Investigation of late-cycle soot oxidation using laser extinction and in-cylinder gas sampling at varying inlet oxygen concentrations in diesel engines

[EN] This study focuses on the relative importance of O-2 and OH as oxidizers of soot during the late cycle in diesel engines, where the soot oxidation is characterized in an optically accessible engine using laser extinction measurements. These are combined with in-cylinder gas sampling data from a single cylinder engine fitted with a fast gas-sampling valve. Both measurements confirm that the in-cylinder soot oxidation slows down when the inlet concentration of O-2 is reduced. A 38% decrease in intake O-2 concentration reduces the soot oxidation rate by 83%, a non-linearity suggesting that O-2 in itself is not the main soot oxidizing species. Chemical kinetics simulations of OH concentrations in the oxidation zone and estimates of the OH-soot oxidation rates point towards OH being the dominant oxidizer.The authors gratefully acknowledge the Swedish Energy Agency, the Competence Center for Combustion Processes KCFP (Project number 22485-3), and the competence center METALUND funded by FORTE for financially supporting this research. The authors acknowledge Volvo AB for providing the gas-sampling valve and personally Jan Eismark (Volvo AB) and Mats Bengtsson (Lund University) for their technical support.Gallo, Y.; Malmborg, VB.; Simonsson, J.; Svensson, E.; Shen, M.; Bengtsson, P.; Pagels, J.... (2017). Investigation of late-cycle soot oxidation using laser extinction and in-cylinder gas sampling at varying inlet oxygen concentrations in diesel engines. Fuel. 193:308-314. https://doi.org/10.1016/j.fuel.2016.12.013S30831419

Investigation of the absorption Ångström exponent and its relation to physicochemical properties for mini-CAST soot

In this work, a mini-CAST soot generator was used to produce soot with different optical and physicochemical characteristics. Absorption Ångström exponents (AAE) expressing the absorption wavelength dependence were assessed by multiwavelength in-situ and filter-based (aethalometer) laser extinction. The two optical techniques showed good agreement. For the chosen mini-CAST operating conditions, AAEs between 1 and 3.5 were found. Soot with high mass-fractions of organic carbon (OC) and pyrolytic carbon (PC) determined with thermal optical analysis were associated with AAEs significantly higher than 1. Heating to 250 and 500°C removed the majority of polycyclic aromatic hydrocarbons. However, the thermal-optical analysis revealed that OC and PC were abundant in the soot with AAE > 2 also after heating the aerosol. Analysis of mass absorption cross section ratios for elemental carbon and OC indicated that elevated AAEs also after heating to 500°C could be related to persistent OC and PC components and/or the refractory soot. By comparing the mini-CAST soot optical properties with soot properties derived from in-situ extinction measurements in a premixed flame, mini-CAST soot with a higher AAE could be identified as less mature soot

Regulated Emissions and Detailed Particle Characterisation for Diesel and RME Biodiesel Fuel Combustion with Varying EGR in a Heavy-Duty Engine

This study investigates particulate matter (PM) and regulated emissions from renewable rapeseed oil methyl ester (RME) biodiesel in pure and blended forms and contrasts that to conventional diesel fuel. Environmental and health concerns are the major motivation for combustion engines research, especially finding sustainable alternatives to fossil fuels and reducing diesel PM emissions. Fatty acid methyl esters (FAME), including RME, are renewable fuels commonly used from low level blends with diesel to full substitution. They strongly reduce the net carbon dioxide emissions. It is largely unknown how the emissions and characteristics of PM get altered by the combined effect of adding biodiesel to diesel and implementing modern engine concepts that reduce nitrogen oxides (NOx) emissions by exhaust gas recirculation (EGR). Therefore, the exhaust from a single-cylinder Scania D13 heavy-duty (HD) diesel engine fuelled with petroleum-based MK1 diesel, RME, and a 20% RME blend (B20), was sampled while the inlet oxygen concentration was stepped from ambient to very low by varying EGR. Regulated gaseous emissions, mass of total black carbon (BC) and organic aerosol (OA), particle size distributions and the soot nanostructure by means of transmission electron microscopy (TEM), were studied. For all EGR levels, RME showed reduced BC emissions (factor 2 for low and 3-4 for higher EGR) and total particulate number count (TPNC) compared with diesel and B20. B20 was closer to diesel than RME in emission levels. RME opens a significant possibility to utilise higher levels of EGR and stay in the region of low NOx, while not producing more soot than with diesel and B20. Adding EGR to 15% inlet O2 did not affect the nanostructure of PM. A difference between the fuels was noticeable: branched agglomerates of diesel and RME were composed of many primary particles, whereas those of B20 were more often “melted” together (necking)

Detailed characterization of particulate matter in alcohol exhaust emissions

A way to reduce net CO2 emission and circumvent the high particle emissions from compression ignition (CI) engines, while retaining high efficiency, is by utilizing lighter alcohols in the partially premixed combustion (PPC) process. Methanol and ethanol have a very short carbon chain, and form less soot/particulate matter (PM) during combustion compared to diesel fuel. This study analyzes and compares the characteristics of PM emissions from methanol, ethanol and diesel in terms of soot mass concentration, number concentration and particle size distribution in one cylinder of a six cylinder Scania D13 heavy duty (HD) engine under two operating loads; 6 bar and 10 bar gross mean indicated effective pressure (IMEPG). An electrostatic precipitator (ESP) was used to sample PM on copper grids for transmission electron microscopy (TEM) and energy dispersive X-ray analysis. Also, new and used lubrication oil together with methanol and diesel were analyzed for their sulphur and metal content. Nucleation mode and the majority of accumulation mode particles from methanol and ethanol combustion, showed mainly Ca, S, P and Zn in the energy dispersive X-ray spectrometry (EDX) analysis and were hypothesized to be emitted mainly from the lubrication oil rather than the combustion of the fuel itself. From diesel combustion, the accumulation mode particles were more abundant in comparison with the alcohols and PM/soot emissions measured with the photo-acoustic technique were 3 to 10 times higher than for the alcohols. There were also fewer nucleation mode particles present; although they consisted of the same four abovementioned elements. Utilizing alcohols in CI engines have a great advantage regarding PM, particle number emissions and efficiency. However, the resulting nucleation mode particles need to be reduced to avoid future health concerns

Genotoxicity by rapeseed methyl ester and hydrogenated vegetable oil combustion exhaust products in lung epithelial (A549) cells

Biofuel is an attractive substitute for petrodiesel because of its lower environmental footprint. For instance, the polycyclic aromatic hydrocarbons (PAH) emission per fuel energy content is lower for rapeseed methyl ester (RME) than for petrodiesel. The present study assesses genotoxicity by extractable organic matter (EOM) of exhaust particles from combustion of petrodiesel, RME and hydrogenated vegetable oil (HVO) in lung epithelial (A549) cells. Genotoxicity was assessed as DNA strand breaks by the alkaline comet assay. EOM from combustion of petrodiesel and RME generated the same level of DNA strand breaks based on equal concentration of total PAH (i.e. net increases of 0.13 [95% confidence interval (CI): 0.002, 0.259 and 0.12 [95% CI: 0.01, 0.24] lesions per million base pairs, respectively). In comparison, the positive control (etoposide) generated much higher level of DNA strand breaks (i.e. 0.84, 95% CI: 0.72, 0.97) lesions per million base pairs). Relatively low concentrations of EOM from RME and HVO combustion particles (<116 ng/ml total PAH) did not cause DNA strand breaks in A549 cells, whereas benzo[a]pyrene and PAH-rich EOM from petrodiesel combusted using low oxygen inlet concentration were genotoxic. The genotoxicity was attributed to high molecular weight PAH isomers with 5-6 rings. In summary, the results show that EOM from combustion of petrodiesel and RME generate the same level of DNA strand breaks on equal total PAH basis. However, the genotoxic hazard of engine exhaust from on-road vehicles is lower for RME than petrodiesel because of lower PAH emission per fuel energy content

Effects of renewable fuel and exhaust aftertreatment on primary and secondary emissions from a modern heavy-duty diesel engine

Compared to petroleum diesel, renewable diesel fuels and exhaust aftertreatment systems can reduce primary exhaust emissions that are hazardous to human health and the environment. Secondary aerosol emissions which form upon atmospheric processing have, however, been less studied. This study aimed to quantify the impacts of replacing petroleum diesel with renewable fuels (hydrotreated vegetable oil [HVO] and rapeseed methyl ester [RME]) on primary and secondary aerosol emissions from a heavy-duty diesel engine at different stages of an exhaust aftertreatment system. Emission characterization was obtained by combining a battery of physical characterization techniques with chemical characterization using aerosol mass spectrometry. At engine-out measurements, RME and HVO reduced primary particulate matter (PM) emissions (for example equivalent black carbon [eBC]) and secondary aerosol production (studied with an oxidation flow reactor [OFR]) by mass compared to petroleum diesel. The diesel oxidation catalyst (DOC) reduced primary nucleation mode emissions, reduced the effective density of soot mode emissions, and reduced secondary particle production by mass. The DOC + a diesel particulate filter removed >99% of the particle number and eBC emissions. Volatile PM emissions (for example organic aerosol) were found to be distributed between the nucleation mode and soot mode for both primary and secondary emissions, to a degree that depends on both fuel type and aftertreatment. A high mass concentration of condensable species and a low condensation sink in the soot mode led to increased fractions of condensable species present in the nucleation mode. Aging in the OFR led to increases in particle effective density. Motoring the engine (running without combustion) showed that the nucleation mode originated primarily from lubricating oil, and nonvolatile nanoparticle emissions were identified down to 1.2 nm in particle size. In conclusion, replacing petroleum diesel with HVO and RME changes emission characteristics and can help reduce key aerosol emissions of relevance for adverse health and climate impact, especially for diesel engines with no or limited exhaust aftertreatment.publishedVersionPeer reviewe

Immersion freezing ability of freshly emitted soot with various physico-chemical characteristics

The immersion freezing ability of soot particles has in previous studies been reported in the range of low/insignificant to very high. The aims of this study were to: (i) perform detailed physico-chemical characterisation of freshly produced soot particles with very different properties, (ii) investigate the immersion freezing ability of the same particles, and (iii) investigate the potential links between physico-chemical particle properties and ice-activity. A miniCAST soot generator was used to produce eight different soot samples representing a wide range of physico-chemical properties. A continuous flow diffusion chamber was used to study each sample online in immersion mode over the temperature (T) range from −41 to −32◦C, at a supersaturation of about 10% with respect to liquid water. All samples exhibited low to no heterogeneous immersion freezing. The most active sample reached ice-activated fractions (AF) of 10−3 and 10−4 at temperatures of 1.7 and 1.9 K, respectively, above the homogeneous freezing temperature. The samples were characterized online with respect to a wide range of physico-chemical properties including effective particle density, optical properties, particle surface oxidation and soot maturity. We did observe indications of increasing immersion freezing ice-activity with increasing effective particle density and increasing particulate PAH fraction . Hence, those properties, or other properties co-varying with those, could potentially enhance the immersion freezing ice-activity of the studied soot particle types. However, we found no significant correlation between the physico-chemical properties and the observed ice-nucleating ability when the particle ensemble was extended to include previously published results including more ice-active biomass combustion soot particles. We conclude that it does not appear possible in general and in any straightforward way to link observed soot particle physico-chemical properties to the ice-nucleating ability using the online instrumentation included in this study. Furthermore, our observations support that freshly produced soot particles with a wide range of physico-chemical properties have low to insignificant immersion freezing ice-nucleating ability

Investigation of the absorption Ångström exponent and its relation to physicochemical properties for mini-CAST soot

<p>In this work, a mini-CAST soot generator was used to produce soot with different optical and physicochemical characteristics. Absorption Ångström exponents (<i>AAE</i>) expressing the absorption wavelength dependence were assessed by multiwavelength <i>in-situ</i> and filter-based (aethalometer) laser extinction. The two optical techniques showed good agreement. For the chosen mini-CAST operating conditions, <i>AAE</i>s between 1 and 3.5 were found. Soot with high mass-fractions of organic carbon (OC) and pyrolytic carbon (PC) determined with thermal optical analysis were associated with <i>AAE</i>s significantly higher than 1. Heating to 250 and 500°C removed the majority of polycyclic aromatic hydrocarbons. However, the thermal-optical analysis revealed that OC and PC were abundant in the soot with <i>AAE</i> > 2 also after heating the aerosol. Analysis of mass absorption cross section ratios for elemental carbon and OC indicated that elevated <i>AAEs</i> also after heating to 500°C could be related to persistent OC and PC components and/or the refractory soot. By comparing the mini-CAST soot optical properties with soot properties derived from <i>in-situ</i> extinction measurements in a premixed flame, mini-CAST soot with a higher <i>AAE</i> could be identified as less mature soot.</p> <p>Copyright © 2018 The Authors</p

Properties and emission factors of cloud condensation nuclei from biomass cookstoves - Observations of a strong dependency on potassium content in the fuel

Residential biomass combustion is a significant source of aerosol particles on regional and global scales influencing climate and human health. The main objective of the current study was to investigate the properties of cloud condensation nuclei (CCN) emitted from biomass burning of solid fuels in different cookstoves mostly of relevance to sub- Saharan east Africa. The traditional three-stone fire and a rocket stove were used for combustion of wood logs of Sesbania and Casuarina with birch used as a reference. A natural draft and a forced-draft pellet stove were used for combustion of pelletised Sesbania and pelletised Swedish softwood alone or in mixtures with pelletised coffee husk, rice husk or water hyacinth. The CCN activity and the effective density were measured for particles with mobility diameters of v65, v100 and v200 nm, respectively, and occasionally for 350 nm particles. Particle number size distributions were measured online with a fast particle analyser. The chemical composition of the fuel ash was measured by application of standard protocols. The average particle number size distributions were by number typically dominated by an ultrafine mode, and in most cases a soot mode was centred around a mobility diameter of v150 nm. The CCN activities decreased with increasing particle size for all experiments and ranged in terms of the hygroscopicity parameter, from v0:1 to v0:8 for the ultrafine mode and from v0:001 to v0:15 for the soot mode. The CCN activity of the ultrafine mode increased (i) with increasing combustion temperature for a given fuel, and (ii) it typically increased with increasing potassium concentration in the investigated fuels. The primary CCN and the estimated particulate matter (PM) emission factors were typically found to increase significantly with increasing potassium concentration in the fuel for a given stove. In order to link CCN emission factors to PM emission factors, knowledge about stove technology, stove operation and the inorganic fuel ash composition is needed. This complicates the use of ambient PM levels alone for estimation of CCN concentrations in regions dominated by biomass combustion aerosol, with the relation turning even more complex when accounting for atmospheric ageing of the aerosol