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A series of multicyclic hydrocarbons were synthesized in high yield and under mild conditions from 2,5-hexanedione, cyclohexanone and cyclopentanone, on a scale of 200 g.
High-level coupled cluster theory, in conjunction with Active Thermochemical Tables (ATcT) and E,J-resolved master equation calculations, was used in a study of the title reactions, which play an important role in the combustion of hydrocarbons. In the set of radical/radical reactions leading to soot formation in flames, the addition of H-atoms to alkenes is likely a common reaction, triggering the isomerization of complex hydrocarbons to aromatics. The heats of formation of C 2 H 3 , C 2 H 4 , and C 2 H 5 are established to be 301.26 ± 0.30 at 0 K (297.22 ± 0.30 at 298 K), 60.89 ± 0.11 (52.38 ± 0.11), and 131.38 ± 0.22 (120.63 ± 0.22) kJ mol -1 , respectively. The calculated rate constants from first principles agree well with experiments where they are available. Under conditions typical of high temperature combustion – where experimental work is very challenging with a consequent dearth of accurate data –here we provide high-level theoretical results for kinetic modeling.
Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the interstellar medium and in meteorites such as Murchison and Allende and signify the missing link between resonantly stabilized free radicals and carbonaceous nanoparticles (soot particles, interstellar grains). However, the predicted lifetime of interstellar PAHs of some 108 years imply that PAHs should not exist in extraterrestrial environments suggesting that key mechanisms of their formation are elusive. Exploiting a microchemical reactor and coupling these data with computational fluid dynamics (CFD) simulations and kinetic modeling, we reveal through an isomer selective product detection that the reaction of the resonantly stabilized benzyl (C 7 H 7 ) and the propargyl (C 3 H 3 ) synthesizes the simplest representative of PAHs – the 10π Hückel aromatic naphthalene (C 10 H 8 ) molecule – via the novel Propargyl Addition–BenzAnnulation (PABA) mechanism. The gas-phase preparation of naphthalene affords a versatile concept of the reaction of combustion and astronomically abundant propargyl radicals with aromatic radicals carrying the radical center at the methylene moiety (aromatic-CH 2 ) as a previously passed over source of aromatics in high temperature environments thus bringing us closer to an understanding of the aromatic universe we live in.
The biphenyl molecule (C 12 H 10 ) acts as a fundamental molecular backbone in the stereoselective synthesis of organic materials due to its inherent twist angle causing atropisomerism in substituted derivatives and in molecular mass growth processes in circumstellar environments and combustion systems. Here, we reveal an unconventional low-temperature phenylethynyl addition–cyclization–aromatization mechanism for the gas-phase preparation of biphenyl (C 12 H 10 ) along with ortho-, meta-, and para-substituted methylbiphenyl (C 13 H 12 ) derivatives through crossed molecular beams and computational studies providing compelling evidence on their formation via bimolecular gas-phase reactions of phenylethynyl radicals (C 6 H 5 CC, X 2 A 1 ) with 1,3-butadiene-d 6 (C 4 D 6 ), isoprene (CH 2 C(CH 3 )CHCH 2 ), and 1,3-pentadiene (CH 2 CHCHCHCH 3 ). The dynamics involve de-facto barrierless phenylethynyl radical additions via submerged barriers followed by facile cyclization and hydrogen shift prior to hydrogen atom emission and aromatization to racemic mixtures (ortho, meta) of biphenyls in overall exoergic reactions. Furthermore, these findings not only challenge our current perception of biphenyls as high temperature markers in combustion systems and astrophysical environments, but also identify biphenyls as fundamental building blocks of complex polycyclic aromatic hydrocarbons (PAHs) such as coronene (C 24 H 12 ) eventually leading to carbonaceous nanoparticles (soot, grains) in combustion systems and in deep space thus affording critical insight into the low-temperature hydrocarbon chemistry in our universe.
Sustainable aviation fuel (SAF) produced from lignocellulosic biomass is emerging as an ideal alternative to conventional jet fuel for aviation sector decarbonization. Catalytic fast pyrolysis (CFP) can convert lignocellulosic biomass into relatively stable bio-oil that can be selectively transformed to various transportation fuels through hydroprocessing under conditions of different severities. In this contribution, two CFP oils produced from pine-based feedstocks over different types of catalysts (i.e., ZSM-5 and Pt/TiO 2 catalysts) were hydrotreated at 125 bar in a non-isothermal process with a maximum temperature of 385 °C over a sulfided NiMo/Al 2 O 3 catalyst to produce SAF with high cycloalkane concentrations of 89–92 wt%. Cycloalkanes are an important component of jet fuel with advantageous fuel properties, such as high energy density, low sooting, and potential for replacing aromatic hydrocarbons to provide good seal swelling properties. The hydrotreating process successfully converted 91–92% of the biogenic carbon in the CFP oil intermediates to liquid-phase hydrotreated products. Through distillation, 39–40 wt% of the hydrotreated oils were collected in the jet-fuel range as SAF fractions. The rest of the hydrotreated product could be valorized as fuels (e.g., diesel) or chemicals. The SAF fractions with oxygen contents below the detection limit (<0.01 wt%) met ASTM D7566 finished fuel blend and D4054 Tier 1 specifications with respect to density, lower heating value (LHV), volatility, flash point, and freeze point. These results indicate hydrotreating lignocellulosic biomass-derived CFP oil as a promising pathway to produce high-quality SAF rich in cycloalkanes. Continued research is required to increase the SAF yield by process improvements, such as increased CFP oil yields, and an enhanced production of SAF-range molecules via e.g., cracking of high-molecular weight compounds either during CFP or hydrotreating, as well as evaluation of a broader range of jet fuel properties and performance requirements.
This study aims to investigate a laser ultrasound (LUS) transducer for high-temperature (>100 °C) applications. For decades, many researchers have investigated efficient LUS transducers, yet studies on laser ultrasound transducers capable of performing at the high-temperature condition are rarely found in the literature. Most current LUS transducers still utilize a polymer-based composite material, that is, not stable at varying temperature conditions. This study introduces a liquid metallic (LM) LUS transducer that utilizes field's metal, which has a high thermal expansion (~3 × 10 -4 K -1 ). We hypothesized that such a high thermal expansion of the liquid metal can effectively produce laser-generated ultrasound waves, substituting for conventional polymer-based transducers. A numerical simulation predicted that the LM LUS transducer would produce higher LUS intensity (~22 dB) than that without the LUS transducer. Experiment results confirmed that the LM transducer effectively intensifies the ultrasound wave signals, obtaining a signal-to-noise gain over 30 dB. Moreover, the transducer was found capable of transmitting detectable wave packets in relatively high-temperature conditions (~400 °C), while conventional candle soot nanoparticle-polydimethylsiloxane could not perform stably at these elevated temperatures. The investigations introduced in this article are scientifically significant since we demonstrated the engineering feasibility of liquid metallic materials for LUS transducers.
The role to which a realistic inflow turbulent boundary layer (TBL) influences transient and mean large-scale pool fire quantities of interest (QoIs) is numerically investigated. High-fidelity, low-Mach large-eddy simulations that activate low-dissipation, unstructured numerics are conducted using an unsteady flamelet combustion modeling approach with mutiphysics coupling to soot and participating media radiation transport. Three inlet profile configurations are exercised for a large-scale, high-aspect rectangular pool that is oriented perpendicular to the flow direction: a time-varying, TBL inflow profile obtained from a periodic precursor simulation, the time-mean of the transient TBL, and a steady power-law inflow profile that replicates the mean TBL crosswind velocity of 10.0 m/s at a vertical height of 10 m. Results include both qualitative transient flame evolution and quantitative flame shape with ground-level temperature and convective/radiative heat flux profiles. While transient fire events, which are driven by burst-sweep TBL coupling, such as blow-off and reattachment are vastly different in the TBL case (contributing to increased root mean square QoI fluctuation prediction and disparate flame lengths), mean surface QoI magnitudes are similar. Quadrant analysis demonstrates that the TBL configuration modifies burst-sweep phenomena at windward pool locations, while leeward recovery is found. In conclusion, positive fluctuations of convective heat flux correlate with fast moving fluid away from the pool surface due to intermittent combustion events.
A limited nuclear war between India and Pakistan could ignite fires large enough to emit more than 5 Tg of soot into the stratosphere. Climate model simulations have shown severe resulting climate perturbations with declines in global mean temperature by 1.8 °C and precipitation by 8%, for at least 5 y. Here we evaluate impacts for the global food system. Six harmonized state-of-the-art crop models show that global caloric production from maize, wheat, rice, and soybean falls by 13 (±1)%, 11 (±8)%, 3 (±5)%, and 17 (±2)% over 5 y. Total single-year losses of 12 (±4)% quadruple the largest observed historical anomaly and exceed impacts caused by historic droughts and volcanic eruptions. Colder temperatures drive losses more than changes in precipitation and solar radiation, leading to strongest impacts in temperate regions poleward of 30°N, including the United States, Europe, and China for 10 to 15 y. Integrated food trade network analyses show that domestic reserves and global trade can largely buffer the production anomaly in the first year. Persistent multiyear losses, however, would constrain domestic food availability and propagate to the Global South, especially to food-insecure countries. By year 5, maize and wheat availability would decrease by 13% globally and by more than 20% in 71 countries with a cumulative population of 1.3 billion people. In view of increasing instability in South Asia, this study shows that a regional conflict using <1% of the worldwide nuclear arsenal could have adverse consequences for global food security unmatched in modern history.
Airborne contaminants from fires containing nuclear waste represent significant health hazards and shape the design and operation of nuclear facilities. Much of the data used to formulate DOE-HDBK-3010-94, “Airborne Release Fractions/Rates and Respirable Fractions for Nonreactor Nuclear Facilities,” from the U.S. Department of Energy, were taken over 40 years ago. The objectives of this study were to reproduce experiments from Pacific Northwest Laboratories conducted in June 1973 employing current aerosol measurement methods and instrumentation, develop an enhanced understanding of particulate formation and transport from fires containing nuclear waste, and provide modeling and experimental capabilities for updating current standards and practices in nuclear facilities. A special chamber was designed to conduct small fires containing 25 mL of flammable waste containing lutetium nitrate, ytterbium nitrate, or depleted uranium nitrate. Carbon soot aerosols showed aggregates of primary particles ranging from 20 to 60 nm in diameter. In scanning electron microscopy, ~200-nm spheroidal particles were also observed dispersed among the fractal aggregates. The 200-nm spherical particles were composed of metal phosphates. Airborne release fractions (ARFs) were characterized by leaching filter deposits and quantifying metal concentrations with mass spectrometry. The average mass-based ARF for 238 U experiments was 1.0 × 10 -3 with a standard deviation of 7.5 × 10 -4 . For the original experiments, DOE-HDBK-3010-94 states, “Uranium ARFs range from 2 × 10 -4 to 3 × 10 -3 , an uncertainty of approximately an order of magnitude.” Therefore, current measurements were consistent with DOE-HDBK-3010-94 values. ARF values for lutetium and ytterbium were approximately one to two orders of magnitude lower than 238 U. Furthermore, metal nitrate solubility may have varied with elemental composition and temperature, thereby affecting ARF values for uranium surrogates (Yb and Lu). In addition to ARF data, solution boiling temperatures and evaporation rates can also be deduced from experimental data.
Black carbon (BC)–a strong indicator of diesel particulate matter and other sources of incomplete carbonaceous fuel combustion–is an important air pollutant that affects public health, yet low-cost sensors capable of long-term, autonomous BC monitoring remain underdeveloped. We report on the development and evaluation of a novel BC prototype sensor that integrates soot collection on a quartz filter, in-situ optical transmission measurement, and thermal filter regeneration. To enable regeneration at lower temperatures, we evaluated the catalytic effects of various alkali metal salts pre-applied to the filter. Among these, cesium carbonate (Cs 2 CO 3 ) exhibited the strongest catalytic activity, lowering the temperature required for complete BC removal by up to 190 °C and reducing energy consumption by more than 75% compared to that required for untreated filters. The catalytic effect persisted through 10 BC collection–regeneration cycles. These findings demonstrate the potential of catalytically aided thermal regeneration in BC sensors and suggest a pathway toward energy-efficient and reduced maintenance air quality monitoring suitable for distributed BC monitoring networks.
Abstract The influence of fuel properties on particulate matter (PM) emissions from a catalytic gasoline particulate filter (GPF) equipped gasoline direct injection (GDI) engine was investigated using novel “virtual drivetrain” software and an engine mated to an engine dynamometer. The virtual drivetrain software was developed in labview to operate the engine on an engine dynamometer as if it were in a vehicle undergoing a driving cycle. The software uses a physics-based approach to determine vehicle acceleration and speed based on engine load and a programed “shift” schedule to control engine speed. The software uses a control algorithm to modulate engine load and braking to match a calculated vehicle speed with the prescribed speed trace of the driving cycle of choice. The first 200 s of the World-harmonized Light-duty Test Procedure (WLTP) driving cycle was tested using six different fuel formulations of varying volatility, aromaticity, and ethanol concentration. The first 200 s of the WLTP was chosen as the test condition because it is the most problematic section of the driving cycle for controlling PM emissions due to the cold start and cold drive off. It was found that there was a strong correlation between aromaticity of the fuel and the engine-out PM emissions, with the highest emitting fuel producing more than double the mass emissions of the low PM production fuel. However, the post-GPF PM emissions depended greatly on the soot loading state of the GPF. The fuel with the highest engine-out PM emissions produced comparable post-GPF emissions to the lowest PM producing fuel over the driving cycle when the GPF was loaded over three cycles with the respective fuels. These results demonstrate the importance of GPF loading state when aftertreatment systems are used for PM reduction. It also shows that GPF control may be more important than fuel properties, and that regulatory compliance for PM can be achieved with proper GPF control calibration irrespective of fuel type.
Partial fuel stratification (PFS) is a promising fuel injection strategy to improve the stability of lean combustion by applying a small amount of pilot injection right before spark timing. Mixed-mode combustion, which makes use of end-gas autoignition following conventional deflagration-based combustion, can be further utilized to speed up the overall combustion. In this study, PFS-assisted mixed-mode combustion in a lean-burn direct injection spark-ignition (DISI) engine is numerically investigated using multi-cycle large eddy simulation (LES). A previously developed hybrid G-equation/well-stirred reactor combustion model for the well-mixed operation is extended to the PFS-assisted operation. The experimental spray morphology is employed to derive spray model parameters for the pilot injection. The LES-based model is validated against experimental data and is further compared with the Reynolds-averaged Navier–Stokes (RANS)-based model. Overall, both RANS and LES predict the mean pressure and heat release rate traces well, while LES outperforms RANS in capturing the cycle-to-cycle variation (CCV) and the combustion phasing in the mass burned space. Liquid and vapor penetrations obtained from the simulations agree reasonably well with the experiment. Detailed flame structures predicted from the simulations reveal the transition from a sooting diffusion flame to a lean premixed flame, which is consistent with experimental findings. LES captures more wrinkled and stretched flames than RANS. Finally, the LES model is employed to investigate the impacts of fuel properties, including heat of vaporization (HoV) and laminar burning speed (SL). Combustion phasing is found more sensitive to SL than to HoV, with a larger fuel property sensitivity of the heat release rate from autoignition than that from deflagration. Moreover, the combustion phasing in the PFS-assisted operation is shown to be less sensitive to SL compared with the well-mixed operation.
In this work, medium scale (30 cm diameter) methanol pool fires were simulated using the latest fire modeling suite implemented in Sierra/Fuego, a low Mach number multiphysics reacting flow code. The sensitivity of model outputs to various model parameters was studied with the objective of providing model validation. This work also assesses model performance relative to other recently published large eddy simulations (LES) of the same validation case. Two pool surface boundary conditions were simulated. The first was a prescribed fuel mass flux and the second used an algorithm to predict mass flux based on a mass and energy balance at the fuel surface. Gray gas radiation model parameters (absorption coefficients and gas radiation sources) were varied to assess radiant heat losses to the surroundings and pool surface. The radiation model was calibrated by comparing the simulated radiant fraction of the plume to experimental data. The effects of mesh resolution were also quantified starting with a grid resolution representative of engineering type fire calculations and then uniformly refining that mesh in the plume region. Simulation data were compared to experimental data collected at the University of Waterloo and the National Institute of Standards and Technology (NIST). Validation data included plume temperature, radial and axial velocities, velocity temperature turbulent correlations, velocity velocity turbulent correlations, radiant and convective heat fluxes to the pool surface, and plume radiant fraction. Additional analyses were performed in the pool boundary layer to assess simulated flame anchoring and the effect on convective heat fluxes. This work assesses the capability of the latest Fuego physics and chemistry model suite and provides additional insight into pool fire modeling for nonluminous, non-sooting flames.
Diesel engines are extensively used in heavy-duty transportation, power generation, and marine vehicles due to their superior thermal efficiency and extended high-load operability compared to spark ignition (SI) engines. However, combustion in diesel engines is generally characterized by locally rich fuel–air mixtures and high combustion temperatures, causing significant amounts of soot and NO x emissions from these engines. Utilizing carbon-free alternative fuels and enhancing fuel efficiency represent promising strategies to mitigate greenhouse gas (GHG) and other emissions in the heavy-duty transportation sector. In this context, ammonia (NH 3 ), as a hydrogen carrier, has received significant attention as a viable substitute for hydrocarbon fuels due to its carbon-free composition, relatively high energy density, and well-established infrastructure. Many previous studies have considered combustion and emission characteristics of ammonia-hydrocarbon fuel blends in engines and simplified flames. But, detailed investigations on the effects of ammonia on the performance of hydrocarbon fuels under engine conditions are lacking. In the present study, we perform large eddy simulations (LES) of the ignition and flame processes in a constant-volume combustion reactor, where n-heptane is injected in an ammonia/air ambient mixture in a diesel-like environment. A detailed and validated reaction mechanism containing 302 species and 1981 reactions is employed. The Engine Combustion Network Spray H experimental data is used to validate the spray model under both non-reacting and reacting conditions. Dual-fuel combustion is simulated using the well-stirred reactor (WSR) approach. Results are presented for two spray cases: (1) single fuel (SF) with n-heptane injected into a mixture of air and combustion products and (2) dual-fuel (DF) with the injection of n-heptane in a mixture of air, ammonia, and combustion products. It is observed that the presence of ammonia has a significant effect on the ignition and flame development processes. With ammonia addition, both the first- and second-stage ignition delay times increase, but the effect of ammonia on the second-stage ignition is significantly more prominent. In addition, the ignition kernel size and growth rate decrease noticeably. For SF spray, the main ignition is characterized by multiple ignition kernels near the spray tip, whereas for DF spray, a single relatively small ignition kernel forms and grows slowly in the downstream direction. The flame development and the final quasi-steady flame structure are also modified due to ammonia. Here, the outcome of this research would enable a better understanding of ammonia–diesel dual-fuel spray flame behavior and guide the development of associated engine combustion strategies.
In response to stringent emissions regulations and the need for higher efficiency engines, the utilization of DME and propane fuel blends in compression ignition (CI) engines has gained interest in the automotive industry. In this study, a range of DME-propane blends are explored in a CI combustion strategy at high injection pressures. A GT-Power model of a 2.2 L Hyundai CI engine was developed to facilitate evaluation of the impacts of variations of DME and propane blends at a light and medium engine speed-torque-load operating condition; specifically at 1500 rpm, 50 Nm and 2.84 bar brake mean effective pressure (BMEP); and 2000 rpm, 150 Nm, 8.53 bar BMEP speed-torque-load combination. Here, the GT-Power model was validated using Computational Fluid Dynamics (CFD) simulations. The results indicate that high diesel-like efficiencies can be achieved with a 100% DME mass substitution and up to 50% propane-DME blends could be implemented without a significant penalty on engine performance indicators. Significant brake specific nitrogen oxides (BSNOx) reductions were also observed along with reductions in carbon dioxide (CO2) and soot when leveraging these fuel blends.
In support of the Daimler SuperTruck I team’s 55% brake thermal efficiency (BTE) pathway goal, researchers at Oak Ridge National Laboratory performed an experimental investigation of the potential efficiency and emissions benefits of dual-fuel advanced combustion approaches on a modified heavy-duty 15-L Detroit™ DD15 engine. For this work, a natural gas port fuel injection system with an independent injection control for each cylinder was added to the DD15 engine. For the dual-fuel strategies investigated, 65%–90% of the total fuel energy was supplied through the added port fuel injection natural gas (NG) fueling system. The remaining fuel energy was supplied by one or more direct injections of diesel fuel using the production high pressure diesel fueling system. The production DD15 air handling system and combustion geometry were unmodified for this study. Efficiency and emissions with dual-fuel strategies including both low temperature combustion (LTC) and non-LTC approaches such as dual fuel direct-injection were investigated along with control authority over combustion phasing. Parametric studies of dual-fuel NG/diesel advanced combustion were conducted in order to experimentally investigate the potential of high-efficiency, dual-fuel combustion strategies to improve BTE in a multi-cylinder engine, understand the potential reductions in engine-out emissions, and characterize the range of combustion phasing controllability. Characterization of mode transitions from mixing-controlled diesel pilot ignition to kinetically controlled ignition is presented. Key findings from this study included a reproducible demonstration of BTE approaching 48% at up to a 13-bar brake mean effective pressure with significant reductions in engine-out NOx and soot emissions. Additional results from investigating load transients in dual-fuel mode and initial characterization of particle size distribution during dual-fuel operation are presented.
Internal combustion engine (ICE) downsizing through various turbocharging configurations is generally known by the powertrain design community as an effective means to reduce frictional losses, increase waste heat recovery, and improve fuel efficiency while increasing engine power density. However, often is the case that turbocharging strategies, including variable geometry turbochargers, and regulated two-stage turbochargers, incur the performance tradeoff between transient response and fuel economy (pumping losses) at high engine speeds. For off-highway vehicles having particularly transient and high-powered duty cycles, efforts to improve this tradeoff and increase operational flexibility have turned to evaluating various electrified air system architectures. In this study, a 4.5 L diesel-ICE configured with an electrically driven compressor (eBooster ® ) is placed in series with a conventional turbocharger and integrated into a 48 V mild-hybrid powertrain architecture. The objective of this powertrain configuration is to enable engine downsizing by 34%, replacing the current 6.8 L ICE platform with the hybridized 4.5 L ICE concept. The commercial 1-D simulation software GT-SUITE is used for powertrain system development and system optimization. Development and validation of the GT-SUITE model and air system controls is concurrently supported through experimental data collection. The simulation model development includes using machine learning methods for optimizing exhaust gas dilution, injection timing, and eBooster ® power to improve steady-state and transient brake-specific fuel consumption while minimizing criteria pollutant emissions. It was found that total specific fluid consumption over the standardized non-road transient engine duty cycle could be reduced by 18% over the current 6.8 L engine by using an optimized eBoosted 4.5 L engine. The hybridized 4.5 L engine concept concurrently showed sufficient transient response capability and nearly an order of magnitude reduction in duty cycle total soot production.
Several ducted fuel injection (DFI) studies have highlighted the importance of accuracy in aligning the duct axis with that of its corresponding spray for optimal effectiveness, as misalignment adversely impacts the method’s performance. The need for accurate alignment could lead to added manufacturing complexity via tighter tolerances. This study systematically explores cases of horizontal, vertical, and rotational misalignment, analyzing their respective effects on DFI performance. Vertical and horizontal misalignments at the duct inlet plane were varied at magnitudes of 6.25%, 12.5%, and 25.0% of the duct diameter, corresponding to 0.125, 0.25, and 0.5 mm, respectively. Rotational misalignments were set at 1°, 2°, and 4°, corresponding to 3.65%, 7.30%, and 14.6%, respectively, of the duct diameter at its inlet plane. The investigation yields spray-duct alignment tolerance limits and highlights the influence of misalignment direction on emissions due to the interactions with swirl and squish inside the combustion chamber. The results indicate that the tolerance limits for the alignment are within 4° and 0.5 mm relative to the geometrically aligned position. If the misalignment exceeds 4°of rotation or 0.5 mm in the horizontal direction, the beneficial effects on soot reduction using this method are no longer observed. The findings contribute to an understanding that can be used to optimize DFI for cleaner and more efficient combustion in compression-ignition engines.