Characterisation of atmospheric single particles in industrial and regional background environments using aerosol time of flight mass spectrometry

The composition of atmospheric particles is an important factor in determining their impact on climate and health. In this study, an aerosol time-of-flight mass spectrometer (ATOFMS) was used to measure the chemical composition of ambient single particles at two contrasting locations – an industrial site in Dunkirk, France and a regional background site in Corsica. The ATOFMS data were combined with meteorological information and other particle measurements to determine the various sources of the particles observed at the sites. The particle classes detected in Dunkirk included carbonaceous species from fossil fuel combustion and biomass burning, metal-containing types from local industries and seasalt. Highest particle number concentrations and mass concentrations of PM2.5, black carbon, organics, nitrate, ammonium and several metallic species (Fe, Mn, Pb, Zn) were found during periods heavily influenced by local industry. Particles from a ferromanganese alloy manufacturing facility were identified by comparing ambient ATOFMS data with single particle mass spectra from industrial chimney filters and ores. Particles from a steelworks were identified based on comparison of the ambient data with previous studies. Based on these comparisons, the steelworks was identified as the dominant emitter of Fe-rich particles, while the ferromanganese alloy facility emitted Mn-rich particles. In Corsica, regional transport of carbonaceous particles from biomass burning and fossil fuel combustion was identified as the major source of particles in the Mediterranean background aerosol. Throughout the campaign the site was influenced by air masses altering the composition of particles detected. During North Atlantic air masses the site was heavily influenced by fresh sea salt. Regional stagnation was the most common type of air mass regime throughout the campaign and resulted in the accumulation of carbonaceous particles during certain periods. Mass concentrations were estimated for ATOFMS particle classes, and good agreement was found between the major carbonaceous classes and other quantitative measurements. Overall the results of this work serve to highlight the excellent ability of the ATOFMS technique in providing source-specific composition and mixing state information on atmospheric particles at high time resolution.

Molecular hydrogen (H2) mixing ratio and stable isotopic composition (dD) at the Cabauw tall tower in the Netherlands (2008-2012)

Measurements of the stable isotopic composition (dD(H2) or dD) of atmospheric molecular hydrogen (H2) are a useful addition to mixing ratio (X(H2)) measurements for understanding the atmospheric H2 cycle. dD datasets published so far consist mostly of observations at background locations. We complement these with observations from the Cabauw tall tower at the CESAR site, situated in a densely populated region of the Netherlands. Our measurements show a large anthropogenic influence on the local H2 cycle, with frequently occurring pollution events that are characterized by X(H2) values that reach up to 1 ppm and low dD values. An isotopic source signature analysis yields an apparent source signature below -400 per mil, which is much more D-depleted than the fossil fuel combustion source signature commonly used in H2 budget studies. Two diurnal cycles that were sampled at a suburban site near London also show a more D-depleted source signature (-340 per mil), though not as extremely depleted as at Cabauw. The source signature of the Northwest European vehicle fleet may have shifted to somewhat lower values due to changes in vehicle technology and driving conditions. Even so, the surprisingly depleted apparent source signature at Cabauw requires additional explanation; microbial H2 production seems the most likely cause. The Cabauw tower site also allowed us to sample vertical profiles. We found no decrease in (H2) at lower sampling levels (20 and 60m) with respect to higher sampling levels (120 and 200m). There was a significant shift to lower median dD values at the lower levels. This confirms the limited role of soil uptake around Cabauw, and again points to microbial H2 production during an extended growing season, as well as to possible differences in average fossil fuel combustion source signature between the different footprint areas of the sampling levels. So, although knowledge of the background cycle of H2 has improved over the last decade, surprising features come to light when a non-background location is studied, revealing remaining gaps in our understanding.

Adsorption Calorimetry for Energy Conversion Technologies: Applications in Organic Photovoltaics, Catalysis, and Atomic Layer Deposition

Thesis (Ph.D.)--University of Washington, 2016-07

An Evaluation of Carbon Concentrations Associted with Biodiesel Particulate Matter in an Underground Metal Mine

Exposure to diesel particulate matter from diesel exhaust has been shown to have adverse health effects in humans. In 2012 The International Agency for Research on Cancer classified diesel exhaust as a group 1 know human carcinogen. Because of the associated health effects, there has been a strong push to reduce the amount of diesel exhaust present in the mining industry. Biodiesel is one to the more common and promising control options used to reduce the amount of diesel particulate matter that is generated during fuel combustion. The use of biodiesel over petroleum diesel has been shown to reduce not only particulate matter, but hydro carbon and carbon monoxide mass emissions as well. Personal and area samples were collected at an underground metal mine in the northwestern United States to evaluate the current blend of B70 biodiesel. The objective of this research was to evaluate the carbon levels associated with diesel particulate matter generated from the combustion of a B70 biodiesel. Data was also compared to past studies on which diesel particulate matter from petroleum diesel was evaluated. Samples were taken on four separate four day campaigns between March and October of 2014. Area samples were taken from 7 different areas in the mine and personal samples were taken from a 20 person cohort. The equipment used for sampling was compliant with the NIOSH 5040 method. Statistical analysis of the results was done using Minitab 17 software. The statistical analysis showed that the total carbon concentrations from biodiesel were well below the MSHA exposure limit. Results also showed that organic/elemental carbon ratios were consistent with past studies as the concentrations of organic carbon were significantly higher than those of elemental carbon.

Co2 capture in power plants-using the oxy-combustion principle

In the C02 capture from power generation, the energy penalties for the capture are one of the main challenges. Nowadays, the post-combustion methods have energy penalties 10wer than the oxy combustion and pre-combustion technologies. One of the main disadvantages of the post combustion method is the fact that the capture ofC02at atmospheric pressure requires quite big equipment for the high flow rates of flue gas, and the 10w partial pressure of the CO2generates an important 10ss of energy. The A1lam cyc1e presented for NETPOWER gives high efficiencies in the power production and 10w energy penalties. A simulation of this cyc1e is made together with a simulation of power plants with pre-combustion and post-combustion capture and without capture for natural gas and forcoa1. The simulations give 10wer efficiencies than the proposed for NETPOWER For natural gas the efficiency is 52% instead of the 59% presented, and 33% instead of51% in the case of using coal as fuel. Are brought to light problems in the CO2compressor due the high flow ofC02that is compressed unti1300 bar to be recyc1ed into the combustor.

Combustion enhancement in a scramjet engine using oxygen enrichment and porous fuel injection

This paper reports on the experimental testing of oxygen-enriched porous fuel injection in a scramjet engine. Fuel was injected via inlet mounted, oxide-based ceramic matrix composite (CMC) injectors on both flow path surfaces that covered a total of 9.2 % of the intake surface area. All experiments were performed at an enthalpy of 3.93−4.25±3.2% MJ kg−1, flight Mach number 9.2–9.6 and an equivalence ratio of 0.493±3%. At this condition, the engine was shown to be on the verge of achieving appreciable combustion. Oxygen was then added to the fuel prior to injection such that two distinct enrichment levels were achieved. Combustion was found to increase, by as much as 40 % in terms of combustion-induced pressure rise, over the fuel-only case with increasing oxygen enrichment. Further, the onset of combustion was found to move upstream with increasing levels of oxygen enrichment. Thrust, both uninstalled and specific, and specific impulse were found to be improved with oxygen enrichment. Enhanced fuel–air mixing due to the pre-mixing of oxygen with the fuel together with the porous fuel injection are believed to be the main contributors to the observed enhanced performance of the tested engine.

Catalytic hydrogen combustion for treatment of combustible gases from fuel cell processors

Catalytic combustion of H-2 was carried out over combustion synthesized noble metal (Pd or Pt) ion-substituted CeO2 based catalysts using a feed stream that simulated exhaust gases from a fuel cell processor The catalysts showed a high activity for H-2-combustion and complete conversion was achieved below 200 C over all the catalysts when O-2 was used in a stoichiometric amount With higher amounts of O-2 the reaction rates Increased and complete conversions were possible below 100 C The reaction was also carried out over Pd-impregnated CeO2 The conversions of H-2 with stoichiometric amount of O-2 were found to be higher over Pd-substituted compound The mechanism of the reaction over noble metal-substituted compounds was proposed on the basis of X-ray photoelectron spectroscopy studies The redox couples between Ce and metal ions were established and a dual site redox mechanism was pi posed for the reaction (C) 2010 Elsevier B V All rights reserved

In-cylinder investigations and analysis of a SI gas engine fuelled with H-2 and CO rich syngas fuel: Sensitivity analysis of combustion descriptors for engine diagnostics and control

The sensitivity of combustion phasing and combustion descriptors to ignition timing, load and mixture quality on fuelling a multi-cylinder natural gas engine with bio-derived H-2 and CO rich syngas is addressed. While the descriptors for conventional fuels are well established and are in use for closed loop engine control, presence of H-2 in syngas potentially alters the mixture properties and hence combustion phasing, necessitating the current study. The ability of the descriptors to predict abnormal combustion, hitherto missing in the literature, is also addressed. Results from experiments using multi-cylinder engines and numerical studies using zero dimensional Wiebe function based simulation models are reported. For syngas with 20% H-2 and CO and 2% CH4 (producer gas), an ignition retard of 5 +/- 1 degrees was required compared to natural gas ignition timing to achieve peak load of 72.8 kWe. It is found that, for syngas, whose flammability limits are 0.42-1.93, the optimal engine operation was at an equivalence ratio of 1.12. The same methodology is extended to a two cylinder engine towards addressing the influence of syngas composition, especially H-2 fraction (varying from 13% to 37%), on the combustion phasing. The study confirms the utility of pressure trace derived combustion descriptors, except for the pressure trace first derivative, in describing the MBT operating condition of the engine when fuelled with an alternative fuel. Both experiments and analysis suggest most of the combustion descriptors to be independent of the engine load and mixture quality. A near linear relationship with ignition angle is observed. The general trend(s) of the combustion descriptors for syngas fuelled operation are similar to those of conventional fuels; the differences in sensitivity of the descriptors for syngas fuelled engine operation requires re-calibration of control logic for MBT conditions. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Luminescence enhancement in monoclinic CaAl2O4:Eu2+, Cr3+ nanophosphor by fuel-blend combustion synthesis

Eu2+ ion doped into a suitable host results in an efficient luminophore with engineering relevance; however stabilizing this ion in a host is known to be a challenge. Here we report a novel approach for the synthesis of efficient CaAl2O4 phosphor containing Eu2+ luminophore and Cr3+ activator. CaAl2O4:Eu2+, Cr3+ is prepared by a solution combustion (SCS) method using (i) urea, (ii) oxalyl dihydrazide (ODH) and (iii) fuel-blend (in which overall fuel to oxidizer ratio (F/O) = 1). A Multi-channel thermocouple setup is used to measure the flame temperatures to study the nature of combustion of various fuel mixtures. The variation of adiabatic flame temperature is calculated theoretically for different urea/ODH mixture ratios according to thermodynamic concept and correlated with the observed flame temperatures. Blue emission of the CaAl2O4:Eu2+ phosphor is enhanced similar to 20 times using the fuel-blend approach. Using the observed reaction kinetics, and the known chemistry of smoldering type combustion, a mechanism is proposed for the observed stabilization of Eu2+ ion in the fuel-blend case. This also explains the observed improvement in blue light emission. We show that the right choice of the fuel ratio is essential for enhancing photoluminescence (PL) emission. The PL intensity is highest for ODH lean and urea rich combination (i.e. when the ratio of ODH:urea is 1:5); measured color purity is comparable to commercial blue phosphor, BAM:Eu2+. (C) 2015 Elsevier B.V. All rights reserved.

Role of Fuel on Cation Disorder in Magnesium Aluminate (MgAl2O4) Spinel Prepared by Combustion Synthesis

Magnesium aluminate spinel (MgAl2O4) forms an interesting system having tetrahedral and octahedral voids filled with near similar sized divalent Mg2+ and trivalent Al3+ cations. Structural disorder (e.g., Mg-Al antisite defects) can be tuned by synthetic conditions. This study reports the evolution of Mg/Al disorder in MgAl2O4 prepared by combustion synthesis using different types of fuels. The effect of nature of fuel and the final calcination temperature (600 degrees C-900 degrees C for 9h) on degree of cation ordering has been investigated combining powder X-ray (XRD) and neutron (NPD) diffraction. The results indicate very high degree of inversion in the samples crystallized at low annealing temperature, which on further annealing reduces toward the thermodynamically stable values. Raman spectroscopy, probing MgO4, and AlO4 tetrahedral bonds, confirmed the results at a local level.

Combustion and heat transfer characteristics of nanofluid fuel droplets: A short review

With the pressing need to meet an ever-increasing energy demand, the combustion systems utilizing fossil fuels have been the major contributors to carbon footprint. As the combustion of conventional energy resources continue to produce significant Green House gas (GHG) emissions, there is a strong emphasis to either upgrade or find an energy-efficient eco-friendly alternative to the traditional hydrocarbon fuels. With recent developments in nanotechnology, the ability to manufacture materials with custom tailored properties at nanoscale has led to the discovery of a new class of high energy density fuels containing reactive metallic nanoparticles (NPs). Due to the high reactive interfacial area and enhanced thermal and mass transport properties of nanomaterials, the high heat of formation of these metallic fuels can now be released rapidly, thereby saving on specific fuel consumption and hence reducing GHG emissions. In order to examine the efficacy of nanofuels in energetic formulations, it is imperative to first study their combustion characteristics at the droplet scale that form the fundamental building block for any combustion system utilizing liquid fuel spray. During combustion of such multiphase, multicomponent droplets, the phenomenon of diffusional entrapment of high volatility species leads to its explosive boiling (at the superheat limit) thereby leading to an intense internal pressure build-up. This pressure upsurge causes droplet fragmentation either in form of a microexplosion or droplet puffing followed by atomization (with formation of daughter droplets) featuring disruptive burning. Both these atomization modes represent primary mechanisms for extracting the high oxidation energies of metal NP additives by exposing them to the droplet flame (with daughter droplets acting as carriers of NPs). Atomization also serves as a natural mechanism for uniform distribution and mixing of the base fuel and enhancing burning rates (due to increase in specific surface area through formation of smaller daughter droplets). However, the efficiency of atomization depends on the thermo-physical properties of the base fuel, NP concentration and type. For instance, at dense loading NP agglomeration may lead to shell formation which would sustain the pressure upsurge and hence suppress atomization thereby reducing droplet gasification rate. Contrarily, the NPs may act as nucleation sites and aid boiling and the radiation absorption by NPs (from the flame) may lead to enhanced burning rates. Thus, nanoadditives may have opposing effects on the burning rate depending on the relative dominance of processes occurring at the droplet scale. The fundamental idea in this study is to: First, review different thermo-physical processes that occur globally at the droplet and sub-droplet scale such as surface regression, shell formation due to NP agglomeration, internal boiling, atomization/NP transport to flame zone and flame acoustic interaction that occur at the droplet scale and second, understand how their interaction changes as a function of droplet size, NP type, NP concentration and the type of base fuel. This understanding is crucial for obtaining phenomenological insights on the combustion behavior of novel nanofluid fuels that show great promise for becoming the next-generation fuels. (C) 2016 Elsevier Ltd. All rights reserved.

A report on increasing the thrust of a turbojet engine by combustion of fuel in the tail pipe

The purpose of this work was to develop a means of increasing the thrust of a turbojet engine by burning kerosene in the tail pipe.

A combustion system was developed which gave the following results:
(l) Maximum thrust increase using a G.E. I-14 engine was 64 per cent over straight tail pipe thrust corresponding to 42 per cent increase over the normal engine thrust. This increase was accomplished at an engine rpm of 12,000.
(2) Increase of maximum thrust obtained was 51 per cent over the straight tail pipe thrust corresponding to 23 per cent over the normal engine thrust. This increase was accomplished at an engine rpm of l6,000.
(3) For the thrust increases mentioned in (1) and (2) above, increases of Specific Fuel Consumption were 66 per cent and 76 per cent respectively over normal engine SFC.