Characterization of wood biochar and evaluation of its adsorption potential for removal of sulphate from produced water in offshore oil and gas industry

This thesis analyses the potential of wood biochar as an adsorbent in removal of sulphate from produced water. In worldwide offshore oil and gas industry, a large volume of waste water is generated as produced water. Sulphur compounds present in these produced water streams can cause environmental problems, regulatory problems and operational issues. Among the various sulphur removal technologies, the adsorption technique is considered as a suitable method since the design is simple, compact, economical and robust. Biochar has been studied as an adsorbent for removal of contaminants from water in a number of studies due to its low cost, potential availability, and adsorptive characteristics. In this study, biochar produced through fast pyrolysis of bark, hardwood sawdust, and softwood sawdust were characterized through a series of tests and were analysed for adsorbent properties. Treating produced water using biochar sourced from wood waste is a two-fold solution to environmental problems as it reduces the volume of these wastes. Batch adsorption tests were carried out to obtain adsorption capacities of each biochar sample using sodium sulphate solutions. The highest sulphur adsorption capacities obtained for hardwood char, softwood char and bark char were 11.81 mg/g, 9.44 mg/g, and 7.94 mg/g respectively at 10 °C and pH=4. The adsorption process followed the second order kinetic model and the Freundlich isotherm model. Adsorption reaction was thermodynamically favourable and exothermic. The overall analysis concludes that the wood biochar is a feasible, economical, and environmental adsorbent for removal of sulphate from produced water.

Phase and partitioning behavior of phenols and polycyclic aromatic hydrocarbons in offshore oil and gas produced water

Produced water constitutes the largest volume of waste from offshore oil and gas operations and is composed of a wide range of organic and inorganic compounds. Although treatment processes have to meet strict oil in water regulations, the definition of “oil” is a function of the analysis process and may include aliphatic hydrocarbons which have limited environmental impact due to degradability whilst ignoring problematic dissolved petroleum species. This thesis presents the partitioning behavior of oil in produced water as a function of temperature and salinity to identify compounds of environmental concern. Phenol, p-cresol, and 4-tert-butylphenol were studied because of their xenoestrogenic power; other compounds studied are polycyclic aromatic hydrocarbon PAHs which include naphthalene, fluorene, phenanthrene, and pyrene. Partitioning experiments were carried out in an Innova incubator for 48 hours, temperature was varied from 4ﾟC to 70ﾟC, and two salinity levels of 46.8‰ and 66.8‰ were studied. Results obtained showed that the dispersed oil concentration in the water reduces with settling time and equilibrium was attained at 48 h settling time. Polycyclic aromatic hydrocarbons (PAHs) partitions based on dispersed oil concentration whereas phenols are not significantly affected by dispersed oil concentration. Higher temperature favors partitioning of PAHs into the water phase. Salinity has negligible effect on partitioning pattern of phenols and PAHs studied. Simulation results obtained from the Aspen HYSYS model shows that temperature and oil droplet distribution greatly influences the efficiency of produced water treatment system.

A study of methods used to analyze total oil and polycyclic aromatic hydrocarbons in produced water: steps towards the validation of molecularly imprinted polymers for use in marine environmetns

Produced water is a by-product of offshore oil and gas production, and is released in large volumes when platforms are actively processing crude oil. Some pollutants are not typically removed by conventional oil/water separation methods and are discharged with produced water. Oil and grease can be found dispersed in produced water in the form of tiny droplets, and polycyclic aromatic hydrocarbons (PAHs) are commonly found dissolved in produced water. Both can have acute and chronic toxic effects in marine environments even at low exposure levels. The analysis of the dissolved and dispersed phases are a priority, but effort is required to meet the necessary detection limits. There are several methods for the analysis of produced water for dispersed oil and dissolved PAHs, all of which have advantages and disadvantages. In this work, EPA Method 1664 and APHA Method 5520 C for the determination of oil and grease will be examined and compared. For the detection of PAHs, EPA Method 525 and PAH MIPs will be compared, and results evaluated. APHA Method 5520 C Partition-Infrared Method is a liquid-liquid extraction procedure with IR determination of oil and grease. For analysis on spiked samples of artificial seawater, extraction efficiency ranged from 85 – 97%. Linearity was achieved in the range of 5 – 500 mg/L. This is a single-wavelength method and is unsuitable for quantification of aromatics and other compounds that lack sp³-hybridized carbon atoms. EPA Method 1664 is the liquid-liquid extraction of oil and grease from water samples followed by gravimetric determination. When distilled water spiked with reference oil was extracted by this procedure, extraction efficiency ranged from 28.4 – 86.2%, and %RSD ranged from 7.68 – 38.0%. EPA Method 525 uses solid phase extraction with analysis by GC-MS, and was performed on distilled water and water from St. John’s Harbour, all spiked with naphthalene, fluorene, phenanthrene, and pyrene. The limits of detection in harbour water were 0.144, 3.82, 0.119, and 0.153 g/L respectively. Linearity was obtained in the range of 0.5-10 g/L, and %RSD ranged from 0.36% (fluorene) to 46% (pyrene). Molecularly imprinted polymers (MIPs) are sorbent materials made selective by polymerizing functional monomers and crosslinkers in the presence of a template molecule, usually the analytes of interest or related compounds. They can adsorb and concentrate PAHs from aqueous environments and are combined with methods of analysis including GC-MS, LC-UV-Vis, and desorption electrospray ionization (DESI)- MS. This work examines MIP-based methods as well as those methods previously mentioned which are currently used by the oil and gas industry and government environmental agencies. MIPs are shown to give results consistent with other methods, and are a low-cost alternative improving ease, throughput, and sensitivity. PAH MIPs were used to determine naphthalene spiked into ASTM artificial seawater, as well as produced water from an offshore oil and gas operation. Linearity was achieved in the range studied (0.5 – 5 mg/L) for both matrices, with R² = 0.936 for seawater and R² = 0.819 for produced water. The %RSD for seawater ranged from 6.58 – 50.5% and for produced water, from 8.19 – 79.6%.

An application of evolutionary algorithms for WAG optimisation in the Norne Field

Water-alternating-gas (WAG) is an enhanced oil recovery method combining the improved macroscopic sweep of water flooding with the improved microscopic displacement of gas injection. The optimal design of the WAG parameters is usually based on numerical reservoir simulation via trial and error, limited by the reservoir engineer’s availability. Employing optimisation techniques can guide the simulation runs and reduce the number of function evaluations. In this study, robust evolutionary algorithms are utilized to optimise hydrocarbon WAG performance in the E-segment of the Norne field. The first objective function is selected to be the net present value (NPV) and two global semi-random search strategies, a genetic algorithm (GA) and particle swarm optimisation (PSO) are tested on different case studies with different numbers of controlling variables which are sampled from the set of water and gas injection rates, bottom-hole pressures of the oil production wells, cycle ratio, cycle time, the composition of the injected hydrocarbon gas (miscible/immiscible WAG) and the total WAG period. In progressive experiments, the number of decision-making variables is increased, increasing the problem complexity while potentially improving the efficacy of the WAG process. The second objective function is selected to be the incremental recovery factor (IRF) within a fixed total WAG simulation time and it is optimised using the same optimisation algorithms. The results from the two optimisation techniques are analyzed and their performance, convergence speed and the quality of the optimal solutions found by the algorithms in multiple trials are compared for each experiment. The distinctions between the optimal WAG parameters resulting from NPV and oil recovery optimisation are also examined. This is the first known work optimising over this complete set of WAG variables. The first use of PSO to optimise a WAG project at the field scale is also illustrated. Compared to the reference cases, the best overall values of the objective functions found by GA and PSO were 13.8% and 14.2% higher, respectively, if NPV is optimised over all the above variables, and 14.2% and 16.2% higher, respectively, if IRF is optimised.

Identifying the major spilled oil constituents and fate in harsh offshore environments

The behaviour and fate of spilled oil in harsh marine environments, such as the North Atlantic and the Arctic Ocean are complex due to environmental factors and the composition of the crude. In order to develop appropriate oil spill prevention and management methods, we must first understand how the oil behaves in these harsh environmental conditions. This study focuses on determining the fate of oil in harsh marine environments by first identifying target compounds in the oil that can be used to determine the fate of a spill. This thesis presents the partitioning behaviour of six polycyclic aromatic hydrocarbons (PAHs), which represent different groups, and phenols in cold conditions. The smallest PAH, naphthalene, dominated in terms of concentration in water accommodated fraction (WAF) of oil, while the larger ringed PAHs presented at lower concentrations. The smallest oil-water partition coefficient was recorded by phenol which partitioned into the seawater more quickly than PAHs. The partitioning of larger PAHs was slower and they indicated high partition coefficients. The oil partitioning increased slightly as temperature increased from 4ᴼC to 15ᴼC. The oil loading (0.1 g/L to 10 g/L) also contributed in deciding the concentrations in water. The use of chemical dispersants is a common response to spills. This study identified that chemical dispersants can change the fate of an oil spill by increasing the availability of oil in seawater. The concentration of larger PAHs such as pyrene and chrysene increased significantly with the application of dispersants. The information obtained are used in developing a molecular imprinted polymer (MIP) sensor to identify oil spills in the North Atlantic Ocean.

The effects of simulated lifeboat motions on carbon dioxide production

A Totally Enclosed Motor Propelled Survival Craft (TEMPSC) is currently the primary mode of escape during a maritime and offshore emergency situation. Although lifeboats have evolved from their original design, the interior comfort and habitability of the craft has remained virtually unchanged and is not considered during the certification process. Ambient carbon dioxide (CO₂) accumulation within TEMPSC is one factor, along with many others that may cause serious health implications for TEMPSC occupants. Previous research has shown that with the hatches closed and the participants at rest, an international 8-hour exposure limit of 4800ppm may be reached in as little as 15 minutes. This study uses simulation as a testing methodology to determine if vessel motions in various sea-states impact the time to reach this same CO₂ exposure limit because of physical exertions of the participants to maintain stability within their seats.

Dynamic safety analysis of managed pressure drilling operations

The exploration and development of oil and gas reserves located in harsh offshore environments are characterized with high risk. Some of these reserves would be uneconomical if produced using conventional drilling technology due to increased drilling problems and prolonged non-productive time. Seeking new ways to reduce drilling cost and minimize risks has led to the development of Managed Pressure Drilling techniques. Managed pressure drilling methods address the drawbacks of conventional overbalanced and underbalanced drilling techniques. As managed pressure drilling techniques are evolving, there are many unanswered questions related to safety and operating pressure regimes. Quantitative risk assessment techniques are often used to answer these questions. Quantitative risk assessment is conducted for the various stages of drilling operations – drilling ahead, tripping operation, casing and cementing. A diagnostic model for analyzing the rotating control device, the main component of managed pressure drilling techniques, is also studied. The logic concept of Noisy-OR is explored to capture the unique relationship between casing and cementing operations in leading to well integrity failure as well as its usage to model the critical components of constant bottom-hole pressure drilling technique of managed pressure drilling during tripping operation. Relevant safety functions and inherent safety principles are utilized to improve well integrity operations. Loss function modelling approach to enable dynamic consequence analysis is adopted to study blowout risk for real-time decision making. The aggregation of the blowout loss categories, comprising: production, asset, human health, environmental response and reputation losses leads to risk estimation using dynamically determined probability of occurrence. Lastly, various sub-models developed for the stages/sub-operations of drilling operations and the consequence modelling approach are integrated for a holistic risk analysis of drilling operations.