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Precise knowledge of vapor–liquid equilibrium (VLE) data of (CO2 + diluent) mixtures is crucial in the design and operation of carbon capture, transportation and storage processes. VLE measurements of the (CO2 + CO) system are reported along seven isotherms at temperatures ranging from just above the triple-point temperature of CO2 to 302.93 K and at pressures from the vapor pressure of pure CO2 to approximately 15 MPa, including near-critical mixture states for all isotherms. The measurements are associated with estimated standard uncertainties of 0.006 K for temperature, 0.009 MPa for pressure and 0.011x(1 − x) for mole fraction x. The new VLE data have been compared with two thermodynamic models: the Peng-Robinson equation of state (PR-EOS) and a multi-fluid Helmholtz-energy equation of state known as EOS-CG. The PR-EOS was used with a single temperature-dependent binary interaction parameter, which was fitted to the experimental data. In contrast, EOS-CG was used in a purely-predictive mode with no parameters fitted to the present results. While PR-EOS generally agrees fairly well with the experimental data, EOS-CG showed significantly better agreement, especially close to the critical point.

Experimental determination and theoretical predictions of the isothermal (344.15 K) mass densities and interfacial tensions for the sys tem carbon dioxide (CO2) with heptol (n - heptane + toluene) mixtures varying liquid volume fraction compositions of toluene (0, 25, 50, 75, 100 % v/v) and over the pressure range 0.1 to 8 MPa are reported. Measurements are carried out on a high - pressure dev ice that includes a vibrating tube densimeter and a pendant drop tensiometer. Theoretical modeling of mass densities phase equilibria and interfacial properties (i.e., interfacial tension and interfacial concentration profiles) are performed by employing t he Square Gradient Theory using an extension of the Statistical Associating Fluid Theory equation of state that accounts for ring fluids. The experimental bulk phase equilibrium densities and interfacial tensions obtained are in very good agreement with th e theoretical predictions. Although there are no previous experimental data of these mixtures at the conditions explored herein, the results follow the same trends observed from experimental data at other conditions. The combination of experimental and mod eling approaches provides a route to simultaneously predict phase equilibrium and interfacial properties within acceptable statistical deviations. For the systems and conditions studied here, we observe that the phase equilibrium of the mixtures display z eotropic vapor - liquid equilibria with positive deviations from ideal behavior. The mass bulk densities behave ordinarily whereas the interfacial tensions decrease as the pressure or liquid mole fraction of CO2 increases and/or the ratio toluene/heptane dec reases. The interfacial concentration along the interfacial region exhibits a remarkable high excess adsorption of CO2, which increases with pressure and it is larger in n - heptane than in toluene. Toluene does not exhibit any special adsorption activity wh ereas n - heptane displays surface activity only at low pressure in a very narrow range for the case of CO2 + (25% n - heptane + 75% toluene) mixture.

A mixed-integer non-linear programming optimisation framework is formulated and developed that combines a molecular-based, group-contribution equation of state, SAFT-γγ Mie, with a thermodynamic description of an organic Rankine cycle (ORC) power system. In this framework, a set of working fluids is described by its constituent functional groups (e.g., since we are focussing here on hydrocarbons: single bondCH3, single bondCH2single bond, etc. ), and integer optimisation variables are introduced in the description the working-fluid structure. Molecular feasibility constraints are then defined to ensure all feasible working-fluid candidates can be found. This optimisation framework facilitates combining the computer-aided molecular design of the working fluid with the power-system optimisation into a single framework, thus removing subjective and pre-emptive screening criteria, and simultaneously moving towards the next generation of tailored working fluids and optimised systems for waste-heat recovery applications. SAFT-γγ Mie has not been previously employed in such a framework. The optimisation framework, which is based here on hydrocarbon functional groups, is first validated against an alternative formulation that uses (pseudo-experimental) thermodynamic property predictions from REFPROP, and against an optimisation study taken from the literature. The framework is then applied to three industrial waste-heat recovery applications. It is found that simple molecules, such as propane and propene, are the optimal ORC working fluids for a low-grade (150 °C) heat source, whilst molecules with increasing molecular complexity are favoured at higher temperatures. Specifically, 2-alkenes emerge as the optimal working fluids for medium- and higher-grade heat-sources in the 250–350 °C temperature range. Ultimately, the results demonstrate the potential of this framework to drive the search for the next generation of ORC systems, and to provide meaningful insights into identifying the working fluids that represent the optimal choices for targeted applications. Finally, the effects of the working-fluid structure on the expander and pump are investigated, and the suitability of group-contribution methods for evaluating the transport properties of hydrocarbon working-fluids are considered, in the context of performing complete thermoeconomic evaluations of these systems.

Embedded Atom Method (EAM) potentials have been fitted for the atomistic simulation of small, ∼2–5 nm, binary, Pt Ni, nanoparticles completely from Density Functional Theory (DFT) total energy calculations. The overall quality of the DFT calculations and the final potential is obtained through the independent calculation of an array of properties of the pure metals and the stable alloys, which are normally used for the fitting of interatomic potentials. The ability of the fitted potentials to simulate nanostructures is evaluated by the reproduction of binary nanoslabs with thickness ∼1 nm, and nanoparticles in the extreme case of the smallest icosahedrons possible, with diameter ∼0.6 nm. The used approach requires high quality of convergence but otherwise low cost DFT as it is based on static total energy calculations. It also provides objective criteria for the evaluation of the fitted potentials during fitting and has been implemented with the open source code GULP.

With increasing penetration of intermittent renewable energy into the electricity grid, one can expect thermal power plants to be required to operate in a more dynamic fashion, with more frequent departures from design point operation. However, the application of optimal control strategies can offer solutions to these operational challenges, associated with the integration of the power plant with the capture plant. In this paper a process control strategy is developed in order to select the optimal control variables for a PCC process. In addition, economically efficient control structures for operation of a post-combustion capture process with minimum energy requirements for coal and natural gas power plant are designed. The results have shown that with an appropriate and well-tuned control strategy, it is possible to maintain critical parameters, such as the degree of CO 2 capture, at the desired set-point, even during periods of significant fluctuation in the power plant load and even if based on simple and well established control technologies, such as PID, avoids the need for more risky solutions such as adding solvent storage tanks to the process.

This paper provides an overview of the aims, objectives and the main findings of the CO(2)QUEST FP7 collaborative project, funded by the European Commission and designed to address the fundamentally important and urgent issues regarding the impact of the typical impurities in CO2 streams captured from fossil fuel power plants and other CO2 intensive industries on their safe and economic pipeline transportation and storage. The main features and results recorded from some of the unique test facilities constructed as part of the project are presented. These include an extensively instrumented realistic-scale test pipeline for conducting pipeline rupture and dispersion tests in China, an injection test facility in France to study the mobility of trace metallic elements contained in a CO2 stream following injection near a shallow-water qualifier and fluid/rock interactions and well integrity experiments conducted using a fully instrumented deep-well CO2/impurities injection test facility in Israel. The above, along with the various unique mathematical models developed, provide the fundamentally important tools needed to define impurity tolerance levels, mixing protocols and control measures for pipeline networks and storage infrastructure, thus contributing to the development of relevant standards for the safe design and economic operation of CCS.

An apparatus consisting of an equilibrium cell connected to two vibrating tube densimeters and two syringe pumps was used to measure the saturated phase densities of (CO2 + H2O) at temperatures from (293 to 450) K and pressures up to 64 MPa, with estimated average standard uncertainties of 1.5 kg · m−3 for the CO2-rich phase and 1.0 kg · m−3 for the aqueous phase. The densimeters were housed in the same thermostat as the equilibrium cell and were calibrated in situ using pure water, CO2 and helium. Following mixing, samples of each saturated phase were displaced sequentially at constant pressure from the equilibrium cell into the vibrating tube densimeters connected to the top (CO2-rich phase) and bottom (aqueous phase) of the cell. The aqueous phase densities are predicted to within 3 kg · m−3 using empirical models for the phase compositions and partial molar volumes of each component. However, a recently developed multi-parameter equation of state (EOS) for this binary mixture, Gernert and Span [32] , was found to under predict the measured aqueous phase density by up to 13 kg · m−3. The density of the CO2-rich phase was always within about 8 kg · m−3 of the density for pure CO2 at the same pressure and temperature; the differences were most positive near the critical density, and became negative at temperatures above about 373 K and pressures below about 10 MPa. For this phase, the multi-parameter EOS of Gernert and Span describes the measured densities to within 5 kg · m−3, whereas the computationally-efficient cubic EOS model of Spycher and Pruess (2010), commonly used in simulations of subsurface CO2 sequestration, deviates from the experimental data by a maximum of about 8 kg · m−3.

Interfacial tension measurements of the (CO2 + N2 + H2O) and (N2 + H2O) systems are reported at pressures of (2 to 40) MPa, and temperatures of (298.15 to 448.15) K. The pendant drop method was used in which it is necessary to know the density difference between the two phases. To permit calculation of this difference, the compositions of the coexisting phases were first computed from a combination of the Peng–Robinson equation of state (applied to the non-aqueous phase) and the NRTL model (applied to the aqueous phase). Densities of the non-aqueous phase were computed from the GERG-2008 equation of state, while those of the aqueous phase were calculated knowing the partial molar volumes of the solutes. The expanded uncertainties at 95% confidence are 0.05 K for temperature, 0.07 MPa for pressure, 0.019γ for interfacial tension in the binary (N2 + H2O) system; and 0.032γ for interfacial tension in the ternary (CO2 + N2 + H2O) system. The interfacial tensions in both systems were found to decrease with both increasing pressure and increasing temperature. An empirical correlation has been developed for the interfacial tension of the (N2 + H2O) system in the full range of conditions investigated, with an average absolute deviation of 0.20 mN · m−1, and this is used to facilitate a comparison with literature values. Estimates of the interfacial tension for the (CO2 + N2 + H2O) ternary system, by means of empirical combining rules based on the coexisting phase compositions and the interfacial tensions of the binary sub-systems, (N2 + H2O) and (CO2 + H2O), were found to be somewhat inadequate at low temperatures, with an average absolute deviation of 1.9 mN · m−1 for all the conditions investigated. To enable this analysis, selected literature data for the interfacial tensions of the (CO2 + H2O) binary system have been re-analysed, allowing for improved estimates of the density difference between the two phases. The revised result on eleven isotherms were fitted with empirical models that generally represent the data to within 1 mN · m−1.

The dynamics of heavy-ion collisions is studied in an energy domain in the vicinity of the Fermi energy, The early history of the collision is analyzed from the theoretical and experimental point of view in which the message conveyed by bremsstrahlung photons and neutral pions is exploited, The Boltzmann-Uehling-Uhlenbeck model and the Dubna Cascade Model, both based on similar principles but each adopting different computation technics, are briefly described and their respective predictions are discussed, In particular the emission pattern of bremsstrahlung photons is discussed. The photon production has been measured in the systems Kr-86+Ni-58 at 60A MeV, Ta-181+Au-197 at 40A MeV and Pb-208+Au-197 at 30A MeV and energy spectra, angular distributions and two-photon correlations have been analyzed. We find that bremsstrahlung photons are emitted from two distinct sources that can be correlated with nuclear-matter density oscillations. The properties of photon emission are discussed in terms of collective properties of nuclear matter. The high energy tail of the photon spectrum is interpreted by pi(0) and Delta decay but predominantly by radiative capture of pions, The pi(0) absorption in the nuclear medium is further analyzed by examining their emission pattern. (C) 1997 Elsevier Science B.V.