The knock-limited performance of several miscellaneous fuels blended with a base fuel I
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Herein, we demonstrate the production of liter quantities of drop-in diesel-range ethers from biomass-derived alcohols. We report scale-up resultsfor the dehydration of a mixture of C 4+ alcohols using powder and pellet zeolite Ycatalyst in continuous flow and batch reactors. The activity of zeolite Y decreaseswith the introduction of an alumina binder. Large alcohols, as well as branchedand secondary alcohols, increase the coke content over the pellet Y catalyst. Thepellet formulation had lower carbon balances and selectivity to C 10+ ethers,suggesting that the pellet formulation increases alcohol absorption and cokeproduction. Crushing the pellet Y catalyst to smaller particle sizes does notrecover the activity of zeolite Y in its powder form. Cold flow experiments showthat particle agglomeration contributes to pressure buildup in the continuous flowreactor. C 10+ ether blends can be produced in batch reactors at high alcohol conversion regimes. One liter of a diesel #2 blend wasproduced by scaling up this reaction. The final blend consists of a substantial portion of C 10+ ethers (63.7 wt %), followed by heavyunknown products (27.4 wt %). Furthermore, the final alcohol and butyl ether concentration values were 7.3 and 1.5 wt %, respectively. Theblendstock reported in this paper can satisfy diesel #2 ASTM standards for density, cloud point, flashpoint, and cetane number.
The transient processes involving lean blowout (LBO) in a RQL combustor such as the single cup combustor in the National Jet Fuels Combustion Program (NJFCP) referee rig are simulated with the reduced mechanisms based on Hybrid Chemistry for two different fuels, Cat-A2 and Cat-C1. Cat-A2 fuel is Jet-A with average or nominal properties based on a survey of the Petroleum Quality Information System database. The Cat-C1, an alternative jet fuel, is a GEVO alcohol-to-jet (ATJ) fuel composed almost entirely of two highly-branched C12 and C16 iso-paraffins. Experiments conducted in the NJFCP referee rig established a stable flame at an equivalence ratio of 0.096 (the near LBO condition) as the starting condition for LBO tests performed with all Category A and C fuels. Simulations of the approach to LBO verify that a stable flame is established at the near-LBO condition for each fuel before reducing fuel flow rate (and thus equivalence ratio) in a step-wise manner. At each new equivalence ratio, the global heat release rate and total fuel evaporation time histories are monitored to verify a new stable flame condition has been established before performing the next reduction in equivalence ratio until the flame is approaching the blowout. Main conclusions are threefold: (1) For Cat-C1 fuel the equivalence ratio for LBO is around 0.087. (2) For Cat-A2 fuel the equivalence ratio for LBO is either 0.082 or 0.078 depended on the time span of equivalence ratio of 0.085. (3) The averaged difference from LES on LBO for Cat-C1 relative to Cat-A2 is 8.75% versus 7.8% from the experimental data.
Oxygenated fuels, such as alcohols, ethers, and esters, are promising alternatives to conventional fuels. These fuels can help reduce detrimental emissions like carbon monoxide and unburned hydrocarbons and enhance octane ratings. Among these oxygenates, ethyl acetate (EA), a small alkyl ester sourced from biomass, emerges as a clean, promising energy carrier. It serves as a surrogate fuel to facilitate investigations into the combustion behaviours of biodiesel. Despite its importance, the literature knowledge of EA combustion characteristics is limited. Therefore, this study aims to broaden the knowledge of the combustion behaviour of this type of oxygenated fuel compound. In this study, we measured the laminar burning velocities of EA by employing a heat flux burner and a closed combustion vessel over the equivalence ratios of 0.7 – 1.7, pressures of 1 – 10 bar and temperatures ranging from 353 – 423 K. Further, we also measured the NOx emissions in exhaust gas of the premixed flames fueled by EA/air for the first time over the equivalence ratio of 0.8 – 1.2. Additionally, we employed a non-premixed counterflow flame setup for extensive characterisation of species and their concentration under diverse conditions encompassing various strain rates and oxygen concentrations. Finally, we utilized these newly measured data to construct and validate a detailed kinetic model developed as part of this work. The newly developed model will help characterize the combustion properties of EA.
Primary electrochemical power systems including gas recombination devices, sterilizable battery, fuel cells, alcohol-air units, etc
We report a polyvinyl alcohol anion exchange resin composite membrane, functionalized with Co and Cu ions, is reported for use in direct borohydride fuel cells (DBFCs). The CoCu-functionalized membrane has a 30.5% lower fuel permeability than that of a blank membrane. Meanwhile, the cell performance of the DBFC can also be improved by employing the CoCu-functionalized membrane, reaching a maximum power density of 304 mW·cm –2 at 60 °C. High-resolution fluorescence images directly demonstrate the formation of Cu/Co core–shell structure microparticles in the CoCu membrane, which not only reduces the Co content but also increases the active surface area of Co species in CoCu-functionalized membranes, resulting in the improvement of cell performance.
As early as 1937 German scientists at Peenemunde experimented with highly unstable fuel blends of nitrous oxide (N2O) and ethanol. These early tests mostly resulted in explosions and destroyed rocket engines. More recently several companies have developed experimental nitrous oxide fuel blends (NOFB) with Isp exceeding 300 sec. Although NOFBx has recently been cleared for tests on the International Space Station, this propellant remains highly experimental and has not been cleared for commercial transport by the US DOT. Recent work by Karabeyoglu et al. has raised concerns about the safety risks of mixing hydrocarbons with N2O. Liquid oxidizer/fuel blends are highly explosive and require extreme care in transport and servicing. By adding small amounts of a liquid organic fuel such as alcohol or a hydrocarbon, the odds of an explosive decomposition event are significantly increased.iv The proposed solution mitigates the explosion hazards of NOFB by separating the oxidizer from the hydrocarbon fuel formed as of a small cylindrical section of ABS thermoplastic. As N2O vapor flows across the grain segment, current enters a 1000 VDC high-tension lead in the ABS fuel grain and produces an inductive spark that vaporizes a small amount of the material. The ablated fuel vapor plus residual energy from the spark seed a localized exothermic N2O dissociation that produces sufficient heat to initiate combustion. The process is also effective when gaseous oxygen is used. A low TRL (2-3) prototype demonstrating the feasibility of controlled hydrocarbon-seeding was recently tested at Utah State University.v The unit features a miniature 2.5 cm ABS fuel grain fabricated using a Stratasys Dimension 3-D printer. The 9-N thruster was pulse-fired up to 27 consecutive times on a single ABS grain segment. Ignition was achieved by as little as 12-15 Joules energy input. This value is contrasted with the typical 30-minute pre-heat requirement for the ECAPS LMP-103S ADN-based monopropellant, requiring an energy input of 14,850 Joules for catalytic dissociation. The hydrocarbon-seeded micro-hybrid was also adapted as a non-pyrotechnic ignitor for a 900 N (200-lbf) thrust hybrid motor. The motor was successfully ignited 4 consecutive times with no hardware swaps or propellant additions. The amount of ABS seed material that can be fit into the injector cap is the only limit to the number of available repeat firings. This series of tests marks the first time a hybrid motor was ever ignited by other than a solid-propellant pyrotechnic charge or bi-propellant flame ignitor. Nitrous oxide hybrid motors are typically difficult to ignite and usually require multiple solid-propellant charges to initiate combustion, so this nonpyrotechnic ignition is a significant accomplishment. The controlled hydrocarbon-seeding approach is fundamentally different from all other green propellant solutions offered by the aerospace industry. Although the proposed system is more correctly a hybrid technology; the system retains all the simple features of a monopropellant design. To date no optimization study has been performed to identify the best grain geometry for electrostatic ignition. Fortunately, because the grain segments are fabricated using rapid-prototyping technology, changing the grain geometry is as simple as modifying the 3-D printer CAD-file. Vacuum Isp exceeding 270 seconds has been demonstrated (Ref v), a value significantly higher than those offered by competing green monopropellant options. The propellants of choice, N2O/GOX and ABS are 100% non-toxic, non-explosive, and environmentally benign. Because the inert oxidizer and fuel components are mixed only within the combustion chamber, the system retains the inherent safety of a hybrid rocket and can be piggy-backed as a secondary payload with no overall mission risk increase to the primary payload, an excellent characteristic for secondary launch systems.
Proton-exchange membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs) are promising power sources from portable electronic devices to vehicles. The high-cost issue of these low-temperature fuel cells can be primarily addressed by using platinum-group metal (PGM)-free oxygen reduction reaction (ORR) catalysts, in particular atomically dispersed metal–nitrogen–carbon (M–N–C, M = Fe, Co, Mn). Furthermore, a significant advantage of M–N–C catalysts is their superior methanol tolerance over Pt, which can mitigate the methanol cross-over effect and offer great potential of using a higher concentration of methanol in DMFCs. In this work, we investigated the ORR catalytic properties of M–N–C catalysts in methanol-containing acidic electrolytes via experiments and density functional theory (DFT) calculations. FeN 4 sites demonstrated the highest methanol tolerance ability when compared to metal-free pyridinic N, CoN 4 , and MnN 4 active sites. The methanol adsorption on MN 4 sites is even strengthened when electrode potentials are applied during the ORR. The negative influence of methanol adsorption becomes significant for methanol concentrations higher than 2.0 M. However, the methanol adsorption does not affect the 4e - ORR pathway or chemically destroy the FeN 4 sites. The understanding of the methanol-induced ORR activity loss guides the design of promising M–N–C cathode catalyst in DMFCs. Accordingly, we developed a dual-metal site Fe/Co–N–C catalyst through a combined chemical-doping and adsorption strategy. Instead of generating a possible synergistic effect, the introduced Co atoms in the first doping step act as “scissors” for Zn removal in metal–organic frameworks (MOFs), which is crucial for modifying the porosity of the catalyst and providing more defects for stabilizing the active FeN 4 sites generated in the second adsorption step. The Fe/Co–N–C catalyst significantly improved the ORR catalytic activity and delivered remarkably enhanced peak power densities (i.e., 502 and 135 mW cm -2 ) under H 2 –air and methanol–air conditions, respectively, representing the best performance for both types of fuel cells. Notably, the fundamental understanding of methanol tolerance, along with the encouraging DMFC performance, will open an avenue for the potential application of atomically dispersed M–N–C catalysts in other direct alcohol or ammonia fuel cells.
Nano-additive aggregation, limited performance, and unclear modification mechanisms are the main obstacles in developing nanocomposite anion exchange membranes (AEMs). In this work, for the first time, an effective and highly stable Poly(vinyl alcohol) (PVA)-based AEMs with dispersive Cu(OH)$_2$ nanoclusters (Cu-AEMs) are prepared by a simple and eco-friendly three-step method: ‘CuCl$_2$ doping-casting-KOH immersing’. The doped Cu$^{2+}$ ions chemically combine with OH- ions to form anionic conductive Cu(OH)2 nanoclusters intermediated by attaching resins. The PVA skeletons wrap around Cu(OH)$_2$ while the hydroxyl groups expose to bulk water, forming Cu(OH)$_2$-PVA complex, which avoids nano-additive aggregation, increases anionic channels, and strengthens additive-matrix connection. A direct borohydride fuel cell using Cu-AEM with 0.56 wt % CuCl$_2$ possess the highest power density of 403.3 mW cm$^{-2}$ at 60 °C and a life span of over 200 h. The high-performance and durability come from the unique structure of Cu(OH)$_2$ nanoclusters-PVA complex. ‘Vehicle’ theory is considered to be the dominant mechanism for enhancing such nanocomposite Cu-AEMs. This work demonstrates a new concept for preparing the stable AEMs toward high-performance fuel cells. The synthetic chemistry involved can be broadly extended for fabricating versatile AEMs.
We discuss how direct utilization of alcohols in Solid Oxide Fuel Cells (SOFCs) can improve the conversion efficiency by using excess heat for internal reforming and simplify the system balance of plant. Thanks to their scarce carbon- formation tendency, perovskite oxide anodes are promising alternatives to Ni-based cermets. Here we show that Sr(Ti 0.3 Fe 0.7 Ru 0.07 )O 3-δ (STF-Ru) exsolution anodes provide both catalytic reforming activity and electro- chemical activity with steam/ethanol (S/E) mixtures at 3:1 and 2:1 M ratio between 700 and 800 °C. Electrolyte- supported scandia stabilized zirconia SOFCs with STF-Ru anodes and Sr 0.95 Ti 0.3 Fe 0.7 O 3-δ (STF) cathodes are reasonably stable in the 3:1 S/E mixture over 20 h at 800 °C, with maximum power density of 195 mW/cm 2 and 140 mW/cm 2 at 0.7 V. Deactivation instead occurs with the 2:1 S/E mixture. Comparatively, cells with Ni-YSZ anodes rapidly coke and fail under the same conditions. Ethanol steam reforming experiments in a fixed bed powder reactor reveal that, above 650 °C, gas phase reactions convert ethanol to CO, hydrogen, acetaldehyde and ethylene, while STF-Ru catalyzes steam reforming. Thermogravimetric and Raman characterizations show that a moderate amount of carbon is deposited on the STF-Ru surface, which is more amorphous than the disruptive carbon which degrades Ni-YSZ.
Large scale implementation of high level computational theoretical chemical kinetics offers the prospect for dramatically improving the fidelity of combustion chemical modeling. To facilitate such efforts, we have developed a suite of codes, collectively referred to as AutoMech, that allow for the automatic prediction of the kinetics for large sets of reactions via ab initio transition-state-theory based master-equation calculations. The primary input is simply the mechanism, a dictionary relating chemically identifiable species descriptors (e.g., SMILES or InChIs) to species labels in the mechanism, and a specification of the electronic structure and transition state theory models to be implemented. Here we illustrate the current utility of AutoMech through a study of the initial stages of pyrolysis for 3 sets of fuels: sequences of alkanes, alcohols, and aldehydes. For simplicity, the analysis focuses on abstractions from the fuel by H, CH 3 , and OH, and the decomposition of the resulting radicals. Altogether, there are a total of 166 input channels in these sets (more than 363 forward reactions when expanded to the full set of elementary reactions). The code successfully produces high quality rate estimates (with apparent uncertainties less than a factor of two in limited comparisons with experiment) for > 95% of these. For the radical decomposition reactions, the analysis includes predictions for the pressure dependence of the kinetics. This wide-ranging exploration illustrates (i) the effect of different levels of prediction on the expected accuracy, (ii) the branching between abstractions at different sites for different abstractors, (iii) the dependence of the rates on the chemical structure, and (iv) the variation in radical stabilities across chemical families. These results, as well as the demonstrated feasibility of the methodology, should find further utility in the development of accurate rate expressions for arbitrary fuels. (c) 2020 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
High-pressure pumps and pulsation-damping devices not needed. Compressed gas provides pressure in liquid-supply system. Proposed to use system to inject alcohol in fuel-additive tests. Principal advantage of system is elimination of costs of high-pressure pumps and of accompanying costs of pulsation-damping devices.
The BETO-funded PNNL collaboration with LanzaTech, Inc. utilizes patented technology to address the need for low aromatic jet fuel blendstocks. The PNNL/LanzaTech alcohol-to-jet (ATJ) process converts ethanol from LanzaTech’s syngas fermentation process to jet-range isoparaffins. The aim of this Cooperative Research Development Agreement (CRADA) project was to improve the commercial viability of the LanzaTech/ PNNL ATJ process by developing two new co-product options. Two Focus Areas (FA) were explored: FA1) Increasing the RON of the lighter-than-jet gasoline fraction above 98; and FA2) Creating a synthetic lubricant base oil from the heavier-than-jet fraction. For FA 1, multiple processing approaches were evaluated, and RONs ranging from 96-100 were obtained, each comprising different processing costs. The most cost effective approach identified was a single-step process and yielded a liquid product of 97. Thus, additional development is required to obtain a RON > 98. We will continue work on this focus area with separate Direct Funding Opportunity (DFO) funding within the DOE-BETO Co-Optima Consortium (expected to begin Q2-FY21). Experimental work will focus on i) increasing single pass conversion to > 50%, and ii) obtaining a > 98 RON product. Technoeconomic analysis performed in this project suggests cost competitiveness provided these technical targets can be met. For FA2, multiple approaches were evaluated for increasing the viscosity index (VI) of the heavier-than-jet fraction to at least 120 in order to meet ASTM specifications for a Group III Base Oil (ASTM D6074). All other ASTM specifications are already met. A viscosity index of 115 was obtained, and with minimal undesirable cracking products. We believe a VI of 115 is about the highest possible from a catalytic approach, per review of the patent literature. In order to further increase the VI to > 120 we believe additives and/or liquid-liquid extraction is required. TEA performed earlier in the project suggests cost competitiveness with market prices assuming cracking byproducts are kept < 10 wt.%. If TEA updated with this additional processing still projects economic feasibility next steps could be taken in a subsequent effort.
An investigation was conducted to determine the effect of a coolant solution of 25 percent ethyl alcohol, 25 percent methyl alcohol, and 50 percent water by volume and maximum-economy spark advance on knock-limited performance and fuel economy of a large air-cooled cylinder. The knock-limited performance of the cylinder at engine speeds of 2100 and 2500 rpm was determined for coolant-fuel ratios of 0.0, 0.2, and 0.4. The effect of water-alcohol injection on fuel economy was determined in constant charge-air flow tests. The tests were conducted at a spark advance of 20 deg B.T.C. and maximum-economy spark advance.
We examine the properties of diesel boiling range ethers made from coupling of alcohols produced by oligomerization of ethanol (Guerbet alcohols) for their utility as low-carbon liquid fuel blendstocks. Basic properties of boiling point, flash point, freezing point, density and viscosity are well suited for blending into diesel fuels. For the mixture of ethers the lightest component, di-n-butyl ether, can be present at up to 20 vol% while still having adequately high flashpoint for safe handling. Soot formation tendency (as yield sooting index) is well below that of conventional diesel. The ethers have similar compatibility with elastomers as conventional diesel, based on Hansen solubility parameter analysis. Oxidation stability was assessed for 30 vol% blends of individual ethers in a conventional diesel fuel using a long-term storage test. Over 6 weeks we observed no formation of peroxides or degradation. n-alkyl ethers with carbon number of 8 or higher have cetane number over 100, which is outside the defined range of cetane number, while branched ethers are over 70. The ethers also blend antagonistically into conventional diesel for cetane number, meaning that the blend cetane value is lower than predicted based on a linear by volume, mass, or mole model. We show that aromatics and naphthenes likely act as radical scavengers to slow or shut down autoignition of the highly reactive ethers at low to medium blend levels. Overall, diesel boiling range ethers show significant promise as high quality low-net carbon diesel blendstocks.
Abstract Background Microalgae possess numerous advantages for use as a feedstock in producing renewable fuels and products, with techno-economic analysis (TEA) frequently used to highlight the economic potential and technical challenges of utilizing this biomass in a biorefinery context. However, many historical TEA studies have focused on the conversion of biomass with elevated levels of carbohydrates and lipids and lower levels of protein, incurring substantial burdens on the ability to achieve high cultivation productivity rates relative to nutrient-replete, high-protein biomass. Given a strong dependence of algal biomass production costs on cultivation productivity, further TEA assessment is needed to understand the economic potential for utilizing potentially lower-cost but lower-quality, high-protein microalgae for biorefinery conversion. Results In this work, we conduct rigorous TEA modeling to assess the economic viability of two conceptual technology pathways for processing proteinaceous algae into a suite of fuels and products. One approach, termed mild oxidative treatment and upgrading (MOTU), makes use of a series of thermo-catalytic operations to upgrade solubilized proteins and carbohydrates to hydrocarbon fuels, while another alternative focuses on the biological conversion of those substrates to oxygenated fuels in the form of mixed alcohols (MA). Both pathways rely on the production of polyurethanes from unsaturated fatty acids and valorization of unconverted solids for use as a material for synthesizing bioplastics. The assessment found similar, albeit slightly higher fuel yields and lower costs for the MA pathway, translating to a residual solids selling price of $899/ton for MA versus $1033/ton for MOTU as would be required to support a $2.50/gallon gasoline equivalent (GGE) fuel selling price. A variation of the MA pathway including subsequent upgrading of the mixed alcohols to hydrocarbon fuels (MAU) reflected a required solids selling price of $975/ton. Conclusion The slight advantages observed for the MA pathway are partially attributed to a boundary that stops at oxygenated fuels versus fungible drop-in hydrocarbon fuels through a more complex MOTU configuration, with more comparable results obtained for the MAU scenario. In either case, it was shown that an integrated algal biorefinery can be economical through optimal strategies to utilize and valorize all fractions of the biomass.
Stirling Technology Company (STC) developed the RG-350 convertor using components from separate Goddard Space Center and U.S. Army Natick SBIR contracts. Based on the RG-350, STC commercialized a product line of Stirling cycle generator sets, known as RemoteGen(TM), with power levels ranging from 10We to 3kWe. Under SBIR agreements with Glenn Research Center, the company refined and extended the capabilities of the RemoteGen convertors. They can provide power in remote locations by efficiently producing electricity from multiple-fuel sources, such as propane, alcohol, gasoline, diesel, coal, solar energy, or wood pellets. Utilizing any fuel source that can create heat, RemoteGen enables the choice of the most appropriate fuel source available. The engines operate without friction, wear, or maintenance. These abilities pave the way for self-powered appliances, such as refrigerators and furnaces. Numerous applications for RemoteGen include quiet, pollution-free generators for RVs and yachts, power for cell phone towers remote from the grid, and off-grid residential power variously using propane, ethanol, and solid biomass fuels. One utility and the National Renewable Energy Laboratory are evaluating a solar dish concentrator version with excellent potential for powering remote irrigation pumps.
The Flame Extinguishment (FLEX) experiment that is currently underway in the Combustion Integrated Rack facility onboard the International Space Station is aimed at understanding the effects of inert diluents on the flammability of condensed phase fuels. To this end, droplets of various fuels, including alkanes and alcohols, are burned in a quiescent microgravity environment with varying amounts of oxygen and inert diluents to determine the limiting oxygen index (LOI) for these fuels. In this study we report experimental observations of methanol droplets burning in oxygen-nitrogen-carbon dioxide and oxygen-nitrogen-helium gas mixtures at 0.7 and 1 atmospheric pressures. The initial droplet size varied between approximately 1.5 mm and 4 mm to capture both diffusive extinction brought about by insufficient residence time at the flame and radiative extinction caused by excessive heat loss from the flame zone. The ambient oxygen concentration varied from a high value of 30% by volume to as low as 12%, approaching the limiting oxygen index for the fuel. The inert dilution by carbon dioxide and helium varied over a range of 0% to 70% by volume. In these experiments, both freely floated and tethered droplets were ignited using symmetrically opposed hot-wire igniters and the burning histories were recorded onboard using digital cameras, downlinked later to the ground for analysis. The digital images yielded droplet and flame diameters as functions of time and subsequently droplet burning rate, flame standoff ratio, and initial and extinction droplet diameters. Simplified theoretical models correlate the measured burning rate constant and the flame standoff ratio reasonably well. An activation energy asymptotic theory accounting for time-dependent water dissolution or evaporation from the droplet is shown to predict the measured diffusive extinction conditions well. The experiments also show that the limiting oxygen index for methanol in these diluent gases is around 12% to 13% oxygen by volume.