The use of gasoline in homogeneous charge compression ignition engines (HCCI) and in duel fuel diesel - gasoline engines, has increased the need to understand its compression ignition processes under engine-like conditions. These processes need to be studied under well-controlled conditions in order to quantify low temperature heat release and to provide fundamental validation data for chemical kinetic models. With this in mind, an experimental campaign has been undertaken in a rapid compression machine (RCM) to measure the ignition of gasoline mixtures over a wide range of compression temperatures and for different compression pressures. By measuring the pressure history during ignition, information on the first stage ignition (when observed) and second stage ignition are captured along with information on the phasing of the heat release. Heat release processes during ignition are important because gasoline is known to exhibit low temperature heat release, intermediate temperature heat release and high temperature heat release. In an HCCI engine, the occurrence of low-temperature and intermediate-temperature heat release can be exploited to obtain higher load operation and has become a topic of much interest for engine researchers. Consequently, it is important to understand these processes under well-controlled conditions. A four-component gasoline surrogate model (including n-heptane, iso-octane, toluene, and 2-pentene) has been developed to simulate real gasolines. An appropriate surrogate mixture of the four components has been developed to simulate the specific gasoline used in the RCM experiments. This chemical kinetic surrogate model was then used to simulate the RCM experimental results for real gasoline. The experimental and modeling results covered ultra-lean to stoichiometric mixtures, compressed temperatures of 640-950 K, and compression pressures of 20 and 40 bar. The agreement between the experiments and model is encouraging in terms of first-stage (when observed) and second-stage ignition delay times and of heat release rate. The experimental and computational results are used to gain insight into low and intermediate temperature processes during gasoline ignition.

Real fuels are complex mixtures of thousands of hydrocarbon compounds including linear and branched paraffins, naphthenes, olefins and aromatics. It is generally agreed that their behavior can be effectively reproduced by simpler fuel surrogates containing a limited number of components. In this work, a recently revised version of the kinetic model by the authors is used to analyze the combustion behavior of several components relevant to gasoline surrogate formulation. Particular attention is devoted to linear and branched saturated hydrocarbons (PRF mixtures), olefins (1-hexene) and aromatics (toluene). Model predictions for pure components, binary mixtures and multi-component gasoline surrogates are compared with recent experimental information collected in rapid compression machine, shock tube and jet stirred reactors covering a wide range of conditions pertinent to internal combustion engines. Simulation results are discussed focusing attention on the mixing effects of the fuel components.

In the first part of this work, ignition of methane-air mixtures under excess air dilution is studied. When excess air is used in SI engine operation, thermal efficiency is increased due to increase in compression ratio together with reduced pumping and heat loses. However, stable operation with excess air is challenging due to poor flammability of the resulting diluted mixture. Hence in order to achieve stable and complete combustion a turbulent jet ignition (TJI) system is used to improve combustion of lean methane-air mixtures. Various nozzle designs and operating strategies for a TJI system were tested in a rapid compression machine. 10-90% burn duration measurements were useful in assessing the performance of the nozzle designs while the 0-10% burn durations indicated if optimal air-fuel ratio is achieved within the pre-chamber at the time of ignition. The results indicated that distributed-jets TJI system offered faster and stable combustion while the concentrated-jets TJI system offered better dilution tolerance.Knock in a SI engine occurs due to autoignition of the end gas mixture and typically occurs in the negative temperature coefficient (NTC) region of the fuel-air mixture. Dilution of intake charge with cold exhaust recirculation gases (EGR) reduces combustion temperatures and decreases mixture reactivity thereby reducing knocking tendency. This enables optimal spark timings to be used, thereby increasing efficiency of SI engines which would otherwise be knock limited. Effect of cold EGR dilution is studied in the RCM by measuring the autoignition delay times of gasoline and gasoline surrogate mixtures diluted with varying levels of CO2. The autoignition experiments in the RCM were performed using a novel direct test chamber (DTC) charge preparation approach. The DTC approach enabled mixture preparation directly within the combustion chamber and eliminated the need for mixing tanks. Effect of CO2 dilution in retarding the autoignition delay times was more pronounced in the NTC region, while it was weaker in the low temperature and high temperature regions. The retarding effect was found to be dependent on both the octane number and the fuel composition of the gasoline being studied.Finally, the effect of substituting ethanol(biofuel) in gasoline surrogates for up to 40% by volume is studied. Ethanol is an octane booster, but it blends antagonistically with aromatics such as toluene and synergistically with alkanes with respect to the resulting octane number of the blends. In order to study this blending effect, two gasoline surrogates containing only alkanes (PRF), and alkanes with large amounts of toluene (TRF) are blended with varying levels of ethanol. The ignition delay times of the resulting mixtures are measured in a rapid compression machine and kinetic analysis was carried out using numerical simulations. The kinetic analysis revealed that ethanol controlled the final stages of ignition for the PRF blends when more than 10% by volume of ethanol is present. However, in the TRF blends, toluene controlled the ignition until mole fractions of ethanol became higher than the toluene indicating the reason for the antagonistic blending nature. It was found that the RON values of the resulting blends matched the trend of the ignition delay times recorded at 740K and 21 bar compressed conditions. This enables qualitative assessment of the RON numbers for new biofuel blends by measuring their ignition delay times in the RCM.

Detailed kinetic models of pyrolysis and combustion of hydrocarbon fuels are nowadays widely used in the design of internal combustion engines and these models are effectively applied to help meet the increasingly stringent environmental and energetic standards. In previous studies by the combustion community, such models not only contributed to the understanding of pure component combustion, but also provided a deeper insight into the combustion behavior of complex mixtures. One of the major challenges in this field is now the definition and the development of appropriate surrogate models able to mimic the actual features of real fuels. Real fuels are complex mixtures of thousands of hydrocarbon compounds including linear and branched paraffins, naphthenes, olefins and aromatics. Their behavior can be effectively reproduced by simpler fuel surrogates containing a limited number of components. Aside the most commonly used surrogates containing iso-octane and n-heptane only, the so called Primary Reference Fuels (PRF), new mixtures have recently been suggested to extend the reference components in surrogate mixtures to also include alkenes and aromatics. It is generally agreed that, including representative species for all the main classes of hydrocarbons which can be found in real fuels, it is possible to reproduce very effectively in a wide range of operating conditions not just the auto-ignition propensity of gasoline or Diesel fuels, but also their physical properties and their combustion residuals [1]. In this work, the combustion behavior of several components relevant to gasoline surrogate formulation is computationally examined. The attention is focused on the autoignition of iso-octane, hexene and their mixtures. Some important issues relevant to the experimental and modeling investigation of such fuels are discussed with the help of rapid compression machine data and calculations. Following the model validation, the behavior of mixtures is discussed on the basis of computational results.

The last three chapters of this book deal with application of methods presented in previous chapters to estimate various thermodynamic, physical, and transport properties of petroleum fractions. In this chapter, various methods for prediction of physical and thermodynamic properties of pure hydrocarbons and their mixtures, petroleum fractions, crude oils, natural gases, and reservoir fluids are presented. As it was discussed in Chapters 5 and 6, properties of gases may be estimated more accurately than properties of liquids. Theoretical methods of Chapters 5 and 6 for estimation of thermophysical properties generally can be applied to both liquids and gases; however, more accurate properties can be predicted through empirical correlations particularly developed for liquids. When these correlations are developed with some theoretical basis, they are more accurate and have wider range of applications. In this chapter some of these semitheoretical correlations are presented. Methods presented in Chapters 5 and 6 can be used to estimate properties such as density, enthalpy, heat capacity, heat of vaporization, and vapor pressure. Characterization methods of Chapters 2-4 are used to determine the input parameters needed for various predictive methods. One important part of this chapter is prediction of vapor pressure that is needed for vapor-liquid equilibrium calculations of Chapter 9.

This book focuses on gasoline compression ignition (GCI) which offers the prospect of engines with high efficiency and low exhaust emissions at a lower cost. A GCI engine is a compression ignition (CI) engine which is run on gasoline-like fuels (even on low-octane gasoline), making it significantly easier to control particulates and NOx but with high efficiency. The state of the art development to make GCI combustion feasible on practical vehicles is highlighted, e.g., on overcoming problems on cold start, high-pressure rise rates at high loads, transients, and HC and CO emissions. This book will be a useful guide to those in academia and industry.