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.     

Preparation and Application of Perovskite Catalysts for Diesel Soot Emissions Control: An Overview

The diesel engines are energy efficient (1), but their particulate matter (soot) emissions are still a matter of concern even though major advances in their control are being made. For soot abatement, catalytic diesel particulate filter (DPF) technique is widely employed to trap and burn the soot. Many types of catalysts have been investigated for the soot combustion i.e. platinum group metal (PGM) based, perovskite-type oxides, spinel-type oxides, rare earth metal oxides, and mixed transient metal oxides etc. The cost of PGM catalysts is high and their availability is questionable. Further they are susceptible to poisoning and have low thermal stability. On the other hand perovskite catalysts show potential as effective soot oxidation catalyst for the DPF because of their low cost, high thermal stability and tailoring flexibility. Many papers related to soot oxidation over perovskite catalysts have been published but no review paper appears in the literature that is dedicated to soot oxidation. Thus, this article provides a summary of published information regarding pure and substituted perovskite catalyst, preparation methods, properties, and their application for diesel soot emission control.     

Evidences of the Cerium Oxide-Catalysed DPF Regeneration in a Real Diesel Engine Exhaust

The active phase Ce_0.5Pr_0.5O₂ has been loaded on commercial substrates (SiC DPF and cordierite honeycomb monolith) to perform DPF regeneration experiments in the exhaust of a diesel engine. Also, a powder sample has been prepared to carry out soot combustion experiments at laboratory. Experiments performed in the real diesel exhaust demonstrated the catalytic activity of the Ce–Pr mixed oxide for the combustion of soot, lowering the DPF regeneration temperature with regard to a counterpart catalyst-free DPF. The temperature for active regeneration of the Ce_0.5Pr_0.5O₂-containing DPF when the soot content is low is in the range of 500–550 °C. When the Ce_0.5Pr_0.5O₂-containing DPF is saturated with a high amount of soot, pressure drop and soot load at the filter reach equilibrium at around 360 °C under steady state engine operation due to passive regeneration. The uncoated DPF reached this equilibrium at around 440 °C. Comparing results at real exhaust with those at laboratory allow concluding that the Ce_0.5Pr_0.5O₂-catalysed soot combustion in the real exhaust is not based on the NO₂-assisted mechanism but is most likely occurring by the active oxygen-based mechanism.     

Effect of Biofuels on Catalyzed Diesel Particulate Filter Regeneration

Under the terms of the Renewable Energy Directive, EU member states are required to use 10 % of transport energy sourced from renewable sources, mainly biofuels, by 2020. The purpose is to reduce greenhouse gas (GHG) emissions from the transport sector. However, biodiesel used as fuel has a significant impact on emissions, as related by most of the literature on the subject. In particular, nitric oxides (NOx) and particulate matter (PM) emissions from current diesel technologies are critical factors because they are already close to the limits permitted by regulations and both limits will be even more stringent in the near future. Soot particles are trapped on a diesel particulate filter (DPF). If the DPF is catalyzed like in this study, the soot is then burned by reaction with NO₂ (CDPF continuous regeneration) which occurs at lower temperatures than reaction with O₂ (active regeneration). Tests of ultra-low sulfur diesel blended with rapeseed-biodiesel at 30 % (B30) and Fischer–Tropsch diesel (FT30) were conducted. The Fischer–Tropsch diesel was chosen to represent a biomass-to-liquid fuel. This work investigated the impact of these two biofuels on engine polluting emissions and the resulting CDPF ability to regenerate. When compared with similar inlet conditions on a synthetic gas bench, an impact of fuel was observed on soot reactivity: the CDPF loaded with FT30 soot regenerated slightly faster. Engine bench tests were also performed to combine the effects of fuel on engine emissions and soot reactivity and to evaluate the CDPF. The increase in NOx and decrease in PM emissions observed for B30 appeared to significantly improve CDPF continuous regeneration by NO₂.     

Kinetics of catalyzed and non-catalyzed oxidation of soot from a diesel engine

To comply with the new regulations on particulate matter, car manufacturers more and more commonly use diesel particulate filters (DPF). The working of these systems needs to periodically burn soot that has been accumulated during the loading of the DPF. This paper describes the kinetics of the non-catalytic and catalytic oxidation of real diesel soot with oxygen. From these experiments, mechanisms for catalyzed and non-catalyzed soot oxidation have been proposed.     

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.     

Evaluation of Performance of Diesel Particulate Filters Through Integrated Multi-Scale Computer Calculations

Wall-flow channel models and soot deposition models based on micro scale considerations are integrated into global 3D diesel particulate filter simulations. In addition, transient and steady-state simulations are combined to understand at the same time short- and long-time behaviour of the diesel particulate filter (DPF). The functionality of the simulation tool is achieved and correlations with measured data encourage the use of the model as a tool to predict DPF behaviour.     

HRTEM Study of diesel soot collected from diesel particulate filters

HRTEM study of several soot samples collected on Diesel Particulate Filters (DPF) under conditions relevant to practical applications of DPF technology, revealed nano-structure, to our knowledge, not reported previously for diesel soot. In particular, some of the primary particles were found to have hollow interior, and the outer shell exhibiting evidence of graphitization, with a higher crystallinity compared to the non-hollowed particles. The percentage of such particles varied between different soot samples and tentatively appeared to be related to the oxidation history of the sample. Remarkably, similar effect was not reproduced for a carbon black sample, Printex-U, suggesting that propensity to such oxidation-induced graphitization is related to the original nano-structure of the particle. These initial observations were independently confirmed for the same set of soot samples by two different HRTEM facilities, at NASA-Glenn and PNNL.     

2D simulation of the regeneration performance of a catalysed DPF for heavy-duty applications

The objective of this work is to study the regeneration performance of a heavy-duty DPF application. The simulation of the local temperatures and pressure drop during the regeneration could be validated with experimental data, indicating the need for a 2D model approach to describe this particular catalysed DPF configuration. Furthermore, the model was applied to illustrate the axial and radial regeneration phenomena focusing on soot and temperature distribution.     

Emissions from a diesel car during regeneration of an active diesel particulate filter

The California Air Resources Board (CARB) and the Joint Research Center of the European Commission (JRC) have collaborated on emissions testing of a light duty diesel vehicle, which is Euro 4 compliant and comes equipped with a diesel particulate filter (DPF). The California testing included an investigation of the regeneration of the DPF over cruise conditions and NEDC test cycles. DPF regeneration is caused by the buildup of soot in the filter, and for the present test vehicle the regeneration process is assisted by a fuel borne catalyst. Regulated exhaust emissions increased substantially during the regeneration events; however, PM emissions levels were below California LEVII emissions standards. There was a very large increase of volatile particles between 5 and 10 nm, and these volatile particles were generated during all of the observed regeneration events. It appears that the particle number instruments that use the PMP methodology do not capture the PM mass increase during DPF regeneration; however, for one regeneration event there was an apparent large increase in solid particles below the PMP size limit. The PM mass increase associated with regeneration appears to be due to semi-volatile particles collected on filters. During the testing, the regeneration events exhibited considerable variations in the time for regeneration as well as the amount of PM emissions. From this investigation, several questions have been posed concerning the emission of very small (<20 nm) volatile and solid particles during DPF regeneration that need further investigation.     

New Tool for Experimental Analysis of Diesel Particulate Filter Loading

The loading of a diesel particulate filters (DPFs) entails the need of trap regeneration by particulate combustion, whose efficiency and frequency are somehow affected by the way soot is deposited along the channels. Great efforts are thus spent to improve the understanding of the filtration process of DPFs, aimed at obtaining a deeper insight into the relationship between engine performance and filter loading so as to take advantage of this insight for DPF design and optimization purposes. Small lab-scale 300 cpsi DPF samples were loaded downstream the Diesel oxidation catalyst (DOC) in an ad hoc designed reactor capable of hosting five samples with part of the entire flow produced by an automotive diesel engine at the 2500 × 8 BMEP operating condition, selected to be representative as one of the critical engine points of the New European Driving Cycle (NEDC). Soot layer thickness was estimated by means of Field emission scanning electron microscope (FESEM) observations after sample sectioning at progressive locations, obtained through a procedure defined not to affect the distribution of the soot inside the filter and to enable estimation of the actual soot thickness along the channel length. This is a pre-requisite to get suitable data for the validation of the DPF models required for trap design and optimisation.     

Simulation of NOx and soot abatement with Cu‐Cha and Fe‐ZSM5 catalysts

The embodiment of the NO_x selective catalytic reduction (SCR) functionality in a diesel particulate filter (DPF), so‐called SCR‐on‐Filter (SCRoF), is investigated through numerical modeling with SCR kinetics corresponding to Cu‐Chabazite and Fe‐ZSM5 catalysts. The results of the simulations of the SCR activity, performed in the absence and presence of soot, indicate that the presence of soot negligibly affects the NO_x conversion efficiency, given the slow dynamics of passive regeneration. Conversely, the reduction in cake thickness by soot passive oxidation is significantly different in the absence of SCR activity (uncatalyzed DPF) compared to that in its presence (SCRoF). In fact, in the SCRoF only 60–80% of the original soot consumption obtained in the absence of SCR reaction over 1 h can be achieved. Individual Cu‐Chabazite and Fe‐ZSM5 catalysts, as well as in‐series layers of the two catalysts, are investigated to devise the widest temperature window for SCRoF. © 2016 American Institute of Chemical Engineers AIChE J, 63: 238–248, 2017     

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.     

负载型La-K-Cu-Mn-O催化剂同时去除颗粒物和NOx性能

通过在柴油机排放颗粒物过滤器上负载La_0.8K_0.2Cu_0.05Mn_0.95O₃复合金属氧化物催化剂并进行实际柴油机尾气挂烟,利用程序升温反应技术,对同时催化去除柴油机颗粒物和氮氧化物反应进行了实验研究。研究结果表明,空白载体上实际柴油机排放颗粒物燃烧生成的CO₂曲线呈双峰,分别对应于可溶性有机物和干碳烟的燃烧。负载型催化剂能有效降低可溶性有机物和干碳烟的燃烧温度,促进NO向N₂转化。与淤浆法相比,浸渍法负载的催化剂效果更好,浸渍法负载催化剂可以将起燃温度降至160 ℃,最高的NOx向N₂转化率达63.4%。     

Char- and Aerosol-associated Polycyclic Aromatic Compounds from Coal Pyrolysis: Relationship Between Particle Size and Surface Composition

In order to investigate the relationship between solid size and polycyclic aromatic compound (PAC) amount and composition, we have pyrolyzed 45–53-μm particles of a high-volatility bituminous coal at 1100–1500 K in a laminar flow, drop-tube furnace. Aerodynamically separated in a cascade impactor, three size cuts of the solid products have been collected for determination of PAC and solid carbon mass yields. We have also examined differences in PAC composition of the three size cuts by employing a liquid chromatographic technique that separates PAC according to their number of fused aromatic rings. Soot yields are found to increase with increasing temperature; char and PAC yields decrease. Yields of the most volatile PAC decay particularly rapidly with increasing temperature. For all pyrolysis conditions investigated, > 90% of the PAC is associated with the soot (the smaller two size cuts), but the proportion associated with the larger particles grows as the total amount of PAC lessens. For all experiments, the larger particles exhibit enrichment in the lighter species, and this enrichment becomes most pronounced when there is the least amount of PAC. The experimental results show qualitative consistency with a model of simultaneous coagulation and condensation. However, if the effective condensation diameter for the soot is the primary particle size, the amounts of PAC associated with the char, relative to those associated with the soot, are much larger than predictions from mass transfer-controlled condensation theory. Various secondary effects—surface curvature, particle terminal velocity, and volume fraction size dependency—help account for the direction of the observed trends but not their magnitude. The higher than predicted ratios of char-associated to soot-associated PAC suggest that the governing dimension for mass transfer to the soot is the agglomerate size.     

A Potential Soot Mass Determination Method from Resistivity Measurement of Thermophoretically Deposited Soot

Miniaturized detection systems for nanometer-sized airborne particles are in demand, for example in applications for onboard diagnostics downstream particulate filters in modern diesel engines. A soot sensor based on resistivity measurements was developed and characterized. This involved generation of soot particles using a quenched co-flow diffusion flame; depositing the particles onto a sensor substrate using thermophoresis and particle detection using a finger electrode structure, patterned on thermally oxidized silicon substrate. The generated soot particles were characterized using techniques including Scanning Mobility Particle Sizer for mobility size distributions, Differential Mobility Analyzer—Aerosol Particle Mass analyzer for the mass–mobility relationship, and Transmission Electron Microscopy for morphology. The generated particles were similar to particles from diesel engines in concentration, mobility size distribution, and mass fractal dimension. The primary particle size, effective density and organic mass fraction were slightly lower than values reported for diesel engines. The response measured with the sensors was largely dependent on particle mass concentration, but increased with increasing soot aggregate mobility size. Detection down to cumulative mass as small as 20–30 μg has been demonstrated. The detection limit can be improved by using a more sensitive resistance meter, modified deposition cell, larger flow rates of soot aerosol and modifying the sensor surface.     

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     

The Detection Efficiency of the Single Particle Soot Photometer

A single particle soot photometer (SP2) uses an intense laser to heat individual aerosol particles of refractory black carbon (rBC) to vaporization, causing them to emit detectable amounts of thermal radiation that are used to quantify rBC mass. This approach is well suited for the detection of the majority of rBC mass loading in the ambient atmosphere, which occurs primarily in the accumulation mode (～ 1–300 fg-rBC/particle). In addition to operator choices about instrument parameters, SP2 detection of rBC number and/or mass can be limited by the physical process inherent in the SP2 detection technique — namely at small rBC mass or low laser intensities, particles fail to heat to vaporization, a requirement for proper detection. In this study, the SP2's ability to correctly detect and count individual flame-generated soot particles was measured at different laser intensities for different rBC particle masses. The flame-generated soot aerosol used for testing was optionally prepared with coatings of organic and non-organic material and/or thermally denuded. These data are used to identify a minimum laser intensity for accurate detection at sea level of total rBC mass in the accumulation mode (300 nW/(220-nm PSL)), a minimum rBC mass (～ 0.7-fg rBC-mass corresponding to 90 nm volume-equivalent diameter) for near-unity number detection efficiency with a typical operating laser intensity (450 nW/(220-nm PSL)), and a methodology using observed color temperature to recognize laser intensity insufficient for accurate rBC mass detection. Additionally, methods for measurement of laser intensity using either laboratory or ambient aerosol are presented.     

A novel laboratory bench for practical evaluation of catalysts useful for simultaneous conversion of NOx and soot in diesel exhaust

This study deals with the development of a laboratory bench for the practical evaluation of catalysts that are useful for the direct conversion of NO_x and soot in the exhaust of diesel engines. The employed model exhaust is generated by using a diffusion burner with additionally dosing some gaseous components to the burner gas to obtain a realistic feed composition. The produced soot is extensively characterized by employing thermogravimetry, transmission electron microscopy, N₂ physisorption and temperature programmed techniques. The results of the different characterization methods show that the present soot is suitable for the intended catalytic investigations. The simultaneous conversion of NO_x and soot is examined like in practice, i.e. the soot is separated from the tail gas by a diesel particulate filter (DPF) that is coated with the catalyst. The deposited soot is then catalytically converted by NO_x and O₂ to form N₂ and CO₂. The conversions of NO_x and soot are measured by exclusively applying gas analysers, whereby a special experimental procedure is developed to determine the soot removal. Hence, additional soot related analytics are not required. To show the suitability of the constructed bench a Pt/Fe₂O₃/β-zeolite sample is taken as test catalyst that is reported to be very active in NO_x/soot reaction. The measurements performed with and without catalyst clearly show the effect of the used sample in simultaneous NO_x/soot conversion. We therefore consider the constructed laboratory bench to be a useful tool for testing and ranking catalytic materials.     

Influence analysis of monolith structure on regeneration temperature in the process of microwave regeneration in the diesel particulate filter

Based on models A, B, and C of three kinds of diesel particulate filter (DPF) with microwave regeneration, a DPF microwave regeneration model is established according to the laws of conservation of mass, momentum, and energy. The trends of internal temperature under different velocities of exhaust gas in channels are simulated and analyzed. The results show that: (1) Regeneration temperature in the process of microwave regeneration will begin to increase from the front to the rear end of along the axial direction, and the maximum temperature value will appear in the rear end of the monolith. (2) The internal flow velocity in the DPF of model C is the most uniform and the temperature gradient is the smallest among the three models. Therefore, it is the most useful for DPF regeneration. (3) The minimal thermal stress is exerted on the DPF of model C. Therefore, this model is most useful for prolonging the service life of a DPF.