Adsorption of propane, propylene and isobutane on a metal–organic framework : molecular simulation and experiment

The separation of propane/propylene mixtures is the most energy-intensive operation practiced in the petrochemical industry. Adsorptive processes are currently viewed as a promising alternative to cryogenic distillation for the separation of these mixtures. In this paper, we explore the possibility of using a new metal-organic framework material, CuBTC, in adsorptive separation processes, particularly in a simulated moving bed (SMB) context using isobutane as a potential desorbent. A gravimetric method has been used to measure the adsorption equilibrium isotherms of propylene, propane and isobutane onto a commercial CuBTC powder over a temperature range from 323 to 423K and pressures up to 100kPa. These were complemented by a detailed experimental characterization of the structure of CuBTC using XRD and SEM techniques. Comparison of experimental isotherms with grand canonical Monte Carlo simulations in CuBTC showed that propane adsorption occurs preferentially in small octahedral pockets, while isobutame is excluded from these pockets due to its bulky structure. Propylene was seen to interact strongly with unsaturated metal sites, due to specific pi-Cu bonds. These interactions significantly enhance the affinity of this MOF for unsaturated hydrocarbons. Furthermore, in a range of temperatures and pressures, the affinity of CuBTC for isobutane is intermediate to that of propane and propylene. Our results suggest that CuBTC-isobutane is a very promising adsorbent-desorbent pair for use in SMB processes for propane/propylene separations

Torus and AGN properties of nearby Seyfert galaxies: Results from fitting IR spectral energy distributions and spectroscopy

We used the CLUMPY torus models and a Bayesian approach to fit the infrared spectral energy distributions (SEDs) and ground-based high-angular resolution mid-infrared spectroscopy of 13 nearby Seyfert galaxies. This allowed us to put tight constraints on torus model parameters such as the viewing angle, the radial thickness of the torus Y, the angular size of the cloud distribution sigma_torus, and the average number of clouds along radial equatorial rays N_0. The viewing angle is not the only parameter controlling the classification of a galaxy into a type 1 or a type 2. In principle type 2s could be viewed at any viewing angle as long as there is one cloud along the line of sight. A more relevant quantity for clumpy media is the probability for an AGN photon to escape unabsorbed. In our sample, type 1s have relatively high escape probabilities, while in type 2s, as expected, tend to be low. Our fits also confirmed that the tori of Seyfert galaxies are compact with torus model radii in the range 1-6pc. The scaling of the models to the data also provided the AGN bolometric luminosities, which were found to be in good agreement with estimates from the literature. When we combined our sample of Seyfert galaxies with a sample of PG quasars from the literature to span a range of L_bol(AGN)~10^{43}-10^{47}erg/s, we found plausible evidence of the receding torus. That is, there is a tendency for the torus geometrical covering factor to be lower at high AGN luminosities than at low AGN luminosities. This is because at low AGN luminosities the tori appear to have wider angular sizes and more clouds along radial equatorial rays. We cannot, however rule out the possibility that this is due to contamination by extended dust structures not associated with the dusty torus at low AGN luminosities, since most of these in our sample are hosted in highly inclined galaxies. (Abridged)Comment: Accepted for publication in Ap

Modeling adsorption in metal-organic frameworks with open metal sites : propane/propylene separations

We present a new approach for modeling adsorption in metal-organic frameworks (MOFs) with unsaturated metal centers and apply it to the challenging propane/propylene separation in copper(II) benzene-1,3,5-tricarboxylate (CuBTC). We obtain information about the specific interactions between olefins and the open metal sites of the MOP using quantum mechanical density functional theory. A proper consideration of all the relevant contributions to the adsorption energy enables us to extract the component that is due to specific attractive interactions between the pi-orbitals of the alkene and the coordinatively unsaturated metal. This component is fitted using a combination of a Morse potential and a power law function and is then included into classical grand canonical Monte Carlo simulations of adsorption. Using this modified potential model, together with a standard Lennard-Jones model, we are able to predict the adsorption of not only propane (where no specific interactions are present), but also of propylene (where specific interactions are dominant). Binary adsorption isotherms for this mixture are in reasonable agreement with ideal adsorbed solution theory predictions. We compare our approach with previous attempts to predict adsorption in MOFs with open metal sites and suggest possible future routes for improving our model

A Second-Generation Device for Automated Training and Quantitative Behavior Analyses of Molecularly-Tractable Model Organisms

A deep understanding of cognitive processes requires functional, quantitative analyses of the steps leading from genetics and the development of nervous system structure to behavior. Molecularly-tractable model systems such as Xenopus laevis and planaria offer an unprecedented opportunity to dissect the mechanisms determining the complex structure of the brain and CNS. A standardized platform that facilitated quantitative analysis of behavior would make a significant impact on evolutionary ethology, neuropharmacology, and cognitive science. While some animal tracking systems exist, the available systems do not allow automated training (feedback to individual subjects in real time, which is necessary for operant conditioning assays). The lack of standardization in the field, and the numerous technical challenges that face the development of a versatile system with the necessary capabilities, comprise a significant barrier keeping molecular developmental biology labs from integrating behavior analysis endpoints into their pharmacological and genetic perturbations. Here we report the development of a second-generation system that is a highly flexible, powerful machine vision and environmental control platform. In order to enable multidisciplinary studies aimed at understanding the roles of genes in brain function and behavior, and aid other laboratories that do not have the facilities to undergo complex engineering development, we describe the device and the problems that it overcomes. We also present sample data using frog tadpoles and flatworms to illustrate its use. Having solved significant engineering challenges in its construction, the resulting design is a relatively inexpensive instrument of wide relevance for several fields, and will accelerate interdisciplinary discovery in pharmacology, neurobiology, regenerative medicine, and cognitive science

Diffusion of propane, propylene and isobutane in 13X zeolite by molecular dynamics

This paper presents single component diffusion data of propane, propylene and isobutane in zeolite 13X obtained by molecular dynamics (MD) simulations, especially its dependence on temperature and concentration. Our results are critically compared to experiments and previous simulation data, when available. One novelty of this work is that the diffusion coefficients are computed taking the framework cations of zeolite 13X into consideration. Furthermore, to our knowledge, we present the first simulation results for propylene diffusion in faujasite frameworks. From the mean squared displacements, self-diffusion coefficients of 7.5 x 10(-9), 9.1 x 10(-9), and 9.6 x 10(-10) m(2) s(-1) for 2 molecules/unit cell were calculated for propane, propylene, and isobutane at 373 K, respectively. The simulations show that the diffusivity decreases with increasing loadings for all adsorbates studied. Finally, transport diffusivities were estimated from the self-diffusion coefficient and the equilibrium adsorption isotherms by using the Darken equation. (C) 2010 Elsevier Ltd. All rights reserved

Isobaric Vapor-Liquid Equilibrium for Binary Systems of 2,2,4-Trimethylpentane with o-Xylene, m-Xylene, p-Xylene, and Ethylbenzene at 250 kPa

Isobaric vapor liquid equilibrium (VLE) data were determined at the pressure of 250 kPa for the four binary mixtures composed of 2,2,4-trimethylpentane (isooctane) + para-, ortho-, or meta-xylene and ethylbenzene (EB) by using a circulation-type apparatus, in which both vapor and liquid phases are recirculated. The vapor- and liquid-phase compositions were analyzed by gas chromatography. All of the data were found to be thermodynamically consistent according to the Herington, van Ness, infinite dilution, and pure component consistency tests. The experimental data were regressed with Aspen Plus 7.3, and binary interaction parameters were reported for the most frequently used activity coefficient models: the nonrandom two-liquid (NRTL) and the universal quasichemical activity coefficient (UNIQUAC) models, respectively. All of the calculated values with these models showed good agreement with the experimental data, as well as with available isobaric and isothermal data from the literature

Isobaric Vapor–Liquid Equilibrium for Binary Systems of 2,2,4-Trimethylpentane with <i>o</i>‑Xylene, <i>m</i>‑Xylene, <i>p</i>‑Xylene, and Ethylbenzene at 250 kPa

Isobaric vapor–liquid equilibrium (VLE) data were determined at the pressure of 250 kPa for the four binary mixtures composed of 2,2,4-trimethylpentane (isooctane) + <i>para</i>-, <i>ortho</i>-, or <i>meta</i>-xylene and ethylbenzene (EB) by using a circulation-type apparatus, in which both vapor and liquid phases are recirculated. The vapor- and liquid-phase compositions were analyzed by gas chromatography. All of the data were found to be thermodynamically consistent according to the Herington, van Ness, infinite dilution, and pure component consistency tests. The experimental data were regressed with Aspen Plus 7.3, and binary interaction parameters were reported for the most frequently used activity coefficient models: the nonrandom two-liquid (NRTL) and the universal quasichemical activity coefficient (UNIQUAC) models, respectively. All of the calculated values with these models showed good agreement with the experimental data, as well as with available isobaric and isothermal data from the literature