Avaliação do potencial anticorrosivo de tiossemicarbazonas solubilizadas em sistemas microemulsionados

In this work thiosemicarbazones [4-N-cinnamoyl-thiosemicarbazone (CTSC), 4-N-(2'-methoxycinnamoyl)-thiosemicarbazone (MCTSC), and 4-N-(4'-hydroxy-3'-methoxybenzoyl)-thiosemicarbazone (HMBTSC)] were solubilized in an microemulsion system (ME_OCS) which is rich in aqueous phase (O/W system). The system ME_OCS was obtained with saponified coconut oil (OCS) as (surfactant), butanol (cosurfactant), and kerosene as oil phase (Fo), using 40% of C/T (cosurfactant/surfactant), 5% of Fo and 55% of aqueous phase. The microemulsions systems CTSC_ME_OCS, MCTSC_ME_OCS and HMBTSC_ME_OCS effectiveness on a AISI 1020 carbon steel corrosion inhibition process were evaluated in a saline solution (NaCl 0.5%), using a galavostatic method. The tested thiosemicarbazones (TSC) showed highest inhibitors effects (85.7% for CTSC_ME_OCS, 84.0% for MCTSC_ME_OCS, and 83.3% HMBTSC_ME_OCS) at lower concentrations [0.19% of CTSC, 0.07% (MCTSC), and 0.26% (HMBTSC)]. Comparatively, the surfactant OCS (solubilized in H2O) as well as the system ME_OCS showed lower efficacy [71% for OCS (at 0.20 - 0.25% of concentration) and 74% for ME_OCS (at 0.5% of concentration)]. Since the microemulsion systems ME_OCS showed satisfactory interfacial adsorption, the greatest inhibitory effect of those TSC_ME_OCS systems could be correlated to both chemical composition of each tested TSC (which is rich in heteroatoms and aromatic ring) and also the presence of the surfactant OCS

Caracterização e aplicação de sistemas micelares e microemulsionados como inibidores de corrosão

Corrosion is an important phenomenon that frequently occurs in the oil industry, causing surface ablation, such as it happens on the internal surfaces of oil pipes. This work aims to obtain new systems to reduce this specific problem. The surfactants SDS, CTAB, and UNITOL L90 (in micellar and microemulsionated systems) were used as corrosion inhibitors. The systems were obtained using a C/S ratio of 2, butanol as cosorfactant, kerosene as oil phase and, as water phase, NaCl solutions of 0.5M with pH = 2, 4, and 7. Microemulsion regions were found both for direct and inverse micelles. SDS had the higher microemulsion region and the area was not dependent of pH. The study of micellization of these surfactans in the liquid-gas interface was carried out via the determination of CMC from surface tension measurements. Regarding microemulsionated systems, in the case of CTAB, CMC increased when pH was increased, being constant for SDS and UNITOL L90. Concerning micellar systems, increase in pH caused decrease and increase in CMC for SDC and CTAB, respectively. In the case of UNITOL L90, CMC was practically constant, but increased for pH = 4. The microemulsionated systems presented higher CMC values, except for UNITOL L90 L90. The negative values of free energy of micellization indicated that the process of adsorption was spontaneous. The results also indicated that, comparing microemulsionated to systems, adsorption was less spontaneous in the case of SDS and CTAB, while it did not change for UNITOL L90. SAXS experiments indicated that micelle geometry was spherical, existing also as halter and flat micelles, resuting in a better inght on the adsorption at the liquid-solid interface. Efficiency of corrosion inhibition as determined by electrochemical measurements, from corrosion currents calculated from Tafel extrapolation indicuting heat showed surfactants to be efficient even at low concentrations. Equilibrium isotherm data were fitted to the Freundlich model, indicating that surfactant adsorption occurs in the form of multilayers

Utilização de microemulsão na remoção da cor de efluentes têxteis contendo corantes dispersos

Polyester fibers are the most used fibers in the world and disperse dyes are used for dyeing these fibers. After dyeing, the colorful dyebath is discharged into effluent streams, which needs a special treatment for color removal. Surfactants interaction with dyes has been evaluated in several studies, including the textile area, specifically in the separation of dyes from textile wastewater. In this work a cationic surfactant was used in a microemulsion system for the extraction of anionic dyes (disperses dyes) from textile wastewater. These microemulsion system was composed by dodecylamonium chloride (surfactant), kerosene oil (organic phase), isoamyl alcohol (cosurfactant) and the wastewater (aqueous phase). The wastewater that results after the dyeing process is acid (pH 5). It was observed that changing the pH value to above 12.8 the extraction could be made, resulting in an aqueous phase with low color level. The Scheffé net experimental design was used for the extraction process optimization, and the obtained results were evaluated using the program "Statistica 7.0". The optimal microemulsion system was composed by 59.8wt.% of wastewater, 30.1wt.% of kerosene, 3.37wt.% of surfactant and 6.73wt.% of cosurfactant, providing extraction upper than 96%. A mix of reactive dyebath (50%) and disperse dyebath (50%) was used as aqueous phase and it presented extraction upper than 98%. The water phase after extraction process can be reused in a new dyeing, being obtained satisfactory results, according to the limits established by textile industry for a good dyeing. Tests were accomplished seeking to study the influence of salt addition and temperature. An experimental design was used for this purpose, which showed that the extraction doesn't depend on those factors. In this way, the removal of color from textile wastewater by microemulsion is a viable technique (that does not depend of external factors such as salinity and temperature), being obtained good extraction results even with in wastewater mixtures

Inibição à corrosão do aço AISI 1020, em meios ácido e salino, por tensoativos e substâncias nitrogenadas microemulsionados

Corrosion inhibition efficiency of saponified coconut oil (SCO) and sodium dodecilbenzene sulfonate (DBS) surfactants in AISI 1020 carbon steel was evaluated by electrochemical methods. These surfactants were also evaluated as microemulsion systems (SCO-ME and DBS-ME), of O/W type (water-rich microemulsion), in a Winsor IV region. They were obtained according to the following composition: 15% SCO, 15% butanol (30% Co-surfactant/Surfactant C/T), 10% organic phase (FO, kerosene) and 60% aqueous phase (FA). These systems were also used to solubilize the following nitrogenated substances: Diphenylcarbazide (DC), 2,4-dinitro-phenyl-thiosemicarbazide (TSC) and the mesoionic type compound 1,3,4-triazolium-2-thiolate (MI), that were investigated with the purpose of evaluating their anticorrosive effects. Comparative studies of carbon steel corrosion inhibition efficiencies of free DBS and DBS-ME, in brine and acidic media (0.5%), showed that DBS presents better inhibition results in acidic media (free DBS, 89% and DBS-ME, 93%). However, the values obtained for DBS in salted solution (72% free DBS and 77% DBS-ME) were similar to the ones observed for the SCO surfactant in brine (63% free SCO and 74% SCO-ME). Analysis of corrosion inhibition of the nitrogenated substances that were solubilized in the SCO-ME microemulsion system by the linear polarization method in brine (0.5% NaCl) showed that such compounds are very efficient an corrosion inhibitors [DC-ME-SCO (92%), TSC-ME-SCO (93%) and MI-ME-SCO (94%)]

Estudo da digestão de sedimento de curtume visando a extração do cromo por microemulsão

Leather tanneries generate effluents with high content of heavy metals, especially chromium, which is used in the mineral tanning process. Microemulsions have been studied in the extraction of heavy metals from aqueous solutions. Considering the problems related with the sediment resulting from the tanning process, due to its high content in chromium, in this work this sediment was characterized and microemulsion systems were applied for chromium removal. The extraction process consists in the removal of heavy metal ions present in an aqueous feeding solution (acid digestion solution) by a microemulsion system. First three different solid sludge digestion methods were evaluated, being chosen the method with higher digestion capacity. For this digestion method, seeking its optimization, was evaluated the influence of granule size, temperature and digestion time. Experimental results showed that the method proposed by USEPA (Method A) was the most efficient one, being obtained 95.77% of sample digestion. Regarding to the evaluated parameters, the best results were achieved at 95°C, 14 Mesh granule size, and 60 minutes digestion time. For chromium removal, three microemulsion extraction methods were evaluated: Method 1, in a Winsor II region, using as aqueous phase the acid digestion solution; Method 2, in a Winsor IV region, being obtained by the addition of the acid digestion solution to a microemulsion phase, whose aqueous phase is distilled water, until the formation of Winsor II system; and Method 3, in a Winsor III region, consisting in the formation of a Winsor III region using as aqueous phase the acid digestion solution, diluted in NaOH 0.01N. Seeking to optimize the extraction process only Method 1 (Systems I, II, and VIII) and Method 2 (System IX) were evaluated, being chosen points inside the interest regions (studied domains) to study the influence of contact time and pH in the extraction percentiles. The studied systems present the following compositions: System I: Surfactant Saponified coconut oil, Cosurfactant 1-Butanol, Oil phase Kerosene, Aqueous phase 2% NaCl solution; System II: Aqueous phase Acid digestion solution with pH adjusted using KOH (pH 3.5); System VIII: Aqueous phase - Acid digestion solution (pH 0.06); and System IX Aqueous phase Distilled water (pH 10.24), the other phases of Systems II, VIII and IX are similar to System I. Method 2 showed to be the more efficient one regarding chromium extraction percentile (up to 96.59% - pH 3.5). Considering that with Method 2 the microemulsion region only appears in the Winsor II region, it was studied Method 3 (System X) for the evaluation and characterization of a triphasic system, seeking to compare with a biphases system. System X is composed by: Surfactant Saponified coconut oil, Cosurfactant 1-Butanol, Oil phase Kerosene, Aqueous phase Acid digestion solution diluted with water and with its pH adjusted using 0.01N NaOH solution. The biphasic and triphasic microemulsion systems were analyzed regarding its viscosity, extraction efficiency and drop effective diameter. The experimental results showed that for viscosity studies the obtained values were low for all studied systems, the diameter of the drop is smaller in the Winsor II region, with 15.5 nm, reaching 46.0 nm in Winsor III region, being this difference attributed to variations in system compositions and micelle geometry. In chromium extraction, these points showed similar results, being achieved 99.76% for Winsor II system and 99.62% for Winsor III system. Winsor III system showed to be more efficient due to the obtaining of a icroemulsion with smaller volume, with the possibility to recover the oil phase in excess, and the use of a smaller proportion of surfactant and cosurfactant (C/S)

Tratamento de borra de petróleo com sistemas microemulsionados

During the storage of oil, sludge is formed in the bottoms of tanks, due to decantation, since the sludge is composed of a large quantity of oil (heavy petroleum fractions), water and solids. The oil sludge is a complex viscous mixture which is considered as a hazardous waste. It is then necessary to develop methods and technologies that optimize the cleaning process, oil extraction and applications in industry. Therefore, this study aimed to determine the composition of the oil sludge, to obtain and characterize microemulsion systems (MES), and to study their applications in the treatment of sludge. In this context, the Soxhlet extraction of crude oil sludge and aged sludge was carried out, and allowing to quantify the oil (43.9 % and 84.7 % - 13 ºAPI), water (38.7 % and 9.15 %) and solid (17.3 % and 6.15 %) contents, respectively. The residues were characterized using the techniques of X-ray fluorescence (XRF), Xray diffraction (XRD) and transmission Infrared (FT-IR). The XRF technique determined the presence of iron and sulfur in higher proportions, confirming by XRD the presence of the following minerals: Pyrite (FeS2), Pyrrhotite (FeS) and Magnetite (Fe3O4). The FT-IR showed the presence of heavy oil fractions. In parallel, twelve MES were prepared, combining the following constituents: two nonionic surfactants (Unitol L90 and Renex 110 - S), three cosurfactants (butanol, sec-butanol and isoamyl alcohol - C), three aqueous phase (tap water - ADT, acidic solution 6 % HCl, and saline solution - 3.5 % NaCl - AP) and an oil phase (kerosene - OP). From the obtained systems, a common point was chosen belonging to the microemulsion region (25 % [C+S] 5 % OP and AP 70 %), which was characterized at room temperature (25°C) by viscosity (Haake Rheometer Mars), particle diameter (Zeta Plus) and thermal stability. Mixtures with this composition were applied to oil sludge solubilization under agitation at a ratio of 1:4, by varying time and temperature. The efficiencies of solubilization were obtained excluding the solids, which ranged between 73.5 % and 95 %. Thus, two particular systems were selected for use in storage tanks, with efficiencies of oil sludge solubilization over 90 %, which proved the effectiveness of the MES. The factorial design delimited within the domain showed how the MES constituents affect the solubilization of aged oil sludge, as predictive models. The MES A was chosen as the best system, which solubilized a high amount of aged crude oil sludge (~ 151.7 g / L per MES)

Influência da densidade de carga e da massa molar da poliacrilamida na reologia de sistemas microemulsionados

The knowledge of the rheological behavior of microemulsionated systems (SME) is of fundamental importance due to the diversity of industrial applications of these systems. This dissertation presents the rheological behavior of the microemulsionated system formed by RNX 95/alcohol isopropyl/p-toulen sodium sulfonate/kerosene/distilled water with the addition of polyacrylamide polymer. It was chosen three polymers of the polyacrylamide type, which differ in molar weight and charge density. It was studied the addition of these polymers in relatively small concentration 0,1% in mass and maximum concentration of 2,0%. It was made analysis of flow to determine the appearing viscosities of the SME and rheological parameters applying Bingham, Ostwald de Waale and Herschell-Buckley models. The behavior into saline environment of this system was studied for a solution of KCl 2,0%, replacing the distilled water. It was determined the behavior of microemulsions in relation with the temperature through curves of flow in temperatures of 25 to 60ºC in variations of 5ºC. After the analysis of the results the microemulsion without the addition of polymer presented a slight increase in its viscosity, but it does not mischaracterize it as a Newtonian fluid. However the additive systems when analyzed with low concentration of polymer adjusted well to the applied models, with a very close behavior of microemulsion. The higher concentration of the polymer gave the systems a behavior of plastic fluid. The results of the temperature variation point to an increase of viscosity in the systems that can be related to structural changes in the micelles formed in the own microemulsion without the addition of polymer

Eficiência de extração de cobre e níquel utilizando sistemas microemulsionados bifásicos e trifásicos

The environmental impact due to the improper disposal of metal-bearing industrial effluents imposes the need of wastewater treatment, since heavy metals are nonbiodegradable and hazardous substances that may cause undesirable effects to humans and the environment. The use of microemulsion systems for the extraction of metal ions from wastewaters is effective when it occurs in a Winsor II (WII) domain, where a microemulsion phase is in equilibrium with an aqueous phase in excess. However, the microemulsion phase formed in this system has a higher amount of active matter when compared to a WIII system (microemulsion in equilibrium with aqueous and oil phases both in excess). This was the reason to develop a comparative study to evaluate the efficiency of two-phases and three-phases microemulsion systems (WII and WIII) in the extraction of Cu+2 and Ni+2 from aqueous solutions. The systems were composed by: saponified coconut oil (SCO) as surfactant, n-Butanol as cosurfactant, kerosene as oil phase, and synthetic solutions of CuSO4.5H2O and NiSO4.6H2O, with 2 wt.% NaCl, as aqueous phase. Pseudoternary phase diagrams were obtained and the systems were characterized by using surface tension measurements, particle size determination and scanning electron microscopy (SEM). The concentrations of metal ions before and after extraction were determined by atomic absorption spectrometry. The extraction study of Cu+2 and Ni+2 in the WIII domain contributed to a better understanding of microemulsion extraction, elucidating the various behaviors presented in the literature for these systems. Furthermore, since WIII systems presented high extraction efficiencies, similar to the ones presented by Winsor II systems, they represented an economic and technological advantage in heavy metal extraction due to a small amount of surfactant and cosurfactant used in the process and also due to the formation of a reduced volume of aqueous phase, with high concentration of metal. Considering the reextraction process, it was observed that WIII system is more effective because it is performed in the oil phase, unlike reextraction in WII, which is performed in the aqueous phase. The presence of the metalsurfactant complex in the oil phase makes possible to regenerate only the surfactant present in the organic phase, and not all the surfactant in the process, as in WII system. This fact allows the reuse of the microemulsion phase in a new extraction process, reducing the costs with surfactant regeneration

Aplicação de sistemas microemulsionados ácidos em acidificação de poços

Stimulation operations have with main objective restore or improve the productivity or injectivity rate in wells. Acidizing is one of the most important operations of well stimulation, consist in inject acid solutions in the formation under fracture formation pressure. Acidizing have like main purpose remove near wellbore damage, caused by drilling or workover operations, can be use in sandstones and in carbonate formations. A critical step in acidizing operation is the control of acid-formation reaction. The high kinetic rate of this reaction, promotes the consumed of the acid in region near well, causing that the acid treatment not achive the desired distance. In this way, the damage zone can not be bypassed. The main objective of this work was obtain stable systems resistant to the different conditions found in field application, evaluate the kinetic of calcite dissolution in microemulsion systems and simulate the injection of this systems by performing experiments in plugs. The systems were obtained from two non ionic surfactants, Unitol L90 and Renex 110, with sec-butanol and n-butanol like cosurfactants. The oily component of the microemlsion was xilene and kerosene. The acqueous component was a solution of HCl 15-26,1%. The results shown that the microemulsion systems obtained were stable to temperature until 100ºC, high calcium concentrations, salinity until 35000 ppm and HCl concentrations until 25%. The time for calcite dissolution in microemulsion media was 14 times slower than in aqueous HCl 15%. The simulation in plugs showed that microemulsion systems promote a distributed flux and promoted longer channels. The permeability enhancement was between 177 - 890%. The results showed that the microemulsion systems obtained have potential to be applied in matrix acidizing

Extração de boro de água produzida sintética por sistema microemulsionado

Boron is a semi-metal present in certain types of soils and natural waters. It is essential to the healthy development of plants and non-toxic to humans, depending on its concentration. It is used in various industries and it s present in water production coming from oil production. More specifically in Rio Grande do Norte, one of the largest oil producers on shore of Brazil, the relationship water/oil in some fields becomes more than 90%. The most common destination of this produced water is disposal in open sea after processing to meet the legal specification. In this context, this research proposes to study the extraction of boron in water produced by microemulsion systems for industrial utilization. It was taken into account the efficiency of extraction of boron related to surfactant (DDA and OCS, both characterized by FT-IR), cosurfactant (butanol and isoamyl alcohol), organic phase (kerosene and heptanes) and aqueous phase (solution of boron 3.6 ppm in alkaline pH). The ratio cosurfactant/ surfactant used was four and the percentage of organic phases for all points of study was set at 5%. It was chosen points with the highest percentage of aqueous phase. Each system was designed for three points of different compositions in relation to the constituents of a pseudoternary diagram. These points were chosen according to studies of phase behavior in pseudoternary diagrams made in previous studies. For this research, points were chosen in the Winsor II region. The excess aqueous solution obtained in these systems was separated and analyzed by ICP OES. For the data set obtained, the better efficiency in the extraction of boron was obtained using the system with DAC, isoamyl alcohol and heptanes, which extracted 49% in a single step. OCS was not viable to the extraction of boron by microemulsion system in the conditions defined in this study

Pirólise de borras oleosas de petroleo utilizando nanomateriais

The oily sludge is a complex mix of hydrocarbons, organic impurities, inorganic and water. One of the major problems currently found in petroleum industry is management (packaging, storage, transport and fate) of waste. The nanomaterials (catalysts) mesoporous and microporous are considered promising for refining and adsorbents process for environment protection. The aim of this work was to study the oily sludge from primary processing (raw and treated) and vacuum residue, with application of thermal analyses technique (pyrolysis), thermal and catalytic pyrolysis with nanomaterials, aiming at production petroleum derived. The sludge and vacuum residue were analyzed using a soxhlet extraction system, elemental analysis, thin layer chromatography, thermogravimetry and pyrolysis coupled in gas chromatography/mass spectrometry (Py GC MS). The catalysts AlMCM-41, AlSBA-15.1 e AlSBA-15.2 were synthesized with molar ratio silicon aluminum of 50 (Si/Al = 50), using tetraethylorthosilicante as source of silicon and pseudobuhemita (AlOOH) as source of aluminum. The analyzes of the catalysts indicate that materials showed hexagonal structure and surface area (783,6 m2/g for AlMCM-41, 600 m2/g for AlSBA-15.1, 377 m2/g for AlSBA-15.2). The extracted oily sludge showed a range 65 to 95% for organic components (oil), 5 to 35% for inorganic components (salts and oxides) and compositions different of derivatives. The AlSBA-15 catalysts showed better performance in analyzes for production petroleum derived, 20% increase in production of kerosene and light gas oil. The energy potential of sludge was high and it can be used as fuel in other cargo processed in refinery