Vapour phase adsorption measurements of c6 hydrocarbon mixtures on synthetic faujasite

A new apparatus is described for measuring pure component isotherms of condensable vapours at temperatures of 25°–150° and pressures up to 600 mm. Facilities are also incorporated into the unit to permit the study of multicomponent adsorption. Without disturbing the adsorption equilibrium, the gas phase can be separated from the adsorbed phase for subsequent analysis by independent methods. With n-hexane, hexene-1, 1,5-hexadiene and benzene on synthetic faujasite at 97°, the pure component isotherms follow the Langmuir equation and the amount adsorbed at saturation has a nearly constant value of 0.23 liq. ml/g. In the adsorption of binary mixtures of benzene and n-hexane at 97°, the separation factor varies strongly with composition and ranges in value from 13 to 52. A maximum factor is observed at intermediate compositions. Hexene-1-n-hexane mixtures under the same conditions give a lower separation factor of 2–3 which is more nearly constant with composition. Data on multicomponent adsorption of other mixtures are also presented.     

ADSORPTION ISOTHERMS AND HEATS OF IMMERSION IN THE ADSORPTION OF BINARY MIXTURES ON ACTIVATED CARBON

The surface excess and the heat of immersion in the adsorption from binary mixtures on the active carbon surface were calculated in terms of the concentrations of adsorbed phase, the adsorption capacity ratios and the heats of immersion of pure compounds. The surface concentrations of binary mixtures were obtained from the thermodynamic model incorporating the intermolecular interactions between the surface and bulk molecules, and a model for surface activity coefficient considering the orientational states of adsorbed molecules, and the UNIQUAC equation. The calculated adsorption isotherms and heats of immersion were fair agreement with experiments of various binary isotherms.     

Propane/Propylene Separation by Simulated Moving Bed II. Measurement and Prediction of Binary Adsorption Equilibria of Propane,Propylene, Isobutane,and 1-Butene on 13X Zeolite

Abstract

The design of a simulated moving bed (SMB) process relies on valid thermodynamic predictions of multicomponent adsorption built up from accurate binary adsorption equilibrium data. Experimental adsorption equilibria of binary mixtures constituted by propane, propylene, isobutane and 1-butene on 13X zeolite were determined using breakthrough experiments at 373 K and 150 kPa. In addition, these binary adsorption experiments allow to confirm the choice of isobutane as an interesting desorbent for the separation of propane-propylene by SMB, since it has an intermediate selectivity between the two species to separate. Various prediction models are available in the literature but only a few of them have both physical and thermodynamical consistency. The ideal adsorbed solution theory (IAST), the thermodynamically consistent extended Toth model (TCET), and the physically-consistent extended Toth isotherm (PCET) were used to predict binary adsorption equilibria from pure component adsorption isotherms parameters. The PCET model was found suitable for representing the adsorption equilibrium of the different hydrocarbon mixtures with a reasonably good accuracy.     

Modeling of adsorption isotherm of a binary mixture with real adsorbed solution theory and nonrandom two‐liquid model

Gas‐phase adsorption equilibria of diluted mixtures of methyl‐ethyl‐ketone and isopropylanol on activated carbon were investigated. Experimental isotherms were determined by a constant volume method. Single‐component adsorption isotherms were fitted by the frequently used Toth model with good accuracy. Then adsorption isotherms were determined for different binary mixtures (with different initial ratio of the two components). Binary mixtures adsorption isotherms were calculated using the adsorbed solution theory. Ideal adsorbed solution theory (IAST) could not represent experimental data, but it was observed that increasing amount of MEK led to higher nonideality of the mixture. Then UNIversal QUAsi Chemical (UNIQUAC) and nonrandom two‐liquids (NRTL) models were considered to describe activity coefficients of the adsorbed phase. The fitted parameters of UNIQUAC model depend on the ratio of the two components, whereas the NRTL model is able to fit all experiments with the same parameters, whatever the initial ratio may be. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

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。     

Binary Adsorption Isotherms of Water and Ethyl Acetate Vapor for Materials Contained in a Box of a Tobacco Product

ABSTRACT

An experimental study has been carried out on the characteristics of binary adsorption isotherms of water and volatile flavor for typical materials used in a box of a tobacco product or cigarettes. Ethyl acetate chosen as a model for water–soluble volatile flavor. Binary adsorption isotherms for the tobacco, papers, filters, and activated carbons were measured with a flow–type multi–component adsorption system under the canstant conditions of temperature a t 303 K and vapor pressure of water a t 2.5 kPain the vapor pressure range of ethyl acetate from 0 to 4.2 kPa. A linear equation was applied to express the binary adsorption isotherms for the tobacco, papers and filters, while a Dubinin–Astakhov equation was applied for the activated carbons. The binary adsorption was characterized into three groups, depending on the selectivity as well as the mechanism of adsorption; i.e.(l) for tobacco and papers, water was adsorbed much greater rather than ethyl acetate, (2) for filters, ethyl acetate was adsorbed on the surface as great as water, (3) for activated carbons, ethyl acetate was adsorbed much greater onto their micropores rather than water. The results showed that ethyl     

Adsorption Equilibria for Ethane and Propane Gas Mixtures on Activated Carbon

Abstract

We measured the transmission curves of binary gas mixtures of esthane and propane (and also of each gas alone) flowing through an adsorber bed at 25°C packed with (Columbia 4LXC 12/28) activated carbon. The adsorption isotherms for pure ethane and propane are described well by a modified Langmuir isotherm known as the Chakravarti-Dhar isotherm. Ethane in the binary mixtures exhibits smaller adsorption capacities than that of pure ethane; however, the presence of ethane does not significantly reduce the adsorption capacity of propane in the mixtures. The ideal adsorbed solution theory (IAST) of Myers and Prausnitz and the semiempirical method of Cook and Basmadjian (C-B) are applied to predict adsorption equilibrium properties of the binary mixtures from the known pure gas isotherms. The pure ethane isotherm data at pressures higher than 10 mmHg are obtained from a correlation formula. Good agreement between the predicted results from the IAST and C-B methods and the experimental results indicates (1) that the correlation formula can be used for estimating isotherms of related hydrocarbons with reliance and (2) that the two methods are useful in predicting the adsorption equilibrium properties for the ethane-propane mixtures on carbon.     

Binary Adsorption Isotherms of Water and Ethyl Acetate Vapor for Materials Contained in a Box of a Tobacco Product

An experimental study has been carried out on the characteristics of binary adsorption isotherms of water and volatile flavor for typical materials used in a box of a tobacco product or cigarettes. Ethyl acetate chosen as a model for water-soluble volatile flavor. Binary adsorption isotherms for the tobacco, papers, filters, and activated carbons were measured with a flow-type multi-component adsorption system under the canstant conditions of temperature a t 303 K and vapor pressure of water a t 2.5 kPain the vapor pressure range of ethyl acetate from 0 to 4.2 kPa. A linear equation was applied to express the binary adsorption isotherms for the tobacco, papers and filters, while a Dubinin-Astakhov equation was applied for the activated carbons. The binary adsorption was characterized into three groups, depending on the selectivity as well as the mechanism of adsorption; i.e.(l) for tobacco and papers, water was adsorbed much greater rather than ethyl acetate, (2) for filters, ethyl acetate was adsorbed on the surface as great as water, (3) for activated carbons, ethyl acetate was adsorbed much greater onto their micropores rather than water. The results showed that ethyl     

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).     

Adsorption from binary and ternary mixtures on activated carbons containing different amounts of chemically bonded oxygen

The adsorption process from the gas and liquid phase on activated carbons was investigated. Unmodified and chemically modified activated carbon Norit RKD-3 with different contents of chemisorbed oxygen were used. The surfaces were characterized by their content of surface functional groups, and the pore structure was characterized on the basis of adsorption-desorption isotherms of benzene vapor. Surface excess isotherms from binary and ternary mixtures of dioxane, n-heptane, and benzene were also determined. The influence of the chemical composition of the carbon surface on the adsorption from the gaseous and liquid phase is discussed.     

正丁烷及丁烯-1在不同硅铝比ZSM-5分子筛上吸附的实验与模型

Four ZSM-5 zeolite catalysts with different Si/Al ratios for the catalytic cracking of C4 fractions to produce ethylene and propylene were prepared in this study.First,the adsorption isotherms of pure n-butane and butene-1 and their mixtures on these catalysts at 300K and p=0—100kPa were measured using the intelligent gravimetric analyzer.The experimental results indicate that the presence of Al can significantly affect the adsorption of butene-1 than that of n-butane on ZSM-5 zeolites.Then,the double Langmuir（DL）model was applied to study the pure gas adsorption on ZSM-5 zeolites for pure n-butane and butene-1.By combining the DL model with the ideal adsorbed solution theory（IAST）,the IAST-DL model was applied to model the butene-1（1）/n-butane（2）binary mixture adsorption on ZSM-5 zeolites with different Si/Al ratios.The calculated results are in good agreement with the experimental data,indicating that the IAST-DL model is effective for the present systems.Finally,the adsorption over a wide range of variables was predicted at low pressure and 300K by the model proposed.It is found that the selectivity of butene-1 over n-butane increases linearly with the decrease of Si/Al ratio.A correlation between the selectivity and Si/Al ratio of the sample was proposed at 300K and p=0.08MPa.     

不同的BET型混合气体吸附公式的应用和比较

本文将Bussey的BET型混合吸附公式应用于30℃时环己烷-乙醇、苯一乙醇和环已烷-苯的混合蒸气在Cab-O-Sil上的吸附,以及—185.6℃时氧-氮和氧-氩混台气体在铬胶上的吸附,并与Hill的和作者的BET型混合吸附公式的结果作了比较.由于Hill的公式太复杂,而其结果又与Bussey公式的差别不大,故从应用的角度看,不宜推荐.Bussey的和作者的公式因只含单纯气体吸附的BET参数,故应用方便;但自现有的实验结果,尚不能判断两者的优劣.     

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.     

Separation of fatty acid methyl esters from tall oil by selective adsorption

Fatty acid methyl esters (FAME) and resin acids (RA) were separated from tall oil by selective adsorption. Commercial nonmodified molecular sieve 13X was used as adsorbent. The adsorption isotherms of fatty acids (FA), FAME, and RA on molecular sieve 13X at 25°C were determined using various solvents. The solvents were methanol, ethanol, isopropanol, acetone, benzene, hexane, isooctane, petroleum ether (40–60°C), and petroleum naphtha (80–180°C). With each solvent, FA and RA were adsorbed to a greater extent than FAME. Adsorption isotherms for RA and FAME in binary adsorption systems were also determined using petroleum ether, petroleum naphtha, benzene, and isopropanol. For each component in the binary adsorption, the equilibrium amounts are lower than the values for pure component adsorption. The adsorption of FAME decreased in the presence of RA markedly in petroleum ether and petroleum naphtha. This fact may be the indication of the phenomenon of selective adsorption. Separation was accomplished by adding a solution of esterified tall oil in solvents used in the binary adsorption systems, through a column packed with molecular sieve 13X. With petroleum naphtha, FAME and RA were recovered in yields of 93 and 94%, respectively, from esterified tall oil. Petroleum naphtha gave the best results. The effects of particle size of adsorbent and flow rate of solvent on the efficiency of the separation were also investigated in fixed-bed column studies. The particle size of adsorbent did not apparently alter the results. Changes in the particle size should not significantly change the number of available adsorption sites in a microporous molecular sieve.     

Adsorption equilibria for oxygen and nitrogen gas mixtures on 5a molecular sieves

Equilibria data for the adsorption of oxygen, nitrogen and binary mixtures of these gases are determined on 5A molecular sieve pellets. Pure component isotherms are presented at pressures up to 9 bar and at 278.15, 293.15 and 303.15 K. The binary equilibria are presented at the same temperatures and at pressures of 1.7 and 4.4bar. The binary data have been examined against values predicted by various models using regression parameters obtained from the pure component isotherms. For these systems the ideal adsorbed solution theory, Cook and Basmadjian model and the statistical thermodynamic model gave the best representation of the experimental data.     

Adsorption of N2, Ar, acetone, chloroform and acetone-chloroform mixture on carbon black in the framework of molecular layer structure theory (MLST)

Adsorption of pure nitrogen, argon, acetone, chloroform and acetone-chloroform mixture on graphitized thermal carbon black is considered at sub-critical conditions by means of molecular layer structure theory (MLST). In the present version of the MLST an adsorbed fluid is considered as a sequence of 2D molecular layers, whose Helmholtz free energies are obtained directly from the analysis of experimental adsorption isotherm of pure components. The interaction of the nearest layers is accounted for in the framework of mean field approximation. This approach allows quantitative correlating of experimental nitrogen and argon adsorption isotherm both in the monolayer region and in the range of multi-layer coverage up to 10 molecular layers. In the case of acetone and chloroform the approach also leads to excellent quantitative correlation of adsorption isotherms, while molecular approaches such as the non-local density functional theory (NLDFT) fail to describe those isotherms. We extend our new method to calculate the Helmholtz free energy of an adsorbed mixture using a simple mixing rule, and this allows us to predict mixture adsorption isotherms from pure component adsorption isotherms. The approach, which accounts for the difference in composition in different molecular layers, is tested against the experimental data of acetone-chloroform mixture (non-ideal mixture) adsorption on graphitized thermal carbon black at 50 °C.     

Multicomponent adsorption equilibrium of ethylene,propane, propylene and CO2 on 13X zeolite

Experimental adsorption isotherms of binary, ternary and quaternary mixtures of ethylene, propane, propylene and CO₂ on 13X zeolite have been obtained at 293 K. Experimental data of mixtures were fitted to three theoretical models, the ideal adsorbed solution (IAS), real adsorbed solution (RAS) and spreading pressure dependence (SPD) models to reproduce and predict equilibrium data. With the SPD model, two other temperatures were also studied, 279 and 308 K, in order to calculate the model parameters. The best models for binary and multicomponent mixtures showing the highest deviation from ideality were RAS and SPD, with RAS better than SPD for ternary mixtures.     

微孔γ-Al2O3膜的蒸汽吸附特性

Vapor permeation has potential applications in the separation of organic solvent-water mixtures.Adsorption property of organic vapor influences mainly the membrane selectivity in vapor permeation.The adsorption isotherms of water,acetone, methanol, ethanol and isopropanol vapors on γ-Al₂O₃ membrane were measured by methods of dynamic chromatography.The parameters of the relevant Pickett isotherms were calculated.

     

Influence of Water Vapor on the Adsorption of VOCs on Lignin‐Based Activated Carbons

Abstract

Activated carbons with a wide range of burn‐off degrees obtained from Eucalyptus kraft lignin have been used to study the influence of the presence of water vapor on VOCs adsorption. The amount adsorbed and the rate of adsorption of both benzene and water vapor increase with activated carbon burn‐off as a consequence of an increase of micropore volume, broadening of micropore size distribution and increasing development of meso‐ and macroporosity. Similar results were found for MEK and methanol. Benzene is only partially desorbed at the adsorption temperature and an appreciable amount of it remains in the carbon, most likely in the narrow micropores. On the contrary, water vapor is completely desorbed at the adsorption temperature and its adsorption profile clearly exhibits two steps with different adsorption rates, associated to water molecules adsorbed on the active sites given rise to cluster formation and further migration and filling of the micropores. Adsorption with mixtures of VOC and water vapor has been carried out. The total amount adsorbed by the carbon, near the equilibrium point, is higher than in the case of the stream containing only the VOC. The adsorption rates for the mixtures streams are similar to that for the corresponding streams containing only the VOC in the case of carbons with a well developed porous structure. However, the presence of water vapor increases the rate of adsorption on the activated carbons with narrower microporosity. Saturation of the activated carbon with water vapor prior to the adsorption of a mixture containing benzene and water vapor has shown little effect on the amount of benzene adsorbed, suggesting that water and benzene molecules are adsorbed in different sites on the carbon surface.     

Vapor sorption characteristics of condensable hydrocarbon vapor in low-density polyethylene

Sorption characteristics of vapors of pure hydrocarbon and their binary mixtures in low-density polyethylene were studied under various conditions of temperature and pressure. A new apparatus devised and utilized for the determination of composition of sorbed vapor in case of binary mixtures is described. The study demonstrates the effect of the presence of one component within the polymer on the sorption of another and also the occurrence of selectivity in sorption.