Selective adsorption and separation of ortho-substituted alkylaromatics with the microporous aluminum terephthalate MIL-53

The metal-organic framework MIL-53(Al) was tested for selective adsorption and separation of xylenes and ethylbenzene, ethyltoluenes, and cymenes using batch, pulse chromatographic, and breakthrough experiments. In all conditions tested, MIL-53 has the largest affinity for the ortho-isomer among each group of alkylaromatic compounds. Separations of the ortho-compounds from the other isomers can be realized using a column packed with MIL-53 crystallites. As evidenced by Rietveld refinements, specific interactions of the xylenes with the pore walls of MIL-53 determine selectivity. In comparison with the structurally similar metal-organic framework MIL-47, the selectivities among alkylaromatics found for MIL-53 are different. Separation of ethyltoluene and cymene isomers is more effective on MIL-53 than on MIL-47; the pores of MIL-53 seem to be a more suitable environment for hosting the larger ethyltoluene and cymene isomers than those of MIL-47.     

Liquid chromatography of dextrans on porous silica beds

Kinetics, equilibrium isotherms and chromatography retention times for sorption of dextrans T-10, T-20, T-40, T-70, T-110, T-161, T-250 and T-500 on porous silica were measured at 25 degrees C. The Henry constant and retention factors for the dextrans were obtained. The values of the partition coefficient for the distribution of the dextrans between the bulk solution and the pore space were calculated within the framework of a pore volume filling model with consideration given to the ratio between the sizes of the macromolecular coils and the pore inlet. The measurements showed that this parameter depends on the structure of the sorbent and the molecular mass distribution of the dextran. The interaction of aqueous dextran solution with porous silica is characterized by the sieve effect. Large macromolecular coils of dextran T-161 cannot penetrate into the pore space of the silica sorbent with pore diameter 14 nm. The difference in Henry law constants calculated from adsorption and chromatographic data for dextrans T-70 and T-110 can be explained by the slow diffusion of dextran macromolecules into silica pores under chromatographic conditions.     

Modeling the effect of structural changes during dynamic separation processes on MOFs

A model able to describe the effect of structural changes in the adsorbent or adsorbed phase during the dynamic (breakthrough) separation of mixtures on metal-organic frameworks (MOFs) is presented. The methodology is exemplified for a few pertinent case studies: the separation of xylene isomers and ethylbenzene on the flexible MOF MIL-53 and the rigid MOF MIL-47. At low pressures, no preferential adsorption of any component occurs on both MOFs. Contrarily, at higher pressures separation of ethylbenzene (EB) from o-xylene (oX) occurs on MIL-53 as a result of the breathing phenomenon within the MIL-53 structure. The increase in selectivity, starting from the gate-opening pressure, could be modeled by using a pressure-dependent saturation capacity for the most strongly adsorbed component oX. In the separation of m-xylene (mX) from p-xylene (pX) on the rigid MOF MIL-47, separation at higher pressures is a result of preferential stacking of pX. Here, the selectivity increases once the adsorption of pX switches from a single to a double file adsorption. By implementing a loading dependent adsorption constant for pX, the different unconventional breakthrough profiles and the observed selectivity profile on MIL-47 can be simulated. A similar methodology was used for the separation of EB from pX on MIL-47, where the separation is a result from steric constraints imposed onto the adsorption of EB.     

Effect of temperature on the adsorption of water in porous carbons

We report experimental and simulation studies to investigate the effect of temperature on the adsorption isotherms for water in carbons. Adsorption isotherms are measured by a gravimetric technique in carbon-fiber monoliths at 378 and 423 K and studied by molecular simulation in ideal carbon pores in the temperature range 298-600 K. Experimental adsorption isotherms show a gradual water uptake, as the pressure increases, and narrow adsorption-desorption hysteresis loops. In contrast, simulated adsorption isotherms at room temperature are characterized by negligible uptake at low pressures, sudden and complete pore filling once a threshold pressure is reached, and wide adsorption-desorption hysteresis loops. As the temperature increases, the relative pressure at which pore filling occurs increases and the size of the hysteresis loop decreases. Experimental adsorption-desorption hysteresis loops are narrower than those from simulation. Discrepancies between simulation and experimental results are attributed to heterogeneities in chemical composition, pore connectivity, and nonuniform pore-size distribution, which are not accounted for in the simulation model. The hysteresis phase diagram for confined water is obtained by recording the pressure-density conditions that bound the simulated hysteresis loop at each temperature. We find that the hysteresis critical temperature, i.e., the lowest temperature at which no hysteresis is detected, can be hundreds of degrees lower than the vapor-liquid critical temperature for bulk model water. The properties of confined water are discussed with the aid of simulation snapshots and by analyzing the structure of the confined fluid.     

Separation of styrene and ethylbenzene on metal-organic frameworks: analogous structures with different adsorption mechanisms

The metal-organic frameworks MIL-47 (V(IV)O{O(2)C-C(6)H(4)-CO(2)}) and MIL-53(Al) (Al(III)(OH)·{O(2)C-C(6)H(4)-CO(2)}) are capable of separating ethylbenzene and styrene. Both materials adsorb up to 20-24 wt % of both compounds. Despite the fact that they have identical building schemes, the reason for preferential adsorption of styrene compared to ethylbenzene is very different for the two frameworks. For MIL-47, diffraction experiments reveal that styrene is packed inside the pores in a unique, pairwise fashion, resulting in separation factors as high as 4 in favor of styrene. These separation factors are independent of the total amount of adsorbate offered. This is due to co-adsorption of ethylbenzene in the space left available between the packed styrene pairs. The separation is of a non-enthalpic nature. On MIL-53, the origin of the preferential adsorption of styrene is related to differences in enthalpy of adsorption, which are based on different degrees of framework relaxation. The proposed adsorption mechanisms are in line with the influence of temperature on the separation factors derived from pulse chromatography: separation factors are independent of temperature for MIL-47 but vary with temperature for MIL-53. Finally, MIL-53 is also capable of removing typical impurities like o-xylene or toluene from styrene-ethylbenzene mixtures.     

Charge distribution in metal organic framework materials: transferability to a preliminary molecular simulation study of the CO(2) adsorption in the MIL-53 (Al) system

Density functional theory calculations have been performed in order to extract the charge distribution in the aluminium-containing MIL-53 structure, to allow further computational studies of adsorption in these materials. Both cluster and periodic methods have been used and the charges calculated for each atom constituting the organic and inorganic part of the material, were discussed. Preliminary grand canonical Monte Carlo simulations, based on a consistent set of potential parameters and this newly derived charge distribution, predicted for enthalpies of adsorption for CO(2) at low coverage in the "large" and "narrow" pore versions of MIL-53 (Al) to be significantly different. These calculated enthalpies reproduced the two distinct ranges of values observed by microcalorimetry on either side of 6 bars quite well. This agreement between experiment and simulation validated our previous assumption, suggesting a structural switching of the hybrid material during the adsorption process. The microscopic mode of interaction between the hybrid porous framework and the CO(2) adsorption was then carefully analysed in both of the MIL-53 (Al) structures.     

Adsorption of CO2 in metal organic frameworks of different metal centres: Grand Canonical Monte Carlo simulations compared to experiments

A Grand Canonical Monte Carlo study has been performed in order to compare the different CO₂ adsorption mechanisms between two members of the MIL-n family of hybrid metal-organic framework materials. The MIL-53 (Al) and MIL-47 (V) systems were considered. The results obtained confirm that there is a structural interchange between a large pore and narrow pore forms of MIL-53 (Al), not seen with the MIL-47 (V) material, which is a consequence of the presence of μ ₂-OH groups. The interactions between the CO₂ molecules and these μ ₂ OH groups mainly govern the adsorption mechanism in this MIL-53 (Al) material. The subsequent breaking of these adsorption geometries after the adsorbate loading increases past the point where no more preferred adsorption sites are available, are proposed as key features of the breathing phenomenon. After this, any new adsorbates introduced into the MIL-53 (Al) large pore structure experience a homogeneous adsorption environment with no preferential adsorption sites in a similar way to what occurs in MIL-47 (V).     

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.     

金属-有机骨架对苯二甲酸酯-铝吸附水中酚类化合物动力学和热力学

以吸附等温线、动力学和热力学等方法研究了金属-有机骨架对苯二甲酸酯-铝[MIL-53(Al),MIL:Materials of Institut Lavoisier]对水中邻硝基苯酚、苯酚和邻苯二酚的吸附行为。 MIL-53(Al)对上述酚类化合物的吸附符合准二级吸附动力学模型,且包含表面吸附和孔内扩散两个过程。 吸附热力学结果表明,MIL-53(Al)对酚类化合物的吸附是自发的,且为吸热和熵增加过程。 在40 ℃条件下,MIL-53(Al)对邻硝基苯酚、苯酚和邻苯二酚的吸附量分别为78.6、30.5和16.5 mg/g。     

高温水热合成具有超低介电常数的规则介孔氧化硅材料

分别以高分子三嵌段共聚物P123(PEO₂₀-PPO₇₀-PEO₂₀)和F127(PEO₁₀₆-PPO₇₀-PEO₁₀₆)为模板剂, 通过高温水热法制备了具有超低介电常数的规则介孔氧化硅材料(OMSs). 当合成温度达到200℃时, 得到的产物仍可保持规则的介孔结构. X射线衍射和氮气吸附结果表明, OMSs系列材料具有规则的二维六方或体心立方介孔结构、 大的比表面积和孔容及均一的孔径分布. ²⁹Si MAS NMR分析表明, OMSs与低温(100℃)合成产物相比具有更高的骨架缩合度, 从而具有优异的水热稳定性. 由于具有大的孔容和高的骨架缩合度, OMSs表现出了超低的介电常数. 以P123为模板剂, 200℃下合成的OMS的介电常数可达1.31. OMSs作为一类稳定的超低介电常数材料, 对于绝缘材料的发展具有潜在的应用价值.     

Simulated water adsorption in chemically heterogeneous carbon nanotubes

Grand canonical Monte Carlo simulations are used to study the adsorption of water in single-walled (10:10), (12:12), and (20:20) carbon nanotubes at 298 K. Water is represented by the extended simple point charge model and the carbon atoms as Lennard-Jones spheres. The nanotubes are decorated with different amounts of oxygenated sites, represented as carbonyl groups. In the absence of carbonyl groups the simulated isotherms are characterized by negligible amounts of water uptake at low pressures, sudden and complete pore filling once a threshold pressure is reached, and wide adsorption-desorption hysteresis loops. In the presence of a few carbonyl groups the simulated adsorption isotherms are characterized by pore filling at lower pressures and by narrower adsorption-desorption hysteresis loops compared to the results obtained in the absence of carbonyl groups. Our results show that the distribution of the carbonyl groups has a strong effect on the adsorption isotherms. For carbonyl groups localized in a narrow section the adsorption of water may be gradual because a cluster of adsorbed water forms at low pressures and grows as the pressure increases. For carbonyl groups distributed along the nanotube the adsorption isotherm is of type V.     

Adsorption of aromatic compounds from solutions in <Emphasis Type="Italic">n</Emphasis>-heptane by modified nanoporous silica

The adsorption of anisole, anthracene, benzoic acid, benzene, naphthalene, phenanthrene, phenol, and carbon tetrachloride from dilute solutions in n-heptane on the modified nanoporous silica sorbents, Silasorb C18 and Phenyl-Silasorb, at 298 K is investigated by developing liquid chromatography. The Henry law constants and Helmholtz energy of adsorption for these aromatic compounds are calculated from their retention values. The adsorption isotherms of the aromatic compounds are calculated from their chromatographic peaks with allowances made for longitudinal smearing. A correlation is made between the Henry law constants calculated from the retention values of the aromatic compounds and from their adsorption isotherms. The influences of the surface modification of the silica adsorbents and the molecular structure of the aromatic compounds on their elution from the chromatographic column with n-heptane as the eluent are discussed. Contributions of functional groups in the molecules of the aromatic compounds to the Helmholtz energy of adsorption on different surfaces are estimated.     

Prediction of the conditions for breathing of metal organic framework materials using a combination of X-ray powder diffraction, microcalorimetry, and molecular simulation

The adsorption of C1 to C4 linear hydrocarbons in the flexible metal organic framework MIL-53(Cr) has been followed by adsorption manometry coupled with microcalorimetry and Synchrotron X-ray powder diffraction. This experimental investigation was completed by molecular modeling. In the case of methane, the solid remains rigid whatever the adsorbate amount. However for the C2-C4 series, an increasing flexibility of the structure is observed, which is ascribed first to a breathing of the material from a large pore to a narrow pore form followed by a further expansion at high pressure. The collected thermodynamic and structural information suggests that a minimum adsorption enthalpy of ca. 20 kJ mol (-1) in the initial large pore structure of MIL-53(Cr) is required to induce the structural transition "large to narrow pore". Further, the enthalpy of adsorption can be used to predict the pressure at which the structure reopens. Finally, the magnitude of the breathing can be related to the size of the probe molecule via the van der Waals volume. The above trends have been successfully verified in the case of water and carbon dioxide. This combined experimental and theoretical approach gives the first elements for the prediction of whether or not the MIL53 and similar flexible structures will respond to gas loading and what would be the pressure required and further the amplitude of the induced breathing.     

Adsorption behaviors of CO<Subscript>2</Subscript> and CH<Subscript>4</Subscript> on zeolites JSR and Na<Subscript>n</Subscript>JSR using the GCMC simulations

The adsorption behaviors of CO₂ and CH₄ on new siliceous zeolites JSR and Na_nJSR (n = 2, 8, 16) were simulated using the Grand Canonical Monte Carlo method. The adsorption isotherms of CO₂ became higher with an increase in the Na⁺ number at a low pressure range (<150 kPa), whereas the isotherms showed a crossover with increasing pressure and the adsorption amount became smaller at a high pressure range (>850 kPa). With an increase in Na⁺ number, the pore volume decreased as the pore space was occupied by increasing Na⁺ ions. Additionally, two energy peaks on the interaction energy curves implied that CO₂ was adsorbed on two active sites. On the other hand, the adsorption amount of CH₄ decreased with an increase in the Na⁺ number and only one energy peak was observed. Adsorption isotherms were well fitted with the Langmuir and Freundlich equations up to 1000 kPa and the adsorption affinity of CO₂ on Na₁₆JSR zeolite was highest. The adsorption capacities of CO₂ in the studied zeolites were up to 38 times higher than those of CH₄. Diffusion constants of CO₂ and CH₄ decreased with an increase in the adsorbed amount and Na⁺ number. Considering the adsorbed amount, adsorption selectivity and affinity, zeolites JSR with a low Na⁺ number (JSR and Na₂JSR) is a good candidate for a pressure swing adsorption in the separation of CO₂/CH₄ mixture whereas JSR zeolites with high Na⁺ ratios (Na₁₆JSR and Na₈JSR) may be a better selection for a vacuum swing adsorption.     

Adsorptive separation of isobutene and isobutane on Cu3(BTC)2

The metal organic framework material Cu3(BTC)2 (BTC = 1,3,5-benzenetricarboxylate) has been synthesized using different routes: under solvothermal conditions in an autoclave, under atmospheric pressure and reflux, and by electrochemical reaction. Although the compounds display similar structural properties as evident from the powder X-ray diffraction (XRD) patterns, they differ largely in specific surface area and total pore volume. Thermogravimetric and chemical analysis support the assumption that pore blocking due to trimesic acid and/or methyltributylammoniummethylsulfate (MTBS) which has been captured in the pore system during reaction is a major problem for the electrochemically synthesized samples. Isobutane and isobutene adsorption has been studied for all samples at different temperatures in order to check the potential of Cu3(BTC)2 for the separation of small hydrocarbons. While the isobutene adsorption isotherms are of type I according to the IUPAC classification, the shape of the isobutane isotherm is markedly different and closer to type V. Adsorption experiments at different temperatures show that a somewhat higher amount of isobutene is adsorbed as compared to isobutane. Nevertheless, the differential enthalpies of adsorption are only different by about 5 kJ/mol, indicating that a strong interaction between the copper centers and isobutene does not drive the observed differences in adsorption capacity. The calculated breakthrough curves of isobutene and isobutane reveal that a low pressure separation is preferred due to the peculiar shape of the isobutane adsorption isotherms. This has been confirmed by preliminary breakthrough experiments using an equimolar mixture of isobutane and isobutene.     

Methane adsorption on AUK microporous carbon adsorbent

The isotherms of absolute methane adsorption on AUK microporous carbon adsorbent are measured at pressures of 1 Pa–6 MPa and temperatures of 177.65–393 K. The pattern of the isotherms remains unchanged when passing through the critical temperature of methane (T _cr = 190.77 K) and, as the temperature is elevated, the isotherms are shifted toward higher pressures in an almost symbate manner. Isosteres plotted for methane adsorption on AUK microporous carbon adsorbent within the same pressure and temperature ranges are adequately approximated by straight lines, with their slopes remaining unchanged when passing into the region of supercritical temperatures under the conditions of a pronounced imperfection of the gas phase. The Henry constant is determined for the system under consideration. It is shown that the Henry constants have close magnitudes for different methane-carbon adsorbent systems.     

Water in carbon nanotubes: adsorption isotherms and thermodynamic properties from molecular simulation

Grand canonical Monte Carlo simulations are performed to study the adsorption of water in single-walled (6:6), (8:8), (10:10), (12:12), and (20:20) carbon nanotubes in the 248-548 K temperature range. At room temperature the resulting adsorption isotherms in (10:10) and wider single-walled carbon nanotubes (SWCNs) are characterized by negligible water uptake at low pressures, sudden and complete pore filling once a threshold pressure is reached, and wide adsorption/desorption hysteresis loops. The width of the hysteresis loops decreases as pore diameter narrows and it becomes negligible for water adsorption in (8:8) and (6:6) SWCNs. Results for the isosteric heat of adsorption, density profiles along the pore axis and across the pore radii, order parameter across the pore radii, and x-ray diffraction patterns are presented. Layered structures are observed when the internal diameter of the nanotubes is commensurate to the establishment of a hydrogen-bonded network. The structure of water in (8:8) and (10:10) SWCNs is ordered when the temperature is 298 and 248 K, respectively. By simulating adsorption isotherms at various temperatures, the hysteresis critical temperature, e.g., the lowest temperature at which no hysteresis can be detected, is determined for water adsorbed in (20:20), (12:12), and (10:10) SWCNs. The hysteresis critical temperature is lower than the vapor-liquid critical temperature for bulk Simple Point Charge-Extended (SPCE) water model.     

Adsorption of toluene, methylcyclohexane and neopentane on silica MCM-41

Adsorption-desorption isotherms of toluene, methylcyclohexane and neopentane were determined on a silica MCM-41 material of pore diameter ∼3.4 nm over the temperature range 258 K to 308 K (278 K for neopentane). The isosteric enthalpies of adsorption were determined from the isotherms at the various temperatures. It was found that the isotherms of toluene and methylcyclohexane have a similar variation with the temperature, exhibiting hysteresis at 268 K and at lower temperature, while the adsorption of neopentane is reversible at all temperatures. The three organic adsorptives interact differently with the silica surface and the isosteric enthalpies of adsorption indicated that methylcyclohexane has the weakest interaction and toluene the strongest. A slight increase in the adsorption enthalpy at the beginning of the capillary condensation step is observed with methylcyclohexane and neopentane but not with toluene.     

Toward understanding the influence of ethylbenzene in p-xylene selectivity of the porous titanium amino terephthalate MIL-125(Ti): adsorption equilibrium and separation of xylene isomers

The potential of the porous crystalline titanium dicarboxylate MIL-125(Ti) in powder form was studied for the separation in liquid phase of xylene isomers and ethylbenzene (MIL stands for Materials from Institut Lavoisier). We report here a detailed experimental study consisting of binary and multi-component adsorption equilibrium of xylene isomers in MIL-125(Ti) powder at low (≤0.8 M) and bulk (≥0.8 M) concentrations. A series of multi-component breakthrough experiments was first performed using n-heptane as the eluent at 313 K, and the obtained selectivities were compared, followed by binary breakthrough experiments to determine the adsorption isotherms at 313 K, using n-heptane as the eluent. MIL-125(Ti) is a para-selective material suitable at low concentrations to separate p-xylene from the other xylene isomers. Pulse experiments indicate a separation factor of 1.3 for p-xylene over o-xylene and m-xylene, while breakthrough experiments using a diluted ternary mixture lead to selectivity values of 1.5 and 1.6 for p-xylene over m-xylene and o-xylene, respectively. Introduction of ethylbenzene in the mixture results however in a decrease of the selectivity.     

Adsorption and diffusion of nitrogen, methane and carbon dioxide in aluminophosphate molecular sieve AlPO4-11

The knowledge about the adsorption and diffusion properties (specially about diffusion) of aluminophosphate molecular sieves is very scarce in the literature. These materials offer interesting properties as adsorbents as they have a polar framework and do not contain charge-balancing cations. In this work, the adsorption isotherms of nitrogen, methane and carbon dioxide over an AlPO₄-11 sample synthesized in our laboratories have been measured with a volumetric method at 25, 35, 50 and 65 °C over a pressure range up to 110 kPa. The adsorption capacities of each gas are determined by the strength of interaction with the pore surface (carbon dioxide > methane > nitrogen). The equilibrium selectivity to carbon dioxide is quite high with respect to other adsorbents without cations due to the polarity of the aluminophosphate framework. The adsorption Henry’s law constants and diffusion time constants of nitrogen, methane and carbon dioxide in the synthesized AlPO₄-11 material have been measured from pulse experiments. A pressure swing adsorption (PSA) process for recovering methane from a carbon dioxide/methane mixture (resembling biogas) has been designed using a dynamic model where the measured adsorption equilibrium and kinetic information has been incorporated. The simulation results show that the proposed process could be simpler than other PSA processes for biogas upgrading based on cation-containing molecular sieves such as 13X zeolite, as it can treat the biogas at atmospheric pressure, and it requires a lower pressure ratio, to produce high purity methane with high recovery.