Advances in the Development of Filterless Soot Deposition Systems for the Continuous Removal of Diesel Particulate Matter

A model catalytic converter system has been developed to investigate and characterize novel catalyst structures for filterless diesel particulate matter deposition and oxidation in modern heavy duty vehicle diesel engine exhaust systems. The particulate traps are designed for low exhaust gas back pressures and to avoid the clogging effects observed in ceramic filters. In experiments under realistic flow conditions deposition efficiencies of up to 70% have been achieved for submicrometer particles in stacks of corrugated stainless steel foil with microsphere surface coating. The model catalytic converter system is also used to study the reaction kinetics of soot oxidation and volatilization by oxygen and nitrogen oxides under a wide range of reaction conditions, for real diesel engine soot, different model soot substances, and different types of converter surfaces.     

Bench Scale Experiments of Diesel Soot Oxidation Using Pr0.7Sr0.2K0.1MnO3 Perovskite Type Catalyst Coated on Ceramic Foam Filters

Potassium and strontium substituted praseodymium manganate type perovskite catalyst coated on ceramic foam filters have been studied for diesel particulate removal. The synthesized catalyst coated filter pieces have been characterized by using XRD, SEM and TG analysis, whereas their catalytic activity towards soot oxidation was tested using a bench scale facility with real diesel engine exhaust. The catalyst coated filters decrease the soot oxidation T_initial value by 150 °C and T_final by 100 °C as compared to bare soot oxidation reaction, which can be considered as high activity under the actual conditions of diesel engine. The catalytic materials show good thermal stability, while their low cost will also add to their potential for practical applications. Although perovskites have been studied for laboratory evaluations of catalytic soot oxidation, present results further substantiate the possibility of using low-cost, supported, non-noble metal based catalysts for diesel exhaust emission control applications, especially for the cost-effective retrofitment of in-use vehicles with old generation engines.     

Performances of a catalytic foam trap for soot abatement

A catalytic trap for soot particles was prepared by deposition of Cu–V–K–Cl catalyst on a ceramic foam. Catalytic trap performances were evaluated by treating the exhaust of a gas oil burner under different operating conditions. The results obtained showed that ceramic foam is a particularly suitable support for this application since it yields low gas pressure drop, good soot collection efficiency (“deep bed” filtration mechanism), high thermal shock resistance and good contact throughout the filter between soot particles and catalyst surface. In addition, the catalytic foam trap is able to spontaneously regenerate at operating conditions comparable to those typical of diesel engine exhaust and after more than 70 test hours it retains its activity towards soot oxidation.     

Development of a Surface Area Dependent Rate Expression for Soot Oxidation in Diesel Particulate Filters

We collected soot from diesel engine exhaust on miniature particulate filter samples and evaluated soot oxidation rates on an automated flow reactor system. A series of isothermal pulsed oxidation experiments quantified reaction rates as a function of gas composition, temperature, flow rate, and soot consumption. An O₂ chemisorption method measured the soot active surface area as filter regeneration progressed. We developed a rate law with an explicit dependence on carbon surface area and estimated the associated kinetic parameters from the pulsed oxidation data. The resulting rate expression successfully captures the soot oxidation behavior over a wide range of operating conditions.     

Potassium‐Activated Wire Mesh: A Stable Monolithic Catalyst for Diesel Soot Combustion

Potassium‐modified FeCrAl alloy wire mesh was developed as a catalytic diesel particulate filter to suppress the emission of soot from a diesel engine. Potassium species were deposited on wire mesh by a chemical vapor deposition method, in which a model soot was used to convert KOH into metallic K at high temperatures to subsequently activate the wire mesh. Tests showed that metallic K reacted with the enriched Al₂O₃ component on the surface derived from segregation and successive oxidation during precalcination. The resulting layer of K‐O‐Al species offers remarkable activity and stability for the catalytic oxidation of diesel soot. The K‐activated wire mesh could lower the initial temperature of soot combustion and maintain the activity for several cycles.     

Synthetic gas bench study of a 4-way catalytic converter: Catalytic oxidation, NOx storage/reduction and impact of soot loading and regeneration

The so-called 4-way catalytic converter (4WCC) has the ability to simultaneously convert CO, HC, NOx and particulate matter on a single support. It allows diesel vehicles to obey to increasingly stringent emission regulations while at the same time decreasing the space needed by the exhaust aftertreatment system. It is combined with fine engine control strategies so as to ensure conversion of all pollutants. It is hence associated with a large number of catalytic reactions which interact with each other and compete for active sites. The behavior of a commercial 4WCC was characterized on a synthetic gas bench. Gas composition, temperatures and gas hourly space velocity were chosen close to real engine operating conditions. Samples were loaded with soot on an engine bench test. Oxidation reactions were dominant in a lean environment: CO oxidation by NO₂ at low temperature followed by H₂, CO, NO and HC oxidation by O₂. NOx were stored on barium storage sites. In rich conditions H₂, CO and HC were used to reduce NOx. NH₃ production from H₂ was also observed. It could be used to further reduce NOx in lean conditions if stored on a downstream SCR system like in the Honda system [1]. A further conversion of HC was obtained at high temperature due to steam reforming. Interactions and inhibitions were also found. NOx storage appeared to be inhibited by CO oxidation with NO₂ at low temperatures and also by HC, maybe through competition for storage sites with CO₂ produced during HC oxidation. Catalytic reactions were affected by the soot deposit. Continuous oxidation of soot by NO₂ also induced a slower NOx storage rate.     

Measurements of diesel soot oxidation kinetics in an isothermal flow reactor–catalytic effects using Pt based coatings

Despite the significant progress in soot oxidation studies, there is still high uncertainty regarding the rate expressions to model the reactions in diesel particulate filters (DPF). This uncertainty arises from inherent difficulties in sampling and measuring the reaction rate in a realistic way, as well as different properties of the examined soot. In this context, the scope of this study is the development of a novel experimental set-up capable of overcoming existing experimental difficulties. The developed set-up allows for real diesel soot oxidation studies in an isothermal flow reactor. The reaction of soot with oxygen and NO₂ is studied with synthetic gas and with real diesel exhaust and the reaction kinetics are derived for both bare and Pt-based catalyzed substrates by combining experimental and model results.     

Application of glass soot catalysts on metal supports to achieve low soot oxidation temperature

K–Ca–Si–O glass was applied to metal supports for use as a catalyst for diesel soot combustion. Glasses were processed from the melt and by a sol–gel route. Catalyst activity for the oxidation of diesel exhaust soot and flame soot from an oil lamp was compared by thermogravimetric analysis (TGA). The results show that a K-based catalytic glass coating on metal substrates can reduce the temperature where half of the engine soot is oxidized (T₅₀) to as low as 360 °C under loose contact conditions, and offers catalytic stability for long term combustion cycling. Scanning electron microscopy observations show that sol–gel glass processing is effective for coating complex wire mesh shapes without pore clogging.     

Effect of Waste Cooking Oil Biodiesel on the Properties of Particulate from a DI Diesel Engine

The present work focuses on the effect of waste cooking oil biodiesel on the particulate mass, number concentration, nanostructure, and oxidative reactivity under different engine speeds and engine loads. Particulate samples were collected from the diluted exhaust of a medium-duty direct injection diesel engine and were used to analyze the physico-chemical properties via the transmission electron microscope (TEM) and the thermogravimetric analyzer/differential scanning calorimeter (TGA/DSC). The TEM images reveal that smaller primary particles are formed at higher engine speed, lower engine load, or using biodiesel. Quantitative analysis of the nanostructures indicates more soot with more disordered configuration, in which shorter and more curved graphene layer is prevailing at lower engine load or when using biodiesel. Furthermore, the TGA results infer that the soot oxidative reactivity is closely related to the nanostructure properties and the effect of engine load is more pronounced than the effect of engine speed. Also biodiesel soot has faster oxidative reactivity than diesel soot. Moreover, results obtained for B30 (30% biodiesel and 70% diesel fuel) lie in between those for biodiesel and diesel fuel.

Copyright 2015 American Association for Aerosol Research     

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.     

Characterization of Soot Deposition and Particle Nucleation in Exhaust Gas Recirculation Coolers

Cooled exhaust gas recirculation (EGR) is used to control engine out NO_x (oxides of nitrogen) emissions from modern diesel engines by re-circulating a portion of the exhaust gases into the intake manifold of an engine after cooling it through a heat exchanger commonly referred to as an EGR cooler. However, EGR cooler fouling due to presence of soot particles and hydrocarbons (HC) in engine exhaust leads to a decrease in cooler efficiency and increased pressure drop across the cooler. This can adversely affect the combustion process, engine durability, and emissions. In this study, a multicylinder diesel engine was used to produce a range of engine out HC and soot concentrations to investigate soot deposition and particle nucleation in an EGR cooler. A portion of the engine exhaust was passed through an EGR cooler, while particle size and HC concentration measurements were made at the cooler inlet and outlet. Tests were conducted over a range of EGR cooler coolant temperatures and engine out soot and HC concentrations to determine the impact on the nucleation and accumulation modes of the exhaust particle size distributions. A reduction in the accumulation mode particle concentration at the EGR cooler outlet was observed for high soot concentrations indicating soot deposition within the EGR cooler. As the EGR coolant temperature was reduced, the outlet accumulation mode particle concentration was reduced further, indicating increased soot deposition in the cooler due to increased thermophoresis. There were no signs of diffusiophoresis due to HC diffusion within the cooler over the range of conditions used in the study. A significant increase in outlet nucleation mode particle concentration was observed for the low soot concentrations. This mode increased with either increasing HC concentration or decreasing coolant temperature, indicating the saturation ratio (SR) dependence of the nucleation mode formation. However, as the soot concentration was increased, the nucleation mode disappeared because of HC adsorption onto the increased soot surface area.

Copyright 2012 American Association for Aerosol Research     

Kinetics of catalyzed and non‐catalyzed soot oxidation with nitrogen dioxide under regeneration particle trap conditions

BACKGROUND: For compliance with the regulations on diesel particulate matter, car manufacturers have developed diesel particulate filters (DPF). These technologies require a regeneration method which oxidizes soot deposits in the filter. In diesel exhaust emissions there are two suitable oxidizing gases: oxygen and nitrogen dioxide. Nitrogen dioxide is much more active than O₂ and can directly attack the carbon surface. This work describes the kinetics of the oxidation of soot by NO₂ over a wide range of conditions relevant for DPF. RESULTS: The catalyzed and the non‐catalyzed oxidation of soot have been performed in a fixed‐bed reactor. The experimental results show that the overall oxidation process can be described by two additive parallel reactions: a direct C ? NO₂ reaction catalyzed by H₂O and a cooperative C ? NO₂ ? O₂ reaction catalyzed by the Pt/Al₂O₃ catalyst. The results obtained allow to propose the following kinetic law for the specific rates of the catalyzed and the non‐catalyzed oxidation of soot in the regeneration filter conditions: CONCLUSION: The kinetic parameters describing the oxidation rate of soot by NO₂ over a range of temperature and gas composition have been obtained. The extracted kinetics data are relevant for modeling the removal of trapping soot in automotive gas exhaust technology. Copyright © 2009 Society of Chemical Industry     

Comprehensive kinetic characterization of the oxidation and gasification of model and real diesel soot by nitrogen oxides and oxygen under engine exhaust conditions: Measurement, Langmuir-Hinshelwood, and Arrhenius parameters

The reaction kinetics of the oxidation and gasification of four types of model and real diesel soot (light and heavy duty vehicle engine soot, graphite spark discharge soot, hexabenzocoronene) by nitrogen oxides and oxygen have been characterized for a wide range of conditions relevant for modern diesel engine exhaust and continuously regenerating particle trapping or filter systems (0-20% O₂, 0-800 ppm NO₂, 0-250 ppm NO, 0-8% H₂O, 303-773 K, space velocities 1.3 × 10⁴-5 × 10⁵ h⁻¹). Soot oxidation and NO₂ adsorption experiments have been performed in a model catalytic system with temperature controlled flat bed reactors, novel aerosol particle deposition structures, and sensitive multicomponent gas analysis by FTIR spectroscopy. The experimental results have been analyzed and parameterized by means of a simple carbon mass-based pseudo-first-order rate equation, a shrinking core model, oxidant-specific rate coefficients, Langmuir-Hinshelwood formalisms (maximum rate coefficients and effective adsorption equilibrium constants), and Arrhenius equations (effective activation energies and pre-exponential factors), which allow to describe the rate of reaction as a function of carbon mass conversion, oxidant concentrations, and temperature. At temperatures up to 723 K the reaction was driven primarily by NO₂ and enhanced by O₂ and H₂O. Within the technically relevant concentration range the reaction rates were nearly independent of O₂ and H₂O variations, while the NO₂ concentration dependence followed a Langmuir-Hinshelwood mechanism (saturation above ∼200 ppm). Reaction stoichiometry (NO₂ consumption, CO and CO₂ formation) and rate coefficients indicate that the reactions of NO₂ and O₂ with soot proceed in parallel and are additive without significant non-linear interferences. The reactivity of the investigated diesel soot and model substances was positively correlated with their oxygen mass fraction and negatively correlated with their carbon mass fraction.     

低温等离子体辅助去除含碳固态混合物

柴油发动机尾气中存在大量颗粒物,它易被人体吸入,对人的身体健康造成极大危害。其主要成分——碳烟及可溶性有机成分（SOF）等,可通过氧化燃烧的方法除去。本文从柴油机尾气颗粒物的治理出发,介绍了传统的颗粒物后处理技术,包括颗粒捕集器结合再生、微粒催化氧化转化（DOC）、静电捕集等技术。主要介绍了近年所发展起来的低温等离子体（NTP）辅助去除含碳固态混合物（PM）技术,包括等离子体反应器中的化学反应,常见的低温等离子体反应器结构及等离子体产生的放电类型。此外,根据等离子体反应器的安装位置不同,还介绍了两种不同的等离子体PM处理方法——直接等离子体方法和间接（远程）等离子体方法,后者可避免高温对等离子体过程的不利影响。总结了等离子体技术的应用特点,提出对等离子体辅助PM去除过程的研究可着眼等离子体技术本身,研究各种对气体放电产生影响的因素,为等离子体反应器的开发和应用提供参考。     

Diesel particulate emission control

This paper reviews the emission control of particulates from diesel exhaust gases. The efficiency and exhaust emissions of diesel engines will be compared with those of otto engines (petrol engines). The formation of particulates (or “soot”), one of the main nuisances of diesel exhaust gases, will be briefly outlined. The effects of various emission components on human health and the environment will be described, and subsequently the emission standards for particulates and for NO_x, which have been introduced worldwide, will be summarized. Possible measures for reducing exhaust emissions of particulates and NO_x will be discussed, such as the use of alternative fuels, modifications to the engine and the use of aftertreatment devices. It will be made clear that aftertreatment devices may become necessary as diesel emission standards become more stringent, in spite of important progress in the other fields of reducing exhaust emissions. Selective catalytic reduction via hydrocarbons, ammonia or urea, a possible aftertreatment method for NO_x emission control, will be discussed briefly. Filters for collecting particulates from diesel exhaust gases will be examined in more detail and aftertreatment control systems for particulate removal will be reviewed. These can be divided into (i) non-catalytic filter based systems which use burners and electric heaters to burn the soot once it has been collected on the filter; (ii) catalytic filter-based systems which consist of filters with a catalyst coating, or filters used in combination with catalytically active precursor compounds added to the diesel fuel; and (iii) catalytic non-filter-based systems in which gaseous hydrocarbons, carbon monoxide and part of the hydrocarbon fraction of the particulates are oxidized in the exhaust gases. Finally, recent trends in diesel particulate emission control will be discussed, indicating the growing importance of the catalytic solutions: the fast introduction of non-filter-based catalysts for diesel engines and the possible application of filters in combination with catalytically active precursor compounds added to diesel fuel.     

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.     

Influence of waste cooking oil biodiesel on the nanostructure and volatility of particles emitted by a direct-injection diesel engine

To reduce air pollution and the reliance on fossil fuel, biodiesel has been widely investigated as an alternative fuel for diesel engines. The purpose of this study is to investigate the influence of waste cooking oil (WCO) biodiesel on the physical properties and the oxidation reactivity of the particles emitted by a diesel engine operating on WCO biodiesel as the main fuel. Experiments were conducted on a direct-injection diesel engine fueled with biodiesel, B75 (75% biodiesel and 25% diesel on volume basis, v/v), B50, B20, and diesel fuel, at five engine loads and at an engine speed of 1920 rev/min. Particulate samples were collected to analyze the particulate nanostructure, volatility, and oxidation characteristics. Biodiesel or low-load operation leads to smaller primary particles and more disordered nanostructures having shorter and more curved graphene layers. It can be found that particles from biodiesel, blended fuels, or low-load operation have higher volatile mass fractions and faster oxidation reaction rates than particles from diesel or heavy-load operation. The higher oxidation reaction rates are due mainly to the smaller particle size, the more disordered nanostructure, and the higher volatile mass fraction. It is also found that changes in primary particle size and particulate nanostructure are not directly proportional to the biodiesel content, while changes in particulate volatility and particulate oxidation reactivity are proportional to the biodiesel content. The use of biodiesel can enhance particulate oxidation reactivity and the regeneration of soot particles in an after-treatment device.

Copyright © 2016 American Association for Aerosol Research     

Study of Catalytic Filters for Soot Particulate Removal from Exhaust Gases

Two ceramic supports (sintered and foam) were employed for the preparation of catalytic filters for soot removal at diesel exhausts. Laboratory tests showed that while the foam filter is appropriate for small size and low engine backpressure, the sintered filter is more suitable for achieving high filtration efficiency. Tests carried out at the exhaust of a diesel engine showed that the catalytic filter can be continuously regenerated at operating conditions typical of diesel exhaust.     

RECP: A Reactor Designed to Test the Effect of a Catalyst on Soot Oxidation in a Diesel Particulate Filter

A new reactor designed to test soot combustion on a filter coated with an oxidation catalyst is described. It is designed to achieve screening investigations of catalysts in realistic conditions, i.e., close to those prevailing in a diesel particulate filter (DPF). In a DPF a soot layer is formed at the surface of a porous wall (filtration area) which may or may not be covered with a catalytic layer. In this new setup, the soot is deposited on a sample of a DPF which can be easily impregnated with oxidation catalysts. A model soot (commercial carbon black) is used for the investigation, and different procedures for the soot „deposit on the filter are tested.     

A One-Dimensional Model for Particulate Deposition and Hydrocarbon Condensation in Exhaust Gas Recirculation Coolers

Cooled exhaust gas recirculation (EGR) is widely used in diesel engines to control engine out NO_x (oxides of nitrogen) emissions. A portion of the exhaust gases is recirculated into the intake manifold of the engine after cooling it through a heat exchanger. EGR cooler heat exchangers, however, tend to lose efficiency and have increased pressure drop as deposit forms on the heat exchanger surface. This adversely affects the combustion process, engine durability, and emissions. In this study, a 1-D model was developed to simulate soot deposition, soot removal, and condensation of several hydrocarbon (HC) species in a circular tube with turbulent gas flow at constant wall temperature. The circular tube, which makes up the computational domain in the model, represents a single channel from any EGR cooler geometry. The model takes into account soot particle deposition due to thermophoresis, diffusion, turbulent impaction, and gravitational drift. However, thermophoresis was found to be the most dominant deposition mechanism for boundary conditions at which EGR coolers typically operate. Soot removal was modeled by considering a force balance between the drag and van der Waals forces. A lognormal distribution of particles was assumed at the tube inlet. The evolution of the particle distribution in the bulk flow along the tube as well as the mass distribution in the deposit layer on the tube walls is predicted by the model. Condensation of six HC species between C₁₅-C₂₄ alkanes was also modeled. Predictions made by the model are in reasonably good agreement with experimental data obtained from a laboratory reactor under the same boundary conditions. There are several assumptions and simplifications built into the model, which can be refined further to improve it.

Copyright 2012 American Association for Aerosol Research