Life cycle analysis is carried out for 11 predicted configurations of pyrolysis biochar systems to determine greenhouse gas balance, using an original spreadsheet model. System parameters reflect deployment in Scotland, and results demonstrate that all major crop and forestry feedstocks offer greater GHG abatement than other bioenergy technologies, regardless of system configuration. Sensitivity analysis determines the relative importance of uncertain variables in the model and optimistic to pessimistic scenarios are used for system operation. Slow pyrolysis is compared to fast pyrolysis and biomass co-firing for GHG abatement and electricity production, using various scenarios for availability of indigenous Scottish feedstocks.

Anthropogenic CO₂ captured from a coal-fired power plant can be used for an enhanced oil recovery (EOR) operation while mitigating the atmospheric impact of CO₂ emissions. Concern about climate change caused by CO₂ emissions has increased the motivation to develop carbon capture and sequestration (CCS) projects to reduce the atmospheric impact of coal and other fossil fuel combustion. Enhanced oil recovery operations are typically constrained by the supply of CO₂, so there is interest from oil producers to use large-volume anthropogenic (LVA) CO₂ for tertiary oil production. The intermittency of LVA CO2 emissions creates an area of concern for both oil producers and electric utilities that may enter into a CO₂ supply contract for EOR. An oil producer wants to know if intermittency from a non-standard source of CO₂ will impact oil production from the large volume being captured. Since the electric utility must supply electricity on an as-needed basis, the CO₂ emissions are inherently intermittent on a daily and seasonal basis. The electric utility needs to know if the intermittent supply of CO₂ would reduce its value compared to CO₂ delivered to the oil field at a constant rate. This research creates an experimental test scenario where one coal-fired power plant captures 90% of its CO₂ emissions which is then delivered through a pipeline to an EOR operation. Using real emissions data from a coal-fired power plant and simplified data from an actual EOR reservoir, a series of reservoir simulations were done to address and analyze potential operational interference for an EOR operator injecting large-volume, intermittent CO₂ characteristic of emissions from a coal-fired power plant. The test case simulations in this study show no significant impact to oil production from CO₂ intermittency. Oil recovery, in terms of CO₂ injection, is observed to be a function of the total pore volumes injected. The more CO₂ that is injected, the more oil that is produced and the frequency or rate at which a given volume is injected does not impact net oil production. Anthropogenic CO₂ sources can eliminate CO₂ supply issues that constrain an EOR operation. By implementing this nearly unlimited supply of CO₂, oil production should increase compared to smaller-volume or water-alternating-gas (WAG) injection strategies used today. Mobility ratio and reservoir heterogeneity have a considerable impact on oil recovery. Prediction of CO₂ breakthrough at the production wells seems to be more accurate when derived from the mobility ratio between CO₂ and reservoir oil. The degree of heterogeneity within the reservoir has a more direct impact on oil recovery and sweep efficiency over time. The volume of CO₂ being injected can eventually invade lower permeability regions, reducing the impact of reservoir heterogeneity on oil recovery. This concept should mobilize a larger volume of oil than a conventional volume-limited or WAG injection strategy that may bypass or block these lower permeability regions. Besides oil recovery, a reservoir's performance in this study is defined by its CO₂ injectivity over time. Elevated injection pressures associated with the large-volume CO₂ source can substantially impact the ability for an oil reservoir to store LVA CO₂. As CO₂, a less viscous fluid, replaces produced oil and water, the average reservoir pressure slowly declines which improves injectivity. This gradual improvement in injectivity is mostly occupied by the increasing volume of recycled CO₂. Sweep efficiency is critical towards minimizing the impact of CO₂ recycling on reservoir storage potential. Deep, large, and permeable oil reservoirs are more capable of accepting LVA CO₂, with less risk of fracturing the reservoir or overlying confining unit. The depth of the reservoir will directly dictate the injection pressure threshold in the oil reservoir as the fracture pressure increases with depth. If EOR operations are designed to sequester all the CO₂ delivered to the field, additional injection capacity and design strategies are needed. / text

Underground injection of acid gas has been studied for several decades for oil field applications, such as enhanced oil recovery (EOR), but is now being studied as a solution to climate change. This research aims to simulate underground conditions at injection sites, such as the pilot scale injection site located near the site of a coal fired power facility in the Black Warrior Basin of Alabama. This proposed carbon capture and sequestration (CCS) location would involve injection of liquid CO2 into a carbonaceous saline aquifer. The objective of this study was to investigate carbonate surface treatments that alter the kinetics and mechanism of mineral dissolution resulting from the injection of an acid gas (CO2) into a geologic formation. A variety of mineral coatings were tested in an attempt to preserve mineral integrity under acidic conditions. Surface active chemicals were first tested, including scale inhibitors, followed by a novel acid induced surface treatment that precipitates an inorganic layer on the calcite to preserve the acid soluble mineral. These experiments are the first to investigate the use of scale inhibitors for mineral preservation, although were found ultimately to have little impact on dissolution kinetics. However, anions of moderate to strong acids induced surface coatings that were determined to effectively inhibit dissolution. Additionally, a novel, high pressure flow-through experimental apparatus was developed to simulate pressure and temperature conditions relevant to injection sites. Similar mineralogical studies in the literature have used pressurized, unstirred, batch systems to simulate mineral interactions. Solids with an acid induced surface coating were tested in the high pressure column and no calcium was found to leave the column.

Underground injection of acid gas has been studied for several decades for oil field applications, such as enhanced oil recovery (EOR), but is now being studied as a solution to climate change. This research aims to simulate underground conditions at injection sites, such as the pilot scale injection site located near the site of a coal fired power facility in the Black Warrior Basin of Alabama. This proposed carbon capture and sequestration (CCS) location would involve injection of liquid CO2 into a carbonaceous saline aquifer. The objective of this study was to investigate carbonate surface treatments that alter the kinetics and mechanism of mineral dissolution resulting from the injection of an acid gas (CO2) into a geologic formation. A variety of mineral coatings were tested in an attempt to preserve mineral integrity under acidic conditions. Surface active chemicals were first tested, including scale inhibitors, followed by a novel acid induced surface treatment that precipitates an inorganic layer on the calcite to preserve the acid soluble mineral. These experiments are the first to investigate the use of scale inhibitors for mineral preservation, although were found ultimately to have little impact on dissolution kinetics. However, anions of moderate to strong acids induced surface coatings that were determined to effectively inhibit dissolution. Additionally, a novel, high pressure flow-through experimental apparatus was developed to simulate pressure and temperature conditions relevant to injection sites. Similar mineralogical studies in the literature have used pressurized, unstirred, batch systems to simulate mineral interactions. Solids with an acid induced surface coating were tested in the high pressure column and no calcium was found to leave the column.

Perfluorocarbon tracers (PFTs) are commonly proposed tracers for use in carbon capture and sequestration (CCS) leak detection and vadose zone monitoring programs. Tracers are co-injected with supercritical CO₂ and monitored in the vadose zone to identify leakage and calculate leakage rates. These calculations assume PFTs exhibit “ideal” tracer behavior (i.e. do not sorb onto or react with porous media, partition into liquid phases or undergo decay). This assumption has been brought into question by lab and field evaluations showing PFT partitioning into soil contaminants and sorbing onto clay. The objective of this study is to identify substrates in which PFTs behave conservatively and quantify non-conservative behavior. PFT breakthrough curves are compared to those of a second, conservative tracer, sulfur hexafluoride (SF₆). Breakthrough curves are generated in 1D flow-through columns packed with 5 different substrates: silica beads, quartz sand, illite, organic-rich soil, and organic-poor soil. Constant flow rate of carrier gas, N₂, is maintained. A known mass of tracer is injected at the head of the columns and the effluent analyzed at regular intervals for tracers at picogram levels by gas chromatography. PFT is expected to behave conservatively with respect to SF₆ in silica beads or quartz sand and non-conservatively in columns with clay or organics. However, results demonstrate PFT retardation with respect to SF₆ in all media (retardation factor is 1.1 in silica beads and quartz sand, 2.5 in organic-rich soil, >20 in organic-poor soil, and >100 in illite). Retardation is most likely due to sorption onto clays and soil organic matter or condensation to the liquid phase. Sorption onto clays appears to be the most significant factor. Experimental data are consistent with an analytical advection/diffusion model. These results show that PFT retardation in the vadose zone has not been adequately considered for interpretation of PFT data for CCS monitoring. These results are preliminary and do not take into account more realistic vadose zone conditions such as the presence of water, in which PFTs are insoluble. Increased moisture content will likely decrease sorption onto porous media and retardation in the vadose zone may be less than determined in these experiments. / text

The Arizona Oil and Gas Commission in conjunction with the Arizona Geological Survey have collected a large amount of data for the oil and gas wells in the State of Arizona. The data covers over 1,000 wells that were drilled from the 1940s to present. This data includes copies of permits, location information, scanned copies of well logs and digitized versions of the well logs in .las file format. These files have been difficult to distribute efficiently because of an unfriendly web user interface. The purpose of this project is to give the Arizona Geological Survey a way to distribute the oil and gas well data through an effective web application. The web application will leverage existing web services at the Arizona Geological Survey. To create this map I used the Esri JavaScript API. In this application the users can select multiple wells by clicking and dragging over the well heads they want. This will then display the metadata in a grid along with hyperlinks to the available files for those wells. This data will be primarily used by companies involved with carbon sequestration or others seeking information for geological exploration.

Numerical simulation has been used, as common practice, to estimate the CO2 storage capacity of depleted reservoirs. However, this method is time consuming, expensive and requires detailed input data. This investigation proposes an analytical method to estimate the ultimate CO2 storage in depleted oil and gas reservoirs by implementing a volume constrained thermodynamic equation of state (EOS) using the reservoir?s average pressure and fluid composition. This method was implemented in an algorithm which allows fast and accurate estimations of final storage, which can be used to select target storage reservoirs, and design the injection scheme and surface facilities. Impurities such as nitrogen and carbon monoxide, usually contained in power plant flue gases, are considered in the injection stream and can be handled correctly in the proposed algorithm by using their thermodynamic properties into the EOS. Results from analytical method presented excellent agreement with those from reservoir simulation. Ultimate CO2 storage capacity was predicted with an average difference of 1.3%, molar basis, between analytical and numerical methods; average oil, gas, and water saturations were also matched. Additionally, the analytical algorithm performed several orders of magnitude faster than numerical simulation, with an average of 5 seconds per run.

Two of the hottest areas in porous materials research in the last decade have been in energy storage, mainly hydrogen and methane, and in carbon capture and sequestration (CCS). Although these topics are intricately linked in terms of our future energy landscape, the specific materials needed to solve these problems must have significantly different properties. High pressure gas storage is most often linked with high surface areas and pore volumes, while carbon capture sorbents require high sorption enthalpies to achieve the needed selectivity. The latter typically involves separating CO2 from mixed gas streams of mostly nitrogen via a temperature swing adsorption (TSA) process. Much of the excitement has arisen because of the potential of metal-organic frameworks (MOFs) and porous polymer networks (PPNs). Both classes of materials have extremely high surface areas (upwards of 4000 m2/g) and can be modified to have specific physical properties, thus enabling high performance materials for targeted applications. This dissertation focuses on the synthesis and characterization of these novel materials for both applications by tuning framework topologies, composition, and surface properties. Specifically, two routes to synthesize a single molecule trap (SMT) highlight the flexibility of MOF design and ability to tune a framework to interact with specifically one guest molecule; computational and experimental evidence of the binding mechanism are shown as well. Furthermore, eight PPNs are synthesized and characterized for post-combustion carbon capture and direct air capture applications. In addition a high-throughput model, grounded in thermodynamics, to calculate the energy penalty associated with the carbon capture step is presented in order to evaluate all materials for TSA applications provide a comparison to the state of the art capture technologies. This includes results of working capacity and energy calculations to determine parasitic loads (per ton of CO2 captured) from readily available experimental data of any material (adsorption isotherms and heat capacities) using a few simple equations. Through various systematic investigations, trends are analyzed to form structure property relationships that will aid future material development.

Motivated by the role of decarbonizing the electric power sector to mitigate climate change, I assess the economic and environmental merits of three key technologies for decarbonizing the electric power sector across four chapters in this thesis. These chapters explore how adding flexibility to power plants equipped with carbon capture and sequestration (CCS) affects system costs and carbon dioxide (CO2) emissions, how grid-scale electricity storage affects system CO2 emissions as a power system decarbonizes, and how distributed solar photovoltaic (distributed PV) electricity generation suppresses wholesale electricity prices. In each chapter, I address these questions through a combination of power system optimization, statistics, and techno-economic analysis, and tie my findings to policy implications. In Chapter 2, I compare the cost-effectiveness of “flexible” CCS retrofits to other compliance strategies with the U.S. Clean Power Plan (CPP) and a hypothetical stronger CPP. Relative to “normal” CCS, “flexible” CCS retrofits include solvent storage that allows the generator to temporarily eliminate the CCS parasitic load and increase the generator’s net efficiency, capacity, and ramp rate. Using a unit commitment and economic dispatch (UCED) model, I find that flexible CCS achieves more cost-effective emissions reductions than normal CCS under the CPP and stronger CPP, but that flexible CCS is less cost-effective than other compliance strategies under both reduction targets. In Chapter 3, I conduct a detailed comparison of how flexible versus normal CCS retrofits affect total system costs and CO2 emissions under a moderate and strong CO2 emission limit. Given that a key benefit of flexible CCS relative to normal CCS is increased reserve provision, I break total system costs into generation, reserve, and CCS capital costs. Using a UCED model, I find that flexible CCS retrofits reduce total system costs relative to normal CCS retrofits under both emission limits. Furthermore, 40-80% of these cost reductions come from reserve cost reductions. Accounting for costs and CO2 emissions, though, flexible CCS poses a trade-off to policymakers under the moderate emission limit, as flexible CCS increases system CO2 emissions relative to normal CCS. No such trade-off exists under the stronger emission limit, as flexible CCS reduces system CO2 emissions and costs relative to normal CCS. In Chapter 4, I quantify how storage affects operational CO2 emissions as a power system decarbonizes under a moderate and strong CO2 emission limit through 2045. In so doing, I aim to better understand how storage transitions from increasing CO2 emissions in historic U.S. systems to enabling deeply decarbonized systems. Additionally, under each target I compare how storage affects CO2 emissions when participating in only energy, only reserve, and energy and reserve markets. Using a capacity expansion (CE) model to forecast fleet changes through 2045 and a UCED model to quantify how storage affects system CO2 emissions, I find that storage quickly transitions from increasing to decreasing CO2 emissions under the moderate and strong emission limits. Whether storage provides only energy, only reserves, or energy and reserves drives large differences in the magnitude, but not the direction, of the effect of storage on CO2 emissions. In Chapter 5, I quantify a benefit of distributed photovoltaic (PV) generation often overlooked by value of solar studies, namely the market price response. By displacing high-cost marginal generators, distributed PV generation reduces wholesale electricity prices, which in turn reduces utilities’ energy procurement costs. Using 2013 through 2015 data from California including a database of all distributed PV systems in the three California investor owned utilities, we estimate historic hourly distributed PV generation in California, then link that generation to reduced wholesale electricity prices via linear regression. From 2013 through 2015, we find that distributed PV suppressed historic median hourly LMPs by up to $2.7-3.1/MWh, yielding avoided costs of up to $650-730 million. These avoided costs are smaller than but on the order of other avoided costs commonly included in value of solar studies, so merit inclusion in future studies to properly value distributed PV.

Recent studies report rapid corrosion of metals and carbonation of minerals in contact with H2O-saturated (or nearly saturated) CO2. One explanation for this behavior is that addition of small amounts of H2O to CO2 leads to significant ionization within the fluid (analogous to corrosion in aqueous fluids). The extent of ionization in the bulk CO2 fluid was determined using a flow-through conductivity cell capable of analyzing very dilute solutions. Experiments were conducted from 25 to 200"C and 25 to 200 bar with H2O concentrations up to ~1650 ppmw. In all experiments, conductivities <10 nS/cm were obtained, indicating that the solution is essentially ion-free. This observation suggests that mobile ions are not present in the bulk CO2--rich fluid, and that the observed corrosion and carbonation reactions are not the result of ionization in the bulk fluid. / Master of Science