Undoubtedly, materials that can be tuned on a molecular level offer tremendous opportunities. However, to understand and customize such materials is challenging. In this context, molecular simulation can be helpful. The work presented in this thesis deals with two types of materials, Metal-Organic Frameworks and Ionic Liquids, and the study with molecular simulation to determine their potential for specific gas separations. For the prediction of their behavior and relevant materials properties with molecular simulation, force fields of sufficient quality are required..@en

Crown-ethers have recently been used to assemble porous liquids (PLs), which are liquids with permanent porosity formed by mixing bulky solvent molecules (e.g., 15-crown-5 ether) with solvent-inaccessible organic cages. PLs and crown-ethers belong to a novel class of materials, which can potentially be used for gas separation and storage, but their performance for this purpose needs to be assessed thoroughly. Here, we use molecular simulations to study the gas separation performance of crown-ethers as the solvent of porous liquids. The TraPPE force field for linear ether molecules has been adjusted by fitting a new set of torsional potentials to accurately describe cyclic crown-ether molecules. Molecular dynamics (MD) simulations have been used to compute densities, shear viscosities, and self-diffusion coefficients of 12-crown-4, 15-crown-5, and 18-crown-6 ethers. In addition, Monte Carlo (MC) simulations have been used to compute the solubility of the gases CO2, CH4, and N2 in 12-crown-4 and 15-crown-5 ether. The computed properties are compared with available experimental data of crown-ethers and their linear counterparts, i.e., polyethylene glycol dimethyl ethers.@en

We present a new plugin for LAMMPS for on-the-fly computation of transport properties (OCTP) in equilibrium molecular dynamics. OCTP computes the self- and Maxwell-Stefan diffusivities, bulk and shear viscosities, and thermal conductivities of pure fluids and mixtures in a single simulation. OCTP is the first implementation in LAMMPS that uses the Einstein relations combined with the order-n algorithm for the efficient sampling of dynamic variables. OCTP has low computational requirements and is easy to use because it follows the native input file format of LAMMPS. A tool for calculating the radial distribution function (RDF) of the fluid beyond the cutoff radius, while taking into account the system size effects, is also part of the new plugin. The RDFs computed from OCTP are needed to obtain the thermodynamic factor, which relates Maxwell-Stefan and Fick diffusivities. To demonstrate the efficiency of the new plugin, the transport properties of an equimolar mixture of water-methanol were computed at 298 K and 1 bar.@en

Mutual diffusion coefficients can be successfully predicted with models based on the Darken equation. However, Darken-based models require composition-dependent self-diffusion coefficients which are rarely available. In this work, we present a predictive model for composition-dependent self-diffusion coefficients (also called tracer diffusion coefficients or intradiffusion coefficients) in nonideal binary liquid mixtures. The model is derived from molecular dynamics simulation data of Lennard-Jones systems. A strong correlation between nonideal diffusion effects and the thermodynamic factor is observed. We extend the model by McCarty and Mason (Phys. Fluids 1960, 3, 908-922) for ideal binary gas mixtures to predict the composition-dependent self-diffusion coefficients in nonideal binary liquid mixtures. Our new model is a function of the thermodynamic factor, the self-diffusion coefficients at infinite dilution, and the self-diffusion coefficients of the pure substances, which are readily available. We validate our model with experimental data of 9 systems. For both Lennard-Jones systems and experimental data, the accuracy of the predicted self-diffusion coefficients is improved by a factor of 2 compared to the correlation of McCarty and Mason. Thus, our new model significantly expands the practical applicability of Darken-based models for the prediction of mutual diffusion coefficients.@en

Vapour–liquid equilibrium (VLE) and volumetric data of multicomponent mixtures are extremely important for natural gas production and processing, but it is time consuming and challenging to experimentally obtain these properties. An alternative tool is provided by means of molecular simulation. Here, Monte Carlo (MC) simulations in the Gibbs ensemble are used to compute the VLE of multicomponent natural gas mixtures. Two multicomponent systems, one containing a mixture of six components ((Formula presented.), (Formula presented.), (Formula presented.), (Formula presented.)S, (Formula presented.)(Formula presented.) and (Formula presented.)(Formula presented.)), and the other containing a mixture of nine components ((Formula presented.), (Formula presented.), (Formula presented.), (Formula presented.)S, (Formula presented.)(Formula presented.), (Formula presented.)(Formula presented.), (Formula presented.)(Formula presented.), (Formula presented.)(Formula presented.) and (Formula presented.)(Formula presented.)) are simulated. The computed VLE from the MC simulations is in good agreement with available experimental data and the GERG-2008 equation of state modelling. The results show that molecular simulation can be used to predict properties of multicomponent systems relevant for the natural gas industry. Guidelines are provided to setup Gibbs ensemble simulations for multicomponent systems, which is a challenging task due to the increased number of degrees of freedom.@en

To use high-temperature waste heat generated by diesel engines for onboard refrigeration of fishing vessels, an ammonia-based double-effect vapor absorption refrigeration cycle is proposed. Non-volatile ionic liquids are applied as absorbents in the double-effect absorption system. In comparison to systems using ammonia/water fluid, the complexity of the system can be reduced by preventing the use of rectification sections. In this study, a multi-scale method is implemented to study the proposed system, including molecular simulations (the Monte Carlo method) for computing vapor-liquid equilibrium properties at high temperatures and pressures, thermodynamic modeling of the double-effect absorption cycles, and system evaluations by considering practical integration. The Monte Carlo simulations provide reasonable vapor-liquid equilibrium predictions. 1-butyl-3-methylimidazolium tetrafluoroborate is found to be the best performing candidate among the investigated commercialized ionic liquids. In the proposed cycle, the best working fluid achieves a coefficient of performance of 1.1 at a cooling temperature of −5 C, which is slightly higher than that obtained with generator-absorber cycles. Integrated with the exhaust gas from diesel engines, the cooling capacity of the system is sufficient to operate two refrigeration seawater plants for most of the engine operating modes in high-latitude areas. Thereby, the carbon emission of onboard refrigeration of the considered fishing vessel could be reduced by 1633.5 tons per year compared to the current practice. Diagrams of vapor pressures and enthalpies of the studied working fluids are provided as appendices.@en

Natural gas, synthesis gas, and flue gas typically contain a large number of impurities (e.g., acidic gases), which should be removed to avoid environmental and technological problems, and to meet customer specifications. One approach is to use physical solvents to remove the acidic gases. If no experimental data are available, the solubility data required for designing the sweetening process can be obtained from molecular simulations. Here, Monte Carlo (MC) simulations are used to compute the solubility of the gas molecules, i.e., carbonyl sulfide, carbon disulfide, sulfur dioxide, hydrogen sulfide, methyl mercaptan, carbon dioxide, and methane in the commercial solvents tetraethylene-glycol-dimethyl-ether (Selexol), n-methyl-2-pyrrolidone, propylene carbonate, methanol (Rectisol), and the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([bmim][Tf2N]). Henry coefficients of the gases in the investigated solvents are obtained from the computed solubilities. The ratio of Henry coefficients is used to compute ideal selectivities of the solvents. The solubilites and selectivities computed from MC simulations are compared with available experimental data. Some guidelines are provided to remove acidic gases using the investigated solvents. Rectisol is the best solvent for acid gas removal, but it should be used at low temperatures. Selexol and the ionic liquid have similar selectivity of sulfur compounds with respect to methane and may be used at elevated pressures and temperatures since both have low vapor pressures. The solubility of carbon disulfide, sulfur dioxide, and methyl mercaptan in these solvents is the highest. Hence, these components can be removed easily prior to hydrogen sulfide, carbonyl sulfide, and carbon dioxide in a pre-absorber.@en

Monte Carlo (MC) simulations in ensembles with a fixed chemical potential or fugacity, for example the grand-canonical or the osmotic ensemble, are often used to compute phase equilibria. Chemical potentials can be computed either with an equation of state (EoS) or from molecular simulations. The accuracy of the computed chemical potentials depends on the quality of the (critical) parameters used in the EoS and the applied force field in the simulations. We investigated the consistency of both approaches for computing fugacities of the industrially relevant gases CO2, CH4, CO, H2, N2, and H2S. The critical temperature (Tc), pressure (Pc), and acentric factors (ω) of these gases are computed from MC simulations in the Gibbs ensemble. The effect of cutoff radius and tail corrections on the computed values of Tc, Pc, and ω is investigated. In addition, MC simulations in the Gibbs ensemble are used to compute the VLE of the 15 possible binary systems comprising the gases CO2, CH4, CO, H2, N2, and H2S, and the ternary systems CO2/CH4/H2S and CO2/CO/H2. Binary interaction parameters (kij) of these natural/synthesis gas mixtures are obtained by fitting the Peng-Robinson (PR) EoS to the binary VLE data from the MC simulations. The computed properties from the MC simulations are compared with the PR EoS, the GERG EoS, and experimental results. The MC results show that including tail corrections in the simulations is crucial to obtain accurate critical properties. The force fields used for the gases can reproduce the fugacities of the gases within 5% of the experimental data. The dew-point curves of all the 15 binaries were predicted correctly by the MC simulations, but the bubble-point curves for the systems H2/CO, CH4/H2, H2S/N2, and H2S/CO significantly deviate from the experiments.@en

An increase in demand for energy efficient processes for the separation of saturated and unsaturated light hydrocarbons mixtures drives the need of noncryogenic processes. The adsorptive separation using Metal-Organic Frameworks with coordinatively unsaturated metal sites may provide a cost-effective alternative due to the strong binding of the metal cation with the unsaturated hydrocarbons. Since experiments on adsorption equilibrium of gas mixtures are challenging, we propose classical force field based simulations to analyse the ability of MOF-74 with different metal substitutions for the separation of C2 and C3 olefin/paraffin binary mixtures. We parametrized the force field by fitting to available experimental single-component adsorption isotherms of ethane, ethene, propane, and propene in M–MOF-74 (M=Co, Fe, Mn, and Ni). The force field was validated for a variety of temperatures ranged from 273 K to 353 K. We then conducted Monte Carlo simulations in the Grand-Canonical ensemble to elucidate the adsorption mechanisms of the saturated/unsaturated hydrocarbon mixtures, at 318 K and 353 K. We computed the adsorption isotherms, and from these the adsorption selectivity, and addressed the variations of MOF properties with different metal cations. Fe-based MOF-74 appears the best option for both ethane/ethene and propane/propene separation applications. This finding partly agrees with previous work based on the Ideal Adsorbed Solution Theory.@en

Force Field based Monte Carlo (MC) simulations are conducted to predict the performance of an absorption heat pump cycle involving NH3/ionic liquid (IL) (refrigerant/absorbent) as working pair. To investigate the thermodynamic performance of the cycle, various properties such as the enthalpy of absorption, heat capacity, and solubility of refrigerant in the absorbent are required. As an alternative to experiments, MC simulations are used to predict the required properties. The simulations are performed at temperatures ranging from 303 K to 373 K and pressures ranging from 4 to 16 bar. The thermodynamic performance parameters such as the coefficient of performance, COP, and the circulation ratio, f, of NH3 paired with [emim][Tf2N] are investigated using MC simulations and compared to results obtained from correlated experimental data, showing a reasonable agreement. MC simulations could be used as an inexpensive alternative for preliminary design considerations involving potential working pairs for absorption heat pump cycles in the absence of available experimental data.@en

Metal organic frameworks are frequently examined as potential solutions to complex gas phase separations problems. In many cases, the gas phase adsorption properties of these materials are quantified using single component gas adsorption isotherms and breakthrough experiments. In adsorption separations, however, it is common that the adsorbent participates in a multicomponent adsorption event. In the literature there is a general absence of multicomponent adsorption data with most data predicted via the Ideal Adsorbed Solution Theory or molecular simulations. Therefore, in this work, binary adsorption data of CO 2 and water on UiO-66 were measured experimentally using a volumetric method at three different water loadings. Molecular simulations of isotherms were compared to the experimental measurements and the impact of two different MOF defect sites on the multicomponent CO 2 /H 2 O adsorption behavior was determined. The experimental data show a slight enhancement of CO 2 loading when CO 2 is co-adsorbed with water, which is a result that was confirmed via molecular simulations. Also, the simulation results show that defect sites can have a greater influence on low-pressure CO 2 adsorption in MOFs than the co-adsorption of water. Furthermore, the simulations provide a molecular-level understanding of the role of these defects on the single and binary adsorption behavior. @en

Metal organic frameworks are frequently examined as potential solutions to complex gas phase separations problems. In many cases, the gas phase adsorption properties of these materials are quantified using single component gas adsorption isotherms and breakthrough experiments. In adsorption separations, however, it is common that the adsorbent participates in a multicomponent adsorption event. In the literature there is a general absence of multicomponent adsorption data with most data predicted via the Ideal Adsorbed Solution Theory or molecular simulations. Therefore, in this work, binary adsorption data of CO 2 and water on UiO-66 were measured experimentally using a volumetric method at three different water loadings. Molecular simulations of isotherms were compared to the experimental measurements and the impact of two different MOF defect sites on the multicomponent CO 2 /H 2 O adsorption behavior was determined. The experimental data show a slight enhancement of CO 2 loading when CO 2 is co-adsorbed with water, which is a result that was confirmed via molecular simulations. Also, the simulation results show that defect sites can have a greater influence on low-pressure CO 2 adsorption in MOFs than the co-adsorption of water. Furthermore, the simulations provide a molecular-level understanding of the role of these defects on the single and binary adsorption behavior. @en

This paper assesses the performance of vapor–liquid equilibrium (VLE) models in ionic liquid based absorption cycles with natural refrigerants. Frequently used equation-of-state (EOS) based models, activity coefficient based models, and generic Clausius–Clapeyron relations are evaluated. Working pairs considered are H2O/[emim][DMP] and NH3/[bmim][BF4]. Firstly, experimental VLE data of those working pairs are correlated by using the models. Mixing enthalpies are then estimated using the models and corresponding correlated parameters. Performances of the different models in reproducing VLE data and estimating mixing enthalpies are compared with each other. Subsequently, total enthalpies and thermodynamic performances of absorption refrigeration cycles are predicted based on the different models. The assessment reveals that the RK-EOS and the NRTL model perform best in reproducing VLE data. In addition, the RK-EOS and the UNIFAC model show the best performance in estimating mixing enthalpies. Hence, the RK-EOS is recommended in correlating VLE data and estimating mixing enthalpies in absorption cycles.@en

Ionic liquid (IL)-NH3 double-effect absorption systems are proposed to utilize the high-temperature exhausted gas (250-500 oC) from engines with the purpose of delivering the required refrigeration of the fishing vessel. In this work, practical concerns on the stabilities, toxicities and viscosities of IL-based fluids have been discussed. Monte Carlo (MC) methods have been applied to extend the vapor-liquid equilibrium properties of selected IL-NH3 working pairs to high-temperature conditions. Additionally, a case study based on a specific fishing vessel has been carried out to investigate the economic feasibility of the proposed systems.@en

Molecular Dynamics simulations were performed for the prediction of the finite-size effects of Maxwell-Stefan diffusion coefficients of molecular mixtures and a wide variety of binary Lennard-Jones systems. A strong dependency of computed diffusivities on the system size was observed. Computed diffusivities were found to increase with the number of molecules. We propose a correction for the extrapolation of Maxwell-Stefan diffusion coefficients to the thermodynamic limit, based on the study by Yeh and Hummer (J. Phys. Chem. B, 2004, 108, 15873-15879). The proposed correction is a function of the viscosity of the system, the size of the simulation box, and the thermodynamic factor, which is a measure for the nonideality of the mixture. Verification is carried out for more than 200 distinct binary Lennard-Jones systems, as well as 9 binary systems of methanol, water, ethanol, acetone, methylamine, and carbon tetrachloride. Significant deviations between finite-size Maxwell-Stefan diffusivities and the corresponding diffusivities at the thermodynamic limit were found for mixtures close to demixing. In these cases, the finite-size correction can be even larger than the simulated (finite-size) Maxwell-Stefan diffusivity. Our results show that considering these finite-size effects is crucial and that the suggested correction allows for reliable computations.@en

(Graph Presented) The family of M-MOF-74, with M = Co, Cr, Cu, Fe, Mg, Mn, Ni, Ti, V, and Zn, provides opportunities for numerous energy related gas separation applications. The pore structure of M-MOF-74 exhibits a high internal surface area and an exceptionally large adsorption capacity. The chemical environment of the adsorbate molecule in M-MOF-74 can be tuned by exchanging the metal ion incorporated in the structure. To optimize materials for a given separation process, insights into how the choice of the metal ion affects the interaction strength with adsorbate molecules and how to model these interactions are essential. Here, we quantitatively highlight the importance of polarization by comparing the proposed polarizable force field to orbital interaction energies from DFT calculations. Adsorption isotherms and heats of adsorption are computed for CO2, CH4, and their mixtures in M-MOF-74 with all 10 metal ions. The results are compared to experimental data, and to previous simulation results using nonpolarizable force fields derived from quantum mechanics. To the best of our knowledge, the developed polarizable force field is the only one so far trying to cover such a large set of possible metal ions. For the majority of metal ions, our simulations are in good agreement with experiments, demonstrating the effectiveness of our polarizable potential and the transferability of the adopted approach.@en

The separation of light olefins from paraffins via cryogenic distillation is a very energy intensive process. Solid adsorbents and especially metal-organic frameworks with open metal sites have the potential to significantly lower the required energy. Specifically, M-MOF-74 has drawn considerable attention for application in olefin/paraffin separation. To investigate how the separation proceeds on a molecular level and to design better materials, molecular simulation can be a useful tool. Unfortunately, it is still a challenge to model the adsorption behavior of many adsorbates in metal-organic frameworks with open metal sites. Previously, the inclusion of explicit polarization has been suggested to improve the quality of classical force fields for such systems. Here, the potential of polarizable force fields for the description of olefins and paraffins in metal-organic frameworks with open metal sites is investigated. In particular, heats of adsorption, binding geometries, and adsorption isotherms are calculated for C2H4, C2H6, C3H6, and C3H8 in M-MOF-74 (with M = Co, Mn, Fe, and Ni). In this study, no force field parameters are adjusted to improve the model. The results show that including explicit polarization significantly improves the description of the adsorption in comparison to non-polarizable generic force fields which do not consider explicit polarization. The study also reveals that simulation predictions are sensitive to the assigned repulsive potential and framework charges. A fully re-parametrized polarizable force field may have the capability to improve the predictions even further.@en

For absorption refrigeration, it has been shown that ionic liquids have the potential to replace conventional working pairs. Due to the huge number of possibilities, conducting lab experiments to find the optimal ionic liquid is infeasible. Here, we provide a proof-of-principle study of an alternative computational approach. The required thermodynamic properties, i.e., solubility, heat capacity, and heat of absorption, are determined via molecular simulations. These properties are used in a model of the absorption refrigeration cycle to estimate the circulation ratio and the coefficient of performance. We selected two ionic liquids as absorbents: [emim][Tf2N], and [emim][SCN]. As refrigerant NH3 was chosen due to its favorable operating range. The results are compared to the traditional approach in which parameters of a thermodynamic model are fitted to reproduce experimental data. The work shows that simulations can be used to predict the required thermodynamic properties to estimate the performance of absorption refrigeration cycles. However, high-quality force fields are required to accurately predict the cycle performance.@en

On the short term, carbon capture is a viable solution to reduce human-induced CO2 emissions, which requires an energy efficient separation of CO2. Metal-organic frameworks (MOFs) may offer opportunities for carbon capture and other industrially relevant separations. Especially, MOFs with embedded open metal sites have been shown to be promising. Molecular simulation is a useful tool to predict the performance of MOFs even before the synthesis of the material. This reduces the experimental effort, and the selection process of the most suitable MOF for a particular application can be accelerated. To describe the interactions between open metal sites and guest molecules in molecular simulation is challenging. Polarizable force fields have potential to improve the description of such specific interactions. Previously, we tested the applicability of polarizable force fields for CO2 in M-MOF-74 by verifying the ability to reproduce experimental measurements. Here, we develop a predictive polarizable force field for CO2 in M-MOF-74 (M = Co, Fe, Mg, Mn, Ni, Zn) without the requirement of experimental data. The force field is derived from energies predicted from quantum mechanics. The procedure is easily transferable to other MOFs. To incorporate explicit polarization, the induced dipole method is applied between the framework and the guest molecule. Atomic polarizabilities are assigned according to the literature. Only the Lennard-Jones parameters of the open metal sites are parameterized to reproduce energies from quantum mechanics. The created polarizable force field for CO2 in M-MOF-74 can describe the adsorption well and even better than that in our previous work.@en