Prediction of the micropore structure parameters and adsorption properties of activated carbons

A regularity govering variations of volume and linear size of micropores in carbon adsorbents during their vapor-gas activation was found. A parameter was proposed that characterizes the degree of development of the micropore system in activating carbons and an initial carbonized material. The parameter is defined as the number (or surface area) of micropores in the volume unit of the micropore zones. This parameter allows one to rationalize the choice of carbonized materials for the preparation of activated carbons with specified adsorption properties and to establish the range of activation beyond which the structure of the micropores loses stability. Furthermore, the parameter serves to predict how activation affects micropore structure parameters and adsorption properties of carbons. This in turn indicates the optimal degrees of microporosity of carbons needed to attain required adsorption properties.     

活性炭吸附CO2与其微孔体积的关系

对五种活性炭样品进行液氮温度下的N2吸附、碘吸附测定和冰点下的CO2吸附表征。结果表明,碘吸附值测定法和基于N2吸附等温线的BET方程、D-R方程,孔结构参数都不能正确反映活性炭对CO2的吸附特性;由CO2吸附等温线得到的D A模型参数也不适合分析活性炭吸附CO2特性;CO2吸附等温线的密度泛函理论（DFT）分析结果表明,CO2在活性炭上的吸附发生在极微孔内,DFT分析的微孔孔容与吸附等温线反映的吸附性能完全一致。因此,根据CO2吸附等温线的DFT模型是准确反映活性炭吸附CO2特性的表征分析方法。     

On the mechanisms of phenol adsorption by carbons

The removal of phenol and related compounds from dilute aqueous solutions by activated carbons corresponds to the coating of the micropore walls and of the external surface by a monolayer. This process is described by an analog of the Dubinin—Radushkevich—Kaganer equation. On the other hand, as suggested by immersion calorimetry at 293 K, in the case of concentrated solutions, the mechanism corresponds to the volume filling of the micropores, as observed for the adsorption of phenol from the vapor phase. The equilibrium is described by the Dubinin—Astakhov equation. It follows that the removal of phenol from mixtures with water depends on the relative concentrations, and the limiting factor for adsorption is either the effective surface area of the carbon, or the micropore volume.     

Critical discussion of simple adsorption methods used to evaluate the micropore size distribution

The well-known simple adsorption methods used to evaluate the micropore size distribution from low pressure adsorption isotherms were examined by employing model isotherms for slit-like graphite micropores obtained from nonlocal density functional theory. It was shown that in the range of pore sizes from about 0.4 to 0.9 nm, the Horvath Kawazoe (HK) method satisfactorily reproduces the shape of the micropore size distribution, but the pore sizes are underestimated. In the case of micropores wider than 0.9 nm, the method fails as the formation of the monolayer on the pore walls produces a peak corresponding to 0.6 nm micropores on the HK pore size distribution. Therefore, the HK method indicates the presence of microporosity even for nonporous samples. The Dubinin-Astakhov adsorption isotherms were also examined and it was shown that their application to represent local adsorption isotherms for homogeneous pores is questionable. However, the adsorption potential distributions seem to be promising for micropore analysis.Nomenclature A Adsorption potential kJ/mol - C ₁ Constant in Eq. 3 and 4 kJ * nm/mol - C ₂ Constant in Eq. 3 and 4 nm³ - C ₃ Constant in Eq. 3 and 4 nm⁹ - C ₄ Constant in Eq. 3 and 4 - d Adsorbate molecule diameter nm - d _A Adsorbent atom diameter nm - G Change in the Gibbs free energy kJ/mol - J Pore size distribution cm³/(g*nm) - R The universal gas constant = 8.31431 J/(mol * K) - T Absolute temperature K - V Amount adsorbed expressed in cm³ of liquid adsorbate per 1 g of the adsorbent = 0.0015468 * amount adsorbed expressed in cm³ STP/g cm³/g - x Pore width nm - X Differential adsorption potential distribution cm³ * mol/(g*kJ) - Constant defined as nm - p Pressure Pa - p ₀ Saturated pressure = 760 torr = 101325 Pa Pa - P _c Condensation pressure Pa - Degree of pore filling - S _BET BET specific surface area m²/g - S _ex External surface area obtained fromt-plot method m²/g - V _mi Micropore volume obtained fromt-plot method cm³/g - V ₁ Total pore volume cm³/g - E Characteristic energy in the Dubinin-Astakhov equation kJ/mol - n Exponent in the Dubinin-Astakhov equation      

Energetics of methane adsorption on microporous activated carbons

The influence of microporous carbon surface oxidation on energetics of methane adsorption at 308 K is discussed. Obtained adsorption heats and integral molar entropies of the adsorbate show that microporous carbon surface oxidation changes the methane adsorption process. This is probably resulted by the existence of an endothermic effect during adsorption in oxidized carbon micropores.     

Dynamics of joint adsorption of mutually soluble substances by activated carbons

A model for the dynamics of isothermal absorption of a binary mixture of an organic substance, soluble in water, and water vapor in a fixed bed of activated carbon was proposed. It includes the equations of material balance and the Myers—Prausnitz model for equilibrium adsorption. The possibility of formation of the condensed phase during the adsorption of an organic substance on moist activated carbon was shown. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1491–1495, August, 1998.     

Effects of micropore size and chemical nature of the surface of carbon adsorbents on the adsorption isotherms of water vapor

Adsorption of benzene and water vapors on activated carbons of various microporous structure was studied. The values of the characteristic energy of adsorption of benzene and water vapors were compared and the affinity coefficients β_H2O for carbons with various degrees of activation were calculated. The values of the β_H2O coefficient for carbons with the same degrees of oxidation remain constant. This makes it possible to use the experimental data on benzene adsorption for prediction of the behavior of microporous activated carbons towards adsorption of water vapor. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2636–2639, December, 2005.     

Determination of the Porous Structure of Activated Carbons Using the IAE Concept. Influence of the Local Adsorption Model

In this paper we study a method for the determination of the micropore volume distribution function of activated carbons. This method is based on the Integral Adsorption Equation concept (IAE). The micropore volume distribution function is assumed to be a Gaussian of which the parameters are unknown. These parameters are determined using adsorption isotherms of carbon dioxide on a given activated carbon (F30/470 CHEMVIRON CARBON) at 278, 288, 298, 303, 308, 318 and 328 K and for pressures up to 100 kPa. Several local adsorption models are used (Langmuir, Volmer, Fowler-Guggenheim, Hill-de Boer). The influence of the choice of the local model on the pore volume distribution function is discussed. The physical validity of this function and the performances of the different models are presented. It appears that the effect of the temperature on the adsorption isotherms is difficult to model over a wide range of relative pressure. The Hill-de Boer and the Langmuir local models are the most efficient (average errors respectively equal to 3.53% and 2.80% in the studied range of temperature and pressure). They provide the most meaningful parameters for the pore volume distribution function.     

Estimation of micropore size distribution in active carbons from adsorption isotherms of water vapor

A possibility of estimation of the micropore size distribution in the carbon adsorbents with the developed micro-and mesoporous structure by analysis of the adsorption isotherms of water vapors was considered. At saturation water condenses in micropores in a form of a weakly compressed liquid. However, water molecules in micropores are packed not so closely as in the liquid because of steric hindrance. Therefore, the real density of water adsorbed in the micropores is lower than that of water adsorbed on an open surface and lower than the density of the normal liquid. An analysis of the adsorption isotherms of water vapors with account for the both opposite effects on the water density gives reliable data on the micropore sizes of the carbon adsorbents. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 40–43, January, 2007.     

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。     

Bimodal micropore size distribution in active carbons

The porous structure of active carbon was compared with that of the original mineral coal and its carbonization products. The parameters of the porous structure were calculated from the adsorption isotherms of CO₂ (298 K) and H₂O (293 K). It was shown that carbonization of the original coal at 1120 K causes changes in the chemical composition, consolidation of the part which is amorphous to X-rays, generation of an ordered defect-containing structure on its basis, an increase in the volume of the micropores, and a decrease in the mean diameter. Activation of the carbonized coal affords a microporous structure with a bimodal size distribution.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 473–475, March, 1993.     

氯化锂活化制备活性炭及吸附锂离子性能研究

采用化学活化法,用猪血粉为前驱体和新型活化剂氯化锂活化制备锂离子活性炭（LB-AC）并进行吸附锂离子研究。用氯化锂对猪血粉进行活化后我们得到比表面积为695 m2?g-1,总孔体积为0.3 cm3?g-1的LB-AC。通过扫描电子显微镜、元素分析、X 射线衍射分析和红外光谱分析等分析手段对LB-AC表面形貌和表面基团进行表征。吸附?解吸实验结果表明,随着温度升高,锂离子的吸附容量随之增加,表明LB-AC对锂离子的吸附是一种吸热反应。当温度增加至35 ℃和45 ℃时,其吸附容量分别增加至1.41 mg?g-1和1.52 mg?g-1。锂离子的初始浓度增加,吸附容量也增加。锂的脱附随着盐酸浓度的升高而增加。LB-AC对锂离子的选择性很高,且吸附剂在碱性环境下吸附容量更高,在酸性环境下基本不吸附。     

Pore structure and adsorption properties of stone active carbons prepared by physicochemical and chemical activation methods

Active carbons (ACs) with diverse microporous and developed mesoporous structures were prepared by chemical and phisochemical activation methods from walnut shells, fruit stones, and grape seeds. The surface chemistry was studied by chemical titration and spectroscopy in the IR, UV, visible, and near IR regions. The ACs prepared by chemical activation contain carboxyl and phosphate groups, which impart acidic properties to the surface. Basic functional groups are mainly formed on the ACs prepared by physicochemical activation. The AC surface has a complicated chemical composition, which results in high adsorpion activity. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 744–748, May, 2006.     

Features of nuclear magnetic relaxation of water and benzene molecules during absorption on activated carbons and estimation of pore size distribution in adsorbents

Nuclear magnetic relaxation in activated carbon—water and activated carbon—benzene adsorption systems was studied by pulse NMR methods. Activated carbons characterized by different porous structures and chemical state of the surface were used. The application of the three-pulse Goldman—Shen sequence to the adsorption system generates a dipole echo caused by the dipole-dipole coupling of structural protons, which is not averaged due to their mobility during experiment. The non-exponential character of relaxation attenuations of the transverse and longitudinal nuclear magnetizations of physically adsorbed molecules in activated carbon pores is a result of differencies in pore sizes. The pore sizes in activated carbon and the size distribution were determined from the data of nuclear magnetic relaxation with allowance for the contribution from the structural protons.     

Steam-carbon gasification catalyzed by calcium: Assessment of the porous structure of active carbons from plum stones and synthetic active carbons

A need for an elaboration of the methods for synthesis and characterization of activated carbons with a requisite porous structure has existed for a long time. One of the methods giving possibility for creating controlled mesopore and micropore structures deals with the steam gasification of various carbon materials. In this work the effects of calcium catalyst on the catalytic steam gasification of active carbons from plum stones and porous polymers are presented. Determination of micropores capacity and specific adsorption in mesopores have been performed by means of the _s method, but adsorption on the heterogeneous solids was described by the integral equation with various local isotherms. This equation has been solved by the regularization method. Based on this method the changes in structural parameters of active carbons depending on the amount of calcium catalyst were estimated.Nomenclature d width of slit-like micropore - F(x) distribution function of the half-width - p vapor pressure of sorbate - p/p _N relative pressure - PSAC Plum Stone Active Carbon - average pore radius, nm - S ₁ relative limit of the validity of experimental point on the adsorption isotherm in the computations by means of regularization method - SAC Synthetic Active Carbon - S _BET specific surface area calculated by means of BET method, m²/g - S _mes mesopore surface area, m²/g - S _mic micropore surface area, m²/g - T absolute temperature, K - V _mes sorption capacity of mesopores, cm³/g - V _mic sorption capacity of micropores, cm³/g - V _p sorption capacity of pores, cm³/g - w/w weight in weight concentration - x half-width of slit-like micropore, nm - x ₁ maximum of half-width of micropore slit, nm - average half-width of slit-like micropore, nm - X _min-X _max integration limits of thex Greek Letters Greek Letters variance of average half-width of slit-like micropore, nm² - local relative filling of micropores - total relative filling of micropores     

Processing methods,characteristics and adsorption behavior of tire derived carbons: A review

The remarkable increase in the number of vehicles worldwide; and the lack of both technical and economical mechanisms of disposal make waste tires to be a serious source of pollution. One potential recycling process is pyrolysis followed by chemical activation process to produce porous activated carbons.     

Determination of adsorption by fluorescence in gas chromatography

PMBF₂, a pyrromethene pigment, can be used in gas chromatography. Because of its fluorescence, adsorption sites on glass columns and connections can be traced in situ. The compound can be employed to check the inertness of glass surfaces after deactivation procedures. Some applications are described.     

活性炭液相吸附去除噻吩硫化物的研究

迄今为止,国内外降低汽油硫含量的方法主要有原料加氢脱硫、汽油加氢脱硫、溶剂抽提脱硫、催化裂化脱硫、氧化脱硫、生物脱硫、吸附脱硫及组合技术,同时一些非常规技术如膜过程脱硫、等离子体和光脱硫也在积极探索之中。