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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

End-gas autoignition fraction and flame propagation rate in laser-ignited primary reference fuel mixtures at elevated temperature and pressure

Knock in spark-ignited (SI) engines is initiated by autoignition of the unburned gasses upstream of spark-ignited, propagating, turbulent premixed flames. Knock propensity of fuel/air mixtures is typically quantified using research octane number (RON), motor octane number (MON), or methane number (MN; for gaseous fuels), which are measured using single-cylinder, variable compression ratio engines. In this study, knock propensity of SI fuels was quantified via observations of end-gas autoignition (EGAI) in unburned gasses upstream of laser-ignited, premixed flames at elevated pressures and temperatures in a rapid compression machine. Stoichiometric primary reference fuel (PRF; n-heptane/isooctane) blends of varying reactivity (50 ≤ PRF ≤ 100) were ignited using an Nd:YAG laser over a range of temperatures and pressures, all in excess of 545 K and 16.1 bar. Laser ignition produced outwardly-propagating premixed flames. High-speed pressure measurements and schlieren images indicated the presence of EGAI. The fraction of the total heat release attributed to EGAI (i.e., EGAI fraction) varied with fuel reactivity (i.e., octane number) and the time-integrated temperature of the end-gas prior to ignition. Flame propagation rates, which were measured using schlieren images, were only weakly correlated with octane number but were affected by turbulence caused by variation in piston timing. Under conditions of low turbulence, measured flame propagation rates approached one-dimensional premixed laminar flame speed computations performed at the same conditions. Experiments were simulated with a three-dimensional CONVERGE™ model using reduced chemical kinetics (121 species, 538 reactions). The simulations accurately captured the measured flame propagation rates, as well as the variation in EGAI fraction with fuel reactivity and time-integrated end-gas temperature. The simulations also revealed low-temperature heat release as well as formaldehyde and hydrogen peroxide formation in the end-gas upstream of the propagating flame, which increased the temperature and degree of chain branching in the end-gas, ultimately leading to EGAI.

42 ENGINEERING↗
DOE OSTI2021

Potential Economic Values of Low-Vapor-Pressure Gasoline-Range Bio-Blendstocks: Property Estimation, and Blending Optimization

Adding non-traditional blendstocks derived from biomass into gasoline has gained renewed interest since it will reduce greenhouse gas emissions and potentially enhance fuel properties and boost engine efficiencies. A competitive bio-blendstock candidate should have either lower prices or superior properties or both relative to conventional gasoline blending components. Gasoline is a mixture of hundreds compounds specified by properties rather than compositions. The addition of bio-blendstocks, most likely oxygenates, will modify the property mixing rules due to the non-ideal interactions between polar and nonpolar components. This paper presents an equation-of-state-based model for predicting Reid vapor pressure, reduced order non-linear property blending models for computing key properties of final gasoline products, and a blending optimization approach to identify key economic drivers. This paper also evaluates the economic values of bio-blendstocks to petroleum refiners using those models. In additional to ethanol, six low-vapor-pressure bio-blendstock candidates were evaluated: i-propanol, n-propanol, i-butanol, diisobutylene, cyclopentanone, and a mixture of furans. Reid vapor pressure, distillation temperatures, and octane numbers were identified as the key economic drivers of adding bio-blendstock. The economic values of those bio-blendstocks range from 2.22 to 4.00 US dollar per gasoline gallon equivalent in 2013 to 2017 5-year averaged price basis. The bio-blendstocks with higher octane numbers may have higher economic values. The uncertainties in property predictions may lead to roughly 15% deviation in the economic value evaluation.

Jiang, Yuan↗
DOE OSTI2021

The intrinsic value of bioblendstocks: Prenol as a case study

Decarbonizing the transportation sector is likely to require both electrification and increased incorporation of biofuels and/or bioblendstocks. While the social and environmental benefits of bioblendstocks are well understood, their real value for the fuel producers has not been established. As such, this work considers prenol as a bioblendstock case study to identify sources of intrinsic value to fuel blenders by studying the properties of binary mixtures with gasoline components. The considered refinery blendstocks were samples of full range naphthas from the distillation, fluidized catalytic cracking, isomerization, alkylation, and reforming units. Octane numbers, Reid vapor pressure, distillation curves, and sulfur content were evaluated. Our results indicate the need for adjusting the formulation of the base fuel, depending on the interplay among the properties of the bioblendstock and those of the base fuel. Prenol increased research octane number (RON) and octane sensitivity (OS) of the base fuel, by up to 25 and 10 octane numbers, respectively. Additionally, 10 vol% prenol reduced RVP up to 2.2 psi, for the more volatile blendstock. Thus, considering prenol as a low volatility, RON/OS boosting bioblendstock, the composition of the preferred base fuel was proposed as containing reduced olefins and aromatics, and increase light fractions. The potential impact of this new gasoline formulation on refining processes and products gives rise to direct sources of value to the refiners, such as exporting products to the chemicals market, increasing the value of intermediate refinery streams, decreasing operating severity of certain refinery units, and broadening of the product suite.

09 BIOMASS FUELS↗
DOE OSTI2022

Numerical Study of PAHs and Soot Emissions from Gasoline–Methanol, Gasoline–Ethanol, and Gasoline– n -Butanol Blend Surrogates

Soot formation is an intricate phenomenon, and soot propensity of a fuel is interwoven with the fuel composition, physical and chemical properties, and combustion environment. Here, the present study examines the hypothesis that in addition to the chemical composition of the fuel, the sooting nature of the fuel is closely coupled with its chemical property known as octane sensitivity (S). With this motivation, the present study numerically investigates the effects of gasoline surrogate composition and its property, octane sensitivity (S), on polycyclic aromatic hydrocarbons (PAHs) and soot emissions. Four-component toluene primary reference fuel (TPRF)–alcohol blends, comprising iso-octane, n-heptane, toluene, and one of the three different alcohols- methanol, ethanol, and n-butanol, are used as gasoline surrogates. A total of 320 TPRF–alcohol mixtures, with S in the range of 1–10, are examined under laminar counterflow diffusion flame conditions. A detailed chemical mechanism coupled with a comprehensive soot model, which includes reactions for soot inception, surface growth, PAH condensation, and oxidation, is adopted. The analysis indicates that the toluene content in the fuel mixture has a prominent effect, while the alcohol content and octane sensitivity of the fuel have a weak correlation with the PAHs and soot. Thus, it is not clear if any of these three variables, namely, toluene content in the fuel, alcohol content in the fuel, and S, are individually sufficient to characterize the PAHs and soot across various blends. For this reason, a new variable (X CHO ) based on the elemental composition of the fuel mixture is identified and it is shown that X CHO along with S of the fuel characterize soot emissions satisfactorily. Further, a reaction path analysis indicates that the efficacy of alcohols in reducing soot emissions follows the order: methanol > ethanol > n-butanol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Economic analysis of the benefits to petroleum refiners for low carbon boosted spark ignition biofuels

A refinery modeling framework is developed to estimate the benefits of blending high-quality biofuels directly with refinery gasoline components for attaining a premium grade fuel (also termed as Co-Optima Boosted SI gasoline here). Our results change the paradigm of bio-blendstocks (BBs) being competitors to fossil components, by identifying opportunities for refineries to add value to their product slate, from some favorable BB properties. This potential value can be characterized by calculating the breakeven value (BEV), as defined down below. The proposed modeling framework incorporates extensive data from (1) projected product over the next few decades, (2) crude oil and refinery products pricing, and (3) fuel specifications. The complete refinery models serve as a basis for assessing the value of biofuels, assuming profitability remains the same for representative petroleum refinery configurations. Our assessment showed wide range of variation of biofuels BEV from $\$$20-$\$$120/bbl, within the considered blending level and crude prices. Further, the BEV was correlated with the fuel octane ratings such as octane numbers (research, RON and motor octane numbers, MON) and both antiknock index (AKI, average of RON and MON) and sensitivity (S, difference between RON and MON), with a slightly higher correlation with the sensitivity. However, the expected decrease in gasoline demand for the upcoming years could negatively impact biofuels demand and value, in a business-as-usual scenario. Our analysis also showed a more valuable bio-blendstocks incorporation in smaller refineries since they can enhance the capabilities for producing specialty, high-value fuels/products, and introduce high octane-barrels into otherwise constrained blending operations. Additional implications towards refiners include opportunities to rebalance operations, access to high-value fuel markets, and synchronization with broader transportation industry trends. Furthermore, results indicate the value of Co-Optima boosted spark ignition (BSI) efficiency gains can extend to refiners to incentivize decarbonization and diversified feedstock production.

09 BIOMASS FUELS↗
DOE OSTI2024

Potential Adoption and Benefits of Co-Optimized Multimode Engines and Fuels for U.S. Light-Duty Vehicles

Exploring a diverse portfolio of technologies for decarbonization is crucial to understanding the potential impacts of different technological solutions and their associated environmental implications. Using high-octane, high-sensitivity biofuel blends in co-optimized multimode engines can increase engine efficiency and reduce vehicle emissions. Here, the multimode engine research focuses on the benefits of light-duty vehicle engines, which can operate in multiple modes depending on the vehicle's load. Low-temperature combustion can improve efficiency and reduce emissions (such as those from oxides of nitrogen and particulate matter) during low-load operation, while spark ignition performance is maintained in high-load operation. These advanced engines can be optimized to run on blends of biobased fuels. This analysis models scenarios for potential market adoption of co-optimized multimode vehicles fueled by three different bioblendstocks: ethanol, isopropanol, and isobutanol. An integrated modeling approach is used to forecast the energy and environmental impacts of the deployment of co-optimized multimode vehicles and fuels in the light-duty sector over the 2020-to-2050 time horizon. The multidisciplinary approach combines vehicle sales modeling, system dynamics modeling of the biorefining industry, and life cycle assessment to estimate the emissions and energy benefits. The models consider market forces such as consumer preferences for vehicle attributes, biofuel supply and demand dynamics subject to biorefinery capacity build-out and bioresource constraints, and forecasted changes to the U.S. bulk energy system over time. Market adoption of co-optimized vehicles is evaluated across a wide parameter space for incremental vehicle cost and engine efficiency improvement. This analysis reveals that the deployment of co-optimized multimode fuels and vehicles results in up to a 5% reduction in annual sector-wide life cycle greenhouse gas (GHG) emissions by 2050, relative to a business-as-usual scenario, but is also indicates environmental trade-offs, such as higher life cycle water-use. Emission benefits could potentially increase beyond 2050, as the new technologies penetrate the market and gain a foothold. Results also show that, under certain circumstances, vehicles with engines co-optimized for use with high-octane, high-sensitivity biofuel blends can be cost-competitive with conventional gasoline, while reducing GHG emissions. Our modeling results indicate that co-optimized multimode fuels and engines can be strategically leveraged in tandem with electrification to decarbonize the light-duty sector. Co-optimized vehicles could play a role in the early years of the time horizon, while electric vehicles (EVs) could become more competitive in the later years, highlighting the complementary benefits of these technologies for GHG reductions.

Oke, Doris↗
DOE OSTI2024

Surveying Phase Modifier Functional Groups for Applications to Ln(III) Separations

The application of N,N,N',N'-tetraoctyl diglycolamide (TODGA) in solvent extraction systems for lanthanide (Ln) separations is well understood. In these systems, the formation of a third phase has motivated the use of phase modifiers to enable higher concentrations of H + and Ln common to industrial processes. Several different phase modifiers with applications to diglycolamide (DGA) systems have previously been reported, with a focus on tri-n-butyl phosphate (TBP), N,N'-dihexylactanamide (DHOA), N,N-dioctyl-2-hydroxyacetamide (DOHyA), N,N'-dimethyl-N,N'-dioctylhexylethoxy malonamide (DMDOHEMA), and octanol. While the primary utility of phase modifiers is the increased metal loading, they can have significant effects on the metal distribution ratios, which are well described by the energetics of the extraction process itself. However, the mechanisms by which phase modifiers impact distribution ratios are not generally understood. This work considers the ability of phase modifiers to affect Ln distribution ratios by using phase modifiers with two different functional groups (–Cl and –C≡N) and an octyl alkyl chain in a TODGA and n-dodecane system. Determining the effect of chlorooctane and octane nitrile is important for understanding how phase modifier functional groups and their hydrogen bonding interactions affect Ln extraction. Through combining distribution ratio measurements with organic phase spectroscopic investigations, the impact of chlorooctane and octane nitrile on Ln extraction and their inner-sphere complexes is reported. The addition of either chlorooctane or octane nitrile to TODGA in n-dodecane decreases Ln extraction while maintaining the same inner-sphere Ln complex. The lack of change in inner-sphere Ln-TODGA coordination upon incorporation of phase modifiers and the significant impact of these phase modifiers on distribution ratios suggest the importance of a supramolecular structure. Understanding the role of chlorooctane and octane nitrile on the organic phase structure at longer length scales has been identified as an avenue for future investigations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Numerical Analysis of Fuel Effects on Advanced Compression Ignition Using a Cooperative Fuel Research Engine Computational Fluid Dynamics Model

Growing environmental concerns and demand for a better fuel economy are driving forces that motivate the research for more advanced engines. Multi-mode combustion strategies have gained attention for their potential to provide high thermal efficiency and low emissions for light-duty applications. These strategies target optimizing the engine performance by correlating different combustion modes to load operating conditions. The extension from boosted spark ignition (SI) mode at high loads to advanced compression ignition (ACI) mode at low loads can be achieved by increasing the compression ratio and utilizing intake air heating. Further, in order to enable an accurate control of intake charge condition for ACI mode and rapid mode-switches, it is essential to gain fundamental insights into the autoignition process. Within the scope of ACI, homogeneous charge compression ignition (HCCI) mode is of significant interest. It is known for its potential benefits, operation at low fuel consumption, low NOx, and particulate matter (PM) emissions. In the present work, a virtual Cooperative Fuel Research (CFR) engine model is used to analyze fuel effects on ACI combustion. In particular, the effect of fuel octane sensitivity (S) (at constant Research Octane Number (RON)) on autoignition propensity is assessed under beyond-RON (BRON) and beyond-MON (BMON) ACI conditions. The three-dimensional CFR engine computational fluid dynamics (CFD) model employs a finite-rate chemistry approach with a multi-zone binning strategy to capture autoignition. Two binary blends with Research Octane Number (RON) of 90 are chosen for this study: primary reference fuel (PRF) with S = 0 and toluene–heptane (TH) blend with S = 10.8, representing paraffinic and aromatic gasoline surrogates. Reduced mechanisms for these blends are generated from a detailed gasoline surrogate kinetic mechanism. Simulation results with the reduced mechanisms are validated against experimental data from an in-house CFR engine, with respect to in-cylinder pressure, heat release rate, and combustion phasing. Thereafter, the sensitivity of combustion behavior to ACI operating condition (BRON versus BMON), air-fuel ratio (λ = 2 and 3), and engine speed (600 and 900 rpm) is analyzed for both fuels. It is shown that the sensitivity of a fuel’s autoignition characteristics to λ and engine speed significantly differs at BRON and BMON conditions. Moreover, this sensitivity is found to vary among fuels, despite the same RON. It is also observed that the presence of low-temperature heat release (LTHR) under BRON condition leads to more sequential autoignition and longer combustion duration than BMON condition. Finally, the study indicates that the octane index (OI) fails to capture the trend in the variation of autoignition propensity with S under the BMON condition.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2023

Experimental measurements of soot formation in fuel-rich homogeneous mixtures using an optical rapid compression machine

Advanced combustion strategies are necessary for the use of more environmentally sustainable fuels than traditional diesel. Alcohol fuels and alcohol/gasoline blends are of particular interest as they are readily available in the marketplace. Heavy-duty engines typically use compression ignited, conventional diesel mixing controlled combustion. Mixing controlled combustion features a non-premixed diffusion flame with a wide range of local equivalence ratios, leading to potentially high rates of soot formation. This work studies the sooting behavior of iso-octane and ethanol as a function of equivalence ratio. Measurements are carried out in a rapid compression machine (RCM) and are reported for pre-ignition conditions of 10–30 bar and temperatures of 650–800 K. Theoretical equilibrium and bulk gas temperatures are calculated for both fuels. These data are used to identify the critical equivalence ratio, the lowest equivalence ratio where soot is detected with a single-pass laser extinction diagnostic. The critical equivalence ratio for iso-octane varies between 1.82 and 1.77 for compressed pressures of 10 and 20 bar, respectively. Ethanol, sometimes considered sootless, had a critical equivalence ratio between 2.37 and 2.12 for compressed pressures of 20 and 30 bar, respectively. When characterizing soot formation by oxygenated equivalence ratio, the critical equivalence ratios for ethanol approach those of iso-octane. This suggests the oxygenated nature of alcohol fuels reduces sooting tendency, but other factors such as fuel molecular structure and morphology may play a role. It was observed that ethanol will form soot at equivalence ratios only slightly higher than iso-octane, which could have implications in mixing controlled combustion. It was seen for both fuels that soot formation is pressure sensitive, with the critical equivalence ratio being inversely proportional to compressed pressure and the rate of soot formation. Future work will investigate the sooting behavior of gasoline/ethanol blends.

02 PETROLEUM↗
DOE OSTI2021

Gasoline fuels properties for multi-mode operation – Observations in a GDI and the CFR engine

The combustion behavior of five full boiling range RON98 gasoline blends was evaluated for multi-mode operation in a GDI and the CFR octane rating engine. The GDI engine tests were conducted with stoichiometric air-fuel ratio in spark-ignition (SI), and with air-diluted homogeneous charge compression ignition (HCCI) mode. In the CFR engine, the knocking combustion was analyzed under standard RON testing conditions at both peak knocking lambda and stoichiometric air-fuel ratios, whereas compression ignited operation was characterized by utilizing the HCCI number test protocol. Disparate knock limited SI and HCCI combustion behavior was observed for the test fuels, despite four of the fuels having the same RON and octane sensitivity. It was found that knock-limited combustion phasing in the GDI engine did not align well with the RON. However, a detailed comparison of knock-limited SI operation in the GDI and CFR engine revealed that a more appropriate effective RON based on a common knock intensity metric (MAPO) and stoichiometric air-fuel ratio resulted in comparable knock characterization between the two engine platforms. Furthermore, the critical intake air temperature and the critical compression ratio were proposed to characterize knock-limited SI operation, while the minimum intake air heating and compression ratio were used to define a fuel's autoignition propensity for compression ignition operation in the GDI and CFR engine, respectively. Finally, each fuel's characteristic compression ratio needed to obtain knock-limited SI (KLSI) and HCCI operation was used to calculate an effective multi-mode octane number (MM-ON) based on the primary reference fuel blends.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2024

Effect of Cyclo-Pentane Impurities on the Autoignition Reactivity and Properties of a Gasoline Surrogate Fuel

Surrogate fuels that reproduce the characteristics of full-boiling range fuels are key tools to enable numerical simulations of fuel-related processes and ensure reproducibility of experiments by eliminating batch-to-batch variability. Within the PACE initiative, a surrogate fuel for regular-grade E10 (10%vol ethanol) gasoline representative of a U.S. market gasoline, termed PACE-20, was developed and adopted as baseline fuel for the consortium. Although extensive testing demonstrated that PACE-20 replicates the properties and combustion behavior of the full-boiling range gasoline, several concerns arose regarding the purity level required for the species that compose PACE-20. This is particularly important for cyclo-pentane, since commercial-grade cyclo-pentane typically shows 60%–85% purity. Here, in the present work, the effects of the purity level of cyclo-pentane on the properties and combustion characteristics of PACE-20 were studied. Chemical kinetic simulations were performed to predict the effects of cyclo-pentane impurities on the properties, octane rating, and autoignition reactivity under homogeneous charge compression-ignition conditions of PACE-20. From the numerical results, cyclo-pentane with 85% purity or higher is required to reasonably match both the research octane number and motor octane number of the target gasoline. Finally, homogeneous charge compression-ignition engine simulations show that impurities have only a modest effect on reactivity at naturally aspirated conditions, but cyclo-pentane purity is critical to properly replicate the pressure dependency of the reactivity.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2023

Ene Reductase Enabled Intramolecular β–C–H Functionalization of Substituted Cyclohexanones for Efficient Synthesis of Bridged Bicyclic Nitrogen Scaffolds

Herein we report that ene reductases (EREDs) can facilitate an unprecedented intramolecular β-C–H functionalization reaction for the synthesis of bridged bicyclic nitrogen heterocycles containing the 6-azabicyclo[3.2.1]octane scaffold. To streamline the synthesis of these privileged motifs, we developed a gram-scale one-pot chemoenzymatic cascade by combining iridium photocatalysis with EREDs, using readily available N-phenylglycines and cyclohexenones that can be obtained from biomass. Further derivatization using enzymatic or chemical methods can convert 6-azabicyclo[3.2.1]octan-3-one into 6-azabicyclo[3.2.1]octan-3α-ols, which can be potentially utilized for the synthesis of azaprophen and its analogues for drug discovery. Furthermore, mechanistic studies revealed the reaction requires oxygen, presumably to produce oxidized flavin, which can selectively dehydrogenate the 3-substituted cyclohexanone derivatives to form the α,β-unsaturated ketone, which subsequently undergoes spontaneous intramolecular aza-Michael addition under basic conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Ene Reductase Enabled Intramolecular β–C–H Functionalization of Substituted Cyclohexanones for Efficient Synthesis of Bridged Bicyclic Nitrogen Scaffolds

Herein we report that ene reductases (EREDs) can facilitate an unprecedented intramolecular β-C–H functionalization reaction for the synthesis of bridged bicyclic nitrogen heterocycles containing the 6-azabicyclo[3.2.1]octane scaffold. To streamline the synthesis of these privileged motifs, we developed a gram-scale one-pot chemoenzymatic cascade by combining iridium photocatalysis with EREDs, using readily available N-phenylglycines and cyclohexenones that can be obtained from biomass. Further derivatization using enzymatic or chemical methods can convert 6-azabicyclo[3.2.1]octan-3-one into 6-azabicyclo[3.2.1]octan-3α-ols, which can be potentially utilized for the synthesis of azaprophen and its analogues for drug discovery. Here, mechanistic studies revealed the reaction requires oxygen, presumably to produce oxidized flavin, which can selectively dehydrogenate the 3-substituted cyclohexanone derivatives to form the α,β-unsaturated ketone, which subsequently undergoes spontaneous intramolecular aza-Michael addition under basic conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

High-pressure ignition delay time measurements of a four-component gasoline surrogate and its high-level blends with ethanol and methyl acetate

Ignition delay times of a gasoline surrogate (iso-octane/toluene/n-heptane/1-hexene at 55/25/15/5% by liquid volume, developed in McCormick et al. 2017) with high-level bioblendstock-gasoline surrogate blends (50% and 85% biofuel by liquid volume of each ethanol and methyl acetate) were collected behind reflected shock waves. Post-reflected-shock temperatures ranged from 968 to 1361 K at pressures of about 4, 10, 25, and 50 atm. Data were collected for real fuel–air mixtures at fuel lean and stoichiometric conditions (φ = 0.5, 1.0) with focus on the more-practical, fuel-lean conditions. Ignition delay times were measured from OH* chemiluminescence around 307 nm using an endwall diagnostic. The RON and MON of the surrogate were 90.3 and 84.7, respectively. Ethanol was chosen due to its wide use in flex-fuel vehicles and availability, while also providing an increased octane rating. Methyl acetate was chosen for its especially high octane rating to investigate the effect of an extreme case. To validate the gasoline surrogate, the data are compared to real gasoline (RD387) and several gasoline surrogate experiments from the literature. Using the wide range of pressures studied, the gasoline surrogate’s pressure dependence was quantified to account for test-to-test variations using regression analysis. Similarly, a global correlation for gasoline and its surrogates was developed using all available data from the literature. Two modern chemical kinetics models targeting gasoline and its surrogates are compared to the ignition delay time measurements. These new high-pressure, high-bioblendstock concentration tests provide required chemical kinetic data for optimizing fuel and engine design.

42 ENGINEERING↗
DOE OSTI2021

Production, fuel properties and combustion testing of an iso-olefins blendstock for modern vehicles

With the increasing pressure to decarbonize the transportation sector, exploring strategies that can reduce emissions from light-duty vehicles (LDV) has become critical. Bioblendstocks that allow for higher engine efficiency and fuel economy could complement vehicle electrification and help reach carbon neutrality by 2050. In this context, the potential of a mixture of iso-olefins as a bioblendstock was investigated for multimode boosted spark-ignition (SI)/advanced compression ignition (ACI) engine operation designed to achieve higher overall vehicle fuel economy. By establishing the relationship between the molecular structure of iso-olefins and research octane number (RON), octane sensitivity (S) (i.e., the difference between RON and motor octane number [MON]), and phi-sensitivity a dimethyl-hexenes rich olefins mixture (DMHROM) was identified as a preferred blendstock for SI/ACI combustion engines. Here, a pathway for DMHROM production from biomass-derived ethanol was developed and scaled up. More than 1 gallon of DMHROM blendstock was produced for fuel properties assessment including engine testing. Measurements in a Cooperative Fuel Research Engine showed that the DMHROM blendstock possesses a RON of 94 and S of 13.5, and blends synergistically. Rapid compression machine tests coupled with single-cylinder gasoline direct injection engine measurements demonstrated the 20 vol.% DMHROM blend has higher phi-sensitivity than an olefin-free gasoline base fuel and a typical California Reformulated Gasoline Blendstock for Oxygenate Blending (CARBOB) gasoline fuel. These results demonstrate the potential of DMHROM for improving gasoline fuel performance and quality for operation under ACI conditions. The effectiveness of the aftertreatment system in mitigating emissions was verified and showed that the pure DMHROM blendstock and 20 vol.% blend would not increase non-methane organic gases, NO x , and carbon monoxide (CO) emissions. The DMHROM blendstock was found to slightly decrease sooting tendency when added to a gasoline-base fuel (i.e., ~6% reduction at 20 vol.% blending level). Oxidation stability and lubricant compatibility were both confirmed for the 20 vol.% blend. Overall, these results demonstrate that dimethyl-hexenes have potential for improving engine efficiency and fuel economy while meeting emissions regulations and ASTM specifications for gasoline fuel.

09 BIOMASS FUELS↗
DOE OSTI2022

Numerical analysis of soot emissions from gasoline-ethanol and gasoline-butanol blends under gasoline compression ignition conditions

In the present work, computational fluid dynamics (CFD) simulations of a single-cylinder gasoline compression ignition (GCI) engine were performed to investigate the impact of blending two biofuels, ethanol and n-butanol, with gasoline on the trade-off between combustion phasing and soot emissions under low load conditions. Here, in order to represent market gasoline (RD5-87), a four-component toluene primary reference fuel (TPRF) + ethanol (ETPRF) surrogate (with 20% ethanol by mole; E20) was formulated using a neural network based octane predictor such that the surrogate had the same ethanol content, Research Octane Number (RON) and Octane Sensitivity (S). In addition, a novel skeletal kinetic mechanism for ETPRF and TPRF + n-butanol (BTPRF) blends, incorporating polycyclic aromatic hydrocarbon (PAH) chemistry, was developed. A three-dimensional (3D) engine CFD formulation employing the skeletal mechanism, adaptive mesh refinement (AMR), finite-rate chemistry approach, and hybrid method of moments (HMOM) was adopted to capture the in-cylinder combustion phenomena and soot emissions. The engine CFD model was validated against RD5-87 experimental data for a broad range of start-of-injection (SOI) timings (-21/-27/-36/-45 crank angle degrees (CAD) after top-dead center (aTDC)), with respect to in-cylinder pressure, heat release rate, combustion phasing, and soot emissions. The closed-cycle simulation results were analyzed to elucidate the non-monotonic trend of soot emissions versus SOI timing: SOI-36 > SOI-45 > SOI-21 > SOI-27. Thereafter, the validated CFD model was employed to simulate the combustion of a gasoline-ethanol blend with 45% (by mole) ethanol (E45) and a gasoline-butanol blend with 45% (by mole) n-butanol (B45) under the same operating conditions to study the effects of fuel composition and SOI timing on combustion phasing and soot emissions. The sooting propensity followed the trend: B45 > E20 > E45 at all SOI timings. Overall, it was observed that the autoignition propensity was primarily related to fuel chemistry. On the other hand, sooting propensity showed strong coupling with both fuel chemistry and physical properties, with greater impact of fuel physical properties at advanced SOI timings.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2020

Ignition Delay Measurements of Four Component Model Gasolines Exploring the Impacts of Biofuels and Aromatics

This study explores the impacts of combinations of biofuel (ethanol, isobutanol and 2-methyl furan) and aromatic (toluene) compounds in a four component fuel blend, at fixed research octane number (RON) on ignition delay measured in an advanced fuel ignition delay analyzer (AFIDA 2805). Ignition delay measurements were performed over a range of temperatures from 400 to 725 °C (673 to 998 K) and two chamber pressures of 10 and 20 bar. The four component mixtures are compared to primary reference fuels at RON values of 90 and 100. The ignition delay measurements show that as the aromatic and biofuel concentrations increased, two stage ignition behavior was suppressed, at both initial chamber pressures. But both RON 100 (isooctane) and RON 90 reference fuels showed two stage ignition behavior, as did fuel mixtures with low biofuel and aromatic content. RON 90 fuels showed stronger two stage ignition behavior than RON 100 fuels, as expected. Depending on the type of biofuel in the mixture, the ignition delay at low chamber temperatures could be far greater than for the reference fuels. In particular, for the RON 100 mixtures at either 10 or 20 bar initial chamber pressure, the ignition delay at 400 °C (673 K) for the high level blend of 2-methyl furan and toluene (30 vol% of each) exhibited an ignition delay that was 10 times longer than for neat isooctane. The results show the strong non-linear octane blending response of these three biofuel compounds, especially in concert with the kinetic antagonism that toluene is known to display in mixtures with isooctane. These results have implications for the formulation of biofuel mixtures for spark ignition and advanced compression ignition engines, where this non-linear octane blending response could be exploited to improve knock resistance, or modulate the autoignition process.

2-methyl furan↗
DOE OSTI2020

Numerical Investigation of a Central Fuel Property Hypothesis Under Boosted Spark-Ignition Conditions

In the present work, a central fuel property hypothesis (CFPH), which states that fuel properties are sufficient to provide an indication of a fuel’s performance irrespective of its chemical composition, was numerically investigated. In particular, the objective of the study was to determine whether Research Octane Number (RON) and Motor Octane Number (MON), as fuel properties, are sufficient to describe a fuel’s knock-limited performance under boosted spark-ignition (SI) conditions within the framework of CFPH. To this end, four TPRF-bioblendstock surrogates having different compositions but matched RON (=98) and MON (=90), were first generated using a non-linear regression model based on artificial neural network (ANN). Additionally, three unconventional bioblendstocks were included in the analysis: di-isobutylene (DIB), isobutanol, and Anisole. Skeletal reaction mechanisms were generated for the TPRF-DIB, TPRF-isobutanol, and TPRF-anisole blends from a detailed kinetic mechanism. Thereafter, numerical simulations were performed for the fuel surrogates using the skeletal mechanisms and a virtual cooperative fuel research (CFR) engine model, under a representative boosted operating condition. In the computational fluid dynamics (CFD) model, the G-equation approach was employed to track the turbulent flame front and the well-stirred reactor model combined with the multi-zone binning strategy was used to capture auto-ignition in the end-gas. In addition, laminar flame speed (LFS) was tabulated for each blend as a function of pressure, temperature, and equivalence ratio a priori, and the lookup tables were used to prescribe laminar flame speed as an input to the G-equation model. Parametric spark timing sweeps were performed for each fuel blend to determine the corresponding knock-limited spark advance (KLSA) and 50% burn point (CA50) at the respective KLSA timing. It was observed that despite same RON, MON, and engine operating conditions, the TPRF-anisole blend exhibited markedly different knock-limited performance from the other three blends. This deviation from the octane index (OI) expectation was shown to be caused by differences in laminar flame speed. However, it was found that relatively large fuel-specific differences in LFS (>20%) would have to be present to cause any appreciable deviation from the OI framework. Otherwise, RON and MON would still be robust enough to predict a fuel’s knock-limited performance.

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