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All sourcesNASA NTRSDOE OSTI
DOE OSTI2012

Intermediate Ethanol Blends Catalyst Durability Program

In the summer of 2007, the U.S. Department of Energy (DOE) initiated a test program to evaluate the potential impacts of intermediate ethanol blends (also known as mid-level blends) on legacy vehicles and other engines.* The purpose of the test program was to develop information important to assessing the viability of using intermediate blends as a contributor to meeting national goals for the use of renewable fuels. Through a wide range of experimental activities, DOE is evaluating the effects of E15 and E20— gasoline blended with 15% and 20% ethanol—on tailpipe and evaporative emissions, catalyst and engine durability, vehicle driveability, engine operability, and vehicle and engine materials. This report provides the results of the catalyst durability study, a substantial part of the overall test program. Results from additional projects will be reported separately. The principal purpose of the catalyst durability study was to investigate the effects of adding up to 20% ethanol to gasoline on the durability of catalysts and other aspects of the emissions control systems of vehicles. Section 1 provides further information about the purpose and context of the study. Section 2 describes the experimental approach for the test program, including vehicle selection, aging and emissions test cycle, fuel selection, and data handling and analysis. Section 3 summarizes the effects of the ethanol blends on emissions and fuel economy of the test vehicles. Section 4 summarizes notable unscheduled maintenance and testing issues experienced during the program. The appendixes provide additional detail about the statistical models used in the analysis, detailed statistical analyses, and detailed vehicle specifications.

DOE catalyst study↗
DOE OSTI2012

Intermediate Ethanol Blends Catalyst Durability Program

In the summer of 2007, the U.S. Department of Energy (DOE) initiated a test program to evaluate the potential impacts of intermediate ethanol blends (also known as mid-level blends) on legacy vehicles and other engines. The purpose of the test program was to develop information important to assessing the viability of using intermediate blends as a contributor to meeting national goals for the use of renewable fuels. Through a wide range of experimental activities, DOE is evaluating the effects of E15 and E20 - gasoline blended with 15% and 20% ethanol - on tailpipe and evaporative emissions, catalyst and engine durability, vehicle driveability, engine operability, and vehicle and engine materials. This report provides the results of the catalyst durability study, a substantial part of the overall test program. Results from additional projects will be reported separately. The principal purpose of the catalyst durability study was to investigate the effects of adding up to 20% ethanol to gasoline on the durability of catalysts and other aspects of the emissions control systems of vehicles. Section 1 provides further information about the purpose and context of the study. Section 2 describes the experimental approach for the test program, including vehicle selection, aging and emissions test cycle, fuel selection, and data handling and analysis. Section 3 summarizes the effects of the ethanol blends on emissions and fuel economy of the test vehicles. Section 4 summarizes notable unscheduled maintenance and testing issues experienced during the program. The appendixes provide additional detail about the statistical models used in the analysis, detailed statistical analyses, and detailed vehicle specifications.

02 PETROLEUM↗
DOE OSTI2012

Legacy Vehicle Fuel System Testing with Intermediate Ethanol Blends

The effects of E10 and E17 on legacy fuel system components from three common mid-1990s vintage vehicle models (Ford, GM, and Toyota) were studied. The fuel systems comprised a fuel sending unit with pump, a fuel rail and integrated pressure regulator, and the fuel injectors. The fuel system components were characterized and then installed and tested in sample aging test rigs to simulate theexposure and operation of the fuel system components in an operating vehicle. The fuel injectors were cycled with varying pulse widths during pump operation. Operational performance, such as fuel flow and pressure, was monitored during the aging tests. Both of the Toyota fuel pumps demonstrated some degradation in performance during testing. Six injectors were tested in each aging rig. The Fordand GM injectors showed little change over the aging tests. Overall, based on the results of both the fuel pump testing and the fuel injector testing, no major failures were observed that could be attributed to E17 exposure. The unknown fuel component histories add a large uncertainty to the aging tests. Acquiring fuel system components from operational legacy vehicles would reduce theuncertainty.

09 BIOMASS FUELS↗
DOE OSTI2012

Analysis of Underground Storage Tanks System Materials to Increased Leak Potential Associated with E15 Fuel

The Energy Independence and Security Act (EISA) of 2007 was enacted by Congress to move the nation toward increased energy independence by increasing the production of renewable fuels to meet its transportation energy needs. The law establishes a new renewable fuel standard (RFS) that requires the nation to use 36 billion gallons annually (2.3 million barrels per day) of renewable fuel in its vehicles by 2022. Ethanol is the most widely used renewable fuel in the US, and its production has grown dramatically over the past decade. According to EISA and RFS, ethanol (produced from corn as well as cellulosic feedstocks) will make up the vast majority of the new renewable fuel requirements. However, ethanol use limited to E10 and E85 (in the case of flex fuel vehicles or FFVs) will not meet this target. Even if all of the E0 gasoline dispensers in the country were converted to E10, such sales would represent only about 15 billion gallons per year. If 15% ethanol, rather than 10% were used, the potential would be up to 22 billion gallons. The vast majority of ethanol used in the United States is blended with gasoline to create E10, that is, gasoline with up to 10% ethanol. The remaining ethanol is sold in the form of E85, a gasoline blend with as much as 85% ethanol that can only be used in FFVs. Although DOE remains committed to expanding the E85 infrastructure, that market will not be able to absorb projected volumes of ethanol in the near term. Given this reality, DOE and others have begun assessing the viability of using intermediate ethanol blends as one way to transition to higher volumes of ethanol. In October of 2010, the EPA granted a partial waiver to the Clean Air Act allowing the use of fuel that contains up to 15% ethanol for the model year 2007 and newer light-duty motor vehicles. This waiver represents the first of a number of actions that are needed to move toward the commercialization of E15 gasoline blends. On January 2011, this waiver was expanded to include model year 2001 light-duty vehicles, but specifically prohibited use in motorcycles and off-road vehicles and equipment. UST stakeholders generally consider fueling infrastructure materials designed for use with E0 to be adequate for use with E10, and there are no known instances of major leaks or failures directly attributable to ethanol use. It is conceivable that many compatibility issues, including accelerated corrosion, do arise and are corrected onsite and, therefore do not lead to a release. However, there is some concern that higher ethanol concentrations, such as E15 or E20, may be incompatible with current materials used in standard gasoline fueling hardware. In the summer of 2008, DOE recognized the need to assess the impact of intermediate blends of ethanol on the fueling infrastructure, specifically located at the fueling station. This includes the dispenser and hanging hardware, the underground storage tank, and associated piping. The DOE program has been co-led and funded by the Office of the Biomass Program and Vehicle Technologies Program with technical expertise from the Oak Ridge National Laboratory (ORNL) and the National Renewable Energy Laboratory (NREL). The infrastructure material compatibility work has been supported through strong collaborations and testing at Underwriters Laboratories (UL). ORNL performed a compatibility study investigating the compatibility of fuel infrastructure materials to gasoline containing intermediate levels of ethanol. These results can be found in the ORNL report entitled Intermediate Ethanol Blends Infrastructure Materials Compatibility Study: Elastomers, Metals and Sealants (hereafter referred to as the ORNL intermediate blends material compatibility study). These materials included elastomers, plastics, metals and sealants typically found in fuel dispenser infrastructure. The test fuels evaluated in the ORNL study were SAE standard test fuel formulations used to assess material-fuel compatibility within a relatively short timeframe. Initially, these material studies included test fuels of Fuel C, CE10a, CE17a, and CE25a. The CE17a test fuel was selected to represent E15 since surveys have shown that the actual ethanol upper limit can be as high as 17%. Later, CE50a and CE85a test fuels were added to the investigation and these results are being compiled for a follow-on report to be published in 2012. Fuel C was used as the baseline reference and is a 50:50 blend of isooctane and toluene. This particular composition was used to represent premium-grade gasoline and was also used as the base fuel for the ethanol blends, where it is denoted by 'C' in the fuel name. The level of ethanol is represented by the number following the letter E. Therefore a 10% blend of ethanol in Fuel C is written as CE10a, where 'a' represents an aggressive formulation of the ethanol that contains water, NaCl, acetic and sulfuric acids per the SAE J1681 protocol.

02 PETROLEUM↗
DOE OSTI2013

Preliminary Examination of Ethanol Fuel Effects on EPA’s R-factor for Vehicle Fuel Economy

The U.S. Department of Energy (DOE) supported a test program from 2007 through 2012 to evaluate the potential impacts of intermediate ethanol blends (also known as mid-level blends) on legacy vehicles and other engines. The purpose of the program was to assess the viability of using intermediate ethanol blends as a contributor to meeting national goals for the use of renewable fuels. Appendix A lists a bibliography of related studies. The catalyst durability program involved aging and emissions testing vehicles on a range of ethanol blends. The study was completed in 2011 and a final report issued shortly after. This report describes a preliminary analysis of the fuel economy data from the catalyst durability study, to determine the proper value for the R factor which is called out in the Code of Federal Regulations (CFR) for computing vehicle fuel economy on the certification cycle. The fuel economy equation that is specified in CFR for gasoline-fuelled vehicles is based on a carbon mass balance (CMB) approach to determine the amount of fuel consumed during the test by measuring the carbon-bearing emissions that are produced; however, it also incorporates a scaling factor (R factor) based on the net heating value of the fuel and the sensitivity of fuel economy to changes in the heating value. The impact of the R factor is a fixed ratio in the resultant fuel economy that is dependent upon fuel properties other than those required for a typical CMB calculation. This equation was put in place in 1988 to correct for differences between certification fuels to address corporate average fuel economy (CAFE) credit issues associated with fuel property variations. The algorithm adjusts the calculated fuel economy to compute what would have been measured had the 1975 certification fuel been used for the test. The R factor was defined as the sensitivity of the fuel economy result to changes in fuel energy content. When R equals 1.0, the fuel economy change exactly tracks the energy density difference between the fuels. If R is less than 1.0, the fuel economy change is smaller than the change in energy density. The R factor was defined to be 0.6 based on tests using 1980s vehicles. Since that time, the Auto/Oil test program has established that the R factor for 1990s vehicles is higher (about 0.93). More recently EPA analyzed the EPAct/V2/E-89 dataset to compute the R factor, resulting in an average of 0.82 to 0.86. It is important to note that the EPAct/V2/E89 test program used the LA92 test cycle, a cycle known to contain more aggressive accelerations than the FTP. To date, EPA has only required emissions and fuel economy testing of gasoline vehicles with a certification fuel that does not contain ethanol. However in 2013 EPA issued a Proposed Rule seeking comment on the establishment of an emissions certification fuel containing ethanol, such as E10 or E15. Calculating modern vehicle fuel economy with the existing CFR equation with an R factor of 0.6 when ethanol blends are used produces significant errors. For the catalyst durability program, a straightforward CMB approach was used to compute fuel economy, thereby allowing a straightforward evaluation of the impact of ethanol content on fuel economy. However, if an ethanol-containing fuel is to become the new certification fuel for light-duty vehicles, consistent application of the CFR equation needs to be considered for the benefit of manufacturers’ CAFE compliance. Analysis of city cycle Federal Test Procedure (FTP) fuel economy test results and fuel analyses from the catalyst durability study indicates that the average R-factor for modern vehicles is very close to unity at about 0.94±0.04. This result is very similar to the results of the 1993 Auto/Oil test program. Future work should examine other drive cycles, and advanced vehicle technologies which may reveal sensitivities to properties other than heating value.

intermediate ethanol blends↗
DOE OSTI2013

Lubricating Oil Consumption on the Standard Road Cycle

Automobile manufacturers strive to minimize oil consumption from their engines due to the need to maintain emissions compliance over the vehicle life. Engine oil can contribute directly to organic gas and particle emissions as well as accelerate emissions degradation due to catalyst poisoning. During the Department of Energy Intermediate Ethanol Blends Catalyst Durability program, vehicles were aged using the Standard Road Cycle (SRC). In this program, matched sets of three or four vehicles were acquired; each vehicle of a set was aged on ethanol-free retail gasoline, or the same base gasoline blended with 10, 15, or 20% ethanol (E0, E10, E15, E20). The primary purpose of the program was to assess any changes in tailpipe emissions due to the use of increased levels of ethanol. Oil consumption was tracked during the program so that any measured emissions degradation could be appropriately attributed to fuel use or to excessive oil consumption. In addition, excessive oil consumption was used to help diagnose potential engine maintenance problems. This paper details the results of analysis of the available oil consumption records from this program. Oil consumption levels for the properly-functioning light-duty vehicles aged on the SRC in this program range from 0.015 to 0.090 g/km. On a fuel specific basis (g oil / kg fuel burned) results range from 0.16 to 1.14 g/kg (0.016% to 0.114 %). Results indicate no statistically significant effect of fuel ethanol level on oil consumption.

West, Brian H.↗
DOE OSTI2013

Compatibility Study for Plastic, Elastomeric, and Metallic Fueling Infrastructure Materials Exposed to Aggressive Formulations of Isobutanol-blended Gasoline

The Energy Independence and Security Act (EISA) of 2007 is an omnibus energy policy law designed to move the United States toward greater energy security and independence. A key provision of EISA is the Renewable Fuel Standard (RFS), which requires the nation to use 36 billion gallons per year (BGPY) of renewable fuel in vehicles by 2022. Ethanol is the most widely used renewable fuel, and increasing the allowable ethanol content from 10% to 15% is expected to push renewable fuel consumption to as much as 21 BGPY. Therefore, a large portion of the 36 billion gallon requirement can be met by increasing the ethanol content in gasoline to 15%. However, raising the ethanol content to 15%, by itself, will still not fully meet the RSF requirement, and concerns have been raised that this increase in ethanol may not be entirely compatible with current and legacy materials used in standard gasoline fueling systems. In the summer of 2008, the U.S. Department of Energy (DOE) recognized the need to assess the impact of intermediate blends of ethanol on the fueling infrastructure, specifically those systems located at the fueling station. A short time later (March 2009), Growth Energy (a coalition of ethanol producers and supporters) requested a waiver from the U.S. Environmental Protection Agency (EPA) to allow the use of 15% ethanol in gasoline. In 1981 the EPA approved a waiver (known as the OCTAMIX waiver) that allowed other alcohol types (such as methanol) to be blended with gasoline as long as the resulting fuel blend was substantially similar to gasoline. Another requirement is that the fuel oxygen content cannot exceed 3.7 wt %. Currently, this requirement limits ethanol in gasoline to 10 vol %. The corresponding oxygen equivalent for isobutanol is 16 vol %; therefore, isobutanol offers a pathway towards meeting the RFS requirement by allowing greater biofuel usage than can be achieved by ethanol alone. In fact, the United States has already hit the “blend wall” for ethanol, the point at which virtually all gasoline sold is E10 and no remaining market is left for ethanol, meaning that the country cannot substantially increase ethanol usage unless the EPA allows for higher levels of ethanol or until E85 use is expanded significantly. Butamax Advanced Biofuels, LLC has developed proprietary technologies to convert corn into isobutanol. Much of the infrastructure already existing at ethanol plants can be readily converted to produce isobutanol instead. The focus of this investigation was to compare the compatibility of fueling infrastructure materials (such as elastomers, plastics, and metals) to test fuels representing E10 and E15 and their corresponding oxygen equivalents with isobutanol (iBu16 and iBu24). Butamax sponsored a research project at Oak Ridge National Laboratory (ORNL) to perform empirical studies using aggressive fuel formulations representing 16 and 24% isobutanol. The results contained within this report include a solubility analysis for each material type and fuel formulation and empirical results for elastomers, plastics, and metals. Data obtained from the preceding ethanol compatibility studies on these materials are included for additional interpretation and summary.

Kass, Michael D.↗
DOE OSTI2021

New insights into fuel blending effects: Intermolecular chemical kinetic interactions affecting autoignition times and intermediate-temperature heat release

Fuel blending effects on chemically-dominated fuel properties, such as gasoline anti-knock quality, are influenced by fundamental chemical kinetic interactions between the blending agent and the base fuel. Historically, quantification of such interactions has focused on changes to the radical pool, including $\dot{O}$H and HO 2 , while intermolecular interactions pertaining to carbonated, non-fuel-specific intermediates are typically overlooked. In this regard, this work aims to derive new insight into intermolecular chemical kinetic interactions that are intrinsic to fuel blending effects via a case study on blends of 0–30% ethanol (by volume) into FGF-LLNL (a multi-component gasoline surrogate for FACE-F research gasoline) using a rapid compression machine at a diluted/stoichiometric fuel loading, compressed pressure of 40 bar and low- to intermediate-temperature regimes that are representative of boosted SI engine operation. Ethanol blending effects on the intermediate temperature heat release (ITHR) of FGF-LLNL are characterized using experimental measurements, where ethanol is found to promote the extent of ITHR and suppress the transition from ITHR to main ignition. Chemical kinetic modeling is undertaken using a recently updated gasoline surrogate model. Sensitivity analyses on ITHR characteristics further corroborate the ethanol blending effects, and highlight the significant dependence of ITHR on both fuel-specific and non-fuel-specific reactions. An approach allowing comprehensive characterization of the complex intermolecular chemical kinetic interactions between constitutes in a fuel blend is then proposed. Application of the approach to FGF-LLNL/E0–E30 reveals that ethanol perturbs the heat release and autoignition characteristics of FGF-LLNL not only by directly changing the $\dot{O}$H and HO 2 radical pools via fuel-specific reactions, but also through intermolecular interactions where participating intermediates can be produced and consumed by various sub-chemistries. Disabling the intermolecular interactions in carbonated species between ethanol and FGF-LLNL sub-chemistries leads to somewhat slower ITHR evolution and lower ignition reactivity. The role of the individual intermolecular interaction is also characterized using the proposed approach. Lastly, implications of intermolecular interactions for future studies that aim to improve model performance are highlighted, where it is found that further investigations on the core C0-C4 chemistry are needed for developing highly accurate chemistry models for complex fuel blends.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Compatibility Study for Plastic, Elastomeric, and Metallic Fueling Infrastructure Materials Exposed to Aggressive Formulations of Ethanol-blended Gasoline

In 2008 Oak Ridge National Laboratory began a series of experiments to evaluate the compatibility of fueling infrastructure materials with intermediate levels of ethanol-blended gasoline. Initially, the focus was elastomers, metals, and sealants, and the test fuels were Fuel C, CE10a, CE17a and CE25a. The results of these studies were published in 2010. Follow-on studies were performed with an emphasis on plastic (thermoplastic and thermoset) materials used in underground storage and dispenser systems. These materials were exposed to test fuels of Fuel C and CE25a. Upon completion of this effort, it was felt that additional compatibility data with higher ethanol blends was needed and another round of experimentation was performed on elastomers, metals, and plastics with CE50a and CE85a test fuels. Compatibility of polymers typically relates to the solubility of the solid polymer with a solvent. It can also mean susceptibility to chemical attack, but the polymers and test fuels evaluated in this study are not considered to be chemically reactive with each other. Solubility in polymers is typically assessed by measuring the volume swell of the polymer exposed to the solvent of interest. Elastomers are a class of polymers that are predominantly used as seals, and most o-ring and seal manufacturers provide compatibility tables of their products with various solvents including ethanol, toluene, and isooctane, which are components of aggressive oxygenated gasoline as described by the Society of Automotive Engineers (SAE) J1681. These tables include a ranking based on the level of volume swell in the elastomer associated with exposure to a particular solvent. Swell is usually accompanied by a decrease in hardness (softening) that also affects performance. For seal applications, shrinkage of the elastomer upon drying is also a critical parameter since a contraction of volume can conceivably enable leakage to occur. Shrinkage is also indicative of the removal of one or more components of the elastomers (by the solvent). This extraction of additives can negatively change the properties of the elastomer, leading to reduced performance and durability. For a seal application, some level of volume swell is acceptable, since the expansion will serve to maintain a seal. However, the acceptable level of swell is dependent on the particular application of the elastomer product. It is known that excessive swell can lead to unacceptable extrusion of the elastomer beyond the sealed interface, where it becomes susceptible to damage. Also, since high swell is indicative of high solubility, there is a heightened potential for fluid to seep through the seal and into the environment. Plastics, on the other hand, are used primarily in structural applications, such as solid components, including piping and fluid containment. Volume change, especially in a rigid system, will create internal stresses that may negatively affect performance. In order to better understand and predict the compatibility for a given polymer type and fuel composition, an analysis based on Hansen solubility theory was performed for each plastic and elastomer material. From this study, the solubility distance was calculated for each polymer material and test fuel combination. Using the calculated solubility distance, the ethanol concentration associated with peak swell and overall extent of swell can be predicted for each polymer. The bulk of the material discussion centers on the plastic materials, and their compatibility with Fuel C, CE25a, CE50a, and CE85a. The next section of this paper focuses on the elastomer compatibility with the higher ethanol concentrations with comparison to results obtained previously for the lower ethanol levels. The elastomers were identical to those used in the earlier study. Hansen solubility theory is also applied to the elastomers to provide added interpretation of the results. The final section summarizes the performance of the metal coupons.

02 PETROLEUM↗
DOE OSTI2014

Selective catalytic reduction of nitric oxide with ethanol/gasoline blends over a silver/alumina catalyst

Lean gasoline engines running on ethanol/gasoline blends and equipped with a silver/alumina catalyst for selective catalytic reduction (SCR) of NO by ethanol provide a pathway to reduced petroleum consumption through both increased biofuel utilization and improved engine efficiency relative to the current stoichiometric gasoline engines that dominate the U.S. light duty vehicle fleet. A pre-commercial silver/alumina catalyst demonstrated high NO x conversions over a moderate temperature window with both neat ethanol and ethanol/gasoline blends containing at least 50% ethanol. Selectivity to NH 3 increases with HC dosing and ethanol content in gasoline blends, but appears to saturate at around 45%. NO 2 and acetaldehyde behave like intermediates in the ethanol SCR of NO. NH 3 SCR of NO x does not appear to play a major role in the ethanol SCR reaction mechanism. Ethanol is responsible for the low temperature SCR activity observed with the ethanol/gasoline blends. In conclusion, the gasoline HCs do not deactivate the catalyst ethanol SCR activity, but they also do not appear to be significantly activated by the presence of ethanol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Estimation of the Fuel Efficiency Potential of Six Gasoline Blendstocks Identified by the U.S. Department of Energy’s Co-Optimization of Fuels and Engines Program

Six blendstocks identified by the Co-Optimization of Fuels & Engines Program were used to prepare fuel blends using a fixed blendstock for oxygenate blending and a target RON of 97. The blendstocks included ethanol, n-propanol, isopropanol, isobutanol, diisobutylene, and a bioreformate surrogate. The blends were analyzed and used to establish interaction factors for a non-linear molar blending model that was used to predict RON and MON of volumetric blends of the blendstocks up to 35 vol%. Projections of efficiency increase, volumetric fuel economy increase, and tailpipe CO2 emissions decrease were produced using two different estimation techniques to evaluate the potential benefits of the blendstocks. Ethanol was projected to provide the greatest benefits in efficiency and tailpipe CO2 emissions, but at intermediate levels of volumetric fuel economy increase over a smaller range of blends than other blendstocks. A bioreformate surrogate blendstock was projected to provide the greatest increase in volumetric fuel economy and the lowest increase in efficiency. Tailpipe CO2 emissions for blends of the bioreformate surrogate were higher at all blend levels compared to the baseline E10 fuel.

02 PETROLEUM↗
DOE OSTI2020

Autoignition behavior of gasoline/ethanol blends at engine-relevant conditions

Ethanol is an attractive oxygenate increasingly used for blending with petroleum-derived gasoline yielding beneficial combustion and emissions behavior for a range of internal combustion engine schemes, including stoichiometric spark-ignition and low temperature combustion (LTC). As such, it is important to fundamentally understand the autoignition behavior of gasoline/ethanol blends. This work utilizes a rapid compression machine (RCM) and a homogeneous charge compression ignition (HCCI) engine to experimentally quantify changes in fuel reactivity, through ignition delay times and preliminary heat release, for blends of 0 to 30% vol./vol. into a full boiling range research gasoline (FACE-F). Diluted/stoichiometric and undiluted/fuel-lean conditions are explored covering a wide range of compressed temperatures and pressures relevant to conventional and advanced, gasoline combustion engines. Detailed chemical kinetic modeling is undertaken using a recently updated gasoline surrogate model in conjunction with a five-component surrogate to model the RCM experiments and provide chemical insight into the perturbative effects of ethanol on the autoignition process. The diluted/stoichiometric RCM measurements reveal that within the low-temperature regime ethanol retards first-stage and main ignition delay times, and suppresses both the rates and extents of low-temperature heat release (LTHR), while within the intermediate-temperature regime ethanol only causes slight changes. Good agreement of ignition delay time and preliminary heat release prediction is found between model and experimental results. Sensitivity and flux analyses further show that ethanol blending effects are dominated by the competition between the H-atom abstraction from ethanol and other fuel components by OH radical at low temperatures and by HO 2 radical at intermediate temperatures. These findings are consistent across both fuel loading conditions explored in this study. In addition, when HCCI engine experiments are mapped onto undiluted/lean RCM measurements under a constant combustion phasing scenario, good correspondence between the two apparatuses is observed for LTHR and start of high-temperature heat release. Finally, the current study highlights the importance of characterizing LTHR in predicting fuel behaviors in high-boost/low-temperature engines, and demonstrates that RCM experiments can provide an alternative, and more-efficient avenue for such characterization.

02 PETROLEUM↗
DOE OSTI2018

The Influence of Intake Pressure and Ethanol Addition to Gasoline on Single- and Dual-Stage Autoignition in an HCCI Engine

Autoignition in HCCI engines is known to be controlled by the combustion kinetics of the in-cylinder fuel/air mixture which is highly influenced by the amount of low-temperature and intermediate-temperature heat release (LTHR and ITHR) that occurs. At lower intake pressures (typically <1.4 bar absolute), it has been observed that gasoline behaves as a single-stage heat release fuel, while at higher intake pressures (typically >1.8 bar absolute) gasoline behaves as a two-stage heat release fuel. Furthermore, ethanol blending into gasoline strongly affects heat release characteristics, and this warrants further investigation. This paper experimentally investigates the conditions under which gasoline transitions from a single-stage heat release fuel to a two-stage heat release fuel as intake pressure is increased. Experiments were performed in single-cylinder HCCI engine fueled with two research-grade gasolines, FACE A and FACE C. These gasolines were tested neat, and with 10% and 20% (by volume) ethanol addition. In addition, these results were compared to results previously obtained for PRF 85, and new results for PRF 84 with 10% and 20% ethanol addition. Moreover, the engine experiments were supported by rapid compression machine (RCM) ignition delay data for the same fuels. The engine experiments revealed that there were minimal differences between the heat release profiles of the two gasolines, FACE A and FACE C, a result which was supported by the RCM experiments that showed similar ignition delay times for the two FACE fuels and PRF 84. On the other hand, with ethanol addition to these gasolines and PRF 84, the occurrence of LTHR shifted to higher intake pressures compared to ethanol-free cases, from 1.4 bar intake pressure for neat fuel to 2.2 bar with 20% ethanol. Consequently, the intake temperatures required to achieve constant combustion phasing for all mixtures were drastically altered. Simulations using a detailed chemical kinetic model were utilized to understand the effects of ethanol blending on the ignition characteristics of PRF 84. The addition of ethanol was found to act as a radical sink where it inhibits the radical pool formation during the low (<850 K) and intermediate (850–1050 K) temperature chemistry regimes resulting in lower reactivity. These results help explain ethanol’s significant antiknock qualities under boosted conditions in spark-ignition engines.

42 ENGINEERING↗
DOE OSTI2019

Heat of Vaporization and Species Evolution Suring Gasoline Evaporation Measured by DSC/TGA/MS for Blends of C1 to C4 Alcohols in Commercial Gasoline Blendstocks

Evaporative cooling of the fuel-air charge by fuel evaporation is an important feature of direct-injection spark-ignition engines that improves fuel knock resistance and reduces pumping losses at intermediate load, but in some cases, may increase fine particle emissions. We have reported on experimental approaches for measuring both total heat of vaporization and examination of the evaporative heat effect as a function of fraction evaporated for gasolines and ethanol blends. In this paper, we extend this work to include other low-molecular-weight alcohols and present results on species evolution during fuel evaporation by coupling a mass spectrometer to our differential scanning calorimetry/thermogravimetric analysis instrument. The alcohols examined were methanol, ethanol, 1-propanol, isopropanol, 2-butanol, and isobutanol at 10 volume percent, 20 volume percent, and 30 volume percent. The results show that total heat of vaporization of the alcohol gasoline blends is in line with the decreasing heat of vaporization in kilojoules per kilogram with increasing alcohol carbon number, as expected. Mass spectrometer results show that methanol fully evaporates at significantly lower fraction evaporated relative to other alcohols even though it is present at higher molar concentration at a fixed volumetric concentration. Certain alcohols, especially methanol and ethanol, can suppress the evaporation of aromatic compounds such as cumene during the evaporation process in some samples. While the use of mass spectrometry to analyze the composition of the evolving gas mixture provided useful results for a relatively simple research gasoline (FACE B), additional research is required to practically apply this methodology to more complex commercial gasolines.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2017

A Hybrid Catalytic Route to Fuels from Biomass Syngas

LanzaTech partnered with the Pacific Northwest National Laboratory (PNNL), Imperium Aviation Fuels, InEnTec, Orochem Technologies, the University of Delaware, Michigan Technological University, the National Renewable Energy Laboratory, and The Boeing Company, to develop a cost-effective hybrid conversion technology for catalytic upgrading of biomass-derived syngas to sustainable alternative jet fuel (SAJF) meeting the price, quality and environmental requirements of the aviation industry. Alternative “synthetic paraffinic kerosene” (SPK) blendstock produced from syngas via “Fischer-Tropsch” (F-T) or from lipids via “hydroprocessing of esters and fatty acids” (HEFA) are currently being used in commercial jet fuel blends containing at least 50% petroleum-based fuel. This project developed an alternative route to SAJF from ethanol, a type of “alcohol to jet” (ATJ) SPK. The project objective was to demonstrate a pathway that combines syngas fermentation to ethanol with catalytic upgrading of ethanol to sustainable alternative jet fuel and shows attractive overall system economics to drive down the price of biomass-derived jet fuel. The hybrid pathway was to be demonstrated on three biomass feedstocks: corn stover, woody biomass, and third biomass feedstock, cellulosic residues. The objective also included the co-production of chemicals, exemplified by 2,3-Butanediol (2,3-BDO), which can be converted to key chemical intermediates. The team successfully demonstrated that biomass syngas fermentation followed by catalytic conversion is a viable alternative to the Fischer-Tropsch process and produces a fuel with properties comparable to F-T and HEFA SPKs. Plasma gasification and gas fermentation were successfully integrated and demonstrated in continuous fermentations on waste wood, corn stover, and cellulosic bagasse. Gas fermentation was demonstrated to produce ethanol suitable for catalytic upgrading, isolating the upgrading from variations in biomass feed, syngas composition, and impurities. Ethanol feedstocks from all three types of biomass were demonstrated to be comparable to grain derived ethanol and suitable for the LT-PNNL ATJ process. The LT-PNNL ATJ catalytic upgrading process was demonstrated at lab scale for over 2000 hours of continuous operation on a single catalyst load. LanzaTech scaled up the ATJ process, producing 4000 gallons of jet and 600 gallons of diesel for testing and a future proving flight. The LT-PNNL ATJ process, at lab and pilot scale, using commercial grain-based ethanol and steel mill waste gas-based ethanol (“Lanzanol”), produces high-quality fuel-range distillates containing primarily normal paraffins and isoparaffins. The LT-PNNL ATJ fuel has equivalent properties to previously-approved SPKs such as F-T, HEFA, and ATJ from isobutanol, and conforms with critical properties needed to blend with conventional jet fuel. The project showed that the 2,3-BDO fermentation co-product can be separated economically utilizing Simulated Moving Bed (SMB) technology. 2,3-BDO can be catalytically converted to 1,3-butadiene (BD) in a two-step process with at least 70% yield, producing a chemical intermediate suitable for downstream applications. Technoeconomic and life cycle analyses of the biomass to jet process with and without 2,3-BDO production showed that capital costs are sensitive to the proportion of the 2,3-BDO co-product and biomass feedstock. The co-product 2,3-BDO, converted through to BD, significantly reduces the cash cost of production of the hydrocarbon fuels. Life cycle GHG emissions of ATJ SPK produced from biomass using a steam gasification system are projected to be significantly lower than those of conventional jet fuel. The project demonstrated that a high quality ATJ SPK, can be produced from biomass via a hybrid gas fermentation/catalytic route. Validation of the LT-PNNL ATJ process using a variety of ethanol feedstocks demonstrated the viability of a future model of distributed ATJ production, in which ethanol may be produced at multiple facilities from local feedstocks and shipped to a central facility for conversion. The project demonstrated that co-production of chemicals has the potential to reduce jet cost of production, thereby accelerating commercial production of SAJF from biomass.

09 BIOMASS FUELS↗
DOE OSTI2014

Intermediate Alcohol-Gasoline Blends, Fuels for Enabling Increased Engine Efficiency and Powertrain Possibilities

The present study experimentally investigates spark-ignited combustion with 87 AKI E0 gasoline in its neat form and in mid-level alcohol-gasoline blends with 24% vol./vol. iso-butanol-gasoline (IB24) and 30% vol./vol. ethanol-gasoline (E30). A single-cylinder research engine is used with a low and high compression ratio of 9.2:1 and 11.85:1 respectively. The engine is equipped with hydraulically actuated valves, laboratory intake air, and is capable of external exhaust gas recirculation (EGR). All fuels are operated to full-load conditions with =1, using both 0% and 15% external cooled EGR. The results demonstrate that higher octane number bio-fuels better utilize higher compression ratios with high stoichiometric torque capability. Specifically, the unique properties of ethanol enabled a doubling of the stoichiometric torque capability with the 11.85:1 compression ratio using E30 as compared to 87 AKI, up to 20 bar IMEPg at =1 (with 15% EGR, 18.5 bar with 0% EGR). EGR was shown to provide thermodynamic advantages with all fuels. The results demonstrate that E30 may further the downsizing and downspeeding of engines by achieving increased low speed torque, even with high compression ratios. The results suggest that at mid-level alcohol-gasoline blends, engine and vehicle optimization can offset the reduced fuel energy content of alcohol-gasoline blends, and likely reduce vehicle fuel consumption and tailpipe CO2 emissions.

Splitter, Derek A↗
DOE OSTI2015

Refinery Upgrading of Hydropyrolysis Oil From Biomass

Cellulosic and woody biomass can be converted to bio-oils containing less than 10% oxygen by a hydropyrolysis process. Hydropyrolysis is the first step in Gas Technology Institute’s (GTI) integrated Hydropyrolysis and Hydroconversion IH2®. These intermediate bio-oils can then be converted to drop-in hydrocarbon fuels using existing refinery hydrotreating equipment to make hydrocarbon blending components, which are fully compatible with existing fuels. Alternatively, cellulosic or woody biomass can directly be converted into drop-in hydrocarbon fuels containing less than 0.4% oxygen using the IH2 process located adjacent to a refinery or ethanol production facility. Many US oil refineries are actually located near biomass resources and are a logical location for a biomass to transportation fuel conversion process. The goal of this project was to work directly with an oil refinery partner, to determine the most attractive route and location for conversion of biorenewables to drop in fuels in their refinery and ethanol production network. Valero Energy Company, through its subsidiaries, has 12 US oil refineries and 11 ethanol production facilities, making them an ideal partner for this analysis. Valero is also part of a 50- 50 joint venture with Darling Ingredients called Diamond Green Diesel. Diamond Green Diesel’s production capacity is approximately 11,000 barrels per day of renewable diesel. The plant is located adjacent to Valero’s St Charles, Louisiana Refinery and converts recycled animal fats, used cooking oil, and waste corn oil into renewable diesel. This is the largest renewable diesel plant in the U.S. and has successfully operated for over 2 years For this project, 25 liters of hydropyrolysis oil from wood and 25 liters of hydropyrolysis oils from corn stover were produced. The hydropyrolysis oil produced had 4-10% oxygen. Metallurgical testing of hydropyrolysis liquids was completed by Oak Ridge National Laboratories (Oak Ridge) and showed the hydropyrolysis oils had low acidity and caused almost no corrosion in comparison to pyrolysis oils, which had high acidity and caused significant levels of corrosion.

09 BIOMASS FUELS↗
DOE OSTI2012

Fuel Economy and Emissions of a Vehicle Equipped with an Aftermarket Flexible-Fuel Conversion Kit

The U.S. Environmental Protection Agency (EPA) grants Certificates of Conformity for alternative fuel conversion systems and also offers other forms of premarket registration of conversion kits for use in vehicles more than two model years old. Use of alternative fuels such as ethanol, natural gas, and propane are encouraged by the Energy Policy Act of 1992. Several original equipment manufacturers (OEMs) produce emissions-certified vehicles capable of using alternative fuels, and several alternative fuel conversion system manufacturers produce EPA-approved conversion systems for a variety of alternative fuels and vehicle types. To date, only one manufacturer (Flex Fuel U.S.) has received EPA certifications for ethanol fuel (E85) conversion kits. This report details an independent evaluation of a vehicle with a legal installation of a Flex Fuel U.S. conversion kit. A 2006 Dodge Charger was baseline tested with ethanol-free certification gasoline (E0) and E20 (gasoline with 20 vol % ethanol), converted to flex-fuel operation via installation of a Flex Box Smart Kit from Flex Fuel U.S., and retested with E0, E20, E50, and E81. Test cycles included the Federal Test Procedure (FTP or city cycle), the highway fuel economy test (HFET), and the US06 test (aggressive driving test). Averaged test results show that the vehicle was emissions compliant on E0 in the OEM condition (before conversion) and compliant on all test fuels after conversion. Average nitrogen oxide (NO X ) emissions exceeded the Tier 2/Bin 5 intermediate life NO X standard with E20 fuel in the OEM condition due to two of three test results exceeding this standard [note that E20 is not a legal fuel for non-flexible-fuel vehicles (non-FFVs)]. In addition, one E0 test result before conversion and one E20 test result after conversion exceeded the NO X standard, although the average result in these two cases was below the standard. Emissions of ethanol and acetaldehyde increased with increasing ethanol, while nonmethane organic gas and CO emissions remained relatively unchanged for all fuels and cycles. Higher fraction ethanol blends appeared to decrease NO X emissions on the FTP and HFET (after conversion). As expected, fuel economy (miles per gallon) decreased with increasing ethanol content in all cases.

02 PETROLEUM↗