Luciana S. Spinelli

Polymer science applied to petroleum production

The science of polymers, more specifically, synthesis, characterization, and physicochemical properties in solutions, has wide application in the petroleum industry, which uses polymers as components of fluids or additives to correct problems that affect oil production and/or increase production costs. Polymers are utilized during all phases, from drilling to treatment of oil and water. Research on the synthesis of polymers and their respective characterization aims to develop new molecules, with controlled structures, for various applications, having one or more objectives, namely: (1) to enhance operating efficiency; (2) to reduce costs; and (3) to elucidate mechanisms of action that can help in the development of new technologies. The evaluation of the physicochemical properties of a polymer in solution in many cases permits establishing useful correlations between its properties and performance in a specific application, besides providing insight into the mechanisms inherent in the production system, as is the case of stabilization of asphaltenes. Our research group has applied the knowledge of polymer science to the petroleum industry, focusing on the following functions: viscosification, inhibition of clay swelling, formation of filter cake, drag reduction, divergence, modification of wax crystals, stabilization of asphaltenes, emulsification, demulsification, and cleaning of solids systems contaminated with petroleum, among others.

THE INFLUENCE OF A HYDROTROPIC AGENT IN THE PROPERTIES OF AQUEOUS SOLUTIONS CONTAINING POLY(ETHYLENE OXIDE)-POLY( PROPYLENE OXIDE) SURFACTANTS

Abstract The aqueous solution behavior of diblock poly(ethylene oxide)–poly(propylene oxide) (PEO–PPO) copolymers coupled with hydrocarbon groups was studied in the presence of the hydrotropic agent sodium p-toluenesulfonate (NaPTS). The change in phase of the aqueous systems was evaluated by building up temperature–concentration phase diagrams. The critical micelle concentrations (CMC) of the copolymers and the aggregation points of NaPTS and NaPTS/copolymer mixtures were obtained by surface tension measurements, viscometry data and dye solubilization. The copolymers and NaPTS adsorb and reduce the surface tension of the solution until the surface becomes saturated: the CMC values are related to the solubility of the copolymers. Solutions containing NaPTS/copolymer mixtures exhibit the opposite behavior: at constant copolymer concentrations and with increasing NaPTS concentration, the surface tension remains constant until the aggregates of NaPTS start to form. Above this concentration, the surface tension increases. The surface tension and the aggregation points of the NaPTS solutions are dependent on the structure of the copolymer. The influence of the length of the hydrocarbon groups and the PPO position segment in the structure of the copolymers were also studied. From viscometric data, a pronounced increase in solution viscosity was observed as aggregates began to form. The results obtained from dye solubilization are in good agreement with the surface tension and viscometric measurements.

Determining hildebrand solubility parameter by ultraviolet spectroscopy and microcalorimetry

The solubility parameter (δ) of a molecule is extremely important, since that new molecules are frequently developed to be applied in liquid systems. In this work, we looked for simple and reliable alternative techniques to determine δ of low and high molecular weight molecules. Pyrene, phenanthrene and naphthalene had their δ determined by microcalorimetry (µDSC), ultraviolet (UV) and calorimetry (DSC). UV results were similar to those obtained by DSC and to those cited in the literature. Polystyrene and sulfonated polystyrene samples had their δ determined by UV, µDSC and intrinsic viscosity ([η]). The [η] results were similar to those obtained by UV. UV procedure was relatively simple, easy operation and reliable for determining δ of molecules in a wide range of molar mass, can be used when developing new molecules. The µDSC procedure still requires some adjustments to become more accurate than [η] procedure.

Behavior of aqueous solutions of poly(ethylene oxide‐b‐propylene oxide) copolymers containing a hydrotropic agent

The effect of the hydrotropic agent, sodium p-toluenesulfonate (NaPTS), was evaluated on the micelle formation process and on phase behavior of aqueous solutions containing poly(ethylene oxide-b-propylene oxide) (PEO–PPO) copolymers. We have studied monofunctional diblock copolymers coupled with hydrocarbons groups (R—PEO—PPO—OH and R—PPO—PEO—OH, where R length is linear C4 and C12–14). The critical micelle concentration (CMC) and critical micelle temperature (CMT) values of the aqueous copolymers solutions were obtained from both surface tension versus concentration plots and the dye solubilization method. The influence of the hydrocarbons groups length and PPO segment position in the structure of the copolymers were also analyzed. The same measures were obtained for the aqueous solutions of hydrotropic agent which, in turn, also presented molecular aggregation. The presence of the hydrotropic agent in the aqueous copolymers solutions altered the surface tension of these solutions and the occupied molecular area per copolymer molecule at air–water interface and CMC and CMT values of the copolymers. On the other hand, the aggregation points and the surface tension of the NaPTS solutions were dependent on the copolymer structure and composition.

Application of Oil/Water Nanoemulsions as a New Alternative to Demulsify Crude Oil

Oil-in-water nanoemulsions were developed and evaluated for effectiveness in breaking down crude oil emulsions. The nanoemulsions were prepared using two types of ethoxylated nonionic surfactants: nonylphenol and lauryl ether, at a concentration of 12 wt%, and the solvent xylene as the oil phase, at different concentrations (5, 7, and 10 wt%). The results of the demulsification tests showed that the nanoemulsions developed are a viable alternative to break down petroleum emulsions, with efficiency ranging from 90 to 95%. Also, the greater the xylene concentration in the nanoemulsion, the faster the demulsification process was.

Nanoemulsões óleo de laranja/água preparadas em homogeneizador de alta pressão

The objective of this work was to use the high-pressure homogenizer (HPH) to prepare stable oil/water nanoemulsions presenting narrow particle size distribution. The dispersions were prepared using nonionic surfactants based on ethoxylated ether. The size and distribution of the droplets formed, along with their stability, were determined in a Zetasizer Nano ZS particle size analyzer. The stability and the droplet size distribution in these systems do not present the significant differences with the increase of the processing pressure in the HPH). The processing time can promote the biggest dispersion in the size of particles, thus reducing its stability.

COMPARISON BETWEEN ASPHALTENES (SUB)FRACTIONS EXTRACTED FROM TWO DIFFERENT ASPHALTIC RESIDUES: CHEMICAL CHARACTERIZATION AND PHASE BEHAVIOR

Asphaltenes are blamed for various problems in the petroleum industry, especially formation of solid deposits and stabilization of water-in-oil emulsions. Many studies have been conducted to characterize chemical structures of asphaltenes and assess their phase behavior in crude oil or in model-systems of asphaltenes extracted from oil or asphaltic residues from refineries. However, due to the diversity and complexity of these structures, there is still much to be investigated. In this study, asphaltene (sub)fractions were extracted from an asphaltic residue (AR02), characterized by NMR, elemental analysis, X-ray fluorescence and MS-TOF, and compared to asphaltene subfractions obtained from another asphaltic residue (AR01) described in a previous article. The (sub)fractions obtained from the two residues were used to prepare model-systems containing 1 wt% of asphaltenes in toluene and their phase behavior was evaluated by measuring asphaltene precipitation onset using optical microscopy. The results obtained indicated minor differences between the asphaltene fractions obtained from the asphaltic residues of distinct origins, with respect to aromaticity, elemental composition (CHN), presence and content of heteroelements and average molar mass. Regarding stability, minor differences in molecule polarity appear to promote major differences in the phase behavior of each of the asphaltene fractions isolated.

Cardanol Polymerization Under Acid Conditions By Addition And Condensation Reactions

Cashew nut shell liquid (CNSL) is a byproduct of the cashew nut industry and consists predominantly of phenolic compounds that have an side chain with different degrees of unsaturation. Cardanol, one of these components, is biodegradable and widely available. Studies have revealed several polymerization reactions involving cardanol. However, the mechanisms and detailed structures of polymerization reactions have not been explored, although the final product shows different applications. In this work, we evaluated the mechanism and the products structure of the reaction of cardanol with: (i) boron trifluoride diethyl etherate (BF3O(CH2CH3)2), and (ii) formaldehyde. The characterizations were performed by FTIR, 1H NMR, SEC and TGA. The results show that the reaction of cardanol with aldehyde produces the expected like-comb structure with a long hydrocarbon pendent chain. Nevertheless, the reaction of cardanol with BF3O(CH2CH3)2 can exhibits a more complex structure since it was identified aromatic ring linkages, besides the expected polymerization through C=C.

Development and Evaluation of Solbrax-Water Nanoemulsions for Removal of Oil from Sand

In recent years, surfactants have been used to clean up soils and aquifers contaminated by petroleum and petroleum derivatives. The purpose of this study was to develop and evaluate nanoemulsions for remediation of soil contaminated by petroleum, by using a commercial solvent Solbrax. The nanoemulsions were prepared by the phase inversion temperature (PIT) method, using oil phase Solbrax (a solvent extracted from naphtha with low aromatics content) and a nonionic ethoxylated lauryl ether surfactant. The surfactant concentrations were varied from 10 to 12 wt% and the oil phase was varied from 5 to 20 wt%. A 23 factorial experimental design with center point run was used to evaluate the soil washing process, varying time, temperature, and shear rate of the system. The results show that the most efficient system (with 90% efficiency) was that using the nanoemulsion containing 5 wt% of Solbrax and 12 wt% of surfactant after four hours of washing, on 240 rotation·min−1 of shear rate and at a temperature of 318 K.

Residue Development Caused by the Simultaneous Use of Chemical Additives in the Oil Industry

Abstract In a complex operation such as the oil and gas production in oil fields, the use of chemical additives to combat operation drawbacks is often necessary as well as relevant. These chemical products are mainly made up of polymeric materials. The combination of two or more chemical additives present in the same fluid can lead to synergistic effects. In this work, the behavior of three types of commercial polymeric additives was evaluated: demulsifiers, flocculants, and scale inhibitors, used together. Gravimetric, photometric, and surface tension tests were used in order to study the problems of residue development in brine and oily water. Gravimetric data showed that residue development actually occurs, which was confirmed through photometric tests. Surface tension tests evidenced a negative synergistic effect in the physical chemical behavior of the additives used together. Therefore, the combination of different additives employed in oil production may cause a system incompatibility, yielding an undesirable residue, which is being dependent on the brine composition.