## Publications

72 results found

Ravipati S, Galindo A, Jackson G,
et al., 2019, An investigation of free-energy-averaged (coarse-grained) potentials for fluid adsorption on heterogeneous solid surfaces, *PHYSICAL CHEMISTRY CHEMICAL PHYSICS*, Vol: 21, Pages: 25558-25568, ISSN: 1463-9076

Ibrahim D, Oyewunmi O, Haslam A, et al., 2019, Computer-aided working fluid design and optimisation of organic Rankine cycle (ORC) systems under varying heat-source conditions, 32ND INTERNATIONAL CONFERENCE ON EFFICIENCY, COST, OPTIMIZATION, SIMULATION AND ENVIRONMENTAL IMPACT OF ENERGY SYSTEMS

Ibrahim D, Oyewunmi O, Haslam A, et al., 2019, COMPUTER-AIDED WORKING FLUID DESIGN AND POWER SYSTEM OPTIMIZATION USING THE SAFT-γ MIE EQUATION OF STATE, 4th Thermal and Fluids Engineering Conference (TFEC)

White M, Oyewunmi OA, Chatzopoulou M,
et al., 2018, Computer-aided working-fluid design, thermodynamic optimisation and technoeconomic assessment of ORC systems for waste-heat recovery, *Energy*, Vol: 161, Pages: 1181-1198, ISSN: 0360-5442

The wider adoption of organic Rankine cycle (ORC) technology for power generation or cogeneration from renewable or recovered waste-heat in many applications can be facilitated by improved thermodynamic performance, but also reduced investment costs. In this context, it is suggested that the further development of ORC power systems should be guided by combined thermoeconomic assessments that can capture directly the trade-offs between performace and cost with the aim of proposing solutions with high resource-use efficiency and, importantly, improved economic viability. This paper couples, for the first time, the computer-aided molecular design (CAMD) of the ORC working-fluid based on the statistical associating fluid theory (SAFT)-γ Mie equation of state with thermodynamic modelling and optimisation, in addition to heat-exchanger sizing models, component cost correlations and thermoeconomic assessments. The resulting CAMD-ORC framework presents a novel and powerful approach with extended capabilities that allows the thermodynamic optimisation of the ORC system and working fluid to be performed in a single step, thus removing subjective and pre-emptive screening criteria that exist in conventional approaches, while also extending to include cost considerations relating to the resulting optimal systems. Following validation, the proposed framework is used to identify optimal cycles and working fluids over a wide range of conditions characterised by three different heat-source cases with temperatures of 150 °C, 250 °C and 350 °C, corresponding to small- to medium-scale applications. In each case, the optimal combination of ORC system design and working fluid is identified, and the corresponding capital costs are evaluated. It is found that fluids with low specific-investment costs (SIC) are different to those that maximise the power output. The fluids with the lowest SIC are isoheptane, 2-pentene and 2-heptene, with SICs of £5620, £2760 an

van Kleef LMT, Oyewunmi OA, Harraz AA, et al., 2018, Case studies in computer-aided molecular design (CAMD) of low- and medium-grade waste-heat recovery ORC systems, ECOS 2018 - 31st International Conference on Efficiency, Cost, Optimization, Simulation and Environmental Impact of Energy Systems, Publisher: ECOS

Organic Rankine cycle (ORC) engines are suitable for theconversion oflow-grade heat into useful power. While numerous substances are available asORC working-fluid candidates, computer-aided molecular design (CAMD) techniques allow the rigorous selection of an optimal working fluid during system optimisation. The aim of this present study is to extend an existing CAMD-ORC framework [1,2] by incorporating, in addition to thermodynamic performance objectives, economic objectives when determining the optimal systemdesign, while maintaining the facility of selecting optimal working fluids. The SAFT-γ Mie equation of state is used to predictthethermodynamic properties of theworking fluids(here, hydrocarbons)that are relevant to the systems’economic appraisalsand critical/transport properties are estimated using empirical group-contribution methods. System investment costs are estimated with equipment cost correlations for the key system components, andthe stochastic NSGA-II solver is used for system optimisation. From a set of NLP optimisations, it is concluded that the optimal molecular size of the working fluid is linked to the heat-source temperature. The optimal specific investment cost (SIC) values were £10,120/kW and£4,040/kW when using heat-source inlet temperatures of 150°Cand250°C (representative of low-and medium-gradeheat) respectively, andthe corresponding optimal working fluids were propane, 2-butane and 2-heptene.

Pantaleo AM, markides, Oyewunmi, et al., 2017, Integrated computer-aided working-fluid design and thermoeconomic ORC system optimisation, ORC-2017, Publisher: Elsevier, Pages: 152-159, ISSN: 1876-6102

The successful commercialisation of organic Rankine cycle (ORC) systems across a range of power outputs and heat-source temperatures demands step-changes in both improved thermodynamic performance and reduced investment costs. The former can be achieved through high-performance components and optimised system architectures operating with novel working-fluids, whilst the latter requires careful component-technology selection, economies of scale, learning curves and a proper selection of materials and cycle configurations. In this context, thermoeconomic optimisation of the whole power-system should be completed aimed at maximising profitability. This paper couples the computer-aided molecular design (CAMD) of the working-fluid with ORC thermodynamic models, including recuperated and other alternative (e.g., partial evaporation or trilateral) cycles, and a thermoeconomic system assessment. The developed CAMD-ORC framework integrates an advanced molecular-based group-contribution equation of state, SAFT-γ Mie, with a thermodynamic description of the system, and is capable of simultaneously optimising the working-fluid structure, and the thermodynamic system. The advantage of the proposed CAMD-ORC methodology is that it removes subjective and pre-emptive screening criteria that would otherwise exist in conventional working-fluid selection studies. The framework is used to optimise hydrocarbon working-fluids for three different heat sources (150, 250 and 350 °C, each with mcp = 4.2 kW/K). In each case, the optimal combination of working-fluid and ORC system architecture is identified, and system investment costs are evaluated through component sizing models. It is observed that optimal working fluids that minimise the specific investment cost (SIC) are not the same as those that maximise power output. For the three heat sources the optimal working-fluids that minimise the SIC are isobutane, 2-pentene and 2-heptene, with SICs of 4.03, 2.22 and 1.84 £/W res

brumby PE, wensink HH, haslam AJ,
et al., 2017, Structure and interfacial tension of a hard-rod fluid in planar confinement., *Langmuir*, Vol: 33, Pages: 11754-11770, ISSN: 0743-7463

The structural properties and interfacial tension of a fluid of hard-spherocylinder rod-like particles in contact with hard structureless flat walls are studied by means of Monte Carlo simulation. The calculated surface tension between the rod fluid and the substrate is characterized by a non-monotonic trend as a function of bulk concentration (density) over the range of isotropic bulk concentrations. As suggested by earlier theoretical studies, a surface-ordering scenario can be confirmed from our simulations: the local orientational order close to the wall changes from uniaxial to biaxial nematic when the bulk concentration reaches about 85% of the value at the onset of the isotropic-nematic phase transition. The surface ordering coincides with a wetting transition whereby the hard wall is wetted by a nematic film. Accurate values of the fluid-solid surface tension, the adsorption, and the average particle-wall contact distance are reported (over a broad range of densities into the dense nematic region for the first time), which may serve as a useful benchmark for future theoretical and experimental studies on confined rod fluids. The simulation data are supplemented with predictions from a second-virial density functional theory, which are in good qualitative agreement with the simulation results.

Schoen M, Haslam AJ, Jackson G, 2017, Perturbation Theory versus Thermodynamic Integration. Beyond a Mean-Field Treatment of Pair Correlations in a Nematic Model Liquid Crystal., *Langmuir*, Vol: 33, Pages: 11345-11365, ISSN: 0743-7463

The phase behavior and structure of a simple square-well bulk fluid with anisotropic interactions is described in detail. The orientation dependence of the intermolecular interactions allows for the formation of a nematic liquid-crystalline phase in addition to the more conventional isotropic gas and liquid phases. A version of classical density functional theory (DFT) is employed to determine the properties of the model, and comparisons are made with the corresponding data from Monte Carlo (MC) computer simulations in both the grand canonical and canonical ensembles, providing a benchmark to assess the adequacy of the DFT results. A novel element of the DFT approach is the assumption that the structure of the fluid is dominated by intermolecular interactions in the isotropic fluid. A so-called augmented modified mean-field (AMMF) approximation is employed accounting for the influence of anisotropic interactions. The AMMF approximation becomes exact in the limit of vanishing density. We discuss advantages and disadvantages of the AMMF approximation with respect to an accurate description of isotropic and nematic branches of the phase diagram, the degree of orientational order, and orientation-dependent pair correlations. The performance of the AMMF approximations is found to be good in comparison with the MC data; the AMMF approximation has clear advantages with respect to an accurate and more detailed description of the fluid structure. Possible strategies to improve the DFT are discussed.

Jimenez-serratos M, Herdes C, Haslam A,
et al., 2017, Group-contribution coarse-grained molecular simulations of polystyrene melts and polystyrene solutions in alkanes using the SAFT-γ force field, *Macromolecules*, Vol: 50, Pages: 4840-4853, ISSN: 0024-9297

A coarse-grained (CG) model for atactic polystyrene is presented and studied with classical molecular-dynamics simulations. The interactions between the CG segments are described by Mie potentials, with parameters obtained from a top-down approach using the SAFT-γ methodology. The model is developed by taking a CG model for linear-chain-like backbones with parameters corresponding to those of an alkane and decorating it with side branches with parameters from a force field of toluene, which incorporate an “aromatic-like” nature. The model is validated by comparison with the properties of monodisperse melts, including the effect of temperature and pressure on density, as well as structural properties (the radius of gyration and end-to-end distance as functions of chain length). The model is employed within large-scale simulations that describe the temperature–composition fluid-phase behavior of binary mixtures of polystyrene in n-hexane and n-heptane. A single temperature-independent unlike interaction energy parameter is employed for each solvent to reproduce experimental solubility behavior; this is sufficient for the quantitative prediction of both upper and lower critical solution points and the transition to the characteristic “hourglass” phase behavior for these systems.

White MT, Oyewunmi OA, Haslam A, et al., 2017, Exploring optimal working fluids and cycle architectures for organic Rankine cycle systems using advanced computer-aided molecular design methodologies, 13th International Conference on Heat Transfer, Fluid Mechanics and Thermodynamics (HEFAT2017), Publisher: ICHMT

The combination of computer-aided molecular design(CAMD) with an organic Rankine cycle (ORC) power-systemmodel presents a powerful methodology that facilitates an in-tegrated approach to simultaneous working-fluid design andpower-system thermodynamic or thermoeconomic optimisation.Existing CAMD-ORC models have been focussed on simplesubcritical, non-recuperated ORC systems. The current workintroduces partially evaporated or trilateral cycles, recuperatedcycles and working-fluid mixtures into the ORC power-systemmodel, which to the best knowledge of the authors has not beenpreviously attempted. A necessary feature of a CAMD-ORCmodel is the use of a mixed-integer non-linear programming(MINLP) optimiser to simultaneously optimise integer working-fluid variables and continuous thermodynamic cycle and eco-nomic variables. In this paper, this feature is exploited by in-troducing binary optimisation variables to describe the cycle lay-out, thus enabling the cycle architecture to be optimised along-side the working fluid and system conditions. After describingthe models for the alternative cycles, the optimisation problemis completed for a defined heat source, considering hydrocar-bon working fluids. Two specific case studies are considered,in which the power output from the ORC system is maximised.These differ in the treatment of the minimum heat-source outlettemperature, which is unconstrained in the first case study, butconstrained in the second. This is done to replicate scenariossuch as a combined heat and power (CHP) plant, or applicationswhere condensation of the waste-heat stream must be avoided.In both cases it is found that a working-fluid mixture can per-form better than a pure working fluid. Furthermore, it is foundthat partially-evaporated and recuperated cycles are optimal forthe unconstrained and constrained case studies respectively.

White MT, Oyewunmi OO, Haslam AJ,
et al., 2017, Industrial waste-heat recovery through integrated computer-aided working-fluid and ORC system optimisation using SAFT-γ Mie, *Energy Conversion and Management*, Vol: 150, Pages: 851-869, ISSN: 0196-8904

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

Oyewunmi OA, white MT, Chatzopoulou M, et al., 2017, Integrated Computer-Aided Working-Fluid Design and Power System Optimisation: Beyond Thermodynamic Modelling, 30th International Conference on Efficiency, Cost, Optimization, Simulation and Environmental Impact of Energy Systems (ECOS 2017), Publisher: ECOS-2017

Improvements in the thermal and economic performance of organic Rankine cycle (ORC) systems are requiredbefore the technology can be successfully implemented across a range of applications. The integration ofcomputer-aided molecular design (CAMD) with a process model of the ORC facilitates the combinedoptimisation of the working-fluid and the power system in a single modelling framework, which should enablesignificant improvements in the thermodynamic performance of the system. However, to investigate theeconomic performance of ORC systems it is necessary to develop component sizing models. Currently, thegroup-contribution equations of state used within CAMD, which determine the thermodynamic properties of aworking-fluid based on the functional groups from which it is composed, only derive the thermodynamicproperties of the working-fluid. Therefore, these do not allow critical components such as the evaporator andcondenser to be sized. This paper extends existing CAMD-ORC thermodynamic models by implementinggroup-contribution methods for the transport properties of hydrocarbon working-fluids into the CAMD-ORCmethodology. Not only does this facilitate the sizing of the heat exchangers, but also allows estimates of systemcosts by using suitable cost correlations. After introducing the CAMD-ORC model, based on the SAFT-γ Mieequation of state, the group-contribution methods for determining transport properties are presented alongsidesuitable heat exchanger sizing models. Finally, the full CAMD-ORC model incorporating the componentmodels is applied to a relevant case study. Initially a thermodynamic optimisation is completed to optimise theworking-fluid and thermodynamic cycle, and then the component models provide meaningful insights into theeffect of the working-fluid on the system components.

White M, Oyewunmi OA, Haslam A, et al., 2017, Incorporating Computer-Aided Working-Fluid Design in the System Optimisation of an Organic Rankine Cycle Using the SAFT-γ Mie Equation of State, SAFT 2017 Conference

White MT, Oyewunmi OA, Haslam AJ, et al., 2017, High-efficiency industrial waste-heat recovery through computer-aided integrated working-fluid and ORC system optimisation, The 4th Sustainable Thermal Energy Management International Conference (SusTEM 2017)

In this paper, we develop a mixed-integer non-linear programming optimisation framework that combines working-fluid thermodynamic property predictions from a group-contribution equation of state, SAFT- Mie, with a thermodynamic description of an organic Rankine cycle. In this model, a number of working-fluids are described by their constituent functional groups (i.e., -CH3, -CH2, etc.), and integer optimisation variables are introduced in the description of the structure of the working-fluid. This facilitates combining the computer-aided molecular design of novel working-fluids 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 organic Rankine cycle systems for industrial waste-heat recovery applications. The thermodynamic model 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. Furthermore, molecular feasibility constraints are defined and validated in order to ensure all feasible working-fluid candidates can be found. Finally, the optimisation problem is formulated using the functional groups from the hydrocarbon family, and applied to three industrial waste-heat recovery case studies. The results demonstrate the potential of this framework to drive the search for the next generation of organic Rankine cycles, and to provide meaningful insights into which working-fluids are the optimal choices for a targeted application.

Eriksen DK, Lazarou G, Galindo A,
et al., 2016, Development of intermolecular potential models for electrolyte solutions using an electrolyte SAFT-VR Mie equation of state, *Molecular Physics*, Vol: 114, Pages: 2724-2749, ISSN: 1362-3028

We present a theoretical framework and parameterisation of intermolecular potentials for aqueous electrolyte solutions using the statistical associating fluid theory based on the Mie interaction potential (SAFT-VR Mie), coupled with the primitive, non-restricted mean-spherical approximation (MSA) for electrolytes. In common with other SAFT approaches, water is modelled as a spherical molecule with four off-centre association sites to represent the hydrogen-bonding interactions; the repulsive and dispersive interactions between the molecular cores are represented with a potential of the Mie (generalised Lennard-Jones) form. The ionic species are modelled as fully dissociated, and each ion is treated as spherical: Coulombic ion–ion interactions are included at the centre of a Mie core; the ion–water interactions are also modelled with a Mie potential without an explicit treatment of ion–dipole interaction. A Born contribution to the Helmholtz free energy of the system is included to account for the process of charging the ions in the aqueous dielectric medium. The parameterisation of the ion potential models is simplified by representing the ion–ion dispersive interaction energies with a modified version of the London theory for the unlike attractions. By combining the Shannon estimates of the size of the ionic species with the Born cavity size reported by Rashin and Honig, the parameterisation of the model is reduced to the determination of a single ion–solvent attractive interaction parameter. The resulting SAFT-VRE Mie parameter sets allow one to accurately reproduce the densities, vapour pressures, and osmotic coefficients for a broad variety of aqueous electrolyte solutions; the activity coefficients of the ions, which are not used in the parameterisation of the models, are also found to be in good agreement with the experimental data. The models are shown to be reliable beyond the molality range considered during parameter estimatio

White MT, Oyewunmi OA, Haslam AJ, et al., 2016, Integrated working-fluid design and ORC system optimisation for waste-heat recovery using CAMD and the SAFT-γ Mie equation of state, 3rd Annual Engine ORC Consortium Workshop

Kirmse CJW, Oyewunmi, Taleb A,
et al., 2016, A two-phase single-reciprocating-piston heat conversion engine: Non-linear dynamic modelling, *Applied Energy*, Vol: 186, Pages: 359-375, ISSN: 0306-2619

A non-linear dynamic framework is presented for the modelling of a novel two-phase heat engine termed ‘Up-THERM’, which features a single solid moving-part (piston). When applied across the device, a constant temperature difference between an external (low- to medium-grade) heat source and an external heat sink is converted into sustained and persistent oscillations of pressure and volumetric fluid displacement. These oscillations are transformed in a load arrangement into a unidirectional flow from which power is extracted by a hydraulic motor. The Up-THERM engine is modelled using a system of first-order differential equations that describe the dominant thermal/fluid processes in each component of the device. For certain components where the deviations from a linear approximation are non-negligible (gas spring in the displacer cylinder, check valves and piston valve, and heat exchangers), a non-linear description is employed. A comparison between the linear and non-linear descriptions of the gas spring at the top of the displacer cylinder reveals that the non-linear description results in more realistic predictions of the oscillation frequency compared to experimental data from a similar device. Furthermore, the shape of the temperature profile over the heat-exchanger surfaces is modelled as following a hyperbolic tangent function, based on findings from an experimental investigation. Following the validation of these important device components, a parametric study is performed on the Up-THERM engine model with the aforementioned non-linear component descriptions, aimed at investigating the effects of important geometric parameters and of the heat-source temperature on key performance indicators, namely the oscillation frequency, power output and exergy efficiency of the engine. The results indicate that the geometric design of the displacer cylinder, including the height of the gas spring at the top of the cylinder, and the heat-source temperature hav

Kirmse CJW, Oyewunmi OA, Haslam AJ,
et al., 2016, Comparison of a novel organic-fluid thermofluidic heat converter and an organic Rankine cycle heat engine, *Energies*, Vol: 9, ISSN: 1996-1073

The Up-THERM heat converter is an unsteady, two-phase thermofluidic oscillator that employs an organic working fluid, which is currently being considered as a prime-mover in small- to medium-scale combined heat and power (CHP) applications. In this paper, the Up-THERM heat converter is compared to a basic (sub-critical, non-regenerative) organic Rankine cycle (ORC) heat engine with respect to their power outputs, thermal efficiencies and exergy efficiencies, as well as their capital and specific costs. The study focuses on a pre-specified Up-THERM design in a selected application, a heat-source temperature range from 210 °C to 500 °C and five different working fluids (three n-alkanes and two refrigerants). A modeling methodology is developed that allows the above thermo-economic performance indicators to be estimated for the two power-generation systems. For the chosen applications, the power output of the ORC engine is generally higher than that of the Up-THERM heat converter. However, the capital costs of the Up-THERM heat converter are lower than those of the ORC engine. Although the specific costs (£/kW) of the ORC engine are lower than those of the Up-THERM converter at low heat-source temperatures, the two systems become progressively comparable at higher temperatures, with the Up-THERM heat converter attaining a considerably lower specific cost at the highest heat-source temperatures considered.

Oyewunmi OA, Kirmse CJW, Haslam AJ,
et al., 2016, Working-fluid selection and performance investigation of a two-phase single-reciprocating-piston heat-conversion engine, *Applied Energy*, Vol: 186, Pages: 376-395, ISSN: 0306-2619

We employ a validated first-order lumped dynamic model of the Up-THERM converter, a two-phase unsteadyheat-engine that belongs to a class of innovative devices known as thermofluidic oscillators, which containfewer moving parts than conventional engines and represent an attractive alternative for remote or off-gridpower generation as well as waste-heat recovery. We investigate the performance the Up-THERM withrespect to working-fluid selection for its prospective applications. An examination of relevant working-fluidthermodynamic properties reveals that the saturation pressure and vapour-phase density of the fluid play importantroles in determining the performance of the Up-THERM – the device delivers a higher power outputat high saturation pressures and has higher exergy efficiencies at low vapour-phase densities. Furthermore,working fluids with low critical temperatures, high critical pressures and exhibiting high values of reducedpressures and temperatures result in designs with high power outputs. For a nominal Up-THERM designcorresponding to a target application with a heat-source temperature of 360 ◦C, water is compared withforty-five other pure working fluids. When maximizing the power output, R113 is identified as the optimalfluid, followed by i-hexane. Fluids such as siloxanes and heavier hydrocarbons are found to maximize theexergy and thermal efficiencies. The ability of the Up-THERM to convert heat over a range of heat-sourcetemperatures is also investigated, and it is found that the device can deliver in excess of 10 kW when utilizingthermal energy at temperatures above 200 ◦C. Of all the working fluids considered here, ammonia, R245ca,R32, propene and butane feature prominently as optimal and versatile fluids delivering high power over awide range of heat-source temperatures.

Kirmse CJW, Oyewunmi OA, Haslam AJ, et al., 2016, A thermo-economic assessment and comparison of the Up-THERM heat converter and an organic Rankine cycle engine, Heat Powered Cycles Conference 2016

In this paper we present a thermodynamic and economic comparison of a recently proposed two-phasethermofluidic oscillator known as the Up-THERM heat converter and the more established organic Rankine cycle(ORC) engine, when converting heat at temperatures below 150 °C using the refrigerant R-227ea as the workingfluid. The Up-THERM heat converter is being considered as a possible prime mover for small- to medium-scalecombined heat and power (CHP) applications. Using suitable thermodynamic models of both systems, it is foundthat the power output and thermal efficiencies of a pre-specified Up-THERM design are generally lower thanthose of an equivalent ORC engine. The Up-THERM, however, also demonstrates higher exergy efficiencies andis associated with lower capital costs, as expected owing to its simple construction and use of fewer and morebasic components. Interestingly, the specific costs (per rated kW) of the ORC engine are lower than those of theUp-THERM converter at lower heat source temperatures, specifically below 130 °C, whereas the Up-THERMbecomes a more cost effective alternative (in terms of the specific cost) to the ORC engine at higher temperatures.

Kirmse CJW, Oyewunmi OA, Haslam A, et al., 2016, A THERMO-ECONOMIC COMPARISON OF THE UP-THERM HEAT CONVERTER AND AN ORGANIC RANKINE CYCLE HEAT ENGINE, 12th International Conference on Heat Transfer, Fluid Mechanics and Thermodynamics

In this paper we compare a recently proposed two-phase thermofluidicoscillator device termed ‘Up-THERM’ to a basic(sub-critical, non-regenerative) equivalent organic Rankine cycle(ORC) engine. In the Up-THERM heat converter, a constanttemperature difference imposed by an external heat source andsink leads to periodic evaporation and condensation of the workingfluid, which gives rise to sustained oscillations of pressureand volumetric displacement. These oscillations are convertedin a load arrangement into a unidirectional flow, which passesthrough a hydraulic motor that extracts useful work from the device.A pre-specified Up-THERM design is being considered in aselected application with two n-alkanes, n-hexane and n-heptane,as potential working fluids. One aim of this work is to evaluatethe potential of this proposed design. The thermodynamic comparisonshows that the ORC engine outperforms the Up-THERMheat converter in terms of power output and thermal efficiency,as expected. An economic comparison, however, reveals that thecapital costs of the Up-THERM are lower than those of the ORCengine. Nevertheless, the specific costs (per unit power) favourthe ORC engine due to its higher power output. Some aspects ofthe proposed Up-THERM design are identified for improvement

Brechtelsbauer C, Haslam A, Shah U,
et al., 2016, Measuring vapour pressure with an isoteniscope - a hands-on introduction to thermodynamic concepts, *Journal of Chemical Education*, Vol: 93, Pages: 920-926, ISSN: 1938-1328

Characterization of the vapor pressure of a volatile liquid or azeotropic mixture, and its fluid phase diagram, can be achieved with an isoteniscope and an industrial grade digital pressure sensor using the experimental method reported in this study. We describe vapor-pressure measurements of acetone and n-hexane and their azeotrope, and how the data can be used to calculate thermodynamic properties of the test liquids, such as the molar heat of vaporization. This hands-on experience allows students to appreciate important thermodynamic concepts such as phase equilibrium, preparing them for more advanced studies of the subject.

Oyewunmi OA, Taleb A, Haslam A,
et al., 2015, On the use of SAFT-VR Mie for assessing large-glide fluorocarbon working-fluid mixtures in organic rankine cycles, *Applied Energy*, Vol: 163, Pages: 263-282, ISSN: 1872-9118

By employing the SAFT-VR Mie equation of state, molecular-based models are developed from which the thermodynamic properties of pure (i.e., single-component) organic fluids and their mixtures are calculated. This approach can enable the selection of optimal working fluids in organic Rankine cycle (ORC) applications, even in cases for which experimental data relating to mixture properties are not available. After developing models for perfluoroalkane (n-C4F10 + n-C10F22) mixtures, and validating these against available experimental data, SAFT-VR Mie is shown to predict accurately both the single-phase and saturation properties of these fluids. In particular, second-derivative properties (e.g., specific heat capacities), which are less reliably calculated by cubic equations of state (EoS), are accurately described using SAFT-VR Mie, thereby enabling an accurate prediction of important working-fluid properties such as the specific entropy. The property data are then used in thermodynamic cycle analyses for the evaluation of ORC performance and cost. The approach is applied to a specific case study in which a sub-critical, non-regenerative ORC system recovers and converts waste-heat from a refinery flue-gas stream with fixed, predefined conditions. Results are compared with those obtained when employing analogue alkane mixtures (n-C4H10 + n-C10H22) for which sufficient thermodynamic property data exist. When unlimited quantities of cooling water are utilized, pure perfluorobutane (and pure butane) cycles exhibit higher power outputs and higher thermal efficiencies compared to mixtures with perfluorodecane (or decane), respectively. The effect of the composition of a working-fluid mixture in the aforementioned performance indicators is non-trivial. Only at low evaporator pressures (< 10 bar) do the investigated mixtures perform better than the pure fluids. A basic cost analysis reveals that systems with pure perfluorobutane (and butane) fluids are associated with rela

Jover J, Galindo A, Jackson G,
et al., 2015, Fluid-fluid coexistence in an athermal colloid-polymer mixture: thermodynamic perturbation theory and continuum molecular-dynamics simulation, *MOLECULAR PHYSICS*, Vol: 113, Pages: 2608-2628, ISSN: 0026-8976

Chow YTF, Eriksen DK, Galindo A,
et al., 2015, Interfacial tensions of systems comprising water, carbon dioxide and diluent gases at high pressures: Experimental measurements and modelling with SAFT-VR Mie and square-gradient theory, *Fluid Phase Equilibria*, Vol: 407, Pages: 159-176, ISSN: 0378-3812

Experimental interfacial tensions of the systems (H<inf>2</inf>O+CO<inf>2</inf>), (H<inf>2</inf>O+N<inf>2</inf>), (H<inf>2</inf>O+Ar), (H<inf>2</inf>O+CO<inf>2</inf> +N<inf>2</inf>) and (H<inf>2</inf>O+CO<inf>2</inf> +Ar) are compared with calculations based on the statistical associating fluid theory for variable range potentials of the Mie form (SAFT-VR Mie) in combination with the square-gradient theory (SGT). Comparisons are made at temperatures from (298 to 473)K and at pressures up to 60MPa. Experimental data for the systems (H<inf>2</inf>O+CO<inf>2</inf>), (H<inf>2</inf>O+N<inf>2</inf>) and (H<inf>2</inf>O+CO<inf>2</inf> +N<inf>2</inf>) are taken from the literature. For the (H<inf>2</inf>O+Ar) and (H<inf>2</inf>O+CO<inf>2</inf> +Ar) systems, we report new experimental interfacial-tension data at temperatures of (298.15-473.15)K and pressures from (2 to 50)MPa, measured by the pendant-drop method. The expanded uncertainties at 95% confidence are 0.05K for temperature, 70kPa for pressure, 0.016× γ for interfacial tension in the binary (Ar+H<inf>2</inf>O) system and 0.018× γ for interfacial tension in the ternary (CO<inf>2</inf> +Ar+H<inf>2</inf>O) system.The parameters in the SAFT-VR Mie equation of state are estimated entirely from phase-equilibrium data for the pure components and binary mixtures. For pure water, the SGT influence parameter is determined from vapour-liquid surface-tension data, as is common practice. Since the other components are supercritical over most or the entire temperature range under consideration, their pure-component influence parameters are regressed by comparison with the binary interfacial-tension data. A geometric-mean combining rule

Kirmse C, Oyewunmi OA, Haslam AJ, et al., 2015, A two-phase single-reciprocating-piston heat conversion engine, 11th International Conference on Heat Transfer, Fluid Mechanics and Thermodynamics (HEFAT2015)

This paper considers an energy-conversion heat-engineconcept termed ‘Up-THERM’. This machine is capable ofconverting low- to medium-grade heat to useful positivedisplacementwork through the periodic evaporation andcondensation of a working fluid in an enclosed space. Thesealternating phase-change processes drive sustained oscillations ofthermodynamic properties (pressure, temperature, volume) as theworking fluid undergoes an unsteady thermodynamic heatenginecycle. The resulting oscillatory flow of the working fluidis converted into a unidirectional flow in a hydraulic loadarrangement where power can be extracted from the machine.The engine is described with lumped dynamic modelsconstructed using electrical analogies founded on previouslydeveloped thermoacoustic and thermofluidic principles, whichare extended here to include a description of the phase-changeheat-transfer processes. For some sub-components of the engine,such as the gas spring, valves and the temperature profile in theheat exchangers, deviations from the linear theory are nonnegligible.These are modelled using non-linear descriptions. Inparticular, the results of linear and non-linear descriptions of thegas spring are compared using three important performanceindicators — efficiency, power output and frequency.The non-linear description of the gas spring results in morerealisticpredictions of the oscillation frequency compared todirect measurements on an experimental prototype of a similarengine. Owing to its mode of operation and lack of moving parts,the Up-THERM engine does offer a much simpler and morecost-efficient solution than alternative engines for heat recoveryand solar applications. The results from this work suggest thatthis technology can be a competitive alternative in terms of costper unit power in low-power, small-scale applications, especiallyin remote, off-grid settings, for example in developing countrieswhere minimising upfront costs is crucial.

Oyewunmi OA, Haslam AJ, Markides CN, 2015, Towards the computer-aided molecular design of organic rankine cycle systems with advanced fluid theories, SusTEM 2015 International Conference, Pages: 180-189

Organic Rankine cycle (ORC) power-generation systems are increasingly being deployed for heat recovery and conversion from geothermal reservoirs and in several industrial settings. Using a case study of an exhaust flue-gas stream, an ORC power output in excess of 20 MW is predicted at thermal efficiencies ranging between 5% and 15%. The considerable influence on cycle performance of the choice of the working fluid is illustrated with alkane and perfluoroalkane systems modelled using the SAFT-VR Mie equation of state (EoS); in general, the more-volatile pure components (n-butane or n-perfluorobutane) are preferred although some mixtures perform better at restricted cycle conditions.The development of computer-aided molecular design (CAMD) platforms for ORC systems requires both cycle and working-fluid models to be incorporated into a single framework, for the purposes of whole-system design and optimization. Using pure alkanes and their mixtures as a case study, we test the suitability of the recent group-contribution SAFT- Mie EoS method for describing the thermodynamic properties of working fluids relevant to the analysis of ORC systems. The theory is shown to predict accurately the relevant properties of these fluids, thereby suggesting that this SAFT-based CAMD approach is a promising approach towards working-fluid design of ORC power systems.

Dufal S, Lafitte T, Galindo A,
et al., 2015, Developing intermolecular-potential models for use with the SAFT-VRMie equation of state, *AIChE Journal*, Vol: 61, Pages: 2891-2912, ISSN: 0001-1541

A major advance in the statistical associating fluid theory (SAFT) for potentials of variable range (SAFT-VR) has recently been made with the incorporation of the Mie (generalized Lennard–Jones [LJ]) interaction between the segments comprising the molecules in the fluid (Lafitte et al. J. Chem. Phys. 2013;139:154504). The Mie potential offers greater versatility in allowing one to describe the softness/hardness of the repulsive interactions and the range of the attractions, which govern fine details of the fluid-phase equilibria and thermodynamic derivative properties of the system. In our current work, the SAFT-VR Mie equation of state is employed to develop models for a number of prototypical fluids, including some of direct relevance to the oil and gas industry: methane, carbon dioxide and other light gases, alkanes, alkyl benzenes, and perfluorinated compounds. A complication with the use of more-generic force fields such as the Mie potential is the additional number of parameters that have to be considered to specify the interactions between the model molecules, leading to a degree of degeneracy in the parameter space. A formal methodology to isolate intermolecular-potential models and assess the adequacy of the description of the thermodynamic properties in terms of the complex parameter space is developed. Fluid-phase equilibrium properties (the vapor pressure and saturated-liquid density) are chosen as the target properties in the refinement of the force fields; the predictive capability for other properties such as the enthalpy of vaporization, single-phase density, speed of sound, isobaric heat capacity, and Joule–Thomson coefficient, is appraised. It is found that an overall improvement of the representations of the thermophysical properties of the fluids is obtained using the more-generic Mie form of interaction; in all but the simplest of fluids, one finds that the LJ interaction is not the most appropriate.

Dufal S, Lafitte T, Haslam AJ,
et al., 2015, The A in SAFT: developing the contribution of association to the Helmholtz free energy within a Wertheim TPT1 treatment of generic Mie fluids, *Molecular Physics*, Vol: 113, Pages: 948-984, ISSN: 1362-3028

An accurate representation of molecular association is a vital ingredient of advanced equations of state (EOSs), providing a description of thermodynamic properties of complex fluids where hydrogen bonding plays an important role. The combination of the first-order thermodynamic perturbation theory (TPT1) of Wertheim for associating systems with an accurate description of the structural and thermodynamic properties of the monomer fluid forms the basis of the statistical associating fluid theory (SAFT) family of EOSs. The contribution of association to the free energy in SAFT and related EOSs is very sensitive to the nature of intermolecular potential used to describe the monomers and, crucially, to the accuracy of the representation of the thermodynamic and structural properties. Here we develop an accurate description of the association contribution for use within the recently developed SAFT-VR Mie framework for chain molecules formed from segments interacting through a Mie potential [T. Lafitte, A. Apostolakou, C. Avendaño, A, Galindo, C. S. Adjiman, E. A. Müller, and G. Jackson, J. Chem. Phys. 139, 154504 (2013)]. As the Mie interaction represents a soft-core potential model, a method similar to that adopted for the Lennard-Jones potential [E. A. Müller and K. E. Gubbins, Ind. Eng. Chem. Res. 34, 3662 (1995)] is employed to describe the association contribution to the Helmholtz free energy. The radial distribution function (RDF) of the Mie fluid (which is required for the evaluation of the integral at the heart of the association term) is determined for a broad range of thermodynamic conditions (temperatures and densities) using the reference hyper-netted chain (RHNC) integral-equation theory. The numerical data for the association kernel of Mie fluids with different association geometries are then correlated for a range of thermodynamic states to obtain a general expression for the association contribution which can be applied for varying values

Kirmse C, Taleb AJ, Oyewunmi OA, et al., 2015, Performance comparison of a novel thermofluidic organic-fluid heat converter and an organic rankine cycle heat engine, 3rd International Seminar on ORC Power Systems (ASME ORC 2015)

The Up-THERM engine is a novel two-phase heat engine with a single moving part–a vertical solidpiston–that relies on the phase change of a suitable working fluid to produce a reciprocating displacementand sustained thermodynamic oscillations of pressure and flow rate that can be converted to useful work.A model of the Up-THERM engine is developed via lumped dynamic descriptions of the various enginesub-components and electrical analogies founded on previously developed thermoacoustic principles.These are extended here to include a description of phase change and non-linear descriptions of selectedprocesses. The predicted first and second law efficiencies and the power output of a particular Up-THERM engine design aimed for operation in a specified CHP application with heat source and sinktemperatures of 360 ○C and 10 ○C, are compared theoretically to those of equivalent sub-critical, nonregenerativeorganic Rankine cycle (ORC) engines. Five alkanes (from n-pentane to n-nonane) are beingconsidered as possible working fluids for the aforementioned Up-THERM application, and these arealso used for the accompanying ORC thermodynamic analyses. Owing to its mode of operation, lackof moving parts and dynamic seals, the Up-THERM engine promises a simpler and more cost-effectivesolution than an ORC engine, although the Up-THERM is expected to be less efficient than its ORCcounterpart. These expectations are confirmed in the present work, with the Up-THERM engine showinglower efficiencies and power outputs than equivalent ORC engines, but which actually approach ORCperformance at low temperatures. Therefore, it is suggested that the Up-THERM can be a competitivealternative in terms of cost per unit power in low-power/temperature applications, especially in remote,off-grid settings, such as in developing countries where minimising upfront costs is crucial.

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