Aplicação da água residuária das salinas no tratamento de efluente têxtil

The treatment of colored and alkaline effluent has been a challenge to the textile industry. An alternative to remove the colors of those effluents is applying magnesium chloride as a coagulant agent. The magnesium ion, in high pH, hydrolyzes itself, forming the magnesium hydroxide which has a large adsorptive area and positive electrostatic charges able to act as an efficient coagulant. The bittern wastewater from the salt industries has been studied as a potential font of this magnesium ion. Nowadays, this bittern wastewater is evicted into the sea, without any treatment or other use. This thesis has evaluated the potential of applying the wastewater from the salt industries in the treatment of dyeing effluent containing indigo dye and alkaline pH. All the experiments were made in jar tests simulating the chemical coagulation, flocculation and decantation steps ranging the pH and the concentration of magnesium ion. Were obtained removals between 96% and 76% for turbidity, apparent color, and true color, respectively, using 200mg/L Mg2+. The reduction of costs with acid, when were used the salt industries wastewater, comparing with Al2(SO4)3, was 62%. For the degradation of organic matter remaining in the clarified, around 900 mg/L, was applyed the advanced process of oxidation: photo-Fenton. The preliminary results showed 57% reduction in DOC. According to the results obtained, the salt industries wastewater can be applied, as coagulant, in the physical-chemical treatment of the denim dyeing wastewater, so it is not necessary a previous adjust of pH, efficiently and economically

Flotação por ar dissolvido na clarificação de águas com baixa turbidez utilizando sulfato de alumínio e sementes de Moringa oleifera como coagulantes

This work aims to investigate the process of Dissolved air Flotation (DAF) for clarifying water samples with low turbidity using aluminum sulphate and Moringa oleifera seeds as coagulants. The experimental procedure was carried out in a bench scale flotation unit. The influences on the pre-treatment conditions (coagulant dosage and flocculation time) and flotation parameters (superficial application rate and recirculation rate) were evaluated considering the efficiency of the process. The efficiency was evaluated by determining the turbidity of the untreated and treated water samples. The results obtained showed that turbidity reduction can be obtained very efficiently by using DAF and the latter coagulant in low turbidity water. Using aluminum sulphate in pH´s 5.0 and 6.0 better efficiencies were obtained with low concentrations (15 mg/L), achieving values of 92% of turbidity reduction. In the case of use of Moringa oleifera better efficiencies of reduction of turbidity were reported when using a concentration of 50 mg/L in all range of pH´s, achieving 86% of reduction. The zeta potential was also determined, in an attempt to aid comprehension of the coagulation mechanisms involved. The coagulation mechanisms with Moringa oleifera seeds were shown to be adsorption and charge neutralization, as well as adsorption and bridging. Concerning aluminum sulphate, the predominant mechanisms are adsorption and charge neutralization and enmeshment in a precipitate. The results indicate that for low turbidity water, Moringa oleifera seeds could potentially be a viable substitute for aluminum sulphate

Nitrificação de efluentes de reatores anaeróbicos em filtros submersos aerados

Although the good performance in organic matter and suspended solids removal, the anaerobic reactors are unable to remove ammonia nitrogen from sewage, which makes indispensable to include a step of post-treatment for removal of ammonia or nitrate as necessary. This paper presents the performance of a new variant technology, where the nitrification unit, preceded by anaerobic units, is a submerged aerated biological filter, without continuous sludge discharge in their daily operation. The oxygenation system is very simple and inexpensive, consisting of perforated hoses and compressors. The anaerobic reactors are a septic tank with two chambers followed (8.82 m³) and two parallel anaerobic filters (36 m³ each) filled with ceramic bricks and conics plastic parts. Both followed aerated filters were filled with cut corrugated conduit. The study evaluated the behavior of the system with constant domestic sewage flow (10 m³/d) and different aeration conditions, are these: stage 01, when applied air flow of 0.01 m³ air/min in both aerated filter; stage 02, remained in the initial air flow rate in the second aerated filter and increased at the first to 0.05 m³ air/min; at last, at last, in stage 03, the air flow rate of first aerated filter was 0.10 m³ air/min and on the second remained at 0.01 m³ air/min. The filter FA1 received load of 0.41 kg COD/m³.d, 0.37 kg COD/m³.d and 0.26 kg COD/m³.d on phases 01, 02 and 03, respectively. The FA2 received loads of 0.25 kg COD/m³.d, 0.18 kg COD/m³.d and 0.14 kg COD/m³.d on phases 01, 02 and 03, respectively. During stage 01, were found the following results: 98% removals of BODtotal and 92% of CODtotal, with effluent presenting 9 mg/L of BODtotal final average and 53 mg/L of CODtotal average; suspended solids removals of 93%, with a mean concentration of 10 mg/L in the final effluent; 47% reduction of ammonia of FA2 to FAN 's, presenting average of 28 mg NNH3/ L of ammonia in the effluent with; the dissolved oxygen levels always remained around 2.0 mg/L. During stage 02, were found removals of 97% and 95% to BODtotal and suspended solids, respectively, with average final concentrations of 8 and 7 mg/L, respectively; was removed 60% of ammonia, whose final concentration was 16.3 mg NNH3/ L, and nitrate was increased to a final average concentration of 16.55 mg N-NO3/L. Finally, the stage 03 provided 6 mg/L of DBOtotal (98% removal) and 23 mg/L of CODtotal (95% removal) of final effluent concentrations average. At this stage was identified the higher ammonia oxidation (86%), with final effluent showing average concentration of 6.1 mg N-NH3/L, reaching a minimum of 1.70 mg N-NH3/L. In some moments, during stage 03, there was a moderate denitrification process in the last aerated filter. The average turbidity in the effluent showed around 1.5 NTU, proving the good biomass physical stability. Therefore, the results demonstrate the submerged biological filters potential, filled with high void ratio material (98%), and aerated with hoses and compressor adoption, in the carbonaceous and nitrogenous matter oxidation, also generating an effluent with low concentration of solids

Decaimento bacteriano em lagoas de estabilização no Nordeste brasileiro

Stabilization pond system consisting in more sewage treatment used in Rio Grande do Norte (RN), Brazil, representing about 90% of all systems. Fecal bacteria are removed mainly facultative ponds and in maturation ponds. Many factors influence bacterial decay, such as the levels of pH and DO, temperature, light intensity, HDT and nutrient availability. The bacterial decay rate (Kb) is calculated considering many variables, but the hydraulic regime is a significant influence for microorganisms removal, and the dispersed flow which best characterizes a stabilization pond. However, some authors developed equations for the Kb accordant plug flow and complete mixing. This research study aimed to evaluate the bacterial decay of fecal coliform and Enterococcus sp. in stabilization ponds designed to treat domestic sewage, full-scale, in RN. All systems have assessed pretreatment, a facultative pond (LF) followed by two maturation (LM1 and LM2). The parameters availed were: temperature, pH, DO, BOD5, COD, fecal coliform, Enterococcus sp., Chlorophyll a, total suspended solids, fixed and volatile. In general, there were not significant differences for pH, DO and temperature in the ponds, except for the new systems, since they have low flow and hydraulic loads. The removal of organic matter in the ponds was low, about 70%, and nearly all are overloaded organic and operational problems. The bacterial removals were low, with average 96% for LF for fecal coliform, and 98% for Enterococcus sp.; LM1 were in itself a removal for fecal coliform about 71%, and 81% for Enterococcus sp.; LM2 have efficiency of 69% for fecal coliform, and 68% for Enterococcus sp. The equation proposed by Von Sperling (1999), according to the dispersed flow regime, generated empirical values of Kb more approximate to calculated values of Kb. On average, the calculated Kb to coliforms in the LF was 0.31 d-1, and for both maturation ponds were 0.35 d-1. For Enterococcus sp. the average was 0.40 d-1 for LF, 0.55 d-1 for LM1, and 0.58 d-1 for LM2. These results also showed that the Kb obtained in full-scale systems are smaller than those found in pilot-scale ponds. Moreover, one can say that the equation proposed by Marais (1974), according to the complete-mix regime, overestimates Kb. Actual results of Kb indicated that fecal coliforms are more resistant to adverse conditions present in stabilization ponds than Enterococcus sp., therefore, an indicator of microbiological safety and efficiency. The factors significant interventions in the rate of bacterial decay were concentrations of COD, the organic loading and HDT. The few Kb relationship between pH, DO and temperature were not significant. Finally, we conclude that it s essential to correct operation and maintenance, for not performing these activities is one of the main factors contributing to low rates of bacterial decay.

Estudo de manejo de águas pluviais urbanas na cidade Natal-Rio Grande do Norte

Urban stormwater can be considered as potential water resources as well as problems for the proper functioning of the manifold activities of the city, resulting from inappropriate use and occupation of the soil, usually due to poor planning of the occupation of the development areas, with little care for the environmental aspects of the drainage of surface runoff. As a basic premise, we must seek mechanisms to preserve the natural flow in all stages of development of an urban area, preserving the soil infiltration capacity in the scale of the urban area, comprising the mechanisms of natural drainage, and noting preserving natural areas of dynamic water courses, both in the main channel and in the secondary. They are challenges for a sustainable urban development in a harmonious coexistence of modern developmental, which are consistent with the authoritative economic environmental and social quality. Integrated studies involving the quantity and quality of rainwater are absolutely necessary to achieve understanding and obtaining appropriate technologies, involving both aspects of the drainage problems and aspects of use of water when subjected to an adequate management of surface runoff , for example, the accumulation of these reservoirs in detention with the possibility of use for other purposes. The purpose of this study aims to develop a computer model, adjusted to prevailing conditions of an experimental urban watershed in order to enable the implementation of management practices for water resources, hydrological simulations of quantity and, in a preliminary way, the quality of stormwater that flow to a pond located at the downstream end of the basin. To this end, we used in parallel with the distributed model SWMM data raised the basin with the highest possible resolution to allow the simulation of diffuse loads, heterogeneous characteristics of the basin both in terms of hydrological and hydraulic parameters on the use and occupation soil. The parallel work should improve the degree of understanding of the phenomena simulated in the basin as well as the activity of the calibration models, and this is supported by monitoring data acquired during the duration of the project MAPLU (Urban Stormwater Management) belonging to the network PROSAB (Research Program in Basic Sanitation) in the years 2006 to 2008

Remoção de matéria orgânica em sistemas de lagoas de estabilização no Nordeste brasileiro

Stabilization pond is the main technology used for treatment wastewater, in northeast Brazil, due to lower cost of deployment, operation and maintenance compared to other technologies. Most systems of stabilization ponds has been in operation for some time, on average 10 years of operation, receiving high organic loads and do not have good removal efficiencies of the main parameters for which have been designed. Therefore it is necessary to work to quantify the efficiency of current systems. This study evaluated the biodegradability of organic matter in raw sewage, the removal of organic matter in reactors and determination of the kinetic constant removal of organic matter (k), both in reactors and in raw sewage, based on the analysis made in the laboratory and through mathematical methods proposed in the literature, in nine systems stabilization ponds, located in Rio Grande do Norte. In relation the degradation kinetics in stabilization ponds, it was observed that many papers published in the literature were obtained in pilot-scale systems, which often, due to the action of external factors such as wind and temperature, these can t be considered as a reference in the analysis of the kinetic constant K, so the need for more research into systems of scale. This study had three distinct phases and simultaneous, routine monitoring, study of the daily cycle and the determination of kinetic constant of degradation of organic matter (K). The monitoring showed that the removal efficiencies of organic matter on most systems were lower than suggested by the literature, the best efficiencies of around 76% (BOD) and 72% (COD) and the worst of the order of 48% (BOD) and 55% (COD). The calculation of K in raw sewage (Ke) was within the range of variation expected in the literature (0.35 to 0.60 days-1). Already for the results obtained for K in the reactors (Kr), there were well below the values recommended in the literature (0.25 to 0.40 d-1 for complete mix and from 0.13 to 0.17 d-1 for flow dispersed), in line with the overloads that organic systems are subject

Análise do uso e ocupação do solo das margens de um reservatório e a sua influência na qualidade da água

The building of water reservoirs has become a solution for water scarcity of the semiarid regions, however, the land use and occupation near the margins of the reservoirs have been causing serious damage to water quality, harming their use. This paper aims to analyze the land use and occupation in the margins of the Northeast reservoir and evaluate their influence on the water quality, to identify the areas and activities that represent an higher risk of contamination to the reservoir. The study was conducted at the reservoir Dourado, located in the city of Currais Novos - RN, during the period from August 2012 to February 2013. Were defined six areas regarding the land use and occupation, then, Water samples were collected from the margins in these areas for the characterization of water quality. The results showed that almost all Permanent Preservation Areas (PPA) from the reservoir is degraded, increasing the susceptibility of large input of nutrients and contaminants loads. The water reservoir showed low quality, being with strong evidence of eutrophication due to the nutrient accumulation arising from the activities surrounding the reservoir, mainly from agriculture and Livestock. The Areas 1 and 2 are the areas that present a greater risk of reservoir degradation, because are the possible major sources of nutrients (phosphorus total, orthophosphate and nitrate), however, due to the small size of the reservoir, any compound that reaches its margins ultimately affects the water quality of the same

Agricultura familiar: uma perspectiva da qualidade de vida do produtor rural orgânico da Paraíba

Knowledge of quality of life is a very complex and rich in cultural and subjective dimensions, understood in a broad sense and multivariate theme. Considering the rural areas from agriculture, it is observed that the production standard defines significant changes in the environmental context and the quality of life of rural workers. To explain the relationship between quality of life and Family Organic Agriculture, we sought to analyze the quality of life of the organic family farmer, after change in agricultural management. The research, based on a procedure exploratory study supported the articulation theoretically constructed, showed their relevance and allowed to delimit with greater security, the central question of work. The WHOQOL - 100 treated the instrument of research on quality of life that directed the field study with organic farmers from the town of Lagoa Seca / PB. Farmers and family members are from rural regions Almeida, Alvinho, Lagoa de Barro, Lagoa Gravatá, Oiti and Pau Ferro. The average time is 39 years farming and organic family farm is 16 years. In the analysis work was found that the process of production of vegetables and fruits is divided into 08 steps and with respect to workloads observations showed the presence of: physical loads, mechanical stresses, psychological burden and ergonomic factors. Most farmers reported symptoms were fatigue and cramps in the legs . Regarding the quality of life was noticed that the Psychological Domain contributed positively to the quality of life with mean and standard deviation (17.83 ± 12.78) and Domain Environment negatively contributing to the quality of life of this group (9.00 ± 6.82). We conclude that the practice of Family Organic Agriculture should be seen as an effective strategy in promoting quality of life and social values in between, since it presents environmental sustainability with regard to life and socio-cultural diversity of populations

Estudo das propriedades psicométricas do inventário de estilos parentais de young no Brasil

Parenting styles concern overall interaction characteristics between parents and children. To assess them, it is important to build and adapt valid and reliable instruments. The main objectives of this dissertation were to translate, adapt and evaluate the psychometric properties of the Young Parenting Inventory (YPI) for the Brazilian context, as seek associations between the YPI and Familiogram Test (FG). In current study, YPI was adapted to Portuguese by backtranslation method. Content analyses were made by five judges. 920 high school and college students (543 females), whose ages were between 14 and 69 years (M = 21.3, SD = 6.1), filled out the research instruments. Data were collected in Natal, Petrolina and Brasilia cities and Porto Alegre metropolitan region. The results confirmed the existence of five factors. Final version of the YPI was composed by 49 items. Exploratory factorial analysis (principal components) were conducted using oblimin rotation. Five factors extracted explained 45.12% of the maternal scale variance and 47.59% of paternal scale. Each factor explained, at least, 3% of the variance and showed Eigenvalue over than 1.5. All items have factorial loadings values above 0.3. The confirmatory factorial analysis has showed fit statistics reasonably adequate: for maternal scale,  ² [1114] = 4636.38, p < 0.001,  ² / df = 4.16, with GFI = 0.83, AGFI = 0.81 and RMSEA = 0.06; for paternal scale,  ² [1114] = 5133.69 p < 0.001,  ² / df = 4.61, with GFI = 0.81, AGFI = 0.79 and RMSEA = 0,06. Thus, final instrument was composed by the following factors: (I) Disconnection and Rejection ( = 0.89 and 0.90), (II) Affectivity and Emotional Stability ( = 0.85 and 0.88); (III) Overvigilance and Other Directedness ( = 0.83 and 0.85), (IV) Overprotection and Impaired Autonomy ( = 0.78 and 0.79) and (V) Impaired Limits ( = 0.66 and 0.71). Finally, relations between the YPI and FG were assessed. Pearson's correlations between the YPI and FG showed moderated associations, particularly between the factors Affectivity (YPI) and Affection (FG) (r = 0.69 and 0.7 for maternal and paternal scale, respectively); and the factors Disconnection and Rejection (YPI) and Conflict (FG) (r = 0.59 and 0.58). The regression models indicated that over than 40% of variance of factors of FG can be predicted by factors of YPI. Beta coefficients for Affection-Affectivity relation were 0.67 (maternal scale) and 0.53 (paternal scale); for Disconnection-Conflict relation were 0.31 (maternal scale) and 0.44 (paternal scale). We conclude the YPI has adequate psychometric parameters and can be used in future research in this area. However, adjustments in the structure of the YPI were made. Moreover, it is suggested further studies to consider other samples and variables, increasing the knowing of parenting styles and the Young‟s theory in the Brazilian context

Síntese e caracterização de materiais nanoporosos para pirólise catalítica de óleos pesados

The present work reports the study of nanoporous structures, aiming at their use in research directed to the current demand of the petroleum industry to value heavy oil. Initially, two ways were chosen for the synthesis of porous structures from the molecular sieves of type Si-MCM-41. In the first way, the structure MCM-41 is precursory for heteroatom substitutes of silicon, generating catalyst of the type Al-MCM-41 from two different methods of incorporation of the metal. This variation of the incorporation method of Aluminum in the structure of Si-MCM-41 was carried out through the conventional procedure, where the aluminum source was incorporated to the gel of synthesis, and the procedure post-synthesis, where the Aluminum source was incorporated in catalyst after the synthesis of Si-MCM-41. In the second way, the MCM-41 acts as a support for growth of nanocrystals of zeolite embedded in their mesoporous, resulting in hybrid MCM-41/ZSM-5 catalyst. A comparative analysis was carried through characterizations by XRD, FTIR, measures of acidity through n-butylamine adsorption for TGA, SEM-XRF and N2 adsorption. Also crystalline aluminosilicate with zeolitic structure MFI of type ZSM-5 was synthesized without using organic templates. Methodologies to the preparation of these materials are related by literature using conventionally reactants that supply oxides of necessary silicon and aluminum, as well as a template agent, and in some cases co-template. The search for new routes of preparation for the ZSM-5 aimed at, above all, the optimization of the same as for the time and the temperature of synthesis, and mainly the elimination of the use of organic templates, that are material of high cost and generally very toxic. The current study is based on the use of the H2O and Na+ cations playing the role of structural template and charge compensation in the structure. Characterizations by XRD, FTIR, SEM-XRF and N2 adsorption were also conducted for this material in order to compare the samples of ZSM-5 synthesized in the absence of template and those used industrially and synthesized using structuring

Hidróxidos duplos lamelares de magnésio e alumínio modificados com carbonato e p123 para adsorção de dióxido de carbono

Muitos mecanismos provocados pela ação humana vêm gerando um aumento na queima de combustíveis fósseis e processos químicos (produtos orgânicos, carvão, madeira, óleo diesel, gasolina e outros derivados de petróleo) e, consequentemente, há um aumento na emissão de CO2 na atmosfera. Uma das alternativas para a captura desse poluente é o processo de adsorção, o qual pode ajudar na redução do CO2. As hidrotalcitas ou hidróxidos duplos lamelares (HDL s) estão dentre esses materiais estudados, já que apresentam alta estabilidade e uma boa porosidade, tornando-se assim um promissor adsorvente de gases poluentes. Os HDL s formam um grupo de argilas do tipo aniônico que consiste em camadas positivamente carregadas de óxido de metal (ou hidróxido de metal) com intercamadas de ânions. Foi constatado que ânions que possuem duas cargas negativas, estabilizam muito mais que ânions monovalentes, sendo o carbonato o mais estável dos ânions divalentes. Neste trabalho, foi proposta uma modificação na síntese direta através da co-precipitação a pH constante utilizando sais de cátions divalentes (Mg2+) e trivalentes (Al3+) reportados na literatura. Durante a síntese dos HDL s retirou-se o carbonato, bem como, utilizou-se um copolímero como um template para o alargamento das lamelas. As amostras foram caracterizadas utilizando as técnicas de DRX, TG/DTG, FTIR, MEV/EDX, MET e adsorção e dessorção de N2. Os dados obtidos indicam que a estrutura, mesmo após a modificação, apresentou resultados condizentes com os encontrados na literatura. Dentre as várias aplicações dos HDL s foi realizado o estudo da adsorção do CO2. A capacidade de adsorção do material foi testada de acordo com o tempo de contato entre o adsorvente e o adsorbato, sendo esperado que os materiais tratados com template apresentassem um maior desempenho

Síntese de catalisadores nanoporosos na ausência total e parcial de direcionadores orgânicos para pirólise catalítica de óleos pesados e intermediários

The processing of heavy oil produced in Brazil is an emergency action and a strategic plan to obtain self-sufficiency and economic surpluses. Seen in these terms, it is indispensable to invest in research to obtain new catalysts for obtaining light fraction of hydrocarbons from heavy fractions of petroleum. This dissertation for the degree of Doctor of Philosophy reports the materials preparation that combine the high catalytic activity of zeolites with the greater accessibility of the mesoporosity, more particularly the HZSM-5/MCM-41 hybrid, done by synthesis processes with less environmental impact than conventional ones. Innovative methodologies were developed for the synthesis of micro-mesoporous hybrid material by dual templating mechanism and from crystalline zeolitic aluminosilicate in the absence of organic template. The synthesis of hybrid with pore bimodal distribution took place from one-single organic directing agent aimed to eliminate the use of organic templates, acids of any kind or organic solvents like templating agent of crystalline zeolitic aluminosilicate together with temperature-programmed microwave-assisted, making the experimental procedures of preparation most practical and easy, with good reproducibility and low cost. The study about crystalline zeolitic aluminosilicate in the absence of organic template, especially MFI type, is based on use of H2O and Na+ cation playing a structural directing role in place of an organic template. Advanced characterization techniques such as X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Highresolution Transmission Electron Microscopy (HRTEM), Adsorption of N2 and CO2, kinetic studies by Thermogravimetric Analysis (TGA) and Pyrolysis coupled to Gas Chromatography/Mass Spectrometry (Pyrolysis-GC/MS) were employed in order to evaluate the synthesized materials. Achieve the proposed objectives, has made available a set of new methodologies for the synthesis of zeolite and hybrid micro-mesoporous material, these suitable for catalytic pyrolysis of heavy oils aimed at producing light fraction

Obtenção de polímeros graftizados de quitosana e estudo das propriedades físico-químicas para aplicação na indústria do petróleo

Chitosan is a biopolymer derived from the shells of crustaceans, biodegradable, inexpensive and renewable with important physical and chemical properties. Moreover, the different modifications possible in its chemical structure generate new properties, making it an attractive polysaccharide owing to its range of potential applications. Polymers have been used in oil production operations. However, growing concern over environmental constraints has prompted oil industry to search for environmentally sustainable materials. As such, this study sought to obtain chitosan derivatives grafted with hydrophilic (poly(ethylene glycol), mPEG) and/or hydrophobic groups (n-dodecyl) via a simple (one-pot) method and evaluate their physicochemical properties as a function of varying pH using rheology, small-angle Xray scattering (SAXS), dynamic light scattering (DLS) and zeta potential. The chitosan derivatives were prepared using reductive alkylation under mild reaction conditions and the chemical structure of the polymers was characterized by nuclear magnetic resonance (1H NMR) and CHN elemental analysis. Considering a constant mPEG/Chitosan molar ratio on modification of chitosan, the solubility of the polymer across a wide pH range (acidic, neutral and basic) could only be improved when some of the amino groups were submitted to reacetylation using the one-pot method. Under these conditions, solubility is maintained even with the simultaneous insertion of n-dodecyl. On the other hand, the solubility of derivatives obtained only through mPEG incorporation using the traditional methodology, or with the ndodecyl group, was similar to that of its precursor. The hydrophilic group promoted decreased viscosity of the polymer solutions at 10 g/L in acid medium. However, at basic pH, both viscosity and thermal stability increased, as well as exhibited a pronounced pseudoplastic behavior, suggesting strong intermolecular associations in the alkaline medium. The SAXS results showed a polyelectrolyte behavior with the decrease in pH for the polymer systems. DLS analyses revealed that although the dilute polymer solutions at 1 g/L and pH 3 exhibited a high density of protonated amino groups along the polymer chain, the high degree of charge contributed significantly to aggregation, promoting increased particle size with the decrease in pH. Furthermore, the hydrophobic group also contributed to increasing the size of aggregates in solution at pH 3, whereas the hydrophilic group helped reduce their size across the entire pH range. Nevertheless, the nature of aggregation was dependent on the pH of the medium. Zeta potential results indicated that its values do not depend solely on the surface charge of the particle, but are also dependent on the net charge of the medium. In this study, water soluble associative polymers exhibit properties that can be of great interest in the petroleum industry

Interações entre a carboximetilcelulose, carbonato de cálcio e bentonita: repercussões sobre as propriedades dos fluidos de perfuração aquosos

The role of carboxymethylcellulose (CMC) in association to calcium carbonate particles (CaCO3) in most water-based drilling fluids is to reduce the fluid loss to the surrounding formation. Another essential function is to provide rheological properties capable of maintaining in suspension the cuttings during drilling operation. Therefore, it is absolutely essential to correlate the polymer chemical structure (degree of substitution, molecular weight and distribution of substituent) with the physical-chemical properties of CaCO3, in order to obtain the better result at lower cost. Another important aspect refers to the clay hydration inhibitive properties of carboxymethylcellulose (CMC) in drilling fluids systems. The clay swelling promotes an undesirable damage that reduces the formation permeability and causes serious problems during the drilling operation. In this context, this thesis consists of two main parts. The first part refers to understanding of interactions CMC-CaCO3, as well as the corresponding effects on the fluid properties. The second part is related to understanding of mechanisms by which CMC adsorption occurs onto the clay surface, where, certainly, polymer chemical structure, ionic strength, molecular weight and its solvency in the medium are responsible to affect intrinsically the clay layers stabilization. Three samples of carboximetilcellulose with different molecular weight and degree of substitution (CMC A (9 x 104 gmol DS 0.7), CMC B (2.5 x 105 gmol DS 0.7) e CMC C (2.5 x 105 gmol DS 1.2)) and three samples of calcite with different average particle diameter and particle size distribution were used. The increase of CMC degree of substitution contributed to increase of polymer charge density and therefore, reduced its stability in brine, promoting the aggregation with the increase of filtrate volume. On the other hand, the increase of molecular weight promoted an increase of rheological properties with reduction of filtrate volume. Both effects are directly associated to hydrodynamic volume of polymer molecule in the medium. The granulometry of CaCO3 particles influenced not only the rheological properties, due to adsorption of polymers, but also the filtration properties. It was observed that the lower filtrate volume was obtained by using a CaCO3 sample of a low average size particle with wide dispersion in size. With regards to inhibition of clay swelling, the CMC performance was compared to other products often used (sodium chloride (NaCl), potassium chloride (KCl) and quaternary amine-based commercial inhibitor). The low molecular weight CMC (9 x 104 g/mol) showed slightly lower swelling degree compared to the high molecular weight (2.5 x 105 g/mol) along to 180 minutes. In parallel, it can be visualized by Scanning Electron Microscopy (SEM) that the high molecular weight CMC (2.5 x 105 g/mol e DS 0.7) promoted a reduction in pores formation and size of clay compared to low molecular weight CMC (9.0 x 104 g/mol e DS 0.7), after 1000 minutes in aqueous medium. This behavior was attributed to dynamic of interactions between clay and the hydrodynamic volume of CMC along the time, which is result of strong contribution of electrostatic interactions and hydrogen bounds between carboxylate groups and hydroxyls located along the polymer backbone and ionic and polar groups of clay surface. CMC adsorbs on clay surface promoting the skin formation , which is responsible to minimize the migration of water to porous medium. With the increase of degree of substitution, it was observed an increase of pores onto clay, suggesting that the higher charge density on polymer is responsible to decrease its flexibility and adsorption onto clay surface. The joint evaluation of these results indicate that high molecular weight is responsible to better results on control of rheological, filtration and clay swelling properties, however, the contrary effect is observed with the increase of degree of substitution. On its turn, the calcite presents better results of rheological and filtration properties with the decrease of average viii particle diameter and increase of particle size distribution. According to all properties evaluated, it has been obvious the interaction of CMC with the minerals (CaCO3 and clay) in the aqueous medium

Avaliação das propriedades físico-químicas de sistemas a base de carboximetilcelulose e poli (N-isopropilacrilamida) em soluções aquosas para aplicação na indústria do petróleo

Sustainable development is a major challenge in the oil industry and has aroused growing interest in research to obtain materials from renewable sources. Carboxymethylcellulose (CMC) is a polysaccharide derived from cellulose and becomes attractive because it is water-soluble, renewable, biodegradable and inexpensive, as well as may be chemically modified to gain new properties. Among the derivatives of carboxymethylcellulose, systems have been developed to induce stimuli-responsive properties and extend the applicability of multiple-responsive materials. Although these new materials have been the subject of study, understanding of their physicochemical properties, such as viscosity, solubility and particle size as a function of pH and temperature, is still very limited. This study describes systems of physical blends and copolymers based on carboxymethylcellulose and poly (N-isopropylacrylamide) (PNIPAM), with different feed percentage compositions of the reaction (25CMC, 50CMC e 75CMC), in aqueous solution. The chemical structure of the polymers was investigated by infrared and CHN elementary analysis. The physical blends were analyzed by rheology and the copolymers by UV-visible spectroscopy, small-angle X-ray scattering (SAXS), dynamic light scattering (DLS) and zeta potential. CMC and copolymer were assessed as scale inhibitors of calcium carbonate (CaCO3) using dynamic tube blocking tests and chemical compatibility tests, as well as scanning electron microscopy (SEM). Thermothickening behavior was observed for the 50 % CMC_50 % PNIPAM and 25 % CMC_75 % PNIPAM physical blends in aqueous solution at concentrations of 6 and 2 g/L, respectively, depending on polymer concentration and composition. For the copolymers, the increase in temperature and amount of PNIPAM favored polymer-polymer interactions through hydrophobic groups, resulting in increased turbidity of polymer solutions. Particle size decreased with the rise in copolymer PNIPAM content as a function of pH (3-12), at 25 °C. Larger amounts of CMC result in a stronger effect of pH on particle size, indicating pH-responsive behavior. Thus, 25CMC was not affected by the change in pH, exhibiting similar behavior to PNIPAM. In addition, the presence of acidic or basic additives influenced particle size, which was smaller in the presence of the additives than in distilled water. The results of zeta potential also showed greater variation for polymers in distilled water than in the presence of acids and bases. The lower critical solution temperature (LCST) of PNIPAM determined by DLS corroborated the value obtained by UV-visible spectroscopy. SAXS data for PNIPAM and 50CMC indicated phase transition when the temperature increased from 32 to 34 °C. A reduction in or absence of electrostatic properties was observed as a function of increased PNIPAM in copolymer composition. Assessment of samples as scale inhibitors showed that CMC performed better than the copolymers. This was attributed to the higher charge density present in CMC. The SEM micrographs confirmed morphological changes in the CaCO3 crystals, demonstrating the scale inhibiting potential of these polymers