Ácidos naftênicos correspondem à complexa mistura de ácidos carboxílicos presentes no petróleo, responsáveis diretamente pela sua acidez e pela sua corrosividade em fase líquida durante o refino. Tais compostos também estão presentes nas frações destiladas do petróleo, causando diversos problemas na qualidade final do produto. Uma possível forma de remover esses ácidos das frações destiladas é através da adsorção em materiais porosos. Contudo, os resultados até então apresentados indicam que resinas trocadoras de íons seriam os melhores adsorventes destes compostos, o que poderia aumentar o custo do processo e diminuir sua viabilidade. Neste trabalho, dois adsorventes comerciais (argila e alumina ativada) foram caracterizados por diversas técnicas físico-químicas e avaliados quanto à sua capacidade de remover os ácidos naftênicos de frações médias e pesadas de petróleo. Avaliou-se, ainda, para fins de comparação, o comportamento de ácidos naftênicos comerciais em óleos sintéticos preparados com óleo mineral. Em complementação, a corrosividade do aço carbono nos meios estudados foi também verificada. A argila apresentou maior afinidade com os ácidos naftênicos, tendo capacidade de adsorção superior e cinética de processo ligeiramente mais rápida às da alumina para as cargas sintéticas. No entanto, em virtude da maior concorrência pelos sítios de adsorção, apresentada pelos outros componentes presentes em óleos reais, observou-se uma perda na eficiência para estas amostras. Neste caso, a alumina apresentou melhores resultados. Embora ambos adsorventes tenham apresentado boa capacidade de remoção do soluto, a resina trocadora de íons ainda apresentou resultado mais eficaz para as amostras reais. Nas condições desse estudo, a taxa de corrosão do aço nas amostras sintéticas e em duas das reais não foi significativa e apenas uma delas apresentou-se corrosiva (Óleo 1). No entanto, a remoção dos ácidos naftênicos por adsorção conseguiu reduzir a taxa de corrosão neste meio em até 99% / Naphthenic acids comprise a complex mixture of carboxylic acids that are present in petroleum. They are directly responsible for the oil acidity and its corrosiveness in liquid phase during the refining process. Such compounds are also presents in the derivatives, causing several problems to product quality. A possible way of removing these acids from those oil fractions is using the adsorption process in porous solids. Nevertheless, results presented so far show that ion exchange resins would be the best adsorbent for these acids, which could make this process very expensive. In this work, two commercial adsorbents (clay and activated alumina) were characterized by several physical-chemistry techniques and evaluated concerning their capacity of removing naphthenic acids from average and heavy fractions of crude oil. For comparison the behavior of commercial naphthenic acids in synthetic commercial samples prepared with mineral oil was also evaluated. In addition, the carbon steel corrosiveness in the studied systems was verified. Clay adsorbent presented better affinity with the acids, showing a greater capacity and a faster kinetics than alumina for synthetic oils. However, because of the higher competition with the other components present in real oils for the adsorption sites, a loss of efficiency for these samples was observed. In that case, alumina showed better results. Although both adsorbents have showed good capacity of removal of acids, the ion exchange resin still presented the best results for real samples. At the conditions of this study, the steel corrosiveness in the synthetic oils, as well as the data obtained for two of the real ones, was not significant, and only one of the real samples (Oil 1) corroded the carbon steel coupon. However, the naphthenic acid removal was able to reduce the corrosiveness in this medium up to 99%

Naphthenic acids (NAs) are carboxylic acids found in crude oil and petroleum products. The objectives of the research presented here were to: a) assess the occurrence and fate of NAs in crude oil and refinery wastewater streams; b) evaluate the biotransformation potential and inhibitory effects of NAs under nitrifying, denitrifying and methanogenic/fermentative conditions; c) investigate the factors affecting NA biotransformation under aerobic conditions and the microbes involved; and d) assess the toxicity of individual model NAs using quantitative structure-activity relationships (QSAR) and examine the effect of structure on NA biotransformation potential. NAs are ubiquitous in refinery wastewater streams and the desalter brine was found to be the main source of NAs in refinery wastewater. A commercial NA mixture was not biodegraded under nitrate-reducing or methanogenic/fermentative conditions. NAs were degraded under aerobic conditions by an NA-enriched culture; however, a residual fraction was not degraded under all conditions studied. The results indicated that NAs are not inherently recalcitrant and the residual fraction was due to the individual NA concentrations being below the minimum substrate concentrations at which they are no longer degraded. A fraction of the NA mixture was completely mineralized to carbon dioxide, with the remaining portion biotransformed to more oxidized intermediates. Overall, the results indicated that NAs were degraded under aerobic conditions; however, biological treatment of NA-bearing wastewater will not completely remove NA concentrations and thus, biological treatment must be combined with physical/chemical treatment to achieve complete NA removal.

The In Situ Aquifer Test Facility (ISATF) has been established on Suncor Energy Inc’s (Suncor) oil sands mining lease north of Fort McMurray, Alberta to investigate the fate and transport of oil sands process-affected (PA) water in the Wood Creek Sand Channel (WCSC) aquifer. In 2008, the ISATF was used for preliminary injection experiments in which 3,000 and 4,000 L plumes of PA water were created in the WCSC. Following injection, the evolution of the plumes was monitored to determine if naphthenic acids (NAs) naturally attenuated in the WCSC and if trace metals were mobilized from the aquifer solids due to changes in redox conditions. Post-injection monitoring found groundwater velocities through the aquifer were slow (~3-10 cm/day) despite hydraulic conductivities on the order of 10-3 m/s. While microbes in the WCSC were capable of metabolizing acetate under the manganogenic/ferrogenic redox conditions, field evidence suggests naphthenic acids behaved conservatively. Following the injections, there was an apparent enrichment in the dissolved concentrations of iron, manganese, barium, cobalt, strontium and zinc not attributable to elevated levels in the PA injectate. Given the manganogenic/ferrogenic conditions in the aquifer, Mn(II) and Fe(II) were likely released through reductive dissolution of manganese and iron oxide and oxyhydroxide mineral coatings on the aquifer solids. Because naphthenic acids make up the bulk of dissolved organic carbon (DOC) in the injectate and are apparently recalcitrant to oxidation in the WCSC, some question remains as to what functioned as the electron donor in this process.

Naphthenic acids (NAs) are a group of carboxylic acids that are found in hydrocarbon deposits such as the oil sands bitumen. These compounds are a well-known corrosive agent and a toxic component in the oil sands process water (OSPW). Due to Alberta’s zero discharge policy, OSPW cannot be released and must be stored until toxic components like NAs are remediated. One technique that has shown potential is to physically adsorb NAs onto a copolymer generated from economical biomaterials. Therefore, the project can be divided into three sections: 1) Synthesis of β-cyclodextrin (β-CD) copolymer for the sorption of p-nitrophenol (PNP); 2) Synthesis of chitosan-based copolymers (Chi-Glu) for the sorption of PNP; 3) Sorption of carboxylates and NAs using Chi-Glu copolymers. PNP sorption was used as a probe to understand the physicochemical properties of the copolymers. In the first section, β-CD was reacted with sebacoyl chloride (SCl) and terephthaloyl chloride (TCl) at various mole ratios. Characterization was done using Fourier Transform Infrared Spectroscopy (FT-IR), thermogravimetric analysis (TGA), 1H NMR spectroscopy (1H NMR), elemental analysis (CHN), and nitrogen porosimetry. Copolymers synthesized at mole ratios of β-CD to SCl from 1:1 to 1:3 were hydrolyzed at acidic and basic conditions. Therefore, sorption studies were not done at these ratios. The same occurred for 1:1 to 1:3 TCl copolymers. Sorption studies with PNP at pH 4.6 demonstrated enhanced sorption capacity when comparing with a standard: granular activated carbon (GAC). The sorption capacity, Qm (mmol/g), ordered from largest to smallest is 1:9 SCl>1:9 TCl>1:6 SCl> GAC> 1:6 TCl. Chi-Glu copolymers were synthesized by cross-linking glutaraldehyde with pristine chitosan. A systematic study on the effects reaction conditions have on the sorption capacity of the materials was done. Three conditions were changed: pH, temperature, and mole ratios. Chi-Glu copolymers were synthesized at various chitosan to glutaraldehyde mole ratios (1:400, 1:700, 1:1000). Sufficient time was allowed for the aging process. Characterization was done using TGA, FT-IR, CHN, and nitrogen porosimetry. Sorption study with PNP were done at pH = 7.0 and 9.0. At pH = 7.0 sorption capacity appears to correlate to the quantity of homo-polymerized glutaraldehyde: 1:700>1:1000>1:400. While at pH = 9.0, the sorption capacity is inversely proportional to the degree of crosslinking: 1:400>1:700>1:1000. By increasing the pH at the shrinkage phase, PNP was weakly bound onto the Chi-Glu copolymer. Varying temperature before gelation caused a decrease in the sorption capacity with PNP. Sorption studies involving carboxylates and NAs were done at pH = 9.0 at ambient temperature using Chi-Glu copolymers (1:400, 1:700, and 1:1000) and chitosan. Three carboxylates were chosen to reflect the diverse components in NAs. Varying degrees of cyclization (Z = 0, -2, -4) and lipophilic surface area were the main criteria for carboxylates. The sorption capacity depended mainly on the lipophilic surface area (LSA) with sorption capacity highest for 2-hexyldecanoic acid (S1) which has the largest LSA and lowest for, trans-4-pentylcyclohexanecarboxylic acid (S2) and dicyclohexylacetic acid (S3). Unfortunately, cross-linking with glutaraldehyde does not enhance sorption as pristine chitosan retained a higher sorption capacity compared to Chi-Glu copolymers. Acros and Fluka NAs were chosen for sorption and no significant sorption was recorded for any copolymers. Problems involving the micellization process can explain the lack of sorption.

Oil sand deposits in the Athabasca Basin in Alberta represent one of the largest global oil reserves. The bitumen contents of oil sand shallow deposits are recovered by surface mining using modified version of the Clark hot water process. Extraction of bitumen results in extremely large volumes of process water, which are contaminated with naphthenic acids. Various ex-situ treatment techniques including ozonation, advanced oxidation, adsorption, and bioremediation have been evaluated for the treatment of these waters. Previous studies conducted by Paslawski et al. (2009) investigated aerobic biodegradation of naphthenic acids in properly designed and carefully operated bioreactors. In the current work, anaerobic biodegradation of naphthenic acids under denitrifying condition was examined as a potential approach to eliminate the aeration cost in ex-situ treatment and as an alternative for application of in-situ treatment of oil sand process water in stabilization ponds was examined. Using trans-4-methyl-1-cyclohexane carboxylic acid (trans-4MCHCA), a microbial mixed culture developed in earlier works (Paslawski et al., 2009), and nitrate as an electron acceptor, anaerobic biodegradation of trans-4MCHCA were studied in batch and continuous bioreactors: continuous stirred tank reactor (CSTR) and biofilm system. Effects of naphthenic acid concentration, temperature, and loading rate on biodegradation process were investigated. The batch studies showed that initial concentration of trans-4MCHCA influenced the biodegradation rate where the increase in initial concentration of trans-4MCHCA from 100 to 250 mg L-1 led to a higher rate but further increase in concentration did not have a marked effect. Moreover, batch experiments at temperatures ranging from 10° to 35°C demonstrated that the optimum temperature was in the range of 20 - 24°C. Continuous anaerobic biodegradation in the CSTR showed that increase in loading rate of trans-4MCHCA caused an increase in removal rate of both trans-4MCHCA and nitrate. Rates were decreased as the system approached the cell washout. The maximum biodegradation rate and nitrate removal rate, achieved at trans-4MCHCA loading rate of 157.8 mg L-1 h-1, were 105.4 mg L-1 h-1 and 144.5 mg L-1 h-1, respectively. A similar dependency between the loading and removal rates was also observed in the biofilm reactor. The maximum removal rate of trans-4MCHCA and nitrate in the biofilm reactor, operated at room temperature (24 ± 2ºC) were 2,028.1 mg L-1 h-1 and 3,164.7 mg L-1 h-1, respectively and obtained at trans-4MCHCA loading rate of 2,607.9 mg L-1 h-1. Comparison of the results from aerobic batch systems obtained by Paslawski et al. (2009) and the current results showed similar profile where increase in initial concentration of naphthenic acid increased the biodegradation rate of trans-4MCHCA. As far as the effect of temperature is concerned, room temperature (20 - 24ºC) was identified as optimum temperature regardless of mode of biodegradation. Under continuous mode of operation (CSTR and biofilm reactors), anaerobic biodegradation was much faster than its aerobic counterpart. For instance the maximum anaerobic removal rate of trans-4MCHCA in the CSTR was 105.4 mg L-1 h-1, while the highest removal rate achieved in the aerobic CSTR was 9.6 mg L-1 h-1. Similarly, anaerobic biofilm reactor achieved a higher maximum removal rate of 2,028.1 mg L-1 h-1 compared to a 924.4 mg L-1 h-1 removal rate in the aerobic biofilm reactor. The overall finding indicated that biodegradation of trans-4MCHCA can be achieved effectively under anaerobic condition with the rates markedly higher than those for aerobic system.

Naphthenic acids (NAs) are carboxylated alkanes and cycloalkanes concentrated in wastewater during oil sands processing. The general chemical formula is C{n}H{n+Z}O{2}, where n represents the number of carbon atoms and Z specifies a homologous family with 0-6 rings (Z=0 to Z=-12). The wastewater is acutely toxic to surface water organisms and is stored in tailings ponds with over 230 million m³ of fines tailings and free water. The purpose of this thesis was to provide a preliminary evaluation of the potential attenuation of NAs during groundwater flow from the ponds. Laboratory studies were conducted to evaluate possible attenuation mechanisms. Aerobes from aquifer material degraded 60% of the NAs over 20 weeks in laboratory microcosms. The greatest decrease occurred in the low molecular weight bicyclic homologues with 12 to 16 carbons. The microbial activity confirms that aerobic naphthenate-degrading bacteria occur naturally in the glacial aquifer near Suncor's Pond 2/3. These results support the hypothesis that limited aerobic biodegradation of the smaller components of NAs could occur relatively rapidly under field conditions. There was no measurable decrease in NA concentration over six months in anaerobic microcosms, although microbial activity did lead to sulfate-reducing and methanogenic conditions. The theoretical retardation in glacio-fluvial sands was calculated using soil-water partitioning coefficients (K{d}) determined by batch equilibration experiments using a mixture of naturally occurring naphthenic acids as well as the nine surrogates. The retardation (porosity of 0. 3, bulk density of 1. 5 g/mL) ranged from 1. 2 to 2. 6. However, no measurable sorption was seen at the field sites. Detailed characterization allows us to examine how the proportions of homologue, or groups of molecules with the same molecular weight and number of cycloalkane rings, vary. Aerobic biodegradation favoured removal of low molecular weight NAs. A 15% mass loss attributed to sorption caused no changes in the 3D signature. Thus, changes in NA "signature" in groundwater systems were then attributed to aerobic biodegradation. Three plumes were examined for evidence of attenuation of NAs via biodegradation. First, the individual samples were classified as background, possibly process-affected or process-affected using a combination of Piper diagrams, the stable isotopes oxygen-18 and deuterium, dissolved chloride and sodium, as well as the total naphthenic acids concentration. Second, in order to estimate attenuation due to dispersive dilution, a linear correlation line was drawn between various conservative tracers and the naphthenic acids concentration. This allowed the identification of certain samples as possibly having a lower concentration of NAs than could be expected from simple dispersive dilution. Third, the 3D signature of certain samples were examined for the presence of the aerobic biodegradation 3D signature. One site showed good evidence for aerobic biodegradation of naphthenic acids. A second site showed some evidence for biodegradation under methanogenic conditions but the evidence was not definitive. The evidence at the third site was contradictory and no conclusions could be drawn from it. This research suggests some attenuation of NAs by biodegradation may be possible during groundwater flow.

The In Situ Aquifer Test Facility (ISATF) has been established on Suncor Energy Inc’s (Suncor) oil sands mining lease north of Fort McMurray, Alberta to investigate the fate and transport of oil sands process-affected (PA) water in the Wood Creek Sand Channel (WCSC) aquifer. In 2008, the ISATF was used for preliminary injection experiments in which 3,000 and 4,000 L plumes of PA water were created in the WCSC. Following injection, the evolution of the plumes was monitored to determine if naphthenic acids (NAs) naturally attenuated in the WCSC and if trace metals were mobilized from the aquifer solids due to changes in redox conditions. Post-injection monitoring found groundwater velocities through the aquifer were slow (~3-10 cm/day) despite hydraulic conductivities on the order of 10-3 m/s. While microbes in the WCSC were capable of metabolizing acetate under the manganogenic/ferrogenic redox conditions, field evidence suggests naphthenic acids behaved conservatively. Following the injections, there was an apparent enrichment in the dissolved concentrations of iron, manganese, barium, cobalt, strontium and zinc not attributable to elevated levels in the PA injectate. Given the manganogenic/ferrogenic conditions in the aquifer, Mn(II) and Fe(II) were likely released through reductive dissolution of manganese and iron oxide and oxyhydroxide mineral coatings on the aquifer solids. Because naphthenic acids make up the bulk of dissolved organic carbon (DOC) in the injectate and are apparently recalcitrant to oxidation in the WCSC, some question remains as to what functioned as the electron donor in this process.

Spent caustic liquors (SCL) generated from crude oil refineries have characteristics of high COD (chemical oxygen demand) contents and relatively small generation rates as compared with general wastewater ones. The odorous naphthenates, phenolates, and sulfides in the liquors adversely affect the normal operation of the related wastewater treatment plants and effluent water qualities. This study aims at the reduction of COD in a naphthenic spent caustic liquor generated from a domestic refinery with crude processing and naphtha cracking units. Primary tests indicated that around 50% of the COD in the SCL could be biodegraded. Chemical oxidation methods were tried to possibly upgrade the COD removal. Experiments indicated that acidification of the SCL sample to pH 2-3 could reduce the COD from an average of 51,600 to 20,800 mg/L by removing the separated naphthenic acids. Fenton¡¦s method with oxidants of 20 mL/L 35% H2O2 and FeSO4.7H2O 5 g/L, oxidation time of 1 hour at conditions of pH 2-3 and 80-100oC, could reduce the COD of the acidified SCL from an average of 20,800 to 11,100 mg/L. The overall COD removal was around 78% and the efficiency is comparable to that of a traditional Wet Air Oxidation (WAO) process of around 75%. Economic analysis indicated that for treating the SCL of 80 m3/day by the traditional WAO process, an initial equipment cost of 10 millions USD and annual operating cost of around 1.5 millions USD are required. By the developed acidification-Fenton¡¦s process, an initial equipment cost of 0.7 million USD and annual operating cost of around 0.5 million USD are expected. The developed process can be superior to the WAO one.

As part of their reclamation plan, oil sands operators propose to transfer the mature fine tailings, which are a by-product of the oil sands extraction process, to open-pits and cap them with either a layer of surface water or oil sands process-affected waters (OSPW). These oil sands pit lakes are expected to develop habitats with productive capabilities comparable to natural lakes in the region. The studies presented in this thesis evaluate the potential impact of OSPW and its associated constituents [i.e. acid-extractable organics (e.g. naphthenic acids; NAs) and salts] on the reproductive physiology of adult fathead minnow (Pimephales promelas). Through 14-21 day fathead minnow reproduction assays it was demonstrated that aged OSPW can impair spawning, lower plasma sex steroid concentrations, and reduce male secondary sexual characteristics. The acid-extractable organics in OSPW were demonstrated to have an adverse effect on fathead minnow reproductive physiology. Other studies showed that the high salinity which characterizes OSPW also influences toxicity. When fathead minnows were exposed to the OSPW extract and 700 mg/l of NaHCO3, the NaHCO3 reduced the inhibitory effects of the extract on the numbers of reproductive tubercles and plasma testosterone levels by reducing the uptake of NAE to the fish. Embyro and larval bioassays also revealed that NaHCO3 reduces the acute toxic effects of the OSPW extract. An assessment of a wild population of fathead minnows inhabiting an OSPW pond determined that there were differences in the condition factor (CF), gonadosomatic indices (GSIs), liver somatic indices (LSIs), male secondary sexual characteristics, and 11-ketotestosterone concentrations in the fathead minnows from the OSPW pond relative to fish collected at reference sites. The opercula of fathead minnows from the OSPW pond also differed from those of reference fish and an examination of the gills revealed that were a number of proliferative and degenerative alterations relative to reference fish. Collectively, these studies demonstrate that aged OSPW has the potential to negatively affect the reproductive physiology of fathead minnows and suggest that aquatic habitats with high NAs concentrations (>10 mg/l) will have adverse effects on fish. / Canadian Natural Resources Ltd., Canadian Water Network, Canadian Oil Sands Network for Research and Development (CONRAD), Imperial Oil Ltd., NSERC, Shell Canada Energy, Suncor Energy Inc., Syncrude Canada Ltd., and Total E&P Canada

No description available.