Effects of non-ideal adsorption equilibria of gas mixtures on column dynamics

A theoretical study has been made for simulating the dynamic behavior of non-ideal gas mixtures in an isothermal fixed-bed adsorber. A mathematical model was developed which takes into account the non-ideality of adsorbable species on the adsorbed phase under equilibrium. The model is based on both the real adsorbed solution theory (RAST), which incorporates the activity coefficients in the multicomponent isotherm equations to account for the deviations from ideality, and the linear driving force (LDF) model for representing diffusion resistance inside the adsorbent particles. To describe the effect of non-ideal adsorption equilibrium of gas mixtures on the breakthrough curves, we considered several model mixtures of binary and ternary components which exhibit non-ideal behavior with azeotropic crossovers in the composition domains at equilibrium. Sample calculations of a fixed-bed adsorption were done with various inlet gas compositions of binary and ternary mixtures, respectively, at a fixed total concentration. From the calculation results, it was shown that the order of breakthrough curves could be changed at a certain value of inlet gas composition ratio. This result implies that the dynamic behaviors of fixed-bed adsorption are greatly influenced by multicomponent equilibrium models. Furthermore, the reversal phenomenon of breakthrough curves could not be simulated by the ideal adsorbed solution theory (IAST).     

Comparison of vapor adsorption characteristics of acetone and toluene based on polarity in activated carbon fixed-bed reactor

Adsorption characteristics according to polarity of acetone and toluene vapors on coconut based activated carbon were investigated by using a fixed bed reactor. Single vapor and binary vapor adsorption of acetone and toluene were conducted. In the single vapor system, the equilibrium adsorption capacity of toluene vapor on activated carbon was five times higher than that of acetone vapor because of polarity difference between adsorbent and adsorbate. The breakthrough curve of acetone vapor in the binary vapor was quite different from that of single acetone vapor. Acetone adsorbed in the binary vapor was substituted with toluene due to the affinity difference during adsorption process and its outlet concentration increased to 1.6 times than inlet concentration. The temperature changes in activated carbon bed during adsorption of acetone vapor and toluene vapor occurred in the time ranges of 10–30 min. The temperature change for acetone vapor adsorption was about 3 °C; however, that for toluene vapor adsorption was increased to 33 °C maximally.     

Studies on the Effects of Certain Non‐dimensional Groups on Dynamic Simultaneous Adsorption Behaviour of Carbon Dioxide and Moisture in Molecular Sieve, 5A

A non‐isothermal model based on linear driving force approximation for a system like CO₂ – moisture – N₂ – molecular sieve, 5A predicted the experimental results satisfactorily for simultaneous adsorption of CO₂ and moisture in a fixed bed. Moisture being the strongly adsorbed component forces carbon dioxide (weakly adsorbed component) to be rolled up. The thermophysical and transport properties of moisture mainly governs the dynamics of the process, control or manipulation of which could give better separation by adsorption of one component from the other lying together in a stream. The major parameters are inlet adsorbate concentration, particle Reynolds number, bed diameter to bed length ratio, Schmidt number, Equilibrium Distribution coefficient, Sherwood number, and Kutateladze number.     

The role of adsorbent pore size distribution in multicomponent adsorption on activated carbon

The impact of adsorbent pore size distribution (PSD) on adsorption mechanism for the multi solute system was evaluated in this study. Anoxic and oxic adsorption equilibrium for the single solute (phenol), binary solute (phenol/2-methylphenol) and ternary solute (phenol/2-methylphenol/2-ethylphenol) systems on one granular activated carbon (GAC) F400 and two types of activated carbon fibers (ACFs), namely, ACC-10 and ACC-15, were determined. F400 has a wide PSD, while ACC-10 and ACC-15 have narrow PSD and their critical pore diameters are 8.0 Å and 12.8 Å, respectively. In single solute adsorption, the increase of adsorptive capacity under oxic conditions as compared to anoxic ones was related to the PSD of the adsorbent. Binary solute adsorption on ACC-10 and ternary solute adsorption on ACC-15 indicated no impact of the presence of molecular oxygen on the adsorptive capacity and the adsorption isotherms were well predicted by the ideal adsorbed solution theory (IAST). Significant differences between oxic and anoxic isotherms were noticed for other multicomponent adsorption systems. The narrow PSD of ACFs was effective in hampering the oligomerization of phenolic compounds under oxic conditions. Such a phenomenon will provide accurate predictions of fixed bed adsorbers in water treatment systems.     

Studies on Dynamic Adsorption Behaviour of Ethyl Acetate from Air on 5A and 13X Molecular Sieves

Experimental data for dynamic adsorption of ethyl acetate present in air using 5A and 13X molecular sieves are generated with variations of inlet adsorbate concentration, inlet velocity and bed diameter to bed length ratio to study their effects on the adsorber bed performance. Mathematical model based on Linear Driving Force approximation is validated with experimental data and simulated to understand effects of other pertinent parameters such as overall mass transfer coefficient, saturation capacity and bed to wall heat transfer coefficient. 13X molecular sieve with higher capacity than 5A shows closer to ideal adsorption behaviour. Mass transfer rate is controlled by pore diffusion.     

C2H4/CO2混合体系在活性炭上吸附的实验与模型

通过重量法测定吸附等温线,研究了C2H4/CO2混合体系在活性炭上的吸附分离。采用高精度的智能重量分析仪,测定了C2H4和CO2纯组分以及混合组分在活性炭上的吸附等温线,将测量值与DL-IAST模型计算值进行比较,并计算出了C2H4的吸附选择性。结果表明,DL-IAST模型可以准确地描述C2H4和CO2纯组分在活性炭上的吸附;不同摩尔分数下,C2H4/CO2混合体系的DL-IAST模型计算值与实验值吻合得较好,C2H4摩尔分数越大,模型的相对偏差就越小;随着压力的增加,C2H4的吸附选择性减小,C2H4摩尔分数越大,C2H4的吸附选择性也减小。DL-IAST可以准确地描述C2H4/CO2混合体系的吸附等温线以及推算出C2H4的吸附选择性。     

Dynamic modeling of fixed-bed adsorption of flue gas using a variable mass transfer model

This study introduces a dynamic mass transfer model for the fixed-bed adsorption of a flue gas. The derivation of the variable mass transfer coefficient is based on pore diffusion theory and it is a function of effective porosity, temperature, and pressure as well as the adsorbate composition. Adsorption experiments were done at four different pressures (1.8, 5, 10 and 20 bars) and three different temperatures (30, 50 and 70 °C) with zeolite 13X as the adsorbent. To explain the equilibrium adsorption capacity, the Langmuir-Freundlich isotherm model was adopted, and the parameters of the isotherm equation were fitted to the experimental data for a wide range of pressures and temperatures. Then, dynamic simulations were performed using the system equations for material and energy balance with the equilibrium adsorption isotherm data. The optimal mass transfer and heat transfer coefficients were determined after iterative calculations. As a result, the dynamic variable mass transfer model can estimate the adsorption rate for a wide range of concentrations and precisely simulate the fixed-bed adsorption process of a flue gas mixture of carbon dioxide and nitrogen.     

The rate of gas adsorption by activated carbon

A study was made of the rate of gas adsorption by activated carbon in terms of the functional dependence of the pseudo first order adsorption rate constant. Benzene was used as the adsorbate vapor and a packed bed column of a Pittsburgh activated carbon as the adsorbent. Benzene at a concentration of 2 × 10^?6 g/cm³, equivalent to a relative pressure of 0·005 at 25°C, was flowed into the carbon bed at superficial linear velocities ranging from 2 to 50 cm/sec. The time at which 1% of the inlet concentration appeared in the exit stream of the bed was the breakpoint time. By applying the Wheeler adsorption kinetic equation to the experimental plot of breakpoint time vs bed weight pseudo first order adsorption rate constants at various linear velocities were determined. Using a presumed mathematical model and an overdetermined set of six equations the Univac 1108 computer provided the coefficients for an expression showing the dependence of the adsorption rate constant on the linear flow velocity.     

Methane and carbon dioxide in dual-porosity organic matter: Molecular simulations of adsorption and diffusion

Shale gas, which predominantly consists of methane, is an important unconventional energy resource that has had a potential game-changing effect on natural gas supplies worldwide in recent years. Shale is comprised of two distinct components: organic material and clay minerals, the former providing storage for hydrocarbons and the latter minimizing hydrocarbon transport. The injection of carbon dioxide in the exchange of methane within shale formations improves the shale gas recovery, and simultaneously sequesters carbon dioxide to reduce greenhouse gas emissions. Understanding the properties of fluids such as methane and methane/carbon dioxide mixtures in narrow pores found within shale formations is critical for identifying ways to deploy shale gas technology with reduced environmental impact. In this work, we apply molecular-level simulations to explore adsorption and diffusion behavior of methane, as a proxy of shale gas, and methane/carbon dioxide mixtures in realistic models of organic materials. We first use molecular dynamics simulations to generate the porous structures of mature and overmature type-II organic matter with both micro- and mesoporosity, and systematically characterize the resulting dual-porosity organic-matter structures. We then employ the grand canonical Monte Carlo technique to study the adsorption of methane and the competing adsorption of methane/carbon dioxide mixtures in the organic-matter porous structures. We complement the adsorption studies by simulating the diffusion of adsorbed methane, and adsorbed methane/carbon dioxide mixtures in the organic-matter structures using molecular dynamics.     

Adsorption of volatile organic compounds by means of activated carbon fibre-based monoliths

Activated carbon fibre monoliths (ACFMs) were prepared from the rejects of polymeric fibres (Nomex™). These were carbonised, agglomerated with a phenolic resin and steam activated at burnoff degrees between 0 and 40%. Adsorption experiments with n-butane at 30 °C show that, at high adsorbate concentrations, the amount adsorbed is a function of pore volume, but at low concentrations this mainly depends on pore size distribution. The porosity of Nomex-based ACFMs is formed by narrow micropores, which permit higher amounts of vapour to be adsorbed in low concentrations compared to monoliths prepared from different commercial activated fibres and a commercial granular activated carbon, which exhibits wider pores. The agglomeration of Nomex-fibres to form ACFMs does not cause any loss in adsorption properties with respect to non-agglomerated activated fibres. From the adsorption experiments of different vapours on a Nomex-based ACFM (40% burnoff) it was found that at high concentrations (p/p_o=1) the adsorbed volume was independent of the nature of the adsorbate and depended only on pore volume. However, at low vapor concentrations (p/p_o=0.004), the amount adsorbed depended on the adsorbate being well correlated to the molecular parachor and the polarizability of the adsorbates     

Comparison of Different Photocatalytic Systems for Acetonitrile Degradation in Gas–solid Regime

Photocatalytic degradation of acetonitrile was carried out in gas–solid regime by using two commercial TiO₂ samples (Merck and Degussa P25) irradiated in two continuous annular photoreactors. The inlet gas flow consisted of oxygen, nitrogen, acetonitrile and water vapours. The influence on the photodegradation rate of gas flow rate, acetonitrile, oxygen and water concentrations and photon flux was investigated. The degradation products of acetonitrile were carbon dioxide and hydrogen cyanide. The photocatalysts performance was not affected by the presence or absence of water vapour in the reacting mixture. The Langmuir–Hinshelwood model describes adequately the photoreactivity results and provides the values of kinetic and equilibrium adsorption constants. FT-IR spectroscopy was used to investigate the adsorption patterns and photo-oxidation intermediates of acetonitrile on fully hydrated surface of TiO₂ powders. Acetonitrile was adsorbed on Ti⁴⁺ surface ions and hydroxyl groups for both types of TiO₂. In the absence of UV light this interaction was completely reversible for Merck catalyst whereas for Degussa P25 part of adsorbed acetonitrile molecules reacted to form acetamide-like species.     

Biofiltration of xylene emissions: bioreactor response to variations in the pollutant inlet concentration and gas flow rate

In order to remove xylene vapors from an air stream, an upflow laboratory scale biofilter was operated for a period of 2 months. The experimental study consisted of two different phases: in the first phase, the biofilter was operated at various gas flow rates and the xylene inlet concentration was maintained at 1.39 g m⁻³. In the second phase, various inlet concentrations of the contaminant were tested at a constant gas flow rate of 0.4 m³ h⁻¹ corresponding to an empty bed residence time of 150 s. The biofilter response to steep and abrupt variations in the xylene inlet concentration and gas flow rate was examined. The results obtained revealed that the removal efficiency of the biofilter regained its high values (above 96%) in less than 24 h following the change to low concentrations and gas flow rate. Temperature measurements showed that the biofilter temperature strongly depends on the intensity of the microbial activity in the filter bed. The experimental mass ratio of carbon dioxide produced to the xylene removed was equal to 2.72 indicating that the contaminant was eliminated exclusively by aerobic biodegradation. These findings suggest that a follow up of the amount of carbon dioxide produced in the filter bed can be very helpful in monitoring the performance of the biofilter. For relatively small inlet loads of xylene, the contributions of the different sections of the biofilter to the removal efficiency of the contaminant and the carbon dioxide production were unevenly balanced but became more uniformly distributed for relatively high inlet loads.     

Henry characteristics for finite adsorption on single adsorbent pellets

A theoretical model is presented describing single component adsorption and desorption kinetics in non-isothermal gas phase adsorption systems which takes into account a finite exchange rate between pore fluid and adsorbed phase. For the exchange mechanism a Henry formulation is assumed, while the pore diffusion model is used to quantify intraparticle mass transport. Applying the model equations for the calculation of single pellet adsorption kinetics of water vapour on activated carbon it may be seen that the assumption of instantaneous establishment of adsorption equilibrium within the pore system is justified. Slight deviations from equilibrium preferentially occur in the initial adsorption period.     

Single component and competitive adsorption of propane, carbon dioxide and butane on Vycor glass

Equilibrium of gas phase adsorption on Vycor glass has been investigated. Adsorption isotherms for propane, carbon dioxide and butane as pure gases, binary mixtures and ternary mixtures were determined experimentally as a function of temperature using a volumetric method. The single-component isotherms were described with the Langmuir and Freundlich equations. Additionally, a second order isotherm based on statistical thermodynamics and an isotherm equation based on vacancy solution theory taking into account real phase behavior were used for fitting single-component equilibrium data. In order to describe the measured partial isotherms for binary mixtures, at first simple extensions of the single-component isotherm models were used, i.e., the conventional competitive Langmuir model and a multi-Freundlich equation based on the ideal adsorbed solution theory (IAS). Since these two simple isotherm models failed to represent the unusual competitive behavior observed, three model extensions using additional mixture parameters were applied, i.e., two modified multi-Langmuir equations based on: (a) statistical thermodynamics and (b) vacancy solution theory and a modified multi-Freundlich IAS model correcting spreading pressure uncertainties. These three model equations were found to be capable to describe the observed behavior better. Finally, the measured partial adsorption equilibrium data of the ternary system were correlated based on the extended equations using the determined additional binary parameters. The results obtained reveal the difficulty to predict accurately multi-component adsorption equilibria.     

一步快速活化法制备生物质活性炭及其对乙酸乙酯的吸附再生

活性炭吸附法因技术成熟、简单易行、吸附效率高等优点而被广泛应用于挥发性有机化合物（VOCs）的处理中。本文以山林废弃物的野山桃核为原料,烟道废气及硝酸铁为活化剂,制备了一系列生物质活性炭,并利用固定床吸附装置对其吸附、再生性能进行了研究。利用二氧化碳和水蒸气模拟烟气,在固定流量的烟气活化氛围中进行活化,并探讨了不同硝酸铁的量对活性炭的孔隙结构及其吸附再生性能的影响。利用N₂ 吸附-脱附实验、扫描电镜、拉曼光谱和红外光谱等技术研究了活性炭详细特征。结果表明：当硝酸铁的质量分数为0.2% 时,所制备的活性炭AC-3具有最大的比表面积和平均孔径,分别为923m2/g及2.57nm。其对乙酸乙酯的饱和吸附量也最大,为973.04mg/g。利用烟气对AC-3活性炭进行活化再生处理,经过3次重复吸附-解吸再生实验,其饱和吸附能力仍可达91.5％以上,实现了废弃烟气资源化利用及活性炭的循环回收,从而达到废气治理的目标。     

Identification of the mechanism of coal char particle combustion by porous structure characterization

Two limiting models—the shell progressive mechanism and the homogeneous mechanism—can describe combustion of a single coal particle. Some information about the real mechanism can be obtained from investigation of the porous structure development during combustion. Using the principles of gas adsorption and mercury penetration, the porous structure of a partially combusted particle was estimated. Experiments were carried out in an equipment by applying the thermogravimetric method and using a single devolatilized coal particle. The inlet concentration of oxygen was 5 and 15 mol%. The initial temperature of combustion was in a range from 450 to 800 °C. The mechanism of coal char particle combustion depends on the initial temperature and the inlet concentration of oxygen. At low temperature and low inlet concentration of oxygen, the rate of principal chemical reactions is comparable with the rate of diffusional transport of oxygen inside the particle. Combustion is governed by the diffusion mechanism. This is evident from the values of the specific surface area of pores and proportional representation of individual pore types. At higher temperatures and low inlet concentrations of oxygen, combustion proceeds by the shell progressive mechanism. The specific surface area is lower in comparison with the previous case. There is a sharp interface between the particle core and the ash shell. The core exhibits a higher value of specific surface area than in the case of a non-combusted coal char particle. This fact can be explained by the consecutive reaction of carbon dioxide with carbon in the core of the particle. The rate of this reaction is sufficiently high at temperatures above 800 °C.     

A thermodynamic investigation of adsorbate‐adsorbate interactions of carbon dioxide on nanostructured carbons

A thermodynamic study of carbon dioxide adsorption on a zeolite‐templated carbon (ZTC), a superactivated carbon (MSC‐30), and an activated carbon (CNS‐201) was carried out at temperatures from 241 to 478 K and pressures up to 5.5?10⁶ Pa. Excess adsorption isotherms were fitted with generalized Langmuir‐type equations, allowing the isosteric heats of adsorption and adsorbed‐phase heat capacities to be obtained as a function of absolute adsorption. On MSC‐30, a superactivated carbon, the isosteric heat of carbon dioxide adsorption increases with occupancy from 19 to 21 kJ?mol^?1, before decreasing at high loading. This increase is attributed to attractive adsorbate–adsorbate intermolecular interactions as evidenced by the slope and magnitude of the increase in isosteric heat and the adsorbed‐phase heat capacities. An analysis of carbon dioxide adsorption on ZTC indicates a high degree of binding‐site homogeneity. A generalized Law of Corresponding States analysis indicates lower carbon dioxide adsorption than expected. © 2017 American Institute of Chemical Engineers AIChE J, 64: 1026–1033, 2018     

Assessment of energetic heterogeneity of coals for gas adsorption and its effect on mixture predictions for coalbed methane studies

This study explains the single-component and binary mixture adsorption studies on two different coals from the Zonguldak Basin (Northwestern Turkey). Assessment of energetic heterogeneity of coal surface and its effect on the equilibrium binary gas adsorption are discussed. Single component adsorption tests were performed using methane and carbon dioxide at 30°C. Binary mixtures prepared with 10, 15 and 20% carbon dioxide were also tested at the same temperature. Various single-component adsorption isotherms were fitted to the experimental data of single gases. The data obtained from these models were interpreted to determine the energetic heterogeneity of the coals towards adsorption of methane and carbon dioxide. Ideal adsorbed solution (IAS) theory was used to predict the data and discrepancies between experimental data, and the model predictions were interpreted. Results showed that coals exhibit a heterogeneous behavior in gas adsorption. This heterogeneity can be different for each coal–gas pair and the extent of the heterogeneity makes the binary gas predictions differ from the experimental data. The deviations between IAS and experimental data increase as the amount of gas, to which the coal shows high heterogeneity, increases in the mixture.     

Interactions between adsorbed carbon monoxide and water on platinum

Detailed analyses of the adsorption of carbon monoxide on platinum show that a previously unknown surface compound, “carbon monoxide monohydrate,” is formed utilizing two adjacent platinum sites, one covered by linear carbon monoxide and the other by a co-adsorbed water molecule. At high coverages of carbon monoxide, the surface concentration of “carbon monoxide monohydrate” is limited by the number of adsorbed water sites.“Reduced carbon dioxide” on platinum is identified as a two-electron reduction species from carbon dioxide and has a rate constant for oxidation higher than that of “carbon monoxide monohydrate.” Oxidation of methanol produces “reduced carbon dioxide” but interactions between “reduced carbon dioxide” and adsorbed water sites cannot be identified at present. Indications of a strong interaction are seen from the effect of “reduced carbon dioxide” on the adsorbed hydrogen isotherms on platinum at those water adsorption sites.This work shows that the unpoisoned catalyst sites available for hydrogen oxidation in the presence of carbon monoxide should not be treated in the same way as the same catalyst sites in the absence of carbon monoxide.The structure of adsorbed water at the platinum catalyst surface may be the most important factor in controlling the oxidation of hydrogen in reformed natural gas.     

On the molecular basis of adsorbed solution behaviour

A theoretical study, based on statistical thermodynamics, of the adsorbed solution behaviour of binary gas monolayers on a homogeneous solid surface is presented. The adsorbate—solid interactions are modelled via the summed 10-4 potential and the adsorbate—adsorbate interactions as those of a two-dimensional fluid mixture in which the molecules interact via Lennard-Jones 12-6 potentials. The thermodynamic properties of the two-dimensional mixture are obtained from the van der Waals one-fluid model. We present results from Monte Carlo computer simulations of two-dimensional fluid mixtures which support the accuracy of this procedure. The model can be used to study the relative importance of adsorbate—solid and adsorbate—adsorbate interactions in determining the adsorbed solution behaviour.Comparisons with experimental adsorption equilibria data for ethane—propane mixtures adsorbed on graphitized carbon black show that the theory gives excellent predictions of the adsorption equilibria, without adjustable parameters. For this system at 298 K and 700 Torr the adsorption selectivity is dominated by the difference in the Henry's law constants. However, it is shown that the adsorbate—adsorbate interactions and nonideal adsorbed solution behaviour become more or less important depending on the conditions in relation to the two-dimensional phase diagram.