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Findings on Subtask 3.1 - Bakken Rich Gas Enhanced Oil Recovery Project

Total in-place oil for the Bakken petroleum system (BPS) (which includes the Bakken and Three Forks Formations) has been estimated to be 600 billion barrels (bbl). However, BPS wells have decline rates as high as 85% over the first 3 years of their lives, and primary recovery factors typically range from 3% to 10% of original oil in place. Given the low initial recovery rates, even small incremental productivity improvements could dramatically increase technically recoverable oil in the BPS. One potential solution is enhanced oil recovery (EOR) using gas injection, such as carbon dioxide (CO2) or hydrocarbon (HC) gases. While commonly used in conventional reservoirs, CO2 EOR in unconventional tight oil reservoirs has been limited to pilot tests. EOR using rich gas (mixture of methane, ethane, and propane) has also been employed in numerous pilots in several unconventional plays and has recently been successfully applied in the Eagle Ford play. If successful, large-scale gas-based EOR in the BPS could dramatically increase oil productivity and recovery factors and extend the life of the play for decades. While CO2 may be a technically suitable working fluid for EOR in the BPS, supplies are limited and costs for using CO2 in EOR pilots are prohibitively high. Meanwhile, produced gas flaring has presented challenges for BPS operators in North Dakota. Analysis conducted by the North Dakota Pipeline Authority indicates that the current gas-gathering infrastructure in North Dakota is insufficient to accommodate all of the associated gas that is produced from the BPS. The geographically isolated location of North Dakota relative to large natural gas markets, combined with suppressed natural gas prices, has made it economically challenging for industry to invest capital in expanding gas-gathering infrastructure in the state. These circumstances led to a research program conducted by the Energy & Environmental Research Center (EERC) in partnership with Liberty Resources Management Company LLC (LR) to examine the potential to use rich gas injection for EOR and mitigate flaring. A rich gas EOR pilot test was designed and executed by LR at its Stomping Horse development area in Williams County, North Dakota. From July 2018 through May 2019, a total of 160 million standard cubic feet (MMscf) of rich produced gas was injected into the BPS using five different wells in a sequential injection strategy. LR’s Leon–Gohrick drill spacing unit (DSU) was used as the test site. Regulatory oversight was provided by the North Dakota Industrial Commission (NDIC). Technical support was provided by the EERC through a series of laboratory, modeling, and field-based activities, and additional post-pilot research activities incorporated learnings from the test, developed new laboratory data, improved fracture modeling methods, and developed machine learning and big data analytics. The results from the Stomping Horse rich gas EOR pilot activities indicate that developing an effective, economical EOR approach for the BPS will require more field tests. Another key lesson learned from the Stomping Horse tests is that detailed pre- and posttest data on reservoir conditions and fluids production are essential. Robust reservoir characterization provides information that is crucial to creating realistic geomodels and conducting valid dynamic simulations of potential EOR scenarios. A detailed understanding of the completions and production history of offset wells is also necessary for valid test result interpretations. This knowledge is essential to designing the operational parameters of injectivity tests and interpreting the results. A conformance control strategy is also essential to success. Laboratory-based examinations of rich gas interactions with reservoir fluids and rocks were conducted, with an emphasis on determining the ability to mobilize oil in the tight reservoir rocks and shales of the BPS. Injection fluid composition was shown to have a positive impact on reducing reservoir oil minimum miscibility pressure (MMP), reducing interfacial tension (IFT), and altering wettability. IFT and contact angle measurements demonstrated that wettability can be altered in the presence of rich gas, suggesting the potential to improve oil recovery. Iterative modeling of surface infrastructure and reservoir performance using data generated by the various project activities was conducted. A geologic model of the Stomping Horse area was built; history-matched oil, gas, and water production was used in simulations of various EOR scenarios. Early programmatic modeling results were used to support LR’s design and operation of the EOR pilot and to provide insight regarding optimization of future commercial-scale BPS EOR design and operations. Post-pilot modeling focused on alternative methods of understanding complex fracture networks and accelerating simulation time. These led to improved simulation run times and provide excellent history-matching results. Several of these iterative models were used as the bases for developing algorithms into machine learning and big data analytics. History matching in reservoir simulation is time-consuming and computer processing-intensive. Machine learning algorithms were created, and an automated history-matching tool was developed. A large set of synthetic reservoir simulations were created to generate well responses (oil, gas, and water production, well bottomhole pressure [BHP], and tracer or propane breakthrough) for a set of EOR operating parameters that included offset well status (open or closed), injectate (rich gas or propane), injection rate, and injection well BHP. A user interface was developed to provide real-time visualization. Machine learning-based models were developed to provide rapid forecasting of well performance given a set of user-defined EOR operating parameters. These predictive models allow the user to modify the offset well status, injection rate, and injection well BHP and rapidly forecast future production performance. The combination of real-time visualization tools with real-time forecasting tools provides a framework for real-time control—operational changes that the EOR site operator can enact (e.g., changing gas injection rates) to affect the observed performance and potentially improve the EOR outcome. There is great reason to be optimistic about the future of EOR in the Bakken. The results of the laboratory studies suggest significant potential for high rates of oil mobilization using produced field gas injection under the right conditions. The results of the lab studies, combined with rigorous statistical analysis of well production data and associated modeling efforts, confirm the notion that fluid mobility within the reservoir is controlled by fractures. As more knowledge is gained about the nature and distribution of fracture networks in the Bakken, the industry will be in a better position to predict and, ultimately, influence fluid mobility. New field tests are necessary to develop a more complete understanding of those conditions. Thoughtful and creatively engineered field tests within a well-characterized geologic setting will yield the fundamental knowledge needed to take Bakken oil production to the next level. 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’s Oil and Gas Research Program and Computer Modelling Group.

04 OIL SHALES AND TAR SANDS↗

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↗

Electrochemical Ammonia Compression

An electrochemical (EC) compressor is a solid-state compression device. For decades, researchers have been studying EC compressors for applications for a variety of energy systems. As the world transitions away from fossil fuel energy sources, EC compression emerges as a promising technique for energy storage, specifically energy stored in the form of pressurized ammonia. Ammonia is also a commonly used refrigerant. The present studies examine the viability of EC compression for ammonia storage and refrigeration. EC ammonia compression increases the concentration of an ammonia-hydrogen mixture via the input of electrical energy and a series of chemical reactions. A polymer electrolyte membrane separates the low-concentration side from the high-concentration side of the device. On the low-pressure (anode) side hydrogen atoms oxidize and react with ammonia molecules, forming positively charge ammonium ions. The ions traverse the membrane electrolytically. The ammonium ions are reduced and revert back to hydrogen and ammonia upon reaching the high-pressure (cathode). An external circuit provides the current needed to sustain the reactions. In this project, we studied the performance of the ammonia EC compressor under a variety of different conditions. We replicated preliminary data and using a small cell with 5 cm2 of active area. We demonstrated the operation of larger cells with 100 cm2 of active area. Further, we used a commercially available hydrogen EC compressor stack to analyze the scaled-up compressor performance. While previous experiments examined only the transient EC compressor performance, we developed test facilities that allowed the compressor to reach steady state. We analyzed the effects of pressure and current on the EC compressor performance. We measured the flow rates of gas leaving the compressors and analyzed the composition using gas chromatography. We tested methods of separating ammonia from the effluent vapor, which contained hydrogen and water vapor. We found that back diffusion adversely affected the performance, especially when we maintained high pressure lifts.

25 ENERGY STORAGE↗

Influence of Nanoconfinement and Elevated Temperatures on Geocolloid-Facilitated Transport of Energy related Contaminants

Fossil fuels obtained using hydraulic fracturing and nuclear energy are deemed crucial for meeting the current and future energy demands of the United States. The utilization of these resources, especially fossil fuels from hydraulic fracturing, has increased rapidly within the last decade. However, with the increasing levels of hydraulic fracturing activities, the occurrence and fate of chemicals used in these processes in the geosystem, as well as the potential consequences of their interactions with environment and geosystems (e.g. mineral-based geocolloids and geosurfaces), have been increasingly recognized as issues warranting consideration owing to the toxic nature of these chemicals. Scientific results originated from this project has brought better understandings on how such contaminants can preferentially or adversely interact with geosystems and how geocolloids can facilitate their transport by realistically mimicking geological conditions and environments in the laboratory level for the first time. Based on such knowledge, it may eventually lead to the development of mitigation strategies for reducing and minimizing the transport and wide distribution of contaminants and pollutants. This aspect is important for the society to ensure that energy-related contaminants do not find their way to waterbodies that are used as drinking water or irrigation. The project is also anticipated to increase public awareness about potential adverse effects of energy systems on the geosphere and environment and may motivate society to consider better mitigation strategies to prevent such occurrences.

(Nano)Confinement↗

SUBTASK 3.12 – GASIFICATION, WARM-GAS CLEANUP, AND LIQUID FUELS PRODUCTION WITH ILLINOIS COAL

The goal of this project was to evaluate the performance of Illinois No. 6 coal blended with biomass in a small-scale entrained-flow gasifier and demonstrate the production of liquid fuels under three scenarios. The first scenario used traditional techniques for cleaning the syngas prior to Fischer–Tropsch (FT) synthesis, including gas sweetening with a physical solvent. In the second scenario, the CO2 was not removed from the gas stream prior to FT synthesis. In the third scenario, only warm-gas cleanup techniques were used, such that the feed gas to the FT unit contained both moisture and CO2. The results of the testing showed that the liquid fuels production from the FT catalyst was significantly hindered by the presence of moisture and CO2 in the syngas. Further testing would be needed to determine if this thermally efficient process is feasible with other FT catalysts. This subtask was funded through the EERC–U.S. Department of Energy (DOE) Joint Program on Research and Development for Fossil Energy-Related Resources Cooperative Agreement No. DE-FC26-08NT43291. Nonfederal funding was provided by the Illinois Clean Coal Institute.

01 COAL, LIGNITE, AND PEAT↗

Subtask 2.18 - Advancing CO 2 Capture Technology: Partnership for CO 2 Capture (PCO 2 C) Phase III

Industries and utilities continue to investigate ways to decrease their carbon footprint. Carbon capture and storage (CCS) can enable existing power generation facilities to meet the current national CO 2 reduction goals. The Partnership for CO2 Capture Phase III focused on several important research areas in an effort to find ways to decrease the cost of capture across both precombustion and postcombustion platforms. Two flue gas pretreatment technologies for postcombustion capture, an SO 2 reduction scrubbing technology from Cansolv Technologies Inc. and the Tri-Mer filtration technology that combines particulate, NOx, and SO 2 control, were evaluated on the Energy & Environmental Research Center’s (EERC’s) pilot-scale test system. Pretreating the flue gas should enable more efficient, and therefore less expensive, CO 2 capture. Both technologies were found to be effective in pretreating flue gas prior to CO 2 capture. Two new postcombustion capture solvents were tested, one from the Korea Carbon Capture and Sequestration R&D Center (KCRC) and one from CO 2 Solutions Incorporated. Both of these solvents showed the ability to capture CO 2 while requiring less regeneration energy, which would reduce the cost of capture. Hydrogen separation membranes from Commonwealth Scientific and Industrial Research Organisation were evaluated through precombustion testing. They are composed of vanadium alloy, which is less expensive than the palladium alloys that are typically used. Their performance was comparable to that of other membranes that have been tested at the EERC. Aspen Plus® software was used to model the KCRC and CO 2 Solutions solvents and found that they would result in significantly improved overall plant performance. The modeling effort also showed that the parasitic steam load at partial capture of 45% is less than half that of 90% overall capture, indicating savings that could be accrued if 90% capture is not required. Modeling of three regional power plants using the Carnegie Mellon Integrated Environmental Control Model showed that, among other things, the use of a bypass during partial capture may minimize the size of the capture tower(s) and result in a slight reduction in the revenue required to operate the capture facility. The results reinforced that a one-size-fits-all approach cannot be taken to adding capture to a power plant. Laboratory testing indicated that Fourier transform infrared spectroscopy could be used to continuously sample stack emissions at CO 2 capture facilities to detect and quantify any residual amine or its degradation products, particularly nitrosamines. The information gathered during Phase III is important for utility stakeholders as they determine how to reduce their CO 2 emissions in a carbon-constrained world. This subtask was funded through the EERC–U.S. Department of Energy (DOE) Joint Program on Research and Development for Fossil Energy-Related Resources Cooperative Agreement No. DE-FC26-08NT43291. Nonfederal funding was provided by the North Dakota Industrial Commission, PPL Montana, Nebraska Public Power District, Tri-Mer Corporation, Montana–Dakota Utilities Co., Basin Electric Power Cooperative, KCRC/Korean Institute of Energy Research, Cansolv Technologies, and CO 2 Solutions, Inc.

01 COAL, LIGNITE, AND PEAT↗

Subtask 5.10 - Testing of an Advanced Dry Cooling Technology for Power Plants

The University of North Dakota’s Energy & Environmental Research Center (EERC) is developing a market-focused dry cooling technology that is intended to address the key shortcomings of conventional dry cooling technologies: high capital cost and degraded cooling performance during daytime temperature peaks. The unique aspect of desiccant dry cooling (DDC) is the use of a hygroscopic working fluid—a liquid desiccant—as a heat-transfer medium between a power plant’s steam condenser and the atmosphere. This configuration enables a number of beneficial features for large-scale heat dissipation to the atmosphere, without the consumptive use of cooling water. The overall goal of this project was to accurately define the performance and cost characteristics of DDC to determine if further development of the concept is warranted. A balanced approach of modeling grounded in applied experimentation was pursued to substantiate DDC-modeling efforts and outline the potential for this technology to cool full-scale power plants. The resulting analysis shows that DDC can be a lower-cost dry cooling alternative to an air-cooled condenser (ACC) and can even be competitive with conventional wet recirculating cooling under certain circumstances. This project has also highlighted the key technological steps that must be taken in order to transfer DDC into the marketplace. To address these issues and to offer an extended demonstration of DDC technology, a next-stage project should include the opportunity for outdoor ambient testing of a small DDC cooling cell. This subtask was funded through the EERC–U.S. Department of Energy (DOE) Joint Program on Research and Development for Fossil Energy-Related Resources Cooperative Agreement No. DE-FC26-08NT43291. Nonfederal funding was provided by the Wyoming State Legislature under an award made through the Wyoming Clean Coal Technologies Research Program.

20 FOSSIL-FUELED POWER PLANTS↗

Subtask 2.17 - CO 2 Storage Efficiency in Deep Saline Formations

As the field of carbon capture and storage (CCS) continues to advance, and large-scale implementation of geologic carbon dioxide (CO 2 ) storage progresses, it will be important to understand the potential of geologic formations to store meaningful amounts of CO 2 . Geologic CO 2 storage in deep saline formations (DSFs) has been suggested as one of the best potential methods for reducing anthropogenic CO 2 emission to the atmosphere, and as such, updated storage resource estimation methods will continue to be an important component for the widespread deployment of CCS around the world. While there have been several methodologies suggested in the literature, most of these methods are based on a volumetric calculation of the pore volume of the DSF multiplied by a storage efficiency term and do not consider the effect of site-specific dynamic factors such as injection rate, injection pattern, timing of injection, pressure interference between injection locations, and overall formation pressure buildup. These volumetric methods may be excellent for comparing the potential between particular formations or basins, but they have not been validated through real-world experience or full-formation injection simulations. Several studies have also suggested that the dynamic components of geologic storage may play the most important role in storing CO 2 in DSFs but until now have not directly compared CO 2 storage resource estimates made with volumetric methodologies to estimates made using dynamic CO 2 storage methodologies. In this study, two DSFs, in geographically separate areas with geologically diverse properties, were evaluated with both volumetric and dynamic CO 2 storage resource estimation methodologies to compare the results and determine the applicability of both approaches. In the end, it was determined that the dynamic CO 2 storage resource potential is timedependent and it asymptotically approaches the volumetric CO 2 storage resource potential over very long periods of time in the two systems that were evaluated. These results indicate that the volumetric assessments can be used as long as the appropriate storage efficiency terms are used and it is understood that it will take many wells over very long periods of time to fully realize the storage potential of a target formation. This subtask was funded through the Energy & Environmental Research Center (EERC)– U.S. Department of Energy (DOE) Joint Program on Research and Development for Fossil Energy-Related Resources Cooperative Agreement No. DE-FC26-08NT43291. Nonfederal funding was provided by the IEA Greenhouse Gas R&D Programme.

54 ENVIRONMENTAL SCIENCES↗

Subtask – CO 2 storage and enhanced bakken recovery research program

Small improvements in productivity could increase technically recoverable oil in the Bakken Petroleum System by billions of barrels. The use of CO 2 for enhanced oil recovery (EOR) in tight oil reservoirs is a relatively new concept. The large-scale injection of CO 2 into the Bakken would also result in the geological storage of significant amounts of CO 2 . The Energy & Environmental Research Center (EERC) has conducted laboratory and modeling activities to examine the potential for CO 2 storage and EOR in the Bakken. Specific activities included the characterization and subsequent modeling of North Dakota study areas as well as dynamic predictive simulations of possible CO 2 injection schemes to predict the potential CO 2 storage and EOR in those areas. Laboratory studies to evaluate the ability of CO 2 to remove hydrocarbons from Bakken rocks and determine minimum miscibility pressures for Bakken oil samples were conducted. Data from a CO 2 injection test conducted in the Elm Coulee area of Montana in 2009 were evaluated with an eye toward the possible application of knowledge gained to future injection tests in other areas. A first-order estimation of potential CO 2 storage capacity in the Bakken Formation in North Dakota was also conducted. Key findings of the program are as follows. The results of the research activities suggest that CO 2 may be effective in enhancing the productivity of oil from the Bakken and that the Bakken may hold the ability to geologically store between 120 Mt and 3.2 Gt of CO 2 . However, there are no clear-cut answers regarding the most effective approach for using CO 2 to improve oil productivity or the storage capacity of the Bakken. The results underscore the notion that an unconventional resource will likely require unconventional methods of both assessment and implementation when it comes to the injection of CO 2 . In particular, a better understanding of the fundamental mechanisms controlling the interactions between CO 2 , oil, and other reservoir fluids in these unique formations is necessary to develop accurate assessments of potential CO 2 storage and EOR in the Bakken. In addition, existing modeling and simulation software packages do not adequately address or incorporate the unique properties of these tight, unconventional reservoirs in terms of their impact on CO 2 behavior. These knowledge gaps can be filled by conducting scaled-up laboratory activities integrated with improved modeling and simulation techniques, the results of which will provide a robust foundation for pilot-scale field injection tests. Finally, field-based data on injection, fluid production, and long-term monitoring from pilot-scale CO 2 injection tests in the Bakken are necessary to verify and validate the findings of the laboratory- and modeling-based research efforts. This subtask was funded through the EERC–U.S. Department of Energy (DOE) Joint Program on Research and Development for Fossil Energy-Related Resources Cooperative Agreement No. DE-FC26-08NT43291. Nonfederal funding was provided by the North Dakota Industrial Commission, Marathon Oil Corporation, Continental Resources Inc., and TAQA North, Ltd.

54 ENVIRONMENTAL SCIENCES↗

Subtask1.10 – CO 2 storage and enhanced bakken recovery research program

Small improvements in productivity could increase technically recoverable oil in the Bakken Petroleum System by billions of barrels. The use of CO 2 for enhanced oil recovery (EOR) in tight oil reservoirs is a relatively new concept. The large-scale injection of CO 2 into the Bakken would also result in the geological storage of significant amounts of CO 2 . The Energy & Environmental Research Center (EERC) has conducted laboratory and modeling activities to examine the potential for CO 2 storage and EOR in the Bakken. Specific activities included the characterization and subsequent modeling of North Dakota study areas as well as dynamic predictive simulations of possible CO 2 injection schemes to predict the potential CO 2 storage and EOR in those areas. Laboratory studies to evaluate the ability of CO 2 to remove hydrocarbons from Bakken rocks and determine minimum miscibility pressures for Bakken oil samples were conducted. Data from a CO 2 injection test conducted in the Elm Coulee area of Montana in 2009 were evaluated with an eye toward the possible application of knowledge gained to future injection tests in other areas. A first-order estimation of potential CO 2 storage capacity in the Bakken Formation in North Dakota was also conducted. Key findings of the program are as follows. The results of the research activities suggest that CO 2 may be effective in enhancing the productivity of oil from the Bakken and that the Bakken may hold the ability to geologically store between 120 Mt and 3.2 Gt of CO 2 . However, there are no clear-cut answers regarding the most effective approach for using CO 2 to improve oil productivity or the storage capacity of the Bakken. The results underscore the notion that an unconventional resource will likely require unconventional methods of both assessment and implementation when it comes to the injection of CO 2 . In particular, a better understanding of the fundamental mechanisms controlling the interactions between CO 2 , oil, and other reservoir fluids in these unique formations is necessary to develop accurate assessments of potential CO 2 storage and EOR in the Bakken. In addition, existing modeling and simulation software packages do not adequately address or incorporate the unique properties of these tight, unconventional reservoirs in terms of their impact on CO 2 behavior. These knowledge gaps can be filled by conducting scaled-up laboratory activities integrated with improved modeling and simulation techniques, the results of which will provide a robust foundation for pilot-scale field injection tests. Finally, field-based data on injection, fluid production, and long-term monitoring from pilot-scale CO 2 injection tests in the Bakken are necessary to verify and validate the findings of the laboratory- and modeling-based research efforts. This subtask was funded through the EERC–U.S. Department of Energy (DOE) Joint Program on Research and Development for Fossil Energy-Related Resources Cooperative Agreement No. DE-FC26-08NT43291. Nonfederal funding was provided by the North Dakota Industrial Commission, Marathon Oil Corporation, Continental Resources Inc., and TAQA North, Ltd.

54 ENVIRONMENTAL SCIENCES↗

Shifting from Fossil Fuel Reliance to Green Energy Sovereignty: Ute Mountain Ute Tribe

Self-determination has been an on-going effort for Native American people and gained much traction with the passing of The Energy Policy Act of 2005, which included the Indian Tribal Energy Development and Self-Determination Act. Congress passed this act to assist Native American tribes and Alaska Native villages with planning, development, and assistance to achieve their energy goals. The Ute Mountain Ute Tribe (UMUT) has relied on oil and natural gas for economic support the last 70 years. Burning fossil fuels, along with oil and gas development, decreases the quality of air and leads to increased greenhouse gas emissions. Subsequently, the burning of fossil fuels to produce energy is now more costly than many renewable energy sources, including solar photovoltaic (PV) systems. Environmental stewardship, along with the need to maintain revenue generation, has led UMUT’s efforts to achieve energy self-determinism employing PV and exploring other technology. In the past, the tribe completed a 1 megawatt PV project near Towaoc, Colorado, which serves as a case study on the tribe’s energy goals: a future where renewables will dominate their energy landscape. This paper explores UMUT’s past and on-going efforts toward energy independence and how it relates to the broader landscape of Native American energy sovereignty.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Do Phycosphere associated bacteria affect the growth and lipid production of Phaeodactylum tricornutum Bohlin?

Microalgae biofuels are a promising alternative to fossil fuel energy. However current microalgal biofuel production is inefficient making it more expensive than fossil fuels. To make microalgal biofuels a realistic alternative energy source, improvements are needed in the production of microalgae biomass. Phycosphere-associated bacteria are known to influence microalgae growth and metabolite production. Understanding these interactions could provide new methods for enhancing microalgae biomass and improving the efficiency of producing microalgae biofuels. Co-cultures of Phaeodactylum tricornutum Bohlin and single bacterial species were compared to determine what impact phycosphere-associated bacteria can have on microalgae. Growth rates, total lipid accumulation and fatty acid profiles for each co-culture were compared to an axenic culture of P. tricornutum to assess the impact of the bacterial association. Marinobacter 3-2 significantly increased the lipid accumulation of P. tricornutum during early exponential growth. Two bacterial strains, Algoriphagus ARW1R1 and Muricaud a ARW1Y1, significantly lowered the maximum growth rate and cell densities of P. tricornutum in early and late exponential growth. Lower cell densities in these co-cultures resulted in lower lipid accumulation. Our results suggest that co-culturing P. tricornutum with a phycosphere-associated bacterial species, Marinobacter 3-2, could help improve the efficiency of producing algal biomass and lipids.

59 BASIC BIOLOGICAL SCIENCES↗

High Temperature Chemistry of Aromatic Hydrocarbons. Final Technical Report

The primary goal of this research was to uncover the principal reaction channels available to polycyclic aromatic hydrocarbons (PAHs) at high temperatures in the gas phase and to establish the factors that determine which channels will be followed in varying circumstances. New structure-property relationships for PAHs were also studied. The efficient production of clean energy from fossil fuels will remain a major component of the DOE mission until alternative sources of energy eventually displace coal and petroleum. Hydrocarbons constitute the most basic class of compounds in all of organic chemistry, and as the dominant species in fossil fuels, they figure prominently into the programs of the DOE. Much is already known about the normal chemistry of hydrocarbons under ambient conditions, but far less is known about their intrinsic chemistry at temperatures close to those reached during combustion. An understanding of the fundamental molecular transformations, rearrangements, and interconversions of PAHs at high temperatures in the gas phase, as revealed by careful studies on small, well-designed, molecular systems, provides insights into the underlying chemistry of many important processes that are more complex, such as the generation of energy by the combustion of fossil fuels, the uncatalyzed gasification and liquefaction of coal, the production of fullerenes in fuel-rich flames, and the formation of soot and carcinogenic pollutants in smoke (e.g., benzo[a]pyrene). The rational control of any of these processes, whether it be the optimization of a desirable process or the minimization of an undesirable one, requires a clear knowledge of the basic chemistry that governs the fate of the species involved. Advances in chemistry at the most fundamental level come about primarily from the discovery of new reactions and from new insights into how reactions occur. Harnessing that knowledge is the key to new technologies. The recent commercialization of a combustion synthesis of C 60 and other fullerenes depended critically on a knowledge of hydrocarbon reactions at high temperatures in the gas phase, and the research supported by this project enabled further advances in the realm of carbon-rich materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Regional Analysis of Building Distributed Energy Costs and CO2 Abatement: A U.S. - China Comparison

The following paper conducts a regional analysis of the U.S. and Chinese buildings? potential for adopting Distributed Energy Resources (DER). The expected economics of DER in 2020-2025 is modeled for a commercial and a multi-family residential building in different climate zones. The optimal building energy economic performance is calculated using the Distributed Energy Resources Customer Adoption Model (DER CAM) which minimizes building energy costs for a typical reference year of operation. Several DER such as combined heat and power (CHP) units, photovoltaics, and battery storage are considered. The results indicate DER have economic and environmental competitiveness potential, especially for commercial buildings in hot and cold climates of both countries. In the U.S., the average expected energy cost savings in commercial buildings from DER CAM?s suggested investments is 17percent, while in Chinese buildings is 12percent. The electricity tariffs structure and prices along with the cost of natural gas, represent important factors in determining adoption of DER, more so than climate. High energy pricing spark spreads lead to increased economic attractiveness of DER. The average emissions reduction in commercial buildings is 19percent in the U.S. as a result of significant investments in PV, whereas in China, it is 20percent and driven by investments in CHP. Keywords: Building Modeling and Simulation, Distributed Energy Resources (DER), Energy Efficiency, Combined Heat and Power (CHP), CO2 emissions 1. Introduction The transition from a centralized and fossil-based energy paradigm towards the decentralization of energy supply and distribution has been a major subject of research over the past two decades. Various concerns have brought the traditional model into question; namely its environmental footprint, its structural inflexibility and inefficiency, and more recently, its inability to maintain acceptable reliability of supply. Under such a troubled setting, distributed energy resources (DER) comprising of small, modular, electrical renewable or fossil-based electricity generation units placed at or near the point of energy consumption, has gained much attention as a viable alternative or addition to the current energy system. In 2010, China consumed about 30percent of its primary energy in the buildings sector, leading the country to pay great attention to DER development and its applications in buildings. During the 11th Five Year Plan (FYP), China has implemented 371 renewable energy building demonstration projects, and 210 photovoltaics (PV) building integration projects. At the end of the 12th FYP, China is targeting renewable energy to provide 10percent of total building energy, and to save 30 metric tons of CO2 equivalents (mtce) of energy with building integrated renewables. China is also planning to implement one thousand natural gas-based distributed cogeneration demonstration projects with energy utilization rates over 70percent in the 12th FYP. All these policy targets require significant DER systems development for building applications. China?s fast urbanization makes building energy efficiency a crucial economic issue; however, only limited studies have been done that examine how to design and select suitable building energy technologies in its different regions. In the U.S., buildings consumed 40percent of the total primary energy in 2010 [1] and it is estimated that about 14 billion m2 of floor space of the existing building stock will be remodeled over the next 30 years. Most building?s renovation work has been on building envelope, lighting and HVAC systems. Although interest has emerged, less attention is being paid to DER for buildings. This context has created opportunities for research, development and progressive deployment of DER, due to its potential to combine the production of power and heat (CHP) near the point of consumption and delivering multiple benefits to customers, such as cost

25 ENERGY STORAGE↗

Heavy fossil hydrocarbon conversion and upgrading using radio-frequency or microwave energy

Conversion of heavy fossil hydrocarbons (HFH) to a variety of value-added chemicals and/or fuels can be enhanced using microwave (MW) and/or radio-frequency (RF) energy. Variations of reactants, process parameters, and reactor design can significantly influence the relative distribution of chemicals and fuels generated as the product. In one example, a system for flash microwave conversion of HFH includes a source concentrating microwave or RF energy in a reaction zone having a pressure greater than 0.9 atm, a continuous feed having HFH and a process gas passing through the reaction zone, a HFH-to-liquids catalyst contacting the HFH in at least the reaction zone, and dielectric discharges within the reaction zone. The HFH and the catalyst have a residence time in the reaction zone of less than 30 seconds. In some instances, a plasma can form in or near the reaction zone.

Strohm, James J.↗

Desalination of brines produced from the geologic storage of carbon dioxide

Geologic carbon dioxide sequestration (GCS) will play a crucial role in limiting anthropogenic greenhouse gas emissions. GCS is the practice of capturing carbon dioxide (CO 2 ) from industrial sources and storing it in subsurface geologic formations, such as saline formations. These saline formations are typified by a porous interconnected rock strata, saturated with saline brine at a depth of >800 m. Because of the large volumes available, storage of CO 2 into deep saline formations with caprock seals and far from exiting faults will be key for long term reductions of anthropogenic CO 2 emissions. The high pressure injection of CO 2 into the subsurface can cause an increase in subsurface pressure. Open and highly porous formations can have CO 2 injected without causing a significant rise in formation pressure; however, closed or low porosity formations are more sensitive to the subsurface injection of CO 2 with regard to subsurface pressure. Such formations would ideally be located near existing fossil fuel power plants or other industrial emitters of CO 2 who would require GCS. In order to reduce the risk of induced seismic activity near minor fault structures, formation pressure management is needed. This will require the extraction of brines from the formation and these brines could be extracted prior to or during GCS. This extraction will maintain or reduce the subsurface pressure and enhance CO 2 storage capacity. The extracted brine can be dewatered/desalinated, becoming both a source of usable water and a concentrated brine which could be either reinjected into a nearby formation, crystallized, or discharged into an evaporation pond. The Department of Energy Office of Fossil Energy’s commitment to studying formation pressure management in GCS has been demonstrated with the recent awarding of $30,000,000 for two Brine Extraction Storage Test (BEST) projects, whose main goal is to develop and validate strategies for managing formation pressure through brine (Martin 2016). A secondary goal of these projects is to develop and demonstrate processes to extract usable water from these high salinity produced brines.

54 ENVIRONMENTAL SCIENCES↗

The impact of tribology on energy use and CO 2 emission globally and in combustion engine and electric cars

Growing concerns over energy and environmental sustainability have lately sparked worldwide interest in more efficient and cleaner transportation systems and industrial activities. Friction roughly consumes one-fifth of all energy used worldwide. One-third of all energy used in transportation goes to overcome friction. At the same time, the fruits of decades of dedicated research on all-electric vehicles powered by advanced batteries are paving the way toward a much cleaner and sustainable transportation future. In this article, we provide a short overview of what are the energy efficiency and environmental impacts of current transportation, industrial, and residential systems and how much of that efficiency is adversely affected by friction and wear losses in moving mechanical parts and components. We also touch upon recent advances in new materials, lubricants, and design changes that could reduce energy losses by 18–40%, mainly resulting from friction and wear. The savings would be up to 8.7% of the total global energy use and 1.4% of the gross national products (GNP). Finally, we calculate the energy consumption and friction losses in battery-powered electric passenger cars and show the benefit of electric cars where the total energy use is in average 3.4 times lower compared to combustion engine powered cars. The CO 2 emissions are 4.5 times higher for a combustion engine car compared to an electric car when the electricity comes from renewable energy sources. Moving from fossil to renewable energy sources may cut down the energy losses due to friction in energy production by more than 60%.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Electrocatalysis in Alkaline Media and Alkaline Membrane-Based Energy Technologies

Hydrogen energy-based electrochemical energy conversion technologies offer the promise of enabling a transition of the global energy landscape from fossil fuels to renewable energy. Here, we present a comprehensive review of the fundamentals of electrocatalysis in alkaline media and applications in alkaline-based energy technologies, particularly alkaline fuel cells and water electrolyzers. Anion exchange (alkaline) membrane fuel cells (AEMFCs) enable the use of nonprecious electrocatalysts for the sluggish oxygen reduction reaction (ORR), relative to proton exchange membrane fuel cells (PEMFCs), which require Pt-based electrocatalysts. However, the hydrogen oxidation reaction (HOR) kinetics is significantly slower in alkaline media than in acidic media. Understanding these phenomena requires applying theoretical and experimental methods to unravel molecular-level thermodynamics and kinetics of hydrogen and oxygen electrocatalysis and, particularly, the proton-coupled electron transfer (PCET) process that takes place in a proton-deficient alkaline media. Extensive electrochemical and spectroscopic studies, on single-crystal Pt and metal oxides, have contributed to the development of activity descriptors, as well as the identification of the nature of active sites, and the rate-determining steps of the HOR and ORR. Among these, the structure and reactivity of interfacial water serve as key potential and pH-dependent kinetic factors that are helping elucidate the origins of the HOR and ORR activity differences in acids and bases. Additionally, deliberately modulating and controlling catalyst-support interactions have provided valuable insights for enhancing catalyst accessibility and durability during operation. The design and synthesis of highly conductive and durable alkaline membranes/ionomers have enabled AEMFCs to reach initial performance metrics equal to or higher than those of PEMFCs. We emphasize the importance of using membrane electrode assemblies (MEAs) to integrate the often separately pursued/optimized electrocatalyst/support and membranes/ionomer components. Operando/in situ methods, at multiscales, and ab initio simulations provide a mechanistic understanding of electron, ion, and mass transport at catalyst/ionomer/membrane interfaces and the necessary guidance to achieve fuel cell operation in air over thousands of hours. We hope that this Review will serve as a roadmap for advancing the scientific understanding of the fundamental factors governing electrochemical energy conversion in alkaline media with the ultimate goal of achieving ultralow Pt or precious-metal-free high-performance and durable alkaline fuel cells and related technologies.

30 DIRECT ENERGY CONVERSION↗