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This report describes the supply chain sustainability analysis (SCSA) of the production of renewable high octane gasoline (HOG) via indirect liquefaction (IDL) of lignocellulosic biomass.
1H and 13C nuclear magnetic resonance spectroscopy are used to determine an accurate, quantitative description of the atom type population of FACE-F, a research-grade gasoline. On this basis, a surrogate palette of seventeen components is proposed. Two surrogate fuels are formulated; a seven-component mixture (FGF-TCD1), and a nine-component mixture (FGF-TCD2). The autoignition behavior of FGF-TCD1 and FGF-TCD2 is investigated. Measurements are compared to tests with FACE-F, and blends of FACE-F with ethanol. Conditions at the transition from low-temperature to NTC chemistry are targeted such that first-stage, main ignition times, and exothermicity can be monitored. From the same manner, perturbed ignition characteristics due to the ethanol addition can be quantified. The results of this study demonstrate that although the atom type populations of both surrogate fuels are consistent with FACE-F and each other, the observed reactivity is different. This is may be attributed to atom type descriptors alone being insufficient to capture the combustion behavior of FACE-F. Interestingly, however, similar degree of reactivity differences in response to ethanol blending is observed.
Recent research on the production of HOG from DME over BEA zeolites suggests that this process offers an attractive alternative to traditional methanol-to-gasoline (MTG) technologies by operating at milder conditions and providing greater carbon efficiency 1. The HOG product is rich in branched olefins and paraffins, particularly triptane (2,2,3-trimethylbutane) which has high research- and motor-octane numbers (RON 112, MON 101), making it an ideal unleaded fuel or fuel additive for aviation or racing applications 2. RON and MON are important fuel metrics and research shows a correlation between them and paraffin and olefin content 3. Copper-modified BEA (Cu/BEA) is more active than HBEA . Research has identified that ionic Cu(I) species are active for alkane dehydrogenation whereas metallic Cu species responsible for hydrogenation chemistry 4. Here we report on the effect of including ionic Zn and Ni as a means of increasing the dehydrogenation activity of Cu/BEA in DME-to-HOG reactions. Bimetallic Cu-Zn/BEA and Cu-Ni/BEA catalysts were synthesized by first incorporating Ni or Zn by ion-exchange, followed by incipient-wetness impregnation of Cu. Similar metal loadings, acid site densities, and Bronsted/Lewis acid ratios were confirmed across all materials. All catalysts were tested in DME-to-HOG reactions with co-fed H2 at 200 degrees C and 15 psia with 1:1 DME:H-2 and DME weight-hourly space velocity of 2.2 gDME-gcat-1-h-1. Compared at similar turnover numbers (TON), Cu-Ni/BEA displayed similar activity to Cu/BEA however, exhibited greater hydrogenation activity as evidenced by the higher C5-8 P:O ratio. The Cu-Zn/BEA demonstrated decreased activity and the lowest P:O ratio, attributed to enhanced dehydrogenation activity at ionic Zn sites. For the HOG-range products (i.e., C5-8 hydrocarbon species), each catalyst had a 98-99 estimated RON, while the MON decreased with decreasing P:O ratio. Compared to Cu/BEA, these bimetallic catalysts demonstrate a unique balance of hydrogenation and dehydrogenation of the hydrocarbon products to access markedly different P:O product ratios without requiring a separate unit operation or a mixed catalyst bed.
A design optimization campaign was conducted to search for improved combustion profiles that enhance gasoline compression ignition in a heavy-duty diesel engine with a geometric compression ratio of 17.3. A large-scale design of experiments approach was used for the optimization, employing three-dimensional computational fluid dynamics simulations. The main parameters explored include geometric features, injector specifications, and swirl motion. Both stepped-lip and re-entrant bowls were included in order to assess their respective performance implications. A total of 256 design candidates were prepared using the software package CAESES for automated and simultaneous geometry generation and combustion recipe perturbation. The design optimization was conducted for three engine loads representing light to medium load conditions. The design candidates were evaluated for fuel efficiency, emissions, fuel-air mixing, and global combustion behavior. Simulation results showed that the optimum designs were all stepped-lip bowls, due to improvements in fuel-air mixing, as well as reduced heat loss and emissions formation. Improvements in indicated specific fuel consumption of up to 3.2% were achieved while meeting engine-out NOx emission targets of 1-1.5 g/kW center dot h. Re-entrant bowls performed worse compared to the baseline design, and significant performance variations occurred across the load points. Specifically, the re-entrant bowls were on par with the stepped-lip bowls under light load conditions, but significant deteriorations occurred under higher load conditions. As a final task, selected optimized designs were then evaluated under full-load conditions.
A multi-functional NiMo-ceria-zirconia composite was developed as an anode for a solid oxide fuel cell (SOFC) running on isooctane that is a commonly used model fuel for gasoline. The anode layer was fabricated on an electrolyte-supported single cell using yttria-stabilized zirconia (YSZ) as the electrolyte and La0.6Sr0.4Co0.2Fe0.8O3-d as the cathode. Our results indicated that the single NiMo-ceria-zirconia layer possessed a dual-functionality: the first function was to internally convert complex hydrocarbons into a synthesis gas and the second function was to electrochemically oxidize the synthesis gas mixture for electric power generation. The addition of Mo to the Ni-ceria-zirconia allowed direct conversion of isooctane in SOFC. It significantly suppressed carbon deposition in the anode and improved the lifetime of a single cell. Additionally, the presence of Mo in the Ni-ceria-zirconia anode appeared to facilitate a higher degree of sintering, which increased the electrical conductivity and maximum power density of the single cell. When operating on isooctane at 800 °C, single cell with the 5 wt.% Mo in the Ni-ceria-zirconia-based anode displayed a maximum power density of 212 mW cm-2 at 0.48V which was higher than that of a single cell with the Ni-YSZ-based anode without the Mo promoter (49 mW cm-2 at 0.48 V).
Passive selective catalytic reduction (SCR) is a promising approach for the control of NOX emissions in lean burn gasoline exhausts. It requires ammonia (NH 3 ) to be produced over a three-way catalyst (TWC) during periods of fuel-rich operation for the reduction of NO X during periods of fuel-lean operation. Previous research has shown the viability of this system but has not examined the effects of hydrothermal degradation. This work is focused on evaluating the effects of hydrothermal aging on the TWC in a passive SCR system. Two catalysts were studied: a Pd-TWC, and a NO X storage and reduction (NSR) TWC. Samples were aged at 920 °C for 100 h using a four-mode hydrothermal aging procedure. This causes the catalyst to be oxidized and reduced, as it would in a real system. The effects of aging were evaluated using simulated exhaust under both steady state and lean-rich cycling conditions. Hydrothermal aging caused significant changes in catalyst activity, leading to a decrease in low temperature conversion of carbon monoxide (CO) and propane (C 3 H 8 ) on both catalysts, and degradation of oxygen storage and NO X storage components. Furthermore, the catalysts maintained their activity for NO X conversion and NH 3 production, showing sufficient activity for the operation of a passive SCR with an optimum projected fuel consumption of 92–98% compared to stoichiometric operation.
We study the influence of blending n-butanol on the ignition delay times of n -heptane and iso-octane, the primary reference fuels for gasoline. The ignition delay times are measured using a rapid compression machine, with an emphasis on the low-to-intermediate temperature conditions. The experiments are conducted at equivalence ratios of 0.4 and 1.0, for a compressed pressure of 20 bar, with the temperatures at the end of compression ranging from 613 K to 979 K. The effect of n -butanol addition on the development of the two-stage ignition characteristics for the two primary reference fuels is also examined. The experimental results are compared to predictions obtained using a detailed chemical kinetic mechanism, which has been obtained by a systematic merger of previously reported base models for the combustion of the individual fuel constituents. In conclusion, a sensitivity analysis on the base, and the merged models, is also performed to understand the dependence of autoignition delay times on the model parameters.
The sooting propensity of a fuel is closely coupled with the fuel composition and chemistry. A detailed understanding of their effects is, therefore, needed to develop next-generation fuels which can minimize particulate emissions. With this overarching goal, the present work numerically investigates the effects of fuel composition and octane sensitivity (S) on polycyclic aromatic hydrocarbons (PAH) and soot emissions, for four-component gasoline-ethanol blend surrogates comprising isooctane, n-heptane, toluene, and ethanol. A partially-premixed counterflow flame is chosen as the canonical configuration for this study and simulations are performed using CHEMKIN-Pro-employing a kinetic mechanism developed by Park et al. (2017). In addition, a, detailed soot model based on the sectional method is used to capture the spatial characteristics of soot emissions. The kinetic mechanism and soot model are validated using available experimental data for various targets. A total of 86 TPRF-E mixtures, spanning a wide range of concentration of each component, and a wide range of S are analyzed. The effect of each non-paraffinic fuel component on the resultant PAH and soot emissions is investigated. PAH and soot emissions are found to vary significantly depending upon the blend composition. Additionally, based on the parametric sweeps, a regression analysis is carried out to identify global parameters that govern the formation of PAHs and soot. The analysis shows that both toluene content and S have a prominent effect on the formation of PAHs and soot, with toluene content having a stronger impact. Moreover, larger PAHs have higher dependency on toluene content and S. Furthermore, a detailed analysis is carried out to understand the physical and chemical phenomena associated with the observed trends of PAH and soot emissions.
Exhaust gas recirculation (EGR) is widely used in advanced internal combustion engines to reduce engine emissions as well as control combustion phasing. Among various species present in EGR gases, CO 2 and H 2 O are two major components that can thermally and chemically affect fuel autoignition. It is of fundamental interest to isolate the thermal and chemical effects of CO 2 and H 2 O on fuel autoignition, especially as such an effort has not been reported in the literature. Moreover, nitric oxide (NO) is known to exhibit strong chemical effects on fuel autoignition, which in turn affects engine combustion phasing. The effects of ultra-low NO addition (< 100 ppm) on fuel autoignition at low temperatures are also not well understood. Recognizing these problems, autoignition experiments of iso-octane (a major gasoline surrogate component) in air are performed in this study using a rapid compression machine at varying compressed pressures, equivalence ratios, dilution levels with an EGR gas analogue (consisting of CO 2 , H 2 O, O 2 , and N 2 ) and N 2 only, and varying amounts of NO addition. Furthermore, the thermal and chemical effects of the EGR gas analogue are isolated and evaluated by comparing the ignition delay time datasets of EGR and N2-only diluted cases.
We report stoichiometric spark-ignition engines suffer efficiency penalties due to throttling losses at low loads, a low specific-heat ratio of the stoichiometric working fluid, and limits on compression ratio due to end-gas autoignition leading to undesirable knocking. Mixed-Mode Combustion (MMC) mitigates these shortcomings by using a lean working fluid where a spark-initiated pilot-stabilized deflagrative flame front is followed by controlled end-gas autoignition. This MMC study investigates the effects of initial conditions (intake air temperature, intake pressure, equivalence ratio, and intake oxygen fraction) on autoignition tendency of four gasoline-range fuels with varying properties and composition. The use of fuels with varying octane sensitivity (S) allowed exploring the importance of low-temperature heat release in triggering autoignition. Fuels with high S were less reactive for conditions that promote low-temperature chemistry (operation at high intake air pressure or without N2 dilution). Conversely, an Alkylate fuel with low S showed a greater autoignition resistance at operating conditions that were unfavorable for low-temperature chemistry. Next, the effect of residual gas composition on autoignition tendency of fuels was examined with a chemical-kinetics model. Among the various molecules in the residual gas, nitric oxide (NO) enhanced the low-temperature chemistry and increased the autoignition tendency most significantly. The fuels’ autoignition response to increasing NO amount corroborates the experimental observations. Next, the sequential autoignition of the end-gas was assessed to be less impacted by thermal stratification because of lean mixtures showing relatively less low-temperature chemistry, when compared to stoichiometric mixtures. Next, the effect of changing equivalence ratio on the autoignition was found to be similar for all fuels, regardless of their S. With changing intake air temperature, the response of fuels’ autoignition tendency depended on the dilution level used. At high dilution (i.e. low intake [O2]), fuels’ reactivity increased with increasing intake air temperature. In contrast, for operation without dilution, the autoignition tendency of the low-S Alkylate fuel decreased with increasing intake air temperature, while that of high-S High Cycloalkane fuel still increased with increasing intake air temperature. In conclusion, conventional octane metrics (RON and MON) have utility in assessing the autoignition tendency under lean MMC operation. Moreover, the fuel requirements for MMC align with that of stoichiometric operation: i.e., high RON and high S fuels are desirable for stable non-knocking operation.
Fuel-rich oxidation of three typical gasoline surrogate components, toluene, isooctane, and n-heptane, was investigated in an atmospheric-pressure flow reactor at mean gas temperatures from 1050 to 1350 K, equivalence ratio of 9.0, and residence times of 0.45 and 1.2 s. Not only polycyclic aromatic hydrocarbons (PAHs) up to 3 ring structure but also small intermediate products from C 1 to C 5 were quantified by a gas chromatograph mass spectrometry coupled with photon ionization and gas chromatograph with flame ionization detector, respectively. The kinetic model recently developed by Lawrence Livermore National Laboratory was revised to reflect the results of many recent investigations. Basically, the updated model could satisfactorily reproduce the experimental mole fractions of many species. The experimental and simulated results showed that PAH mole fractions produced were in the order of toluene, isooctane, and n-heptane. The kinetic analysis using the model was carried out to explore PAH formation pathways, especially focusing on naphthalene, acenaphthylene, and phenanthrene. Through rate of production analysis, it was found that the main formation pathways of many PAHs were affected by the fuels. Although resonantly stabilized radicals, such as benzyl and fulvenallenyl radicals, played a crucial role in the formation pathways of many PAHs in every fuel, they were produced through hydrogen elimination of toluene in toluene fuel, while they were formed from small intermediate products in isooctane and n-heptane fuels. Sensitivity analysis revealed the difference and similarity of the reactions with large positive coefficients according to the fuels studied here. In conclusion, the molecular growth reactions of aromatic species were influential in PAH production in every fuel, whereas the ring formation reactions from small species and the reactions involving toluene had large positive sensitivity coefficients in isooctane/n-heptane and toluene fuels, respectively.
Increased particle number and mass emissions in gasoline direct injection (GDI) engines should require to investigate in-cylinder flame and combustion characteristics associated with primary source of particle emissions. In this article, in-cylinder spatiotemporal flame luminosity is quantitatively characterized to features combustion process and solid particle emissions from a GDI engine operating in two lean and one stoichiometric modes. Low- and high-steady state operating points were used to compare combustion strategies on flame development and emission characteristics. A fiber-optic sensor composed of eight measurement channels detected the flame front and the direction of the flame propagation in the combustion chamber. Solid particle emissions in the exhaust were measured using an engine exhaust particle sizer and a micro soot sensor. Results of the experiments showed that two lean combustion modes by injection strategies resulted in distinct combustion and flame development. Lean combustion modes generated high diffusion flame by burning stratified rich-mixture. Although the lean cases resulted in strong diffusion flames, the lean-homogeneous produced similar particle size distributions with the stoichiometric mode with high ash particles. Piston pool fires on the piston surface in the lean-stratified mode induced a large accumulation mode with high particle mass concentrations.
Engine oil-derived ash particles emitted from internal combustion (IC) engines are unwanted by-products, after oil is involved in in-cylinder combustion process. Since they typically come out together with particulate emissions, no detail has been reported about their early-stage particles other than agglomerated particles loaded on aftertreatment catalysts and filters. To better understand ash formation process during the combustion process, here differently formulated engine oils were dosed into a fuel system of a gasoline direct injection (GDI) engine that produces low soot mass emissions at normal operating conditions to increase the chances to find stand-alone ash particles separated from soot aggregates in the sub-20-nm size range. In addition to them, ash/soot aggregates in the larger size range were examined using scanning transmission electron microscopy (STEM)-X-ray electron dispersive spectroscopy (XEDS) to present elemental information at different sizes of particles from various oil formulations. The STEM-XEDS results showed that regardless of formulated oil type and particle size, Ca, P and C were always contained, while Zn was occasionally found on relatively large particles, suggesting that these elements get together from an early stage of particle formation. The S, Ca and P K-edge X-ray absorption near edge structure (XANES) analyses were performed for bulk soot containing raw ash. The linear combination approach & cross-checking among XANES results proposed that Ca 5 (OH)(PO 4 ) 2 , Ca 3 (PO 4 ) 2 and Zn 3 (PO 4 ) 2 are potentially major chemical compounds in raw ash particles, when combined with the STEM-XEDS results. Despite many reports that CaSO 4 is a major ash chemical when ash found in DPF/GFP systems was examined, it was observed to be rarely present in raw ashes using the S K-edge XANES analysis, suggesting ash transformation.
Homogeneous Charge Compression Ignition (HCCI) is a promising advanced combustion concept with high thermal efficiency and low exhaust emissions. This work purposes a computationally-efficient, zero-dimensional (0-D) HCCI combustion model that does not need to solve any differential equations. To develop the burn rate correlations, experimental HCCI data of ethanol, natural gas, E10-gasoline, and Primary Reference Fuel (PRF) blends was collected on a CFR engine. The burn rate model is built based on the individual cycle mass fraction burned (MFB) curves calculated from the experimental data. CA0 can be predicted from an ignition delay correlation. Once CA0 is known, CA50 and CA90 can be predicted based on CA0 and the charge-mass equivalence ratio Φ'. Then, with CA0, 50 and 90 known, a Wiebe function can be constructed to represent the MFB curve and burn rate. For PRF blends, low-temperature and high-temperature heat releases (LTHR and HTHR) are modeled by two Wiebe functions with Φ' and PRF number dependence. The fitted model has high accuracy compared to the experimental data with R 2 values generally greater than 0.97. Finally, various ignition delay correlations from the literature are also tested against the experimentally collected data and some modifications to the correlations are suggested.
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.
Kinetic mechanisms for aromatics are needed to successfully simulate the autoignition of transportation fuels using the surrogate fuel approach. An aromatic detailed kinetic mechanism that describes kinetics of C7-C11 methylated aromatics, including toluene, o-xylene, p-xylene, 1,2,4-trimethylbenzene, 1,3,5, trimethyl-benzene and alpha-methylnaphthalene has been developed in the current study. The kinetic mechanism was built hierarchically using similar set of reaction pathways and reaction rate rules. In the mechanism developed, special emphasis is put on describing the detailed low-temperature ignition chemistry of o-xylene and 1,2,4-trimethylbenzene and, to our knowledge, this is the first attempt to do so in a detailed kinetic mechanism. In addition to kinetic modeling, new experimental data were acquired for toluene, o-xylene, and 1,2,4-trimethylbenzene using a rapid compression machine at low-to-intermediate temperatures and engine relevant pressures. In addition, the mechanism has been compared against data sets from the literature covering ignition delay times, flame speeds, and speciation profiles measured in a jet-stirred reactor and flow reactor. Good agreement is observed between the mechanism predictions and the experimental data. Kinetic analysis demonstrated the importance of including the low temperature chemistry of the benzylperoxy radicals to accurately capture the ignition propensity of o-xylene and 1,2,4-trimethylbenzene at low-to-intermediate temperatures and high pressures. The kinetic mechanism developed in the current study can be used for surrogate modeling of gasoline, jet and diesel fuels. (C) 2018 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
This study investigates the ability of Particulate Matter Index (PMI) to describe the sooting behavior of various gasoline formulations in a stratified-charge (SC) spark-ignition engine. Specifically, the engine was operated at 2000 rpm with an intake pressure of 130 kPa where soot formation is known to primarily occur in the bulk gases. Exhaust soot emissions were measured for nine test fuels at various exhaust gas recirculation levels. A comparison between measured soot levels and PMI shows that PMI is a relatively poor predictor of the sooting tendency of the tested fuels under lean SC combustion. Among the fuels, three fuels, namely the diisobutylene blend, High Olefin, and E30 fuels exhibit measured soot behavior opposite of that predicted by PMI. Optical diagnostics were utilized to further investigate the in-cylinder phenomena for these three fuels. Analysis of natural luminosity and diffused back-illumination extinction imaging suggests that fuel-induced differences in the amount of soot formed are responsible for a majority of the discrepancy in measured versus predicted sooting tendency. Fuel-induced differences in soot oxidation and spray development seem to play minor roles. Because the combustion and air-fuel mixing processes for lean SC combustion are different from conventional stoichiometric operation it is hypothesized that the PMI correlation needs to be modified to account for differences in stoichiometric air-fuel ratio and level of oxygenation between fuels. Furthermore, the role of fuel volatility in PMI possibly needs to be de-emphasized for SC operation with fuel injection into compression-heated gases.
Increasing standards for emissions and fuel economy have driven the need for downsizing of the internal combustion engines. To accommodate this change and prevent the possibility of knocking, fuels with higher octane numbers are needed. However, octane requirements are not uniform across the whole vehicle drive cycle, which leads to inefficient use of the high-octane fuel components. In approach that has been shown to substantially increase fuel economy, a dual-fuel solution, also called octane-on-demand, can be used and supply fuel with the required octane rating by metering in the appropriate ratio of high and low octane fuels, as dictated by the driving conditions. Barriers associated with introducing two fuels in the marketplace for an octane-on-demand approach can be mitigated by the use of an onboard separation system, which separates a single fuel, such as market E10 gasoline, into the high-octane oxygenate, like ethanol, and the a lower-octane base fuel. Currently investigated onboard separation systems rely on pervaporation membranes, which lose efficiency as the oxygenate is removed, and do not separate the entirety of it, leading to loses of this valuable component. Here, we present chemical separation strategies, such as liquid-solid and liquid-liquid extraction that provide advantages over membrane separation. This paper introduces applications of tailored chemical reactions, solid sorbent materials, and ionic liquids that are shown to have a high oxygenate recovery, and utility extended beyond ethanol to potential future oxygenate additives, such as isomers of butanol.