21 research outputs found

    Experimental and modeling study of the phase behavior of synthetic crude oil + CO2

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    A full understanding of the phase behavior of CO2–hydrocarbon mixtures at reservoir conditions is essential for the proper design, construction and operation of carbon capture and storage (CCS) and enhanced oil recovery (EOR) processes. While equilibrium data for binary CO2–hydrocarbon mixtures are plentiful, equilibrium data and validated equations of state having reasonable predictive capability for multi-component CO2–hydrocarbon mixtures are limited. In this work, a new synthetic apparatus was constructed to measure the phase behavior of systems containing CO2 and multicomponent hydrocarbons at reservoir temperatures and pressures. The apparatus consisted of a thermostated variable-volume view cell driven by a computer-controlled servo motor system, and equipped with a sapphire window for visual observation. Two calibrated syringe pumps were used for quantitative fluid injection. The maximum operating pressure and temperature were 40 MPa and 473.15 K, respectively. The apparatus was validated by means of isothermal vapor–liquid equilibrium measurement on (CO2 + heptane), the results of which were found to be in good agreement with literature data. In this work, we report experimental measurements of the phase behavior and density of (CO2 + synthetic crude oil) mixtures. The ‘dead’ oil contained a total of 17 components including alkanes, branched-alkanes, cyclo-alkanes, and aromatics. Solution gas (0.81 methane + 0.13 ethane + 0.06 propane) was added to obtain live synthetic crudes with gas-oil ratios of either 58 or 160. Phase equilibrium and density measurements are reported for the ‘dead’ oil and the two ‘live’ oils under the addition of CO2. The measurements were carried out at temperatures of 298.15, 323.15, 373.15 and 423.15 K and at pressures up to 36 MPa, and included vapor–liquid, liquid–liquid and vapor–liquid–liquid equilibrium conditions. The results are qualitatively similar to published data for mixtures of CO2 with both real crude oils or and simple hydrocarbon mixtures containing both light and heavy components. The present experimental data have been compared with results calculated with two predictive models, PPR78 and PR2SRK, based on the Peng–Robinson 78 (PR78) and Soave–Redlich–Kwong (SRK) equations of state with group-contribution formulae for the binary interaction parameters. Careful attention was paid to the critical constants and acentric factor of high molar-mass components. Since the mixture also contained several light substances with critical temperatures below some or all experimental temperatures, we investigated the use of the Boston–Mathias modification of the PR78 and SRK equations. The results showed that these models can predict with reasonable accuracy the vapor–liquid equilibria of systems containing CO2 and complex hydrocarbon mixtures without the need to regress multiple binary parameters against experimental data

    Gas Hydrate Research Database and Web Dissemination Channel

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    To facilitate advances in application of technologies pertaining to gas hydrates, a United States database containing experimentally-derived information about those materials was developed. The Clathrate Hydrate Physical Property Database (NIST Standard Reference Database {number_sign} 156) was developed by the TRC Group at NIST in Boulder, Colorado paralleling a highly-successful database of thermodynamic properties of molecular pure compounds and their mixtures and in association with an international effort on the part of CODATA to aid in international data sharing. Development and population of this database relied on the development of three components of information-processing infrastructure: (1) guided data capture (GDC) software designed to convert data and metadata into a well-organized, electronic format, (2) a relational data storage facility to accommodate all types of numerical and metadata within the scope of the project, and (3) a gas hydrate markup language (GHML) developed to standardize data communications between 'data producers' and 'data users'. Having developed the appropriate data storage and communication technologies, a web-based interface for both the new Clathrate Hydrate Physical Property Database, as well as Scientific Results from the Mallik 2002 Gas Hydrate Production Research Well Program was developed and deployed at http://gashydrates.nist.gov

    A pairwise surface contact equation of state : COSMO-SAC-Phi

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    In this work a new method for inclusion of pressure effects in COSMO-type activity coefficient models is proposed. The extension consists in the direct combination of COSMO-SAC and lattice-fluid ideas by the inclusion of free volume in form of holes. The effort when computing pressure (given temperature, volume, and mole numbers) with the proposed model is similar to the cost for computing activity coefficients with any COSMO-type implementation. For given pressure, computational cost increases since an iterative method is needed. This concept was tested for representative substances and mixtures, ranging from light gases to molecules with up to 10 carbons. The proposed model was able to correlate experimental data of saturation pressure and saturated liquid volume of pure substances with deviations of 1.16% and 1.59%, respectively. In mixture vapor-liquid equilibria predictions, the resulting model was superior to Soave-Redlich-Kwong with Mathias-Copeman a-function and the classic van der Waals mixing rule in almost all cases tested and similar to PSRK method, from low pressures to over 100 bar. Good predictions of liquid-liquid equilibrium were also observed, performing similarly to UNIFAC-LLE, with improved responses at high temperatures and pressures

    Hydrate mitigation in sour and acid gases

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    While global demand for energy is increasing, it is mostly covered by fossil energies, like oil and natural gas. Principally composed of hydrocarbons (methane, ethane, propane...), reservoir fluids contain also impurities such as carbon dioxide, hydrogen sulphide and nitrogen. To meet the request of energy demand, oil and gas companies are interested in new gas fields, like reservoirs containing high concentrations of acid gases. Natural gas transport is done under high pressure and these fluids are also saturated with water. These conditions are favourable to hydrates formation, leading to pipelines blockage. To avoid these operational problems, thermodynamic inhibitors, like methanol or ethanol, are injected in lines. It is necessary to predict with more accuracy hydrates boundaries in different systems to avoid their formation in pipelines for example, as well as vapour liquid equilibria (VLE) in both sub-critical regions. Phase equilibria predictions are usually based on cubic equations of state and applied to mixtures, mixing rules involving the binary interaction parameter are required. A predictive model based on the group contribution method, called PPR78, combined with the Cubic – Plus – Association (CPA) equation of state has been developed in order to predict phase equilibria of mixtures containing associating compounds, such as water and alcohols. To complete database for multicomponent systems with acid gases, VLE and hydrate dissociation point measurements have been conducted. The developed model, called GC-PR-CPA, has been validated for binary systems and applied for different multicomponent mixtures. Its ability to predict hydrate stability zone and mixing enthalpies has also been tested. It has been found that the model is generally in good agreement with experimental data

    Modelling of phase equilibria and related properties of mixtures involving lipids

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    Functional-segment activity coefficient equation of state : F-SAC-Phi

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    COSMO-RS refinements and applications have been the focus of numerous works, mainly due to their great predictive capacity. However, these models do not directly include pressure effects. In this work, a methodology for the inclusion of pressure effects in the functional-segment activity coefficient model, F-SAC (a COSMO-based group-contribution method), is proposed. This is accomplished by the combination of F-SAC and lattice-fluid ideas by the inclusion of free volume in the form of holes, generating the F-SAC-Phi model. The computational cost when computing the pressure (given temperature, volume, and molar volume) with the proposed model is similar to the cost for computing activity coefficients with any COSMO-type implementation. For a given pressure, the computational cost increases since an iterative method is needed. The concept is tested for representative substances and mixtures, ranging from light gases to molecules with up to 10 carbons. The proposed model is able to correlate experimental data of saturation pressure and saturated liquid volume of pure substances with deviations of 1.7 and 1.1%, respectively. In the prediction of mixture vapor−liquid equilibria, the resulting model is superior to COSMO-SAC-Phi, SRK-MC (Soave−Redlich−Kwong with the Mathias−Copeman α-function) with the classic van der Waals mixing rule, and PSRK in almost all tested cases, from low pressures to over 100 bar

    Systematic computer aided methods and tools for lipid process technology

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    CAPEC-PROCESS Research Report 2013

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