Thermodynamic Description of Excess Isotherms in High-Pressure Adsorption of Methane, Argon and Nitrogen

In the present work the supercritical fluids argon, methane and nitrogen were picked out as examples, and the results of analysis concerning the adsorption of these fluids at activated carbon Norit R1 (Norit company, Germany) and SCS-3 (ISPE, Kiev) at different temperatures up to a pressure of 50 MPa are presented and discussed in this paper. The principle of working of the measuring device is described in this context as well.A three-parameter isothermal equation is used to represent the adsorption equilibrium. The isothermal equation is based on a physical model concept which has already been used for the modelling of adsorption processes with a pressure up to 15 MPa.     

Contactless Weighing Up to High Pressures For Analysing Adsorption And Density of Fluids

Adsorption of supercritical fluids methane, nitrogen and argon by active carbons was studied up to a pressure of 500 bar. A three-parameter isothermal equation was used to represent the adsorption equilibrium. This isothermal equation is based on a physical model conception which had already been used for the modelling of adsorption processes with a pressure up to 150 bar. Beside the exact knowledge of the measurable parameters pressure, temperature and fluid composition, the density of the adsorbate are essential for the evaluation of the adsorption analysis. The fluid density can be determined either via equations of state, which is normally the most practicable and fastest way, or via lift measurements of a lowering body in the fluid based on the principle of Archimedes. This work represents and discusses the question of to what extent the fluid density determined under real conditions via equations of state, using, for example, equation of Bender, corresponds to the fluid density measured under high-pressure. This revised version was published online in August 2006 with corrections to the Cover Date.     

Multicomponent adsorption on activated carbons under supercritical conditions

Adsorption of binary mixtures onto activated carbon Norit R1 for the system nitrogen-methane-carbon dioxide was investigated over the pressure range up to 15 MPa. A new model is proposed to describe the experimental data. It is based on the assumption that an activated carbon can be characterized by the distribution function of elements of adsorption volume (EAV) over the solid-fluid potential. This function may be evaluated from pure component isotherms using the equality of the chemical potentials in the adsorbed phase and in the bulk phase for each EAV. In the case of mixture adsorption a simple combining rule is proposed, which allows determining the adsorbed phase density and its composition in the EAV at given pressure and compositions of the bulk phase. The adsorbed concentration of each adsorbate is the integral of its density over the set of EAV. The comparison with experimental data on binary mixtures has shown that the approach works reasonably well. In the case of high-pressure binary mixture adsorption, when only total amount adsorbed was measured, the proposed model allows reliably determining partial amounts of the adsorbed components.     

Single and Mixed Gas Adsorption Equilibria of Carbon Dioxide/Methane on Activated Carbon

Single gas adsorption isotherms of methane and carbon dioxide on micro-porous Norit RB1 activated carbon were determined in a gravimetric analyser in the temperature range of 292 to 349 K and pressures to 0.8 Mpa. Furthermore binary isotherms of carbon dioxide and methane mixtures were determined at 292 K and pressures up to 0.65 MPa. Adsorbed phase compositions were determined from the gravimetric data by the rigorous thermodynamic method of Van Ness.These experimental binary equilibrium data were compared with equilibrium data calculated by the Ideal Adsorbed Solution (IAS) model. Only moderate agreement could be obtained.Finally, activity coefficients, accounting for the non-ideality of the adsorbate mixture, were calculated from the experimental data. The Wilson equation, derived for bulk solutions, was fitted on these activity data and the Wilson interaction parameters were determined. The Wilson equation proved to correlate the experimental data reasonably. However, the Wilson interaction parameters are not only completely different from those found for bulk solutions, but also the physical interpretation of these parameter values is completely lacking.It is concluded that new solution models should be developed encompassing both non-ideal solution behaviour and surface heterogeneity.     

超临界条件下甲烷在纳米活性炭表面的吸附机理

在273-373 K、0-10 MPa范围内测量了甲烷在纳米活性炭表面的吸附等温线和等量吸附热. 结果发现, 在实验涉及的温度范围内, 吸附平衡特性在低压下能够很好地遵循Dubinin-Astakhov (DA)微孔填充模型, 但是当压力超过特定范围时, 吸附等温线及等量吸附热测量数据都与DA模型计算结果发生了偏离, 吸附行为更接近单层定位吸附.文中参照Cerofolini对亚单层吸附提出的Freundlich-Dubinin-Radushkevich (FDR)混合模型, 对纳米活性炭在较高压力条件下的吸附使用通用Freundlich (GF)模型进行了修正, 从而提出了一种分段模型GFDA. 根据GFDA模型对甲烷在广泛的压力范围内在纳米活性炭表面的吸附机理进行了完整的解释, 并对纳米活性炭表面的能量非均匀性进行了分析.     

Mechanism of Methane's Adsorption on Nanometer Active Carbon at Supercritical State

Isosteric heats and adsorption isotherms of methane on nanometer active carbon were measured at supercritical temperature (273-373 K) and pressure from 0 to 10 MPa. The measured data agreed well with Dubinin-Astakhov (DA) model at lower pressure but failed when pressure exceeded a special range. General Freundlich (GF) equation was used to modify the DA equation at high pressure and thus formed a combined bisection model GFDA. The adsorption mechanism of methane on nanometer active carbon was raised according to GFDA model and the heterogeneous energy distribution of the adsorbent was analyzed.     

Competitive adsorption and desorption of a bi-solute mixture: effect of activated carbon type

This study aims to clarify the effects of carbon activation type and physical form on the extent of adsorption capacity and desorption capacity of a bi-solute mixture of phenol and 2-chlorophenol (2-CP). For this purpose, two different PACs; thermally activated Norit SA4 and chemically activated Norit CA1, and their granular countertypes with similar physical characteristics, thermally activated Norit PKDA and chemically activated Norit CAgran, were used. The thermally activated carbons were better adsorbers for phenol and 2-CP compared with chemically activated carbons, but adsorption was more reversible in the latter case. 2-CP was adsorbed preferentially by each type of activated carbon, but adsorption of phenol was strongly suppressed in the presence of 2-CP. The simplified ideal adsorbed solution (SIAS) model underestimated the 2-CP loadings and overestimated the phenol loadings. However, the improved and modified forms of the SIAS model could better predict the competitive adsorption. The type of carbon activation was decisive in the application of these models. For each activated carbon type, phenol was desorbed more readily in the bi-solute case, but desorption of 2-CP was less compared with single-solute. This was attributed to higher energies of 2-CP adsorption.     

甲烷在活性炭上吸附平衡模型的研究

比较吸附模型分析甲烷在活性炭上吸附平衡的适用性,为吸附式天然气(ANG)的工程应用提供准确的预测模型。基于在温度268.15～338.15 K、压力0～12.5 MPa测试的甲烷在Ajax活性炭上的吸附平衡数据,选择Langmuir、Langmuir-Freundlich和Toth方程,应用非线性回归拟合方程参数后,确定绝对吸附量和甲烷吸附相态,并比较方程在不同压力区域内的预测精度。结果表明,甲烷吸附相密度随平衡温度和压力变化;由绝对吸附量确定的甲烷在Ajax活性炭上的平均等量吸附热为15.72 kJ/mol,小于由过剩吸附量的标绘结果;Langmuir、Langmuir-Freundlich和Toth方程预测结果在0～0.025 MPa的累积相对误差为6.449 8%、7.918 4%和0.910 0%,在1～10 MPa为0.491 1%、0.161 3%和0.369 4%。Toth方程在整个压力范围内的预测结果最为准确,但Langmuir-Freundlich方程在较高压力区域内具有较高的预测精度。     

Modeling of gas adsorption equilibrium over a wide range of pressure: a thermodynamic approach based on equation of state

A thermodynamic approach based on the Bender equation of state is suggested for the analysis of supercritical gas adsorption on activated carbons at high pressure. The approach accounts for the equality of the chemical potential in the adsorbed phase and that in the corresponding bulk phase and the distribution of elements of the adsorption volume (EAV) over the potential energy for gas-solid interaction. This scheme is extended to subcritical fluid adsorption and takes into account the phase transition in EAV. The method is adapted to gravimetric measurements of mass excess adsorption and has been applied to the adsorption of argon, nitrogen, methane, ethane, carbon dioxide, and helium on activated carbon Norit R1 in the temperature range from 25 to 70 degrees C. The distribution function of adsorption volume elements over potentials exhibits overlapping peaks and is consistently reproduced for different gases. It was found that the distribution function changes weakly with temperature, which was confirmed by its comparison with the distribution function obtained by the same method using nitrogen adsorption isotherm at 77 K. It was shown that parameters such as pore volume and skeleton density can be determined directly from adsorption measurements, while the conventional approach of helium expansion at room temperature can lead to erroneous results due to the adsorption of helium in small pores of activated carbon. The approach is a convenient tool for analysis and correlation of excess adsorption isotherms over a wide range of pressure and temperature. This approach can be readily extended to the analysis of multicomponent adsorption systems.     

Adsorption equilibrium of binary methane/ethane mixtures in BPL activated carbon: isotherms and calorimetric heats of adsorption

The adsorption of pure methane and ethane in BPL activated carbon has been measured at temperatures between 264 and 373 K and at pressures up to 3.3 MPa with a bench-scale high-pressure open-flow apparatus. The same apparatus was used to measure the adsorption of binary methane/ethane mixtures in BPL at 301.4 K and at pressures up to 2.6 MPa. Thermodynamic consistency tests demonstrate that the data are thermodynamically consistent. In contrast to two sets of data previously published, we found that the adsorption of binary methane/ethane in BPL behaves ideally (in the sense of obeying ideal adsorbed solution theory, IAST) throughout the pressure and gas-phase composition range studied. A Tian-Calvet type microcalorimeter was used to measure low-pressure isotherms, the isosteric heats of adsorption of pure methane and ethane in BPL activated carbon, and the individual heats of adsorption in binary mixtures, at 297 K and at pressures up to 100 kPa. The mixture heats of adsorption were consistent with IAST.     

Methane adsorption on microporous carbon adsorbent with wide pore size distribution

Methane adsorption on a microporous carbon adsorbent with a bimodal pore size distribution is studied at temperatures of 303–333 K at pressures up to 30 MPa. The total micropore volume of the adsorbent, as determined by the Dubinin method, is as large as 1.02 cm³/g. Maximum values of methane adsorption of ≈18 mmol/g are attained at a temperature of 303 K and a pressure of 30 MPa. Methane adsorption isosteres are plotted based on experimental data, and adsorption equilibria at low temperatures are calculated using the linearity of the plots. Experimental isotherms of methane adsorption are compared with the isotherms calculated by the Dubinin–Nikolaev equation with variations in parameters E and n. Temperature dependences of these parameters are determined. Specific characteristics of methane adsorption accumulation are calculated.     

Determination of the average heat and characteristic energy from the adsorption isotherm

The isotherms of the total content, isosteric and average heats of adsorption, as well as characteristic energies of adsorption were determined from the isotherms of excess adsorption of carbon dioxide on six different carbon adsorbents at temperature ranging from 293 to 423 К at pressures up to 6 MPa. The average isosteric heats are in agreement with the average heats of adsorption, which were determined from the equation relating the heat of adsorption with the characteristic energy of adsorption.     

Experimental Determination and Analysis of High Pressure Adsorption Data of Pure Gases and Gas Mixtures

Adsorption data of the pure gases ethane, methane and their mixtures on zeolite 13X and the pure gases carbon dioxide, nitrogen and their mixtures on activated carbon Norit R1 were measured gravimetrically at a temperature of 298 K and pressures up to 15 MPa. From the total loads the partial loads were calculated by the modified van Ness approach. The calculated loads show a good agreement with the experimental data.     

甲烷在层状石墨烯和活性炭上的吸附平衡

以吸附式天然气（ANG）吸附剂的工程应用为目的,以0-10 MPa、283.15-303.15 K甲烷在层状石墨烯（GS（3D）,比表面积2062 m²/g）和活性炭SAC-01（比表面积1507 m²/g）上的吸附平衡数据作分析。首先,在77.15 K下由氮气吸附表征样品的孔径大小及分布（PSD）和比表面积。其次,选择极低压力下的吸附平衡数据标定亨利定律常数,确定甲烷在两吸附剂上的极限吸附热,并由维里方程和10-4-3势能函数计算甲烷与两吸附剂壁面之间的相互作用势。最后,依据测试的甲烷在吸附剂上的高压吸附平衡数据,比较了Langmuir系列方程的关联数据后的拟合精度,并由绝对吸附量计算了甲烷的等量吸附热。结果表明,甲烷在GS（3D）和活性炭SAC-01上的平均极限吸附热为23.07、20.67 kJ/mol;283.15 K下甲烷分子与GS（3D）和活性炭SAC-01之间的交互作用势ε_sf/k为67.19、64.23 K,与洛伦混合法则的计算值64.60 K相近;Toth方程关联甲烷在活性炭SAC-01和GS（3D）上吸附平衡数据的拟合累计相对误差为0.25%和2.29%;甲烷在活性炭SAC-01和GS（3D）上的等量吸附热平均值为16.8和18.3 kJ/mol。相对于活性炭SAC-01,比表面积和微孔容积均较高的GS（3D）对甲烷的吸附更具有优势。     

Metal–Organic Frameworks for Oxygen Storage

We present a systematic study of metal–organic frameworks (MOFs) for the storage of oxygen. The study starts with grand canonical Monte Carlo simulations on a suite of 10 000 MOFs for the adsorption of oxygen. From these data, the MOFs were down selected to the prime candidates of HKUST‐1 (Cu‐BTC) and NU‐125, both with coordinatively unsaturated Cu sites. Oxygen isotherms up to 30 bar were measured at multiple temperatures to determine the isosteric heat of adsorption for oxygen on each MOF by fitting to a Toth isotherm model. High pressure (up to 140 bar) oxygen isotherms were measured for HKUST‐1 and NU‐125 to determine the working capacity of each MOF. Compared to the zeolite NaX and Norit activated carbon, NU‐125 has an increased excess capacity for oxygen of 237 % and 98 %, respectively. These materials could ultimately prove useful for oxygen storage in medical, military, and aerospace applications.     

Adsorption equilibria of binary gas mixtures on graphitized carbon black

Adsorption equilibria for binary gas mixtures (methane-carbon dioxide, methane-ethane, and carbon dioxide-ethane) on the graphitized carbon black STH-2 were measured by the open flow method at 293.2 K. The experimental pressure range was (0 to 1.6) MPa. The extended Langmuir (EL) model and the ideal adsorption solution theory (IAST) have been adopted to predict the equilibria of binary gas mixtures. The results indicate that gas mixtures adsorbed on the homogeneous surface of STH-2 exhibit the nonideal behavior, which is mainly induced by adsorbate-adsorbate interactions. The real adsorption solution theory (RAST) has been used to analyze the property of the adsorbed mixtures. The activity coefficients have been correlated with the Wilson equation. The investigation demonstrates that the nonideality of adsorbed phase is completely dissimilar with the bulk liquid phase. The adsorption of the heavier component would benefit the adsorption of the lighter component.     

Hydrogen adsorption on model adsorbents from the viewpoint of the theory of volumetric filling of micropores

Hydrogen adsorption on model microporous adsorbents with slit-shaped pores was calculated on the basis of Dubinin’s theory of volumetric filling of micropores using the property of linearity of adsorption isosters. Model adsorbents with micropore widths of 0.5, 0.9, and 1.2 nm obtained by the successive exclusion of one, two, and three layers of hexagonal carbon in the crystalline lattice of graphite were used. Hydrogen adsorption was calculated in the structures with single-layer and two-layer carbon walls at temperatures 20, 33, 77, 200, 300, and 400 K and pressures up to 20 MPa. The maximal hydrogen desorption for the AU structure (1:3) with the pressure drop from 20 to 0.1 MPa was 8 wt.% at 200K. The parameters of the porous adsorbent structure were calculated.     

Hydrogen adsorption on a carbon adsorbent with slitlike micropores below and above the critical temperature

Hydrogen adsorption is calculated for model microporous adsorbents with slitlike micropore widths of 0.538, 0.878, and 1.218 nm obtained by the consecutive exclusion of one, two, and three layers of hexagonal carbon from graphite structure taken as a model cell. Calculations are performed using the basic concepts of the theory of volume filling of micropores, Dubinin-Radushkevich equation, and linear adsorption isosteres. For structures with one-and two-layer carbon walls, the calculation is carried out at temperatures of 20, 33, 77, 200, 300, and 400 K and pressures up to 20 MPa. For AC3:5 structure, the maximum hydrogen adsorption amounts to 7.9 wt % at 20 MPa and 300 K. The parameters of adsorbent porous structure are established. Hydrogen adsorption is shown to be governed by the capacity and the energy of adsorption.     

ADSORPTION ISOTHERMS AND POTENTIAL DISTRIBUTIONS OF NITROGEN ON VARIOUS ACTIVATED CARBONS

The adsorption isotherms of four activated carbons (Norit RB1, Chemviron BPL, Monolit, and Ambersorb-572) have been examined by nitrogen adsorption at 77.5 K. A method for adsorption potential distribution calculation has been proposed based on the adsorption isotherms. This distribution provides information about possible changes in the Gibbs free energy caused by the energetic and geometrical heterogeneities of an activated carbon as well as by the adsorbate-related entropic effects. The general character of the adsorption potential distribution is clearly visible by its simple relation to the micropore and mesopore distribution.     

ADSORPTION ISOTHERMS AND POTENTIAL DISTRIBUTIONS OF NITROGEN ON VARIOUS ACTIVATED CARBONS

1. INTRODUCTION Activated carbon, a kind of microporous materials, is widely used as adsorbents and catalytic supports. The knowledge of their basic sorption and structural characteristics is an important factor that determines or limits their applications. Various modern techniques, such as electron microscopy, small angle X-ray scattering, NMR, and some classical measurements, such as calorimetric measurements, adsorption-desorption of vapors and liquids, have been applied. Classical a…