Internal combustion engines are a key aspect of society, and their continued use poses challenges from an environmental standpoint since they emit pollutant and greenhouse gas emissions. This dissertation focuses on experimental analysis of dual-fuel low temperature combustion (LTC), which can be used as a strategy to reduce engine-out emissions and increase engine efficiencies. Dual fuel LTC uses two different fuels, a high reactivity fuel (HRF) and a low reactivity fuel (LRF). The HRF has a higher cetane number than the LRF, which allows for easier auto-ignition in compression ignition engines. Dual fuel engines also utilize high air to fuel ratios to achieve LTC. This, combined with early injection timings of the HRF, helps to reduce oxides of nitrogen (NOx) emissions. At low load conditions, this is a problem since higher cycle-to-cycle variations can increase pollutants such as unburned hydrocarbons (UHC) and carbon monoxide (CO). To combat this, a firm understanding of dual fuel LTC is required, as well as a strategy for reducing the cycle-to-cycle variations. The first part of this work further identifies a combustion heat release 'transformation region' across different HRF injection timings wherein in-cylinder conditions arise that are conducive for ultra-low NOx emissions. This phenomenon occurs for different IC engine platforms and different fueling combinations. An experimental analysis, 0D chemical kinetic analysis, and 3D computation fluid dynamic (CFD) analysis were combined to elucidate the underlying causes for this phenomenon. The local stratification level of the fuel/air mixture was identified as the likely cause of combustion heat release transformation with changing HRF injection timing. The second part of the present work builds upon the findings of the first part by utilizing local stratification to mitigate cycle-to-cycle variations that are present at low loads. A framework of experiments was formulated for both a low engine load of 5 bar gross indicated mean effective pressure (IMEPg) and a high load of 15 bar IMEPg, wherein an injection strategy concept termed Spray TArgeted Reactivity Stratification (STARS) was utilized using both diesel and Polyoxymethelene-dimethyl-ether (POMDME) as HRFs. A steep decrease in UHC and CO emissions (> 80% reductions) as well as improved engine operation stability were demonstrated using both HRFs with dual fuel LTC at 5 bar IMEPg. Further, potential for emissions mitigation and efficiency improvement are discussed, as well as differences in the experimental results shown between the differing HRFs.

Low temperature combustion strategies have demonstrated high thermal efficiency with low emissions of pollutants, including oxides of nitrogen and particulate matter. One such combustion strategy, called Reactivity Controlled Compression Ignition (RCCI), which involves the port injection of a low reactivity fuel such as gasoline, ethanol, or natural gas, and a direct injection of a high reactivity fuel, such as diesel, has demonstrated excellent control over the heat release event due to the introduction of in-cylinder stratification of equivalence ratio and reactivity. The RCCI strategy is inherently fuel flexible, however the direct injection strategy needs to be tailored to the combination of premixed and direct injected fuels. Experimental results demonstrate that, when comparing different premixed fuels, matching combustion phasing with premixed mass percentage or SOI timing is not sufficient to retain baseline efficiency and emissions results. If the bulk characteristics of the heat release event can be matched, however, then the efficiency and emissions can be maintained. A 0-D methodology for predicting the required fuel stratification for a desired heat release for kinetically-controlled stratified-charge combustion strategies is proposed and validated with 3-D reacting and non-reacting CFD simulations performed with KIVA3Vr2 in this work. Various heat release rate shapes, phasing, duration, and premixed and DI fuel chemistries are explored using this analysis. This methodology provides a means by which the combustion process of a stratified-charge, kinetically-controlled combustion strategy could be optimized for any fuel combination, assuming that the fuel chemistry is well characterized.

The goal of this research is to identify how nitrogen oxide (NOx) emissions and flame stability (blowout) are impacted by the use of fuels that are alternatives to typical pipeline natural gas. The research focuses on lean, premixed combustors that are typically used in state-of-the-art natural gas fueled systems. An idealized laboratory lean premixed combustor, specifically the jet-stirred reactor, is used for experimental data. A series of models, including those featuring detailed fluid dynamics and those focusing on detailed chemistry, are used to interpret the data and understand the underlying chemical kinetic reasons for differences in emissions between the various fuel blends. An ultimate goal is to use these data and interpretive tools to develop a way to predict the emission and stability impacts of changing fuels within practical combustors. All experimental results are obtained from a high intensity, single-jet stirred reactor (JSR). Five fuel categories are studied: (1) pure H2, (2) process and refinery gas, including combinations of H2, CH4, C2H6, and C3H8, (3) oxygen blown gasified coal/petcoke composed of H2, CO, and CO2, (4) landfill and digester gas composed of CH4, CO2, and N2, and (5) liquified natural gas (LNG)/shale/associated gases composed of CH4, C2H6, and C3H8. NOx measurements are taken at a nominal combustion temperature of 1800 K, atmospheric pressure, and a reactor residence time of 3 ms. This is done to focus the results on differences caused by fuel chemistry by comparing all fuels at a common temperature, pressure, and residence time. This is one of the few studies in the literature that attempts to remove these effects when studying fuels varying in composition. Additionally, the effects of changing temperature and residence time are investigated for selected fuels. At the nominal temperature and residence time, the experimental and modeling results show the following trends for NOx emissions as a function of fuel type: 1.) NOx emissions decrease with increasing H2 fuel fraction for combustion of CH4/H2 blends. This appears to be caused by a reduction in the amount of NO made by the prompt pathway involving the reaction of N2 with hydrocarbon radicals as the CH4 is replaced by H2. 2.) For category 2 (the process and refinery blend) and category 5 (the LNG, shale, and associated gases), NOx emissions increase with the addition of C2 and C3 hydrocarbons. This could be due to an increased production of free radicals resulting from increasing CO production when higher molecular weight hydrocarbons are broken down. 3.) For category 3 (the O2 blown gasified coal/petcoke), NOx emissions increase with increasing CO fuel fraction. The reason for this is attributed to CO producing more radicals per unit heat release than H2. When CO replaces H2, an increase in NOx emissions is seen due to an increase in the productivity of the N2O, NNH, and Zeldovich pathways. 4.) For category 4 (the landfill gas) the addition of diluents such as CO2 and N2 at constant air flow produces more NOx per kg of CH4 consumed, and N2 is more effective than CO2 in increasing the NOx emission index. The increase in emission index appears to be due to an enhancement of the prompt NOx pathway as the diluents are added and the mixture moves towards stoichiometric. In addition, the presence of CO2 as a diluent catalyzes the loss of flame radicals, leading to less NOx formation than when an equivalent amount of N2 is used as a diluent. For a selected set of fuels, detailed spacial reactor probing is carried out. At the nominal temperature and residence time, the experimental results show the following trends for flame structure as a function of fuel type: 1.) Pure H2 is far more reactive in comparison to CH4 and all other pure alkane fuels. This results in relatively flat NOx and temperature profiles; whereas, the alkane fuels drop in both temperature and NOx production in the jet, where more fresh reactor feed gases are present. 2.) For category 2 (the Process and Refinery blends), H2 addition increases reactivity in the jet while decreasing overall NOx emissions. The increased reactivity is especially evident in the CO profiles where the fuels blended with C2H6 and H2 have CO peaks on jet centerline and CO emissions for pure CH4 peaks slightly off centerline. 3.) For category 3 (the O2 blown gasified coal/petcoke), the temperature profiles for the gasification blend and pure H2 are nearly identical, which is likely due to the high reactivity of H2 dominating the relatively low reactivity of CO. Despite a small temperature difference, the addition of CO causes an increase in NOx production. 4.) For category 4 (the landfill gas), the temperature profiles are virtually indistinguishable. However, the addition of diluent decreases reactivity and spreads out the reaction zone with the CO concentration peaking at 2 mm off of centerline instead of 1 mm. Diluent addition increases NOx production in comparison to pure CH4 for reasons explained above. 5.) For category 5 (the LNG, shale, and associated gases), the temperature profiles are all very similar. The increased reactivity of C2H6 is evident from looking at the CO profiles. Increased C2H6 promotes CO production on jet centerline which is indicative of the hydrocarbon material breaking down earlier in the jet. At temperatures and residence times other than the nominal conditions, the experimental results show the following trends: 1,) The NOx emissions from LPM combustion of pure CH4, H2, C2H6, and C3H8 are shown to vary linearly with residence time and in an Arrhenius fashion with temperature. This occurs because (1) more reaction time leads to more NOx formation, and (2) NOx formation is a strong, non-linear function of temperature. 2.) The addition of both H2 and C2H6 to a LPM CH4 flame is effective at extending its lean blowout limit. The results of both two and three dimensional CFD simulations are presented to illustrate the general flow, temperature, and species structure within the reactor. Since the two dimensional model is far more computationally efficient, it is employed to study various fuel mixtures with more sophisticated chemical mechanisms. The CFD results from the LPM combustion of H2, H2/CO, and CH4 with NOx formation are presented. A three dimensional CFD simulation is run for LPM CH4 combustion that uses a global CH4 oxidation mechanism. While this model does not predict intermediate radicals and NOx, the CO contours and flow field can be used as guidelines to develop a chemical reactor network (CRN), which can incorporate detailed chemistry. In addition, this model runs quickly enough that it is a good way to initialize the temperature and flow field for simulations that do incorporate more complex chemistry. The two dimensional model is used to illustrate the difference in combustion behavior between the various fuels tested. In particular, it illustrates the geometric locations of the super-equilibrium radical fields and shows where and through which pathways NOx is formed. The pathway breakdowns show good agreement with the CRN modeling results. The main goal of the CFD modeling is to use the results of each model to develop Chemical Reactor Networks, CRNs, that are customized for a particular burner. The CRN can then be used to estimate the impacts due to fuel variation.

Reactivity Controlled Compression Ignition (RCCI) is a novel combustion process that utilizes two fuels with different reactivity to stage and control combustion and enable homogeneous combustion. The technique has been proven experimentally in previous work with diesel and gasoline fuels; low NOx emissions and high efficiencies were observed from RCCI in comparison to conventional combustion. In previous studies on a multi-cylinder engine, particulate matter (PM) emission measurements from RCCI suggested that hydrocarbons were a major component of the PM mass. Further studies were conducted on this multi-cylinder engine platform to characterize the PM emissions in more detail and understand the effect of a diesel oxidation catalyst (DOC) on the hydrocarbon-dominated PM emissions. Results from the study show that the DOC can effectively reduce the hydrocarbon emissions as well as the overall PM from RCCI combustion. The bimodal size distribution of PM from RCCI is altered by the DOC which reduces the smaller mode 10 nm size particles.

The diversity of reactivities, intermediates, and pathways associated with the low-temperature oxidation of various component classes that constitute real fuels is perhaps the most challenging aspect of modeling combustion chemistry of these fuels. Unlike high-temperature oxidation (T > 1000 K), where the law of large numbers renders global combustion properties of real, multicomponent fuels weakly sensitive to compositional variability, reactions controlling low-temperature oxidation are very sensitive to fuel composition. Despite this fuel specificity, the formation of intermediates during low-temperature oxidation exhibits certain commonalities which can be observed in carefully designed shock tube experiments. Combining these observations with elemental balance, chemical kinetic considerations, and with the already mature Hybrid Chemistry (HyChem) approach for high-temperature oxidation of real fuels, I first propose an approach to develop simplified, physics-based chemical kinetic models for low-temperature oxidation of real fuels. In this approach, the low-temperature oxidation is described by lumped, fuel-specific reactions whose rate constants and stoichiometric parameters are determined using shock tube species time history measurements. These reactions augment the already developed high-temperature HyChem models which encompass fuel-specific reactions describing thermal and oxidative pyrolysis at high temperatures, and a detailed model describing kinetics of small hydrocarbons. Detailed arguments in support of the model formulation are presented. The model is then exercised to identify species to be targeted for measurements in shock tubes. Carbon monoxide (CO), and formaldehyde (CH2O) were identified as the most important species for determining the model parameters followed by OH, and HO2. Laser absorption spectroscopy based diagnostics for measuring some of these species were also developed in parallel with this work. The feasibility of the targeted speciation studies is first demonstrated during oxidation of five neat hydrocarbons, i.e., n-decane, n-octane, n-heptane, and its two branched isomers, 2-methyl hexane, and 3,3-dimethyl pentane. These studies not only demonstrated the feasibility of the diagnostics, but also highlighted the deficiency in the existing detailed models for low-temperature oxidation of heavy hydrocarbons. They also provided further evidence supporting some of the assumptions made while formulating the LT-HyChem approach. With the speciation strategy developed, and target experimental conditions verified, the application of the LT-HyChem approach to three classes of fuels is presented: a) A simple, three-component hydrocarbon mixture (TPRF-60), b) A jet fuel, c) Two high-performance gasoline fuels. Validation of the model against a range of ignition delay time (IDT) measurements conducted across a range of facilities worldwide is presented. The model predictions for all fuels show excellent agreement with the IDTs reported in the literature over a wide range of conditions. Moreover, the constraints imposed on the model parameters by the species time history measurements conducted in shock tubes result in a significant reduction in the uncertainty in the model's predictions. A detailed uncertainty analysis is presented and is supplemented with sensitivity analysis to identify the dominant contributing factors to the uncertainty in model predictions. The success of the LT-HyChem approach is encouraging as this approach can be extended to the sustainable fuels that will drive the engines of tomorrow. This will enable a rapid screening of candidates for the sustainable fuels of tomorrow.