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The use of vanadia selective catalytic reduction (V-SCR) catalysts for NOX reduction from diesel engine exhaust is well known. These catalysts are also active for hydrocarbon (HC) and particulate matter (PM) oxidation. This dual functionality (oxidation and reduction) of V-SCR catalysts can help certain applications achieve the legislative limits with an improved margin. In this work, NOX reduction, HC and CO oxidation over V-SCR were studied independently and simultaneously in microreactor tests. The effect of various parameters (HC speciation, concentration, ANR, and NO₂/NOX ratio) was investigated and the data was used to develop a kinetic model. Oxidation of CO, C₃H₆, and n-C₁₀H₂₂ is first order in CO/HC, while C₇H₈ oxidation is less than first order in C₇H₈. All these reactions were zero order in O₂. Oxidation activity decreased in order: C₇H₈ ≻ n-C₁₀H₂₂ ≻ C₃H₆ ≻ CO. HC oxidation was inhibited by NH₃.

A one-dimensional model of a NOx trap system was developed to describe NOx storage during the lean operation, and NOx release and subsequent reduction during the rich regeneration process. The development of a NOx trap model potentially enables the optimisation of catalyst volume, precious metal loading, substrate type and regeneration strategy for these complex systems. To develop a fundamental description of catalytic activity, experiments were conducted to investigate the key processes involved in isolation (as far as possible), using a Pt/Rh/BaO/Al2O3 model catalyst. A description of the storage capacity as a function of temperature was determined using NOx breakthrough curves and the storage portion of more dynamic lean-rich cycling experiments. NOx breakthrough curves were also used for determination of rate of NOx storage. Kinetics for NOx reduction, as well as CO and HC oxidation, were determined using steady state reactor experiments.

Two approaches were adopted to study soot oxidation by NO₂; firstly microreactor tests were performed on soot produced by a soot generator over a range of NO₂ concentrations and temperatures. This enabled measurement to be made under well-controlled conditions. Secondly, soot oxidation measurements were made on an engine bench to obtain data under more realistic, if less controlled, conditions. In the microreactor work NO₂ consumption by soot oxidation and the selectivity of the soot oxidation to CO and CO₂ were measured. The latter was found to vary only slightly with temperature and to be independent of NO₂ concentration. By modeling this data using a 1-dimensional model, rate equations for the soot-NO₂ reaction were determined. These were then tested against the engine data. The soot used in this study was characterized by thermogravimetric analysis, N₂ physisorption and transmission electron microscopy.

The hydrocarbon-SCR activity of a silver catalyst has been examined using actual exhaust gas from a diesel engine, without any fuel being added to the reactor inlet. This work is a further step in the development of an active lean-NOx catalyst for aftertreatment of exhaust streams that contain an excess of hydrocarbon relative to NOx. The engine tests follow on from laboratory studies, in which the activity was related to the composition and formulation of the catalyst, the concentration and speciation of the hydrocarbon reductants, and the composition and temperature of simulated exhaust gas. In all the tests described here, the exhaust gas has been provided by an engine operating on ultra-low sulphur diesel fuel. NOx-reduction has been measured as a function of engine load, engine speed, in-cylinder fuel injection timing, exhaust gas temperature, and exhaust gas recirculation. Over 60% conversion to N2 has been achieved at exhaust gas temperatures around 290°C.

A prototype catalyst has been developed and integrated within the aftertreatment exhaust system to control the HC, CO, PM and NOx emissions from diesel exhaust gas. The catalyst activity in removing HC and nano-particles was examined with exhaust gas from a diesel engine operating on biodiesel - Rapeseed Methyl Ester (RME). The tests were carried out at steady-state conditions for short periods of time, thus catalyst tolerance to sulphur was not examined. The prototype catalyst reduced the amount of hydrocarbons (HC) and the total PM. The quantity of particulate with electrical mobility diameter in nucleation mode size < 10nm, was significantly reduced over the catalyst. Moreover, it was observed that the use of EGR (20% vol.) for the biodiesel fuelled engine significantly increases the particle concentration in the accumulation mode with simultaneous reduction in the particle concentration in the nuclei mode.

Limits on the total future potential of biodiesel fuel due to the availability of raw materials mean that ambitious 20% fuel replacement targets will need to be met by the use of both first and next generation biodiesel fuels. The use of higher percentage biodiesel blends requires engine recalibration, as it affects engine performance, combustion patterns and emissions. Previous work has shown that the combustion of 50:50 blends of biodiesel fuels (first generation RME and next generation synthetic fuel) can give diesel fuel-like performance (i.e. in-cylinder pressure, fuel injection and heat release patterns). This means engine recalibration can be avoided, plus a reduction in all the regulated emissions. Using a 30% biodiesel blend (with different first and next generation proportions) mixed with Diesel may be a more realistic future fuel.

The aftertreatment challenge in the non-road market is making the same system work and fit not just in one machine, but in hundreds of different machines, some of which can be used for many different purposes. This huge diversity of applications and the relatively small unit numbers for each application, coupled with the rapid introduction of new standards and the very high performance needed from the engines and machines, requires a sophisticated approach to product development. Furthermore, as emissions requirements become ever more stringent, designing a system to meet the legislation subject to packaging and cost constraints becomes progressively more difficult. This is further exacerbated by increasing system complexity, where more than one technology may be required to control all the legislated pollutants and/or an active control strategy is involved. Also a very high degree of component integration is required.

A 1-D numerical model describing the ammonia selective catalytic reduction (SCR) de-NOx process has been developed based on data measured on a laboratory microreactor for a vanadia-titania washcoated catalyst system. Kinetics for various NH3-NOx reactions were investigated, as well as those for ammonia, CO and hydrocarbon oxidation. The model has been successfully validated against engine bench measurements, over light-off and ESC tests, under a wide range of conditions, e.g. flow rate, temperature, NO2/NO ratio, and ammonia injection rate. A very good agreement between the experimental data and the model has been achieved. The model has now been used to predict the effect of NO2/NO ratio on NOx conversion, and the effect of different ammonia injection rates on the efficiency of the SCR process.

A one-dimensional numerical model for a Cu-zeolite SCR catalyst has been developed. The model is based on kinetics developed from laboratory microreactor data for the various NH₃-NOX reactions, as well as for NH₃ oxidation. The kinetic scheme used is discussed and evidence for it presented. The model is capable of predicting the conversion of NO and NO₂, NH₃ slip and the formation of N₂O, as well as effects associated with NH₃ storage and desorption. To obtain a good prediction of catalyst temperature during cold start tests, it was found necessary to include storage and desorption of H₂O in the model; storage of H₂O is associated with a sizable exotherm and the subsequent desorption of this water produces a correspondingly large endotherm.

In recent years, ammonia slip catalysts (ASC) are being used downstream of an SCR system to minimize the ammonia slip. The dual-layer ASC is more attractive for its bi-functionality in reducing the ammonia and NOX emissions. It consists of two layers with the upper layer comprising a component with SCR functionality and the lower layer a PGM containing catalyst with oxidation functionality. Thus, both oxidation and SCR reactions take place in two different layers and are interlinked by the inter-layer mass transfer mechanism. In addition, adsorption and desorption kinetics between the gas and solid phases play a significant role. Mathematically, the overall system is a complex system of mass, momentum and energy transfer equations with temporal and spatial variables in both axial and radial directions. In this work, we focus on devising a suitable, computationally inexpensive model for such ASCs to be efficiently used for design, control and system optimization studies.

Diesel emissions legislation continues to tighten around the world, and Particulate Matter (PM) emissions are currently the focus of much attention. Diesel PM can be controlled using Diesel Particulate Filters (DPFs), which can effectively reduce the level of carbon (soot) emissions to ambient background levels. In the Heavy Duty Diesel (HDD) area, the Continuously Regenerating Trap (CRT®) [1] has been widely applied in the retrofit market. This system will henceforth be referred to as the Continuously Regenerating DPF (CR-DPF). There are currently over 100,000 of these systems in use in retrofit applications worldwide. This system comprises a specially formulated Diesel Oxidation Catalyst (DOC) upstream of a DPF; the NO2 generated by the DOC is used to combust the carbon collected in the DPF at low temperatures. A model describing the performance of the CR-DPF has been developed.

Selective Catalytic Reduction (SCR) technology has been widely studied for removal of NOX from the exhaust of diesel engines. To design and optimize diesel engine aftertreatment systems including an SCR catalyst component, a reliable SCR model is a very useful tool, to aid in system integration and control algorithm testing. In this paper, the development of a one-dimensional numerical model for a Fe-Zeolite-based SCR catalyst (hydrothermally aged for 100 hours at 650°C in 10% H₂O in air) is presented, followed by its validation and application. The resulting model is capable of predicting NOX reduction efficiency under various operating conditions as a function of gas hourly space velocity (SV), temperature, NO₂/NOX ratio and NH₃ to NOX (ANR) ratios; NH₃ slip and N₂O formation are also correctly predicted by the model. Extensive validation of the model has been carried out against engine test data for both steady state light-off and the heavy-duty FTP transient cycle (HD-FTP).

Microreactor, engine bench tests and modelling studies have been carried out to understand the influence of cold start (low temperatures) on the performance of NH3/urea-SCR automotive exhaust aftertreatment systems. Water storage experiments using Simultaneous Thermal Analysis (STA) coupled with numerical modelling demonstrated that the exo/endo-therms associated with water adsorption and desorption at temperatures below 150°C strongly influence the catalyst temperature. Appreciable amounts of NO and NO2 could be stored on the catalyst during reactor or engine testing in the absence of any NH3 (blank tests). Modelling studies at different inlet NO2/NOx ratios demonstrated some of the influences of these surface adsorbed species on the performance of the SCR system during cold start.