Juha Heikkilä

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.

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.

Reductions in Particulate and NOx Emissions by Diesel Engine Parameter Adjustments with HVO Fuel

Hydrotreated vegetable oil (HVO) diesel fuel is a promising biofuel candidate that can complement or substitute traditional diesel fuel in engines. It has been already reported that by changing the fuel from conventional EN590 diesel to HVO decreases exhaust emissions. However, as the fuels have certain chemical and physical differences, it is clear that the full advantage of HVO cannot be realized unless the engine is optimized for the new fuel. In this article, we studied how much exhaust emissions can be reduced by adjusting engine parameters for HVO. The results indicate that, with all the studied loads (50%, 75%, and 100%), particulate mass and NO(x) can both be reduced over 25% by engine parameter adjustments. Further, the emission reduction was even higher when the target for adjusting engine parameters was to exclusively reduce either particulates or NO(x). In addition to particulate mass, different indicators of particulate emissions were also compared. These indicators included filter smoke number (FSN), total particle number, total particle surface area, and geometric mean diameter of the emitted particle size distribution. As a result of this comparison, a linear correlation between FSN and total particulate surface area at low FSN region was found.

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%.

Sulfur driven nucleation mode formation in diesel exhaust under transient driving conditions

Sulfur driven diesel exhaust nucleation particle formation processes were studied in an aerosol laboratory, on engine dynamometers, and on the road. All test engines were equipped with a combination of a diesel oxidation catalyst (DOC) and a partial diesel particulate filter (pDPF). At steady operating conditions, the formation of semivolatile nucleation particles directly depended on SO2 conversion in the catalyst. The nucleation particle emission was most significant after a rapid increase in engine load and exhaust gas temperature. Results indicate that the nucleation particle formation at transient driving conditions does not require compounds such as hydrocarbons or sulfated hydrocarbons, however, it cannot be explained only by the nucleation of sulfuric acid. A real-world exhaust study with a heavy duty diesel truck showed that the nucleation particle formation occurs even with ultralow sulfur diesel fuel, even at downhill driving conditions, and that nucleation particles can contribute 60% of total particle number emissions. In general, due to sulfur storage and release within the exhaust aftertreatment systems and transients in driving, emissions of nucleation particles can even be the dominant part of modern diesel vehicle exhaust particulate number emissions.

Study of Miller timing on exhaust emissions of a hydrotreated vegetable oil (HVO)-fueled diesel engine

The effect of intake valve closure (IVC) timing by utilizing Miller cycle and start of injection (SOI) on particulate matter (PM), particle number, and nitrogen oxide (NOx) emissions was studied with a hydrotreated vegetable oil (HVO)-fueled nonroad diesel engine. HVO-fueled engine emissions, including aldehyde and polyaromatic hydrocarbon (PAH) emissions, were also compared with those emitted with fossil EN590 diesel fuel. At the engine standard settings, particle number and NOx emissions decreased at all the studied load points (50%, 75%, and 100%) when the fuel was changed from EN590 to HVO. Adjusting IVC timing enabled a substantial decrease in NOx emission and combined with SOI timing adjustment somewhat smaller decrease in both NOx and particle emissions at IVC −50 and −70 °CA points. The HVO fuel decreased PAH emissions mainly due to the absence of aromatics. Aldehyde emissions were lower with the HVO fuel with medium (50%) load. At higher loads (75% and 100%), aldehyde emissions were slightly higher with the HVO fuel. However, the aldehyde emission levels were quite low, so no clear conclusions on the effect of fuel can be made. Overall, the study indicates that paraffinic HVO fuels are suitable for emission reduction with valve and injection timing adjustment and thus provide possibilities for engine manufacturers to meet the strictening emission limits. Implications: NOx and particle emissions are dominant emissions of diesel engines and vehicles. New, biobased paraffinic fuels and modern engine technologies have been reported to lower both of these emissions. In this study, even further reductions were achieved with engine valve adjustment combined with novel hydrotreated vegetable oil (HVO) diesel fuel. This study shows that new paraffinic fuels offer further possibilities to reduce engine exhaust emissions to meet the future emission limits. Supplementary Materials: Supplementary materials are available for this paper. Go to the publishers online edition of the Journal of the Air & Waste Management Association for a complete list of analysed PAH compounds.