Hydrogels Applied for Conformance-Improvement Treatment of Oil Reservoirs

This chapter aims at presenting a review of gelling polymer systems that are commercially available or under academic development with potential to control the anisotropic permeability profile of heterogeneous oil reservoirs. In these reservoirs, the oil recovery and sweep efficiency tend to be low, even after applying secondary and enhanced oil recovery methods, because the injected fluid flows preferably through the matrix’s most permeable regions leaving behind part of the displaceable oil retained at the nonswept volume. For that, cross-linked polymers can be used to plug the high-permeability main paths by means of: (i) the formation of an in situ hydrogel or (ii) the adsorption or swelling of pre–cross-linked hydrogel within the reservoir pores, thus causing the diversion of the subsequently injected fluid to low-permeability zones and/or preventing the channeling and early breakthrough of the injected fluid (water or gas) in production wells. The selection of the most suitable hydrogel for the reservoir conformance-improvement treatment should take into account the nature of the conformance problem, the reservoir’s lithology, mineralogy, temperature, pH value, salinity, and hardness of the formation water, as well as the gelling system toxicity and cost

Estudo das propriedades térmicas de filmes poliméricos compostos de Speek, derivados do benzoimidazol e ácido fosfotúngstico Thermal properties of Speek-based polymeric films containing benzimidazole derivatives and fosfotungstic acid

Filmes poliméricos foram desenvolvidos a partir de poli (éter éter cetona) sulfonado (SPEEK), derivados do benzoimidazol e ácido fosfotúngstico (HPW). Neste trabalho foi realizado um estudo utilizando a análise termogravimétrica com o objetivo de avaliar a estabilidade térmica e determinar as condições de temperatura a que podem ser submetidos os filmes produzidos, tendo em vista a aplicação de tais filmes como membranas em células a combustível. Os resultados obtidos mostram que a estabilidade térmica é afetada pela composição dos filmes. A maioria dos filmes se mostrou estável até 140 °C.Polymeric films were developed from sulfonated poly(ether ether ketone) (SPEEK), benzimidazole derivatives and phosphotungstic acid (HPW). In this study, thermogravimetric analysis was performed with the aim of evaluating the temperature conditions to which polymeric films can be submitted. The results showed that thermal stability depended on film composition and the majority of the tested films showed to be stable up to 140 °C

Principais métodos de caracterização da porosidade de resinas à base de divinilbenzeno The most important methods for the characterization of porosity of styrene-divinylbenzene based resins

<abstract language="eng">This paper reviews the most important methods used to characterize the porosity of styrene-divinylbenzene resins. Methods such as adsorption of nitrogen for determination of surface area and mercury intrusion porosimetry for characterization of pore size distribution are related

Síntese e caracterização de copolímeros de estireno e divinilbenzeno clorometilados Synthesis and characterization of chloromethylated styrene-divinylbenzene copolymers

A reação de clorometilação de copolímeros de estireno e divinilbenzeno (S-DVB) em presença de HCl, formaldeído e cloreto de zinco foi estudada em meios aquoso e orgânico. O copolímero S-DVB foi, primeiramente, sintetizado por polimerização em suspensão e caracterizado quanto às suas propriedades porosas. Em meio aquoso, o copolímero foi clorometilado borbulhando-se HCl na mistura de solução aquosa de formaldeído a 37% (formalina 37%) e solução aquosa de cloreto de zinco (catalisador). Em meio orgânico (1,2-dicloroetano), foram usados HCl (borbulhado na solução reacional), paraformaldeído e cloreto de zinco sólido. A presença de grupos clorometila foi identificada por espectroscopia na região do infravermelho e o teor desses grupos foi determinado por titulação potenciométrica dos íons cloreto, liberados após a reação de quaternização com piridina. A reação em meio aquoso originou copolímeros com baixos graus de clorometilação, mesmo sob condições drásticas (uso do catalisador sólido e ácido clorídrico concentrado como meio reacional). Em meio orgânico, devido à maior estabilidade do eletrófilo, foram originados copolímeros com teores mais altos de grupos clorometila. Foi estudada a influência dos parâmetros reacionais sobre o grau de clorometilação dos copolímeros em meio orgânico. A temperatura e a razão copolímero/catalisador foram parâmetros determinantes do grau de clorometilação obtido.<br>Cloromethylation of styrene-divinylbenzene copolymer (S-DVB) in presence of hydrogen chloride, formaldehyde and zinc chloride was studied in aqueous and organic media. S-DVB was first synthesized by suspension polymerization and its porosity was characterized. In aqueous medium, S-DVB was chloromethylated by using a mixture of hydrogen chloride, aqueous formaldehyde solution (formalin 37%) and aqueous zinc chloride solution as catalyst. In organic medium (1,2-dichloroethane), a mixture of hydrogen chloride, paraformaldehyde and solid zinc chloride was employed. The presence of chloromethyl groups in the copolymer was investigated by infrared spectroscopy analysis and titration of chloride ions, after a quaternization reaction between the chloromethylated copolymer and pyridine. The reaction in aqueous medium seems to be very difficult to occur even in the presence of solid zinc chloride (catalyst) and concentrated hydrochloric acid as reaction medium. Organic medium offers a better condition for aromatic eletrophilic substitution, where the reaction occurred in a more satisfactory way. The influence of reaction parameters was studied. Temperature and copolymer/catalyst ratio were the main responsible factors for the attained chloromethylation degree

Estudo cinético da cristalização dinâmica de um poliéster líquido-cristalino termotrópico com espaçadores flexíveis na cadeia principal Study of dynamic crystallization kinetics of a thermotropic liquid crystalline polyester with flexible spacer in the main chain

Foi realizado o estudo cinético da cristalização dinâmica de um poliéster líquido-cristalino termotrópico com espaçadores flexíveis na cadeia principal. O objetivo deste estudo foi verificar o mecanismo da cinética de cristalização do poliéster termotrópico semi-flexível através de um método não-isotérmico. O método empregado (método de Ozawa) permitiu descrever a cinética de cristalização dinâmica do poliéster e os valores de n (expoente de Avrami) encontrados correspondem a um crescimento de cristais em forma de feixe sem crescimento esferulítico posterior.<br>The study of dynamic crystallization kinetics of a thermotropic polyester with flexible spacers in the main chain was done. The aim of this study was to verify the crystallization kinetics mechanism of a thermotropic semi-flexible polyester by a dynamic method. The selected method (Ozawa method) has allowed to describe the crystallization kinetics and the values of n (Avrami exponent) correspond to sheaf-like aggregation without further growing into spherulites

Gelation Kinetics of Hydrogels Based on Acrylamide–AMPS–NVP Terpolymer, Bentonite, and Polyethylenimine for Conformance Control of Oil Reservoirs

Relatively smaller volumes of gelling systems had been used to address conformance problems located near the wellbore in oil reservoirs with harsh temperature and salinity conditions. These gelling systems were formulated with high concentrations of low-molecular-weight acrylamide-based polymers crosslinked with polyethylenimine (PEI). However, for in-depth conformance control, in which large gelant volumes and long gelation times were required, lower-base polymer loadings were necessary to ensure the economic feasibility of the treatment. In this study, a gelling system with high-molecular weight 2-acrylamido-2-methylpropane sulfonic acid (AMPS), N-vinyl-2-pyrrolidone (NVP), acrylamide terpolymer, and PEI, with the addition of bentonite as a filler, was formulated. The influence of the gelant formulation and reservoir conditions on the gelation kinetics and final gel strength of the system was investigated through bottle tests and rheological tests. The addition of clay in the formulation increased the gelation time, thermal stability, and syneresis resistance, and slightly improved the final gel strength. Furthermore, samples prepared with polymer and PEI concentrations below 1 wt %, natural bentonite, and PEI with molecular weight of 70,000 kg/kmol and pH of 11: (i) presented good injectivity and propagation parameters (pseudoplastic behavior and viscosity ~25 mPa&#183;s); (ii) showed suitable gelation times for near wellbore (~5 h) or far wellbore (~21 h) treatments; and (iii) formed strong composite hydrogels (equilibrium complex modulus ~10&#8315;20 Pa and Sydansk code G to H) with low syneresis and good long-term stability (~3 to 6 months) under harsh conditions. Therefore, the use of high-molecular-weight base polymer and low-cost clay as active filler seems promising to improve the cost-effectiveness of gelling systems for in-depth conformance treatments under harsh conditions of temperature and salinity/hardness

Principais rotas de síntese de resinas complexantes de mercúrio Chelating resins for recovery of mercury: the main routes of synthesis

A recuperação de espécies contendo mercúrio utilizando resinas complexantes obtidas a partir da modificação de suportes poliméricos vem atraindo cada vez mais a atenção dos pesquisadores. São muitas as combinações de suportes e grupos complexantes para a síntese desses materiais. Assim, este trabalho apresenta uma revisão sobre os principais grupos funcionais avaliados, bem como as rotas de síntese adotadas para a imobilização desses grupos nos suportes. É abordada também a problemática da síntese de uma resina eficiente, produzida a partir de um processo limpo e acessível às indústrias que utilizam mercúrio em seus processos.The recovery of mercury and its compounds by using chelating resins produced by modification of polymer supports has been studied by many researchers. There are many combinations of supports and functional groups for producing chelating resins that are appropriate for mercury complexation. This paper presents an overview of the main functional groups applied for mercury complexation and the routes used for immobilization of these groups in polymer supports. Also discussed are the problems involved in the synthesis of an efficient chelating resin, produced through a non-polluting route, which are appropriate for companies employing mercury in their processes