Statistical physics modeling of water vapor adsorption isotherm into kernels of dates: Experiments,microscopic interpretation and thermodynamic functions evaluation

In this paper, water sorption isotherms into date kernels give interesting insights about the sorption mechanism. The equilibrium adsorption data expressing the change in moisture content of date kernels were collected at three different temperatures using the static gravimetric technique. The adsorption isotherm profiles demonstrated that this process was performed via an infinite number of layers. A modified form of the Brunauer, Emett and Teller (BET) model is obtained based on the use of the real gas law and statistical physics treatment so the interaction between molecules is considered. This advanced model is used to fit experimental isotherms by numerical simulation. The sorption mechanism is theoretically explained by the parameters that could be related to the water adsorption process. Based on fitting results, we find that the number of molecules per site (parameter n) has a linear tendency with temperature thanks to the thermal agitation effect. A deeper analysis of adsorption energy demonstrates that the water vapors are physisorbed in the date kernels. Through the exploitation of our model, three classic thermodynamic functions are investigated to interpret the macroscopic aspect of the adsorption mechanism.     

An improvement on the two-dimensional convolution method of image reconstruction and its application to SPECT

In single-photon emission computed tomography (SPECT) and X-ray CT one-dimensional (1-D) convolution method is used for their image reconstruction from projections. The method makes a 1-D convolution filtering on projection data with a 1-D filter in the space domain, and back projects the filtered data for reconstruction. Images can also be reconstructed by first forming the 2-D backprojection images from projections and then convoluting them with a 2-D space-domain filter. This is the reconstruction by the 2-D convolution method, and it has the opposite reconstruction process to the 1-D convolution method. Since the 2-D convolution method is inferior to the 1-D convolution method in speed in reconstruction, it has no practical use. In the actual reconstruction by the 2-D convolution method, convolution is made on a finite plane which is called convolution window. A convolution window of size N X N needs a 2-D discrete filter of the same size. If better reconstructions are achieved with small convolution windows, the reconstruction time for the 2-D convolution method can be reduced. For this purpose, 2-D filters of a simple function form are proposed which can give good reconstructions with small convolution windows. They are here defined on a finite plane, depending on the window size used, although a filter function is usually defined on the infinite plane. They are however set so that they better approximate the property of a 2-D filter function defined on the infinite plane. Filters of size N X N are thus determined. Their value varies with window size. The filters are applied to image reconstructions of SPECT.(ABSTRACT TRUNCATED AT 250 WORDS)     

Grafting of alumina on SBA-15: effect of surface roughness

Alumina-grafted materials were prepared by postsynthesis alumination of mesoporous SBA-15 silica in an aqueous solution of aluminum chlorhydrol. Prepared samples were characterized by nitrogen adsorption, scanning electron microscopy, X-ray powder diffraction, and (27)Al magic-angle-spinning NMR. The successive grafting of alumina on SBA-15 leads to a gradual filling of the corona surrounding the mesopores. As a consequence smoothing of the mesopore surface takes place. The in-depth analysis of nitrogen adsorption data proves that the alpha s method affords real values of the structure parameters, while the Kruk, Jaroniec, and Sayari (KJS) procedure based on the BJH algorithm provides only effective data corresponding to cylindrical mesopores of smooth geometrical surface. The quantification of the roughness of the SBA-15 mesopore surface based on the comparison of data obtained from the alpha s plot and KJS method was carried out.     

Impact of an error in the column hold-up time for correct adsorption isotherm determination in chromatography I. Even a small error can lead to a misunderstanding of the retention mechanism

The impact of a realistic error in the column hold-up time on the determination of the adsorption isotherm model was systematically investigated. Frontal analysis and the inverse method were used for the accurate determination of the adsorption isotherm. The true retention times of the breakthrough curves were used with a known hold-up time as reference. The adsorption isotherms were calculated using the same procedure that is used for real experimental adsorption isotherms, where the true hold-up time is unknown. The raw data were analyzed with calculations of adsorption energy distributions (AEDs), Scatchard plots, fitting to different rival adsorption models and finally their ability to predict true profiles. The results show that for a true Langmuir and bi-Langmuir model with an underestimated hold-up time the error may lead to a more heterogeneous model and for overestimated cases false adsorption processes like multi-layer adsorption or solute-solute interaction are assumed. The Scatchard plots for data obtained using a Langmuir adsorption isotherm are nonlinear and the AEDs show clear deviations from Langmuir behavior already at small deviations from the true hold-up time at a moderate surface coverage. The inverse method confirms the result that was obtained from the frontal analysis procedure.     

Separation of CO2-CH4 mixtures in the mesoporous MIL-100(Cr) MOF: experimental and modelling approaches

Carbon dioxide is the main undesirable compound present in raw natural gas and biogas. Physisorption based adsorption processes such as pressure swing adsorption (PSA) are one of the solutions to selectively adsorb CO(2) from CH(4). Some hybrid crystalline porous materials that belong to the family of metal-organic frameworks (MOFs) show larger CO(2) adsorption capacity compared to the usual industrial adsorbents, such as zeolites and most activated carbons, which makes them potentially promising for such applications. However, their selectivity values have been most often determined using only single gas adsorption measurements combined with simple macroscopic thermodynamic models or by means of molecular simulations based on generic forcefields. The transfer of this systematic approach to all MOFs, whatever their complex physico-chemical features, needs to be considered with caution. In contrast, direct co-adsorption measurements collected on these new materials are still scarce. The aim of this study is to perform a complete analysis of the CO(2)-CH(4) co-adsorption in the mesoporous MIL-100(Cr) MOF (MIL stands for Materials from Institut Lavoisier) by means of a synergic combination of outstanding experimental and modelling tools. This solid has been chosen both for its fundamental interests, given its very large CO(2) adsorption capacities and its complexity with a combination of micropores and mesopores and the existence of unsaturated accessible metal sites. The predictions obtained by means of Grand Canonical Monte Carlo simulations based on generic forcefields as well as macroscopic thermodynamic (IAST, RAST) models will be compared to direct the co-adsorption experimental data (breakthrough curve and volumetric measurements).     

Use of Concentration Pulse Chromatography for Determining Binary Isotherms: Comparison with Statically Determined Binary Isotherms

The characterization of adsorption properties of binary gas mixtures is an important factor in the design of cyclic periodic adsorption processes. Presently, there are a few methods for determining the binary adsorption behaviour. However, most of these methods are very time demanding (static approaches). One dynamic approach for determining the binary adsorption behaviour is by employing the concentration pulse method. Although this experimental method has been shown to reliably reproduce the data obtained with static approaches, the application has been limited to systems where the adsorption capacities are similar. In our previous work, a novel method (HT-CPM) was shown to be capable of handling systems where the adsorption capacity of the heavy component is much greater than the light component.In order to further validate the novel method, HT-CPM, previously published statically determined binary adsorption data have been used to supply the data required for the concentration pulse method (CPM) data reduction techniques. From this data, the HT-CPM was then applied and the resulting data compared. The two other CPM approaches were also applied and these results are shown.Four binary systems were chosen so that a range of heavy/light adsorption capacities was examined. The results show that the HT-CPM was able to produce results that were consistent with the static data taken from the literature. The other data reduction techniques used with the CPM could only produce meaningful data when the adsorption capacities of the heavy and light components were similar.     

Comparative characterization study of microporous carbons by HRTEM image analysis and gas adsorption

The present work presents a useful comparison of micropore size distributions (MPSDs) obtained from gas adsorption and image analysis of high-resolution transmission electron micrographs. It is shown that the MPSD obtained for a chemical activated carbon is concordant with that obtained from CO2 adsorption. In addition, this technique has allowed us to obtain the MPSD of a carbon molecular sieve (CMS) prepared in our laboratory by a copyrolysis process, which could only be characterized by CO2 adsorption at 273 K (not by N2 adsorption at 77 K due to diffusional problems). The MPSD obtained by high-resolution transmission electron microscopy (HRTEM) for the CMS is wider than that obtained by CO2 adsorption, suggesting that HRTEM is detecting the closed porosity existing in this sample, which is not accessible to gas adsorption. The existence of closed porosity in the CMS is explained considering the preparation method used. Thus, HRTEM combined with image analysis seems to be useful for structural analysis of narrow micropores including closed porosity.     

Extension of the Dubinin-Astakhov equation for evaluating the micropore size distribution of a modified carbon molecular sieve

A new method for the characterization of the pore size distribution of microporous solids is applied on data obtained for activated carbon molecular sieve samples. In this method, based on the Dubinin-Astakhov equation, a simple numerical algorithm is used for the reconstruction of the micropore size distribution from the integral equation that represents the experimental nitrogen adsorption isotherm. The results are compared with the ones obtained on the basis of the well-known Horvath-Kawazoe method. The samples used in this study come from a carbon molecular sieve that has been treated with solutions of concentrated HNO3 at various temperatures and with solutions of H2O2 of various concentrations.     

机器学习筛选用于气体吸附分离和存储的金属有机骨架材料

金属有机框架（Metal-organic framework ,MOF）因其高孔隙率、高比表面积和结构可调性,在气体吸附分离领域广泛应用。随着MOF数量激增,传统分子模拟和实验方法验证MOF性能成本高且速度慢,因此目前MOF筛选工作已转向高通量计算辅助的机器学习（Machine-learning,ML）。机器学习作为一种高效的大数据处理方法,能够在高通量筛选（High-Throughput Computational Screening,HTCS）的基础上对数据进行拟合,从而快速而准确地筛选出气体吸附分离材料,并深入挖掘其结构与性能之间的关系。本文回顾了近年机器学习应用于MOF筛选的研究。本文重点讨论了一些运用机器学习从大量结构中筛选出可用于CH4、H2和CO2等气体吸附分离与储存的MOF材料的工作。同时,我们梳理了当前MOF材料筛选工作中的研究思路和进展,并指出了机器学习在筛选MOF材料工作中面临的一些瓶颈和挑战。最后,对该领域的未来发展前景进行了展望。     

In situ determination of the adsorption characteristics of a zeolite membrane

A methodology based on adsorption-branch porosimetry is described for in situ measurement of the adsorption of condensable gases within the pore structure of inorganic membranes. The method is applied to the study of n-hexane and p-xylene adsorption in a high-silica, MFI zeolite membrane. The results, interpreted in terms of a simple model for competitive adsorption effects on the permeance of a non-adsorbing gas, yield Langmuir adsorption constants and Henry’s law constants for n-hexane and p-xylene that are in excellent agreement with measurements on bulk materials. The method is proposed for the fundamental study of fouling characteristics of inorganic membranes, especially in cases where a true bulk surrogate is not available.     

Inverse gas chromatographic method for measuring the dispersive surface energy distribution for particulates

Inverse gas chromatography (IGC) is a widely used method for determining the dispersive component of the surface energy (gamma s (d)) of particulate and fibrous solids. Such measurements are normally conducted at very low solute concentrations (infinite dilution), and they result in a single numerical value of gamma s (d) for homogeneous materials which exhibit Henry's Law adsorption behavior. However, many real solid surfaces are heterogeneous and this may be demonstrated by the nonlinear isotherms obtained at low solute surface coverages resulting in reported gamma s (d) values which are not unique. This paper presents a new method for determining of gamma s (d) distributions as a function of the solute surface coverage using adsorption isosteres for an homologous series of hydrocarbon adsorbates. gamma s (d) distributions reported here were successfully determined using two different solid materials (glass beads and alumina particles) up to typical surface coverages of approximately 10% and clearly show significant variations in gamma s (d) with solute surface coverage. The effects of sample aging and pretreatment also exhibited clear differences in the gamma s (d) distributions obtained. gamma s (d) was determined using both the Dorris-Gray and Schultz methods, with the Dorris-Gray method exhibiting a much lower experimental error. It was established that the errors associated with this statistical measurement of surface energy were strongly dependent on the quality of the experimental data sets obtained. R (2) for the linearity of fit of the retention data to the Dorris-Gray gamma s (d) analysis was found to be a valid criterion for predicting the robustness of gamma s (d) distributions obtained. Detailed discussions of other critical experimental and analysis factors relevant to this methodology, as well as the reproducibility of gamma s (d) profiles are also presented. This paper establishes that IGC can be used for determining the gamma s (d) distributions of particulate solids and is demonstrated that this method is very useful way for studying the surface energy heterogeneity of complex particulate solids.     

A new integrated method for characterizing surface energy heterogeneity from a single adsorption isotherm

To characterize surface energy heterogeneity of fine particles, this paper presents an integrated strategy from a single adsorption isotherm. By coupling the well-known integral equation method and derivative isotherm summation (DIS) procedure based on a patchwise model, the newly proposed strategy could calculate adsorption energy distributions (AEDs) for different surface patches. Correspondingly, the surface heterogeneity of materials can be described by weighted summation of patch AEDs, that is, the total AED. The validity of this new method is confirmed by both tests of rutile nanoparticles and multiwalled carbon nanotubes (MWNTs). The total AED obtained by the new method agrees well with the result from solving the integral equation directly, and it shows that AED peaks can be assigned to specific energy patches of real surface exactly. Furthermore, a detailed comparison showed that some artificial oscillation in the results can be identified with the new strategy, and the patches with low area and high surface energy could be characterized as well. In conclusion, this strategy constructs a correspondence between derived AEDs and different patches of real surface, so it will be more effective to understand surface heterogeneity by using the adsorption probe method.     

Method and kit for adsorbent performance evaluation

Commercial gas separation plants running adsorption processes, including pressure swing adsorption, vacuum pressure swing adsorption and temperature swing adsorption are intended to operate continuously and meet design performance levels over the complete service life of the facility. Performance degradation of the adsorbent materials in extended commercial usage is a common problem. Issues such as adsorbent aging and poisoning by unwanted or unexpected contaminants, represent some of the causes of declining adsorbent performance. Lower adsorption capacity can result in declining productivity and/or product purity for the gas separation plant. Adsorbent troubleshooting is usually accomplished by taking samples from the plant and sending them to off-site laboratories for analyses such as moisture content determination by Karl Fischer titration, or BET surface area or other adsorption capacity measurements. The turnaround time for these laboratory analyses is on the order of days. To short-cut this lengthy process of analysis, we have developed a simple test method and kit for rapid diagnosis of adsorbent performance issues which can be used directly at a plant site. The test method involves the determination of the gas capacity of an adsorbent by equilibrating the adsorbent with an appropriate test gas, deactivating the adsorbent and measuring the amount of test gas released. Once a sample has been acquired, the test can be executed and results obtained in less than 15 min. We show that the test method is accurate to within 5 % of the adsorption capacity determined from isotherm measurements, at equivalent temperature and pressure, and can be used to test common commercial adsorbent types, including low silica zeolites and activated carbons.     

The Finite Pore Volume GAB Adsorption Isotherm Model as a Simple Tool to Estimate a Diameter of Cylindrical Nanopores

The finite pore volume Guggenheim–Anderson–de Boer (fpv-GAB) adsorption isotherm model has been considered as a simple tool which not only enables us to analyze the shape of isotherms theoretically, but also provides information about pore diameter. The proposed methodology is based on the geometrical considerations and the division of the adsorption space into two parts: the monolayer and the multilayer space. The ratio of the volumes of these two spaces is unambiguously related to the pore diameter. This ratio can be simply determined from the N₂ adsorption isotherm by its fitting with the use of fpv-GAB model. The volume ratio is equal to the ratio of the adsorption capacities in the monolayer and the multilayer—two of the best-fit parameters. The suggested approach has been verified using a series of isotherms simulated inside ideal carbon nanotubes. The adsorption data for some real adsorbents has also been used during tests. The studies performed have proven that diameters estimated with the use of the proposed method are comparable with the geometrical sizes or diameters published by others and based on the application of more sophisticated methods. For pores wider than 3 nm, the relative error does not exceed a few percent. The approach based on the fpv-GAB model reflects well the differences in pore sizes for the series of materials. Therefore, it can be treated as a convenient tool to compare various samples.     

Experimental determination of adsorption energies, adsorption isotherms, probability density functions, and lateral molecular interactions on CXHY/CaO systems

Reversed-flow gas chromatography (RF-GC) is extended to the measurements of the probability density function for the adsorption energies as well as the differential energies of adsorption due to lateral interactions of molecules adsorbed on different heterogeneous solid surfaces. All these calculations are based on a non-linear adsorption isotherm model as it is well accepted that the linear one is inadequate for substances such as these used in this work. Thus, some new important physicochemical parameters have been obtained for the characterization of the heterogeneous systems studied. The adsorbent used in this study was calcium oxide. The adsorption of many significant hydrocarbons was investigated. With these systematic experiments under conditions which are similar to the atmospheric ones, an extrapolation of the results obtained to "real" atmospheres with a high degree of confidence is possible.     

A systematic investigation of algorithm impact in preparative chromatography with experimental verifications

Computer-assisted optimization of chromatographic separations requires finding the numerical solution of the Equilibrium-Dispersive (ED) mass balance equation. Furthermore, the competitive adsorption isotherms needed for optimization are often estimated numerically using the inverse method that also solves the ED equations. This means that the accuracy of the estimated adsorption isotherm parameters explicitly depends on the numerical accuracy of the algorithm that is used to solve the ED equations. The fast and commonly used algorithm for this purpose, the Rouchon Finite Difference (RFD) algorithm, has often been reported not to be able to accurately solve the ED equations for all practical preparative experimental conditions, but its limitations has never been completely and systematically investigated. In this study, we thoroughly investigate three different algorithms used to solve the ED equations: the RFD algorithm, the Orthogonal Collocation on Finite Elements (OCFE) method and a Central Difference Method (CDM) algorithm, both for increased theoretical understanding and for real cases of industrial interest. We identified discrepancies between the conventional RFD algorithm and the more accurate OCFE and CDM algorithms for several conditions, such as low efficiency, increasing number of simulated components and components present at different concentrations. Given high enough efficiency, we experimentally demonstrate good prediction of experimental data of a quaternary separation problem using either algorithm, but better prediction using OCFE/CDM for a binary low efficiency separation problem or separations when the compounds have different efficiency. Our conclusion is to use the RFD algorithm with caution when such conditions are present and that the rule of thumb that the number of theoretical plates should be greater than 1000 for application of the RFD algorithm is underestimated in many cases.     

全盘自动化气相色谱仪单纯形寻优

自行研制的全盘自动化气相色谱仪在通用计算机的支持下,通过单纯形自动寻优,在色谱专家水平上建立了分析样品的最佳气相色谱分析方法。     

层柱粘土吸附甲烷的模拟和参数优化研究

用巨正则系综Monte Carlo方法(GCMC)来模拟ZrO₂柱撑粘土对天然气主要成分甲烷的吸附. 为了更好地反映甲烷与层柱粘土无机层板的相互作用, 对墙势模型中的尺寸参数σ_fw和能量参数ε_fw取值进行了优化. 我们系统地改变甲烷在蒙脱土晶体结构中的位置, 建立起一系列甲烷与层板相互作用的Lennard-Jones势能曲线, 通过最小二乘法拟合这些Lennard-Jones势能曲线得到一系列的σ_fw和ε_fw值, 利用拟合得到的σ_fw和ε_fw算术平均值作为墙势模型中两个交互作用参数的取值进行分子模拟, 模拟结果与文献实验值符合较好. 在此基础上, 进一步模拟了3种不同孔率, 层间距为0.64 nm的ZrO₂柱撑粘土(ZPC)在245 K下对临界态甲烷的吸附, 发现 3～4 MPa是ZPC材料吸附甲烷较适合的压力范围, 而且孔率大的ZPC有利于甲烷的吸附.     

Applicability of the BET method for determining surface areas of microporous metal-organic frameworks

The surface area is one of the most important quantities for characterizing novel porous materials. The BET analysis is the standard method for determining surface areas from nitrogen adsorption isotherms and was originally derived for multilayer gas adsorption onto flat surfaces. Metal-organic frameworks (MOFs) are a relatively new class of crystalline, porous materials that have been shown to exhibit very large BET surface areas. These materials are microporous and possess surfaces that are far from flat. In some MOFs, adsorption occurs through a pore-filling mechanism rather than by layer formation. Thus, it is unclear whether BET surface area numbers reported for these materials are truly meaningful. Given the standard practice of reporting BET surface areas for novel porous materials, a critical test of the BET method is much needed. In this work, grand canonical Monte Carlo simulations were used to predict adsorption isotherms for nitrogen in a series of MOFs. The predicted isotherms were used as pseudoexperimental data to test the applicability of the BET theory for obtaining surface areas of microporous MOFs. BET surface areas calculated from the simulated isotherms agree very well with the accessible surface areas calculated directly from the crystal structures in a geometric fashion. In addition, the surface areas agree well with experimental reports in the literature. These results provide a strong validation that the BET theory can be used to obtain surface areas of MOFs.