PARAMETRIC INFERENCE APPLIED TO ADSORPTION PROCESSES FELIPE ROCHA PINTO Ph.D. Researcher / E-mail: [email protected] In this research, we use the Bayesian inference to analyze data obtained through adsorption equilibrium experiments conducted with a Magnetic Suspension Balance (MSB). The Bayesian framework is a powerful approach for parameter and model evaluation, enabling the incorporation of prior information and continuous updating with new data to obtain more accurate estimates and well-quantified uncertainties. The MSB-derived adsorption data serve as crucial inputs for solving the system of differential-algebraic equations (DAE) of more complex processes, as for Temperature Swing Adsorption (TSA) units. For the calculations, we rely on the computational aptitude of high-level programming languages like Python and Julia. Contributions to process modelling and simulation. This comprehensive approach provides a robust foundation for enhancing efficiency and enabling an evaluation of how TSA processes respond to a range of parameters, offering invaluable insights for optimizing adsorption-based systems across diverse applications. 23
MODELING AND CONTROL OF CRYSTALLIZATION PROCESSES OF PHARMACEUTICAL COMPOUNDS FERNANDO ARRAIS ROMERO DIAS LIMA Ph.D. Researcher / E-mail: [email protected] Crystallization is a separation and purification process relevant to the pharmaceutical industry. In order to produce crystals with desired size, shape and purity, models are developed to describe this phenomenon and control approaches are proposed to have an efficient crystallization process. In this work, we are developing models to describe the crystallization process of praziquantel, which is a racemic compound used in the treatment of schistosomiasis. Praziquantel batch experiments are being developed to be used for the proposal of a population balance model (PBM) to describe the particle-size distribution (PSD) of this compound. Crystallization experimental setup from LABCADS/UFRJ. Then, the phenomenological model will be combined with neural networks for the elaboration of a hybrid model and their performances will be compared. Therefore, this work will provide praziquantel crystallization experimental data, and models and control approaches for this process that can present the potential for being used by industry. 24
SOLID-LIQUID PHASE EQUILIBRIA BY MOLECULAR SIMULATIONS GABRIELA BARRETO CORREA Ph.D. Researcher / E-mail: [email protected] The study of solid-liquid equilibrium is of great interest in crystallization and solvent selection for separation processes applied to several industries, such as petroleum and pharmaceutical. It can also aid in the discovery of new compounds, contributing to the field of material design. In these cases, computational techniques are desirable to perform preliminary analyses and even enable studies under extreme pressure and temperature conditions. PSCP alchemical cycle with five main intermediate states In this context, our work aims to apply molecular dynamics simulations to calculate free energy differences between solid and liquid phases to study their equilibrium conditions. We use the PseudoSupercritical Path (PSCP) method, in which we directly connect solid and liquid phases and scale their molecular interactions through non-physical (or alchemical) intermediate states. The work has focused on applying more accurate free energy calculation methods and modifying the current PSCP cycle to make it more compact while maintaining its efficiency. 25
ALGORITHMS FOR CHEMICAL AND PHASE EQUILIBRIUM WITH APPLICATION IN ELECTROLYTIC SYSTEMS AND SPECIATION GERSON FRANCISCO DA SILVA JUNIOR Ph.D. Researcher / E-mail: [email protected] In the oil industry scale deposition in the pipes, is a commonly encountered, generating production and financial losses. One of the main salts found in these depositions is CaCO3 due to the high concentration of gaseous CO2 under good conditions and the significant amounts of calcium ions in the formation water. There, CO2 dissociates into ionic species, and these bind to Ca+2 present. During the extraction process, a pressure drop occurs, causing a decrease in the solubility of CO2 . Calcite solubility versus Sodium Chloride concentration. Thus, the phase equilibrium of the system is shifted and the CaCO3 precipitation is favored. A reliable algorithm for predicting salt precipitation under different operating conditions is needed, and this work aims to develop an algorithm based on the Gibbs free energy minimization to obtain the chemical and phase equilibrium condition in electrolytic systems originating from CO2 speciation. 26
MOISTURE QUANTIFICATION IN CO2 -RICH MIXTURES AT LOW TEMPERATURE AND HIGH PRESSURE: EXPERIMENTAL STUDY AND THERMODYNAMIC MODELING LARISSA FERREIRA TORRES Ph.D. Researcher / E-mail: [email protected] The natural gas produced in Brazil has high CO2 content in some pre salt reservoirs. These special conditions can significantly affect the production at subsea conditions, characterized by ultraDeepwater (low temperatures and high pressures). Thus, the capability to accurately predict the water content associated to natural gas in these conditions is essential for flow assurance purposes and natural gas processing. In this context, accurate and reliable experimental data of water content in synthetic mixture are required. . This work aims to obtain water content data for of synthetic gas mixture (Methane, ethane propane, nbutane) with high CO2 contents at low temperature and high pressure. The Quartz Crystal Microbalance (QCM) and the Tunable Diode Laser Spectroscopy (TDLAS) techniques are used. The saturation process is carried out using an innovative apparatus for synthetic dry mixtures. The CPA and Polar PC-SAFT equations of state, with several association schemes, are then used to correlate the water content. 27
THERMODYNAMICS OF SALTS USING THE ELECTROLYTE-NRTL MODEL LEONARDO TOURASSE GALDINO Ph.D. Researcher / E-mail: [email protected] Systems containing electrolytes are present in many processes within several industry branches. The production and processing of lithium compounds, essential to the battery industry, or flow assurance topics such as hydrate and scale formation, vital to the oil and gas industry, are examples in which electrolytes play an essential role. The accurate thermodynamic modeling of electrolytic systems is important for predicting properties such as activity, solubility, and solid-liquid equilibria, among others. Phase diagram of the CaCl2 -Water system. The development of thermodynamic models for electrolytic systems is still an active field, including equations of state and the excess Gibbs energy models. The Electrolyte-NRTL model, an example of the latter, is versatile, describing systems containing multiple salts and molecules. The present work implemented this model with a term that accounts for association and used it to model systems containing various solvents and in solid-liquid equilibrium calculations. 28
PREDICTION OF THE FLASHPOINT OF FLAMMABLE MIXTURES LEONARDO TOURASSE GALDINO1 ; IURI SOTER VIANA2 SEGTOVICH 1Ph.D. and 2Postdoctoral Researcher / E-mail: [email protected] Chemical process safety is critical in the chemical industry. Fire occurrence is among the most common chemical plant accidents due to the widespread presence of flammable liquids and gases. The flashpoint is the temperature at which the flammable vapor can be ignited. To reduce the fire hazard, the flashpoint of the flammable compounds must be known. If the flammable compound is pure, the flashpoint can be easily measured or calculated. Flash-point of the ethanol MEG water mixture. However, it is most common to find flammable mixtures in the industry. In that case, due to the great number of possible mixtures, it is impossible to measure the flashpoint of every one of them. Moreover, non-linearity effects in the mixture, due to the molecular interactions, can yield flashpoints very different from the flashpoint of the pure compounds. The present work uses Le Chatelier’s rule, associated with fundamental thermodynamics, to calculate the flashpoint of mixtures based on the properties of the pure components. 29
THERMODYNAMIC MODELING OF DEEP EUTECTIC SOLVENTS USING THE SOFT-SAFT EQUATION LUAN VITTOR TAVARES DUARTE DE ALENCAR Ph.D. Researcher / E-mail: [email protected] In the search for environmentally greener solvents, Deep Eutectic Solvents (DES) proved attractive for applications in various chemical processes. These compounds consist of mixtures between hydrogen bond donors and acceptors where, due to the strength of these bonds, at a certain proportion, they have a melting point lower than that of their pure components and lower than that of an ideal liquid mixture. Experimental and soft-SAFT predicted densities of choline chloride: ethylene glycol DESs Their highly non-ideal behavior has encouraged the study of these systems from different modeling perspectives. In this regard, the use of advanced equations of state, such as the soft-SAFT approach, provides an attractive framework for reliable estimates of the physicochemical behavior of DES, as the hydrogen bonding and other association effects can be explicitly considered in the model. Thus, our main goal is the thermodynamic characterization of DESs based on choline chloride using soft-SAFT by developing accurate transferable and semi-predictive models. 30
CLASSICAL 3D DENSITY FUNCTIONAL THEORY APPLIED TO CARBON CAPTURE AND STORAGE LUCAS JOSÉ DOS SANTOS Ph.D. Researcher / E-mail: [email protected] Carbon capture, utilization, and storage (CCS) are widely regarded as the foremost strategic technologies for effectively and economically achieving sustainable carbon emission reduction goals. Efficient process design for CCS requires detailed knowledge of how CO2 interacts with an adsorbent material (for capture) or the interaction with a rock formation (storage). Classical density functional theory (cDFT) stands as a well-established and powerful tool, extensively employed for the examination of non-uniform systems, having the advantage over molecular simulations due to their computational efficiency. 10 20 x (˚A) 5 10 15 20 25 y (˚A) 0.0000 0.0002 0.0004 0.0006 0.0008 0.0010 0.0012 Density (˚A − 3) Density profile of CO2 inside the IRMOF-1 solid structure at 300 K and 1 bar obtained by 3D-cDFT. It has broad application in the exploration of interface properties, phase transitions along solid-fluid interfaces, as well as the behavior of fluids confined within porous materials. Our interest is in the development of 3D-cDFT for calculating density profiles and adsorption isotherms of CO2 and their mixtures inside MOFs, carbon materials, and rock formations. 31
THERMODYNAMIC MODELING OF PHASE AND IONIC EQUILIBRIA: CHEMICAL SPECIATION OF GAS-OIL-WATER MIXTURES WITH HIGH CO2 CONTENT AND SALT PRECIPITATION MARCELO DE ALENCASTRO PASQUALETTE Ph.D. Researcher / E-mail: [email protected] The research aims to explore new thermodynamic models to describe phase equilibria for systems containing high content of CO2 nd salts, with strong and weak electrolytes. Focus is given to the Gibbs energy minimization problem solution, using the electroneutrality axiom and the phase equilibria conditions as constraints.Different models for the activity coefficients (e.g., eUNIQUAC, eNTRL) and equations of states (eCPA and eSAFT-VR Mie) shall be used for the ions and the neutral species. Validation of the implemented models will be performed against experimental data from the literature and calculations made in available software. The methodology will be used to improve the accuracy of the prediction of the supersaturation index and the precipitated mass of minerals, which can lead to better estimates for inorganic scaling (of calcite, for example) in pipelines and equipment in the oil and gas industry. Contributions to electrolyte equations of state. 32
STUDY OF THE PHASE EQUILIBRIA BETWEEN PETROLEUM FRACTIONS AND CO2 AT HIGH PRESSURE: EXPERIMENTS AND MODELING MARÍA NATHALIA HERNÁNDEZ CUPAJA Ph.D. Researcher / E-mail: [email protected] Reservoir fluids are primarily a mixture of hydrocarbons, which can be classified as natural gas mixture, condensate gas mixture, volatile oils, and heavy oil. The heavy oil can be further classified into saturates, aromatics, resins, and asphaltenes (SARA). CO2 injection in advanced recovery processes is widely used, resulting in good interaction for extracting nonpolar and moderately polar compounds. Flow assurance issues are related to heavy fraction precipitation during injection. In a reservoir with high carbon dioxide content, a complex phase behavior can be observed, including liquid-liquid and solid-liquid-vapor transitions. PVT scheme for fluid-phase behavior investigation. In this work, we compare the SARA method fractioning with CO2 fractioning of crude oils. The phase behavior of the resulting fractions in the presence of CO2 at several concentration is investigated, using the synthetic method, in a high-pressure cell. The PCSAFT EOS and the CPA EOS with appropriate parameters are used to correlate experimental data. 33
DESCRIPTION OF MULTICOMPONENT NON-IDEAL MASS TRANSFER WITH THE LATTICE BOLTZMANN METHOD RAMON G. C. LOURENÇO Ph.D. Researcher / E-mail: [email protected] Understanding mass transfer phenomena is crucial, as it impacts the design and optimization of technologies and environmental sustainability. The lattice Boltzmann method, grounded in the Boltzmann equation, serves as a valuable bridge between micro- and macroscales. It provides a versatile computational framework for simulating mass transfer, accommodating intricate factors such as thermodynamic information and the interplay of advection between mass and momentum transfer. Among the available strategies, the split collision model is a multifluid approach that is particularly convenient. Advection-diffusion in a porous medium with solid dissolution, where C represents the concentration. In this model, the collision operator is separated into two contributions: collisions between particles of the same type and collisions between different particles. Such modeling considers the individual contributions of each species, such as their densities, velocities, and viscosities, to calculate the overall properties of the mixture, enabling a deeper understanding of the multicomponent processes. 34
INVESTIGATION OF BEHAVIOR OF ASPHALTENE MOLECULES IN CO2 INJECTION PROCESS REZA HASSANZADEH KHADAR Ph.D. Researcher / E-mail: [email protected] Production from oil reservoirs with a high percentage of asphaltene is associated with many problems, including the reduction of the reservoir uptake, serious problems in the wellbore and processing facilities and, therefore, a significant increase in the cost of extraction and exploitation. Gas injection is the most important method in the enhanced oil recovery (EOR) project that causes asphaltene precipitation during oil production and transmission. Simulation box corresponding to a solution of asphaltene in toluene in contact with reservoir rock and carbon dioxide. Therefore, the behavior of asphaltene molecules must be recognized in the CO2 injection. By using MD simulations for investigating the behavior of asphaltene molecules in the CO2 injection process is the aim of this study. The concentration distribution analysis, radial distribution function, and mean squared displacement have been used to investigate asphaltene molecules aggregation and asphaltene-solvent interaction in different temperature and pressure conditions. 35
WATER CONTENT DETERMINATION IN NATURAL GAS STREAMS THALES CAINÃ DOS SANTOS BARBALHO Ph.D. Researcher / E-mail: [email protected] Determination of water content in sweet and sour natural gas streams represents a significant challenge at low water concentration in the hydrocarbon phase, especially when streams contain acid gases such as CO2 and H2S. Experimental data with high carbon dioxide concentration and reliable equations of state to predict the mole fractions of saturated water under different temperature and pressure conditions are essential for the industry. The unified model and a spinodal decomposition benchmark. TB = Thermostat Bath, TI = Temperature Indicator, PI = Pressure Indicator, HPF = High Pressure Cell, VS = Vapour Phase Sample, SC = Saturation Cylinder, SP = Syringe Pump In this work, measurements and modeling of water content in natural gas streams are performed. The experimental methodology uses an equilibrium cell to promote contact between the water and the gas mixture, as shown in the figure. Thus, the water content in the gas is obtained by a quartz crystal microbalance and dew point in the differential scanning calorimetry. The calculations are performed using the PC-SAFT and the CPA EoS, with good agreement for water content calculation in gaseous mixtures when compared with the experimental data. 36
HIGH-PRESSURE MICRO DIFFERENTIAL SCANNING CALORIMETRY (µ DSC) APPLIED TO ASPHALTENE FRACTION STABILITY: EXPERIMENTS AND THERMODYNAMIC MODELING VANESSA ANDREA MASCIETTI Ph.D. Researcher / E-mail: [email protected] In this project asphaltene stability are investigated the High-Pressure Micro Differential Scanning Calorimetry (µDSC) technique. In a first step, liquid-liquid phase transition of known synthetic system are performed, using calorimetric behavior of mixtures with known composition. Since liquid to liquid-liquid are low energy transitions, we investigate the appropriate heat rate and then these conditions are used for investigating the mixture toluene/asphaltene in the presence of CO2 stability. a) Dsc measurements scheme b) Thermogram illustrating the liquid-liquid transition. In the second step, the Peng-Robinson (PR) and RedlichKwong-Peng-Robinson equations (RK-PR) are used to correlate the stability of asphaltene fractions in toluene and CO2 . Quadratic, Huron-Vidal and Segment-Density Dependent Local Composition mixing rules are used to perform the thermodynamic modeling of such asymmetric systems. 37
EVALUATION OF CALCIUM CARBONATE SCALING FORMATION VANESSA PIMENTEL LAGES Ph.D. Researcher / E-mail: [email protected] Calcium carbonate scale formation commonly occurs in hard water pipelines, resulting in severe flow assurance problems in the oil industry. The thermodynamic and kinetic behavior related to the formation and deposition of calcium carbonate nuclei is important to understand the scaling phenomenon. Zeta potential of calcium carbonate for different rest time and concentrations of Ca and Mg. The main objective of this work is the evaluation of the effect of ionic specificity on the electrophoretic mobility of calcium carbonate nanoparticles, the effect of some parameters on the kinetics of CO2 bubble formation and the surface zeta potential of different materials to measure the surface fouling potential and its effect on fouling. The results are intended to understand better the phenomena involved in the formation of calcium carbonate scale, making predictions about deposit properties that will be applied in hydrodynamic studies. 38
HIGH PRESSURE PHASE EQUILIBRIA IN CARBON DIOXIDE + WAXY SYSTEMS: EXPERIMENTAL AND THERMODYNAMIC STUDY WILFRED ANDRES GOMEZ Ph.D. Researcher / E-mail: [email protected] Worldwide, the oil and gas industry accounts for about 55% of total energy demand. The Brazilian pre-salt is one of the biggest reservoirs zones with technical challenges such as production in ultra-deepwater, high gas-oil, ratio and high CO2 content, which may reach 79% mol. In addition, there are those related to flow assurance whit the precipitation of different substances, such as hydrates, asphaltenes, and waxes. P-T diagram for the system CO2 + oil + wax (H01 Pre-salt). The Pre-salt crudes contain paraffins. This can be a concern for the wax deposits is one of the most worrisome problems that have serious consequences such as loss of production, the low deep-water temperature and the elevated WAT. Therefore, the study of oils with high CO2 content is very relevant. The objective is to determine the phase behavior in synthetic wax systems + CO2 at high pressures. The figure shows the phase behavior of the CO2 + oil + wax system, which may occur in typical Pre-Salt reservoirs conditions. 39
INTERACTION BETWEEN NANOPLASTICS AND ORGANIC CONTAMINANTS VIA MOLECULAR DYNAMICS SIMULATIONS YAMARA MATOS OLIVEIRA Ph.D. Researcher / E-mail: [email protected] The continuous increase in the production of synthetic plastics and the inadequate disposal of plastic waste have provided a considerable increase of these materials in aquatic environments, becoming a major environmental concern. The interest in understanding the mechanisms, at the molecular level, of the interaction of nanoplastics (NP) with other compounds using molecular simulation techniques is growing in the literature. NP can affect the secondary structure of proteins and change the lateral organization and diffusion of lipid membranes. Adsorption of bisphenol A on polyethylene in an aqueous medium. As a result, they can alter the lipid digestion in the gastrointestinal system representing a risk to the nutrient assimilation by humans, for example. Therefore, knowing the mechanism involved in these interactions is crucial to predict dangerous combinations and outline action strategies that reduce negative impacts on the ecosystem. Depending on the chemical properties of contaminants and NP, electrostatic and/or van der Waals interactions can be more important to explain the adsorption process. 40
EXPERIMENTAL AND THEORETICAL PROPERTIES OF SURFACTANTS ANDRESSA CHRISTINE DUTRA DA SILVA Master’s Degree Researcher / E-mail: [email protected] Surfactants hold a significant position in various industrial applications, spanning from pharmaceuticals to environmental management. Many physicochemical properties are not fully elucidated. A deeper understanding can help to control the quality of products and enhance industrial methodologies either to stabilize or break the emulsions. This research aims to probe the structure and composition of surfactants using experimental techniques (NMR, HPLC-MS and FTIR spectroscopy), relating these surfactant characteristics with solution properties such as Critical Micellar Concentration, Interfacial Tensions and Emulsion stability. Thermodynamic Modeling and Experimental Study of Surfactants, showing some Industrial Applications. It also examines bulk properties of emulsions, viscosity and particle size distribution. Moreover, there is a focus on thermodynamic modeling to forecast emulsion stability from surfactant properties. The goal is to deeply understand surfactant molecular structures and create models aiding in optimal formulation and production, benefiting industrial applications. 41
EXPLORING PRODUCTIVE CAPABILITIES WITH EQUATIONS OF STATE MODELING THROUGH GROUP CONTRIBUTION USING AUTOMATIC DERIVATIVES ANTONIO CAVALCANTE DE LIMA NETO Master’s Degree Researcher / E-mail: [email protected] Industrial process optimization is crucial for cost reduction, productivity enhancement, and environmental impact minimization. Accurate thermodynamic modeling is vital for achieving these goals. Equations of state (EoS) mathematically describe complex mixtures, allowing the calculation of essential thermodynamic properties. The SAFT EoS family, based on statistical mechanics, effectively represents various fluids, particularly complex ones. SAFT-γ-Mie, a group-contribution EoS, offers a unique advantage by parameterizing functional groups, enabling the prediction of properties for newly created molecules. However, implementing this EoS is challenging due to its complexity and numerous equations. Analytically calculating derivatives is even more demanding. Automatic differentiation (AD) offers an efficient and precise alternative to compute derivatives. This study uses the SAFT-γ-mie EoS, combined with AD, to predict the thermodynamic properties of complex mixtures. VLE of N-Heptane/Pentanoic Acid and N-Heptane/1-Propanol Binary Mixtures 42
ALGORITHM FOR SIMULATING THE CHEMICAL AND PHASE EQUILIBRIUM OF CO2 STORAGE IN SALINE AQUIFERS ARTHUR SCALCO CAMPAGNOLO Master’s Degree Researcher / E-mail: [email protected] As the earth’s temperature rises, there is a need to capture carbon in order to control the greenhouse effect, especially considering that humanity will continue to use fossil fuels for a long time to come. The storage of CO2 in saline aquifers is a promising technology for achieving this control. This occurs through the mineralization of CO2 dissolved in the aqueous solution and the solid formed depends on the rock present in the saline aquifer, which will make the cation available for the reaction to take place. Equilibrium concentration of carbon species in aqueous phase at pH 1-13 This process is dependent on the acidity of the aqueous phase, as it determines in which anion the carbon is present in the water, whether the cation will be available and whether CO2 mineralization will take place. The aim of this work is to develop an algorithm to obtain the equilibrium of multiphase systems with various chemical reactions and thus predict how CO2 storage will occur. 43
INVESTIGATION OF THE KINETIC EFFECTS OF THERMODYNAMIC INHIBITORS CLARISSA FERNANDA DA SILVA MACEDO COSTA Master’s Degree Researcher / E-mail: [email protected] Gas hydrates are crystalline structures formed when light gases are trapped by water molecules under high pressures and low temperatures. Their formation poses challenges in oil production, causing pipeline blockages and the need of shutdowns. The research centers on preventive strategies employing nucleation theory to predict the hydrate formation by considering factors such as time, subcooling, and inhibitor concentration. Effective prevention involves using thermodynamic (THI) and/or kinetic inhibitors (KHI). The study evaluates methanol and mono-ethylene glycol (THIs) in different concentrations to understand their influence on methane hydrate kinetics. Methane nucleation temporal profile with MeOH and MEG using HPS-ALTA. The next step involves coupling a phenological growth model with the nucleation theory to describe the complete kinetic behavior. We are also setting up an experimental HPSALTA apparatus to test ethanol inhibitor’s effects on hydrate formation kinetics advancing comprehension on preventive strategies. 44
STABILITY OF MICROEMULSIONS THROUGH MOLECULAR THERMODYNAMICS APPROACH DIULIE BORN Master’s Degree Researcher / E-mail: [email protected] Understanding the stability of emulsions is crucial at every stage of the petroleum industry. Surfactant molecules play a fundamental role in reducing interfacial tension and maintaining the stability of these emulsions. The complexity of these systems encourages modeling and simulation to predict the behavior of simple surfactants in solutions using molecular information. Molecular thermodynamic models allow equilibrium calculations based on the minimum of total Gibbs free energy, indicating the stability of microemulsions in different scenarios and providing crucial data such as the critical micelle concentration. We aim to increase the applicability of this model to describe complex situations such as those found in the industry. Thermodynamic pathway for the formation of normal micelles from non-ionic surfactants. This study evaluates the model’s predictive capacity for surfactants featuring more intricate structures, encompassing aromatic tails and/or branching by incorporating additional information obtained from experimental data and molecular dynamic simulation. 45
HYDROGEN CONFINEMENT IN NANOPORES VIA 3D CLASSICAL DENSITY FUNCTIONAL THEORY WITH QUANTUM EFFECTS IGOR PEREIRA DOS SANTOS PEREIRA Master’s Degree Researcher / E-mail: [email protected] Hydrogen storage in simple devices is one of the most challenging problems that the energy industry is currently facing. Hydrogen adsorption in porous media or ground reservoirs can be a possible solution. This work intends to study the behavior of hydrogen confined in nanopores at low temperatures. Hydrogen PVT behavior in bulk phase. The threedimensional classical Density Function Theory (cDFT) will be the technique used for that purpose. However, hydrogen molecules present a wellknown quantum effect that must be considered to describe hydrogen PVT behavior and adsorption adequately. In this project, we will implement the Feynman–Hibbs quantum corrections in the three-dimensional classical Density Function Theory. 46
NON-EQUILIBRIUM STATES OF TRAPPED COLLOIDAL PARTICLES: A STUDY USING DYNAMIC DENSITY FUNCTIONAL THEORY IGOR PEREIRA DOS SANTOS PEREIRA Master’s Degree Researcher / E-mail: [email protected] The study of colloidal particles has long captivated researchers in fields like statistical physics, soft matter, and complex systems. Exploring non-equilibrium states is particularly intriguing, mainly when colloidal particles are confined or trapped. Equilibrium statistical mechanics offers a solid foundation for understanding particle behavior, but phenomena outside of equilibrium require a more nuanced approach. Dynamics of the density distribution. Dynamic Density Functional Theory (DDFT) is a valuable framework for investigating these phenomena. DDFT extends classical density functional theory to encompass time dependence, allowing it to describe both equilibrium and non-equilibrium states of colloidal particles. Unlike traditional computational methods like Brownian dynamics or Dynamics Monte Carlo simulations, DDFT provides an analytically tractable means to explore the intricate microscopic dynamics of colloidal systems. 47
MEASUREMENT OF PERMEABILITY VIA THE LATTICE BOLTZMANN METHOD JOÃO RICARDO FRIGGO E BARROS Master’s Degree Researcher / E-mail: [email protected] This work uses the Lattice Boltzmann Method (LBM) to predict permeability in porous media such as reservoir rock structures. Permeability is an important property because it measures the resistance of the medium to fluid flow in homogenous systems. The study explores the impact of geometric parameters such as tortuosity and porosity on permeability. The in-house implementation is benchmarked with analytical solutions such as the plane Poiseuille flow. Then, on the prediction of permeability, the results demonstrated good agreement with Darcy’s Law for low Reynolds numbers. Permeability relates velocity to pressure gradient via Darcy’s law. The model is able to accurately simulate fluid flow through porous media. This methodology offers a fast and reproducible way to determine permeability in various porous geometries, enabling further investigations into complex flow regimes and interactions between fluids and rocks. 48
STUDY OF LIQUID-LIQUID EQUILIBRIA BY MICRO DIFFERENTIAL SCANNING CALORIMETRY (µDSC) LUIS CLAUDIO BRAGA DA SILVA Master’s Degree Researcher / E-mail: [email protected] Phase equilibrium data are typically acquired through visual methods, which prove impractical for complex, opaque mixtures, like crude oil. The inherent difficulty in detecting phase transitions within such systems underscores the need to develop alternative approaches. For this reason, this study focuses on a novel method for determining liquid-liquid equilibrium data: identifying the enthalpy change when a liquid mixture demixes into two distinct phases, by using µDSC. Notably, the enthalpy of the homogeneous system differs from that of the two-phase mixture, rendering the enthalpy jump upon demixing that should be detectable through calorimetric means. Example of a DSC scan identifying the transition from a homogeneous system to a heterogeneous system. Acquiring such data presents a big challenge, as the heat flow variation during this transition is subtle and characterized by minimal energy changes. Nevertheless, this technology will be very useful for acquiring phase equilibrium data because this is a practical, reliable method that consumes small sample quantities. 49
MULTIPHASE FLASH WITH HYDRATE FORMATION IN GAS-DOMINANT SYSTEMS MARVIN MARTINS DOS SANTOS Master’s Degree Researcher / E-mail: [email protected] The formation of hydrates under different thermodynamic conditions and fluid compositions needs to be known for process design involving wet gas (dominant gas) in which the mole fraction of gas is greater than that of water. These scenarios are found in offshore gas fields, which improve current thermodynamic models for adequate calculations. The use of equations of state together with the van der Waals and Platteeuw model plays a fundamental role in predicting phase equilibrium conditions including solid phases. Fluid Phase Equilibrium Diagram Including Hydrates Phase HsI. Here, the objective is to identify how the models can be improved by reducing the existing gap in the literature for reliability calculations and a better understanding of hydrate formation in undersaturated gas systems. Therefore, this work improves the calculations using multiphase flash algorithms and stability analysis for predicting hydrate formation in gas-dominant systems. 50
ARTIFICIAL NEURAL NETWORK FOR FLUID PHASE EQUILIBRIA: A DIGITAL PVT APPROACH RÔMULO COSTA DE HOLANDA Master’s Degree Researcher / E-mail: [email protected] Phase equilibria of complex mixtures containing carbon dioxide (CO2 ) plays a relevant role in industrial applications, such as supercritical fluid extractions and advanced oil recovery. The importance of CO2 - systems thermodynamics is reflected by the number of models applied to different phase equilibria conditions and mixtures. Such models vary from cubic equations of state to those based on statistical thermodynamics. The accuracy of such models tends to be lower mainly because of the CO2 quadrupole nature. Predictive tools must be flexible when modeling multiple mechanisms of action, dealing with high dimensional data sets with good accuracy. Artificial Neural Network (ANN) construction and prediction variable calculation. Artificial Neural Networks (ANN) appears as a tool capable of attending these requisites. The present work proposes the development of an ANN for the prediction of phase equilibria behavior in CO2 mixtures, by means of NearInfrared Transmittance (NIR), pressure, and temperature data retrieved from experimental essays carried out in a PVT cell. 51
POLARIZABLE WATER MODEL FOR MARTINI 3 FORCE FIELD FOR INTERFACIAL PROPRIETIES EVALUATION OF WATER/ORGANIC SYSTEMS BY COARSE-GRAINED MOLECULAR DYNAMICS SIMULATIONS THIAGO GUEDES GARROT Master’s Degree Researcher / E-mail: [email protected] Interfacial properties can be determined by Molecular Dynamics. The Martini force field is a leading approach for coarse-grained simulations. In this work, we intend to parametrize a polarizable water model for Martini 3. To compare different approaches, simulations of water/hydrocarbons and water/long-chain alcohols were conducted in all-atoms and coarse-grained models with and without the polarizable water model. Furthermore, we conduct studies with surfactant systems in this version of Martini. All-atom simulations presented good accuracy when the organic molecule was far from its melting point. Polarizable water model for Martini 3 Force Field. Martini 3 simulations showed that the force field with the standard water is worse than its previous version for systems with hydrocarbons and better with alcohols. The polarizable water improved the results with hydrocarbons but did not have the same performance with alcohols, showing that a better parametrization of LJ interaction should be done. 52
MODELING AND SIMULATION OF WATER VAPOR ADSORPTION AT HIGH PRESSURE. YURI DE PAIVA ALVES Master’s Degree Researcher / E-mail: [email protected] Simulation is crucial for researching Temperature Swing Adsorption (TSA) in natural gas dehydration. This method is vital for treating highpressure natural gas with high CO2, as it prevents corrosion and hydrate formation. Through TSA simulation, we understand water adsorption, enabling the selection of suitable adsorbents. The right adsorbent choice impacts TSA’s efficacy and cost-efficiency. Understanding adsorbent aging is essential for reducing operational costs and ensuring consistent performance. This research delves into TSA for dehydrating CO2-rich natural gas, studying different adsorbents and their aging effects. Zeolite aging effects. 53
CHARACTERIZATION OF ROCKS FOR CCS (CO2 CAPTURE AND STORAGE) VIA ADSORPTION AND MINERALIZATION MECHANISM DAVID DOS SANTOS PEREIRA Technical Researcher and Undergraduate Student / E-mail: [email protected] The process for CCS using rocks via adsorption and mineralization mechanisms has high potential for minimizing emissions. To study the viability of these mechanisms and build models, it is important to carry out characterization. Since, it depends on the geological region in which the rock was formed, its composition and CCS capacity can be changed. The research focuses on using techniques for: elementary composition via spectroscopy and thermal analysis (FRX, FTIR and TGA), composition of crystalline phases using x-ray diffraction (DRX) and RAMAN spectroscopy, surface area, volume and classification of pores using the principle of adsorption with the ASAP2020 equipment via , reaction behavior against mineralization via gravimetry, study of phase equilibrium at low and high pressure via high-precision gravimetry to obtain thermodynamic properties with equipment such as IGA-002 and MSB. Thus, carrying out precise mapping for building models and studying experimental cases. Generic composition of different rocks 54
AGING PHENOMENON DURING THE NATURAL GAS DEHYDRATION PROCESS - CHARACTERIZATION OF ADSORBENTS DAVID DOS SANTOS PEREIRA Technical Researcher and Undergraduate Student / E-mail: [email protected] Systems involving the purification of natural gas present consolidated methodologies in the oil and gas industry. However, due to the high concentration of CO2 in NG streams from the pre-salt, conventional dehydration methods need to be improved, considering phenomena that occur in parallel with purification and that accelerate the aging phenomenon of the adsorbents. Therefore, the characterization of adsorbents with an emphasis on the study of textural properties, chemical composition and thermodynamic properties are important tools for collecting experimental data and modeling systems with the purpose of diagnosing and minimizing accelerated aging, which can be provided by carbonation or coke formation. Analysis of CHA type zeolite via micro CT and MEVEDS The laboratory aims to structure a porous materials characterization center for mapping thermodynamic properties and organic and inorganic composition of adsorbents for various applications. 55
DEVELOPMENT AND VALIDATION OF ANALYTICAL METHODOLOGY FOR QUANTIFICATION OF PRAZIQUANTEL ENANTIOMERS USING HPLC HENRIQUE PUGA DE ABREU LEANDRO Undergraduate Student / E-mail: [email protected] Analytical methodology validation is increasingly required for regulatory agencies throughout the world. Comparability, traceability and confiability are desired features in a study that can be assured through the validation process. To validate a methodology, there are systemic guidelines developed from these regulatory agencies that must be strictly followed. This study aims to develop and validate a quantification method of the schistosomicidal drug, praziquantel (PZQ) and its enantiomers, by employing High-Performance Liquid Chromatography (HPLC) on the separation of L-PZQ and D-PZQ, where L-PZQ is the desired component. HPLC separation and quantification method for PZQ enantiomer We expect our results can lead to a method where it is possible to accurately quantify each enantiomer in the streams of production processes like Simulated Moving Bed. The results presented good linear tendency for both enantiomers (R² = 0,998) and they are valuable to quantitatively assess the performance of the production process of L-PZQ on industrial level. 56
EXPERIMENTAL STUDY OF HYDRATE DISSOCIATION WITH HIGH CONCENTRATION OF THERMODYNAMIC INHIBITORS ISABELLE RODRIGUES DE OLIVEIRA Undergraduate Student / E-mail: [email protected] In offshore oil and gas production conditions, hydrate occurrence can obstruct pipelines. One of the hydrate inhibition methods to avoid blockages is the addition of thermodynamic hydrate inhibitors (THI). So, a high amount of THI is required to ensure production is free of hydrate in deep or ultra-deep-water reserves. An experimental procedure using calorimetry is applied to obtain the hydrate equilibrium temperature in those conditions. Equilibrium data comparation between metastable and sI methane hydrate structures at 30 wt% MEG. We evaluate the hollow glass microspheres’ influence on the hydrate formation dynamics. Those microspheres improve the crystallization process, resulting in more significant observation of the heat during the dissociation and more adequate equilibrium temperature measurement by differentiating stable structures from metastable structures. This methodology allows more suitable equilibrium data at THI high concentration. The study evaluates that effect with 30 wt% of MEG and observed promising results on methane hydrate equilibrium data at 100 bar. 57
DETERMINATION OF THE LIQUID-LIQUID EQUILIBRIUM OF THE TERNARY SYSTEMS DODECANE + ETOH + MEG AND HEXADECANE + ETOH + MEG AT LOW PRESSURE KAUI RIBEIRO MADEIRA Undergraduate Student / E-mail: [email protected] In the oil industry, flow assurance is a crucial step in the upstream process, as crude oil transport, the pipelines can be obstructed due to the formation and precipitation of hydrates. Ethylene glycol (MEG) is used as a thermodynamics inhibitor in the oil extraction process, altering the pressure and/or temperature of hydrate formation. However, MEG must be separated from the oil phase before the downstream step to avoid MEG crusting and refinery equipment degradation. This is a picture of the equipment used to determine the vapor pressure of the compounds. Therefore, the use of ethanol to separate the MEG from the oil phase is considered an alternative due to its good solubility and affinity. This work aims to determine the liquid-liquid equilibrium conditions of ternary systems of MEG, ethanol, and dodecane/hexadecane at temperatures of 283.15, 288.15, and 293.15 K, under atmospheric pressure. 58
MEASURING CARBON DIOXIDE SOLUBILITY IN AQUEOUS SOLUTIONS MANUELLA PESTANA FELICE Undergraduate Student / E-mail: [email protected] Carbon dioxide (CO2 ) is one of the main greenhouse gases and its emission from burning fossil fuel acts directly intensifying the climate-change phenomena. The main alternative for this problem is the carbon capture and storage (CCS) process, which is based on the storage of the gas in appropriate locations, such as geological formations and aquifers. For carbon capture processes, we need data on CO2 solubility in aqueous solutions. Illustrative scheme of the current solubility measurement equipment. In this work, we built a solubility measurement apparatus that operates in pressures from 5 to 70 bar, suitable to measure the solubility of CO2 in aqueous solutions. During the project, the equipment has suffered some modifications in order to improve solubility results having more accuracy when compared to literature. Our recent experiments show solubility results of 0,0048 mol/mol of CO2 at 8 bar and 0,006117 mol/mol of CO2 at 12 bar.For future resolutions, once the equipment is validated, we aim to work with more complex systems, like saline solutions. 59
SEMIPREPARATIVE ENANTIOSEPARATION AND RECOVERY OF 1,2,3-TRIAZOLE DERIVATIVES BY CHIRAL LIQUID CHROMATOGRAPHY MATEUS BARBOSA RODRIGUES Undergraduate Student / E-mail: [email protected] Separating and purifying racemate enantiomers is crucial in drug manufacturing. This ensures the active, safe enantiomer is used, optimizing drug efficacy. 1,2,3-Triazole Derivatives (TZd) are potent against cancer cells, and their structural flexibility makes them versatile for drug development. They exhibit antibacterial and antiinflammatory properties and even potential antiprotozoal activity. Current evidence suggests one enantiomer’s efficacy against Cystic Fibrosis. TZd synthesis, enantioseparation by chiral chromatography, recovery and crystallization TZd racemate was synthesized by the telescopic reaction between acetophenones and aryl azides with further carbonyl reduction by LabSint group (PUC-Rio, Brazil) and furnished to ATOMS labs for enantioseparation and recovery of enantiomers. Semipreparative separation was done by sequential injection of 50 µL of TZd in hexane:2-propanol (90:10). Further studies will evaluate the effects of injection volume, and extraction of adsorption and thermodynamics data for process optimization. 60
TRANSPORT PROPERTIES OF METHANE AND CO2 IN HYDROCARBON COMPOUNDS AT HIGH PRESSURES: A COMPARISON OF FORCE FIELDS USING MOLECULAR DYNAMICS SIMULATIONS. SARAH WICTORIA EVANGELISTA CRUZ DA SILVA Undergraduate Student / E-mail: [email protected] The transport properties play a crucial role in chemical engineering, particularly in the oil and gas industry. Accurate values of mass diffusivity, Soret coefficient, thermal diffusivity, and viscosity enable efficient modeling of injection processes for enhanced oil recovery, CO2 capture and storage, and the behavior of reservoir fluids. Mass diffusivities of CO2 in n-heptane in three temperatures at pressures up to 700 bar. In this work, we apply molecular dynamics simulations to calculate the transport properties of CO2 - hydrocarbon systems under typical reservoir conditions, which means very high pressures. We focus on mass diffusivity and viscosity calculations in binary mixtures containing CO2 , methane, n-heptane, and toluene. The performance of different force fields are evaluated, including GROMOS, TraPPE, GAFF, and OPLS-AA. Initial results demonstrate good agreement with experimental data across a wide range of analyzed conditions. 61