Topi Rönkkö

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.

Can real-world diesel exhaust particle size distribution be reproduced in the laboratory? A critical review.

Abstract Real-world particulate emission measurements usually include a fresh nanoparticle mode called the nucleation mode. The formation of the nucleation mode during mixing, dilution, and cooling of diesel exhaust is discussed based on existing experimental and modeling data. The further evolution of the nucleation mode and the local dilution ratio within the vehicle exhaust is reviewed. The nucleation mode forms at low dilution ratios (≤10) and is fully formed at the dilution ratio of approximately 100. The findings of the studies comparing real-world and dynamometer measurements are reviewed. A qualitative agreement of nucleation mode formation is generally observed. The geometric mean diameter of the nucleation mode, measured on-road, is well reproduced in the laboratory. However, the number concentration of the nucleation mode is too low in the laboratory (by a factor of 2–10). Nevertheless, the trends are reproduced, including those caused by differences in vehicle speed and engine load, engine and aftertreatment technology, as well as fuel and lubricant composition.

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.

Nanoparticle emissions from a heavy-duty engine running on alternative diesel fuels.

We have studied the effect of three different fuels (fossil diesel fuel (EN590); rapeseed methyl ester (RME); and synthetic gas-to-liquid (GTL)) on heavy-duty diesel engine emissions. Our main focus was on nanoparticle emissions of the engine. Our results show that the particle emissions from a modern diesel engine run with EN590, GTL, or RME consisted of two partly nonvolatile modes that were clearly separated in particle size. The concentration and geometric mean diameter of nonvolatile nucleation mode cores measured with RME were substantially greater than with the other fuels. The soot particle concentration and soot particle size were lowest with RME. With EN590 and GTL, a similar engine load dependence of the nonvolatile nucleation mode particle size and concentration imply a similar formation mechanism of the particles. For RME, the nonvolatile core particle size was larger and the concentration dependence on engine load was clearly different from that of EN590 and GTL. This indicates that the formation mechanism of the core particles is different for RME. This can be explained by differences in the fuel characteristics.

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.

Effects of fresh lubricant oils on particle emissions emitted by a modern gasoline direct injection passenger car.

Particle emissions from a modern turbocharged gasoline direct injection passenger car equipped with a three-way catalyst and an exhaust gas recirculation system were studied while the vehicle was running on low-sulfur gasoline and, consecutively, with five different lubrication oils. Exhaust particle number concentration, size distribution, and volatility were determined both at laboratory and on-road conditions. The results indicated that the choice of lubricant affected particle emissions both during the cold start and warm driving cycles. However, the contribution of engine oil depended on driving conditions being higher during acceleration and steady state driving than during deceleration. The highest emission factors were found with two oils that had the highest metal content. The results indicate that a 10% decrease in the Zn content of engine oils is linked with an 11-13% decrease to the nonvolatile particle number emissions in steady driving conditions and a 5% decrease over the New European Driving Cycle. The effect of lubricant on volatile particles was even higher, on the order of 20%.

The Effect of Sulphur in Diesel Exhaust Aerosol: Models Compared with Measurements

A nodal aerosol dynamics model TUTEAM (Tampere University of Technology Exhaust Aerosol Model) was developed to study the number and mass evolution of exhaust particles in a dilution system. The model includes processes such as nucleation, condensation, coagulation, and wall losses and it takes into account the dilution and temperature cooling profiles. The model considers nucleation and soot modes separately. For soot particles the fractal structure was implemented in the model to take the density and size, which continuously vary due to condensation, into account accurately. The model was compared with a set of dynamometer measurements of a heavy-duty diesel vehicle with different lubricant oils and fuels, and with a sectional aerosol dynamics model AEROFOR. The trends of nucleation mode geometric median diameter and number concentration as a function of fuel and lubricant sulphur contents were reproduced well. Also the predicted particle composition was in agreement with the measurements of Schneider et al. (2005).

Physical and Chemical Characterization of Real-World Particle Number and Mass Emissions from City Buses in Finland.

Exhaust emissions of 23 individual city buses at Euro III, Euro IV and EEV (Enhanced Environmentally Friendly Vehicle) emission levels were measured by the chasing method under real-world conditions at a depot area and on the normal route of bus line 24 in Helsinki. The buses represented different technologies from the viewpoint of engines, exhaust after-treatment systems (ATS) and fuels. Some of the EEV buses were fueled by diesel, diesel-electric, ethanol (RED95) and compressed natural gas (CNG). At the depot area the emission factors were in the range of 0.3-21 × 10(14) # (kg fuel)(-1), 6-40 g (kg fuel)(-1), 0.004-0.88 g (kg fuel)(-1), 0.004-0.56 g (kg fuel)(-1), 0.01-1.2 g (kg fuel)(-1), for particle number (EFN), nitrogen oxides (EFNOx), black carbon (EFBC), organics (EFOrg), and particle mass (EFPM1), respectively. The highest particulate emissions were observed from the Euro III and Euro IV buses and the lowest from the ethanol and CNG-fueled buses, which emitted BC only during acceleration. The organics emitted from the CNG-fueled buses were clearly less oxidized compared to the other bus types. The bus line experiments showed that lowest emissions were obtained from the ethanol-fueled buses whereas large variation existed between individual buses of the same type indicating that the operating conditions by drivers had large effect on the emissions.