The impact of carbon dioxide and exhaust gas recirculation on the oxidative reactivity of soot from ethylene flames and diesel engines .

摘要

Restrictive emissions standards to reduce nitrogen oxides (NOx) and particulate matter (PM) emissions from diesel engines necessitate the development of advanced emission control technology. The engine manufacturers in the United States have implemented the exhaust gas recirculation (EGR) and diesel particulate filters (DPF) to meet the stringent emissions limits on NOx and PM, respectively. Although the EGR-DPF system is an effective means to control diesel engine emissions, there are some concerns associated with its implementation. The chief concern with this system is the DPF regenerability, which depends upon several factors, among which are the physicochemical properties of the soot. Despite the plethora of research that has been conducted on DPF regenerability, the impact of EGR on soot reactivity and DPF regenerability is yet to be examined. This work concerns the impact of EGR on the oxidative reactivity of diesel soot. It is part of ongoing research to bridge the gap in establishing a relationship between soot formation conditions, properties, and reactivity.;The second phase of this research was motivated by the findings from the first phase. In this phase, post-flame ethylene soot was produced from a laboratory co-flow laminar diffusion flame to better understand the mechanism by which the CO2 affects soot reactivity. This phase was accomplished by successfully isolating the dilution, thermal, and chemical effects of the CO2. The results showed that all of these effects account for a measurable increase in soot reactivity. Nevertheless, the thermal effect was found to be the most important factor governing the soot reactivity.;In the third phase of this research, diesel soot was generated under 0 and 20% EGR using a four-cylinder, four-stroke, turbocharged common rail direct injection (DI) DDC diesel engine. The objective of this work was to examine the relevance of the single cylinder engine and flame studies to practical engine operation. The key engine parameters such as load, speed, and injection timing were kept constant to isolate the EGR effect on soot properties from any other engine effects.;The thermokinetic analyses of the flame soot and engine soot showed a significant increase in soot oxidation rate as a result of the CO2 or EGR inclusion into the combustion process. The activation energy of soot oxidation was found to be independent of soot origin or formation history. The increase in soot oxidation rate is attributed solely to the increase in soot active sites, which are presented implicitly in the pre-exponential factor (A) of the oxidation rate equation. This latter statement was confirmed by measuring the initial active site area (ASA i) of all soot samples considered in this study. As expected, higher oxidation rates are associated with higher ASAi.;This work is divided into three phases. In the first phase, carbon dioxide (CO2) was added to the intake charge of a single cylinder engine via cylinders of compressed CO2. This approach simulates the cold-particle-free EGR. The results showed that inclusion of CO2 changes the soot properties and yields synergistic effects on the oxidative reactivity of the resulting soot.;The chemical properties of the soot were investigated to determine their effects upon soot reactivity. The results showed that the H/C and O/C ratios were not modified by CO2 or EGR addition. Therefore, these ratios are not reactivity parameters and their effects upon soot reactivity were ruled out. In distinct contrast, the physical properties of the soot were modified by the addition of CO2 or EGR. The interlayer spacing (d002) between the aromatic sheets increased, the crystallite width (La) decreased and the crystallite height (Lc) decreased as a consequence of CO 2 or EGR addition. The modified physical properties of the soot are responsible for the increased rate of soot oxidation.;In order to examine the soot oxidation behavior in the DPF, the soot samples produced from the DDC engine under 0 and 20% EGR were partially oxidized in a thermogravimetric analyzer (TGA) to specific conversion levels. Unreacted and partially oxidized soot samples were then subjected to comprehensive characterization. The Raman spectroscopy showed that the disordered fraction of the soot (ID/IG) decreases with the oxidation progression. Electron energy loss spectroscopy (EELS) results showed an increase in the (I pi/Isigma) for soot generated under 0% EGR but no significant increase in this ratio was observed for the soot generated under 20% EGR. These results indicate that soot generated without EGR is likely to be more highly ordered in its nanostructure.;Visual inspection of the unreacted and partially oxidized soot (produced under 0 and 20% EGR) was obtained by the use of high resolution transmission electron microscopy (HRTEM). The results suggested that the initial nanostructure of the soot primary particles is the same for soot produced under 0 and 20% EGR. However, soot produced under 0% EGR condition exhibits strictly external burning (i.e., from the outside in). On the other hand, soot generated under 20% EGR possesses dual burning modes, that is, slow external burning and fast internal burning. This internal burning of the 20% EGR soot clarifies the importance of the burning modes upon soot reactivity. This study confirmed that EGR exerted a strong influence on the diesel soot physical properties. Consistent with the flame study, a separate engine study confirmed that the most important factors to enhance the soot reactivity are the thermal effect of the EGR followed by the dilution effect.