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%.

Computational fluid dynamics (CFD) based approach to consequence assessment of accidental release of hydrocarbon during storage and transportation

This thesis investigated the risk of accidental release of hydrocarbons during transportation and storage. Transportation of hydrocarbons from an offshore platform to processing units through subsea pipelines involves risk of release due to pipeline leakage resulting from corrosion, plastic deformation caused by seabed shakedown or damaged by contact with drifting iceberg. The environmental impacts of hydrocarbon dispersion can be severe. Overall safety and economic concerns of pipeline leakage at subsea environment are immense. A large leak can be detected by employing conventional technology such as, radar, intelligent pigging or chemical tracer but in a remote location like subsea or arctic, a small chronic leak may be undetected for a period of time. In case of storage, an accidental release of hydrocarbon from the storage tank could lead pool fire; further it could escalate to domino effects. This chain of accidents may lead to extremely severe consequences. Analyzing past accident scenarios it is observed that more than half of the industrial domino accidents involved fire as a primary event, and some other factors for instance, wind speed and direction, fuel type and engulfment of the compound. In this thesis, a computational fluid dynamics (CFD) approach is taken to model the subsea pipeline leak and the pool fire from a storage tank. A commercial software package ANSYS FLUENT Workbench 15 is used to model the subsea pipeline leakage. The CFD simulation results of four different types of fluids showed that the static pressure and pressure gradient along the axial length of the pipeline have a sharp signature variation near the leak orifice at steady state condition. Transient simulation is performed to obtain the acoustic signature of the pipe near leak orifice. The power spectral density (PSD) of acoustic signal is strong near the leak orifice and it dissipates as the distance and orientation from the leak orifice increase. The high-pressure fluid flow generates more noise than the low-pressure fluid flow. In order to model the pool fire from the storage tank, ANSYS CFX Workbench 14 is used. The CFD results show that the wind speed has significant contribution on the behavior of pool fire and its domino effects. The radiation contours are also obtained from CFD post processing, which can be applied for risk analysis. The outcome of this study will be helpful for better understanding of the domino effects of pool fire in complex geometrical settings of process industries. The attempt to reduce and prevent risks is discussed based on the results obtained from the numerical simulations of the numerical models.