High Pressure Adsorption Data of Methane, Nitrogen, Carbon Dioxide and their Binary and Ternary Mixtures on Activated Carbon

Adsorption equilibria of the gases CH₄, N₂, and CO₂ and their binary and ternary mixtures on activated carbon Norit R1 Extra have been measured in the pressure range 0 P 6 MPa at T = 298 K. Pure gas adsorption equilibria were measured gravimetrically. Coadsorption data of the three binary mixtures CH₄/N₂, CH₄/CO₂, and CO₂/N₂ were obtained by the volume-gravimetric method. Isotherms of five ternary mixtures CH₄/CO₂/N₂ were measured using the volumetric-chromatographic method. First, we present in a short overview the method and procedure of measurement. In a second part, the measured data of pressures, surface excess amounts adsorbed and absolute amounts adsorbed are presented and analyzed. In the last part of the paper the resulting pure gas adsorption data are correlated using a generalized dual-site Langmuir isotherm. Mixture adsorption can be predicted by this model using only pure component parameters with fair accuracy. Results are presented and discussed in several tables and figures.     

Measurement of Gas Mixture Adsorption Equilibria of Natural Gas Compounds on Microporous Sorbents

Physisorption equilibria of multicomponent gases on microporous solids like zeolites or activated carbons are considered. In view of lack of reliable and simple methods to calculate mixture adsorption isotherms from pure component data, experiments are still indispensable. An overview of classical and new methods to measure multicomponent gas adsorption equilibria is given. Some of the basic concepts like the Gibbs excess mass and the absolute mass adsorbed underlying these methods are discussed. Experimental data and a class of new adsorption isotherms for inhomogeneous microporous adsorbents of fractal dimension will be given in another subsequent paper (ADSO 635-98) by the same group of authors.     

在不同复盖度下二组分气体在硅胶上的吸附规律

通过测定不同复盖度下的丙酮－正己烷、苯－正己烷、甲苯－正己烷和正戊烷－正己烷四个二组分气体在硅胶组成吸附等温线，发现它们有着共同的规律，随着复盖度的增加，各体系的组成吸附等温线都逐渐向下靠近它们各自的气液平衡曲线，因此基本上可以反组分吸附相看成二组分液相，其中除了形成最低人沸点的丙酮－正己烷体系以外，其它三个体系的组成吸附等温基本上都可以理想溶液的相对挥发度议程式模拟得到。     

A Thermodynamic Model for Gas Adsorption Isotherms

In this paper based on the principle of solution thermodynamics for gas–solid equilibrium, a relation is developed to express gas adsorption isotherms. An activity coefficient model based on weight fraction of sorbate in the solid phase has been derived that well describes the behavior of various gases on different types of adsorbents. The proposed model has been evaluated and compared with four other models commonly used for gas adsorption isotherms in the literature. For 12 different systems at various isotherms for the temperature range −128 to 100°C and the pressure range 0.02 to 1219 kPa for 689 data points, the proposed model predicts equilibrium pressure with an average deviation of 5.3%, which is about half of the error obtained from other methods. The proposed model clearly outperforms other available methods such as the vacancy solution theory, the ideal adsorption solution model, and other various modified forms of the Langmuir isotherm. Unique features of the proposed model are its simplicity, generality, and accuracy over the entire pressure and temperature ranges.     

阴、阳离子表面活性剂混合体系在硅胶/水及硅胶/矿化水界面上的吸附

研究阴、阳离子表面活性剂混合体系(十二烷基氯代吡啶,辛基磺酸钠,辛基三乙基溴化铵/十二烷基苯磺酸钠)在硅胶,纯水和硅胶,矿化水界面上的吸附作用,探讨阴(阳)离子表面活性剂的存在对阳(阴)离子表面活性剂吸附作用的影响．结果表明,阴离子表面活性剂的存在基本不影响阳离子表面活性剂在带负电固体表面的吸附;而阳离子表面活性剂的存在却使本来吸附量就不大的阴离子表面活性剂在带负电的固体表面上不再吸附．在矿化水中阳离子表面活性剂的吸附量比在纯水中明显降低．从硅胶表面吸附机制解释了所得结果．     

Adsorption from Ternary Liquid Mixtures on Partially Dehydroxylated Silica Gel

The formation of mixed adsorbed layers has been tested for ternary mixtures containing a specifically adsorbed component—acetone and binary solvent benzene +n-hepane. The specific excess adsorption isotherms from the liquid phase were measured on silica gel samples partially dehydroxylated. The competition of liquid components for silica surface is discussed on the basis of changes in the mixed solvent composition.     

Characterization of Titania/Silica Gel by Means of Low-Pressure Nitrogen Adsorption

Adsorbents synthesized by grafting of titania onto mesoporous silica gel surfaces at different temperatures were studied by means of nitrogen adsorption–desorption and water desorption. The pore size distribution f(R_p) of titania/silica gel depends on the titania concentration (C_TiO2) and the temperature of titania synthesis. Nonuniformity of TiO₂ phase is maximal at a low C_TiO2 value (3.2 wt.% anatase deposited at 473 K), and two peaks of the fractal dimension distribution f(D) are observed at such a concentration of titania, but at larger C_TiO2 values, only one f(D) peak is seen. More ordered filling of pores and adsorption sites by nitrogen, reflecting in the shape of adsorption energy distributions f(E) at different pressures of adsorbate, is observed for adsorbent with titania (rutile+anatase) grafted on silica gel at a higher temperature (673 K).     

Selective Adsorption of Arsenic Ions on Silica Gel Impregnated with Ferric Hydroxide

Abstract

Selective adsorption of trace arsenite- and arsenate anions in an aqueous solution by ferric hydroxyde supported on silica gel particles was investigated. Silica gel particles were loaded with ferric hydroxide of the range of 1 – 3 wt. % in terms of Fe based on the dry gel, and the extent of adsorption of arsenite or arsenate ion measured by batch- and column processes, being the highest at pH 6 in the presence of diverse foreign ions. With the use of silica gel containing 3.3 wt. % Fe, as much as 0.07 m mol of arsenic per gram of dry gel was adsorbed.     

有机试剂键合硅胶对牛血清白蛋白的吸附行为

介绍几种偶氮，卟啉，三苯甲烷类有机试剂键合硅胶的合成方法，研究其吸附牛血清白蛋白（ＢＳＡ）的行为，研究结果表明：ＴＰＰ．ＳＧ吸附性能最佳，对ＢＳＡ吸附平衡１ｈ即可达到，最大吸附率为９０％，最大吸附容量为１２．２ｍｇ／ｇ。     

Correlation and Calculation of Multicomponent Adsorption Equilibria Data Using a Generalized Adsorption Isotherm

Enhanced by the need for reliable and accurate data of multicomponent gas adsorption equilibria on porous solids like activated carbons or zeolites, a new method to measure and correlate coadsorption equilibria has been developed. This method is a combination of gravimetric or volumetric measurements of the total load of pure or multicomponent adsorbates (Staudt, 1994; Gregg and Sing, 1982) and a correlation and calculation procedure using a new adsorption isotherm (AI) (Keller, 1990). This AI is thermodynamically consistent and describes adsorbates with fractal dimension for single- or multicomponent systems and load dependent adsorption energies. This method allows calculation of partial loads of multicomponent coadsorption equilibria from pure component data and the total loads of the mixture adsorption equilibria. This will be demonstrated for binary and ternary adsorption equilibria of CH₄, C₂H₄ and C₂H₆ on activated carbon (Reich et al., 1980).     

Adsorption of Metallocenes on Silica

The adsorption of the metallocenes ferrocene, doubly deuterated ferrocene, cymantrene and nickelocene, as well as molybdenum hexacarbonyl, proceeds in the absence of a solvent. Large single pieces of silica gel were placed in contact with the solid metallocenes and the adsorption process was visualized on a macroscopic scale and the maximal loadings were determined. ¹H, ²H, and ¹³C solid‐state NMR studies confirmed fast isotropic reorientation of the surface‐adsorbed metallocene molecules within the pores of the silica. All prevalent anisotropic solid‐state interactions were averaged out. The solid diamagnetic and paramagnetic materials were amenable to measurements with a standard solution NMR instrument. All metallocenes adsorbed in a monolayer. In the case of ferrocene and cymantrene, different ¹³C MAS signals were obtained for the cyclopentadienyl ring carbon nuclei and assigned to one ring interacting with the surface and one ring pointing away from it. The relative adsorption strengths of ferrocene on different silica supports, nanotubes, and activated carbon were determined by a novel straightforward method recording the desorption temperature. The reversibility of adsorption has been demonstrated by competition experiments using ferrocene, doubly deuterated ferrocene, and cymantrene. Adsorbed nickelocene could be reduced to small Ni⁰ aggregates on the surface and the catalytic activity of the resulting material for the cyclotrimerization of phenylacetylene was proven.     

Adsorption of SO2 on alumina

The adsorption of SO₂ on alumina used in the aluminium industry, the so-called smelter-grade alumina, was studied in the temperature range 15–120°C. It was found that at temperatures lower than 40°C, sulphur dioxide was bonded to alumina reversibly by physical forces, and the adsorption could be described satisfactorily by the Langmuir adsorption isotherm. The heat of adsorption was estimated to be −33 kJ mol⁻¹. At temperatures ranging from 80°C to 120°C, which prevail in dry scrubbers in the aluminium industry, the heat of adsorption was determined to be −56 kJ mol⁻¹. When SO₂ was adsorbed at temperatures higher than 80°C, about 30 % of the SO₂ could not be desorbed even if the samples were heated up to 250°C. In the presence of SO₂ and oxygen, the formation of sulphate was observed at temperatures above 90°C.     

Measurement and Modeling of Water Vapor Adsorption on Zeolite 4A—Equilibria and Kinetics

The adsorption of water vapor on Zeolite 4A has been analyzed. Both equilibrium and kinetics are examined. The equilibrium is measured with a static-volumetric method in a wide range of partial pressure and temperature and is modeled by several conventional approaches and a new type isotherm model, which fitted the obtained data best. Kinetics are determined by measuring breakthrough curves. The breakthrough curves are matched by a detailed model based on a modified linear driving force (LDF) approximation for the mass exchange. An analytic expression for the corresponding LDF-coefficient is designed in order to describe its dependency on water concentration, temperature and pressure. For the practical range of operating conditions the dependency on concentration can be described by the nonlinearity of the adsorption isotherm. The dependency on temperature and pressure corresponds to that of molecular diffusion. The presented data and models for equilibria and kinetics provide a basis for modeling and optimizing air-drying processes containing Zeolite 4A.An erratum to this article can be found at     

囊泡状二氧化硅的合成及油气吸附性能

以正硅酸四甲酯(TMOS)为硅源,P123(EO20PO70EO20)为表面活性剂,在p H=6的磷酸缓冲体系中制备了囊泡状二氧化硅材料.利用乙醇萃取脱除模板剂P123,电镜观测结果表明所得二氧化硅具有大孔囊泡结构,N2吸附结果表明其具有高比表面积和大孔容.通过Boehm滴定法确定了硅羟基数量与吸水率呈正相关.用囊泡状二氧化硅材料与商业化活性炭(AC)和硅胶(SG)对水蒸气、正己烷和油气进行静态吸附.在自建的动态正己烷吸附装置上用对囊泡状二氧化硅材料和商业化AC和SG对正己烷进行动态吸附.吸附结果表明,囊泡状二氧化硅材料的静/动态吸附容量和稳定性都远高于商业化活性炭和硅胶.     

Adsorption of helium on zeolite NaA

Isotherms of helium adsorption on zeolite NaA were measured by the volumetric method under static conditions at 23–50 K and pressures from 1 Pa to 65 kPa. The Henry constants and the initial heat of helium adsorption were calculated; the isosteric heat was calculated, and its dependence on the adsorption was determined.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1291–1292, May, 1996.     

Adsorption isotherm for a solid electrode: The link between the differential surface tension and capacitance curves

Investigation of thermodynamically equilibrium single-component adsorption from a liquid solution on a solid electrode with allowance made for elastic deformation of its surface is continued. A full electrocapillarity equation is derived from thermodynamics equations for an interphase layer in the absence of irreversible processes. Thermodynamic aspects of the Shuttleworth equation are discussed and the equation is compared with two-dimensional Murnaghan formulas for elastic isotropic media. An adsorption isotherm equation and compatibility equations that had been derived previously are examined in a special case where the derivative of a surface concentration with respect to depends solely on (=()) and a rigorous solution of these is obtained for a deformed electrode ( 0). The effect of and dimensionless electrode potential on the extreme (at an infinitely high adsorbate concentration) value of is studied. The model of two parallel capacitors is considered in detail for a general case. Owing to the use of capacitance curves for an elastically stretched electrode, a formula that expresses the differential surface tension of a nondeformed electrode through such curves is derived for the first time ever.To the memory of my motherTranslated from Elektrokhimiya, Vol. 41, No. 1, 2005, pp. 20–34.Original Russian Text Copyright © 2005 by Podgaetskii.     

Adsorption of Pure Nonionic Alkylethoxylated Surfactants down to Low Concentrations at a Silica/Water Interface as Determined Using a HPLC Technique

The adsorption of pure nonionic alkylethoxylated surfactants of the C₁₂E_nseries at silica/water interface has been determined using a very precise HPLC technique. The number of ethoxylated groups was varied from 2 to 9. The adsorption isotherms were constructed with special attention to the very low surface coverage domain. It is shown that at very low concentration, the adsorption amounts are higher as the number of ethoxylated groups increases but the reverse trend is found at higher surfactant concentration and above the critical micelle concentration. It is shown that this behavior is the consequence of the interplay of the primary and secondary adsorption mechanisms depending upon the length of the ethoxylated chain. The maximum adsorption quantities is not a linear function of the number of ethoxylated groups. This and other observations confirm the viewpoint that the behavior of nonionic surfactant aggregates adsorbed at a hydrophilic surface carries many similarities with the properties of this class of nonionic surfactant aggregates in bulk aqueous solutions.     

Trimethylsilyl Protection of Alcohols Over Phosphorus Pentoxide Supported on Silica Gel

Abstract

An eco-friendly and mild protocol for trimethylsilyl protection of alcohols over phosphorus pentoxide supported on silica gel using hexamethyldisilazane has been described. Solvent-free and ambient reaction conditions, easy workup, short reaction times, excellent yields, and reusability of the catalyst are the noticeable features of this methodology.

GRAPHICAL ABSTRACT     

Pure and Binary Gas Adsorption Equilibria and Kinetics of Methane and Nitrogen on 4A Zeolite by Isotope Exchange Technique

The Isotope Exchange Technique (IET) was used to simultaneously measure pure and binary gas adsorption equilibria and kinetics (self-diffusivities) of CH₄ and N₂ on pelletized 4A zeolite. The experiment was carried out isothermally without disturbing the adsorbed phase. CH₄ was selectively adsorbed over N₂ by the zeolite because of its higher polarizability. The multi-site Langmuir model described the pure gas and binary adsorption equilibria fairly well at three different temperatures. The selectivity of adsorption of CH₄ over N₂ increased with increasing pressure at constant gas phase composition and temperature. This curious behavior was caused by the differences in the sizes of the adsorbates. The diffusion of CH₄ and N₂ into the zeolite was an activated process and the Fickian diffusion model described the uptake of both pure gases and their mixtures. The self-diffusivity of N₂ was an order of magnitude larger than that for CH₄. The pure gas self-diffusivities for both components were constants over a large range of surface coverages (0 < < 0.5). The self-diffusivities of CH₄ and N₂ from their binary mixtures were not affected by the presence of each other, compared to their pure gas self-diffusivities at identical surface coverages.