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Are we modeling the properties of unconventional shales correctly?

Technological advancements have led to impressive growth in hydrocarbon (HC) production from unconventional shale reservoirs. However, major limiting factors in shale gas development are i) low recovery of gas in place (<20%), (ii) a rapid decline in well productivity, iii) release of contaminants, despite the use of advanced hydraulic fracturing fluids and multiple fracturing stages. This is mainly due to a lack of understanding of the nanoscale physicochemical properties of shales, especially that of kerogen, the macromolecule that is not only the source of the majority of the HC’s in shales but also holds most of the HC’s in adsorbed state. Over the last few years, a large number of studies have been published on simulating the physicochemical properties of shale utilizing molecular models of kerogen. However, the molecular models of kerogen input into these simulations are based on the kerogen “type” derived from a very limited number of shale samples. In this paper, we examine the variations that can exist in kerogen structure within a particular kerogen “type” across different shale basins and single shale basin at similar thermal maturity levels. We propose that using kerogen “type” based structural models for molecular simulations could lead to inaccurate estimation of HC reserves, HC recovery, HC production, frackability, and quantity and quality of produced water. Our study highlights the need for developing a better classification of kerogen based on its “molecular structure” instead of “type” for a more accurate prediction of physicochemical properties of shales.

04 OIL SHALES AND TAR SANDS↗

Directing the adsorption and assembly of laponite nano-discs at oil–water interfaces

Achieving tunable controls on the adsorption and self-assembly of nanoscale building blocks at immiscible fluid interfaces is essential for synthesizing advanced materials, stabilizing emulsions, and the sustainable storage and recovery of fluids. Although extensive efforts have been directed toward resolving the assembly of spherical nanoparticles at water–hydrocarbon interfaces, 2D nanoparticles have received far less attention. In this study, we developed novel controls to direct the adsorption and assembly of 2D laponite nano-discs (diameter = ∼30 nm and thickness = ∼1 nm) at water–heptane interfaces using traces of sodium dodecyl sulfate (SDS) surfactant, demonstrated by advanced in situ small-angle X-ray scattering, atomic force microscopy, spinning drop tensiometer measurements and molecular dynamics simulations. The results show that SDS surfactant displaces the adsorbed laponite nano-discs from the interface toward the aqueous phase. The extent of this displacement increases with SDS concentration such that high SDS concentrations convert laponite-rich interfaces to SDS-rich interfaces free of laponite nano-discs. This transformation is associated with significant alterations in the rheological and nanomechanical properties of the host interface. In this context, reduction in interfacial tension and interfacial stiffness and an increase in the interfacial deformation is observed on increasing the SDS concentration from 0 to 0.1 wt%. The displacement of laponite nano-discs from the interface is driven by strong electrostatic interactions between the hydrophilic SDS group and interfacial water molecules. These studies unlock new insights into the adsorption and assembly of 2D nanoscale particles at water–hydrocarbons interfaces that are relevant for various applications related to energy and environmental science and engineering.

interfacial tension↗

CO 2 Storage Site Screening Platform Development and CO 2 Storage Resource Analysis in SECARB Offshore Reservoirs Using SAS Viya

A major goal of the SECARB Offshore Partnership (DE-FE0031557) is to screen deep saline aquifers and hydrocarbon reservoirs in the central Gulf of Mexico for CO 2 sequestration and CO 2 -enhanced oil and gas recovery (EOR/EGR) and estimate the corresponding CO 2 storage resources for select reservoirs. CO 2 storage potential associated with offshore CO 2 -EOR is considerable and likely represents “low hanging fruit” for near-term CO 2 storage given the in-place infrastructure in the region. It is for these reasons that this assessment focuses on oil and gas fields. To this end, three major objectives have been completed and include (1) managing geological data derived from different sources, (2) building a reservoir screening platform for CO 2 storage, and (3) ranking the reservoirs based on the estimated CO 2 storage resources. The SAS ® Viya platform was used for data management and analytics. The Viya platform is a cloud service platform that provides data integration, data management, quick analytics, data visualization, machine learning functions, and application programming interfaces (APIs) for multi-programming languages. Different sources of data containing geologic information, reservoir properties, and EOR/EGR information were collected, cleaned, formatted, and loaded into the SAS ® Viya platform for evaluation. The major geological characteristics of both shelf and deep-water areas of the central Gulf were examined and compared to define the appropriate reservoir screening criteria. Next, a CO 2 storage site screening system was built in the SAS ® Viya platform with the pre-defined criteria. Finally, the CO 2 storage resources of the screened reservoirs were calculated and reported at the BOEM field level to identify fields with the highest estimated CO 2 storage resource. The fields with the largest total estimated CO 2 storage resource are located in the Mississippi Canyon protraction area. Due to proximity to the Mississippi Delta (indicative of less infrastructure) and large estimated CO 2 storage resources, future development activities may wish to focus efforts in the Mississippi Canyon protraction area.

02 PETROLEUM↗

Un-Numbered Operational Areas PRL 229 Railroad Tie Disposal Area Pond Confirmation Sampling Report

This Confirmatory Sampling (CS) Report (CSR) was prepared for the National Aeronautics and Space Administration (NASA), Kennedy Space Center (KSC), Florida in accordance with the CS Work Plan (CSWP) (HGL, 2022a). The CSR summarizes investigation activities performed on the Railroad Tie Disposal Area (RTDA) of the Un-Numbered Operational Areas (UNOA), Potential Release Location (PRL) 229 located at KSC. HydroGeoLogic, Inc. (HGL) prepared this report under Contract Number 80KSC019D0012. The purpose of the CSR is to provide information to evaluate the level of potential contamination in surface water and sediment samples collected from the RTDA PRL 229 Pond and determine if contaminants pose unacceptable risks to ecological receptors. The CSR provides analytical data of 10 sets of surface water and sediment samples collected in 2021. Surface water samples were analyzed for volatile organic compounds (VOCs), semi-volatile organic compounds (SVOCs), polynuclear aromatic hydrocarbon (PAHs), metals, hardness, and salinity, while sediment samples were analyzed for metals, total organic carbon (TOC), SVOCs, PAHs, and total petroleum hydrocarbons (TPH). The CSR includes a Screening Level Ecological Risk Assessment (SLERA) conducted under KSC’s Resource Conservation and Recovery Act (RCRA) Corrective Action Program to determine if unacceptable risks to ecological receptors exist at PRL 229 Pond. Metals and PAHs were detected in surface water samples, including detections of antimony, arsenic, barium, calcium, copper, lead, magnesium, thallium, zinc, anthracene, benzo(a)anthracene, benzo(a)pyrene, benzo(b)fluoranthene, benzo(g,h,i)perylene, benzo(k)fluoranthene, chrysene, dibenzo(a,h)anthracene, fluoranthene, indeno(1,2,3-c,d)pyrene and pyrene. Based on measured salinity (1.03 to 1.21 parts per thousand), the pond was identified as freshwater. Sediment analytical results also contained detections of metals and PAHs, including antimony, arsenic, barium, beryllium, cadmium, chromium, copper, lead, mercury, nickel, selenium, thallium, zinc, anthracene benzo(a)anthracene, benzo(a)pyrene, benzo(b)fluoranthene, benzo(g,h,i)perylene, benzo(k)fluoranthene, chrysene, dibenzo(a,h)anthracene, fluoranthene, indeno(1,2,3-c,d)pyrene and pyrene. Potential risks to ecological receptors were evaluated in accordance with the SLERA Work Plan and the Decision Process Document for the Resource Conservation and Recovery Act (RCRA) Corrective Action Program at KSC (DPD) (Geosyntec, 2019), and using the 2021 sediment and surface water analytical results. Potential ecological receptors evaluated in the SLERA include the aquatic community, benthic invertebrates, aquatic birds, and aquatic mammals. The SLERA included Steps 2a through 2c of the Ecological Risk Assessment (ERA) process in accordance with the DPD. Using multiple lines of evidence, the SLERA concluded that many of the detected analytes are present at concentrations similar to those in background or reference locations at KSC, and/or at concentrations that would not pose a significant risk to ecological communities. There are no screening values available for the avian community, and PAHs are bioaccumulative compounds. For this reason, food web modeling was completed as a supplement to Step 2c to provide a quantitative evaluation of this exposure pathway. Food web modeling indicates that PAHs are unlikely to pose a risk to birds exposed to site sediment and surface water. Based on the results of the SLERA, the contaminants in sediment and surface water pose no to minimal risk to the ecological communities that could live or forage at the site. Based on the results of the SLERA, no further study is recommended for the RTDA Pond at PRL 229.

Confirmation Sampling↗

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↗

Atmospheric Capture On Mars (and Processing)

The ultimate destination of NASA's human exploration program is Mars. In Situ Resource Utilization (ISRU) is a key technology required to enable such missions, as first proposed by Prof. Robert Ash in 1976. This presentation will review progress in the systems required to produce rocket propellant, oxygen, and other consumables on Mars using the carbon dioxide atmosphere and other potential resources. For many years, NASA, commercial companies, and academia have been developing, and demonstrating techniques to capture and purify Martian atmospheric gases for their utilization for the production of hydrocarbons, oxygen, and water in ISRU systems. Other gases will be required to be separated from Martian atmospheric gases to provide pure CO2 for processing elements. Significant progress has been demonstrated in CO2 collection via adsorption by molecular sieves, freezing, and direct compression. Early stage work in adsorption in Ionic Liquids followed by electrolysis to oxygen is also underway. In addition, other Martian gases, such as nitrogen and argon, occur in concentrations high enough to be useful as buffer gas and could be captured as well. Gas separation requirements include, but are not limited to the selective separation of: (1) methane and water from unreacted carbon oxides (CO2-CO) and hydrogen typical of a Sabatier-type process, (2) carbon oxides and water from unreacted hydrogen from a Reverse Water-Gas Shift process, and (3) carbon oxides from oxygen from a trash/waste processing reaction.

propellant production↗

Assessment of Air Quality in the Shuttle and International Space Station (ISS) Based on Samples Returned by STS-102 at the Conclusion of 5A.1

The toxicological assessment of air samples returned at the end of the STS-102 (5A.1) flight to the ISS is reported. ISS air samples were taken in late February 2001 from the Service Module, FGB, and U.S. Laboratory using grab sample canisters (GSCs) and/or formaldehyde badges . A "first-entry" sample of the multipurpose logistics module (MPLM) atmosphere was taken with a GSC, and preflight and end-of-mission samples were obtained from Discovery using GSCs. Analytical methods have not changed from earlier reports, and all quality control measures were met for the data presented herein. The two general criteria used to assess air quality are the total-non-methane-volatile organic hydrocarbons (NMVOCs) and the total T-value (minus the CO2 contribution). Control of atmospheric alcohols is important to the water recovery system engineers, hence total alcohols were also assessed in each sample. Formaldehyde is quantified separately.

James, John T.↗

Development of a water recovery subsystem based on Vapor Phase Catalytic Ammonia Removal (VPCAR)

An integrated engineering breadboard subsystem for the recovery of potable water from untreated urine was designed, fabricated and tested. It was fabricated from commercially available components without emphasis on weight, volume and power requirement optimization. Optimizing these parameters would make this process competitive with other spacecraft water recovery systems. Unlike other phase change systems, this process is based on the catalytic oxidation at elevated temperatures of ammonia and volatile hydrocarbons to innocuous products; therefore, no urine pretreatment is required. The testing program consisted of parametric tests, one month of daily tests, and a continuous run of 165 hours. The recovered water is low in ammonia, hydrocarbons and conductivity and requires only adjustment of its pH to meet drinking water standards.

Budininkas, P.↗

The Potential for Electrons to Molecules Using Solar Energy

Solar photovoltaics (PV) do and will continue to play an important role in the electric power sector and can potentially support other sectors that are in need of decarbonized energy sources. Chemicals such as hydrogen, ammonia, and hydrocarbons including ethylene are currently produced from natural gas and crude oil. Thus, processes to produce them emit carbon dioxide and other greenhouse gases both directly and in upstream feedstock recovery processes. Electrons-to-molecules (E2M) technologies are being developed to convert carbon dioxide, water, and atmospheric nitrogen to desired chemical products and they are large electricity loads. Thus, they are emerging as a potential applications for PV. In its essence, they can act as electrochemical energy storage, thereby providing a means to further utilize the energy generated from PV and store it in molecular form. E2M systems offer an array of potential products and system designs that can be tailored to different end-uses and applications. It involves electrochemical conversion which uses electricity to break molecular bonds and produce new molecules. Various electrochemical conversion technologies split water into hydrogen and oxygen, reduce carbon dioxide into other hydrocarbon molecules, and several other possible combinations. While this Chapter does not attempt to provide an exhaustive summary or analysis of the potential products from E2M systems, it does provide an initial overview of the potential opportunities and challenges for PV and E2M systems in this space. This Chapter considers the potential for E2M to produce key chemicals and fuels that currently rely on hydrocarbons for production, either as a reactant or a source of high-grade heat.

14 SOLAR ENERGY↗

Catalytic distillation water recovery subsystem

An integrated engineering breadboard subsystem for the recovery of potable water from untreated urine based on the vapor phase catalytic ammonia removal was designed, fabricated and tested. Unlike other evaporative methods, this process catalytically oxidizes ammonia and volatile hydrocarbons vaporizing with water to innocuous products; therefore, no pretreatment of urine is required. Since the subsystem is fabricated from commercially available components, its volume, weight and power requirements are not optimized; however, it is suitable for zero-g operation. The testing program consists of parametric tests, one month of daily tests and a continuous test of 168 hours duration. The recovered water is clear, odorless, low in ammonia and organic carbon, and requires only an adjustment of its pH to meet potable water standards. The obtained data indicate that the vapor phase catalytic ammonia removal process, if further developed, would also be competitive with other water recovery systems in weight, volume and power requirements.

Budininkas, P.↗

Two-stage reusable launch system utilizing a winged core vehicle and glideback boosters

A near-term technology launch system is described in which Space Shuttle main engines are used on a manned orbiter and also on twin strap-on unmanned boosters. The orbiter has a circular body and clipped delta wings. The twin strap-on boosters have a circular body and deployable oblique wings for a glideback recovery. The dry and gross weights of the system, capable of delivering 70klb of cargo to orbit, are compared with a similar system with hydrocarbon-fueled boosters and with the current Shuttle.

Macconochie, Ian O.↗

Hydrocarbon Burn Facility SWMU 007 Interim Groundwater Monitoring Report Kennedy Space Center, Florida

This Interim Groundwater Monitoring (IGWM) Report presents the findings of IGWM activities completed in November/December 2020 for the Volatile Organic Compound (VOC) Area of the Hydrocarbon Burn Facility (HBF) at Kennedy Space Center (KSC), Florida. HBF has been designated as Solid Waste Management Unit 007 under the KSC Resource Conservation and Recovery Act Corrective Action Program.

Jennifer Buel↗

Hydrocarbon Burn Facility SWMU 007 Interim Groundwater Monitoring Report Kennedy Space Center, Florida

This Interim Groundwater Monitoring (IGWM) Report presents the findings of IGWM activities completed in November 2021 along with an October 2021 direct push technology (DPT) investigation to confirm plume stability for the Volatile Organic Compound (VOC) Area of the Hydrocarbon Burn Facility (HBF) at Kennedy Space Center (KSC), Florida. HBF has been designated as Solid Waste Management Unit 007 under the KSC Resource Conservation and Recovery Act Corrective Action Program.

Jennifer Buel↗

Nano-crystalline porous tin oxide film for carbon monoxide sensing

A tin oxide sol is deposited on platinum electrodes (12) of a sensor (10). The sol is calcined at a temperature of 500 to 800.degree. C. to produce a thin film of tin oxide with a thickness of about 150 nm to 2 .mu. and having a nano-crystalline structure with good stability. The sensor rapidly detects reducing gases, such as carbon monoxide, or hydrocarbons and organic vapors. Sensors using films calcined at around 700.degree. C. have high carbon monoxide selectivity with a response time of around 4 minutes and a recovery time of 1 minute, and therefore provide good detection systems for detection of trace amounts of pollutants such as toxic and flammable gases in homes, industrial settings, and hospitals.

Liu, Chung-Chiun↗

Hydrocarbon Burn Facility SWMU 007 Interim Groundwater Monitoring Report Kennedy Space Center, Florida

This Interim Groundwater Monitoring (IGWM) Report presents the findings of IGWM activities completed in November 2022, and March through May 2023 including results from existing and newly installed groundwater monitoring wells and direct push technology (DPT) groundwater sampling in the Volatile Organic Compound (VOC) Area of the Hydrocarbon Burn Facility (HBF) at Kennedy Space Center (KSC), Florida. HBF has been designated as Solid Waste Management Unit (SWMU) 007 under the KSC Resource Conservation and Recovery Act Corrective Action Program.

Jennifer Buel↗

Four-man rated dual catalyst system for the recovery of water from urine

The catalytic system was integrated with a 4-man rated urine wick evaporator. During operation, urine vapor produced by the wick-evaporator was treated in the catalytic system to remove ammonia and volatile hydrocarbons, and water was recovered by condensation in a water cooled condenser. The system operated completely automatically and required no manual adjustments, except periodic supply of urine and removal of the recovered water. Although the system was designed for treating 0.325 kg urine per hour, this rate could be achieved only with a fresh wick, then gradually decreased as the wick became saturated with urine solids. The average urine treatment rates achieved during each of the three endurance tests were 0.137, 0.217, and 0.235 kg/hr. The quality of the recovered water meets drinking water standards, with the exception of a generally low pH.

Budininkas, P.↗

Hydrocarbon Burn Facility, SWMU 007 PER- and Polyfluoroalkyl Substances (PFAS) Assessment report Addendum Kennedy Space Center, Florida

This document discusses the Per-and Polyfluoroalkyl Substances (PFAS) assessment activities performed from December 2020 through November 2021 at the Hydrocarbon Burn Facility (HBF) located at Kennedy Space Center (KSC), Florida. The HBF site has been designated Solid Waste Management Unit (SWMU) 007 under KSC’s Resource Conservation and Recovery Act (RCRA) Corrective Action Program. This PFAS Assessment Report Addendum (ARA) was prepared by Tetra Tech, Inc., for the National Aeronautics and Space Administration (NASA) under Indefinite Delivery Indefinite Quantity (IDIQ) Contract 80KSC019D0011-80KSC019F0077.

Jennifer M. Buel↗

Integrated Simulations of the Sabatier and Carbon Vapor Deposition Reactor to Understand Its Impacts to Operations and Performance

The carbon vapor deposition (CVD) reactor is a technology developed by Honeywell Aerospace to convert methane, at high temperatures, into hydrogen and solid carbon. This element is coupled with a Sabatier reactor to support a closed-loop environmental control and life support system with the aim of achieving nearly complete oxygen recovery (> 95%). Initial open-loop, brassboard CVD reactor tests and simulations have shown the CVD’s ability to achieve moderately high methane conversion and high hydrogen selectivity. However, in an integrated system, additional deficiencies are expected due to recycling of unreacted or extraneous species from the Sabatier reactor (e.g., carbon dioxide, hydrogen, water) and CVD reactor (e.g., hydrocarbons, methane, etc.). Sabatier and CVD reactor models were integrated and simulated to predict potential impacts to individual reactors’ and the overall system’s performance. The simulations showed that increasing the recycle of the CVD effluent hydrogen combined with decreasing the system inlet hydrogen flow rate (i.e., drawing a stoichiometric flow rate from an electrolyzer) can lead to an oxygen recovery of > 95%. However, system integration comes at a detriment to the individual reactors. The simulations show the initial conversion from the integrated system (Sabatier = 87% and CVD = 59%) to be lower than the standalone systems (Sabatier = 91% and CVD = 69%). Furthermore, transient simulations show substrate densification, leading to worsening methane conversion coupled with increasing acetylene production, which is commensurate with soot formation. Simulations predict a shortening of the maintenance interval (i.e., time until CVD methane conversion drops below 50%) in the integrated system, which would increase the consumable substrate mass. These analyses highlight the importance of long-duration, integrated tests to corroborate these findings as well as suggest potential modifications (e.g., intermediate gas separations) to improve performance.

Air Revitalization↗