A physico-chemical characterisation of particulate emissions from a compression ignition engine : the influence of biodiesel feedstock

This study undertook a physico-chemical characterisation of particle emissions from a single compression ignition engine operated at one test mode with 3 biodiesel fuels made from 3 different feedstocks (i.e. soy, tallow and canola) at 4 different blend percentages (20%, 40%, 60% and 80%) to gain insights into their particle-related health effects. Particle physical properties were inferred by measuring particle number size distributions both with and without heating within a thermodenuder (TD) and also by measuring particulate matter (PM) emission factors with an aerodynamic diameter less than 10 μm (PM10). The chemical properties of particulates were investigated by measuring particle and vapour phase Polycyclic Aromatic Hydrocarbons (PAHs) and also Reactive Oxygen Species (ROS) concentrations. The particle number size distributions showed strong dependency on feedstock and blend percentage with some fuel types showing increased particle number emissions, whilst others showed particle number reductions. In addition, the median particle diameter decreased as the blend percentage was increased. Particle and vapour phase PAHs were generally reduced with biodiesel, with the results being relatively independent of the blend percentage. The ROS concentrations increased monotonically with biodiesel blend percentage, but did not exhibit strong feedstock variability. Furthermore, the ROS concentrations correlated quite well with the organic volume percentage of particles – a quantity which increased with increasing blend percentage. At higher blend percentages, the particle surface area was significantly reduced, but the particles were internally mixed with a greater organic volume percentage (containing ROS) which has implications for using surface area as a regulatory metric for diesel particulate matter (DPM) emissions.

Physicochemical characterization of particulate emissions from a compression ignition engine employing two injection technologies and three fuels

Alternative fuels and injection technologies are a necessary component of particulate emission reduction strategies for compression ignition engines. Consequently, this study undertakes a physicochemical characterization of diesel particulate matter (DPM) for engines equipped with alternative injection technologies (direct injection and common rail) and alternative fuels (ultra low sulfur diesel, a 20% biodiesel blend, and a synthetic diesel). Particle physical properties were addressed by measuring particle number size distributions, and particle chemical properties were addressed by measuring polycyclic aromatic hydrocarbons (PAHs) and reactive oxygen species (ROS). Particle volatility was determined by passing the polydisperse size distribution through a thermodenuder set to 300 °C. The results from this study, conducted over a four point test cycle, showed that both fuel type and injection technology have an impact on particle emissions, but injection technology was the more important factor. Significant particle number emission (54%–84%) reductions were achieved at half load operation (1% increase–43% decrease at full load) with the common rail injection system; however, the particles had a significantly higher PAH fraction (by a factor of 2 to 4) and ROS concentrations (by a factor of 6 to 16) both expressed on a test-cycle averaged basis. The results of this study have significant implications for the health effects of DPM emissions from both direct injection and common rail engines utilizing various alternative fuels.

An investigation of gaseous and particulate emissions from compression ignition engines operated with alternative fuels, injection technologies, and combustion strategies

Whilst the compression ignition (CI) engine exhibits many design advantages relative to its spark ignition engine counterpart; such as: high thermal efficiency, fuel economy and low carbon monoxide and hydrocarbon emissions, the issue of Diesel Particulate Matter (DPM) emissions continues to be an unresolved problem for the CI engine. Primarily, this thesis investigates a range of DPM mitigation strategies such as alternative fuels, injection technologies and combustion strategies conducted with a view to determine their impact on the physico-chemical properties of DPM emissions, and consequently to shed light on their likely human health impacts. Regulated gaseous emissions, Nitric oxide (NO), Carbon monoxide (CO), and Hydrocarbons (HCs), were measured in all experimental campaigns, although the major focus in this research program was on particulate emissions...

The economic impact of proposed regulations to reduce particulate emissions from steel mills and industrial fugitive sources, R 78-10 and R 78-11 /

Project officer: Michael H. Friedman.

Particulate emissions of a cotton gin in the Texas stripper area /

Includes bibliographical references.

The application of a profluorescent nitroxide probe to detect reactive oxygen species derived from combustion-generated particulate matter

Particulate pollution has been widely recognised as an important risk factor to human health. In addition to increases in respiratory and cardiovascular morbidity associated with exposure to particulate matter (PM), WHO estimates that urban PM causes 0.8 million premature deaths globally and that 1.5 million people die prematurely from exposure to indoor smoke generated from the combustion of solid fuels. Despite the availability of a huge body of research, the underlying toxicological mechanisms by which particles induce adverse health effects are not yet entirely understood. Oxidative stress caused by generation of free radicals and related reactive oxygen species (ROS) at the sites of deposition has been proposed as a mechanism for many of the adverse health outcomes associated with exposure to PM. In addition to particle-induced generation of ROS in lung tissue cells, several recent studies have shown that particles may also contain ROS. As such, they present a direct cause of oxidative stress and related adverse health effects. Cellular responses to oxidative stress have been widely investigated using various cell exposure assays. However, for a rapid screening of the oxidative potential of PM, less time-consuming and less expensive, cell-free assays are needed. The main aim of this research project was to investigate the application of a novel profluorescent nitroxide probe, synthesised at QUT, as a rapid screening assay in assessing the oxidative potential of PM. Considering that this was the first time that a profluorescent nitroxide probe was applied in investigating the oxidative stress potential of PM, the proof of concept regarding the detection of PM–derived ROS by using such probes needed to be demonstrated and a sampling methodology needed to be developed. Sampling through an impinger containing profluorescent nitroxide solution was chosen as a means of particle collection as it allowed particles to react with the profluorescent nitroxide probe during sampling, avoiding in that way any possible chemical changes resulting from delays between the sampling and the analysis of the PM. Among several profluorescent nitroxide probes available at QUT, bis(phenylethynyl)anthracene-nitroxide (BPEAnit) was found to be the most suitable probe, mainly due to relatively long excitation and emission wavelengths (λex= 430 nm; λem= 485 and 513 nm). These wavelengths are long enough to avoid overlap with the background fluorescence coming from light absorbing compounds which may be present in PM (e.g. polycyclic aromatic hydrocarbons and their derivatives). Given that combustion, in general, is one of the major sources of ambient PM, this project aimed at getting an insight into the oxidative stress potential of combustion-generated PM, namely cigarette smoke, diesel exhaust and wood smoke PM. During the course of this research project, it was demonstrated that the BPEAnit probe based assay is sufficiently sensitive and robust enough to be applied as a rapid screening test for PM-derived ROS detection. Considering that for all three aerosol sources (i.e. cigarette smoke, diesel exhaust and wood smoke) the same assay was applied, the results presented in this thesis allow direct comparison of the oxidative potential measured for all three sources of PM. In summary, it was found that there was a substantial difference between the amounts of ROS per unit of PM mass (ROS concentration) for particles emitted by different combustion sources. For example, particles from cigarette smoke were found to have up to 80 times less ROS per unit of mass than particles produced during logwood combustion. For both diesel and wood combustion it has been demonstrated that the type of fuel significantly affects the oxidative potential of the particles emitted. Similarly, the operating conditions of the combustion source were also found to affect the oxidative potential of particulate emissions. Moreover, this project has demonstrated a strong link between semivolatile (i.e. organic) species and ROS and therefore, clearly highlights the importance of semivolatile species in particle-induced toxicity.

Gaseous and particle emissions from an ethanol fumigated compression ignition engine

A 4-cylinder Ford 2701C test engine was used in this study to explore the impact of ethanol fumigation on gaseous and particle emission concentrations. The fumigation technique delivered vaporised ethanol into the intake manifold of the engine, using an injector, a pump and pressure regulator, a heat exchanger for vaporising ethanol and a separate fuel tank and lines. Gaseous (Nitric oxide (NO), Carbon monoxide (CO) and hydrocarbons (HC)) and particulate emissions (particle mass (PM2.5) and particle number) testing was conducted at intermediate speed (1700 rpm) using 4 load settings with ethanol substitution percentages ranging from 10-40 % (by energy). With ethanol fumigation, NO and PM2.5 emissions were reduced, whereas CO and HC emissions increased considerably and particle number emissions increased at most test settings. It was found that ethanol fumigation reduced the excess air factor for the engine and this led to increased emissions of CO and HC, but decreased emissions of NO. PM2.5 emissions were reduced with ethanol fumigation, as ethanol has a very low “sooting” tendency. This is due to the higher hydrogen-to-carbon ratio of this fuel, and also because ethanol does not contain aromatics, both of which are known soot precursors. The use of a diesel oxidation catalyst (as an after-treatment device) is recommended to achieve a reduction in the four pollutants that are currently regulated for compression ignition engines. The increase in particle number emissions with ethanol fumigation was due to the formation of volatile (organic) particles; consequently, using a diesel oxidation catalyst will also assist in reducing particle number emissions.

The influence of oxygenated organic aerosols (OOA) on the oxidative potential of diesel and biodiesel particulate matter

Generally, the magnitude of pollutant emissions from diesel engines running on biodiesel fuel is ultimately coupled to the structure of respective molecules that constitutes the fuel. Previous studies demonstrated the relationship between organic fraction of PM and its oxidative potential. Herein, emissions from a diesel engine running on different biofuels were analysed in more detail to explore the role different organic fractions play in the measured oxidative potential. In this work, a more detailed chemical analysis of biofuel PM was undertaken using a compact Time of Flight Aerosol Mass Spectrometer (c-ToF AMS). This enabled a better identification of the different organic fractions that contribute to the overall measured oxidative potentials. The concentration of reactive oxygen species (ROS) was measured using a profluorescent nitroxide molecular probe 9-(1,1,3,3-tetramethylisoindolin-2-yloxyl-5-ethynyl)-10-(phenylethynyl)anthracene (BPEAnit). Therefore the oxidative potential of the PM, measured through the ROS content, although proportional to the total organic content in certain cases shows a much higher correlation with the oxygenated organic fraction as measured by the c-ToF AMS. This highlights the importance of knowing the surface chemistry of particles for assessing their health impacts. It also sheds light onto new aspects of particulate emissions that should be taken into account when establishing relevant metrics for assessing health implications of replacing diesel with alternative fuels.

Performance and gaseous and particle emissions from a liquefied petroleum gas (LPG) fumigated compression ignition engine

In this study, an LPG fumigation system was fitted to a Euro III compression ignition (CI) engine to explore its impact on performance, and gaseous and particulate emissions. LPG was introduced to the intake air stream (as a secondary fuel) by using a low pressure fuel injector situated upstream of the turbocharger. LPG substitutions were test mode dependent, but varied in the range of 14-29% by energy. The engine was tested over a 5 point test cycle using ultra low sulphur diesel (ULSD), and a low and high LPG substitution at each test mode. The results show that LPG fumigation coerces the combustion into pre-mixed mode, as increases in the peak combustion pressure (and the rate of pressure rise) were observed in most tests. The emissions results show decreases in nitric oxide (NO) and particulate matter (PM2.5) emissions; however, very significant increases in carbon monoxide (CO) and hydrocarbon (HC) emissions were observed. A more detailed investigation of the particulate emissions showed that the number of particles emitted was reduced with LPG fumigation at all test settings – apart from mode 6 of the ECE R49 test cycle. Furthermore, the particles emitted generally had a slightly larger median diameter with LPG fumigation, and had a smaller semi-volatile fraction relative to ULSD. Overall, the results show that with some modifications, LPG fumigation systems could be used to extend ULSD supplies without adversely impacting on engine performance and emissions.

EMISSIONS CHARACTERISTICS OF A RESIDENTIAL PELLET BOILER AND A STOVE

Gaseous and particulate emissions from a residential pellet boiler and a stove are measured at a realistic 6-day operation sequence and during steady state operation. The aim is to characterize the emissions during each phase in order to identify when the major part of the emissions occur to enable actions for emission reduction where the savings can be highest. The characterized emissions comprised carbon monoxide (CO), nitrogen oxide (NO), total organic carbon (TOC) and particulate matter (PM 2.5). In this study, emissions were characterised by mass concentration and emissions during start-up and stop phases were also presented in accumulated mass. The influence of start-up and stop phases on the emissions, average emission factors for the boiler and stove were analysed using the measured data from a six-days test. The share of start-up and stop emissions are significant for CO and TOC contributing 95% and 89% respectively at the 20kW boiler and 82% and 89% respectively at the 12 kW stove. NO and particles emissions are shown to dominate during stationary operation.

Study of combustion of different biomass and its atmospheric emissions

One of the energy alternatives that provide utility, flexibility, cleanliness and economy is biomass, such as forest waste (wood) and agricultural (sugarcane bagasse, rice husks, coffee pods, etc.). However, with its increasing supply and use grows also the concern of industries to invest in monitoring and control of emissions into the atmosphere, because during biomass burning are emitted as exhaust gases, fine particles known as particulates, which greatly contribute to the triggering of serious health problems to humans, in addition to the environmental damage. With that, this work aimed to conduct a monitoring of particulate and gaseous pollutants emissions to the atmosphere from the burning of various types of biomass used by industries. The equipment used for sampling were the optical monitor DataRAM 4 and the Unigas3000 + gas sampler. The results showed that biomass coffee pods presented the greatest concentration of particulates (485119 μg m-3) with particle diameters between 0.0602 μm and 0.3502 μm, i.e. the most ultrafine particles, harmful to human health and the environment. The largest emissions of CO and NOx were observed, respectively, for the coffee pods (3500 ppm) and for the rice husk (48 ppm). As for the superior calorific value (PCS), the best of fuel, with higher PCS, was the Eucalyptus grandis.

Combustion of coal, bagasse and blends thereof Part I: Emissions from batch combustion of fixed beds of fuels

Batch combustion of fixed beds of coal, bagasse and blends thereof took place in a pre-heated two-stage electric laboratory furnace, under high-heating rates. The average input fuel/air equivalence ratios were similar for all fuels. The primary and secondary furnace temperatures were varied from 800 degrees C to 1000 degrees C. The effects of fuel blending, combustion staging, and operating furnace temperatures on the emissions from the two fuels were assessed. Furnace effluents were analyzed for carbon dioxide and for products of incomplete combustion (PIC) including CO, volatile and semi-volatile hydrocarbons, as well as particulate matter. Results showed that whereas CO2 was generated during both the observed sequential volatile matter and char combustion phases of the fuels, PICs were only generated during the volatile matter combustion phase. CO2 emissions were the highest from coal, whereas CO and other PIC emissions were the highest from bagasse. Under this particular combustion configuration, combustion of the volatile matter of the blends resulted in lower yields of PIC, than combustion of the volatiles of the neat fuels. Though CO and unburned hydrocarbons from coal as well as from the blends did not exhibit a clear trend with furnace temperature, such emissions from bagasse clearly increased with temperature. The presence of the secondary furnace (afterburner) typically reduced PIC, by promoting further oxidation of the primary furnace effluents. (C) 2012 Elsevier Ltd. All rights reserved.

Experimental and modeling study of the filtration and oxidation characteristics of a diesel oxidation catalyst and a catalyzed particulate filter

A diesel oxidation catalyst (DOC) with a catalyzed diesel particulate filter (CPF) is an effective exhaust aftertreatment device that reduces particulate emissions from diesel engines, and properly designed DOC-CPF systems provide passive regeneration of the filter by the oxidation of PM via thermal and NO2/temperature-assisted means under various vehicle duty cycles. However, controlling the backpressure on engines caused by the addition of the CPF to the exhaust system requires a good understanding of the filtration and oxidation processes taking place inside the filter as the deposition and oxidation of solid particulate matter (PM) change as functions of loading time. In order to understand the solid PM loading characteristics in the CPF, an experimental and modeling study was conducted using emissions data measured from the exhaust of a John Deere 6.8 liter, turbocharged and after-cooled engine with a low-pressure loop EGR system and a DOC-CPF system (or a CCRT® - Catalyzed Continuously Regenerating Trap®, as named by Johnson Matthey) in the exhaust system. A series of experiments were conducted to evaluate the performance of the DOC-only, CPF-only and DOC-CPF configurations at two engine speeds (2200 and 1650 rpm) and various loads on the engine ranging from 5 to 100% of maximum torque at both speeds. Pressure drop across the DOC and CPF, mass deposited in the CPF at the end of loading, upstream and downstream gaseous and particulate emissions, and particle size distributions were measured at different times during the experiments to characterize the pressure drop and filtration efficiency of the DOCCPF system as functions of loading time. Pressure drop characteristics measured experimentally across the DOC-CPF system showed a distinct deep-bed filtration region characterized by a non-linear pressure drop rise, followed by a transition region, and then by a cake-filtration region with steadily increasing pressure drop with loading time at engine load cases with CPF inlet temperatures less than 325 °C. At the engine load cases with CPF inlet temperatures greater than 360 °C, the deep-bed filtration region had a steep rise in pressure drop followed by a decrease in pressure drop (due to wall PM oxidation) in the cake filtration region. Filtration efficiencies observed during PM cake filtration were greater than 90% in all engine load cases. Two computer models, i.e., the MTU 1-D DOC model and the MTU 1-D 2-layer CPF model were developed and/or improved from existing models as part of this research and calibrated using the data obtained from these experiments. The 1-D DOC model employs a three-way catalytic reaction scheme for CO, HC and NO oxidation, and is used to predict CO, HC, NO and NO2 concentrations downstream of the DOC. Calibration results from the 1-D DOC model to experimental data at 2200 and 1650 rpm are presented. The 1-D 2-layer CPF model uses a ‘2-filters in series approach’ for filtration, PM deposition and oxidation in the PM cake and substrate wall via thermal (O2) and NO2/temperature-assisted mechanisms, and production of NO2 as the exhaust gas mixture passes through the CPF catalyst washcoat. Calibration results from the 1-D 2-layer CPF model to experimental data at 2200 rpm are presented. Comparisons of filtration and oxidation behavior of the CPF at sample load-cases in both configurations are also presented. The input parameters and selected results are also compared with a similar research work with an earlier version of the CCRT®, to compare and explain differences in the fundamental behavior of the CCRT® used in these two research studies. An analysis of the results from the calibrated CPF model suggests that pressure drop across the CPF depends mainly on PM loading and oxidation in the substrate wall, and also that the substrate wall initiates PM filtration and helps in forming a PM cake layer on the wall. After formation of the PM cake layer of about 1-2 µm on the wall, the PM cake becomes the primary filter and performs 98-99% of PM filtration. In all load cases, most of PM mass deposited was in the PM cake layer, and PM oxidation in the PM cake layer accounted for 95-99% of total PM mass oxidized during loading. Overall PM oxidation efficiency of the DOC-CPF device increased with increasing CPF inlet temperatures and NO2 flow rates, and was higher in the CCRT® configuration compared to the CPF-only configuration due to higher CPF inlet NO2 concentrations. Filtration efficiencies greater than 90% were observed within 90-100 minutes of loading time (starting with a clean filter) in all load cases, due to the fact that the PM cake on the substrate wall forms a very efficient filter. A good strategy for maintaining high filtration efficiency and low pressure drop of the device while performing active regeneration would be to clean the PM cake filter partially (i.e., by retaining a cake layer of 1-2 µm thickness on the substrate wall) and to completely oxidize the PM deposited in the substrate wall. The data presented support this strategy.