A reactor model that deconvolutes thermodynamics of adsorption of hydrocarbon in the pores of zeolite Beta, obtained by Configurational-bias Monte Carlo simulations, from intrinsic, intraporous kinetics of hydroisomerization and hydrocracking reactions, provides a good quantitative description of all significant reactions in the kinetic network for interconversion and cracking of different heptane isomers. Activation enthalpies obtained for intraporous reactions follow the expected order according to the carbenium ion formalism: methyl shift< ethyl shift < isom(B) ∼ crack(B2) < crack(B1) < crack(C) ∼ crack(D) < crack(E) and apparently within each isomerization class, in terms of carbenium ions formally involved: sec → tert < sec → sec ∼ tert → tert < tert → sec. except for the ethyl shift reaction forming 3-ethylpentane. Cracking happens primarily through 2,4-dimethylpentane (type B2), regardless of the initial reactant. The model can be subsequently used to separate the effect of pore structure on selective adsorption and on intraporous reaction kinetics. Zeolite Beta will serve as a base case for a comparison of different zeolite structures.@en

The alkylation of isobutane with light alkenes plays an essential role in modern petrochemical processes for the production of high-octane gasoline. In this study we have employed periodic DFT calculations combined with microkinetic simulations to investigate the complex reaction mechanism of isobutane–propene alkylation catalyzed by zeolitic solid acids. Particular emphasis was given to addressing the selectivity of the alkylate formation versus alkene formation, which requires a high rate of hydride transfer in comparison to the competitive oligomerization and deprotonation reactions resulting in catalyst deactivation. Our calculations reveal that hydride transfer from isobutane to a carbenium ion occurs via a concerted C–C bond formation between a tert-butyl fragment and an additional olefin, or via deprotonation of the tert-butyl fragment to generate isobutene. A combination of high isobutane concentration and low propene concentration at the reaction center favor the selective alkylation. The key reaction step that has to be suppressed to increase the catalyst lifetime is the deprotonation of carbenium intermediates that are part of the hydride transfer reaction cycle.@en

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.@en

In this study, Pt nanoparticles on zeolite/γ-Al2O3 composites (50/50 wt) were located either in the zeolite or on the γ-Al2O3 binder, hereby varying the average distance (intimacy) between zeolite acid sites and metal sites from "closest"to "nanoscale". The catalytic performance of these catalysts was compared to physical mixtures of zeolite and Pt/γ-Al2O3 powders, which provide a "microscale"distance between sites. Several beneficial effects on catalytic activity and selectivity for n-heptane hydroisomerization were observed when Pt nanoparticles are located on the γ-Al2O3 binder in nanoscale proximity with zeolite acid sites, as opposed to Pt nanoparticles located inside zeolite crystals. On ZSM-5-based catalysts, mostly monobranched isomers were produced, and the isomer selectivity of these catalysts was almost unaffected with an intimacy ranging from closest to microscale, which can be attributed to the high diffusional barriers of branched isomers within ZSM-5 micropores. For composite catalysts based on large-pore zeolites (zeolite Beta and zeolite Y), the activity and selectivity benefitted from the nanoscale intimacy with Pt, compared to both the closest and microscale intimacies. Intracrystalline gradients of heptenes as reaction intermediates are likely contributors to differences in activity and selectivity. This paper aims to provide insights into the influence of the metal-acid intimacy in bifunctional catalysts based on zeolites with different framework topologies. @en

Chemical potentials of coexisting gas and liquid phases for water, methanol, hydrogen sulphide and carbon dioxide for the temperature range (Formula presented.) K to (Formula presented.) K are computed using two different methodologies: (1) Widom’s test particle insertion (WTPI) method in the conventional Gibbs Ensemble (GE), and (2) the Continuous Fractional Component Gibbs Ensemble Monte Carlo (CFCGE MC) method. It is shown that the WTPI method fails to accurately compute the chemical potentials of water and methanol in the liquid phase at low temperatures, while accurate chemical potentials in the liquid phase are computed using CFCGE MC method. For the CFCGE MC method, the statistical uncertainty for computed chemical potentials of water and methanol in the liquid phase are considerably smaller compared to the WTPI method. For the water models considered in this study (SPC, TIP3P-EW, TIP4P-EW, TIP5P-EW), computed excess chemical potentials based on three-site models are in better agreement with the chemical potentials computed from an empirical equation of state from the NIST database. For water, orientational biasing is applied during test particle insertion to check whether certain orientations of test particle are energetically unfavourable. A two-dimensional Overlapping Distribution Method (ODM) in the NVT ensemble is derived for this purpose. It is shown that failure of the WTPI method for systems with a strong hydrogen bonding network does not depend on orientation of the test molecule in that system. For all systems in this study, the WTPI method breaks down when the void fraction of the system drops below approximately 0.50.@en

It is shown that ensemble averages computed in the Gibbs Ensemble with Continuous Fractional Component Monte Carlo (CFCMC GE) are different from those computed in the conventional Gibbs Ensemble (GE). However, it is possible to compute averages corresponding to the conventional GE while performing simulations in the CFCMC GE. In this way, one can benefit from the nice features of CFCMC GE (e.g. more efficient particle exchange) and at the same time compute the ensemble averages that correspond to the conventional GE. As a case study, the equilibrium pressure and densities of the systems of 256 and 512 LJ particles at different reduced temperatures ((Formula presented.)) are computed in the conventional GE and CFCMC GE. The validity of the expressions derived for computation of the thermodynamic pressure and densities corresponding to the conventional GE and computed in the CFCMC GE is examined numerically. The thermodynamic pressure in the conventional GE and CFCMC GE typically differs by at most 4%. It is shown that a very good estimate of the average pressure and densities corresponding to the conventional GE can be obtained by performing simulation in CFCMC GE and ignoring the contributions of the fractional molecule. It is also shown that the fractional molecule does not have an influence on the structure of the liquid, even for very small system sizes (e.g. 40 particles). The approach used here to compute the equilibrium pressure and densities of the conventional GE using the CFCMC GE can be easily extended to other thermodynamic properties and other ensembles.@en

The influence of product shape selectivity on the bifunctional conversion of n-C7 by zeolite catalysts is investigated. Three different zeolite catalysts with different pore sizes (MFI-type, MEL-type, and BEA-type zeolites) have been investigated experimentally. For all three catalysts, n-C7 is isomerized to monobranched isomers which are further isomerized into dibranched isomers, and these dibranched molecules are converted into cracking products. More dibranched isomers and less cracking products are produced by BEA-type zeolite compared to MFI-type and MEL-type zeolites and clear differences are observed in the distribution of dibranched isomers produced by different catalysts. Molecular simulation is used to compute the adsorption isotherms and free energy barriers for diffusion of dibranched isomers in MFI-type, MEL-type, and BEA-type zeolites. Combining simulation results and experimental observations, it is shown that product shape selectivity can explain the distribution of dibranched molecules while transition state shape selectivity fails to do so. For the medium-pore zeolites (MFI-type and MEL-type zeolites), free energy barriers for diffusion of dibranched molecules are significant. For MFI-type and MEL-type zeolites, the dibranched molecule that has to overcome lower diffusion barrier is produced with a higher yield and the distribution of dimethylpentane molecules is determined by their diffusion rate. It is shown that there is almost no free energy barrier for the diffusion of any of these molecules in BEA-type zeolite. As BEA-type zeolite imposes no free energy barrier for diffusion of any of dibranched isomers, the distribution of dibranched isomers is very close to the equilibrium distribution in the gas phase. Due to the limited mobility of dimethylpentanes within the pores of MFI-type and MEL-type zeolites, most of the dimethylpentane molecules are trapped inside the zeolite and undergo consecutive cracking. Dimethylpentane molecules diffuse sufficiently fast in the large pores of BEA-type zeolite and transfer to the gas phase, before consecutive reaction converts these molecules into cracking products. Moreover, the effect of the MFI-type crystal size on the production of dibranched isomers is investigated. The yield of dibranched isomers reduces by increasing the size of the crystal and larger part of dibranched isomers are cracked as the crystal size of MFI-type is increased.@en

Monte Carlo simulation (MC) is combined with equations of state (EoS) to develop a methodology for the calculation of the vapor–liquid equilibrium (VLE) of multicomponent hydrocarbon mixtures with high asymmetry. MC simulations are used for the calculation of the VLE of binary methane mixtures with long n-alkanes, for a wide range of temperatures and pressures, to obtain sufficient VLE data for the consistent fitting of binary interaction parameters (BIPs) for the EoS. The Soave-Redlich-Kwong (SRK), Peng-Robinson (PR), and Perturbed Chain - Statistical Associating Fluid Theory (PC-SAFT) EoS are considered. The ability of each EoS to correlate the VLE data is assessed and the selected ones are used to predict the VLE of multicomponent gas condensate mixtures. MC simulations proved to be very accurate in predicting the VLE in all conditions and mixtures considered. The BIPs regressed from the simulation dataset lead to equally accurate modeling results for multicomponent mixtures, compared to those regressed from experimental data.@en

An alternative method for calculating partial molar excess enthalpies and partial molar volumes of components in Monte Carlo (MC) simulations is developed. This method combines the original idea of Frenkel, Ciccotti, and co-workers with the recent continuous fractional component Monte Carlo (CFCMC) technique. The method is tested for a system of Lennard–Jones particles at different densities. As an example of a realistic system, partial molar properties of a [NH3, N2, H2] mixture at chemical equilibrium are computed at different pressures ranging from P = 10 to 80 MPa. Results obtained from MC simulations are compared to those obtained from the PC-SAFT Equation of State (EoS) and the Peng–Robinson EoS. Excellent agreement is found between the results obtained from MC simulations and PC-SAFT EoS, and significant differences were found for PR EoS modelling. We find that the reaction is much more exothermic at higher pressures.@en

According to the European Commission, in 2016 the residential sector represented 25.4% of the final energy consumption. Heating and cooling in EU households account for 69.1% of the total energy consumption. The fraction of 84% for heating and cooling is still generated from fossil fuels, and only 16% is generated from renewable energy. To decrease carbon dioxide emissions of fossil fuel consumption, it is crucial to find alternatives to supply the heating and cooling demand. Alternatives such as adsorption-based heat pumps and desiccant cooling systems are receiving much attention because of their moderate energy consumption. These systems are based on the energetic exchange during the adsorption/desorption of working fluids. In this work, we combined experiments and simulations to evaluate the viability of several zeolites and MOFs with water for cooling systems applications. We combined the study of adsorption mechanisms and the dynamics of water inside the pores of the structures, thereby obtaining an overall understanding of the working pair. We found that the Al content in FAU-topology zeolites is a key factor for an efficient process. We also identify ZJNU-30 metal–organic framework as a suitable candidate for cooling applications because of its outstanding water capacity, cooling capacity, and coefficient of performance.@en

A mathematical model is used to predict adsorption isotherms from experimentally measured breakthrough curves. Using this approach, by performing only breakthrough experiments for a mixture of two (or more) components, one can obtain pure component adsorption isotherms up to the pressure of the experiment. As a case study, the adsorption of an equimolar mixture of CO2 and CH4 in zeolite ITQ-29 is investigated. Pure component linear adsorption isotherms for CO2 and CH4 are predicted by fitting the theoretical breakthrough curves to the experimental ones. Henry coefficients obtained from our approach are in excellent agreement with those measured experimentally. A similar procedure is applied to predict the complete Langmuir adsorption isotherm from breakthrough curves at high pressures. The resulting adsorption isotherms are in very good agreement with those measured experimentally. In our model for transient adsorption, mass transfer from the gas phase to the adsorbed phase is considered using the Linear Driving Force model and dispersion of the gas phase in the packed bed is taken into account. IAST is used to compute the equilibrium loadings for a mixture of gases. The influence of the dispersion coefficient and the effective mass transfer coefficient on the shape of breakthrough curves is investigated and discussed. Rough estimations of these values are sufficient to predict adsorption isotherms from breakthrough curves.@en

The separation and purification of light hydrocarbons is challenging in the industry. Recently, a ZJNU-30 metal-organic framework (MOF) has been found to have the potential for adsorption-based separation of olefins and diolefins with four carbon atoms [H. M. Liu et al. Chem. - Eur. J. 2016, 22, 14988-14997]. Our study corroborates this finding but reveals Fe-MOF-74 as a more efficient candidate for the separation because of the open metal sites. We performed adsorption-based separation, transient breakthrough curves, and density functional theory calculations. This combination of techniques provides an extensive understanding of the studied system. Using this MOF, we propose a separation scheme to obtain a high-purity product.@en

The complicated interplay between mass and photon transfer within a photocatalytic reactor calls for an integrated design approach. A model-based optimization approach for LED-based photocatalytic reactors is presented. First, a model that describes the distribution of reactants and photons within a photocatalytic reactor is developed. Then, several design variables related to the reactor dimensions and light sources are optimized simultaneously using the photocatalytic degradation of toluene as a model system. The results demonstrate how different formulations of the problem can be used to either minimize the reactor cost or to obtain a specified concentration profile within the reactor.@en

The design and operation of reactors for photocatalytic degradation of organic pollutants remains challenging due to the complex interplay of photon, mass, and heat transfer. An integrated process model including a radiation field, reaction kinetics, and material balances of an annular LED-based photocatalytic reactor for photocatalytic degradation of toluene is validated using experimental data from a mini-pilot plant. A particular emphasis is on the effect of water on reaction kinetics, toluene conversion, mineralization, and catalyst deactivation, which is currently not well understood. The results from parameter estimation demonstrate that a competitive reaction rate model describes the experimental data with varying water concentration best. Furthermore, experimental trends demonstrate that toluene conversion is highest at low water concentrations, however, mineralization and catalyst lifetime are enhanced by the presence of water. The validation of the integrated process model and understanding of the role of water allow for improved design and operation of future photocatalytic reactors.@en

The design and operation of reactors for photocatalytic degradation of organic pollutants remains challenging due to the complex interplay of photon, mass, and heat transfer. An integrated process model including a radiation field, reaction kinetics, and material balances of an annular LED-based photocatalytic reactor for photocatalytic degradation of toluene is validated using experimental data from a mini-pilot plant. A particular emphasis is on the effect of water on reaction kinetics, toluene conversion, mineralization, and catalyst deactivation, which is currently not well understood. The results from parameter estimation demonstrate that a competitive reaction rate model describes the experimental data with varying water concentration best. Furthermore, experimental trends demonstrate that toluene conversion is highest at low water concentrations, however, mineralization and catalyst lifetime are enhanced by the presence of water. The validation of the integrated process model and understanding of the role of water allow for improved design and operation of future photocatalytic reactors.@en

Many important industrial separation processes based on adsorption operate close to saturation. In this regime, the underlying adsorption processes are mostly driven by entropic forces. At equilibrium, the entropy of adsorption is closely related to the enthalpy of adsorption. Thus, studying the behavior of the enthalpy of adsorption as a function of loading is fundamental in the understanding of the separation processes. Unfortunately, close to saturation, the enthalpy of adsorption is hard to measure experimentally and hard to compute in simulations. In simulations the enthalpy of adsorption is usually obtained from energy/particle fluctuations in the grand-canonical ensemble, but this methodology is hampered by vanishing insertions/deletions at high loading. To investigate the fundamental behavior of the enthalpy and entropy of adsorption at high loading, we develop a simplistic model of adsorption in a channel and show that at saturation the enthalpy of adsorption diverges to large positive values due to repulsive intermolecular interactions. However, there are many systems that can avoid repulsive intermolecular interactions and hence do not show this drastic increase in enthalpy of adsorption close to saturation. We find that the conventional grand-canonical Monte Carlo (GCMC) method is incapable of determining the enthalpy of adsorption from energy/particle fluctuations at high loading. Here, we show that by using the Continuous Fractional Component Monte Carlo (CFCMC), the enthalpy of adsorption close to saturation conditions can be reliably obtained from the energy/particle fluctuations in the grand-canonical ensemble. The best method to study properties at saturation is the NVT energy (local-) slope methodology. @en

A new formulation of the Reaction Ensemble Monte Carlo technique (RxMC) combined with the Continuous Fractional Component Monte Carlo method is presented. This method is denoted by serial Rx/CFC. The key ingredient is that fractional molecules of either reactants or reaction products are present and that chemical reactions always involve fractional molecules. Serial Rx/CFC has the following advantages compared to other approaches: (1) One directly obtains chemical potentials of all reactants and reaction products. Obtained chemical potentials can be used directly as an independent check to ensure that chemical equilibrium is achieved. (2) Independent biasing is applied to the fractional molecules of reactants and reaction products. Therefore, the efficiency of the algorithm is significantly increased, compared to the other approaches. (3) Changes in the maximum scaling parameter of intermolecular interactions can be chosen differently for reactants and reaction products. (4) The number of fractional molecules is reduced. As a proof of principle, our method is tested for Lennard-Jones systems at various pressures and for various chemical reactions. Excellent agreement was found both for average densities and equilibrium mixture compositions computed using serial Rx/CFC, RxMC/CFCMC previously introduced by Rosch and Maginn (Journal of Chemical Theory and Computation, 2011, 7, 269–279), and the conventional RxMC approach. The serial Rx/CFC approach is also tested for the reaction of ammonia synthesis at various temperatures and pressures. Excellent agreement was found between results obtained from serial Rx/CFC, experimental results from literature, and thermodynamic modeling using the Peng–Robinson equation of state. The efficiency of reaction trial moves is improved by a factor of 2 to 3 (depending on the system) compared to the RxMC/CFCMC formulation by Rosch and Maginn.@en

Separation and selective production of branched paraffins are among the most important and still challenging processes in the oil and gas industry. Addition of branched hydrocarbons can increase the octane number of a fuel without causing additional environmental concerns. Conversion of linear hydrocarbons into branched ones also improves the performance of lubricants at low temperatures. Zeolites are commonly used for separation of branched hydrocarbons and selective conversion of linear long chain hydrocarbons into shorter branched ones...@en

A new formulation of the Gibbs ensemble (GE) combined with the continuous fractional component Monte Carlo method is presented. In the proposed formulation, only a single fractional molecule per component is used instead of two in the original formulation by Shi and Maginn ( J. Comput. Chem. 2008, 29, 2520−2530). This has the following advantages: (1) one directly obtains chemical potentials, without using test particles. We show analytically that the expressions for the chemical potential are identical to those in the conventional Gibbs ensemble; (2) biasing is applied to each simulation box independently; (3) maximum allowed changes in the scaling parameter of intermolecular interactions can be chosen differently in each simulation box. Obtaining chemical potentials directly facilitates thermodynamic modeling using equations of state, and it can be used as an independent check to ensure that chemical equilibrium is achieved. As a proof of principle, our method is tested for Lennard-Jones (LJ) particles and the TIP3P-Ew water model. Results are compared with the conventional GE. Excellent agreement was found both for average densities and chemical potentials. In our new approach, the acceptance probability for molecule exchanges between the boxes is much higher (typically larger than 40% for LJ particles) than for the conventional GE (typically lower than 2% for LJ particles). It is also shown that the contribution of the fractional molecule should be disregarded when computing ensemble averages such as the average energy per molecule and the average densities. The algorithm can be easily extended to mixtures and molecules with intramolecular interactions.@en