The separation of C8 aromatic hydrocarbons (e.g. xylenes) is one of the most important processes in the petrochemical industry. Current research efforts are focused on materials that can decrease the energy consumption and increase the efficiency of the separation process. Industrial processing of C8 aromatics typically considers adsorption in a zeolite from a vapor or liquid stream of mixed aromatics. Adsorption in porous materials can be used to separate the isomers or to promote catalytic reactions to transform aromatics into high value products. However, little is known about the chemical equilibrium of the adsorbed phase at reaction conditions. Most studies of adsorption of aromatics in zeolites, either experimental or computational, have focused on adsorption of pure components from the vapor phase. Experimentally, it is very difficult to determine adsorption equilibrium at saturation conditions. In molecular simulations, very difficult insertions and deletions of molecules make simulations very inefficient. Nowadays, advanced simulations techniques can be used to overcome this issue. Computer simulations of adsorption of aromatics in zeolites are typically performed using rigid zeolite frameworks. However, it is known that adsorption isotherms for aromatics are very sensitive to small differences in the atomic positions of the zeolite. In this thesis, the following types of questions are addressed: (1) how does framework flexibility influence adsorption and diffusion of C8 aromatics in zeolites?; (2) what is the role of the pore topology? For the separation and catalytic conversion of xylenes; (3) how does the type of framework influence the product distribution of xylene isomers?; (4) are there any possible zeolite structures that may have been overlooked for the processing of aromatics? For this, the different aspects that affect the interactions between aromatic molecules and the aromatics/zeolite systems in the simulations are discussed. The intermolecular interactions between aromatic molecules are studied by computing the vapor-liquid equilibria of pure xylenes and binary mixtures using four different force fields. The densities of pure p-xylene and m xylene can be well estimated using the TraPPE-UA and AUA force fields. The largest differences of computed VLEs with experiments are observed for o-xylene. Binary mixtures of p xylene and o-xylene are simulated, leading to an excellent agreement for the predictions of the composition of the liquid phase compared to experiments. For the vapor phase, the accuracy of the predictions of the composition are linked to the quality of the density predictions of the pure components of the mixture. The phase composition of the binary system of xylenes is very sensitive to small differences in vapor phase density of each xylene isomer, and how well the differences are captured by the force fields. Most of the models commonly used for framework flexibility in zeolites include a combination of Lennard-Jones and electrostatic intra framework interactions. The effect of these models for framework flexibility on the predictions of adsorption of aromatics in zeolites is studied. It is observed that the intra framework interactions in flexible framework models induce small but important changes in the atom positions of the zeolite, and hence in the adsorption isotherms. Framework flexibility is differently ’rigid’: flexible force fields produce a zeolite structure that vibrates around a new equilibrium configuration with limited capacity to accommodate to bulky guest molecules. The simulations show that models for framework flexibility should not be blindly applied to zeolites and a general reconsideration of the parametrisation schemes for such models is needed. The effect of framework flexibility on the adsorption and diffusion of aromatics in MFI-type zeolite is systematically studied. It is found that framework flexibility has a significant effect on the adsorption of aromatics in zeolites, specially at high pressures. For very flexible zeolite frameworks, loadings up to two times larger than in a rigid zeolite framework are obtained at a given pressure. Framework flexibility increases the rate of diffusion of aromatics in the straight channel of MFI-type zeolites by many orders of magnitude compared to a rigid zeolite framework. The simulations show that framework flexibility should not be neglected and that it significantly affects the diffusion and adsorption properties of aromatics in a MFI-type zeolite. The interactions of aromatic molecules inside different zeolite types are studied by computing adsorption isotherms of pure xylenes and a mixture of xylenes at chemical equilibrium. It is observed that for zeolites with one dimensional channels, the selectivity for a xylene isomer is determined by a competition of entropic and enthalpic effects. Each of these effects is related to the diameter of the zeolite channel. For zeolites with two intersecting channels, the selectivity is determined by the orientation of the methyl groups of xylenes. m-Xylene is preferentially adsorbed if xylenes fit tightly in the intersection of the channels. If the intersection is much larger than the adsorbed molecules, p-xylene is preferentially adsorbed. This thesis provides insight on how the zeolite framework can influence the competitive adsorption and selectivity of xylenes at reaction conditions. Different selectivities are observed when molecules are adsorbed from a vapor phase compared to the adsorption from a liquid phase. This suggests that screening studies that consider adsorption only from a vapor phase may have overlooked well-performing candidates for C8 aromatics processing. This insight has a direct impact on the design criteria for future applications of zeolites in industry. It is observed that MRE-type and AFI-type zeolites exclusively adsorb p-xylene and o-xylene from a mixture of xylenes in the liquid phase, respectively. These zeolite types show potential to be used as high-performing molecular sieves for xylene separation and catalysis.

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The separation of xylenes is one of the most important processes in the petrochemical industry. In this article, the competitive adsorption from a fluid-phase mixture of xylenes in zeolites is studied. Adsorption from both vapor and liquid phases is considered. Computations of adsorption of pure xylenes and a mixture of xylenes at chemical equilibrium in several zeolite types at 250 °C are performed by Monte Carlo simulations. It is observed that shape and size selectivity entropic effects are predominant for small one-dimensional systems. Entropic effects due to the efficient arrangement of xylenes become relevant for large one-dimensional systems. For zeolites with two intersecting channels, the selectivity is determined by a competition between enthalpic and entropic effects. Such effects are related to the orientation of the methyl groups of the xylenes. m-Xylene is preferentially adsorbed if xylenes fit tightly in the intersection of the channels. If the intersection is much larger than the adsorbed molecules, p-xylene is preferentially adsorbed. This study provides insight into how the zeolite topology can influence the competitive adsorption and selectivity of xylenes at reaction conditions. Different selectivities are observed when a vapor phase is adsorbed compared to the adsorption from a liquid phase. These insight have a direct impact on the design criteria for future applications of zeolites in the industry. MRE-type and AFI-type zeolites exclusively adsorb p-xylene and o-xylene from the mixture of xylenes in the liquid phase, respectively. These zeolite types show potential to be used as high-performing molecular sieves for xylene separation and catalysis.@en

We systematically study how the degree of framework flexibility affects the adsorption and diffusion of aromatics in MFI-type zeolites as computed by Monte Carlo simulations. It is observed that as the framework is more flexible, the zeolite structure is inherently changed. We have found that framework flexibility has a significant effect on the adsorption of aromatics in MFI-type zeolites, especially at high pressure. Framework flexibility allows the zeolite framework to accommodate to the presence of guest aromatic molecules. For very flexible zeolite frameworks, loadings up to two times larger than that in a rigid zeolite framework are obtained at a given pressure. We assessed the "flexible snapshot"method, which captures framework flexibility using independent snapshots of the framework. We have found that this method only works well when the loadings are low. This suggests that the effect of the guest molecules on the zeolite framework is important. Framework flexibility lowers the free-energy barriers between low energy states, increasing the rate of diffusion of aromatics in the straight channel of MFI-type zeolites for many orders of magnitude compared to a rigid zeolite framework. The simulations show that framework flexibility should not be neglected and that it significantly affects the diffusion and adsorption properties of aromatics in an MFI-type zeolite.

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We present a new molecular simulation code, Brick-CFCMC, for performing Monte Carlo simulations using state-of-the-art simulation techniques. The Continuous Fractional Component (CFC) method is implemented for simulations in the NVT/NPT ensembles, the Gibbs Ensemble, the Grand-Canonical Ensemble, and the Reaction Ensemble. Molecule transfers are facilitated by the use of fractional molecules which significantly improve the efficiency of the simulations. With the CFC method, one can obtain phase equilibria and properties such as chemical potentials and partial molar enthalpies/volumes directly from a single simulation. It is possible to combine trial moves from different ensembles. This enables simulations of phase equilibria in a system where also a chemical reaction takes place. We demonstrate the applicability of our software by investigating the esterification of methanol with acetic acid in a two-phase system.

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Vapor-liquid equilibria of xylenes were computed using Monte Carlo simulations in the Gibbs ensemble. For binary mixtures, the predicted composition of the liquid phase is in agreement with experiments. The computed vapor phase densities of each isomer showed an effect on the predicted composition of the vapor phase of the mixture. Unfortunately, the Monte Carlo code used to calculate the vapor-liquid equilibrium contained an error in the acceptance rule for molecule transfer in multi-component mixtures. The Continuous Fractional Component (CFCMC) [1–3] algorithm in the Gibbs ensemble adds an extra molecule -the fractional molecule-per molecule type. In the CFCMC algorithm, trial moves are attempted to transform a fractional molecule of type a in box i to a whole molecule and, simultaneously, transform a molecule of type a in box j [Formula presented] i to a fractional molecule. These trial moves should be accepted according to Ref. [1]: [Formula presented] where [Formula presented] is the number of molecules of type a in box j, [Formula presented] is the number of molecules of type a in box i, and [Formula presented] is the energy difference between the old and the new configuration. Unfortunately, what was implemented (incorrectly) in the computer code is: [Formula presented] where [Formula presented] and [Formula presented] are the total number of molecules of all types in box i and j, respectively, and not only of type a. For the simulation of a single component, [Formula presented] and [Formula presented]. Therefore, the mistake in the acceptance rule only affects the simulations that include more than one component. As such, Figs. 1, Fig. 2, Fig. 3, Fig. 4, and Table 1 of the article are not affected by this error. This error was hard to detect for xylene isomers, as the boiling point of these isomers are close, and therefore [Formula presented] is close to [Formula presented]. The corrected code has been tested to yield the same results as the RASPA software [4,5] for various multi-component systems. The phase composition diagram using the correct code is shown in Fig. 5. The observations based on the incorrect results remain. The composition of the liquid phase is not affected by the choice of force field or method for electrostatic interactions. For all the force fields, the correct vapor phase composition calculated with the Ewald and the Wolf methods are closer than in the incorrect simulations. In the incorrect results, the largest difference between vapor phase composition calculated with the Wolf and the Ewald method was 0.089 [mol/mol]. In the correct results, this difference is reduced to 0.067 [mol/mol]. [Figure presented] The predicted composition of the liquid phase is in excellent agreement with the experimental data. The correct simulations of the vapor phase compositions are closer to the experimental data than the incorrect simulations. The simulations with the incorrect acceptance rules showed an azeotrope behaviour that is not present in the correct simulations of the phase compositions. [Figure presented] The phase composition of the binary mixture and the excess chemical potential are not related. This is consistent with the observations from the incorrect simulations. [Formula presented] The predicted composition of the liquid phase is in excellent agreement with the experimental data. The correct simulations of the vapor phase compositions are closer to the experimental data than the incorrect simulations. The simulations with the incorrect acceptance rules showed an azeotrope behaviour that is not present in the correct simulations. [Figure presented]@en

Computer simulations of adsorption of aromatics in zeolites are typically performed using rigid zeolite frameworks. However, adsorption isotherms for aromatics are very sensitive to small differences in the atomic positions of the zeolite (Chem. Phys. Lett., 1999, 308, 155-159). This article studies the effect of framework flexibility on the adsorption of aromatics in MFI-type zeolites computed by grand-canonical Monte Carlo simulations. New experimental data of adsorption of ethylbenzene in a MFI-type zeolite at 353 K is presented. The adsorption of n-heptane, ethylbenzene, and xylene isomers is computed in three MFI-type zeolite structures. It is observed that the intraframework interactions in flexible framework models induce small but important changes in the atom positions of the zeolite and hence in the adsorption isotherms. Framework flexibility is differently "rigid": flexible force fields produce a zeolite structure that vibrates around a new equilibrium configuration with limited capacity to accommodate to a bulky guest molecule. The vibration of the zeolite atoms only plays a role at high loadings, and the adsorption is mainly dependent on the average positions of the atoms. The simulations show that models for framework flexibility should not be blindly applied to zeolites and a general reconsideration of the parametrization schemes for such models is needed.

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This article explores how well vapor-liquid equilibria of pure components and binary mixtures of xylenes can be predicted using different force fields in molecular simulations. The accuracy of the Wolf method and the Ewald summation is evaluated. Monte Carlo simulations in the Gibbs ensemble are performed at conditions comparable to experimental data, using four different force fields. Similar results using the Wolf and the Ewald methods can be obtained for the prediction of densities and the phase compositions of binary mixtures. With the Wolf method, up to 50% less CPU time is used compared to the Ewald method, at the cost of accuracy and additional parameter calibration. The densities of p-xylene and m-xylene can be well estimated using the TraPPE-UA and AUA force fields. The largest differences of VLE with experiments are observed for o-xylene. The p-xylene/o-xylene binary mixtures at 6.66 and 81.3 kPa are simulated, leading to an excellent agreement in the predictions of the composition of the liquid phase compared to experiments. The composition of the vapor phase is dominated by the properties of the component with the largest mole fraction in the liquid phase. The accuracy of the predictions of the phase composition are related to the quality of the density predictions of the pure component systems. The phase composition of the binary system of xylenes is very sensitive to slight differences in vapor phase density of each xylene isomer, and how well the differences are captured by the force fields.

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