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At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Standard Analytical Methods for Pyrolysis Bio-Oils

There has been significant recent interest in the production of renewable fuels and chemicals from biomass and waste feedstocks. Pyrolysis pathways produce a liquid bio-oil product, which must be processed further, or upgraded, to yield fuel or chemical products. Bio-oils are very complex and often unstable samples, and research and development on upgrading processes needs reliable analytical information. In particular, chemical characterization techniques are needed to quantify both functional groups and individual compounds present in bio-oils. Reliable analytics are also needed to enable the bioenergy industry, as industrial facilities often have different analytical needs and capabilities than research facilities. In this presentation, we will discuss the development of a suite of standard analytical methods for pyrolysis bio-oils. Analytical methods to be discussed include: Determination of Carbon, Hydrogen, Nitrogen, and Oxygen in bio-oils; Accelerated Aging of Fast Pyrolysis Bio-oil using Carbonyl Titration; Determination of Water Content in Bio-oils by Volumetric Karl Fischer Titration; Determination of Carbon Functional Groups; Elemental Analysis of Bio-oils by Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) - Na, K, Mg, Ca, S, P, and Fe; Determination of Phenolic Groups in Bio-oils using Revised Folin-Ciocalteu Methods: Single Cuvette and Plate Reader; Corrosivity of Bio-oils: Screening Test using Metal Leaching; Determination of Biogenic Content by 14C Measurement using Liquid Scintillation Counter. These new analytical methods are publicly available as Laboratory Analytical Procedures (https://www.nrel.gov/bioenergy/bio-oil-analysis.html), along with previously developed standard methods: GC-MS, Acid Titration, Carbonyl Titration, and 31P NMR. Additionally, the development of diffusion ordered NMR for characterization of bio-oil molecular weight will be discussed. Collectively, this suite of analytical methods represents the most comprehensive set of standard methods available for pyrolysis bio-oils. These standard methods are commonly used by the bioenergy community, and provide reliable information that enables research, scaleup, and industrial processing of biomass to produce renewable fuels and chemicals.

analytical↗
DOE OSTI2025

Bacterial response to the 2021 Orange County, California, oil spill was episodic but subtle relative to natural fluctuations

ABSTRACT An oil spill began in October 2021 off the coast of Orange County, California, releasing 24,696 gallons of crude oil into coastal environments. Although oil spills, such as this one, are recurrent accidents along the California coast, no prior studies have been performed to examine the severity of the local bacterial response. A coastal 10-year time series of short-read metagenomes located within the impacted area allowed us to quantify the magnitude and duration of the disturbance relative to natural fluctuations. We found that the largest change in bacterial beta-diversity occurred at the end of October. The change in taxonomic beta-diversity corresponded with an increase in the sulfur-oxidizing clade Candidatus Thioglobus, an increase in the total relative abundance of potential hydrocarbon-degrading bacteria, and an anomalous decline in the picocyanobacteria Synechococcus . Similarly, changes in function were related to anomalous declines in photosynthetic pathways and anomalous increases in sulfur metabolism pathways as well as aromatic degradation pathways. There was a lagged response in taxonomy and function to peaks in total PAHs. One week after peaks in total PAH concentrations, the largest shifts in taxonomy were observed, and 1 week after the taxonomy shifts were observed, unique functional changes were seen. This response pattern was observed twice during our sampling period, corresponding with the combined effect of resuspended PAHs and increased nutrient concentrations due to physical transport events. Thus, the impact of the spill on bacterial communities was temporally extended and demonstrates the need for continued monitoring for longer than 3 months after initial oil exposure. IMPORTANCE Oil spills are common occurrences in waterways, releasing contaminants into the aquatic environment that persist for long periods of time. Bacterial communities are rapid responders to environmental disturbances, such as oil spills. Within bacterial communities, some members will be susceptible to the disturbance caused by crude oil components and will decline in abundance, whereas others will be opportunistic and will be able to use crude oil components for their metabolism. In many cases, when an oil spill occurs, it is difficult to assess the oil spill’s impact because no samples were collected prior to the accident. Here, we examined the bacterial response to the 2021 Orange County oil spill using a 10-year time series that lies within the impacted area. The results presented here are significant because (i) susceptible and opportunistic taxa to oil spills within the coastal California environment are identified and (ii) the magnitude and duration of the in situ bacterial response is quantified for the first time.

Brock, Melissa L. (ORCID:0000000340329241)↗
DOE OSTI2015

Refinery Upgrading of Hydropyrolysis Oil From Biomass

Cellulosic and woody biomass can be converted to bio-oils containing less than 10% oxygen by a hydropyrolysis process. Hydropyrolysis is the first step in Gas Technology Institute’s (GTI) integrated Hydropyrolysis and Hydroconversion IH2®. These intermediate bio-oils can then be converted to drop-in hydrocarbon fuels using existing refinery hydrotreating equipment to make hydrocarbon blending components, which are fully compatible with existing fuels. Alternatively, cellulosic or woody biomass can directly be converted into drop-in hydrocarbon fuels containing less than 0.4% oxygen using the IH2 process located adjacent to a refinery or ethanol production facility. Many US oil refineries are actually located near biomass resources and are a logical location for a biomass to transportation fuel conversion process. The goal of this project was to work directly with an oil refinery partner, to determine the most attractive route and location for conversion of biorenewables to drop in fuels in their refinery and ethanol production network. Valero Energy Company, through its subsidiaries, has 12 US oil refineries and 11 ethanol production facilities, making them an ideal partner for this analysis. Valero is also part of a 50- 50 joint venture with Darling Ingredients called Diamond Green Diesel. Diamond Green Diesel’s production capacity is approximately 11,000 barrels per day of renewable diesel. The plant is located adjacent to Valero’s St Charles, Louisiana Refinery and converts recycled animal fats, used cooking oil, and waste corn oil into renewable diesel. This is the largest renewable diesel plant in the U.S. and has successfully operated for over 2 years For this project, 25 liters of hydropyrolysis oil from wood and 25 liters of hydropyrolysis oils from corn stover were produced. The hydropyrolysis oil produced had 4-10% oxygen. Metallurgical testing of hydropyrolysis liquids was completed by Oak Ridge National Laboratories (Oak Ridge) and showed the hydropyrolysis oils had low acidity and caused almost no corrosion in comparison to pyrolysis oils, which had high acidity and caused significant levels of corrosion.

09 BIOMASS FUELS↗
DOE OSTI2019

Oil and gas flow through fractures and along interfaces in well cement

A number of wells at the Strategic Petroleum Reserve (SPR) have shown sustained, positive pressure (referred to as sustained casing pressure or SCP) in the cemented annulus behind the production casing. To better understand how SCP may develop for SPR conditions, we conducted gas and oil flow tests on cement specimens with flaws including cement fractures and discrete interfaces along a cement-steel contact. Many specimens were tested initially with gas, followed by oil, and finally with gas again to identify how the fluid type may affect the flow through flaws in the well cement. Nitrogen was used as the gas, and silicone oil with properties similar to typical crude oil was used in most tests. One set of measurements were made with crude oil. Composite steel-cement specimen with corroded steel were also tested. For both gas and oil tests, the measured flow test data were used to interpret permeability and, assuming the cubic law for flow between parallel plates, the corresponding hydraulic aperture of the flaw. The hydraulic apertures for the flawed specimens ranged from about 20 to >100 μm, which corresponds to permeabilities of about 10 -14 to 10 -12 m 2 , respectively; these hydraulic apertures are consistent with the range of values interpreted from field measurements on leaky wells. Observed differences between the flow of gas and oil were attributed to a number of factors, including non-linear flow of gas, possible blocking of flow paths by solids within the crude oil, two-phase gas and oil flow and the presence of residual oil in the cement flaw. Furthermore, we determined that corroded steel itself is permeable. Using input values consistent with the gas and oil flow measurements, we conducted one-dimensional simulations of gas and oil flow through cemented annulus systems to investigate the role of flaw size and fluid type on the expected response (i.e., pressure build-up) in the annular cement.

02 PETROLEUM↗
DOE OSTI2019

A Nonconventional CO 2 -EOR Target in the Illinois Basin: Oil Reservoirs of the Thick Cypress Sandstone

The Illinois State Geological Survey (ISGS) identified and quantified nonconventional carbon dioxide (CO 2 ) enhanced oil recovery (EOR) target opportunities within the thick Cypress Sandstone in the Illinois Basin. Up to 60 m thick Cypress Sandstone bodies define a northeast-southwest fairway that is approximately 230 km long and 100 km wide across the central portion of the Illinois Basin. These sandstones commonly contain relatively thin oil reservoirs and were found to have associated underlying residual oil zones (ROZs). The presence of a thick brine aquifer underlying the ROZ and high vertical permeability results in characteristic low primary oil recovery caused by excessive brine production from the aquifer. Nonconventional CO 2 -EOR in these oil reservoirs are expected to require more CO 2 to produce a unit of oil compared to conventional CO 2 -EOR. Consequently, nonconventional CO 2 -EOR will have a higher storage component and offer a unique storage opportunity. An integrated approach of detailed site-specific geologic reservoir characterization, three-dimensional geocellular modeling, and reservoir simulation of multiple development cases at Noble Field was employed to determine development strategies for CO 2 -EOR and storage. The findings of Noble Field research were leveraged to assess the regional CO 2 -EOR and associated storage resource within the nonconventional reservoirs of the thick Cypress Sandstone in the Illinois Basin. Regional characterization shows that thick, multistory fluvial facies of the Cypress Sandstone exhibits porosity from 15% to 21% and horizontal and vertical permeability up to approximately 0.98 µm 2 (1,000 mD). Oil saturation indicators screened from well records and well log analyses were used to map 27 brownfield and greenfield ROZ prospects with residual oil saturation (S OR ) values ranging from 14 to 35%. ROZ thickness varies from 2.7 to 21.6 m (9 to 71 ft). The 27 Cypress Sandstone ROZ prospects have approximately 290.8 million m 3 (1.8 billion barrels) of oil in place. Specific CO 2 -EOR development strategies depend on the goals of the project (prioritizing EOR performance vs. storage performance and NCNO) and geologic setting (brownfield vs greenfield), and company’s business strategies (economic metrics). Nevertheless, applying two unique development strategies derived from reservoir simulation of the depleted main pay zone and ROZ in the Cypress Sandstone at Noble Field, 31.1 million m 3 (196 million barrels) of oil is estimated to be recoverable using the 80-acre blanket WAG development strategy (which favors EOR and economic metrics, but is carbon positive) whereas 21.3 million m 3 (144 million barrels) of oil is estimated to be recoverable using the 40-acre high CO 2 injection rate development strategy (which favors storage and economic metrics and results in net carbon negative oil production). Storage of CO 2 associated with EOR in these ROZ prospects alone, not accounting for associated main pay zones, underlying brine formation, or intervals adjacent to or between prospects, is estimated to be up to 10.4 billion tonnes using the latter development strategy.

02 PETROLEUM↗
NASA NTRS2021

Oil Spill Thickness Determination from L-band Synthetic Aperture Radar

Efficient and effective oil spill response requires accurate information regarding slick location, extent, and thickness to direct remediation activities. Of these three, the most challenging to determine is thickness. Ideally, the needed information would be provided by remote sensing instruments, particularly those operating from space. In this study we consider the capability of L-band synthetic aperture radar (SAR) for identifying oil layer thickness for slicks in open water given the range of oil properties and environmental conditions typical in this setting. The goal is to determine layer thickness with precision equivalent to that of the Bonn Agreement Oil Appearance Code. Here we report preliminary results of an ongoing study to determine whether either relative or absolute slick thickness can be determined from L-band SAR. The study has an experimental component, which uses low noise airborne SAR data acquired over slicks to evaluate the capability to determine relative thickness, i.e., to differentiate sheen from zones of varying thicker oil within a slick. The component of the study to evaluate whether absolute thickness can be determined from SAR uses backscatter simulations within a physics- based model of electromagnetic scattering from slicked and unslicked ocean surfaces accounting for oil properties, meteorological conditions, and sea state. As part of the theoretical component of the study, we evaluate the backscatter sensitivity to oil characteristics to determine which properties most influenced the SAR measurements. These results are used to determine whether the oil-to-water ratio or the oil thickness can be quantified with reasonable accuracy based upon SAR backscatter intensities alone or whether it requires calibration to go from relative to absolute thickness. The ratio of the backscatter contrast between clean and slicked ocean surfaces is shown to be sensitive to variations within slicks that well correlate with the oil layer thickness. Determination of absolute thickness is much more challenging given the variation of oil properties as the oil weathers on the sea surface.

Holt, Benjamin↗
DOE OSTI2017

Experimental investigation on oil migration and accumulation in tight sandstones

Here, this study presents an experimental investigation to simulate and analyze the physical processes of oil migration and accumulation with 19 tight sandstone cores. Characteristic curves of oil migration were obtained by using the experimental results. It shows that the curve variations were mainly influenced by two factors: the permeability of the core and the viscosity of the injected oil. Based on the experimental results, we introduced three important parameters to quantitatively characterize and determine the processes of oil migration and accumulation in tight sandstones. The apparent permeability was introduced to describe the level of oil migration during experiments. The minimum migration pressure gradient (MMPG) and the terminal oil saturation were proposed to evaluate the features of the beginning and final stages of the migration, respectively. The relationships between MMPG, terminal oil saturation and mobility were analyzed, all showed strong linear relationships in the double logarithmic coordinate system. Furthermore, a prediction map of tight oil accumulation was plotted according to the measured oil saturation data, which could be used for estimating the scale and size of oil accumulation in tight reservoirs. Lastly, the concepts and results in this study provide valuable insight for understanding and quantitatively analyzing the processes of oil migration and accumulation in tight sandstones.

58 GEOSCIENCES↗
DOE OSTI2014

Metagenomic analysis of microbial consortium from natural crude oil that seeps into the marine ecosystem offshore Southern California

Crude oils can be major contaminants of the marine ecosystem and microorganisms play a significant role in the degradation of the main constituents of crude oil. To increase our understanding of the microbial hydrocarbon degradation process in the marine ecosystem, we collected crude oil from an active seep area located in the Santa Barbara Channel (SBC) and generated a total of about 52 Gb of raw metagenomic sequence data. The assembled data comprised ~500 Mb, representing ~1.1 million genes derived primarily from chemolithoautotrophic bacteria. Members of Oceanospirillales, a bacterial order belonging to the Deltaproteobacteria, recruited less than 2% of the assembled genes within the SBC metagenome. In contrast, the microbial community associated with the oil plume that developed in the aftermath of the Deepwater Horizon (DWH) blowout in 2010, was dominated by Oceanospirillales, which comprised more than 60% of the metagenomic data generated from the DWH oil plume. This suggests that Oceanospirillales might play a less significant role in the microbially mediated hydrocarbon conversion within the SBC seep oil compared to the DWH plume oil. We hypothesize that this difference results from the SBC oil seep being mostly anaerobic, while the DWH oil plume is aerobic. Within the Archaea, the phylum Euryarchaeota, recruited more than 95% of the assembled archaeal sequences from the SBC oil seep metagenome, with more than 50% of the sequences assigned to members of the orders Methanomicrobiales and Methanosarcinales. These orders contain organisms capable of anaerobic methanogenesis and methane oxidation (AOM) and we hypothesize that these orders and their metabolic capabilities may be fundamental to the ecology of the SBC oil seep.

archaea↗
DOE OSTI2015

Double-Blind, Placebo-Controlled Pilot Study of Processed Ultra Emu Oil Versus Placebo in the Prevention of Radiation Dermatitis

Purpose: The purpose of this single-institution pilot study was to evaluate the feasibility and safety of an oil-based skin agent, Ultra Emu Oil, on skin-related toxicity in patients undergoing radiation therapy to the breast or chest wall. Methods and Materials: Patients were randomized 2:1 in a double-blind fashion and were instructed to apply processed Ultra Emu Oil or placebo (cottonseed oil) twice daily during the course of radiation therapy. The oils were applied before the third fraction and continued for 6 weeks after completion of treatment. The primary endpoint was the area under the curve (AUC) of Skindex-16 scale scores over time. Secondary outcomes included maximum grade of radiation dermatitis using the Common Terminology Criteria (CTC) for Adverse Events (CTCAE 3.0), the Skin Toxicity Assessment Tool, quality of life (QOL) measured by Linear Analogue Self-Assessment, and a symptom experience diary (SED). Results: In all, 42 of 45 patients completed the study and were evaluable. The median times to peak rash, skin redness, peeling, and skin swelling were weeks 6, 6, 7, and 7, respectively as measured by the SED. The Skindex AUC scores tended to be lower in emu oil patients than in placebo patients (mean total AUC 7.2 vs 10.4, respectively). This trend was also seen in all the Skindex subdomains. The overall QOL was slightly better in the emu oil group but remained stable throughout the study for both arms. Peak CTC toxicity occurred at week 6. Patients using emu oil appeared slightly worse on maximum CTC grade, but the difference was not significant. Conclusions: This pilot study confirmed the safety of oil-based skin treatments during radiation therapy and suggests a trend for reduced skin toxicity for patients receiving emu oil. A larger study is needed to evaluate the efficacy of emu oil in reducing radiation dermatitis in patients receiving breast radiation.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2022

Better together: Protein partnerships for lineage-specific oil accumulation

Plant-derived oils are a major agricultural product that exist in both ubiquitous forms such as common vegetable oils and in specialized forms such as castor oil and coconut oil. These specialized oils are the result of lineage-specific metabolic pathways that create oils rich in unusual fatty acids. Considerable progress has been made toward understanding the enzymes that mediate fatty acid biosynthesis, triacylglycerol assembly, and oil storage. However, efforts to translate this knowledge into renewable bioproducts via engineered oil-producing plants and algae have had limited success. Here, we review recent evidence that protein–protein interactions in each of the three major phases of oil formation appear to have profound effects on specialized oil accumulation. We suggest that furthering our knowledge of the noncatalytic attributes of enzymes and other proteins involved in oil formation will be a critical step toward creating renewable bioproducts derived from high performing, engineered oilseeds.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

Oil in Alaska North Slope Gas Hydrate Reservoir: Micro-CT and Flow Simulation Insights into Permeability

Gas hydrate-bearing sands on the Alaska North Slope (ANS) host minor volumes of crude oil whose impact on formation permeability has never been quantified relative to a gas hydrate reservoir system. Here, we combine in situ pressure-core microcomputed-tomography (μ-CT), thermogravimetric analysis (TGA), gas-chromatography–mass-spectrometry (GC–MS), scanning-electron microscopy coupled with energy-dispersive spectroscopy (SEM-EDS), and Stokes-flow simulation to (i) quantify oil saturation, (ii) infer its source, and (iii) evaluate its influence on permeability after gas-hydrate dissociation. μ-CT and SEM-EDS imaging identify the host sediment as silty, with some grain-coating clay present. Eight representative 3003-voxel subvolumes extracted from a preserved pressure core (Core 15P-3c, from the B1 sand (unit B), HYDRATE 02 Geo Data Well (GDW), 886.96–887.29 m measured depth, MD) exhibit porosities of 0.34–0.37 and an average oil saturation of 0.09 ± 0.03, in comparison to an independent TGA-based estimate of 0.16. GC-MS fingerprints obtained from an adjacent depressurized core (Core 17P-1, 891.37–891.44 m MD), together with oil pore habit revealed by μ-CT, suggest that the oil is partly native but also includes contributions from mineral oil-based drilling fluid contamination. Further analysis of oil–porewater interactions and flushing tests confirms that native oil saturation in the analyzed samples ranges from 0.04 to 0.08 with an average of approximately 0.06, and the oil is highly immobile. Flow simulations demonstrate that the native oil saturation of ≈0.06 reduces permeability by approximately 50% due to both pore blockage and increased flow-path tortuosity. These findings reveal the potential presence of native oil within the ANS gas hydrate reservoir and suggest that future simulation models may need to account for its impact on permeability to improve long-term performance predictions of gas and water production.

02 PETROLEUM↗
DOE OSTI2020

Joint Optimization of Well Completions and Controls for CO 2 Enhanced Oil Recovery and Storage

CO 2 storage through CO 2 enhanced oil recovery (EOR) is considered as one of the technologies to help promote larger scale deployment of CO 2 storage because of associated economic benefits through oil recovery, 45Q tax credits and the utilization of existing infrastructure. The objective of this study is to demonstrate how optimal reservoir management and operation strategies (including well completions and controls) can be used to optimize both CO 2 storage and oil recovery. The optimization problem was focused on jointly estimating the well completions (i.e., fraction of injection/production well perforations in each reservoir layer) and CO 2 injection/oil production controls that maximize the net present value (NPV) in a CO 2 EOR and storage operation. We utilized the newly developed StoSAG algorithm, one of the most efficient optimization algorithms in the reservoir management community, to solve the optimization problem. The performance of joint optimization approach was compared with the performance of well control only optimization approach. In addition, the performance of co-optimization of CO 2 storage and oil recovery approach was compared with the performances of maximization of only CO 2 storage and maximization of only oil recovery approaches. The optimization results showed that a joint optimization of well completions and well controls can achieve an 8.84% higher final NPV than the one obtained from the optimization of only well controls. It was observed that the NPV incremental for joint optimization is mainly due to the fact that the optimal well completions and controls approach results in efficient CO 2 storage and oil production from different reservoir layers depending on the differences in individual layer properties. Comparison of co-optimization (i.e., maximization of NPV) and maximization of only CO 2 storage or only oil recovery showed that the co-optimization and maximization of only oil recovery result in significantly higher final NPV than that obtained through maximization of only CO 2 storage approach while maximization of only CO 2 storage can achieve significantly higher CO 2 storage in the reservoir compared to the other two scenarios. The similar results for co-optimization and maximization of oil production are obtained because of the difference in oil revenue compared to CO 2 storage tax credit. To the best of our knowledge, this is the first study in oil/gas industry and CO 2 storage community to perform joint optimization of well completions and well controls in the fields. We expect that the proposed optimization framework will be a useful and efficient tool for field engineers to optimally manage CO 2 EOR projects to maximize revenue through oil recovery as well as CO 2 storage by taking advantage of the new 45Q tax law.

Artificial intelligence↗
DOE OSTI2020

Air Pollutant Emissions and Regulatory Implications of Co-Processing Raw Bio-Oil in U.S. Petroleum Refineries

Pyrolysis oil, often referred as bio-oil or biocrude, has attracted considerable attention because it has higher energy density and carbon content compared to the raw biomass. Using pyrolysis oil derived from low cost and underutilized biomass to produce renewable hydrocarbon fuels provides a viable link between the agriculture/forestry and (petro-) chemical industry. Co-processing bio-oil with vacuum gas oil (VGO) in petroleum refinery is appealing due to the relatively low capital requirement to retrofit refinery and the compatibility of fuel products with existing infrastructure. In order to implement co-processing, a petroleum refinery would need to consider several process modifications and therefore could be subject to varying levels of air permitting requirements based on bio-oil co-processing ratio, co-processing capacity in existing units, the amount of regulated pollutants expected to be emitted, among other factors. This analysis considers co-processing 5% (by weight) of raw bio-oil with VGO in the fluidized catalytic cracking (FCC) unit(s) in a petroleum refinery. We estimate the potential increase in emissions of regulated air pollutants resulting from the modifications required to implement bio-oil co-processing and evaluate the regulatory and permitting implications for three FCC size categories in the U.S. refineries, which could co-processes raw bio-oil to produce partially renewable transportation fuels. We also assess technically feasible emission control options petroleum refineries could adopt to avoid being subject to major source permitting requirements if the estimated increase in regulated air pollutant emission exceeds the applicable threshold for major modifications. Insights from our analysis can help overcome challenges and risks associated with timely obtaining air permits required to implement bio-oil co-processing in existing refineries. Our analysis also provides needed information for decision makers (e.g., local air quality agencies) to understand the potential air quality implications for retrofitting refineries to co-process bio-oil, particularly in areas with high concentration of petroleum refineries.

09 BIOMASS FUELS↗
NASA NTRS1950

Rise of Air Bubbles in Aircraft Lubricating Oils

Lubricating and antifoaming additives in aircraft lubricating oils may impede the escape of small bubbles from the oil by forming shells of liquid with a quasi-solid or gel structure around the bubbles. The rates of rise of small air bubbles, up to 2 millimeters in diameter, were measured at room temperature in an undoped oil, in the same oil containing foam inhibitors, and in an oil containing lubricating additives. The apparent diameter of the air bubbles was measured visually through an ocular micrometer on a traveling telescope. The bubbles in the undoped oil obeyed Stokes' Law, the rate of rise being proportional to the square of the apparent diameter and inversely proportional to the viscosity of the oil. The bubbles in the oils containing lubricating additives or foam inhibitors rose more slowly than the rate predicted by Stokes 1 Law from the apparent diameter, and the rate of rise decreased as the length of path the bubbles traveled increased. A method is derived to calculate the thickness of the liquid shell which would have to move with the bubbles in the doped oils to account for the abnoi'I!l8.lly slow velocity. The maximum thickness of this shell, calculated from the velocities observed, was equal to the bubble radius.

LUBRICATING OILS - FOAMING↗
DOE OSTI2017

Production of low-oxygen bio-oil via ex situ catalytic fast pyrolysis and hydrotreating

Catalytic fast pyrolysis (CFP) bio-oils with different organic oxygen contents (4-18 wt%) were prepared in a bench-scale dual fluidized bed reactor system by ex situ CFP of southern pine over HZSM-5, and the oils were subsequently hydrotreated over a sulfided CoMo catalyst at 170 bar. The goal was to determine the impact of the CFP oil oxygen content on hydrotreating requirements. The CFP oils with higher oxygen contents included a variety of oxygenates (phenols, methoxyphenols, carbonyls, anhydrosugars) whereas oxygenates in the 4 wt% oxygen oil were almost exclusively phenols. Phenols were the most recalcitrant oxygenates during hydrotreating as well, and the hydrotreated oils consisted mainly of aromatic and partially saturated ring hydrocarbons. The temperature required to produce oil with <1% oxygen was approximately 350 °C for the CFP oil with the lowest oxygen content whereas temperatures around 400 °C were required for the other CFP oils. The carbon efficiency during hydrotreating slightly decreased as the CFP oil oxygen content increased but remained above 90% in all cases, and the carbon efficiency for the integrated process was dominated by the efficiency of the CFP process. In conclusion, a preliminary technoeconomic evaluation suggested that with the current zeolite-based CFP catalysts, it is economically beneficial to preserve carbon during CFP, at the expense of higher oxygen contents in the CFP oil.

09 BIOMASS FUELS↗
DOE OSTI2015

Alkaline hydrothermal liquefaction of swine carcasses to bio-oil

Highlights: • Swine carcasses can be converted to bio-oil by alkaline hydrothermal liquefaction. • It seems that the use of the bio-oil for heat or CHP is technically suitable. • Some valuable chemicals were found in the bio-oils. • The bio-oil and the solid residue constituted an energy efficiency of 93.63% for the feedstock. • The solid residue can be used as a soil amendment, to sequester C and for preparing activated carbon. - Abstract: It is imperative that swine carcasses are disposed of safely, practically and economically. Alkaline hydrothermal liquefaction of swine carcasses to bio-oil was performed. Firstly, the effects of temperature, reaction time and pH value on the yield of each liquefaction product were determined. Secondly, liquefaction products, including bio-oil and solid residue, were characterized. Finally, the energy recovery ratio (ERR), which was defined as the energy of the resultant products compared to the energy input of the material, was investigated. Our experiment shows that reaction time had certain influence on the yield of liquefaction products, but temperature and pH value had bigger influence on the yield of liquefaction products. Yields of 62.2 wt% bio-oil, having a high heating value of 32.35 MJ/kg and a viscosity of 305cp, and 22 wt% solid residue were realized at a liquefaction temperature of 250 °C, a reaction time of 60 min and a pH value of 9.0. The bio-oil contained up to hundreds of different chemical components that may be classified according to functional groups. Typical compound classes in the bio-oil were hydrocarbons, organic acids, esters, ketones and heterocyclics. The energy recovery ratio (ERR) reached 93.63%. The bio-oil is expected to contribute to fossil fuel replacement in stationary applications, including boilers and furnaces, and upgrading processes for the bio-oil may be used to obtain liquid transport fuels.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2019

Hydrocarbon Recovery from Williston Basin Shale and Mudrock Cores with Supercritical CO 2 : 2. Mechanisms That Control Oil Recovery Rates and CO 2 Permeation

In part 1 (10.1021/acs.energyfuels.9b01177), CO2 was used to recover oil from 51 source shale and reservoir mudrock cores collected from the Bakken Petroleum System in the Williston Basin. Oil hydrocarbon recoveries after 24 hexposures to CO2 at reservoir pressure and temperature were >94% for the reservoir mudrock cores and ranged from a few percent to as much as 80% for the source shales depending on the well location. In part 2, the experimental parameters that control oil recoveries were investigated, and the results show that exposed rock surface areas and CO2 contact times are primary factors controlling oil recovery at reservoir temperature and pressure. Compared to the 11.2 mm diameter rods used in part 1,increasing the surface area by splitting the rods into a stack of 2−3 mm thick “coins” doubled the oil recovery rates from both reservoir and source rocks, while further increasing the surface area using ground and sieved 1−3.4 mm samples at least tripledrecovery rates. In addition, extending the exposure time for the 11.2 mm diameter source shale rods to 96 h yielded nearly complete oil recoveries (as did the 24 h exposures with the 1−3.4 mm samples), indicating that pore spaces in the source shales as well as the more permeable reservoir rocks can be accessed by the CO2 and the associated oil hydrocarbons recovered. Higher CO 2 pressures yielded higher oil recoveries from both the reservoir rocks and source shales regardless of whether the exposure pressure was at or a little below, somewhat above, or substantially above the minimum miscibility pressure (MMP).Laboratory experiments also demonstrated that crude oil recoveries are based primarily on the ability of the CO 2 to penetrate the rock matrix and dissolve the oil hydrocarbons via hydrocarbon vaporization into the CO 2 phase rather than bulk physical processes (e.g., swelling, lowered viscosity, the physical “sweeping” effect) that are important in conventional CO 2 floods. Lighter hydrocarbons (e.g., C7 to C14) were recovered at much faster rates than heavier hydrocarbons (e.g., >C20) from all rock samples and geometries as well as for all CO2 pressures tested, as might be expected because lighter hydrocarbons have both higher diffusion coefficients and higher solubilities in CO 2 than heavier hydrocarbons. Limiting the amount of CO2 had little or no effect on the recovery rates of the lighter hydrocarbons but greatly reduced those of the heavier hydrocarbons. These two observations are consistent with a concentration-gradient-driven diffusion recovery mechanism. Laboratory results suggest that oil recovery in the Bakken play with CO2 will be enhanced by longer soak times, larger exposed rock surface areas, and higher pressures.

Energy & Fuels↗
DOE OSTI2020

Nonspecific phospholipase C6 increases seed oil production in oilseed Brassicaceae plants

Summary Plant oils are valuable commodities for food, feed, renewable industrial feedstocks and biofuels. To increase vegetable oil production, here we show that the nonspecific phospholipase C6 (NPC6) promotes seed oil production in the Brassicaceae seed oil species Arabidopsis, Camelina and oilseed rape. Overexpression of NPC6 increased seed oil content, seed weight and oil yield both in Arabidopsis and Camelina, whereas knockout of NPC6 decreased seed oil content and seed size. NPC6 is associated with the chloroplasts and microsomal membranes, and hydrolyzes phosphatidylcholine and galactolipids to produce diacylglycerol. Knockout and overexpression of NPC6 decreased and increased, respectively, the flux of fatty acids from phospholipids and galactolipids into triacylglycerol production. Candidate‐gene association study in oilseed rape indicates that only BnNPC6.C01 of the four homeologues NPC6s is associated with seed oil content and yield. Haplotypic analysis indicates that the BnNPC6.C01 favorable haplotype can increase both seed oil content and seed yield. These results indicate that NPC6 promotes membrane glycerolipid turnover to accumulate TAG production in oil seeds and that NPC6 has a great application potential for oil yield improvement.

Cai, Guangqin↗