressure drop.     

Reduction of soot pollution from automotive diesel engine by ceramic foam catalytic filter

Recent progress in diesel technology demonstrates the possibility of reducing the particulate matter (PM) emissions level combining the high efficiency of common rail engine with exhaust gas after-treatment devices, such as diesel PM filter. Ceramic foam catalytic filter (CFCF), prepared by coating of ceramic foam (CFUF), results in lower temperature and shorter regeneration time due to the higher specific surface, lower pressure drop and good filtration efficiency with respect to CFUF.     

Innovative means for the catalytic regeneration of particulate traps for diesel exhaust cleaning

Catalytic traps for diesel particulate removal are multifunctional reactors coupling filtration and catalytic combustion of soot. This paper reviews the most recent developments carried out at Politecnico di Torino concerning two different trap types: zirconia-toughened-alumina foams catalysed with Cs–V catalysts, operating according to a deep filtration mechanism, and cordierite or SiC wall-flow filters catalysed with perovskite catalysts (e.g. LaCr_0.9O₃), enabling shallow-bed filtration. The preparation and characterisation of these two trap types are described and the performance of the traps (filtration efficiency, pressure drops, etc.) evaluated on a diesel engine bench under various operating conditions. A final critical assessment points out that most chances of practical application in mobile sources lie in wall-flow type traps for their superior filtration efficiency (>95%) and their compatibility with active trap regeneration means (e.g. fuel post-injection) that can occasionally rise on purpose the exhaust gas temperature to accelerate the catalytic combustion of trapped soot. Conversely, completely passive solutions based on deep filtration catalytic traps show only promise for stationary applications at temperatures higher than 350°C, due to insufficient catalyst activity at lower temperatures.     

Control of NO x emissions from diesel engine by selective catalytic reduction (SCR) with urea

Topics in Catalysis - Among the catalysts screened, Cu-ion exchanged ZSM5 zeolite exhibited the highest NO removal activity, particularly at low reaction temperatures below 200&nbsp;°C,...     

Single wall diesel particulate filter (DPF) filtration efficiency studies using laboratory generated particles

Diesel engines offer higher fuel efficiency, but produce more exhaust particulate than conventional gasoline engines. Diesel particulate filters are presently the most efficient means to reduce these emissions. These filters typically trap particles in two basic modes: at the beginning of the exposure cycle the particles are captured in the filter holes, and at longer times the particles form a “cake” on which particles are trapped. Eventually the “cake” is removed by oxidation and the cycle is repeated. We have investigated the properties and behavior of two commonly used filters: silicon carbide (SiC) and cordierite (DuraTrap^® RC) by exposing them to nearly-spherical ammonium sulfate particles. We show that the transition from deep bed filtration to “cake” filtration can easily be identified by recording the change in pressure across the filters as a function of exposure. We investigated the performance of these filters as a function of flow rate and particle size and found that the filters have the highest filtration efficiencies for particles smaller than ∼80 nm and larger than ∼200 nm. A comparison between the experimental data and a simulation using incompressible lattice-Boltzmann model shows good qualitative agreement, but the model over-predicts the filter's trapping efficiency.     

Diesel particulate traps regenerated by catalytic combustion

The development of catalytic means for the regeneration of particulate-laden traps for diesel exhaust cleaning is the main topic of this paper. All the steps of the catalytic trap preparation are dealt with, including: the synthesis and choice of the proper catalyst and trap materials, the development ofin situ catalyst deposition, and the bench testing of the derived catalytic traps. Two different traps were considered (i.e., silicon carbide and cordierite wallflow monoliths operating via a shallow-bed filtration mechanism), whereas the best catalyst selected was the perovskite LaCr_0.9O₃. The filtration efficiency and the pressure drops of the catalytic and non-catalytic monoliths were evaluated on a diesel engine bench under various operating conditions. On the basis of the obtained results the catalysed SiC converter was found to be the most satisfactory converter to be placed on the exhaust line of the modern common rail diesel-engine cars.     

A novel diesel particulate converter

A novel design of an electrochemical reactor for filtering and continuous combustion of soot particles was developed. Such a reactor consists of a porous, oxygen-ion conducting material covered by catalytically active, electron-conductive electrodes, electrical connections and an external power supply. The manufacturing process was developed for high-porosity, ion- and electron-conducting ceramic monoliths from nanosize powders by extrusion followed by coating techniques. The performed catalytic tests proved that the efficiency of the reactor for soot removal is above 90% at low flow conditions (GHSV=13 000⁻¹) and 75% for high flow (GHSV=39 000⁻¹) in the temperature range 250–500 °C.     

Deep desulfurization of diesel fuels by catalytic oxidation

Reaction feed was prepared by dissolving dibenzothiophene (DBT), which was selected as a model organosulfur compound in diesel fuels, in n-octane. The oxidant was a 30 wt-% aqueous solution of hydrogen peroxide. Catalytic performance of the activated carbons with saturation adsorption of DBT was investigated in the presence of formic acid. In addition, the effects of activated carbon dosage, formic acid concentration, initial concentration of hydrogen peroxide, initial concentration of DBT and reaction temperature on the oxidation of DBT were investigated. Experimental results indicated that performic acid and the hydroxyl radicals produced are coupled to oxidize DBT with a conversion ratio of 100%. Catalytic performance of the combination of activated carbon and formic acid is higher than that of only formic acid. The concentration of formic acid, activated carbon dosage, initial concentration of hydrogen peroxide and reaction temperature affect the oxidative removal of DBT. The higher the initial concentration of DBT in the n-octane solution, the more difficult the deep desulfurization by oxidation is. Translated from Journal of Chemical Engineering of Chinese Universities, 2006, 20(4): 616–621 [译自: 高校化学工程学报]