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Phosphorus speciation analysis of fatty-acid-based feedstocks and fast pyrolysis biocrudes via gel permeation chromatography inductively coupled plasma high-resolution mass spectrometry

Renewable feedstocks, such as lignocelulosic fast pyrolysis oils and both vegetable oil and animal fats, are becoming a viable alternative to petroleum for producing high-quality renewable transportation fuels. However, the presence of phosphorus-containing compounds, mainly from phospholipids, in these renewable feedstocks is known to poison and deactivate hydrotreating catalysts during fuel production. In this work, gel permeation chromatography (GPC) combined with inductively coupled plasma high-resolution mass spectrometry (ICP-HRMS) was used to analyze feedstocks including unprocessed soybean oil, animal fat, and pyrolysis oils from red oak and milorganite to identify phosphorus species. The results have shown the presence of a wide range of different phosphorous compounds among all the samples analysed in this work. The GPC-ICP-HRMS analyses of a vegetable oil and two animal fats have shown different fingerprints based on the molecular weight of each of the samples, highlighting the structural differences among their corresponding phosphorus-containing compounds. While the presence of low-molecular-weight species, such as phospholipids, was expected, several high-molecular-weight species (MW > 10 000 Da) have been found, suggesting that high-molecular-weight micelles or liposomes might have been formed due to the high concentration of phospholipids in these samples. Results obtained through the hydroxylation of a mix of phospholipids (asolectin) and its posterior GPC-ICP-HRMS agree with this hypothesis. With respect to the lignocellulosic catalytic fast pyrolysis oil samples, the GPC-ICP-HRMS results obtained suggest that either aggregation or polymerization reactions might have occurred during the pyrolysis process, yielding phosphorus-containing compounds with an approximate molecular weight above 91 000 kDa. In addition, an aggregation phenomenom has been observed for those phosphorus species present within the fast pyrolysis oils after being stored for 3 months, especially for those pyrolysis oils contaning pre-processed feedstocks, such as milorganite.

09 BIOMASS FUELS↗

Aliphatic Amines from Waste Polyolefins by Tandem Pyrolysis, Hydroformylation, and Reductive Amination

Pyrolysis of waste plastics can produce a product mixture with a high concentration of olefins (>50 wt%). The olefins, as building blocks in the petroleum industry, are potential precursors for valuable commodity chemicals with higher values (>$2000 per ton). In this work, we produce aldehydes by hydroformylation of the olefins present in pyrolysis oil from colored post-consumer recycled high-density polyethylene (PCR-HDPE). The obtained aldehydes in the oil are then converted into aliphatic amines via reductive amination with a Ru/C catalyst. The aminated oil was characterized by multiple analytical chemistry techniques including elemental analysis, nuclear magnetic resonance spectroscopy, high-resolution liquid chromatography-mass spectrometry, and gas chromatography-mass spectrometry with a Polyarc flame ionization detector. The concentration of metals in the PCR-HDPE and oil changes during the tandem processes, showing limited effects of these elements (e.g., Al, Ca, Fe, Mg, Ti, Zn) on hydroformylation and reductive amination. Additionally, we demonstrated that reductive amination of aldehydes with varied carbon numbers and branching properties can be achieved in the presence of a complex mixture, including paraffins and aromatics. The results indicate that waste plastics have the potential to serve as a renewable source for mono and di aliphatic amines, thereby diminishing reliance on fossil feedstocks as the current primary amine source.

aliphatic amines↗

Paying it Forward: How an Emerging Unconventional Play can Hit the Ground Running

While every tight oil play is unique, there are lessons that can be transferred from one play to another to improve the efficiency and pace of production operations and development. These improvements may not fit precisely in every basin or play but generally hold to themes that can be tested against and built upon. Themes such as the quantity of proppant, longer lateral length, or the number of stages can be directly tied to increased productivity. However, there are diminishing returns on these investment activities for which each operator, within a given play, will be required to identify and mitigate against. This is especially true as the industry steps in and begins developing new tight oil plays. In their nascent stages, these plays may have limited well penetrations and, as a result, limited geological and performance data from which to extrapolate. Pulling together an understanding of where the industry currently resides in terms of how to exploit these resources can provide a boost in terms of working towards greatly improved well completions. In 2019, the US EIA estimated that nearly 8 million barrels of oil per day were produced from tight oil reservoirs in the United States (US EIA, 2020). This represents over 60% of the domestic crude production, originating from multiple reservoirs in the Permian Basin (TX) as well as the Bakken (MT, ND), Eagle Ford (TX), Niobrara (CO, WY), and Anadarko Basin (OK) formations, among others. As such, there are 1,000s of wells across these numerous tight oil plays that can relate an informative story. To build this story, the interplay of geology, well spacing, lateral length, and stimulation, all critical to economic success, will be explored. This paper proposes to look back at these mature tight oil (and gas) basins and bring forth an understanding of what lessons can be applied to the emerging Powder River Basin tight oil reservoirs (Mowry and the Turner/Frontier). The authors will delve into the four broad topics of geology, well spacing, lateral length, and stimulation, highlighting case studies to demonstrate those lessons from established tight oil plays that will underpin planned activities at a Field Laboratory Test Site in the southern Powder River Basin.

02 PETROLEUM↗

Experimental Study of Microgel Conformance-Control Treatment for a Polymer-Flooding Reservoir Containing Superpermeable Channels

Summary Polymer flooding has been widely used to improve oil recovery. However, its effectiveness would be diminished when channels (e.g., fractures, fracture-like channels, void-space conduits) are present in a reservoir. In this study, we designed a series of particular sandwich-like channel models and tested the effectiveness and applicable conditions of micrometer-sized preformed particle gels (PPGs, or microgels) in improving the polymer-flooding efficiency. We studied the selective penetration and placement of the microgel particles, and their abilities for fluid diversion and oil-recovery improvement. The results suggest that polymer flooding alone would be inefficient to achieve a satisfactory oil recovery as the heterogeneity of the reservoir becomes more serious (e.g., permeability contrast kc/km > 50). The polymer solution would vainly flow through the channels and leave the majority of oil in the matrices behind. Additional conformance-treatment efforts are required. We tried to inject microgels in an attempt to shut off the channels. After the microgel treatment, impressive improvement of the polymer-flooding performance was observed in some of our experiments. The water cut could be reduced significantly by as high as nearly 40%, and the sweep efficiency and overall oil recovery of the polymer flood were improved. The conditions under which the microgel-treatment strategy was effective were further explored. We observed that the microgels form an external impermeable cake at the very beginning of microgel injection and prevent the gel particles from entering the matrices. Instead, the microgel particles could selectively penetrate and shut off the superpermeable channels under proper conditions. Our results suggest that the 260-µm microgel particles tested in this study are effective to attack the excessive-water-production problem and improve the oil recovery when the channel has a high permeability (>50 darcies). The gels are unlikely to be effective for channels that are less than 30 darcies because of the penetration/transport difficulties. After the gels effectively penetrate and shut off the superpermeable channel, the subsequent polymer solution is diverted to the matrices (i.e., the unswept oil zones) to displace the bypassed oil. Overall, this study provides important insights to help achieve successful polymer-flooding applications in reservoirs with superpermeable channels.

Engineering↗

Development of Algal Biomass Yield Improvements in an Integrated Process (Final Report)

This project built on the success of Global Algae Innovations Algae Biomass Yield Phase 1 project to accelerate the commercialization of algal biofuels through development of an integrated, economical, photosynthetic, open raceway system to produce algal oil. Two parallel pathways to a biofuel were investigated. In the algal crude oil pathway, highlighted in blue, the dewatered algal biomass slurry is used as a feed to hydrothermal liquefaction to produce an algae crude oil and recycle aqueous stream. In the algal lipid oil pathway, highlighted in green, the algal biomass slurry is dried, and the oil is extracted to produce an algal lipid oil biofuel intermediate and a high protein algae meal co-product. Upgrading to drop-in fuels has been demonstrated for the biofuel intermediates in both pathways. Since the algal lipid oil pathway requires lipid accumulation, the productivity is generally lower than the algal crude oil pathway, but the required productivity for economical algal biofuel production is also lower because the coproduct value is greater. The outdoor cultivation was performed at the Kauai Algae Farm. The project team has expertise across the full breadth strain development, advanced algal cultivation, open raceway contamination control, CO 2 supply, harvesting, dewatering, extraction, hydrothermal liquefaction, technoeconomic analysis and life cycle analysis: Hildebrand laboratory at Scripps Institution of Oceanography – diatom strain development. Mayfield laboratory at UCSD - green algae strain development. TSD Management Associates- CO 2 supply, algal harvesting and dewatering, and algal drying and extraction. Qualitas - large-scale test site for algal harvesting technology. Texas A&M University - algal drying and extraction technology. Pacific Northwest National Laboratory - hydrothermal liquefaction technology. GE Water and Power - membrane technology. National Renewable Energy Laboratory - algal techno-economic analysis. Phase 1 of the project resulted in tremendous productivity and pre-processing improvements in an integrated, large-scale, low-cost cultivation and pre-processing process that moved algal technology closer to economic viability for biofuels than ever before. Phase 2 accomplishments further facilitate development of a commercial algal biofuel industry by adding: several top performing strains and strain development tools including breeding; open-pond cultivation innovations that achieved a 30% improvement in overall productivity, an 83% reduction in cost, and a 95% reduction in energy use relative to conventional technology; further improvements in harvesting that led to the Zobi harvester ® as a universal, economical, low energy, commercially available microalgae harvesting solution; breakthroughs in drying and extraction including a new low energy drying process and several new low energy extraction unit operations that together with the Zobi harvester ® achieve a 90% reduction in cost and 97% reduction in energy use relative to conventional technology. These improvements are sufficient to enable economical production of algae biofuel and protein meal co-product if the process were scaled up to a commercial-scale 5,000-acre algae farm.

09 BIOMASS FUELS↗

Can a Nuclear-Assisted Biofuels System Enable Liquid Biofuels as the Economic Low-carbon Replacement for All Liquid Fossil Fuels and Hydrocarbon Feedstocks and Enable Negative Carbon Emissions?

This report integrates the results of a series of studies and workshops to address the question: Can a nuclear-assisted biofuels system enable liquid biofuels as the economic low-carbon replacement for all liquid fossil fuels and hydrocarbon feedstocks and simultaneously enable negative carbon emissions? “Economic” is defined as economically competitive relative to other low-carbon replacement options for crude oil. “All” refers to the capability to replace the 18 million barrels of oil per day used by the United States. “Nuclear-assisted” refers to the provision of massive quantities of low-carbon heat and hydrogen at the refinery to fully utilize the carbon content of the cellulosic biomass feedstocks for liquid hydrocarbon production. A system is proposed that decarbonizes about half of the U.S. economy while improving long-term soil productivity and sequestering carbon from the atmosphere. In the U.S. almost half the energy consumed by the final customer is in the form of liquid hydrocarbons produced from crude oil. Liquid hydrocarbons are used as (1) an energy source, (2) a method for daily-to-seasonal energy storage, (3) a chemical feedstock, (4) a chemical reducing agent, (5) a method to enhance high-temperature heat transfer in many furnaces and industrial processes and (6) other purposes. As a consequence, the U.S. consumes ~18 million barrels of crude oil per day to produce liquid hydrocarbons. While there are substitutes for liquid hydrocarbons for some applications, our assessment is that the costs and difficulty will dramatically increase if liquid hydrocarbon use goes much below the equivalent of 10 million barrels per day of crude oil. New uses of liquid hydrocarbons to partly replace coal and natural gas could increase demand beyond the equivalent of 10 million barrels of oil per day. One can produce and burn liquid hydrocarbons from biomass without any net addition of carbon dioxide to the atmosphere. Plants grow by removing carbon dioxide from the atmosphere; thus, burning biomass does not result in any net addition of carbon dioxide to the atmosphere. Biomass is typically 40% oxygen. To remove this oxygen to create hydrocarbon liquids, there are two options. The first option is to use biomass as (1) a feedstock, (2) an energy source to operate the process and (3) a supply of carbon to remove the biomass oxygen as carbon dioxide. The second option is to use external heat and hydrogen to remove the oxygen as water and produce liquid hydrocarbons. The use of massive quantities of external heat and hydrogen for hydrocarbon liquid fuels production reduces the biomass feedstock per unit of liquid hydrocarbon product by more than a factor of two reducing land use by more than a factor of two. Many cellulosic feedstocks unsuitable for liquid hydrocarbon production are viable feedstocks with external heat and hydrogen inputs. As a result, there is sufficient cellulosic feedstocks to meet U.S. and global liquid fuels hydrocarbon demand without significant impacts on food and fiber prices. The heat and hydrogen (heat plus electricity) are produced using base-load nuclear power plants—the most economic form of nuclear energy. If low-price natural gas, there is also the option of producing hydrogen from natural gas with sequestration of the carbon dioxide. The biomass is locally processed in depots to produce commodity feedstocks that can be shipped long distances to large biorefineries (250,000 barrels per day, oil equivalent) similar to existing refineries except modifications of front-end processes. The depot system enables local recycle of nutrients back to the soil. The biorefinery can produce variable quantities of liquid hydrocarbon fuels and carbon dioxide for sequestration enabling removal of carbon dioxide from the atmosphere. Preliminary estimates are that the liquid hydrocarbon costs are equivalent to crude oil at between $60 and $70 per barrel. The largest cost is for hydrogen with biomass feedstocks and refinery costs a smaller fraction of the total cost.

09 BIOMASS FUELS↗

EM-Enhanced HyPOR Loop for Fast Fusion Cycles

Vacuum pumps are the heart of a fusion energy facility – fusion power cannot be generated without them. Nevertheless, the vacuum technology needed to operate a viable fuel cycle for a compact fusion power plant does not exist. Commercial vacuum technology offers the best solution to this challenge, but a pump oil recycling and detritiation system is necessary. Conventional oil detritiation processes have only been developed to deal with legacy waste and are too slow and destructive to the oil. Further, post hoc detritiation strategies are intrinsically inefficient. Our approach is to rethink the challenge holistically by designing the pumping fluid and tritium extraction system in an integrated manner to achieve an innovative solution. By selecting an oil for the specific task of pumping tritium and then designing our catalytic system to selectively target the tritium-bearing functional groups, an effective detritiation system (hydrocarbon pump oil recycling, HyPOR, loop) for fusion power plants can be obtained. The project demonstrated a HyPOR loop process that can selectively remove heavier hydrogen isotopes from pump oil, reaching the target of 99.5 % removal, with an uptake of less than 0.01% of tritium throughput, while also purifying the oil of radiation-induced damage. The recycled oil retained its pumping characteristics over 7 recycles and gamma irradiation over 30 MGy. By meeting these targets, the project enable a reduction in pump operational costs from $\$$14.5M/year to $\$$103k/year (>140× reduction), reducing pump electric power consumption from 2.8 MW to 0.25 MW (>10× reduction), and reducing in-process tritium inventory from 2.03 kg to 0.48 kg (>4× reduction).

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Investigation of damping liquids for aircraft instruments

This report covers the results of an investigation carried on at the Bureau of Standards under a research authorization from, and with the financial assistance of, the National Advisory Committee for Aeronautics. The choice of a damping liquid for aircraft instruments is difficult owing to the range of temperature at which aircraft operate. Temperature changes affect the viscosity tremendously. The investigation was undertaken with the object of finding liquids of various viscosities otherwise suitable which had a minimum change in viscosity with temperature. The new data relate largely to solutions. The effect of temperature on the kinematic viscosity of the following liquids and solutions was determined in the temperature interval -18 degrees to +30 degrees C. (1) solutions of animal and vegetable oils in xylene. These were poppy-seed oil, two samples of neat's-foot oils, castor oil, and linseed oil. (2) solutions of mineral oil in xylene. These were Squibb's petrolatum of naphthene base and transformer oil. (3) glycerine solutions in ethyl alcohol and in mixture of 50-50 ethyl alcohol and water. (4) mixtures of normal butyl alcohol with methyl alcohol. (5) individual liquids, kerosene, mineral spirits, xylene, recoil oil. The apparatus consisted of four capillary-tube viscometers, which were immersed in a liquid bath in order to secure temperature control. The method of calibration and the related experimental data are presented.

Keulegan, G H↗

System Being Developed to Measure the Rotordynamic Characteristics of Air Foil Bearings

Because of the many possible advantages of oil-free engine operation, interest in using air lubricated foil-bearing technology in advanced oil-free engine concepts has recently increased. The Oil-Free Turbomachinery Program at the NASA Glenn Research Center at Lewis Field has partially driven this recent push for oil-free technology. The program's goal of developing an innovative, practical, oil-free gas turbine engine for aeropropulsion began with the development of NASA's high-temperature solid-lubricant coating, PS304. This coating virtually eliminates the life-limiting wear that occurs during the startup and shutdown of the bearings. With practically unlimited life, foil air bearings are now very attractive to rotating machinery designers for use in turbomachinery. Unfortunately, the current knowledge base of these types of bearings is limited. In particular, the understanding of how these types of bearings contribute to the rotordynamic stability of turbomachinery is insufficient for designers to design with confidence. Recent work in oil-free turbomachinery has concentrated on advancing the understanding of foil bearings. A high-temperature fiber-optic displacement probe system and measurement method were developed to study the effects of speed, load, temperature, and other environmental issues on the stiffness characteristics of air foil bearings. Since high temperature data are to be collected in future testing, the testing method was intentionally simplified to minimize the need for expensive test hardware. The method measures the displacement induced upon a bearing in response to an applied perturbation load. The early results of these studies, which are shown in the accompanying figure, indicate trends in steady state stiffness that suggest stiffness increases with load and decreases with speed. It can be seen, even from these data, that stiffness is not expected to change by orders of magnitude over the normal operating range of most turbomachinery; a promising sign for their eventual integration into oil-free turbomachines. Planned future testing will generate similar plots for stiffness changes with temperature and geometry, as well as damping data. The data collected by this method represent a critical step toward understanding how to successfully apply foil air bearings to future oil-free turbomachinery systems.

Howard, Samuel A.↗

Influence of interfacial responses of Berea Sandstone in low-salinity waterflooding environments

Wetting conditions and fluid-fluid interfacial properties are essential to understanding oil recovery in the context of low-salinity and smart waterflooding. Many have deemed wettability alteration to be the dominant interaction, while some highlight the importance of fluid-fluid interactions. In some rock-fluid systems, benefits from the use of additives can arise to favor hydrocarbon production. Understanding the balance between the fluid-fluid and rock-fluid interactions when utilizing additives is crucial to evaluate benefits in improved efficiency. Ultimately, this understanding will shed light on recovery mechanisms. Regarding oil recovery, previous studies indicate that the injection of a naphthenic acid (NA) blend dissolved in an injection brine improves oil recovery in Berea Sandstone, particularly under low-salinity conditions. Interfacial rheology results for the brine-oil interface correlated well with the recovery response. This observation was speculated to serve as a potential improved recovery mechanism through oil-trapping suppression. However, the said studies did not evaluate potentially concurrent rock wettability alteration during recovery or the initial wetting condition. The purpose of this work is to determine the production behavior in systems with NAs, namely NA-10 (3-Cyclohexanepropinoic acid), NA-14 (Cyclopentane carboxylic acid), NA-18 (Cyclohexane carboxylic acid), and NA-mix (Naphthenic acid mixture), at different initial wetting conditions under spontaneous imbibition. In addition, we tested the NAs ability to alter wettability in Berea Sandstone and determine each “additive’s” capacity to improve recovery. Here, time-domain nuclear magnetic resonance (TD-NMR), contact angle, and Amott cell tests, i.e. spontaneous imbibition, were used to analyze the influence of the selected naphthenic acids on oil displacement under different initial wetting conditions. Our results indicate that individual naphthenic acids indeed have potential as additives in low-salinity waterflooding for oil-wet systems while negatively impacting recovery in water-wet systems. However, results suggest that the evolution of the interfacial properties and wettability conditions are equally important on the recovery behavior.

54 ENVIRONMENTAL SCIENCES↗

Suspended Membrane Evaporators Integrating Environmental and Solar Evaporation for Oily Wastewater Purification

Solar-driven evaporation is promising in oily wastewater treatment, in particular for emulsions, but conventional evaporators suffer from pore blocking by residual oil or contamination by volatile oil compounds in the condensed water. In the current research, we develop a suspended membrane evaporator integrating solar evaporation with oil-in-water emulsion separation. The heating and evaporating interface is separated from the rejecting interface to avoid oil escape and improve heat management. A temperature gradient forms on the membrane surface that can promote evaporation performance by combining both solar and environmental evaporation. Such an evaporator achieves a maximum evaporation rate of 1.645 kg/(m 2 ·h) as well as an apparent evaporation efficiency of 111.9%. Moreover, the superhydrophilic and superoleophobic membrane shows excellent oil repellence and emulsion rejection, which can achieve an oil removal efficiency above 98.8% in oil-in-water emulsion separation, and high evaporation rate recovery in cycling tests. Furthermore, a scaled-up membrane evaporator array produces ~8 kg/(m 2 ·d) of clean water from oily wastewater in outdoor experiments, further demonstrating the strong purification performance of this evaporator in oily wastewater treatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

INVESTIGATION OF ROCK-FLUID INTERACTIONS USING GEOMATERIAL MICROFLUIDICS

Illite and Illite-Smectite clays are reportedly the Caney Shale's most prevalent clay minerals. The swelling and fines migration of clays may occur when water-based fluids contact the clay minerals. This may result in the reduction of pore space and permeability, and wettability alteration. Therefore, we quantified the swelling potentials, fines migration and wettability alteration of Illite and Illite-Smectite clays upon exposure to model brines and a produced water, and a model oil and a crude oil. We measured density, viscosity, pH, TDS, and interfacial tension as they are important in multiphase flow and displacement characteristics. Geomaterial microfluidics is recently being used to study physicochemical interactions of solid-fluid systems. It facilitates visualizing the surface behavior upon exposure to various fluids. This study includes preparation and characterization of Illite-Smectite clay-coated glass capillary tubes. Illite and Illite-Smectite clay-coated geomaterial microfluidic surfaces were prepared to investigate the effects of first contact fluid, brine salinity, and aging on wettability. In this work, advancing and receding contact angles of model brine-air, model oil-air, produced water-air, crude oil-air, model brine-model oil systems, and produced water-crude oil systems have been measured in the untreated, and clay-coated microfluidic channels of 1000 µm width and 50 µm depth. The aging effect was studied by retaining the non-aqueous and aqueous solutions in the corresponding microfluidic channels for approximately 24 h in the case of channels first contacted by aqueous and non-aqueous solutions, respectively. The advancing and receding contact angles of Caney shale-crude oil-produced water systems were also measured. The experimental findings indicate the swelling potential, fines migration, and wettability alteration of Illite and Illite-Smectite clays. The results signify the influence of first contact fluid, brine salinity, and aging on wettability of the untreated and clay-coated microfluidic surfaces. The experiments also demonstrate the wetting nature of the Caney shale samples from reservoir and non-reservoir zones.

02 PETROLEUM↗

The effects of in-situ emulsion formation and superficial velocity on foam performance in high-permeability porous media

Foam has been considered as a mobility control agent for Enhanced Oil Recovery (EOR) applications in heterogeneous and fractured reservoirs. Foam enhances sweep efficiency by enabling the injected gas to flow from high-permeability to low-permeability regions. The foam injection velocity is an essential factor affecting foam mobility control and flow behavior. Furthermore, the presence of remaining oil adversely impacts foam generation leading to a failure in governing mobility control. In this study, foam performance in establishing mobility control effect and favorable apparent viscosity was experimentally investigated under a range of total superficial velocities in the presence and absence of crude oil during foam propagation in high permeability sand packs representing a propped fracture network. In the absence of oil, a pronounced effect of total superficial velocity on the mobility control performance was observed at the transition foam quality regime. Co-injection of oil and foam led to noticeable foam destabilization, as expected. However, a further increase in oil fractional flow resulted in larger overall flow resistance. We found that the formation of in-situ surfactant/oil emulsion contributed to the high apparent viscosity exhibited at the steady-state condition. These findings suggest that the steady-state flow resistance established during foam flooding at high oil saturations should be interpreted as the mobility control effect resulting from emulsion formation rather than the development of strong foam.

02 PETROLEUM↗

Life-cycle energy use and greenhouse gas emissions of palm fatty acid distillate derived renewable diesel

This study aims to quantify life-cycle fossil energy use and greenhouse gas (GHG) emissions for palm fatty acid distillate (PFAD) derived renewable diesel (RD) taking into consideration different feedstock classifications that are applicable to PFAD (residue, byproduct, or coproduct), and incorporating updated data for key processes. Under the three classifications, the PFAD to RD pathway was modeled using the Greenhouse gases, Regulated Emissions, and Energy Use in Technologies (GREET®) model. PFAD-derived RD could reduce fossil energy consumption by 77%–88%, relative to petroleum diesel. GHG emissions are very sensitive to PFAD classification and coproduct handling methods. Considering the production of palm oil and PFAD and economic value, we maintain that PFAD should be treated as a byproduct in palm oil refineries. With this treatment, PFAD-derived RD could achieve 84% GHG emissions reductions, compared to the emissions of petroleum diesel. We also employed a substitution method to address the substitution of PFAD by other materials in the marketplace. Compared to coproduct allocation results, we found substituting PFAD by tallow, soy oil, barley, and canola oil results in lower GHG emissions. Due to high induced land-use change emissions associated with palm farming, if PFAD is treated as a coproduct with refined palm oil, PFAD-derived RD may not deliver GHG reductions. A sensitivity analysis identified key parameters such as palm fruit yield, oil extraction efficiency in oil mills, and energy use intensity for RD production affects LCA results significantly; future efforts to improve these parameters could result in further GHG reductions.

09 BIOMASS FUELS↗

Genome-wide approaches delineate the additive, epistatic, and pleiotropic nature of variants controlling fatty acid composition in peanut ( Arachis hypogaea L.)

Abstract The fatty acid composition of seed oil is a major determinant of the flavor, shelf-life, and nutritional quality of peanuts. Major QTLs controlling high oil content, high oleic content, and low linoleic content have been characterized in several seed oil crop species. Here, we employ genome-wide association approaches on a recently genotyped collection of 787 plant introduction accessions in the USDA peanut core collection, plus selected improved cultivars, to discover markers associated with the natural variation in fatty acid composition, and to explain the genetic control of fatty acid composition in seed oils. Overall, 251 single nucleotide polymorphisms (SNPs) had significant trait associations with the measured fatty acid components. Twelve SNPs were associated with two or three different traits. Of these loci with apparent pleiotropic effects, 10 were associated with both oleic (C18:1) and linoleic acid (C18:2) content at different positions in the genome. In all 10 cases, the favorable allele had an opposite effect—increasing and lowering the concentration, respectively, of oleic and linoleic acid. The other traits with pleiotropic variant control were palmitic (C16:0), behenic (C22:0), lignoceric (C24:0), gadoleic (C20:1), total saturated, and total unsaturated fatty acid content. One hundred (100) of the significantly associated SNPs were located within 1000 kbp of 55 genes with fatty acid biosynthesis functional annotations. These genes encoded, among others: ACCase carboxyl transferase subunits, and several fatty acid synthase II enzymes. With the exception of gadoleic (C20:1) and lignoceric (C24:0) acid content, which occur at relatively low abundance in cultivated peanuts, all traits had significant SNP interactions exceeding a stringent Bonferroni threshold (α = 1%). We detected 7682 pairwise SNP interactions affecting the relative abundance of fatty acid components in the seed oil. Of these, 627 SNP pairs had at least one SNP within 1000 kbp of a gene with fatty acid biosynthesis functional annotation. We evaluated 168 candidate genes underlying these SNP interactions. Functional enrichment and protein-to-protein interactions supported significant interactions (P-value < 1.0E−16) among the genes evaluated. These results show the complex nature of the biology and genes underlying the variation in seed oil fatty acid composition and contribute to an improved genotype-to-phenotype map for fatty acid variation in peanut seed oil.

Otyama, Paul I.↗

Characteristics and combustion of future hydrocarbon fuels

As the world supply of petroleum crude oil is being depleted, the supply of high-quality crude oil is also dwindling. This dwindling supply is beginning to manifest itself in the form of crude oils containing higher percentages of aromatic compounds, sulphur, nitrogen, and trace constituents. The result of this trend is described and the change in important crude oil characteristics, as related to aircraft fuels, is discussed. As available petroleum is further depleted, the use of synthetic crude oils (those derived from coal and oil shale) may be required. The principal properties of these syncrudes and the fuels that can be derived from them are described. In addition to the changes in the supply of crude oil, increasing competition for middle-distillate fuels may require that specifications be broadened in future fuels. The impact that the resultant potential changes in fuel properties may have on combustion and thermal stability characteristics is illustrated and discussed in terms of ignition, soot formation, carbon deposition flame radiation, and emissions.

Rudey, R. A.↗

Aircraft Engine Sump Fire Mitigation, Phase 2

The effect of changes in the input parameters (air leakage flow rate and temperature and lubricating oil inlet flow rate and temperature) over a specified range on the flammability conditions within an aircraft engine bearing sump was investigated. An analytical study was performed to determine the effect of various parameters on the generation rate of oil vapor from oil droplets in a hot air stream flowing in a cylindrical tube. The ignition of the vapor-air mixture by an ignition source was considered. The experimental investigation demonstrated that fires would be ignited by a spark ignitor over the full range of air and oil flow rates and air temperatures evaluated. However, no fires could be ignited when the oil inlet temperature was maintained below 41.7 K (290 F). The severity of the fires ignited were found to be directly proportional to the hot air flow rate. Reasonably good correlation was found between the mixture temperature in the sump at the ignitor location and the flammability limits as defined by flammability theory; thus a fairly reliable experimental method of determining flammable conditions within a sump was demonstrated. The computerized mathematical model shows that oil droplet size and air temperature have the greatest influence on the generation rate of oil vapor.

Rosenlieb, J. W.↗

Piston-Skirt Lubrication System For Compressor

Piston-skirt lubrication system provides steady supply of oil to piston rings of gas compressor. No need for oil-filled crankcase or external oil pump. Instead, part of each piston acts as its own oil pump circulating oil from reservoir. Annular space at bottom of piston and cylinder constitutes working volume of small oil pump. Depending on application, reservoir open to atmosphere, or sealed and pressurized in bellows to prevent contact between oil and atmosphere. Filter removes particles worn away from piston rings and cylinder wall during normal operation.

Schroeder, Edgar C.↗