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DOE OSTI2022

Effect of a nanoparticle on wettability alteration and wettability retainment of carbonate reservoirs

The oil recovery in many carbonate reservoirs is low due to oil-wetness and heterogeneity. In this study, nanoparticles are evaluated for altering the wettability of oil-wet limestones and their properties are compared with those of an anionic surfactant. A surface-modified silica nanoparticle (SiNP) with a negative zeta potential was found to be aqueous stable in brines. Wettability studies showed that the SiNP cannot change the wettability of an initially oil-wet calcite plate, but SiNP treated calcite surface can remain water-wet after aging in oil. Spontaneous imbibition tests confirmed the observations of wettability tests and showed that a SiNP treated carbonate core retained its water-wettability during oil injection and aging. The imbibition into a SiNP treated and oil aged core was comparable to that in a water-wet core. However, SiNP was not able to remove the oil layers in initially oil-wet cores and imbibe water into these cores. In contrast, the anionic surfactant could alter the oil-wet carbonate rocks to a more water-wet condition, but failed to prevent the water-wet surface from getting oil-wet during oil-aging. The results suggest that the SiNP can be injected into wettability-altered (water-wet) reservoirs/regions to help retain the water-wettability during the long-term oil production. The 0.5 wt% SiNP dispersions transported through 18 mD limestone cores without any plugging. The SiNP retention was measured to be 2.5 mg/m 2 , much higher than that of the anionic surfactant.

02 PETROLEUM↗

DOE OSTI2022

EERC Final Topical Report – Findings on Subtask 3.2 – Produced Water Management Through Geologic Homogenization, Conditions, and Reuse

The Energy & Environmental Research Center (EERC) was awarded a contract by the North Dakota Industrial Commission (NDIC) Oil and Gas Research Program (NDIC No. G-051-101) to conduct a study on the recycling of water used in oil and gas operations, also known as produced water, from oil- and gas-producing regions of North Dakota as directed by Section 19 of North Dakota House Bill 1014. This final report provides a compilation of results of the study, which include regulatory, scientific, technological, and feasibility methods and considerations associated with North Dakota produced water management. The report provides a synopsis of this project’s previously submitted produced water assessment report entitled “Produced Water Management and Recycling Options in North Dakota” (Energy & Environmental Research Center, 2020), with updated values provided as appropriate. The report provides the results from the investigation of a novel produced water management strategy, referred to as geologic homogenization, conditioning, and reuse (GHCR), which aims to use a subsurface geologic formation as a natural medium for managing produced water recycling and reuse. Water management is a significant technical and economic challenge for sustainable oil and gas production, and water volumes are intrinsically linked to oil production volumes. North Dakota oil production rose to over 1.5 million barrels (MMbbl)/day in 2019, and despite a downturn in oil price in early 2020, North Dakota oil production has recovered to 1.1 MMbbl/day as of August 2021. Bakken petroleum system development between 2008 and 2020 has resulted in a nearly fourfold increase in produced water volumes to 642 MMbbl/yr in 2020 after peaking at 740 MMbbl/yr in 2019 and a fivefold increase in saltwater disposal (SWD) volumes to 565 MMbbl/yr in 2020 after a peak of 682 MMbbl/yr in 2019. Produced water and SWD volumes are forecasted to double by 2030. SWD is the primary method of produced water management used in North Dakota, with approximately 95% of the SWD volume occurring through subsurface injection into sandstones of the Dakota Group (Dakota). Localized pressurization of the Dakota resulting from SWD and projected increases in produced water volumes could impact the economics of North Dakota oil production. As a result, there is an emerging need to pursue alternative produced water management approaches, including recycling and reuse. While produced water recycling is not yet widespread, commercial operators are making strides in overcoming the technical challenges of using high salinity produced water in completion operations (Marathon Oil, 2020). As water management continues to be a key focal point in companies’ environmental, social, and governance (ESG) initiatives, focus on water management, including recycling, will likely continue to increase. Laboratory column testing, field sample collection, geologic modeling and numerical simulation, and techno-economic analysis all indicate that GHCR could feasibly be implemented as a potential water management option. Laboratory column testing and field sample collection indicate that the Inyan Kara sandstone and native formation fluid are capable of homogenizing with the Bakken produced water to a point where the fluid composition appears to stabilize. Extracting that stabilized fluid could be considered homogeneous and capable of providing individual batches of hydraulic fracturing fluid. Numerical simulation results indicate that extraction of fluids from the Inyan Kara in a GHCR implementation scenario is capable of reducing formation pressure, which would help ease localized pressurization of the Inyan Kara and extend the available capacity for nearby existing SWD wells. Economic analysis indicates that there are scenarios where GHCR implementation can be a competitive or even lower-cost option than a conventional water management approach. Site-specific conditions will dictate the economic potential of GHCR, but potentially attractive sites for GHCR implementation will be those that are located above a pressurized zone of the Inyan Kara, need six or more Bakken infill wells, and face high costs for conventional SWD and/or freshwater. Based on the regulatory review, drilling into the Inyan Kara for SWD and to harness as a source water for industrial use have precedent in North Dakota, and a workable regulatory solution for GHCR seems likely. However, restrictions in the state regarding surface storage and transport of produced fluids may limit some activities, which will affect how GHCR could ultimately be implemented. In summary, this study reveals pursuing GHCR can be a viable approach to water management in North Dakota. The GHCR concept addresses some of the challenges that hinder the more traditional approaches to recycling in the industry. Furthermore, an assessment of the current landscape of water management within the state reveals the ongoing trend of increasing volumes of produced water and SWD. Projections reveal that the volumes of produced water that need to be managed are expected to double over the next decade (Energy & Environmental Research Center, 2020). With the continued development of the Bakken and continuing driving factors related to ESG initiatives, implementing a practice such as GHCR is a feasible approach to adding recycling of produced water to industry within the state. This subtask was cofunded through the EERC–U.S. Department of Energy Joint Program on Research and Development for Fossil Energy-Related Resources Cooperative Agreement No. DE-FE0024233. Nonfederal funding was provided by the North Dakota Industrial Commission Oil and Gas Research Program. References Energy & Environmental Research Center, 2020, Produced water management and recycling options in North Dakota: Final Report for North Dakota Legislative Management Energy Development and Transmission Committee and North Dakota Industrial Commission. Marathon Oil, 2020, Sustainability report: https://cdn.sanity.io/files/ghcnw9z2/website/ 91744eb6ef8fbe59505a911c6b8d2e8dd9a537fa.pdf?dl (accessed November 2021).

02 PETROLEUM↗

DOE OSTI2026

Upcycling plastic waste into polyhydroxyalkanoates with high carbon conversion via CO 2 plasma-enabled deconstruction

Plastic deconstruction into fermentable intermediates is a key step for microbial bio-upcycling into value-added products. In this study, CO 2 plasma deconstruction was used as an electrified route to convert polyethylene into oxygenated intermediates and liquid (OIL). The resulting OIL was rich in fatty acids, fatty alcohols, and hydrocarbons, making it a suitable feedstock for medium-chain-length polyhydroxyalkanoate (mcl-PHA) production by Pseudomonas putida NRRL B-14688 and Pseudomonas resinovorans NRRL B-2649. Compared with batch fermentation and monocultures, fed-batch co-cultivation markedly improved biomass formation and PHA accumulation, likely due to complementary substrate utilization, particularly hydrocarbon conversion by P. resinovorans. Using virgin polyethylene-derived OIL (Vir-OIL), the co-culture achieved 40.11% mcl-PHA content and about 18% PHA yield based on total OIL fed. More importantly, OIL produced from post-consumer single-use plastic films (PCR-OIL) was directly fermented and well supported the cell growth and PHA accumulation, achieving 38.11% PHA content and about 14.7% PHA yield. Based on emulsified OIL fractions, PHA yields for Vir-OIL and PCR-OIL were comparable (∼28%). PHA granules were extracted from PCR-OIL-grown cells with high recovery (88.25%) and purity (94.8%). Five monomers were identified in the polymer, including 3-hydroxyhexanoate (3HHx), 3-hydroxyoctanoate (3HO), 3-hydroxydecanoate (3HD), 3-hydroxydodecanoate (3HDD), and 3-hydroxytetradecanoate (3HTD), with 3HO (44.28%) and 3HD (40.60%) as the dominant units. The polymer exhibited moderate molecular weight and narrow dispersity (M n = 65.4 kDa, M w = 92.1 kDa, Đ = 1.40) and low crystallinity (T m ≈ 76.6 °C, X c ≈ 15.5%). These characteristics indicate elastomer-like behavior, making the material suitable for flexible applications such as films, coatings, adhesives, and blend modifiers. Overall, this study establishes a CO 2 plasma-assisted route for generating fermentable polyethylene-derived intermediates and demonstrates that fed-batch co-culture fermentation can effectively funnel plastic-derived carbon into mcl-PHA.

42 ENGINEERING↗

DOE OSTI2025

Hybrid HEFA-HDCJ Process for the Production of Jet Fuel Blendstocks

The hydrotreatment of bio-oil derived from the pyrolysis and biocrude from hydrothermal liquefaction of lignocellulosic materials to produce hydrocarbons faces significant technological challenges, mainly due to the high reactivity and poor thermal stability of bio-oil, resulting in the formation of large quantities of coke. This problem has been addressed by existing PNNL patents with a two-step hydrotreatment technology in which the bio-oil is first stabilized with a noble hydrogenation metal (often Pt or Ru). Then, in the second step, the bio-oil is deoxygenated with a Ni-Mo or Co-Mo sulfide catalyst. The main problem with this approach is that the Pt/Ru catalysts deactivate easily in the presence of S or other impurities, which are commonly present in pyrolysis oils. In this project, we explored technological solutions to mitigate coke formation, avoiding the use of Pt/Ru catalysts. Our strategy is based on three actions: (1) Bio-oil stabilization in the presence of alcohols. In this project, we studied the stabilization with butanol. (2) the use of a cosolvent to solubilize the bio-oil. Because coke formation reactions are second-order reactions a reduction in the concentration of reactive bio-oil molecules. In this case, we used yellow greases as a co-solvent. (3) Separation of bio-oil reactive fractions. In this project, we studied the removal of water-soluble fractions. Our batch co-hydrotreatment studies confirmed that the addition of butanol and methanol and the blend with lipids effectively contributed to mitigating coke formation (reducing coke yield to about 1 wt.% %). The removal of sugars did not have a noticeable effect on the overall coke yield, suggesting that coke precursors are present in all bio-oil fractions. Our analytical work suggests that they may be concentrated in the water-insoluble/CH 2 Cl 2 insoluble fractions of pyrolysis oils. Although the technological strategies tested resulted in significant coke reductions, the levels achieved were not sufficiently low to ensure a reliable operation in continuous, fixed-bed trickle-bed reactors. Long runs of more than 100 hours (maximum: 255 h) of co-processing time on stream were achieved in a continuous 40 mL reactor. When the same test was conducted in a larger 400 mL reactor, pressure drop increases associated with coke formation were observed. This increase in coke formation could be due to larger temperature gradients in the bed. Hydrodeoxygenation tests in moving bed reactors and using more active hydrogenation catalysts (for example Ni) could lead to more reliable operations. Unfortunately, our team did not have access to such experimental setups. The technoeconomic analysis suggests that although alcohol use is an effective means to reduce coke formation, the use of alcohol increases production cost. Thus, its use needs to be minimized. A delicate balance needs to be found between the use of technological solutions that allow the reliable operation of the system (stabilization with Ni catalysts, use of small quantities of solvents, processing in moving bed reactors) with a tolerable level of coke formation for the hydrodeoxygenation reactor used and that result in minimum production costs.

09 BIOMASS FUELS↗

DOE OSTI2022

Study on Emulsification/Demulsification Behavior and Mechanism of Produced Liquid from Polymer Flooding on Alaska North Slope

Heavy oil reservoirs on Alaska North Slope (ANS) are unconsolidated and contain abundant clay minerals, where the first-ever field pilot is currently implemented to validate the use of polymer floods for heavy oil enhanced oil recovery (EOR). The polymer molecules and/or fine clay particles carried with the produced liquid could potentially affect the oil/water separation, which is one of the major concerns for field operators. This dissertation aims to investigate the emulsification behavior of produced liquid, understand the emulsifying mechanism, and seek an adaptive and cost-effective method to treat the produced liquid from polymer flooding. Emulsions were prepared by mechanically mixing the actual heavy oil and the produced water from the pilot site, of which the stability was investigated by bottle test method or multiple light scattering method. Drop size distribution and interfacial properties were measured via microscope and pendant drop technique to probe the stability mechanism further. Results showed that oil-continuous or water-continuous emulsion could be generated depending on the water cut, clay types, clay concentration, and polymer concentration. In the crude oil/water system, the increasing water cut triggered the phase inversion of oil-continuous emulsion to water-continuous emulsion, resulting in faster separation and lower emulsion stability. Whereas, clay particles, no matter added to the oil or water phase, resulted in an unfavorable phase inversion from the loose water-continuous emulsion to the tight oil-continuous emulsion as clay concentration increased. For all four types of clay except Ca-montmorillonite, clay particles added to water led to an earlier phase inversion and higher emulsion stability than that added to the oil. The dual function of polymer on emulsion stability was observed. On the one hand, both sheared and unsheared polymer tended to convert the oil-continuous emulsion formed in either crude oil/water system or complex crude oil/water/clay particle system to the water-continuous emulsion, acting as a weak demulsifier to accelerate the oil/water separation. On the other hand, the addition of polymer to the water-continuous emulsion could result in enhanced emulsion stability, which is primarily attributed to the increased viscosity of the continuous phase and the decreased drop size of the dispersed oil phase. Particularly, the sheared polymer had a weaker ability to stabilize the o/w emulsion than the unsheared polymer due to the lower viscosity of the sheared polymer solution resulting from the breakdown of the polymer macromolecules. As for the chemical demulsification tests, the performance of demulsifiers showed a complex dependency upon the water cut, the shearing intensity, demulsifier type and dosage, and the polymer concentration. A compound emulsion breaker, E12+E18, exhibited the most satisfactory demulsification performance despite the varied test conditions. For severe water-continuous emulsions that might require a multi-fold dosage of demulsifier, a less expensive electrolyte, KCl, was proposed to be used in combination with demulsifier E12+E18 to improve the demulsification performance. In the proposed demulsifier formula, the effectiveness of the commercial demulsifier relied on its destructive effect on the interfacial film, while the efficacy of KCl was mainly dependent on its viscosity reduction effect on the continuous phase. This dissertation illustrates that intermediate layer elimination and water clarification are the major challenges for produced liquid treatment from polymer flooding. It also provides practical and theoretical guidance in advance for the demulsification strategy of the produced liquid from the ongoing first-ever polymer flooding pilot on ANS.

Chang, Hongli↗

DOE OSTI2025

Hybrid HEFA-HDCJ Process for the Production of Jet Fuel Blendstocks

09 BIOMASS FUELS↗

DOE OSTI2021

Product Characteristics and Synergy Study on Supercritical Methanol Liquefaction of Lignocellulosic Biomass and Plastic

Bio-oil originating from lignocellulosic biomass (LCB) is a potential next-generation fuel because of its abundant, renewable, and sustainable resources compared to other types. However, these bio-oils are typically of low quality compared to petroleum-derived oils due to their low calorific value, high acidity, and oxygen content. This work intends to provide a feasible method for producing hydrocarbon-rich oils by supercritical methanol (scMeOH) coliquefaction of LCB and plastic waste. Both rice straw (RS) and linear low-density polyethylene (LLDPE) are coliquefied under 300 °C for 60 min in scMeOH at various RS/LLDPE mass ratios of 2:1, 1:1, and 1:2. Positive effects were found in terms of oil yield and fuel quality, such as higher hydrocarbons content and calorific value. The oil yield increased from 26.72 to 30.07 wt % with LLDPE addition of 67%. Around 79.15–92.24% of the oil was hydrocarbons, phenols, ketones, and diverse functional group compounds. The complex compounds led to various degrees of the synergetic effect on oil chemical compositions. Among various RS/LLDPE ratios in this work, RS/LLDPE of 1:2 was supposed to be an optimal ratio for hydrocarbon-rich fuel production because it presented the highest oil yield of 30.07 wt % and quality-high oil with 71.42% hydrocarbons. In addition, scMeOH coliquefaction of LCB and plastic waste shows a synergetic effect on the improvement of carbon and hydrogen contents in solid products. These results indicate that scMeOH coliquefaction of LCB with plastic is a feasible and promising means to improve fuel quality and also to realize the thermal recycling of plastic wastes.

09 BIOMASS FUELS↗

NASA NTRS1951

Comparison of High-Speed Operating Characteristics of Size 215 Cylindrical-Roller Bearings as Determined in Turbojet Engine and in Laboratory Test Rig

A comparison of the operating characteristics of 75-millimeter-bore (size 215) cylindrical-roller one-piece inner-race-riding cage-type bearings was made using a laboratory test rig and a turbojet engine. Cooling correlation parameters were determined by means of dimensional analysis, and the generalized results for both the inner- and outer-race bearing operating temperatures are compared for the laboratory test rig and the turbojet engine. Inner- and outer-race cooling-correlation curves were obtained for the turbojet-engine turbine-roller bearing with the same inner- and outer-race correlation parameters and exponents as those determined for the laboratory test-rig bearing. The inner- and outer-race turbine roller-bearing temperatures may be predicted from a single curve, regardless of variations in speed, load, oil flow, oil inlet temperature, oil inlet viscosity, oil-jet diameter or any combination of these parameters. The turbojet-engine turbine-roller-bearing inner-race temperatures were 30 to 60 F greater than the outer-race-maximum temperatures, the exact values depending on the operating condition and oil viscosity; these results are in contrast to the laboratory test-rig results where the inner-race temperatures were less than the outer-race-maximum temperatures. The turbojet-engine turbine-roller bearing, maximum outer-race circumferential temperature variation was approximately 30 F for each of the oils used. The effect of oil viscosity on inner- and outer-race turbojet-engine turbine-roller-bearing temperatures was found to be significant. With the lower viscosity oil (6x10(exp -7) reyns (4.9 centistokes) at 100 F; viscosity index, 83), the inner-race temperature was approximately 30 to 35 F less than with the higher viscosity oil (53x10(exp -7) reyns (42.8 centistokes) at 100 F; viscosity index, 150); whereas the outer-race-maximum temperatures were 12 to 28 F lower with the lower viscosity oil over the DN range investigated.

BEARINGS, ANTI-FRICTION↗

NASA NTRS1999

Life of Pennzane and 815Z-Lubricated Instrument Bearings Cleaned with Non-CFC Solvents

This report takes the form of two papers: (1) "Life of Pennzane and 815Z-Lubricated Instrument Bearings cleaned with Non-CFC Solvents" and (2) a published paper, entitled "Instrument bearing life with NON-CFC cleaners". Abstract for paper # 1 : Bearings used in spacecraft mechanisms have historically been cleaned with chlorofluorocarbon CFC-1 13 (Freon) solvents and lubricated with a perfluorinated polyalkylether (PFPE) oils like 815-Z. Little full-scale bearing life test data exists to evaluate the effects of the newer class environmental-friendly bearing cleaners or improved synthetic hydrocarbon space oils like Pennzane. To address the lack of data, a cooperative, bearing life test program was initiated between NASA, Lockheed Martin and MPB. The objective was to obtain comparative long-term, life test data for flight-quality bearings, cleaned with non-CFC solvents versus CFC-1 13 under flight-like conditions with two space oils. A goal was to gain a better understanding of the lubricant surface chemistry effects with such solvents. A second objective was to obtain well-controlled, full-scale bearing life test data with a relatively new synthetic oil (Pennzane), touted as an improvement to Bray 815Z, an oil with considerable space flight history. The second paper, which serves as an attachment, is abstracted below: Bearings used in spacecraft mechanisms have historically been cleaned with chlorofluorocarbon CFC-113 (Freon) solvents and lubricated with a perfluorinated polyalkylether (PFPE) oils like 815-Z. Little full-scale bearing life test data exists to evaluate the effects of the newer class environmental-friendly bearing cleaners or improved synthetic hydrocarbon space oils like Pennzane. To address the lack of data, a cooperative, bearing life test program was initiated between NASA, Lockheed Martin and MPB. The objective was to obtain comparative long-term, life test data for flight-quality bearings, cleaned with non-CFC solvents versus CFC-1 13 under flight-like conditions with two space oils. A goal was to gain a better understanding of the lubricant surface chemistry effects with such solvents. A second objective was to obtain well-controlled, full-scale bearing life test data with a relatively new synthetic oil (Pennzane), touted as an improvement to Bray 815Z, an oil with considerable space flight history.

Loewenthal, Stuart↗

DOE OSTI2022

Sustainable Biofuels for Low-Carbon Maritime Transportation

The marine shipping sector heavily depends on fossil fuels and is one of the largest petroleum fuel consumers [1,2]. The annual global marine fuel consumption was estimated to be around 400 million metric tons in 2019 (2.5 billion barrels). Moreover, ocean shipping is one of the most significant contributors to sulfur oxides, nitrogen oxides, and particulate matter emissions. Global shipping contributes 13% of human-caused sulfur emissions and 2.6% of anthropogenic carbon dioxide emissions. As a major source of pollutant emissions, the marine industry faces several challenges related to emission regulations. The International Maritime Organization (IMO) has established a framework for reducing the carbon intensity of shipping: 40% reduction relative to 2008 levels by 2030 and 70% reduction by 2050. As the aviation sector, the maritime shipping sector is difficult to decarbonize through electrification. Biofuels offer the best opportunities for decarbonizing marine shipping in the near and medium-term. Advanced biofuels such as pyrolysis bio-oil offer the low-cost potential for meeting carbon reduction goals. For instance, the pyrolysis bio-oil exhibited promising marginal CO2 abatement costs at less than $100/tonne CO2-equivalent at a heavy fuel oil price greater than $1.10/gal [1]. As a potential biofuel option for low-carbon maritime shipping, this presentation focuses on a comparative techno-economic analysis (TEA) of bio-oils produced via a fast pyrolysis-based conversion pathway. The pathway converts a 50/50 blend of forest residues and clean pine to bio-oil via three process options: fast pyrolysis without vapor upgrading, and fast pyrolysis with vapor phase upgrading over ZSM-5 zeolite catalyst and Pt/TiO2 catalyst. The process configuration and operation variation led to different capital and operating costs, as well as the resulting raw bio-oil’s yield and quality, e.g., the water content, total acid number, and carboxylic acid number. The study also determined the minimum upgrading of bio-oils required to enable blending with very low sulfur fuel oil (VLSFO), with the associated costs reflected in TEA. This study shows that bio-oil could be a cost-effective fuel option for decarbonizing maritime shipping. Further research is required with respect to biofuel blending properties, such as compatibility with existing fuel system infrastructure and suitable engine performance.

BIOMASS FUELS↗

DOE OSTI2023

Refinery Perspective on Decarbonizing with Marine Biofuels

This work seeks to understand what biofuel production pathways a refinery might prefer to produce very low sulfur fuel oil (VLSFO) for marine applications. A comprehensive refinery optimization model was modified to allow for (1) direct blending of soy biodiesel, renewable diesel, Fischer-Tropsch diesel, and several pyrolysis oils and (2) indirect blending of all pyrolysis oils via co-processing in a fluidized catalytic cracker (FCC) and diesel hydrotreater into the marine fuel pool. Results showed that preferred pathways to bio-VLSFO production included co-processing low-quality pyrolysis oil in a FCC to blend the resulting biogenic light cycle oil, directly blending soy biodiesel, and directly blending small quantities of pyrolysis oil. Bio-VLSFO production costs were compared to those of fossil VLSFO subject to different marine fuel demands, benchmark crude oil prices, and biogenic fractions in the finished product. Given benchmark crude oil prices over 60 $/bbl, bio-VLSFO production appeared to be significantly cheaper than fossil VLSFO. Corresponding marginal abatement costs of CO 2 mostly ranging from -300 to 350 $/ton of CO 2 were also determined using a simplified but novel approach to allow for a comparison to other decarbonization strategies. In conclusion, this work indicates that low-sulfur contents in biofuels, relatively relaxed specifications for marine fuels, and current difficulties in meeting VLSFO specifications with crude oils can combine to make bio-VLSFO production cost-effective. Moreover, marine fuels appear to be a good entry point for refiners to start decarbonizing with biofuel pathways that could eventually be extended to other product pools.

09 BIOMASS FUELS↗

DOE OSTI2020

In Situ Catalytic Fast Pyrolysis using Red Mud Catalyst: Impact of catalytic fast pyrolysis temperature and biomass feedstocks

Catalytic fast pyrolysis (CFP) has been considered as a very promising approach for converting lignocellulosic biomass into higher-quality bio-oils followed by hydrotreating to produce fuelrange products. A reactive, robust, and low-cost catalyst is required to drive the CFP process. Red mud, a side-product produced during the refining of bauxite to alumina, appears to be an effective catalyst for in situ CFP of biomass. In this paper, we report the impact of CFP reaction temperature on the conversion of a pinyon juniper feedstock to bio-oils using red mud as the catalyst and then to fuel-range hydrocarbons by hydrotreating of the produced bio-oil. The yield and quality of the CFP bio-oil produced and the yield and quality of hydrotreated final products were determined. When the CFP process temperature was lowered from 450 to 400ºC, the bio-oil yield increased with minimal differences in the oxygen content, hydrogen-to-carbon ratio, water content, etc. In addition, CFP bio-oils at both temperatures were processed in a single-stage continuous hydrotreater without reactor plugging during the testing period (i.e., ~100 hours on stream). The yield of CFP bio-oil produced at 400ºC was lower than the yield at 450ºC. However, the overall yield, from biomass to hydrocarbon fuel, was still higher for CFP processing at 400ºC than for processing at 450ºC. This indicates the potential for enhancing overall carbon efficiency, including CFP processing and hydrotreating, by employing red mud catalysts for biomass pyrolysis and tuning the CFP parameters. Detailed analysis of bio-oil and hydrotreated products showed a lower content of lignin-derived species in both samples. Furthermore, CFP processing of three different biomass feedstocks corroborated red mud catalyst development for producing improved quality bio-oil and, when combined with hydrotreating, for the production of fuel range hydrocarbons.

Santosa, Daniel M.↗

DOE OSTI2023

Proteomes reveal metabolic capabilities of Yarrowia lipolytica for biological upcycling of polyethylene into high-value chemicals

ABSTRACT Polyolefins derived from plastic wastes are recalcitrant for biological upcycling. However, chemical depolymerization of polyolefins can generate depolymerized plastic (DP) oil, comprising of a complex mixture of saturated, unsaturated, even, and odd hydrocarbons suitable for biological conversion. While DP oil contains a rich carbon and energy source, it is inhibitory to cells. Understanding and harnessing robust metabolic capabilities of microorganisms to upcycle the hydrocarbons in DP oil, both naturally and unnaturally occurring, into high-value chemicals are limited. Here, we discovered that an oleaginous yeast, Yarrowia lipolytica, undergoing short-term adaptation to DP oil robustly utilized a wide range of hydrocarbons for cell growth and production of citric acid and neutral lipids. When growing on hydrocarbons, Y. lipolytica partitioned into planktonic and oil-bound cells with each exhibiting distinct proteomes and amino acid distributions invested in establishing these proteomes. Significant proteome reallocation toward energy and lipid metabolism, belonging to 2 of the 23 Eukaryotic Orthologous Groups classes C and I, enabled robust growth of Y. lipolytica on hydrocarbons, with n-hexadecane as the preferential substrate. This investment was even higher for growth on DP oil where classes C and I were ranked one and two, respectively, and many associated proteins and pathways were expressed and upregulated including the hydrocarbon degradation pathway, Krebs cycle, glyoxylate shunt and, unexpectedly, propionate metabolism. However, a reduction in proteome allocation for protein biosynthesis, at the expense of the observed increase toward energy and lipid metabolisms, might have caused the inhibitory effect of DP oil on cell growth. IMPORTANCE Sustainable processes for biological upcycling of plastic wastes in a circular bioeconomy are needed to promote decarbonization and reduce environmental pollution due to increased plastic consumption, incineration, and landfill storage. Strain characterization and proteomic analysis revealed the robust metabolic capabilities of Yarrowia lipolytica to upcycle polyethylene into high-value chemicals. Significant proteome reallocation toward energy and lipid metabolisms was required for robust growth on hydrocarbons with n-hexadecane as the preferential substrate. However, an apparent over-investment in these same categories to utilize complex depolymerized plastic (DP) oil came at the expense of protein biosynthesis, limiting cell growth. Taken together, this study elucidates how Y. lipolytica activates its metabolism to utilize DP oil and establishes Y. lipolytica as a promising host for the upcycling of plastic wastes.

1-alkenes↗

DOE OSTI2022

Pressure Barrier Applicability to Polymer Flood Design

Effective oil displacement from a reservoir requires adequate and properly directed pressure gradients in areas of high oil saturation. If the polymer bank is too large or too viscous during a polymer flood, the pressure drop from the injection well to the polymer front may act as a pressure barrier by usurping most of the downstream driving force for oil displacement. Polymer injection pressures must be limited. The maximum allowable injection pressure is commonly constrained by caprock integrity, injection equipment, and/or regulations, even though fractures can be beneficial to polymer injectivity (and even sweep efficiency in some cases). This paper examines when the pressure-barrier concept limits the size and viscosity of the polymer bank during a polymer flood. Both analytical and numerical methods are used to address this issue. We examine the relevance of the pressure barrier concept for a wide variety of circumstances, including oil viscosities ranging from 10-cp (like at Daqing, China) to 1650-cp (like at Pelican Lake, Alberta), vertical wells (like at Tambaredjo, Suriname) versus horizontal wells (like at Milne Point, Alaska), single versus multiple layered reservoirs, permeability contrast, and with versus with crossflow between layers. We also examine the relation between the pressure-barrier concept and fractures and fracture extension during polymer injection. We demonstrate that in reservoirs with single layers, the pressure-barrier concept only limits the optimum viscosity of the injected polymer if the mobility of the polymer bank is less than the mobility of the displaced oil bank. The same is true for multi-zoned reservoirs with no crossflow between layers. Thus, for these cases, the optimum polymer viscosity is likely to be dictated by the mobility of the oil bank, unless other factors (like fracture extension) intervene. For multi-zoned reservoirs with free crossflow between layers, the situation is different. A compromise must be reached between injected polymer viscosity and the efficiency of oil recovery. The relevance of our findings is applied to operations for several existing polymer floods. This work is particularly relevant to viscous-oil reservoirs (like Pelican Lake and others) where the injected polymer viscosities are substantially lower than the oil viscosity

Wang, Dongmei↗

NASA NTRS1984

Behaviors of Polymer Additives Under EHL and Influences of Interactions Between Additives on Friction Modification

Polymer additives have become requisite for the formulation of multigrade engine oils. The behavior of polymethacrylate (PMA)-thickened oils as lubricants in concentrated contacts under nominal rolling and pure sliding conditions was investigated by conventional optical interferometry. The PMA thickened oils behaved differently from the base oil in the formation of elastohydrodynamic (EHL) films. The higher the elastohydrodynamic molecular weight of the PMA contained in the lubricant, the thinner was the oil film under EHL conditions. The film thickness of shear-degraded PMA-thickened oils was also investigated. The behavior of graphite particles dispersed in both the base oil and the PMA-thickened oil was studied under pure sliding by taking photomicrographs. Many kinds of additives are contained in lubricating oil and the interactions between additives are considered. The interactions of zinc-organodithiophosphates (ZDP) with other additives is discussed.

Sakurai, T.↗

NASA NTRS2002

In-situ, On-demand Lubrication System for Space Mechanisms

Many of today's spacecraft have long mission lifetimes. Whatever the lubrication method selected, the initial lubricant charge is required to last the entire mission. Fluid lubricant losses are mainly due to evaporation, tribo-degradation, and oil creep out of the tribological regions. In the past, several techniques were developed to maintain the appropriate amount of oil in the system. They were based on oil reservoirs (cartridges, impregnated porous parts), barrier films, and labyrinth seals. Nevertheless, all these systems have had limited success or have not established a proven record for space missions. The system reported here provides to the ball-race contact fresh lubricant in-situ and on demand. The lubricant is stored in a porous cartridge attached to the inner or the outer ring of a ball bearing. The oil is released by heating the cartridge to eject oil, taking advantage of the greater thermal expansion of the oil compared to the porous network. The heating may be activated by torque increases that signal the depletion of oil in the contact. The low surface tension of the oil compared to the ball bearing material is utilized and the close proximity of the cartridge to the moving balls allows the lubricant to reach the ball-race contacts. This oil resupply system can be used to avoid a mechanism failure or reduce torque to an acceptable level and extend the life of the component.

Marchetti, Mario↗

DOE OSTI2021

Use of a Lewis acid, a Brønsted acid, and their binary mixtures for the hydrothermal liquefaction of lignocellulose

The main objective of the present study is to investigate the effect of a Lewis acid, Brønsted acid, and their combined use on the hydrothermal liquefaction of lignocellulosic biomass. Hydrothermal liquefaction of teak wood was conducted at 250, 300 and 350 °C for 15, 30 and 60 min. Hydrothermal liquefaction of teak wood was carried out at 300 °C for 30 min (the best optimum conditions) without and with the use of Mg(ClO 4 ) 2 , HClO 4 , and HClO 4 /Mg(ClO 4 ) 2 at various loadings (2–10 mmol/15 g wood). The highest bio-oil yield was obtained with the non-catalytic run. All tested catalysts have negative effect on bio-oil yields. The bio-oil yields generally decreased with increasing the catalyst loadings. The deoxygenation degree in bio-oils changed depending on the type of catalyst and loading. A high degree of de-oxygenation took place with Mg(ClO 4 ) 2 catalysts. An increased catalyst loading led to decreased aromatic contents of bio-oils catalyzed by either Mg(ClO 4 ) 2 or HClO 4 . The use of a catalyst increased total naphtha fractions in bio-oils. The highest heating value of the bio-oil was estimated to be approximately 30 MJ/kg. Gas chromatography–mass spectrometry analysis revealed that the bio-oils from the non-catalytic and catalytic runs contained aldehydes, ketones, phenols, acids, esters and alcohols. Furthermore, the relative yields of the oxygenated compounds were affected by catalyst type.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Co-depolymerization of lignin and plastic waste using hydrothermal liquefaction process

Sustainable valorization of underutilized lignin and plastic waste beyond incineration is critical for producing renewable fuels. Hydrothermal liquefaction (HTL) provides a promising approach to convert wet lignin and plastics into high-quality oils without the need for prior drying of wet lignin. Here, this study examines the effects of temperature (300–400 °C), residence time, and polymer molecular weight on product yield and composition during HTL of polyethylene (PE), polypropylene (PP), and lignin under subcritical and supercritical water conditions. For PE, oil yields increased with temperature, with low molecular weight (LMW) PE achieving a maximum of ∼93 % at 400 °C for 30 min, while high molecular weight (HMW) PE reached ∼86 % at 400 °C for 1 h. Lignin and PP exhibited optimal oil yields at intermediate temperatures, decreasing at higher temperatures due to secondary reactions and char formation. Lignin yielded a maximum of ∼22 % oil at 300 °C for 30 min, LMW PP ∼88 % at 375 °C for 1 h, and HMW PP ∼83 % at 400 °C for 1 h. GC–MS analysis revealed that lignin oils were rich in phenols and alkylphenols, while PE and PP oils were dominated by paraffins and olefins. Oxygenated compounds in PE decreased at higher temperatures, improving oil quality. Co-liquefaction of lignin with plastics enhanced oil yields and energy content under specific conditions, demonstrating synergistic effects dependent on plastic type, molecular weight, and HTL conditions. These findings highlight the potential of HTL to produce high-energy, value-added fuels from lignin–plastic mixtures.

09 - BIOMASS FUELS↗