Alcohol combustion chemistry

Biofuels have grabbed the attention of engine researchers ever since the oil-crisis and escalating costs of petro-chemicals cropped up in the ׳70s. Ethanol and methanol were the most widely researched alcohols in IC engines. However, the last decade has witnessed significant amount of research in higher alcohols due to the development of modern fermentation processes using engineered micro-organisms that improved yield. Higher alcohols are attractive second/third generation biofuels that can be produced from sugary, starchy and ligno-cellulosic biomass feedstocks using sustainable pathways. The present work reviews the current literature concerning the effects of using higher alcohols ranging from 3-carbon propanol to 20-carbon phytol on combustion, performance and emission characteristics of a wide range of diesel engines under various test conditions. The literature is abound with evidence that higher alcohols reduce carcinogenic particulate emissions that are prevalent in diesel engines. NOx emissions either increased or decreased based on the domination of either cetane number or heat of evaporation. Brake specific fuel consumption (BSFC) of the engine usually suffered due to low energy content of alcohols. A notable feature is that the combination of higher alcohols (like butanol or pentanol), high exhaust gas recirculation (EGR) rates and late injection timing enabled low temperature combustion (LTC) in diesel engines that can simultaneously reduce smoke and NOx emissions with improved engine efficiency. It can be concluded that higher alcohols reduce smoke emissions with their fuel-borne oxygen; enhance air/fuel mixing by offering long ignition delay and eventually replace fossil diesel (partially or wholly) to enable a clean and efficient combustion in compression-ignition engines. The chief thrust areas include developing mutant strains with higher yield, higher tolerance to toxic inhibition and low-cost substrates for fermentation. Further work is required in stipulating optimum blend-fuel characteristics and ensuring the long-term durability of the engines using these fuels.

Use of higher alcohol biofuels in diesel engines: A review

The fundamental combustion and emissions properties of advanced biofuels are reviewed, and their impact on engine performance is discussed, in order to guide the selection of optimal conversion routes for obtaining desired fuel combustion properties. Advanced biofuels from second- and third-generation feedstocks can result in significantly reduced life-cycle greenhouse-gas emissions, compared to traditional fossil fuels or first-generation biofuels from food-based feedstocks. These advanced biofuels include alcohols, biodiesel, or synthetic hydrocarbons obtained either from hydrotreatment of oxygenated biofuels or from Fischer–Tropsch synthesis. The engine performance and exhaust pollutant emissions of advanced biofuels are linked to their fundamental combustion properties, which can be modeled using combustion chemical-kinetic mechanisms and surrogate fuel blends. In general, first-generation or advanced biofuels perform well in existing combustion engines, either as blend additives with petro-fuels or as pure “drop-in” replacements. Generally, oxygenated biofuels produce lower intrinsic nitric-oxide and soot emissions than hydrocarbon fuels in fundamental experiments, but engine-test results can be complicated by multiple factors. In order to reduce engine emissions and improve fuel efficiency, several novel technologies, including engines and fuel cells, are being developed. The future fuel requirements for a selection of such novel power-generation technologies, along with their potential performance improvements over existing technologies, are discussed. The trend in the biofuels and transportation industries appears to be moving towards drop-in fuels that require little changes in vehicle or fueling infrastructure, but this comes at a cost of reduced life-cycle efficiencies for the overall alternative-fuel production and utilization system. In the future, fuel-flexible, high-efficiency, and ultra-low-emissions heat-engine and fuel-cell technologies promise to enable consumers to switch to the lowest-cost and cleanest fuel available in their market at any given time. This would also enable society as a whole to maximize its global level of transportation activity, while maintaining urban air quality, within an energy- and carbon-constrained world.

A review of the combustion and emissions properties of advanced transportation biofuels and their impact on existing and future engines

Recent progress in gasoline surrogate fuels

Optimized chemical mechanism for combustion of gasoline surrogate fuels

Abstract Auto-ignition characteristics of ethanol were experimentally investigated using two Shock Tube (ST) facilities and a Rapid Compression Machine (RCM). Ignition delay times for stoichiometric ethanol-air mixtures were measured for temperatures between 775–1300 K in a High Pressure Shock Tube (HPST) at pressures close to 80 bar by probing pressure time histories and CH* emission. In some experiments the HPST was additionally employed for schlieren imaging to visualize ignition behavior by probing density gradients during ignition for ethanol-air mixtures. The ignition delay experiments in HPST were complemented by RCM measurements for extending the temperature regime to the Low Temperature Combustion (LTC) regime, down to 705 K, providing kinetic model validation data over a very wide temperature and pressure range. The current results also extend the earlier shock tube measurements performed in the same laboratory for pressures around 40 bar for temperatures down to 800 K [Heufer et al., Shock Waves 20 (2010) 307]. Furthermore, a Rectangular Shock Tube (RST) was solely used for additional schlieren imaging experiments to acquire information on ignition modes in stoichiometric ethanol-air mixtures around 10 bar. An improved chemical kinetic model was developed based on the Li et al. mechanism [Li et al., “Ethanol Model v1.0”, Princeton University, 2009] which was updated with evaluated rate parameters from the literature and validated through results obtained from the aforementioned facilities. The model predictions were compared to previously published low-pressure, premixed flat flame molecular beam mass spectrometry speciation data [Kasper et al., Combust. Flame 150 (2007) 220; Wang et al., J. Phys. Chem. A 112 (2008) 9255] where reasonable agreement is obtained considering the uncertainties in experiments and model. However, the model provides excellent agreement for the auto-ignition results obtained in the RCM and the high temperature shock induced ignition delays. Significant disparities with the model predictions are obtained for the shock tube results at temperatures below 1000 K as it transitions from the intermediate to the low temperature regime. The reasons for these deviations are assigned to strong fuel specific “pre-ignition” effects observed in ethanol auto-ignition, in contrast to other investigated fuels, which was satisfactorily explained through schlieren experimental results. To our knowledge this work is first of its kind that combines results from complementary experimental methods from three different facilities providing a holistic description on the auto-ignition behavior of ethanol. Furthermore, this paper reports ignition delay measurements for ethanol in air, at the highest pressures applicable to practical combustors.

On the Chemical Kinetics of Ethanol Oxidation: Shock Tube, Rapid Compression Machine and Detailed Modeling Study

A high pressure ignition delay time study of 2-methylfuran and tetrahydrofuran in shock tubes

This study presents the first investigation on the combustion chemistry of n -octanol, a long chain alcohol. Ignition delay times were determined experimentally in a high-pressure shock tube, and stable species concentration profiles were obtained in a jet stirred reactor for a range of initial conditions. A detailed kinetic model was developed to describe the oxidation of n -octanol at both low and high temperatures, and the model shows good agreement with the present dataset. The fuel’s combustion characteristics are compared to those of n -alkanes and to short chain alcohols to illustrate the effects of the hydroxyl moiety and the carbon chain length on important combustion properties. Finally, the results are discussed in detail.

Yasar Uygun

Papers

On the Chemical Kinetics of Ethanol Oxidation: Shock Tube, Rapid Compression Machine and Detailed Modeling Study

A high pressure ignition delay time study of 2-methylfuran and tetrahydrofuran in shock tubes

An experimental and modeling study of n-octanol combustion

A comprehensive experimental and kinetic modeling study of butanone

Analysis of the Effects of Certain Alcohol and Furan-Based Biofuels on Controlled Auto Ignition