Thesis (Ph.D.)--University of Alabama at Birmingham, 2007. / Title from PDF title page (viewed on Feb. 19, 2010). Includes bibliographical references.

Hydrocarbon reserves are generally produced through wells drilled into reservoir pay zones. During production, gas liberation from the oil phase occurs due to pressure decline in the wellbore. Thus, we expect multiphase flow in some sections of the wellbore. As a multi-phase/multi-component gas-oil mixture flows from the reservoir to the surface, pressure, temperature, composition, and liquid holdup distributions are interrelated. Modeling these multiphase flow parameters is important to design production strategies such as artificial lift procedures. A wellbore fluid flow model can also be used for pressure transient test analysis and interpretation. Considering heat exchange in the wellbore is important to compute fluid flow parameters accurately. Modeling multiphase fluid flow in the wellbore becomes more complicated due to heat transfer between the wellbore fluids and the surrounding formations. Due to mass, momentum, and energy exchange between the wellbore and the reservoir, the wellbore model should be coupled with a numerical reservoir model to simulate fluid flow accurately. This model should be non-isothermal to consider the effect of temperature. Our research shows that, in some cases, ignoring compositional effects may lead to errors in pressure profile prediction for the wellbore. Nearly all multiphase wellbore simulations are currently performed using the "black oil" approach. The primary objective of this study was to develop a non-isothermal wellbore simulator to model transient fluid flow and temperature and couple the model to a reservoir simulator called General Purpose Adaptive Simulator (GPAS). The coupled wellbore/reservoir simulator can be applied to steady state problems, such as production from, or injection to a reservoir as well as during transient phenomena such as well tests to accurately model wellbore effects. Fluid flow in the wellbore may be modeled either using the blackoil approach or the compositional approach, as required by the complexity of the fluids. The simulation results of the new model were compared with field data for pressure gradients and temperature distribution obtained from wireline conveyed pressure recorder and acoustic fluid level measurements for a gas/oil producer well during a buildup test. The model results are in good agreement with the field data. Our simulator gave us further insights into the wellbore dynamics that occur during transient problems such as phase segregation and counter-current multiphase flow. We show that neglecting these multiphase flow dynamics would lead to unreliable results in well testing analysis.

A significant percentage of computational time in compositional simulations is spent performing flash calculations to determine the equilibrium compositions of hydrocarbon phases in situ. Flash calculations must be done at each time step for each grid block; thus billions of such calculations are possible. It would be very important to reduce the computational time of flash calculations significantly so that more grid blocks or components may be used. In this dissertation, three different methods are developed that yield fast, robust and accurate phase behavior calculations useful for compositional simulation and other applications. The first approach is to express the mixing rule in equations-of-state (EOS) so that a flash calculation is at most a function of six variables, often referred to as reduced parameters, regardless of the number of pseudocomponents. This is done without sacrificing accuracy and with improved robustness compared with the conventional method. This approach is extended for flash calculations with three or more phases. The reduced method is also derived for use in stability analysis, yielding significant speedup. The second approach improves flash calculations when K-values are assumed constant. We developed a new continuous objective function with improved linearity and specified a small window in which the equilibrium compositions must lie. The calculation speed and robustness of the constant K-value flash are significantly improved. This new approach replaces the Rachford-Rice procedure that is embedded in the conventional flash calculations. In the last approach, a limited compositional model for ternary systems is developed using a novel transformation method. In this method, all tie lines in ternary systems are first transformed to a new compositional space where all tie lines are made parallel. The binodal curves in the transformed space are regressed with any accurate function. Equilibrium phase behavior calculations are then done in this transformed space non-iteratively. The compositions in the transformed space are translated back to the actual compositional space. The new method is very fast and robust because no iteration is required and thus always converges even at the critical point because it is a direct method. The implementation of some of these approaches into compositional simulators, for example UTCOMP or GPAS, shows that they are faster than conventional flash calculations, without sacrificing simulation accuracy. For example, the implementation of the transformation method into UTCOMP shows that the new method is more than ten times faster than conventional flash calculations.

Many hydrocarbon reservoirs have sufficient porosity but low permeability (for example, tight gas sands and coal beds). However, such reservoirs are often naturally fractured. The fracture patterns in these reservoirs can control flow and transport properties, and therefore, play an important role in drilling production wells. On the scale of seismic wavelengths, closely spaced parallel fractures behave like an anisotropic media, which precludes the response of individual fractures in the seismic data. There are a number of fracture parameters which are needed to fully characterize a fractured reservoir. However, seismic data may reveal only certain fracture parameters and those are fracture orientation, crack density and fracture infill. Most of the widely used fracture characterization methods such as Swave splitting analysis or amplitude vs. offset and azimuth (AVOA) analysis fail to render desired results in laterally varying media. I have conducted a systematic study of the response of fractured reservoirs with laterally varying elastic and fracture properties, and I have developed a scheme to invert for the fracture parameters. I have implemented a 3D finite-difference method to generate multicomponent synthetic seismic data in general anisotropic media. I applied the finite-difference algorithm in both Standard and Rotated Staggered grids. Standard Staggered grid is used for media having symmetry up to orthorhombic (isotropic, transversely isotropic, and orthorhombic), whereas Rotated Staggered grid is implemented for monoclinic and triclinic media. I have also developed an efficient and accurate ray-bending algorithm to compute seismic traveltimes in 3D anisotropic media. AVOA analysis is equivalent to the first-order Born approximation. However, AVOA analysis can be applied only in a laterally uniform medium, whereas the Born-approximation does not pose any restriction on the subsurface structure. I have developed an inversion scheme based on a ray-Born approximation to invert for the fracture parameters. Best results are achieved when both vertical and horizontal components of the seismic data are inverted simultaneously. I have also developed an efficient positivity constraint which forbids the inverted fracture parameters to be negative in value. I have implemented the inversion scheme in the frequency domain and I show, using various numerical examples, that all frequency samples up to the Nyquist are not required to achieve desired inversion results.

The objective of reservoir management is to maximize a key performance indicator (net present value in this study) at a minimum cost. A typical approach includes engineering analysis, followed by the economic value of the technical study. In general, operators are inclined to spend more effort on the engineering side to the detriment of the economic area, leading to unbalanced and occasionally suboptimal results. Moreover, most of the optimization methods used for production scheduling focus on a given recovery phase, or medium-term strategy, as opposed to an integrated solution that allocates resources from discovery to field abandonment. This thesis addresses the optimization of a reservoir under both technical and economic constraints. In particular, the method presented introduces a life cycle maximization approach to establish the best exploitation strategy throughout the life of the project. Deterministic studies are combined with stochastic modeling and risk analysis to assess decision making under uncertainty. To demonstrate the validity of the model, this document offers two case studies and the optimal times associated with each recovery phase. In contrast with traditional depletion strategies, where the optimization is done myopically by maximizing the net present value at each recovery phase, our results suggest that time is dramatically reduced when the net present value is optimized globally by maximizing the NPV for the life of the project. Furthermore, the sensitivity analysis proves that the original oil in place and non-engineering parameters such as the price of oil are the most influential variables. The case studies clearly show the greater economic efficiency of this life cycle approach, confirming the potential of this optimization technique for practical reservoir management. / text

Numerical simulations indicate that hydrocarbon migration and entrapment in stacked fault-bounded reservoirs are mainly affected by the following factors: charge time, faults, pressure and geological structures. The charge time for commercial hydrocarbon accumulation is much longer in oil-water systems than in oil-gas-water systems. Faults are classified into charging faults and 'back doors' faults other than charging faults in stacked fault-bounded reservoirs. The lower the displacement pressure of a fault, the higher its updip oil transportation ability. The downdip oil transportation ability of a fault is usually low and cannot cause commercial downdip oil accumulation. Back doors affect both hydrocarbon percent charge and hydrocarbon migration pathways. Updip back doors improve updip oil charge. The lower the displacement pressure of an updip back door, the more efficient the updip oil charge before 3,000 years. Back doors whose displacement pressure is equal to or higher than 28.76 psi are effective in sealing faults in oil-water systems. On the contrary, only sealing faults result in commercial gas accumulations in stacked fault-compartmentalized reservoirs. Otherwise gas is found over oil. Downdip back doors generally have few effects on downdip hydrocarbon charge. Geopressure enhances the updip oil transportation of a fault and improves the positive effects of updip back doors during updip oil charge. Geopressure and updip back doors result in more efficient updip oil charge. A physical barrier is not necessarily a barrier to oil migration with the aid of geopressure and updip back doors. The chance for hydrocarbon charge into reservoirs along growth faults is not equal. Any one of the above controlling factors can change the patterns of hydrocarbon charge and distribution in such complex geological structures. Generally, lower reservoirs and updip reservoirs are favored. Reservoirs along low-permeability charging faults may be bypassed. Gas can only charge the updip reservoirs. Both updip and downdip back doors can facilitate oil penetrating a barrier fault to charge reservoirs offset by the barrier fault. Interreservoir migration among stacked fault-compartmentalized reservoirs is an important mechanism for hydrocarbon accumulation and trap identification. The interreservoir migration is a very slow process, even though the displacement pressures of bounding faults may be very low.

Metal-cyclic hydrocarbon complexes were prepared in a laser-vaporization molecular beam source and studied by single-photon zero electron kinetic energy (ZEKE) and IR-UV resonant two-photon ionization (R2PI) spectroscopy. The ionization energies and vibrational frequencies of the metal complexes were measured from the ZEKE spectra. Metal-ligand bonding and low-lying electronic states of the neutral and ionized complexes were analyzed by combining the ZEKE measurements with density functional theory (DFT) calculations. In addition, C-H stretching frequencies were measured from the R2PI spectra. In this dissertation, metal complexes of 1, 3, 5, 7-cyclo-octatetraene (COT), toluene, p-xylene, mesitylene, hexamethylbenzene, biphenyl, naphthalene, pyrene, perylene, and coronene were studied. For each metal-ligand complex, different effects from the metal coordination have been identified. Although free COT is a nonaromatic molecule with a tub-shaped structure, the group III transition metal atoms (Sc, Y, and La) donate two electrons to a partially filled π orbital of COT, making the ligand a dianion. As a result, metal coordination converts COT into a planar, aromatic structure and the resulting complex exhibits a half-sandwich structure. For the Sc(methylbenzene) complexes, the benzene rings of the ligands are bent and the π electrons are localized in a 1, 4-diene fashion due to differential Sc binding with the carbon atoms of the rings. Due to differential metal binding, the degenerate d orbitals split and the Sc-methylbenzene complexes prefer the low-spin ground electronic states. In addition, as the number of methyl group substituents in the ligand increases, the ionization energies (IEs) of the Sc-methylbenzene complexes decrease. However, Ti, V, or Co coordination does not disrupt the delocalized π electron network within the carbon skeleton in the high-spin ground states of the metal complexes. For group VI metal (Cr, Mo, and W)-bis(toluene) complexes, methyl substitution on the benzene ring yields complexes with four rotational conformers of 0°, 60°, 120°, and 180° conformation angles between two methyl groups. In addition, variable-temperature ZEKE spectroscopy using He, Ar, or their mixtures has determined the totally eclipsed 0° rotamer to be the most stable. When there are two equivalent benzene rings, the metal (Ti, Zr or Hf) binds to both the benzene rings of biphenyl, or the metal (Li) binds to one of the benzene rings of naphthalene. On the other hand, the metal (Li) favors the ring-over binding site of the benzene ring with a higher π electron content and aromaticity in pyrene, perylene, and coronene.

Aryl hydrocarbon receptor (AHR) is a sensor protein, activated by aromatic chemical species for transcriptionally regulating xenobiotic metabolizing enzymes. AHR is also known to be involved in a variety of pathogenesis such as cancer, diabetes mellitus, cirrhosis, asthma, etc. The AHR signaling induced by xenobiotics has been intensively studied whereas its physiological role in the absence of xenobiotics is poorly understood. Despite a number of ligands of AHR have been reported thus far, further applications are still hampered by the lack of specificity and/or the partially agonistic activity. Thus, a pure AHR antagonist is needed for deciphering the AHR cryptic as well as potential therapeutic agent. The Proteolysis Targeting Chimera (PROTAC) is a bi-functional small molecule containing a ligand and proteolysis inducer. PROTAC recruits the target protein to proteolysis machinery and elicits proteolysis. Thus far, a number of PROTAC have been prepared and demonstrated to effectively induce the degradation of targeted protein in cultured cells, validating PROTAC as a useful research tool. In the present study, PROTACs based on apigenin was prepared and demonstrated to induce the degradation of AHR, providing the proof of concept. To improve activity, a synthetic structure, CH-223191, was optimized for antagonistic activity by positional scanning identifying several AHR antagonists. PROTACs based on the optimal structure were prepared and assessed their biological activity. The products and synthetic scheme described hereby will be helpful for the further understanding on AHR biology as well as for developing therapeutic agents targeting AHR.

Metal-hydrocarbon complexes were prepared in a laser-vaporization molecular beam source and studied by single-photon zero electron kinetic energy (ZEKE) and mass-analyzed threshold ionization (MATI) spectroscopy. The ionization energies and vibrational frequencies of the metal complexes were measured from the ZEKE and MATI spectra. Metal-ligand bonding and low-lying electronic states of the neutral and ionized complexes were analyzed by combining the spectroscopic measurements with quantum chemical calculations and spectral simulations. In this dissertation, the metal complexes of mesitylene, aniline, cyclooctatetraene, benzene, ethene, and propene were studied. For each complex, different effects from metal coordination have been identified. Although metal-bis(mesitylene) sandwich complexes may adopt eclipsed and staggered conformations, the group VI metal-bis(mesitylene) complexes are determined to be in the eclipsed form. In this form, rotational conformers with the methyl group dihedral angles of 0 and 60° are identified for the Cr complex, whereas the 0° rotamer is observed for the Mo and W species. The unsuccessful observation of the 60° rotamer for the Mo and W complexes is the result of its complete conversion to the 0° rotamer in both He and He/Ar carriers. For group III metal aniline complexes, the ZEKE spectrum of each complex exhibits a strong origin band, a short M+-aniline stretching progression, and several low-frequency ligand based vibrational modes. The intensities of most of the transitions can be explained by the Franck-Condon (FC) principle within the harmonic approximation. However, the intensity of the low frequency out-of-plane ring deformation mode is greatly overestimated by the FC calculations and may be caused by the anharmonic nature of the mode. Although aniline offers two possible binding modes for the metal atoms, a п binding mode is identified with the metal atom over the phenyl ring. For Ce, Pr, and Nd(cyclooctatetraene) complexes multiple band systems are observed. This is assigned to the ionization of several low-lying electronic states of the neutral complex. This observation is different from the Gd(cyclooctatetraene) complex, for which a single band system is observed. The presence of the multiple low-energy electronic states is caused by the splitting of the partially filled lanthanide 4f orbitals in the ligand field. The ZEKE spectrum of the Gd(benzene) complex exhibits a strong origin band, whereas the spectrum of Lu(benzene) displays a weak one. The benzene ring is planar in the Gd complex, but bent in the Lu complex. Dehydrogenation and C-C coupling products are observed in the reaction of La atom and ethene/propene. For the La and ethene reaction, La(C2H2) and La(C4H6) complexes are identified. With propene, C-H bond activation leads to the formation of the La(C3H4) and H-La(C3H5) complexes, whereas the C-C coupling yields the La(trimethylenemethane) complex. In addition, the La(CHCCH3) and La(CHCHCH2) isomers of La(C3H4) are observed, which are produced by the 1,2- and 1,3-hydrogen elimination of propene.

The production of hydrogen (H2) and methane (CH4) related to olivine hydration (i.e. serpentinization) is considered a major contributor to abiotic hydrocarbon synthesis on Earth. Recent discoveries have highlighted the importance of low temperature (<100oC) serpentinization at continental peridotite outcrops. Such sites produce substantial fluxes of abiotic CH4 from gas seeps and/or springs. A limited number of studies in the southern hemisphere offer research on low temperature abiotic hydrocarbon synthesis in natural ultramafic environments, though large areas of exposed ophiolite are prevalent. This study assesses the origin and flux of CH4 and related water-rock interactions from a previously undiscovered site in the Dun Mountain Ophiolite Belt (DMOB), located at Red Hills, New Zealand. Methane emissions from a hyper-alkaline (pH >11.6) and reduced spring of calcium hydroxide (Ca2+-OH-) type waters near the Maitlands Fault were between 730 to 17,000 mg m 2day 1. The δ13C and δD values of CH4 emitting from this spring are consistent with CH4 of abiotic origin (δ13C: 32.7 ‰ VPDB, δD: 363 ‰ V SMOW). Hyper-alkaline fluids emitting from the spring are concentrated in dissolved CH4 (2.2 mg/L) and H2 (0.7 mg/L) and display δ13CCH4 signatures consistent with other sites worldwide. Extensive and localised carbonate precipitation occurs at the hyper-alkaline Ca-rich spring. Isotopic evaluation of carbonate nodules are kinetically fractionated with 13C and 18O depletions up to 30.8 ‰ and 9.3 ‰, respectively. This disequilibrium between the mineralogy and interacting fluids and gases represents a potential habitable environment for microorganisms. Porous, layered carbonates located on the outer edges of the hyper-alkaline spring are the result of atmospheric CO2 interaction with magnesium bicarbonate (Mg2+-HCO3) and Ca2+-OH- hyper-alkaline waters. The precipitation of these carbonates offers potential insight towards low temperature CO2 sequestration. Additionally, various forms of Fe-rich amorphous material precipitate in association with Mg2+-HCO3 type waters at the Red Hills. The identification of bacteria and diatoms within this material offers supporting information regarding microbial survival in metal-rich, reduced environments. This multidisciplinary study demonstrates the interconnected nature of geological, biological and atmospheric interactions in ultramafic environments at low temperature on Earth.