Accurate simulation of chemical flooding requires a detailed understanding of numerous complex mechanisms and model parameters where grid size has a substantial impact upon results. In this research we show the effect of grid size on parameters such as phase behavior, interfacial tension, surfactant dilution and salinity gradient for chemical flooding of a very heterogeneous oil reservoir. The effective propagation of the surfactant slug in the reservoir is of paramount importance and the salinity gradient is a key factor in ensuring the process effectiveness. The larger the grid block size, the greater the surfactant dilution, which in turn erroneously reduces the effectiveness of the process indicated with low simulated oil recoveries. We show that the salinity gradient is not adequately captured by coarse grid simulations of heterogeneous reservoirs and this leads to performance predictions with lower recovery compared to fine grid simulations. Due to the highly coupled, nonlinear interactions of the many chemical and physical processes involved in chemical flooding, it is better to use fine-grid simulations rather than coarse grids with upscaled physical properties whenever feasible. However, the upscaling methodology for chemical flooding presented in this work accounts approximately for some of the more important effects, as demonstrated by comparison of fine grid and coarse grid results and is very different than the way other enhanced oil recovery methods are upscaled. This is a step towards making better performance predictions of chemical flooding for large field projects where it is not currently feasible to perform the large number of simulations required to properly consider different designs, optimization, risk and uncertainty using fine-grid simulations. / text

The ability to select low-cost, high-performance surfactants for a wide range of crude oils under a wide range of reservoir conditions has improved dramatically in recent years. Surfactant formulations (surfactant, co-surfactant, co-solvent, alkali, polymer, and electrolyte) were developed by using a refined phase behavior approach. Such formulations nearly always result in more than 90% oil recovery in core flood when good surfactants with good mobility control are used. The advances that have improved performance, reduced cost, increased robustness, and extended the range of reservoir conditions for these formulations are described in this work. There are thousands of possible combinations of the chemicals that could be tested for each oil and each chemical combination requires many observations over a long time period at reservoir temperature for proper evaluation. It would take too long, cost too much and in many cases not even be feasible to test all combinations. In practice the scientific understanding is used to match up the surfactant/co-surfactant/co-solvent characteristics with the oil characteristics, temperature, salinity, hardness and so forth. Synthesized and new surfactants with much larger hydrophobes and more branching than previously available were tested. New classes of co-solvents and co-surfactants with superior performance were test to improve aqueous solubility. These new developments resulted in improved ASP formulations for both oils that react with alkali to make soap and oils that do not. Many of these developments are synergistic and taken together represent a breakthrough in reducing the cost of chemical flooding and thus its commercial potential. / text

Foam-assisted low interfacial tension and foam-improved sweep efficiency are attractive enhanced oil recovery (EOR) methods with numerous studies and researches have been conducted in the past few decades. For example, CO₂-Enhanced Oil Recovery (CO₂-EOR) is very efficient in terms of oil displacement. However, due to the low viscosity of super critical CO₂, the process usually suffers from poor sweep efficiency. One method of increasing sweep efficiency in CO₂-EOR has been identified through the use of surfactants to create "foams" or more correctly CO₂-in-water (C/W) macroemulsions. Polymer flooding techniques such as Alkali -- Polymer (AP), Surfactant -- Polymer (SP), and Alkali -- Surfactant -- Polymer (ASP) have been the only proven chemical EOR method in sandstone reservoirs with many successful pilot tests and field projects. However, the use of polymer is limited in carbonates due to unfavorable conditions related to natural characteristics of this type of lithology. In this case, foam-assisted EOR, specifically Alkali -- Surfactant -- Gas (ASG) process, can be an alternative for polymer flooding. It is a fact that large amount of the world's oil reserves resides in carbonate reservoirs. Therefore, an increase in oil recovery from carbonates would help meet the world's increasing energy demand. This study consists of two parts: (1) the development of new surfactant for creating CO₂ -- in -- water macroemulsions for improving sweep efficiency in CO₂ -- EOR processes; (2) systematic study of ASG method as a novel EOR technique and an alternative for polymer flooding in carbonate reservoirs. Both studies are related to the use of foam as a mobility control agent. In the first part, the design and synthesis of twin tailed surfactants for use at the CO₂/water interface is discussed. The hydrohobes for these surfactants are synthesized from epichlorohydrin and an excess alcohol. Subsequent ethoxylation of the resulting symmetrical dialkyl glycerin yields the water soluble dual tailed surfactants. The general characteristics of these surfactants in water are described. A comparison is carried out between twin-tailed dioctylglycerine surfactants and linear secondary alcohol surfactant based on results from a core flood. The results show that even above the cloud point of the surfactants, the twin tailed surfactants create a significant mobility reduction, likely due to favorable partitioning into the CO₂ phase. The data covers surfactant structures designed specifically for the CO₂-water interface and can be used by producers and service companies in designing new CO₂-floods, especially in areas that might not have been considered due to problems with reservoir heterogeneity. Second part contains a systematic study of ASG process on carbonate rocks through a series of experiments. The purpose is to demonstrate the performance as well as the potential of ASG as a new EOR technique. In this study, basic concepts in chemical EOR are presented, while the design of chemical formulation, phase behavior, and the role of foam are discussed in details. Experimental results showed relatively good recovery, low surfactant retention. However, pressure drop during chemical injections were high, which indicates the formation of both strong foam and viscous microemulsion at the displacement front when surfactant starts solubilizing oil. Overall, ASG showed good performance on carbonate rocks. Optimization can be made on surfactant formula to form less viscous microemulsion and therefore improve efficiency of the process. / text

Highly fractured carbonate reservoirs are a class of reservoirs characterized by high conductivity fractures surrounding low permeability matrix blocks. In these reservoirs, wettability alteration is a key method for recovering oil. Water imbibes into the matrix blocks upon water flooding if the reservoir rock is water-wet. However, many carbonate reservoirs are oil-wet. Surfactant solution was used to enhance spontaneous imbibition between the fractures and the matrix by both wettability alteration and ultra-low interfacial tensions. The first part of this study was devoted to determining the wettability of reservoir rocks using Amott-Harvey Index method, and also evaluating the performance of surfactants on wettability alteration, based on the contact angle measurement and spontaneous imbibition rate and ultimate oil recovery on oil-wet reservoir cores. The reservoir rocks have been found to be slightly oil-wet. One cationic surfactant BTC8358, one anionic surfactant and one ultra-low IFT surfactant formulation AKL-207 are all found to alter the wettability towards more water-wet and promote oil recovery through spontaneous imbibition. The second part of the study focused on the parameters that affect wettability alteration by surfactants. Some factors such as core dimension, permeability and heterogeneity of porous medium are evaluated in the spontaneous imbibition tests. Higher permeability leads to higher imbibition rate and higher ultimate oil recovery. Heterogeneity of core samples slows down the imbibition process if other properties are similar. Core dimension is critical in upscaling from laboratory conditions to field matrix blocks. The imbibition rate is slower in larger dimension of core. Further, we investigated the effects of EDTA in surfactant-mediated spontaneous imbibition. Since high concentration of cationic divalent ions in the aqueous solution markedly suppresses the surfactant-mediated wettability alteration, EDTA improved the performance of surfactant in the spontaneous imbibition tests. It is proposed in the thesis that surfactant/EDTA-enhanced imbibition may involve the dissolution mechanism. More experiments should be conducted to verify this mechanism. The benefits of using EDTA in the surfactant solution include but not limited to: altering the surface charge of carbonate to negative, producing the in-situ soap, reducing the brine hardness, decreasing the surfactant adsorption, and creating the water-wet area by dissolving the dolomite mineral. / text

No description available.

Stricter greenhouse gas emission limits and renewable energy requirements are expected to further increase the worldwide practices of firing biomass and co-firing biomass with coal, which are both considered more sustainable energy sources than coal-only combustion. Reuse options for the by-products of these processes -biomass ash and co-fired fly ash -remain limited. Therefore, this research examines their use as supplementary cementitious materials (SCMs) in concrete and as precursors for alkali-activated geopolymers. Toward their potential use as an SCM, after characterizing these ashes assessing their compliance with ASTM C618 requirements, their impact on early-age hydration kinetics, rheology, setting time and permeability was assessed. Furthermore, the pozzolanic reactivity and the microstructural and hydrated phase development of the cement-ash samples were analyzed. The results show that a wood biomass ash sample was not satisfactory for use as an SCM. On the other hand, the findings demonstrate that co-fired fly ashes can significantly improve the strength and durability properties of concrete compared to ordinary portland cement, in part due to their pozzolanicity. Thus, it is recommended that the ASTM C618 standard be modified to permit co-fired fly ash sources that meet existing requirements and any additional requirements deemed necessary to ensure their satisfactory performance when used in concrete. Toward their potential use in geopolymers, this study characterized the early-age reaction kinetics and rheological behavior of these materials, showing that their exothermic reactivity, plastic viscosity and yield stress are significantly influenced by the activator solution chemistry and other characteristics of the ash. Two co-fired fly ashes were successfully polymerized, with compressive strengths generally highest for ashes activated with solutions with a molar ratio of SiO₂/(Na₂O + K₂O) = 1. The results show that geopolymerization is a viable beneficial reuse for these emerging by-products. Further characterization of these materials by scanning transmission X-ray microscopy analysis revealed the heterogeneity of the aluminosilicate phase composition of the co-fired fly ash geopolymer gel at the nano- to micro-scale.

The Accelerated Mortar Bar test (AMBT) is rapid, reproducible, and perhaps the most widely used technique for examining the potential alkali-silica reactivity of aggregates. Unfortunately, this test is often unreliable as it may identify non-reactive aggregate as reactive and vice versa. With the aim of improving the accuracy of AMBT, two modifications to the current procedure were evaluated: 1) the maturity of mortar bars prior to alkali hydroxide exposure and 2) reduction of the storage temperature. The original and modified versions were performed on six aggregates with alkali-silica reactive (ASR) components, and their expansions and ASR classifications were compared. Results show that increasing the maturity had no significant impact on expansions. However, modifying the storage temperature to 60˚C and extending the period of testing to 28 days can be very effective in terms of more reliably identifying the existing falsely identified aggregates.

The Accelerated Mortar Bar test (AMBT) is rapid, reproducible, and perhaps the most widely used technique for examining the potential alkali-silica reactivity of aggregates. Unfortunately, this test is often unreliable as it may identify non-reactive aggregate as reactive and vice versa. With the aim of improving the accuracy of AMBT, two modifications to the current procedure were evaluated: 1) the maturity of mortar bars prior to alkali hydroxide exposure and 2) reduction of the storage temperature. The original and modified versions were performed on six aggregates with alkali-silica reactive (ASR) components, and their expansions and ASR classifications were compared. Results show that increasing the maturity had no significant impact on expansions. However, modifying the storage temperature to 60˚C and extending the period of testing to 28 days can be very effective in terms of more reliably identifying the existing falsely identified aggregates.

No description available.

Novel Studies on the Formation and Chemical Reactivity of Compound Clusters and Their Precursors in the Gas and Liquid Phase James A. Bradshaw 139 Pages Directed by Dr. Robert L. Whetten Presented are four separate and unique studies on molecular and nanoscale systems: Atmospheric hydration and aggregation of NaCl clusters, highly water-soluble aurous-thiolate oligomers, water-soluble gold clusters from aurous-thiolate oligomer precursors, and gold iodide clusters. Adsorption of water on cationic and anionic sodium chloride clusters is investigated to elucidate active sites of molecular interaction as well as primary aggregate formation kinetics. Considered an exceptionally abundant atmospheric species, experiments are conducted to further quantify gas phase chemistry and hydration/solvation of alkali halides. Currently the most soluble of all known gold-thiolates, para-mercaptobenzoic acid-based (pMBA) aurous-thiolate oligomers are investigated and physical and chemical properties quantified. Solubility, structural conformation, and poly-dispersity of higher homologs are observed with the goal of further applications in clusters research, medical and biomedical, and industry. Gold thiolate clusters, synthesized using pMBA-based oligomers, are investigated through reductive formation in solution. UV-VIS and UV-VIS-NIR spectroscopy is undertaken to assign structures based on predictions of the HOMO-LUMO gap and other electronic transitions. Gold iodide is investigated in relation to the common thiolate-halide analogy. Synthesis and characterization of a solid precursor as well as anion and cation cluster formation is presented as part of an ongoing collaboration.