Characterization of Particulate Matter from Direct Injected Gasoline Engines

The reactivity and reaction kinetics of particulate matter (PM) from direct injected gasoline (GDI) engines has been studied by O₂ and NO₂ based temperature programmed and isothermal step-response experiments, and the PM nano-structure has been characterized using HRTEM. The reactivity of the PM samples collected in filters during on-road driving was found to increase in the following order: Printex U < diesel < gasoline PI ≈ gasoline DI < ethanol for O₂ based combustion. The activation energies for O₂ and NO₂ based oxidation of PM collected from a GDI engine in an engine bench set-up was estimated to 146 and 71 kJ/mol respectively, which is comparable to corresponding values reported for diesel and model soot. Similar nano-structure features (crystallites plane dimensions, curvature and relative orientation) as observed for diesel soot were observed for gasoline PM.     

Performance of potassium-promoted catalysts for NO x and soot removal from simulated diesel exhaust

In order to elucidate the effect of support in the catalytic performance, two selected potassium-promoted catalysts (K1Cu/beta and KCu2/Al₂O₃) were tested for the simultaneous NO _x /soot removal from a simulated diesel exhaust. For comparative purpose, the behaviour of a platinum catalyst (Pt/beta) was also studied. Isothermal experiments revealed that the potassium-promoted catalysts show a high activity for NO _x /soot removal in the 350–450 °C temperature range. In addition, the catalysts present the advantage that the main reaction products are N₂ and CO₂. Among the catalysts tested, KCu2/Al₂O₃ presents the best global performance at 450 °C: the highest soot consumption rate, even higher than the platinum catalysts, and a high NO _x reduction.     

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.     

Highly Active La1−x K x CoO3 Perovskite-type Complex Oxide Catalysts for the Simultaneous Removal of Diesel Soot and Nitrogen Oxides Under Loose Contact Conditions

The nanometric La_1?x K _x CoO₃ (x = 0–0.30) perovskite-type oxides were prepared by a citric acid-ligated method. The catalysts were characterized by means of XRD, IR, BET, XPS and SEM. The catalytic activity for the simultaneous removal of soot and nitrogen oxides was evaluated by a technique of the temperature-programmed oxidation reaction. In the LaCoO₃ catalyst, the partial substitution of La³⁺ at A-site by alkali metal K⁺ enhanced the catalytic activity for the oxidation of soot particle and reduction of NO _x . The La_0.70K_0.30CoO₃ oxides are good candidate catalysts for the simultaneous removal of soot particle and NO _x . The combustion temperatures for soot particles over the La_0.70K_0.30CoO₃ catalyst are in the range from 289 to 461 °C, the selectivity of CO₂ is 98.4% and the conversion of NO to N₂ is 34.6% under loose contact conditions. The possible reasons that can lead to the activity enhancement for the K-substitution samples compared to the unsubstituted sample (LaCoO₃) were given. The particle size has a large effect on its catalytic performance for the simultaneous removal of diesel soot and nitrogen oxides.     

Application of NOX storage/release materials based on alkali-earth oxides supported on Al2O3 for high-temperature diesel soot oxidation

Alkali-earth oxides and nitrates supported on alumina were studied as model systems for NO_X storage/release. Their impact on the high-temperature soot oxidation has been investigated. The stability of surface nitrates and temperature of NO_X release increase parallel to the basicity of the cation. The presence of soot decreases the temperature of NO_X release. The storage capacity depends on the several factors, such as basicity, dispersion of the cation, and pre-treating conditions. Adsorption of NO with O₂ at 200 °C leads to the formation of surface nitrates that mainly exist as ionic nitrates. Stored nitrates contribute to the soot oxidation and assist to lower the temperature of soot oxidation up to almost 100 °C. In the presence of only NO_X storage material the efficiency of NO_X utilization is, however, quite low, around 30%. Therefore, the presence of an oxidation catalyst is essential to increase the efficiency of NO_X utilization for soot oxidation up to 140% and selectivity towards CO₂. A combination of oxidation catalyst with NO_X storage materials enables to lower the temperature of soot oxidation more than 100 °C for the Sr- and Ca-based systems.     

A highly efficient and porous catalyst for simultaneous removal of NOx and diesel soot

A highly efficient and porous catalyst (La_0.8K_0.2Cu_0.05Mn_0.95O₃) for simultaneous removal of nitrogen oxides (NOx) and diesel soot was synthesized and the sample was characterized by XRD, BET, SEM–EDS, XRF, and XPS. The results indicate that this catalyst is perovskite and it possesses the very good characteristics for multiphase catalytic reactions. The catalytic properties were appraised under simulated diesel engine exhaust by temperature programmed reaction (TPR). TPR results indicate that this catalyst is a promising candidate for simultaneous removal of NOx and diesel soot. The maximum NO conversion into N₂ and the ignition temperature of soot are 54.8% and 260 °C, respectively. Comparing with those in previous reports, the comprehensive performance of this catalyst is greatly improved by partial substitution of La with K and Mn with Cu at the same time.     

A Multifunctional Converter for Purifying Diesel Exhaust Gas with a Self-Heat Exchange Function

As a continuation of our study of heat-integrated converters, we have fabricated a multifunctional converter that can treat all the components of emissions from diesel vehicles, namely CO, hydrocarbons, nitrogen oxides (NO _x ), and particulate matter (PM). NO _x is reduced over a NH₃-SCR catalyst while PM is removed by a diesel particulate filter. The converter is also equipped with a self-heat exchanger that transfers heat from downstream to upstream of the converter, increasing the converter temperature and thereby substantially improving its performance. In an experiment using a 2.2-L engine vehicle operated at a constant speed of 60 km/h, the NO _x and PM reduction rates respectively reached 98 and 99.97 % due to efficient heating of the exhaust gas from 117 to 320 °C in the converter by the addition of H₂ in the exhaust gas combined with the self-heat exchange function. Under transient driving conditions (Japanese 10–15 mode), the total NO _x reduction rate was 96 %.     

Biodiesel engine performance and emissions in low temperature combustion

Engine performance and emission comparisons were made between the use of soy, Canola and yellow grease derived B100 biodiesel fuels and an ultra-low sulphur diesel fuel in the high load engine operating conditions. Compared to the diesel fuel engine-out emissions of nitrogen oxides (NO_x), a high-cetane number (CN) biodiesel fuel produced comparable NO_x while the biodiesel with a CN similar to the diesel fuel produced relatively higher NO_x at a fixed start of injection. The soot, carbon monoxide and un-burnt hydrocarbon emissions were generally lower for the biodiesel-fuelled engine. Exhaust gas recirculation (EGR) was then extensively applied to initiate low temperature combustion (LTC) mode at medium and low load conditions. An intake throttling valve was implemented to increase the differential pressure between the intake and exhaust in order to increase and enhance the EGR. Simultaneous reduction of NO_x and soot was achieved when the ignition delay was prolonged by more than 50% from the case with 0% EGR at low load conditions. Furthermore, a preliminary ignition delay correlation under the influence of EGR at steady-state conditions was developed. The correlation considered the fuel CN and oxygen concentrations in the intake air and fuel. The research intends to achieve simultaneous reductions of NO_x and soot emissions in modern production diesel engines when biodiesel is applied.     

Influence of the Alkali Promoter on the Activity and Stability of Transition Metal (Cu, Co, Fe) Based Structured Catalysts for the Simultaneous Removal of Soot and NOx

Structured catalysts prepared by means of coating cordierite monoliths with alumina-based suspensions containing transition metals such as Cu, Co and Fe and alkali/alkali-earth promoters such as K and Ba. Textural and structural features of these catalysts were analyzed by means of N₂ adsorption and SEM. Their activity in the simultaneous removal of soot and NO_x was assayed in a lab-scale installation, using a carbon black as diesel surrogate. Catalysts exhibited significant activity in deNO_x and soot oxidation. K and Ba enhanced both NO_x adsorption and soot–catalyst contact. However Ba contributed to a greater extent to the adsorption of N-species, which moreover presented higher thermal stability than on K-catalysts, and K showed higher mobility than Ba. Thus, Ba-containing catalysts showed increased activity towards NO_x reduction but shifted to higher temperatures in comparison to K-catalysts, which on the other hand resulted more active towards soot oxidation than Ba-ones. Fe-based catalyst turned out to be less active both in soot oxidation and NO_x reduction than Co and Cu-based ones. Intensive calcination of the catalysts at 800 °C for 5 h resulted in substantial loss of K and Ba. Loss of promoter depends, however, on the metal contained in the catalyst. In this sense Fe-containing catalysts showed higher stability. Calcination has a substantial effect on catalytic activity. Catalyst significantly lost their NO_x adsorption capacity and showed similar activity than a catalyst prepared in absence of promoter, pointing to a substantial change in reaction mechanism and reaction predominantly occurring on metallic sites upon the loss of alkali/alkali-earth compound.     

Chemical composition of diesel particulate matter and its control

In this review, we have systematically discussed diesel particulate composition and its formation, understanding of which is essential to design the effective catalyst compositions. The most commonly used after treatment strategies such as diesel oxidation catalysts, diesel particulate filters, and partial flow filters are described followed by chronological and category-wise discussions on various groups of reported soot oxidation catalysts. A detailed review is also presented on mechanistic and kinetics aspects of non-catalytic direct particulate matter (PM) or soot oxidation in air/O₂ and NO₂. Recent progress in catalyst development with a focus on the low-cost catalyst for diesel PM oxidation has been given more emphasis considering their renewed importance.     

NO2-aided Soot Oxidation on LaMn0.7Ni0.3O3 Perovkite-type Catalyst

The LaMnO₃-based perovskite-type mixed oxides were studied for both trapping of NO _x and combustion of diesel soot. The LaMn_0.7Ni_0.3O₃ (LMN3) perovskite shows high NO _x adsorption capacity, quick adsorption rate and efficient adsorbed species. After the catalyst interacts with NO at low temperature around 325 °C, decomposition of the nitrates leads to the decrease of the maximum soot oxidation temperature to 430 °C. The fine crystallite size, increased surface area and readily reducibility at low temperature also favor the oxidation of soot over LMN3 under loose contact conditions.     

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.     

Katalysatoren für den Umweltschutz

Catalysts for environmental protection. The main emitters of anthropogenic air pollution are internal combustion engines, power plants, and production processes. Components of exhaust gases which are regarded as pollutants are hydrocarbons (HC), carbon monoxide (CO), nitrogen oxides (NO_x), sulfur dioxide (SO₂), and dust. Three main types of catalyst are understood to improve the environment; namely automotive emission control, NO_x abatement and oxidation. To reduce the pollutants HC, CO, and NO_x in automobile exhaust gas, three-way catalysts are currently applied. The reduction of particle emissions in diesel exhaust gas is achieved by diesel filters and oxidation catalysts. Pollutants from power plants are mainly the inorganic components NO_x and SO₂. In the SCR process, NO_x is catalytically reduced to nitrogen and water. The DESONOX process is suited for the simultaneous catalytic abatement of NO_x and SO_x. Exhaust gases from production processes in many areas require after-treatment. Therefore catalyst formulations depend on process parameters and exhaust gas components. This overview presents and explains catalyst types, design, mode of operation, and processes.     

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.     

Reduction of lean NO2 with diesel soot over metal-exchanged ZSM5, perovskite and γ-alumina catalysts

The catalytic performances of metal-exchanged ZSM5, perovskite and γ-alumina catalysts for the reduction of nitrogen dioxide (NO₂) by diesel soot were investigated. The reaction tests were performed through temperature-programmed reaction (TPR), in which NO₂ and O₂ were passed through a fixed bed of catalyst-soot mixture. On the three types of catalyst, NO₂ was reduced to N₂ by model soot (Printex-U) and most of the soot was converted into CO₂. Pt-, Cu- and Co-exchanged ZSM5 catalysts exhibited reduction activities with conversions of NO₂ into N₂ of about 20%. Among the perovskite catalysts tested, La_0.9K_0.1FeO₃ showed a 32% conversion of NO₂ into N₂. The catalytic activities of the perovskite catalysts were largely influenced by the number and stability of oxygen vacancies. For the γ-alumina catalyst, the peak reduction activity appeared at a relatively high temperature of around 500 °C, but the NO₂ reduction was more effective than the NO reduction, in contrast to the results of the ZSM-5 and perovskite catalysts.     

Thermal ageing phenomena and strategies towards reactivation of NO x - storage catalysts

The thermal ageing and reactivation of Ba/CeO₂ and Ba/Al₂O₃ based NO _x -storage/ reduction (NSR) catalysts was studied on model catalysts and catalyst systems at the engine. The mixed oxides BaAl₂O₄ and BaCeO₃, which lower the storage activity, are formed during ageing above 850 °C and 900 °C, respectively. Interestingly, the decomposition of BaCeO₃ in an atmosphere containing H₂O/NO₂ leads again to NO _x -storage active species, as evidenced by comparison of fresh, aged and reactivated Pt-Ba/CeO₂ based model catalysts. This can be technically exploited, particularly for the Ba/CeO₂ catalysts, as reactivation studies on thermally aged Ba/CeO₂ and Ba/Al₂O₃ based NSR catalysts on an engine bench showed. An on-board reactivation procedure is presented, that improved the performance of a thermally aged catalyst significantly.     

Experimental study of n-butanol additive and multi-injection on HD diesel engine performance and emissions

Experimental study was conducted to investigate the influence of the diesel fuel n-butanol content on the performance and emissions of a heavy duty direct injection diesel engine with multi-injection capability. At fixed engine speed and load, exhaust gas recirculation rates were adjusted to keep NO_x emission at 2.0 g/kW h. Diesel fuels with different amounts (0%, 5%, 10% and 15% by volume) of n-butanol were used. The results show that the n-butanol addition can significantly improve soot and CO emissions at constant specific NO_x emission without a serious impact on the break specific fuel consumption and NO_x. The impacts of pilot and post injection on engine characteristics by using blended fuels are similar to that found by using pure diesel. Early pilot injection reduces soot emission, but results in a dramatic increase of CO. Post injection reduces soot and CO emissions effectively. Under each injection strategy, the increase of fuel n-butanol content leads to further reduction of soot. A triple-injection strategy with the highest n-butanol fraction used in this study offers the lowest soot emission.     

Comparison of emissions of a direct injection diesel engine operating on biodiesel with emulsified and fumigated methanol

Biodiesel is an alternative fuel for internal combustion engines. It can reduce carbon monoxide (CO), hydrocarbon (HC) and particulate matter (PM) emissions, compared with diesel fuel, but there is also an increase in nitrogen oxides (NO_x) emission. This study is aimed to compare the effect of applying a biodiesel with either 10% blended methanol or 10% fumigation methanol. The biodiesel used in this study was converted from waste cooking oil. Experiments were performed on a 4-cylinder naturally aspirated direct injection diesel engine operating at a constant speed of 1800 rev/min with five different engine loads. The results indicate a reduction of CO₂, NO_x, and particulate mass emissions and a reduction in mean particle diameter, in both cases, compared with diesel fuel. It is of interest to compare the two modes of fueling with methanol in combination with biodiesel. For the blended mode, there is a slightly higher brake thermal efficiency at low engine load while the fumigation mode gives slightly higher brake thermal efficiency at medium and high engine loads. In the fumigation mode, an extra fuel injection control system is required, and there is also an increase in CO, HC and NO₂ (nitrogen dioxide) and particulate emissions in the engine exhaust, which are disadvantages compared with the blended mode.     

Simultaneous catalytic removal of NOx and soot particulate over Co–Al mixed oxide catalysts derived from hydrotalcites

Co–Al mixed oxides (CAO) was prepared by co-precipitation method from hydrotalcites (HT) as precursors, and their catalytic activity was investigated for the simultaneously catalytic removal of NO_x and diesel soot particulates by the temperature-programmed reaction (TPR) technique. All HT samples present well crystallized, layered structures, no excess phases were detected. A nonstoichiometric spinel phase was formed by calcining the CAO at 500 °C and 800 °C, irrespective of the Co/Al ratio. Both the activity of soot oxidation and the selectivity to N₂ formation of CAO catalysts calcined at 800 °C were higher than that at 500 °C. The observed difference in the catalytic performance was related to the redox properties of the catalysts and the crystallite size of HT precursors. The active species might come from Co₃O₄, which acted for redox-type mechanism for soot oxidation in the NO_x-soot reaction.