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First Online Measurements of Sulfuric Acid Gas in Modern Heavy-Duty Diesel Engine Exhaust: Implications for Nanoparticle Formation

To mitigate the diesel particle pollution problem, diesel vehicles are fitted with modern exhaust after-treatment systems (ATS), which efficiently remove engine-generated primary particles (soot and ash) and gaseous hydrocarbons. Unfortunately, ATS can promote formation of low-vapor-pressure gases, which may undergo nucleation and condensation leading to formation of nucleation particles (NUP). The chemical nature and formation mechanism of these particles are only poorly explored. Using a novel mass spectrometric method, online measurements of low-vapor-pressure gases were performed for exhaust of a modern heavy-duty diesel engine operated with modern ATS and combusting low and ultralow sulfur fuels and also biofuel. It was observed that the gaseous sulfuric acid (GSA) concentration varied strongly, although engine operation was stable. However, the exhaust GSA was observed to be affected by fuel sulfur level, exhaust after-treatment, and driving conditions. Significant GSA concentrations were measured also when biofuel was used, indicating that GSA can be originated also from lubricant oil sulfur. Furthermore, accompanying NUP measurements and NUP model simulations were performed. We found that the exhaust GSA promotes NUP formation, but also organic (acidic) precursor gases can have a role. The model results indicate that that the measured GSA concentration alone is not high enough to grow the particles to the detected sizes.

Effect of open channel filter on particle emissions of modern diesel engine.

Abstract Particle emissions of modern diesel engines are of a particular interest because of their negative health effects. The special interest is in nanosized solid particles. The effect of an open channel filter on particle emissions of a modern heavy-duty diesel engine (MAN D2066 LF31, model year 2006) was studied. Here, the authors show that the open channel filter made from metal screen efficiently reduced the number of the smallest particles and, notably, the number and mass concentration of soot particles. The filter used in this study reached 78% particle mass reduction over the European Steady Cycle. Considering the size-segregated number concentration reduction, the collection efficiency was over 95% for particles smaller than 10 nm. The diffusion is the dominant collection mechanism in small particle sizes, thus the collection efficiency decreased as particle size increased, attaining 50% at 100 nm. The overall particle number reduction was 66–99%, and for accumulation-mode particles the number concentration reduction was 62–69%, both depending on the engine load.

Effects of Gaseous Sulphuric Acid on Diesel Exhaust Nanoparticle Formation and Characteristics

Diesel exhaust gaseous sulphuric acid (GSA) concentrations and particle size distributions, concentrations, and volatility were studied at four driving conditions with a heavy duty diesel engine equipped with oxidative exhaust after-treatment. Low sulfur fuel and lubricant oil were used in the study. The concentration of the exhaust GSA was observed to vary depending on the engine driving history and load. The GSA affected the volatile particle fraction at high engine loads; higher GSA mole fraction was followed by an increase in volatile nucleation particle concentration and size as well as increase of size of particles possessing nonvolatile core. The GSA did not affect the number of nonvolatile particles. At low and medium loads, the exhaust GSA concentration was low and any GSA driven changes in particle population were not observed. Results show that during the exhaust cooling and dilution processes, besides critical in volatile nucleation particle formation, GSA can change the characteristics of all nucleation mode particles. Results show the dual nature of the nucleation mode particles so that the nucleation mode can include simultaneously volatile and nonvolatile particles, and fulfill the previous results for the nucleation mode formation, especially related to the role of GSA in formation processes.

Dependence between nonvolatile nucleation mode particle and soot number concentrations in an EGR equipped heavy-duty Diesel engine exhaust.

Heavy duty diesel engine exhaust characteristics were studied with direct tailpipe sampling on an engine dynamometer. The exhaust particle size distributions, total particle mass, and gaseous emissions were measured with different load conditions without after-treatment. The measured particle size distributions were bimodal; distinctive accumulation and nucleation modes were detected for both volatile and dry particle samples. The condensing volatile compounds changed the characteristics of the nonvolatile nucleation mode while the soot/accumulation mode characteristics (concentration and diameter) were unchanged. A clear dependence between the soot and the nonvolatile nucleation mode number concentrations was detected. While the concentration of the soot mode decreased, the nonvolatile nucleation mode concentration increased. The soot mode number concentration decrease was related to soot-NOx trade-off; the decrease of the exhaust gas recirculation rate decreased soot emission and increased NOx emission. Simultaneously detected increase of the nonvolatile nucleation mode concentration may be caused by the decrease of the soot mode sink or by changed combustion characteristics. However, the total particle number concentration increased with decreasing soot mode number concentration. The proportion of the particle number concentration between the nonvolatile nucleation and soot mode followed the NO2:NO ratio linearly. While ratio NO2:NO increased the proportion of soot mode number concentration in total number concentration increased. Regardless of the mechanism that causes the balance between the soot mode and the nonvolatile nucleation mode emissions, the changes in the particle number size distribution should be taken into account while the particle mass emissions are controlled with combustion optimization.

Effect of fuel injection pressure on a heavy-duty diesel engine nonvolatile particle emission.

The effects of the fuel injection pressure on a heavy-duty diesel engine exhaust particle emissions were studied. Nonvolatile particle size distributions and gaseous emissions were measured at steady-state engine conditions while the fuel injection pressure was changed. An increase in the injection pressure resulted in an increase in the nonvolatile nucleation mode (core) emission at medium and at high loads. At low loads, the core was not detected. Simultaneously, a decrease in soot mode number concentration and size and an increase in the soot mode distribution width were detected at all loads. Interestingly, the emission of the core was independent of the soot mode concentration at load conditions below 50%. Depending on engine load conditions, growth of the geometric mean diameter of the core mode was also detected with increasing injection pressure. The core mode emission and also the size of the mode increased with increasing NOx emission while the soot mode size and emission decreased simultaneously.

Heavy-duty, off-road diesel engine low-load particle number emissions and particle control

Exhaust gas particle and ion size distributions were measured from an off-road diesel engine complying with the European Stage IIIB emission standard. The measurements were performed at idling and low load conditions on an engine dynamometer. Nucleation-mode particles dominated the diesel exhaust particle number emissions at idle load. The nonvolatile nucleation-mode geometric mean diameter was detected at 10 nm or below. The nonvolatile nucleation-mode charge state implied that it has evolved through a highly ionizing environment before emission from the engine. The determined charging probabilities were 10.0 ± 2.2% for negative and 8.0 ± 2.0% for positive polarity particles. The nonvolatile nucleation particle concentration and size was also shown to be dependent on the lubricant oil composition. The particle emissions were efficiently controlled with a partial filter or with partial filter + selective catalytic reduction (SCR) combination. The particle number removal efficiencies of the aftertreatment systems were over 95% for wet total particle number (>3nm) and over 85% for dry particle total number. Nevertheless, the aftertreatment systems’ efficiencies were around 50% for the soot-mode particles. The low-load nonvolatile nucleation particle emissions were also dependent on the engine load, speed, and fuel injection pressure. The low load particle number emissions followed the soot-core trade-off, similar to medium or high operating loads. Implications: Idling and low-load diesel engine exhaust emissions affect harmfully the ambient air quality. The low-load particle number emissions are here shown to peak in the 10-nm size range for a modern off-road engine. The particles are electrically charged and nonvolatile and they originate from the combustion process. Tailpipe particle control by open channel filter can remove more than 85% of the nonvolatile 10-nm particles and about 50% of the soot-mode particles, while the fuel injection pressure increase can lead to particle number increase. The study provides a new viewpoint for low-load particle emissions and control.