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.     

Simultaneous abatement of diesel soot and NOX emissions by effective catalysts at low temperature: An overview

The diesel engine generally achieves the highest fuel, energy, and thermal efficiency due to its very high compression/expansion ratio (14:1 to 25:1). Diesel engines can have a thermal efficiency that exceeds 50%. The main problem is that they emit more pollution like fine black soot particulates (C₈H to C₁₀H) and nitrogen oxides (NO_X). These pollutants have been causing serious problems for human health and the global environment and also impacts on the engine. There are many types of catalysts investigated for simultaneous control of these two pollutants, i.e., platinum group metals (PGM; Pt, Pd, Rh, and Ir) based, spinel-type oxides, hydrotalcite, rare earth metal oxides, mixed transient metal oxides, etc. The high raw material cost of PGM catalysts has become a significant issue, so developing non-PGM catalysts are one of the promising challenges. There are no extra reductants required because soot catalytically oxidizes itself in the presence of NO_X at a faster rate than molecular oxygen and simultaneously NO_X is reduced to nitrogen. The order of oxidation potential of NO_X to oxidized soot in comparison to molecular oxygen is as follows: NO₂ > NO > O₂. To meet the very strict EPA US 2010 and Euro VI regulations of particulate matter (PM) and NO_X for heavy-duty and light-duty vehicular stringent emission, it is very important to apply the integrated catalytic systems to significantly remove PM and NO_X simultaneously. Many papers related to simultaneous control of soot and NO_X over different catalysts have been published but till now some of effective catalysts showing high conversion at low temperatures (possibly within the range typical of diesel exhaust: 150–450°C) have not been reviewed. Thus, this article provides a summary of published information regarding the effective catalysts, their preparation methods, properties, and application for simultaneous control of diesel soot and NO_X.     

Low Cost, Ceria Promoted Perovskite Type Catalysts for Diesel Soot Oxidation

Perovskite type catalysts with SrCoO₃ and Sr_0.8Ce_0.2CoO₃ compositions have been prepared by co-precipitation and other methods and, their catalytic activity towards diesel particulate matter (PM)/carbon oxidation has been evaluated under the loose contact condition. These catalysts show excellent catalytic activity for PM/carbon oxidation, despite their low surface area and under the loose contact condition. The synergistic effects of Ce incorporation in perovskite and presence of a small amount of potassium appears to be responsible for the high soot oxidation activity of these perovskite type materials. The Ce incorporation seems to be contributing by enhancing the redox property of the catalyst, while it appears unlikely that potassium is contributing by improving the catalyst–soot contact through its volatization. The catalysts show excellent thermal stability and stable activity under repeated cycles of use.     

A Novel α-Al2O3 Diesel Particulate Filter with Alkali Metal-Based Catalyst for Diesel Soot Oxidation

A diesel particulate filter (DPF) substrate was fabricated from alkali-resistant α-Al₂O₃ to make a practical use of alkali metal catalysts for diesel soot oxidation. The fundamental properties of the α-Al₂O₃-DPF, including its particle filtration efficiency, pressure drop, and thermal durability were comparable to those of the conventional DPFs. The diesel soot oxidation activity of the catalyzed α-Al₂O₃-DPF with a washcoat of alkali metal-based catalyst was, even after thermal aging, much higher than that of the conventional catalyzed-DPF with platinum group metal catalysts.     

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.     

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.     

Co3O4–CeO2 mixed oxide-based catalytic materials for diesel soot oxidation

Co₃O₄–CeO₂ type mixed oxide catalyst compositions have been prepared by using co-precipitation method and, their catalytic activity towards diesel particulate matter (PM)/carbon oxidation has been evaluated under both loose and tight contact conditions. These catalysts show excellent catalytic activity for PM/carbon oxidation, despite their low surface area. The activation energy observed for non-catalyzed and catalyzed reactions are 163 kJ/mol and 140 kJ/mol, respectively, which also confirm the catalytic activity of catalyst for carbon/soot oxidation. The promotional effects of an optimum amount of cobalt oxide incorporation in ceria and presence of a small amount of potassium appears to be responsible for the excellent soot oxidation activity of this mixed oxide type material. The catalytic materials show good thermal stability, while their low cost will also add to their potential for practical applications.     

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.     

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%。     

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.     

High-throughput approach to the catalytic combustion of diesel soot

A methodology for the evaluation of diesel soot oxidation catalysts by high-throughput (HT) screening was developed. The optimal experimental conditions (soot amount, catalyst/soot ratio, type of contact, composition and flow rate of gas reactants) ensuring a reliable and reproducible detection of light-off temperatures in a 16 parallel channels reactor were set up. The temperature profile measured in the catalyst/soot bed under TPO conditions when the exothermic combustion of soot takes place was shown to provide an accurate measurement of the ignition. Its reproducibility and relevance were checked. The results obtained with a reference noble metal free catalyst (La_0.8Cr_0.8Li_0.2O₃ perovskite) agree very well with literature data. Qualitative mechanistic features could be derived from these experiments, stressing the likely limiting step of oxygen transfer from catalyst surface to soot particulates to ignite the soot combustion. Ceria material was shown to be more appropriate than perovskite one. From an HT screening of a large diverse library (over 100 mixed oxides catalysts) under optimized conditions, about 10 new formulations were found to perform better than selected noble metal free reference materials.     

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.

     

同时消除柴油机尾气排放炭颗粒和NOx催化剂的研究进展

介绍了简单氧化物、复合氧化物(尖晶石和钙钛矿)催化剂都具有同时消除柴油机尾气中的炭颗粒和NO的活性．但是炭颗粒的起燃温度较高,生成N2的选择性差。在消除炭颗粒和氮氧化物时,有N2O生成,造成二次污染,炭颗粒与催化剂的接触形式直接影响炭颗粒的燃烧温度。     

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     

Study of perovskite‐type oxides and their supported Ag derivatives for catalytic oxidation of diesel soot

A series of perovskite‐type oxides and derived Ag catalysts were prepared, and characterized by N₂‐adsorption, X‐ray diffraction and X‐ray photoelectron spectroscopy. The influences of pretreatment and Ag loading on catalytic activity for diesel soot oxidation were also investigated. Prereduction resulted in a decrease in catalytic activity. An increase in activity with Ag addition was observed, especially with more than 5% Ag loading. This catalyst could be a promising candidate for the catalytic elimination of diesel soot. © 2002 Society of Chemical Industry     

Effect of Ag, Cu, and Au Incorporation on the Diesel Soot Oxidation Behavior of SiO2: Role of Metallic Ag

The catalytic behaviors of Ag, Cu, and Au loaded fumed SiO₂ have been investigated for diesel soot oxidation. The diesel soot generated by burning pure Mexican diesel in laboratory was oxidized under air flow in presence of catalyst inside a tubular quartz reactor in between 25 and 600 °C. UV–Vis optical spectroscopy was utilized to study the electronic states of Ag, Cu, and Au(M) in M/SiO₂ catalysts. The soot oxidation was seen to be strongly enhanced by the presence of metallic silver on 3 % Ag/SiO₂ surface, probably due to the formation of atomic oxygen species during the soot oxidation process. The catalyst is very stable due to the stability of Ag⁰ species on the catalyst surface and high thermal stability of SiO₂. Obtained results reveal that though the freshly prepared 3 % Cu/SiO₂ is active for soot oxidation, it gets deactivated at high temperatures in oxidizing conditions. On the other hand, 3 % Au/SiO₂ catalyst does not present activity for diesel soot oxidation in the conventional soot oxidation temperature range. The catalytic behaviors of the supported catalyst samples have been explained considering the electron donating ability of the metals to generate atomic oxygen species at their surface.     

柴油车排气碳微粒催化燃烧研究新进展

主要介绍了国内外柴油车排气碳微粒催化燃烧的研究现状和最新进展,重点分析了贵金属、金属氧化物、金属氧化物碱金属复合型以及过渡金属复合型催化剂在去除柴油车排气中碳微粒中的特点、存在问题以及在实际中的应用,指出未来柴油车排气后处理的发展趋势是同时去除CO、HC、NOx和微粒的四元催化剂。     

Simultaneous removal of NO and carbon particulates over lanthanoid perovskite-type catalysts

The simultaneous removal of carbon particulate and NO_x has been studied over perovskite-type oxides prepared by malic acid method. The catalysts were modified to enhance the activity by substitution of metal into A- or B-site of perovskite oxide. In the LaCoO₃ catalyst, the partial substitution of Cs into A-site enhanced the catalytic activity in the combustion of soot particulate and NO reduction. In La_1−xCs_xCoO₃ catalysts, the ignition temperature of carbon particulate decreases with increasing x values and shows almost constant values at substitution of x>0.2 and NO conversion also shows the similar tendency. In the Cs-substituted oxide, the ignition temperature of carbon particulate slightly decreased in the order Co>Mn>Fe of B-site metal cation but NO conversion showed almost similar values. With increasing NO concentration, NO conversion decreased but the ignition temperature moved to high temperature when the NO concentration was higher than 1000 ppm. The carbon particulate played an important role on the reduction of NO, but NO had little effect on the oxidation of carbon particulate.     

Development of Mn-based perovskite materials: Chemical structure and applications

In this article, we summarize current progress on the bulk and surface characteristics of Mn-containing perovskite oxides known for their good catalytic activity in atmospheric pollutant abatement. These materials are emphasized as serious alternatives for noble metal-based catalysts (Pt, Rh, Pd) in many catalytic applications particularly in automotive exhaust catalytic converters, mainly due to their low cost, good thermal stability at high temperature and ease of preparation compared to supported noble metal catalysts. The success of such materials is mainly related to Mn³⁺ and Mn⁴⁺ mixed valence and the resulted point defects formed after incorporation of a large variety of metals with different size and charge in the perovskite structure. These parameters could also affect the Mn reducibility and oxygen species mobility considered as one of the most determining factors in catalytic activity. The effect of perovskite metallic composition on the surface Mn oxidation state and relative cations segregation as well as applications of Mn-containing perovskite oxides as catalysts for several deep oxidation reactions at low and high temperatures are presented. Particular attention is devoted to the solution combustion synthesis for Mn-containing perovskite catalysts due to its time and energy saving characteristics and high surface areas of the obtained products. These advantages open new attractive opportunities for the use of this economic process to prepare supported perovskite oxide catalysts with the aim to better control morphology and stability of both surface catalyst and supports.     

Sn催化剂对柴油车排气颗粒去除效果

制备了以Sn为活性组分,以Cu、K、V为助催化剂,以TiO₂/γ-Al₂O₃/堇青石为载体的催化剂,催化剂在700℃下于空气中在马弗炉活化3h.采用DSC/TG测试方法确定催化剂的活性.研究发现,以Sn为活性组分的催化剂能显著降低颗粒的起燃温度和扩大燃烧温度范围,Cu、 K、V的添加能进一步降低起燃温度,而燃烧温度范围却稍有所变窄.活化会降低催化活性,活化导致活性下降的原因不是由催化剂的烧结引起的,而是由活性组分的挥发流失造成的.