Browsing by Subject "COMBUSTION"

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  • Palonen, V.; Uusitalo, J.; Seppälä, E.; Oinonen, M. (2017)
    Radiocarbon measurements can be used to deduce the proportion of renewable to fossil carbon in materials. While these biofraction measurements are performed routinely on solid and liquid substances, measurements of gaseous samples, such as methane, are still scarce. As a pioneering effort, we have developed a field-capable sampling system for the selective capture of CH4 for radiocarbon-concentration measurements. The system allows for biofraction measurements of methane by accelerator mass spectrometry. In environmental research, radiocarbon measurements of methane can be used for fingerprinting different sources of methane emissions. In metrology and industry, biofraction measurements can be utilized to characterize biogas/natural gas mixtures within gas-line networks. In this work, the portable sampling system is described in detail and reference measurements of biofractions of gaseous fuel samples are presented. Low-concentration (1-ppm-CH4) sampling for environmental applications appears feasible but has not been fully tested at present. This development allows for multitude of future applications ranging from Arctic methane emissions to biogas insertion to gas networks. Published by AIP Publishing.
  • Kröger, Leif C.; Döntgen, Malte; Firaha, Dzmitry; Kopp, Wassja A.; Leonhard, Kai (2019)
    Diethoxymethane (DEM) is a promising oxygenated fuel and fuel additive, which has similar positive combustion characteristics as dimethoxymethane. DEM contains C-C bonds and can form ethylene via beta-scission, which potentially increases its sooting tendency. Since DEM is rarely studied, however, kinetic modeling attempts are forced to rely on rate constant analogies. Therefore, we employ high level CCSD(T)/aug-cc-pV(T+D)Z//B2PLYPD3BJ/6-311++(d,p) theory along with transition state theory to predict reaction rate constants for H-abstraction by H and CH3 and the subsequent unimolecular reactions. We further prove that the DLPNO approximation to CCSD(T) leads to a deviation of less than 0.25 k/mol in barrier heights for the presently studied open-shell electronic structures and use it for the prediction of reaction rate constants for H-abstraction by C2H5 radicals. We find that H-abstraction by ethyl radicals might denote a significant pathway, which should not be neglected in kinetic modeling studies of DEM. It is also shown that reaction pathways leading to ethylene formation are of minor importance and give thereby a first insight into the fate of the C-C bonds. To the best of our knowledge, this study represents the first high-level ab-initio study of DEM, which makes the reaction kinetics and thermochemistry data provided by this study vital for future comprehensive kinetic modeling of DEM. (C) 2018 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
  • Mohr, Claudia; Lopez-Hilfiker, Felipe D.; Zotter, Peter; Prevot, Andre S. H.; Xu, Lu; Ng, Nga L.; Herndon, Scott C.; Williams, Leah R.; Franklin, Jonathan P.; Zahniser, Mark S.; Worsnop, Douglas R.; Knighton, W. Berk; Aiken, Allison C.; Gorkowski, Kyle J.; Dubey, Manvendra K.; Allan, James D.; Thornton, Joel A. (2013)
  • Epie, Kenedy E.; Artigas, Olga M.; Santanen, Arja; Mäkelä, Pirjo S. A.; Stoddard, Frederick L. (2018)
    The biomass potential of eight high yielding maize cultivars was studied in the sub-boreal climate of southern Finland. The effects of harvest date on lignin and sugar production, biomass yield, mineral element composition, bioenergy potential and soil nutrient management were determined in two years. The eight maize cultivars produced 17.6-33.3 t ha(-1) of biomass. The ear fraction contained 50-60% of the biomass, and ash and mineral element composition of the plant fractions were significantly different (p <0.001), with more ash, Ca and S in the above-ear fractions of the plants than in the mid-stalk portions, whereas the C:N ratio was highest in the lower stalk. Cultivars with less lignin content produced more fermetable sugars. Despite the relatively cool growing conditions and short season of the sub-boreal region, maize has potential for use as biomass, for biofuel or other uses. The crop can be fractioned into ear and stalk, with the lower 20 cm of stalk left in the field to maintain soil organic matter content.
  • Minwegen, Heiko; Döntgen, Malte; Hemken, Christian; Büttgen, Rene Daniel; Leonhard, Kai; Heufer, Karl Alexander (2019)
    Recently the possibility of hot beta-scission pathways gained attention. These reactions give a shortcut during the important fuel consumption phase in combustion processes leading from H-atom abstraction directly to the beta-scission products without fuel radical thermalization. Methyl formate (MF) was shown to be prone to hot beta-scission due to a low beta-scission barrier height. Furthermore, MF as smallest methyl ester can be considered as biodiesel surrogate and it is an important intermediate product during combustion of various ethers. In this work a predominantly ab-initio derived detailed kinetic model of MF combustion is developed including hot beta-scission pathways and compared to a sophisticated literature model based on classical estimation methods. For this, new stoichiometric MF in air ignition delay time measurements in a shock tube and a rapid compression machine over a wide temperature range (790 K-1250 K) and pressures of 10, 20 and 40 bar served as validation targets. The experimental ignition delay times (IDT) show Arrhenius type behavior in both facilities at all conditions. The newly developed quantum-based model catches the pressure dependency and low-temperature reactivity well although overpredicting the IDT at higher temperatures. It was found that hot beta-scission is the major depletion pathway of formate group-centered MF radicals. This, however, does not change the overall reactivity of MF combustion due to the low stability of the alkyl peroxide (RO2) at the formate group. For species with competing thermal beta-scission and RO2 formation, however, hot beta-scission may have a significant impact. (C) 2018 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
  • Epie, Kenedy E.; Santanen, Arja; Makela, Pirjo S. A.; Stoddard, Frederick L. (2018)
    Jerusalem artichoke (Helianthus tuberosus L.) produces substantial shoots not used as food. To test its potential as a sustainable bioenergy crop, we studied the effects of synthetic fertilizer and intercropped legumes as nitrogen (N) sources on the growth, aboveground biomass dry matter yield and energy qualities of this crop. Plant height, leaf area index (LAI), SPAD-value, biomass yield, ash content and mineral element composition were determined. Mean aboveground biomass yields were not significantly affected by N source (legume intercrops and synthetic fertilizer) and ranged from 13 to 17 t ha(-1). Remarkably, plants given no fertilizer yielded equally to plants given 90 N kg ha(-1). These results confirm that Jerusalem artichoke, compared to other energy crops, have less need for N and can potentially be sustained by N fixing legumes in an intercropped system. This could reduce or eliminate production and environmental cost in cultivation of biomass feedstock for energy use.
  • Dällenbach, Kaspar; Kourtchev, Ivan; Vogel, Alexander L.; Bruns, Emily A.; Jiang, Jianhui; Petäjä, Tuukka; Jaffrezo, Jean-Luc; Aksoyoglu, Sebnem; Kalberer, Markus; Baltensperger, Urs; El Haddad, Imad; Prevot, Andre S. H. (2019)
    This study presents the molecular composition of organic aerosol (OA) using ultra-high-resolution mass spectrometry (Orbitrap) at an urban site in Central Europe (Zurich, Switzerland). Specific source spectra were also analysed, including samples representative of woodburning emissions from Alpine valleys during wood-burning pollution episodes and smog chamber investigations of woodsmoke, as well as samples from Hyytiala, which were strongly influenced by biogenic secondary organic aerosol. While samples collected during winter in Alpine valleys have a molecular composition remarkably similar to fresh laboratory wood-burning emissions, winter samples from Zurich are influenced by more aged wood-burning emissions. In addition, other organic aerosol emissions or formation pathways seem to be important at the latter location in winter. Samples from Zurich during summer are similar to those collected in Hyytiala and are predominantly impacted by oxygenated compounds with an H/C ratio of 1.5, indicating the importance of biogenic precursors for secondary organic aerosol (SOA) formation at this location (summertime Zurich - carbon number 7.6, O : C 0.7; Hyytiala - carbon number 10.5, O : C 0.57). We could explain the strong seasonality of the molecular composition at a typical European site by primary and aged wood-burning emissions and biogenic secondary organic aerosol formation during winter and summer, respectively. Results presented here likely explain the rather constant seasonal predominance of non-fossil organic carbon at European locations.
  • Rissanen, Matti P.; Eskola, Arkke J.; Timonen, Raimo S. (American Chemical Society, 2010)
  • Ciarelli, Giancarlo; Aksoyoglu, Sebnem; El Haddad, Imad; Bruns, Emily A.; Crippa, Monica; Poulain, Laurent; Äijälä, Mikko; Carbone, Samara; Freney, Evelyn; O'Dowd, Colin; Baltensperger, Urs; Prevot, Andre S. H. (2017)
    We evaluated a modified VBS (volatility basis set) scheme to treat biomass-burning-like organic aerosol (BBOA) implemented in CAMx (Comprehensive Air Quality Model with extensions). The updated scheme was parameterized with novel wood combustion smog chamber experiments using a hybrid VBS framework which accounts for a mixture of wood burning organic aerosol precursors and their further functionalization and fragmentation in the atmosphere. The new scheme was evaluated for one of the winter EMEP intensive campaigns (February March 2009) against aerosol mass spectrometer (AMS) measurements performed at 11 sites in Europe. We found a considerable improvement for the modelled organic aerosol (OA) mass compared to our previous model application with the mean fractional bias (MFB) reduced from 61 to 29 %. We performed model-based source apportionment studies and compared results against positive matrix factorization (PMF) analysis performed on OA AMS data. Both model and observations suggest that OA was mainly of secondary origin at almost all sites. Modelled secondary organic aerosol (SOA) contributions to total OA varied from 32 to 88 % (with an average contribution of 62 %) and absolute concentrations were generally under-predicted. Modelled primary hydrocarbon-like organic aerosol (HOA) and primary biomass-burning-like aerosol (BBPOA) fractions contributed to a lesser extent (HOA from 3 to 30 %, and BBPOA from 1 to 39 %) with average contributions of 13 and 25 %, respectively. Modelled BBPOA fractions were found to represent 12 to 64 % of the total residential-heating-related OA, with increasing contributions at stations located in the northern part of the domain. Source apportionment studies were performed to assess the contribution of residential and non-residential combustion precursors to the total SOA. Non-residential combustion and road transportation sector contributed about 30-40 % to SOA formation (with increasing contributions at urban and near industrialized sites), whereas residential combustion (mainly related to wood burning) contributed to a larger extent, around 60-70 %. Contributions to OA from residential combustion precursors in different volatility ranges were also assessed: our results indicate that residential combustion gas-phase precursors in the semivolatile range (SVOC) contributed from 6 to 30 %, with higher contributions predicted at stations located in the southern part of the domain On the other hand, the oxidation products of higher-volatility precursors (the sum of intermediate-volatility compounds (IVOCs) and volatile organic compounds (VOCs)) contribute from 15 to 38 % with no specific gradient among the stations. Although the new parameterization leads to a better agreement between model results and observations, it still under predicts the SOA fraction, suggesting that uncertainties in the new scheme and other sources and/or formation mechanisms remain to be elucidated. Moreover, a more detailed characterization of the semivolatile components of the emissions is needed.
  • Wang, Yang; Kangasluoma, Juha; Attoui, Michel; Fang, Jiaxi; Junninen, Heikki; Kulmala, Markku; Petäjä, Tuukka; Biswas, Pratim (2017)
    While flame aerosol reactor (FLAR) synthesis of nanoparticles is widely used to produce a range of nano-materials, incipient particle formation by nucleation and vapor condensation is not well understood. This gap in our knowledge of incipient particle formation is caused by limitations in instruments, where, during measurements, the high diffusivity of sub 3 nm particles significantly affects resolution and transport loss. This work used a high resolution differential mobility analyzer (DMA) and an atmospheric pressure interface-mass spectrometer (APi-TOF) to observe incipient particle formation during flame synthesis. By tandemly applying these two instruments, differential mobility analysis-mass spectrometry (DMA-MS) measured the size and mass of the incipient particles simultaneously, and the effective density of the sub 3 nm particles was estimated. The APi-TOF further provided the chemical compositions of the detected particles based on highly accurate masses and isotope distributions. This study investigated the incipient particle formation in flames with and without the addition of synthesis precursors. Results from FLAR using two types of precursors including tetraethyl orthosilicate (TEOS) and titanium isopropoxide (TTIP) are presented. The effect of the precursor feed rates on incipient particle growth was also investigated. (C) 2016 by The Combustion Institute. Published by Elsevier Inc.
  • Eskola, Arrke J.; Blitz, Mark A.; Pilling, Michael J.; Seakins, Paul W.; Shannon, Robin J. (2020)
    The rate coefficient for the unimolecular decomposition of CH3OCH2,k(1), has been measured in time-resolved experiments by monitoring the HCHO product. CH3OCH2 was rapidly and cleanly generated by 248 nm excimer photolysis of oxalyl chloride, (ClCO)(2), in an excess of CH3OCH3, and an excimer pumped dye laser tuned to 353.16 nm was used to probe HCHO via laser induced fluorescence. k(1)(T,p) was measured over the ranges: 573-673 K and 0.1-4.3 x 10(18) molecule cm(-3) with a helium bath gas. In addition, some experiments were carried out with nitrogen as the bath gas. Ab initio calculations on CH3OCH2 decomposition were carried out and a transition-state for decomposition to CH3 and H2CO was identified. This information was used in a master equation rate calculation, using the MESMER code, where the zero-point-energy corrected barrier to reaction, Delta E-0,E-1, and the energy transfer parameters, x T-n, were the adjusted parameters to best fit the experimental data, with helium as the buffer gas. The data were combined with earlier measurements by Loucks and Laidler (Can J. Chem. 1967, 45, 2767), with dimethyl ether as the third body, reinterpreted using current literature for the rate coefficient for recombination of CH3OCH2. This analysis returned Delta E-0,E-1 = (112.3 +/- 0.6) kJ mol(-1), and leads to k(1)(infinity)(T) = 2.9 x 10(12) (T/300)(2)(.5) exp(-106.8 kJ mol(-1)/RT). Using this model, limited experiments with nitrogen as the bath gas allowed N-2 energy transfer parameters to be identified and then further MESMER simulations were carried out, where N-2 was the buffer gas, to generate k(1)(T,p) over a wide range of conditions: 300-1000 K and N-2 = 10(12) -10(25) molecule cm(-3). The resulting k(1)(T,p) has been parameterized using a Troe-expression, so that they can be readily be incorporated into combustion models. In addition, k(1)(T,p) has been parametrized using PLOG for the buffer gases, He, CH3OCH3 and N-2.
  • Siponen, Taina; Yli-Tuomi, Tarja; Tiittanen, Pekka; Taimisto, Pekka; Pekkanen, Juha; Salonen, Raimo O.; Lanki, Timo (2019)
    A six-month winter-spring study was conducted in a suburb of the northern European city of Kuopio, Finland, to identify and quantify factors determining daily personal exposure and home indoor levels of fine particulate matter (PM2.5, diameter