Computational Study of Adsorption and Separation of CO(2), CH(4), and N(2) by an rht-Type Metal-Organic Framework

In this work, a computational study is performed to evaluate the adsorption-based separation of CO(2) from flue gas (mixtures of CO(2) and N(2)) and natural gas (mixtures of CO(2) and CH(4)) using microporous metal organic framework Cu-TDPAT as a sorbent material. The results show that electrostatic interactions can greatly enhance the separation efficiency of this MOF for gas mixtures of different components. Furthermore, the study also suggests that Cu-TDPAT is a promising material for the separation of CO(2) from N(2) and CH(4), and its macroscopic separation behavior can be elucidated on a molecular level to give insight into the underlying mechanisms. On the basis of the single-component CO(2), N(2), and CH(4) isotherms, binary mixture adsorption (CO(2)/N(2) and CO(2)/CH(4)) and ternary mixture adsorption (CO(2)/N(2)/CH(4)) were predicted using the ideal adsorbed solution theory (IAST). The effect of H(2)O vapor on the CO(2) adsorption selectivity and capacity was also examined. The applicability of IAST to this system was validated by performing GCMC simulations for both single-component and mixture adsorption processes.     

Molecular dynamics simulations of gas separations using faujasite-type zeolite membranes

Gas separations with faujasite zeolite membranes have been examined using the method of molecular dynamics. Two binary mixtures are investigated, oxygen/nitrogen and nitrogen/carbon dioxide. These mixtures have been found experimentally to exhibit contrasting behavior. In O(2)/N(2) mixtures the ideal selectivity (pure systems) is higher than the mixture selectivity, while in N(2)/CO(2) the mixture selectivity is higher than the ideal selectivity. One of the key goals of this work was to seek a fundamental molecular level understanding of such divergent behavior. Our simulation results (using previously developed intermolecular models for both the gases and zeolites investigated) were found to replicate this experimental behavior. By examining the loading of the membranes and the diffusion rates inside the zeolites, we have been able to explain such contrasting behavior of O(2)/N(2) and N(2)/CO(2) mixtures. In the case of O(2)/N(2) mixtures, the adsorption and loading of both O(2) and N(2) in the membrane are quite competitive, and thus the drop in the selectivity in the mixture is primarily the result of oxygen slowing the diffusion of nitrogen and nitrogen somewhat increasing the diffusion of oxygen when they pass through the zeolite pores. In N(2)/CO(2) systems, CO(2) is rather selectively adsorbed and loaded in the zeolite, leaving very little room for N(2) adsorption. Thus although N(2) continues to have a higher diffusion rate than CO(2) even in the mixture, there are so few N(2) molecules in the zeolite in mixtures that the selectivity of the mixture increases significantly compared to the ideal (pure system) values. We have also compared simulation results with hydrodynamic theories that classify the permeance of membranes to be either due to surface diffusion, viscous flow, or Knudsen diffusion. Our results show surface diffusion to be the dominant mode, except in the case of N(2)/CO(2) binary mixtures where Knudsen diffusion also makes a contribution to N(2) transport.     

Separation of CO2 and N2 by adsorption in C168 schwarzite: a combination of quantum mechanics and molecular simulation study

Using a hierarchical multiscale approach combining quantum mechanics and molecular simulation, we have investigated the adsorption of pure CO(2) and N(2) and their mixture at room temperature in C(168) schwarzite, as a model for nanoporous carbons. First, the adsorbate-adsorbent interaction potential is determined using ab initio quantum mechanics computations, and then the adsorption is predicted using full atomistic Monte Carlo simulations. The extents of adsorption, adsorption energies, and isosteric heats of pure CO(2) and N(2) simulated with the ab initio potential are found to be higher than those with the empirical Steele potential that had been developed from gas adsorption on planar graphite. The inclusion of the electric quadrupole moment of adsorbate in simulation has no discernible effect on N(2) adsorption but results in a larger extent of CO(2) adsorption at high coverages. The selectivity of CO(2) over N(2) in the C(168) schwarzite from a model flue gas is predicted to be significantly larger with the ab initio potential than with the Steele potential. This illustrates the importance of an accurate adsorbate-adsorbent interaction potential in determining gas adsorption and suggests that nanoporous carbons might be useful for the separation of flue gases. As a comparison, the adsorption and selectivity of CO(2) and N(2) in ZSM-5 zeolites are also simulated with the experimentally validated potential parameters. The selectivity in the C(168) schwarzite predicted with the ab initio or Steele potential is found to be larger than the selectivity in all-silica ZSM-5, but less than that in Na-exchanged ZSM-5 zeolites.     

In silico screening of metal-organic frameworks in separation applications

Porous materials such as metal-organic frameworks (MOFs) and zeolitic imidazolate frameworks (ZIFs) offer considerable potential for separating a variety of mixtures such as those relevant for CO(2) capture (CO(2)/H(2), CO(2)/CH(4), CO(2)/N(2)), CH(4)/H(2), alkanes/alkenes, and hydrocarbon isomers. There are basically two different separation technologies that can be employed: (1) a pressure swing adsorption (PSA) unit with a fixed bed of adsorbent particles, and (2) a membrane device, wherein the mixture is allowed to permeate through a micro-porous crystalline layer. In view of the vast number of MOFs, and ZIFs that have been synthesized there is a need for a systematic screening of potential candidates for any given separation task. Also of importance is to investigate how MOFs and ZIFs stack up against the more traditional zeolites such as NaX and NaY with regard to their separation characteristics. This perspective highlights the potency of molecular simulations in determining the choice of the best MOF or ZIF for a given separation task. A variety of metrics that quantify the separation performance, such as adsorption selectivity, working capacity, diffusion selectivity, and membrane permeability, are determined from a combination of Configurational-Bias Monte Carlo (CBMC) and Molecular Dynamics (MD) simulations. The practical utility of the suggested screening methodology is demonstrated by comparison with available experimental data.     

Molecular insight into the high selectivity of double-walled carbon nanotubes

Combining experimental knowledge with molecular simulations, we investigated the adsorption and separation properties of double-walled carbon nanotubes (DWNTs) against flue/synthetic gas mixture components (e.g. CO(2), CO, N(2), H(2), O(2), and CH(4)) at 300 K. Except molecular H(2), all studied nonpolar adsorbates assemble into single-file chain structures inside DWNTs at operating pressures below 1 MPa. Molecular wires of adsorbed molecules are stabilized by the strong solid-fluid potential generated from the cylindrical carbon walls. CO(2) assembly is formed at very low operating pressures in comparison to all other studied nonpolar adsorbates. The adsorption lock-and-key mechanism results from perfect fitting of rod-shaped CO(2) molecules into the cylindrical carbon pores. The enthalpy of CO(2) adsorption in DWNTs is very high and reaches 50 kJ mol(-1) at 300 K and low pore concentrations. In contrast, adsorption enthalpy at zero coverage is significantly lower for all other studied nonpolar adsorbates, for instance: 35 kJ mol(-1) for CH(4), and 14 kJ mol(-1) for H(2). Applying the ideal adsorption solution theory, we predicted that the internal pores of DWNTs have unusual ability to differentiate CO(2) molecules from other flue/synthetic gas mixture components (e.g. CO, N(2), H(2), O(2), and CH(4)) at ambient operating conditions. Computed equilibrium selectivity for equimolar CO(2)-X binary mixtures (where X: CO, N(2), H(2), O(2), and CH(4)) is very high at low mixture pressures. With an increase in binary mixture pressure, we predicted a decrease in equilibrium separation factor because of the competitive adsorption of the X binary mixture component. We showed that at 300 K and equimolar mixture pressures up to 1 MPa, the CO(2)-X equilibrium separation factor is higher than 10 for all studied binary mixtures, indicating strong preference for CO(2) adsorption. The overall selective properties of DWNTs seem to be superior, which may be beneficial for potential industrial applications of these novel carbon nanostructures.     

Ca2＋交换的几种分子筛的氮氩分离性能

采用水溶液离子交换法制备了Ca2＋交换的4A、13X和LSX分子筛，并在25 ℃下测定了它们的静态吸附等温线和动态穿透曲线.研究发现， Ca2＋交换的4A、13X和LSX分子筛对氮的吸附性能都明显优于其相应的钠型分子筛，而它们对氩的吸附量变化不大，说明Ca2＋交换的这三种分子筛是较好的氮氩分离吸附剂.从动态吸附的结果来看，所研究的各种分子筛都有一个最优的吸附分离压力，在本论文研究的压力范围内，这个最优压力在0.6 MPa附近.由穿透曲线可推算出混合气体的吸附量，通过氮和氩在混合气体中的吸附量和相应纯气体吸附量的对比可以得出，对于氮氩吸附选择性较高的分子筛，氮的存在对氩的吸附量有较大的影响.     

短链烷烃二元混合物在分子筛上吸附分离的分子模拟

用巨正则是系综Monte Carlo(GCMC)与构型偏倚(CBMC)相结合的方法模拟了 MFI分子筛对甲烷-丙烷、乙烷-丙烷体系(300K，345kPa)的吸附平衡，模拟结果与 文献实验结果相吻合，分别模拟了FER，ISV，MEL，MFI，MOR，TON等六种分子筛对 甲烷－丙烷、乙烷－丙烷体系（300K，345kPa）的吸附，得出甲烷－丙烷体系中分 子筛对较长链烷烃的选择性大小顺序（气相乙烷摩尔分数为0.5时）为ISV＞MEI＞ MEL＞FER＞TON＞MOR,对乙烷－丙烷体系选择性大小顺序（气相乙烷摩尔分数为0. 5时）为ISV＞MOR＞MFI＞FER＞MEL＞TON. MOR型分子筛对两个不同体系的吸附行为 表现出明显的不同，两个体中ISV的吸附量均最大，MFI，MEL，FER次之，此三种分 子筛具有相拟的吸附量，MOR和TON型分子筛吸附量较低。     

Entropy effects during sorption of alkanes in zeolites

Recent developments in Configurational-Bias Monte Carlo (CBMC) techniques allow the accurate calculation of the sorption isotherms for alkanes, and their mixtures, in various zeolites. The CBMC simulations give new insights into subtle entropy effects affecting mixture adsorption. Three types of entropy effects can be distinguished. (1) Size entropy effects favour the component with the smaller number of C atoms because the smaller molecule finds it easier to fill in the 'gaps' within the zeolite matrix at high molecular loadings. (2) Configurational entropy effects come into play for mixtures of alkanes that differ in the degree of branching. For a mixture of linear and branched alkanes with the same number of C atoms, configurational entropy effects favour the linear isomer because such molecules 'pack' more efficiently within, say, the intersecting channel topology of MFI zeolite. (3) Length entropy effects comes into force for sorption of linear and branched alkanes within the cylindrical channels of say AFI and MOR zeolites; here the double branched alkane has the shortest length and can be packed more efficiently within the channels. We demonstrate that CBMC simulations allow the efficient screening of zeolite structures for a given separation duty and aid the development of novel separation processes exploiting entropy effects.     

Adsorptive behavior of CO2, CH4 and their mixtures in carbon nanospace: a molecular simulation study

Using molecular simulation, four types of nanoporous carbons are examined as adsorbents for the separation of CO(2)/CH(4) mixtures at ambient temperature and pressures up to 10 MPa. First, the adsorption selectivity of CO(2) is investigated in carbon slit pores and single-walled carbon nanotube bundles in order to find the optimal pore dimensions for CO(2) separation. Then, the adsorptive properties of the optimized slit pore and nanotube bundle are compared with two realistic nanoporous carbon models: a carbon replica of zeolite Y and an amorphous carbon. For the four carbon models, adsorption isotherms and isosteric heats of adsorption are presented for both pure components and mixtures. Special attention is given to the calculation of excess isotherms and isosteric heats, which are necessary to assess the performance of model nanoporous materials in the context of experimental measurements. From these results, we discuss the impact that variables such as pore size, pore morphology, pressure and mixture composition have on the performance of nanoporous carbons for CO(2) separation.     

Titanium-decorated graphene oxide for carbon monoxide capture and separation

We propose titanium-decorated graphene oxide (Ti-GO) as an ideal sorbent for carbon monoxide (CO) capture and separation from gas mixtures. Based on first-principles calculations, Ti-GO exhibits a large binding energy of ~70 kJ mol(-1) for CO molecules, while the binding energies for other gases, such as N(2), CO(2), and CH(4), are significantly smaller. The gas adsorption properties of Ti-GO are independent of the local GO structures once Ti atoms are anchored by the oxygen-containing groups on the GO surface. The strong interaction between CO molecule and Ti is a result of dative bonding, i.e., hybridization between an empty d orbital of Ti and an occupied p orbital of CO. Adsorption isotherms from grand canonical Monte Carlo simulations clearly demonstrate the strong selectivity of Ti-GO for CO adsorption in a mixture with other gas.     

The adsorption and localization of mixtures of C4-C7 alkane isomers in zeolites by computer simulation

Grand canonical Monte Carlo and configurational-bias Monte Carlo techniques were employed to simulate the adsorption of binary mixtures of C(4)-C(7) alkane isomers in ISV and MOR zeolites at 300 K, and the results were compared to that in MFI. Unlike in MFI, the amount of adsorption of the linear and branched alkanes all increases with pressure increasing in ISV and MOR for 0.5-0.5 gas-phase mixtures. The location of alkane isomers is astatic, and it does not exhibit obvious orientation in ISV and MOR. The interaction energy of 2-methylpropane-zeolite is obviously higher than that of n-butane-zeolite in MFI. As to ISV and MOR, the interaction energy between 2-methylpropane and zeolite is a little lower than that between n-butane and zeolite. It can be found that the zeolite MFI behaves quite differently in adsorption from ISV and MOR.     

Synthesis of MIL-102, a chromium carboxylate metal-organic framework, with gas sorption analysis

A new three-dimensional chromium(III) naphthalene tetracarboxylate, CrIII3O(H2O)2F{C10H4(CO2)4}1.5.6H2O (MIL-102), has been synthesized under hydrothermal conditions from an aqueous mixture of Cr(NO3)3.9H2O, naphthalene-1,4,5,8-tetracarboxylic acid, and HF. Its structure, solved ab initio from X-ray powder diffraction data, is built up from the connection of trimers of trivalent chromium octahedra and tetracarboxylate moieties. This creates a three-dimensional structure with an array of small one-dimensional channels filled with free water molecules, which interact through hydrogen bonds with terminal water molecules and oxygen atoms from the carboxylates. Thermogravimetric analysis and X-ray thermodiffractometry indicate that MIL-102 is stable up to approximately 300 degrees C and shows zeolitic behavior. Due to topological frustration effects, MIL-102 remains paramagnetic down to 5 K. Finally, MIL-102 exhibits a hydrogen storage capacity of approximately 1.0 wt % at 77 K when loaded at 3.5 MPa (35 bar). The hydrogen uptake is discussed in relation with the structural characteristics and the molecular simulation results. The adsorption behavior of MIL-102 at 304 K resembles that of small-pore zeolites, such as silicalite. Indeed, the isotherms of CO2, CH4, and N2 show a maximum uptake at 0.5 MPa, with no further significant adsorption up to 3 MPa. Crystal data for MIL-102: hexagonal space group P(-)6 (No. 169), a = 12.632(1) A, c = 9.622(1) A.     

Finding MOFs for highly selective CO2/N2 adsorption using materials screening based on efficient assignment of atomic point charges

Electrostatic interactions are a critical factor in the adsorption of quadrupolar species such as CO(2) and N(2) in metal-organic frameworks (MOFs) and other nanoporous materials. We show how a version of the semiempirical charge equilibration method suitable for periodic materials can be used to efficiently assign charges and allow molecular simulations for a large number of MOFs. This approach is illustrated by simulating CO(2) and N(2) adsorption in ~500 MOFs; this is the largest set of structures for which this information has been reported to date. For materials predicted by our calculations to have promising adsorption selectivities, we performed more detailed calculations in which accurate quantum chemistry methods were used to assign atomic point charges, and molecular simulations were used to assess molecular diffusivities and binary adsorption isotherms. Our results identify two MOFs, experimentally known to be stable upon solvent removal, that are predicted to show no diffusion limitations for adsorbed molecules and extremely high CO(2)/N(2) adsorption selectivities for CO(2) adsorption from dry air and from gas mixtures typical of dry flue gas.     

CO2／CH4分离膜及沸石填料影响渗透过程的研究

报导了甲基硅橡胶和纤维素（ＣＡ、ＣＴＡ、ＥＣ）膜对ＣＯ２、ＣＨ４的选择透气性能，并讨论了沸石作为填料所引起的分子筛作用的气体渗透过程。甲基硅橡胶的气体渗透系数最高，而选择性最低，且不受填料沸石的影响。纤维素膜的气体选择性较大，渗透系数可以通过沸石的加人而明显增加。特别是沸石１３Ｘ．沸石３Ａ、４Ａ、５Ａ在ＥＣ膜中对气体分子筛作用，改变了气体原有的渗透过程，提高了选择性。使用Ａｒｒｈｅｎｉｕｓ公式计算出ＥＣ－沸石３Ａ膜的气体渗透活化能。     

Differential Adsorption of l- and d-Lysine on Achiral MFI Zeolites as Determined by Synchrotron X-Ray Powder Diffraction and Thermogravimetric Analysis

Reported here is the first crystallographic observation of stereospecific bindings of l - and d -lysine (Lys) in achiral MFI zeolites. The MFI structure offers inherent geometric and internal confinement effects for the enantiomeric difference in l - and d -Lys adsorption. Notable differences have been observed by circular dichroism (CD) spectroscopy and thermogravimetric analysis (TGA). Distinct l - and d -Lys adsorption behaviours on the H-ZSM-5 framework have been revealed by the Rietveld refinement of high-resolution synchrotron X-ray powder diffraction (SXRD) data and the density-functional theory (DFT) calculations. Despite demonstrating the approach for l - and d -Lys over MFI zeolites at an atomistic resolution, the differential adsorption study sheds light on the rational engineering of molecular interaction(s) with achiral microporous materials for chiral separation purposes.     

Separation and permeation characteristics of a DD3R zeolite membrane

Permeation of various gases (carbon dioxide, nitrous oxide, methane, nitrogen, oxygen, argon, krypton, neon) and their equimolar mixtures through DD3R membranes have been investigated over a temperature range of 220–373 K and a feed pressure of 101–400 kPa. Helium was used as sweep gas at atmospheric pressure. Adsorption isotherms were determined in the temperature range 195–298 K, and modelled by a single and dual site Langmuir model. The permeation flux is determined by the size of the molecule relative to the window opening of DD3R, and its adsorption behaviour. As a function of temperature, bulky molecules (methane) show activated permeation, weakly adsorbing molecules decreasing permeation behaviour and strongly adsorbing molecules pass through a maximum. Counter diffusion of the sweep gas (helium) ranged from almost zero up to the order of the feed gas permeation and was strongly influenced by the adsorption of the feed gas.

DD3R membranes have excellent separation performance for carbon dioxide/methane mixtures (selectivity 100–3000), exhibit good selectivity for nitrogen/methane (20–45), carbon dioxide and nitrous oxide/air (20–400), and air/krypton (5–10) and only a modest selectivity for oxygen/nitrogen (2) separation. The selectivity of mixtures of a strongly and a weakly adsorbing component decreased with increasing temperature and pressure. The selectivity of mixtures of weakly adsorbing components was independent of pressure.

The permeation and separation characteristics of light gases through DD3R membranes can be explained by taking into account: (1) steric effects introduced by the window opening of DD3R leading to molecular sieving and activated transport, (2) competitive adsorption effects, as observed for mixtures involving strongly adsorbing gases, and (3) interaction between diffusing molecules in the cages of the zeolite.     

Differential Adsorption of l‐ and d‐Lysine on Achiral MFI Zeolites as Determined by Synchrotron X‐Ray Powder Diffraction and Thermogravimetric Analysis

Reported here is the first crystallographic observation of stereospecific bindings of l ‐ and d ‐lysine (Lys) in achiral MFI zeolites. The MFI structure offers inherent geometric and internal confinement effects for the enantiomeric difference in l ‐ and d ‐Lys adsorption. Notable differences have been observed by circular dichroism (CD) spectroscopy and thermogravimetric analysis (TGA). Distinct l ‐ and d ‐Lys adsorption behaviours on the H‐ZSM‐5 framework have been revealed by the Rietveld refinement of high‐resolution synchrotron X‐ray powder diffraction (SXRD) data and the density‐functional theory (DFT) calculations. Despite demonstrating the approach for l ‐ and d ‐Lys over MFI zeolites at an atomistic resolution, the differential adsorption study sheds light on the rational engineering of molecular interaction(s) with achiral microporous materials for chiral separation purposes.     

不同分子筛的氮氩分离性能

采用水溶液离子交换法制备了不同离子交换的13X和4A分子筛,并在25℃下测 定了它们的静态吸附等温线和动态穿透曲线。研究发现,Ca~(2+)离子和Li~+离子 交换的13X和4A分子筛对氮的吸附性能都明显优于其相应的钠型分子筛,而它们对 氩的吸附量变化不大,说明这两种离子交换的分子筛是较好的氮氩分离吸附剂。从 动态吸附的结果来看,所研究的各种分子筛都有一个最优的吸附分离压力,在本论 文研究的压力范围内,这个最优压力在0.6MPa附近。通过穿透曲线推算出的混合气 体吸附量和纯气体吸附量的对比可以得出,对于氮氩吸附选择性较高的分子筛,氮 的存在对氩的吸附量有较大的影响。     

Development and evaluation of porous materials for carbon dioxide separation and capture

The development of new microporous materials for adsorption separation processes is a rapidly growing field because of potential applications such as carbon capture and sequestration (CCS) and purification of clean-burning natural gas. In particular, new metal-organic frameworks (MOFs) and other porous coordination polymers are being generated at a rapid and growing pace. Herein, we address the question of how this large number of materials can be quickly evaluated for their practical application in carbon dioxide separation processes. Five adsorbent evaluation criteria from the chemical engineering literature are described and used to assess over 40 MOFs for their potential in CO(2) separation processes for natural gas purification, landfill gas separation, and capture of CO(2) from power-plant flue gas. Comparisons with other materials such as zeolites are made, and the relationships between MOF properties and CO(2) separation potential are investigated from the large data set. In addition, strategies for tailoring and designing MOFs to enhance CO(2) adsorption are briefly reviewed.     

沸石的孔口改性与气体吸附分离

沸石由干具有独特的微孔结构和表面性质，对物质的吸附表现出高度的选择性，已被广泛用于许多工业吸附分离过程．在气体分离方面，最常见的是利用沸石制造纯净的稀有气体和富氧空气．Niwa等［‘－‘］和本实验室［‘’］已成功地采用出（OCH小化学气相沉积方法对HM和Hi8M七沸石进行孔径精细调变，改善了沸石的择形吸附分离和催化性能．本文试图进一步研究沸石孔口改性在气体吸附分离方面的应用潜力．我们选择的H元气体混合物体系是NZ／OZ和CH。川。，因为O。，NZ和CH。三种分子的动力学直径分别为0．346O．364和0．380urn，相差甚…