The performance of a submerged membrane bioreactor for the duty of gas field produced water treatment was appraised. The system was operated under steady state conditions at a range of mixed liquor suspended solids (MLSS) concentrations and treatment and membrane performance examined. Organics removal (COD and TOC) display removal rates between 90 and 97%. Removal of specific target compounds Benzene, Toulene, Ethylbenzene and Xylene were removed to above 99% in liquid phase with loss to atmosphere between 0.3 and 1%. Comparison of fouling rates at a number of imposed fluxes has been made between long term filtration trials and short term tests using the flux step method. Produced water fed biomass displays a greater fouling propensity than municipal wastewater fed biomass from previous studies. Results indicate an exponential relationship between fouling rate and flux for both long and short term trials, although the value was an order of magnitude lower during long term tests. Moreover, operation during long term trials is characterised by a period of pseudo stable operation followed by a catastrophic rise in TMP at a given critical filtration time (tfi, ) during trials at 6 g. L"1. This time of stable operation, tfit, is characterised by a linear relationship between fouling rate and flux. Results have been compared with the literature. Data for membrane fouling prior to the end of t fit yielded a poor fit with a recently proposed model. Trends recorded at t> trlt revealed the fouling rate to follow no definable trend with flux. The system showed resilience to free oil shocking up to an oil concentration of 200ppmv. Following an increase in oil concentration to 500 ppmv, rapid and exponential fouling ensued.

Produced water (PW), or water associated with crude oil extraction, is the largest oily wastewater stream generated worldwide. The reuse and reclamation of these important water volumes are critical for more sustainable operation in the oilfield. Ceramic membrane filtration is a promising technology for PW treatment; however, fouling is the major drawback for a broader application. Fouling leads to higher resistance to flow, reducing membrane lifetime, and ultimately leading to higher capital expenditures and operating expenses. Further understanding of the interactions between PW foulants and the ceramic materials is needed for designing fouling control strategies and cleaning protocols for ceramic membranes. This work explored different techniques to characterize, visualize, and quantify the submicron PW contaminants content and its adsorption interactions with metal oxides. We visualized and characterized submicron oil droplets in oilfield PW samples by applying suitable advanced microscopy techniques. For the first time, crude oil droplets as small as 20 nm were found in oilfield PW together with other submicron contaminants. The adsorption studies performed by quartz crystal microbalance with dissipation (QCM-D) showed that the interactions of organic surface-active compounds with the metal oxides are driven by the nature of the surfactant and not by the surface properties. This has implications in the selection of the ceramic membrane material, wherein electrostatic interactions should not be taken as the only predicting factor of adsorption and fouling during PW treatment. Furthermore, our results suggested that the more fluid or viscoelastic-like the contaminant layer, the more difficult the cleaning process from the metal oxide. It demonstrates that the mechanical property of the attached films is a crucial factor in designing appropriate cleaning protocols for ceramic membranes. Finally, QCM-D and advanced microscopy techniques were applied to analyze adsorption and cleaning of contaminants in a complex Bahraini PW into alumina as a case study. Bacteria were found to attach irreversibly on the alumina surface, promoting nucleation points for calcium precipitates. The protocols developed in this work are suitable for understanding membrane fouling phenomena in the micron scale and could be implemented before filtration pilot testing to save time and expenses at larger scales.

The simultaneous treatment of different produced water streams with the forward osmosis membrane distillation hybrid system (FO-MD) has been suggested recently. This work investigates the need for pretreatment of produced water prior to filtration with FO-MD in order to reduce the level of fouling and scaling in the system. The desalter effluent (DE) stream was selected as FO feed solution, and the water oil separator (WO) stream was used as FO draw solution/MD feed solution, and a significant flux decline was observed in FO and MD within the first 5 hours of operations. SEM and EDX analysis indicated that the formation of scale layer on both membranes was the main reason for the sharp flux decline. Silica was the major contributor to the scaling of the support layer of the FO membrane. While the scaling layer on MD membrane consisted mainly of CaSO4 crystals with some deposition of Silica. Therefore, electrocoagulation (EC) was selected for the pretreatment of produced water to target the removal of Ca, SiO2 and SO4 ions in order to reduce the likelihood of inorganic fouling in FO-MD. The different parameters of EC, namely, the current density, electrolysis time, and initial pH were tested at a wide range of values of 7-70 mA/cm2 , 10-60 minutes, 5-9, respectively. calcium and sulfate ions were not effectively removed at the relatively high applied current density of 70 mA/cm2 , while high removal of silica was achieved even at low applied current densities. The optimum conditions of EC for silica removal were found to be 7 mA/cm2 for the current density and 10 minutes for the electrolysis time which resulted in a 97% removal of silica. it was found that due to pretreatment, the average FO and MD fluxes increased by 49% (9.93 LMH) and 39% (8.55 LMH), respectively. Therefore, even though EC did not show promising results in terms of the removal of calcium and sulfate, efficient silica removal was achieved with minimum energy requirements which suggests that it could have a potential to be integrated with the FO-MD hybrid system for the treatment and reclamation of produced water.

Aqueous industrial effluents containing organic pollutants, such as textile dyes and crude oil, represent environmental and human health concerns due to their toxicity and possible carcinogenic effects. Adsorption is the most promising wastewater treatment method due to its efficiency, ease of operation, and low cost. However, currently used adsorbents have either high regeneration costs or low adsorption capacities. In this work, new organic/inorganic hybrids based on hollow silica microspheres were successfully synthesized, and their ability to remove Methylene Blue from wastewater and crude oil from simulated produced water was evaluated. By employing four different silanes, namely triethoxy (octyl) silane, triethoxy (dodecyl) silane, trichloro (octadecyl) silane, and triethoxy (pentafluorophenyl) silane, hydro and fluorocarbons were grafted onto the surface of commercially available silica microspheres. These silica derivatives were tested as adsorbents by exposing them to Methylene Blue aqueous solutions and synthetic produced water. Absorbance and oil concentration were measured via a UV/Vis Spectrophotometer and an HD-1000 Oil-in-Water Analyzer respectively. Methylene Blue uptake experiments showed that increasing the adsorbent dosage and decreasing initial dye concentration might increase adsorption percentage. On the other hand, adsorption capacities were improved with lower adsorbent dosages and higher initial dye concentrations. Varying the initial solution pH, from pH 5 to pH 9, and increasing ionic strength did not seem to have a significant impact on the extent of adsorption of Methylene Blue. Overall, the silica derivative containing aromatic functional groups, Caro, was proven to be the most effective adsorbent due to the presence of π-π and cation-π interactions in addition to the van der Waals and hydrophobic interactions occurring with all four adsorbents. Although the Langmuir Model did not accurately represent the equilibrium data, it produced consistent maximum adsorption values and adsorption equilibrium constants. Preliminary experiments demonstrated the potential to recover and reuse the silica microspheres by washing with NaOH and organic solvents. The preferential adsorption of oil micro-droplets onto the surface of functionalized hollow silica microspheres was evidenced. However, preparing synthetic produced water that was stable enough to carry out kinetics experiments remained a challenge.

Co-precipitation and absorption methods were investigated for removal of boron from produced water, which is groundwater brought to the surface during oil and natural gas extraction. Boron can be toxic to many crops and often needs to be controlled to low levels in irrigation water. The present research focused on synthetic reverse osmosis (RO) concentrate modeled on concentrate expected from a future treatment facility at the Arroyo Grande Oil Field on the central coast of California. The produced water at this site is brackish with a boron concentration of 8 mg/L and an expected temperature of 80°C. The future overall produced water treatment process will include lime softening, micro-filtration, cooling, ion exchange, and finally RO. Projected boron concentrations in the RO concentrate are 20 to 25 mg/L. Concentrate temperature will be near ambient. This RO concentrate will be injected back into the formation. To prevent an accumulation of boron in the formation, it is desired to reduce boron concentrations in this concentrate and partition the boron into a solid sludge that could be transported out of the area. The primary method explored for boron removal during this study was adsorption and co-precipitation by magnesium chloride. Some magnesium oxide tests were also conducted. Jar testing was used to determine the degree of boron removal as a function of initial concentration, pH, temperature, and reaction time. Synthetic RO concentrate was used to control background water quality factors that could potentially influence boron removal. The standard synthetic RO concentrate contained 8 g NaCl/L, 150 mg Si/L and 30 mg B/L. After synthetic RO concentrate was prepared, amendments (e.g. sulfate, sodium chloride) were added and the pH adjusted to the desired value. Each solution was then carried through a mixing and settling protocol (5 min at 200 RPM, 10 min at 20 RPM, followed by 30 min settling and filtration). Boron concentrations from the jar tests were determined using the Carmine colorimetric method. Boron removal with magnesium chloride was greatest at a pH of 11.0. At this pH 87% of boron was removed using 5.0 g/L MgCl2◦6H2O at 20°C. Mixing time did not greatly affect boron removal for mixing periods of 5 to 1321 minutes. This result indicates equilibrium was achieved during the 45-min experimental protocol. Maximum boron removal was observed in the temperature range of 29°C to 41°C. At 68°C boron removal decreased five-fold compared to the reduction observed at 29°C to 41°C. For treatment of the cool concentrate, this relatively low optimal temperature range gives magnesium chloride an advantage over magnesium oxide, which is effective only at high temperatures. Neither sodium chloride nor sodium sulfate affected boron removal by magnesium chloride for the chloride and sulfate concentrations expected in the produced water at this site. In contrast, silica did inhibit boron removal, with removal decreasing from 30% to 5% when silica concentration was increased from 0 to 100 mmols/L. This result was unexpected because other researchers have reported silica is necessary for effective removal of boron by magnesium chloride. To investigate the reasons for the differing boron removal results for magnesium chloride and magnesium oxide, solids produced by the two reagents were compared using X-ray diffraction spectroscopy (XRD). Solids from magnesium chloride contained 30% amorphous material versus 10% for magnesium oxide. The crystalline components from the magnesium oxide treatment were for the most part magnesium oxide, whereas magnesium chloride crystalline solids were a combination of brucite (Mg(OH)2) and magnesium chloride hydroxide. The greater boron adsorption observed with magnesium chloride could thus either be attributed to the greater surface area of the amorphous precipitate and/or the higher boron affinity of brucite and magnesium chloride hydroxide. Adsorption isotherms were plotted for boron removal by magnesium compounds formed during precipitation. Boron adsorption followed a linear isotherm (r2= 0.92) for boron concentrations up to 37.8 mg B/L. While the data also fit Langmuir and Freundlich models the data fell in the linear range of those models. The linearity of the adsorption curves indicates that adsorption sites for boron were not saturated at these concentrations. The linearity means that higher boron concentrations in the RO concentrate will lead to greater mass removal, up to concentrations of at least 37.8 mg/L boron. Using magnesium chloride, boron removal by co-precipitation was more effective than by adsorption to pre-formed precipitate. Removal approximately doubled for a given dose of magnesium chloride. The effectiveness of co-precipitation presumably occurs due to entrapment of boron as the precipitate forms. This study has shown the potential of magnesium chloride as an agent for boron removal by determining those conditions most effective for boron co-precipitation and adsorption. Magnesium chloride has been shown to be more effective than magnesium oxide. Magnesium chloride also out-performed treatment with slaked quicklime, which was tested previously by others. Two important limitations of boron removal with magnesium chloride are the high chemical requirements (5 g/L MgCl2) and sludge production (1 g/g MgCl2 used). These are greatly mitigated by treatment of RO concentrate rather than the full produced water flow. In addition, reagent use and sludge production might be decreased by recycling sludge from the up-front lime softening process. Compared to magnesium oxide, magnesium chloride removes greater quantities of boron per mole of magnesium added (20 mg B/g MgCl2). The magnesium chloride isotherm demonstrated that treatment of RO concentrate required less reagent and produced less sludge per mass of boron removed than treatment of the more dilute feed water.

No description available.

<p>There is an increased discharge of produced water in the USA, which is causing decrease in the amount of usable water and is being rendered useless by refinery and extraction operations. Produced water that is obtained from these activities is usually not feasible to be used in any form. So, it becomes necessary to get the water to a quality standard, as per the US EPA, which will make this water suitable for both commercial as well as household purposes.</p><p> </p><p>There have been a number of studies on Au, Ag and Carbon Nanotubes solar enabled steam generation with potential applications in water purification, distillation and sterilization of medical equipment. The key challenge with these nanoparticles is cost of production, hence limiting its wide application for clean water production. This work, for the first time, reports on activated carbon enabled steam generation hence addressing the cost limitations of metallic nanoparticles. Activated carbon has high solar absorptivity at various wavelengths of visible light.</p><p> </p>This work uses Activated Carbon coated Polyurethane foam to simultaneously adsorb oil from the produced water and also yield surface vapors under application of solar light to get a clean distillate which can be used in various ways be it commercial or household. The given fabricated system will be an inexpensive and simple method to get clean water. The temporal evolution of the distillate has been measured as well as the temperature characteristics. Experiments were carried out using activated carbon and CNT nanofluids and polyurethane membrane with immobilized activated carbon and CNT. A simulated solar light of 1 KW ~1 Sun was used. The rate of evaporation, temporal and spatial evolution of bulk temperature in the water were monitored automatically and recorded for further data reductions. Parametric studies of the effect of nanoparticle concentration, water quality and salinity were performed. Experimental evidence showed that activated carbon has potential. Previous work reported for the first time that optimal activated carbon concentration for maximum steam generation is 60 % vol. There was a 160 % increase in steam production rate at 60 % concentration of activated carbon when compared with D.I. water.Different atmospheric conditions were varied and the concentration of the sun to see the effects on the production of water. The recovery capacity of the foam was also tested so as to determine the waste oil that can be obtained from the foam and if the foam can be reused without being disposed of. More than 95% oil can be recovered The quality analysis has been performed and is an integral focus of the work as the comparison with the USA EPA (Environmental Protection Agency) will make it more robust and real world ready. The inclusion of Polyurethane foam, which is a major accumulating waste in the environment because of its use in packaging industry, and solar light as the energy source, to drive the distillation process, makes this a very clean and green process to treat produced water.

Induction of the cytochrome P450(CYP)1A protein and the connected increase in 7-ethoxyresorufin O-deethylase (EROD) activity are common biomarkers in fish. Enhanced activity of this protein signals exposure to Ah-receptor agonists such as chlorinated dioxins, co-planar polychlorinated biphenyls (PCBs) and certain polycyclic aromatic hydrocarbons (PAHs). The EROD biomarker is commonly analyzed in liver microsomes. However, the gill is directly exposed to waterborne pollutants, and in this thesis the gill filament EROD assay was therefore evaluated as a monitoring tool for waterborne CYP1A inducers in fish. Originally developed in rainbow trout (Oncorhynchus mykiss), the assay was here applied in various limnic and marine species. Following exposure to low waterborne concentrations of the readily metabolized CYP1A inducers benzo(a)pyrene (BaP) and indigo, a strong EROD induction was observed in the gill but not in the liver. This likely reflected metabolic clearance of the inducers in gill and other extrahepatic tissues. The high sensitivity of the gill was confirmed in studies of fish caged in waters in urban and rural areas in Sweden where the gill consistently showed a more pronounced EROD induction compared with the liver and the kidney. Fish caged in the reference waters showed surprisingly strong gill EROD induction and CYP1A immunostaining. Consequently, there may be CYP1A inducers present in the aquatic environment that are not yet identified. The assay was further applied in Atlantic cod (Gadus morhua) as a biomarker of exposure to crude oil and produced water (PW) from oil fields in the North Sea. The assay was finally adapted to detect inhibiting compounds, and an imidazole, a triazole and a plant flavonoid turned out to be potent gill EROD inhibitors. The overall conclusion from the studies of this thesis is that the gill filament EROD assay is a practical and sensitive biomarker of exposure to waterborne CYP1A inducers in various fish species. The induction of gill EROD activity in fish also at the reference sites in the field studies calls for further studies on background contamination in Swedish waters.

Produced water is one of the major by products of oil and gas exploitation which is produced in large amounts up to 80% of the waste stream. Oil and grease concentration in produced water is the key parameter that is used for compliance monitoring, because it is easy to measure. For Canadian offshore operations, the current standard is a 30-day volume weighted average oil-in-water concentration in discharged produced water not exceeding 30 mg/L. Treatment of produced water may therefore be required in order to meet pre-disposal regulatory limits. The measurement of oil in produced water is important for both process control and reporting to regulatory authorities. Without the specification of a method, reported concentrations of oil in produced water can mean little, as there are many techniques and methods available for making this measurement, but not all are suitable in a specific application. The first part of this study focused on selecting a suitable analytical method for oil and grease measurement in oil field produced water. Petroleum ether was found to offer a comparative dissolution of crude oil as dichloromethane and hexane; it was therefore used as the solvent of choice for the UV-Vis spectrophotometric analysis of oil and grease in synthetic produced water. Results from the UV-Vis spectrophotometric and FTIR spectrometric analytical methods were found to be comparable; it confirmed that UV-Vis spectrometry could potentially serve as an alternative method for measuring oil and grease in oil field produced water. However, while the UV-Vis method may have limitations in measuring oil and grease concentrations below 30 mg/L, the FT-IR method was found to be equally efficient at measuring both high and low oil and grease concentrations. Dissolved air flotation (DAF) was the primary treatment technology investigated in this study for removing oil and grease from synthetic produced water. By itself, DAF achieved less than 70% oil and grease (OG) removal, and was not able to achieve a clarified effluent OG concentration of 30 mg/L required for regulatory discharge limits. At an optimum condition of 20 mg/L ferric chloride (FeCl3) at pH 8 (70.6% OG removal), coagulation was found to significantly improve the performance of the DAF unit (p < 0.05). At the optimum conditions of 100 mg/L PAC dose, pH 8 and a mixing time of 10 minutes (77.5% OG removal) and 300 mg/L OC dose, pH 8 and a mixing time of 10 minutes (78.1% OG removal), adsorption was also found to significantly improve the performance of the DAF unit (p < 0.05 in both cases). Adsorption with organoclay was recommended as the best pre-treatment for optimizing the performance of DAF in removing oil and grease from offshore oil field produced water. The bench-scale experiments showed that turbidity removal results were consistent with the OG removal results. Without pre-treatment, DAF achieved significant removal of benzene from produced water due to the volatile nature of benzene. Therefore comparable levels of benzene removal was observed by the DAF, FeCl3/DAF, PAC/DAF and OC/DAF treatment schemes; 79.3 %, 86.6 %, 86.5 %, 83.5% respectively. Finally, as benzene is known to be carcinogenic to humans, this study recommends the incorporation auxiliary equipment in its design, for the treatment of the off-gas (VOCs, particularly BTEX) released during the removal of dissolved oil from the oil field produced water.

Made available in DSpace on 2014-12-17T14:08:36Z (GMT). No. of bitstreams: 1 RodrigoCS.pdf: 3685250 bytes, checksum: 36c02ba21672c99c459225abadc4fe02 (MD5) Previous issue date: 2009-08-21 / Petr?leo Brasileiro SA - PETROBRAS / Produced water is the main effluent linked to the activity of extraction of oil and their caring management is necessary due to the large volume involved, to ensure to minimize the negative impacts of discharges of these waters in the environment. This study aimed to analyze the use of retorted shale, which is a reject from the pyrolysis of pirobituminous shale, as adsorbent for the removal of phenols in produced water. The material was characterized by different techniques (grain sized analysis, thermal analysis, BET, FRX, FT-IR, XRD and SEM), showing the heterogeneity in their composition, showing its potential for the removal of varied compounds, as well as the phenols and their derivatives. For the analysis of the efficiency of the oil shale for the adsorption process, assays of adsorption balance were carried through, and also kinetic studies and dynamics adsorption, in the ETE of the UTPF of Petrobras, in Guamar?-RN. The balance assays shown a bigger conformity with the model of Langmuir and the kinetic model more adjusted to describe the adsorption of phenols in retorted shale was of pseudo-second order. The retorted shale presented a low capacity of adsorption of phenols (1,3mg/g), when related to others conventional adsorbents, however it is enough to the removal of these composites in concentrations presented in the produced water of the UTPF of Guamar?. The assays of dynamics adsorption in field had shown that the concentration of phenol in the effluent was null until reaching its rupture (58 hours). The results showed the possibility of use of the reject for removal of phenols in the final operations of the treatment process, removing as well, satisfactorily, the color and turbidity of the produced water, with more than 90% of removal / A ?gua Produzida ? o principal efluente ligado ? atividade de extra??o de Petr?leo e seu gerenciamento cuidadoso ? necess?rio devido ao grande volume envolvido de forma a garantir a minimiza??o dos impactos negativos dos descartes destas ?guas no meio ambiente. Este estudo teve o objetivo de analisar a utiliza??o de xisto retortado, rejeito proveniente da pir?lise do xisto pirobetuminoso, como adsorvente para remo??o de fen?is em ?guas Produzidas. O material foi caracterizado por diferentes t?cnicas (an?lise granulom?trica, an?lise t?rmica, BET, FRX, FT-IR, DRX e MEV), mostrando a heterogeneidade em sua composi??o, comprovando seu potencial para remo??o de compostos variados, assim como para os fen?is e seus derivados. Para a an?lise da efici?ncia do xisto retortado para o processo de adsor??o, foram realizados ensaios de equil?brio de adsor??o, estudos cin?ticos e din?mica de adsor??o, na ETE da UTPF da Petrobras, em Guamar?-RN. Os ensaios de equil?brio mostraram uma maior conformidade com o modelo de Langmuir e o modelo cin?tico mais adequado para descrever a adsor??o dos fen?is em xisto retortado foi o de pseudo-segunda ordem. O xisto retortado apresentou uma capacidade de adsor??o de fen?is baixa (1,3mg/g), quando relacionada a de outros adsorventes convencionais, por?m suficiente para a remo??o desses compostos em concentra??es apresentadas na ?gua Produzida da UTPF de Guamar?. Os ensaios de din?mica de adsor??o em campo mostraram que a concentra??o de fen?is no efluente foi nula at? atingir sua ruptura (58 horas). Os resultados mostraram a possibilidade do uso do rejeito para remo??o de fen?is em opera??es finais do processo de tratamento, removendo tamb?m, de forma satisfat?ria, a cor e turbidez da ?gua produzida, com remo??o superior a 90%.