Analysis of the Micropore Structure of Various Microporous Materials from Nitrogen Adsorption at 77 K

The micropore structure of four microporous materials (two zeolites, ZSM-5 and Y-82; an activated carbon and an alumina pillared clay) and their binary physical mixtures (50-50 wt%) have been examined by nitrogen adsorption at 77 K. Various micropore sizes have been considered from the stages on the micropore filling mechanism in the microporous materials. The application of the Dubinin-Astakhov (DA) equation to characterize and obtain the adsorption potential distributions of the microporous materials is presented.     

Adsorption on nonporous and supermicroporous adsorbents

The mean values of the characteristic energy of C₆H₆ adsorption in large micropores were calculated from the adsorption isotherms of benzene vapor on carbon blacks. The supermicropores are characterized by the significant dispersion of the adsorption potential resulted from the pore-size distribution, which imparts the polymolecular character to adsorption. The effect of enhancement of the characteristic energy of adsorption was analyzed, which was caused by the overlap of the force fields of the opposite pore walls and the reduction of the adsorption film surface with micropore volume filling. The both factors are comparable by magnitude and depend on the micropore sizes.     

活性炭纤维的微孔结构水吸附

测定了两种活性炭纤维（ACF）的氮气、水吸附等温线和XPS,研究了ACF的微孔结构和表面性质,用αs图分析氮吸附等温线获得了ACF的比表面积、微孔容量和微孔径。XPS表明在ACF表面存在多种不同结合状态的氧。水在ACF上的吸附等温线呈V型,具有很大的脱附滞后环。水通过与ACF表面的氧形成氢键发生吸附。ACF表面的初始吸附点多,则在低、中压时的水吸附量就大。     

Nonideality of binary mixtures in the adsorbent micropores

Analysis of a binary equilibrium in a distinct micropore showed that the noouniformity of the adsorption field results in a negative deviation of the adsorption solution from ideal behavior. This deviation is due to a decrease in the entropy and internal energy caused by rearrangement of adsorbed molecules. Different interactions between identical and different molecules in distinct micropores also result in a negative deviation from ideal behavior. A criterion was formulated that allows one to elucidate how the deviation from ideality depends on the nonuniformity of the adsorption space and the character of the interaction between molecules in a micropore. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No.6, pp. 1011–1017, June, 2000.     

Adsorption of benzene and perfluorobenzene vapor from a flow of moist air by a layer of equilibrium moistened active carbon

The equilibrium adsorption of benzene and perfluorobenzene vapor from a flow of moist air by a layer of active carbon (AC) hydrated to equilibrium were considered. It was ascertained that these organic substances partly displace the water from the adsorptive micropore volume of AC. The equilibrium adsorption values of benzene, perfluorobenzene, and water vapors on AC were calculated. The adsorption of benzene and perfluorobenzene from a flow of moist air by a layer of AC is characterized by volume filling of the micropore adsorption space. This work is part of the research devoted to the study of the dynamics of the adsorption of organic substances from a flow of moist air by a layer of AC hydrated to equilibrium.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1398–1401, August, 1994.     

Adsorption Characteristics in Zeolite Nano-Pore Evaluated by use of Nitrogen Monoxide as a Probe Adsorbate

Adsorption isotherms of nitrogen monoxide (NO) and in situ EPR spectra of adsorbed NO on mordenite zeolites (MOR) of different cation types (HM, NaM and CaM) are measured at different temperatures to elucidate the effect of the strong adsorption promoted by the enhancement of potential field in micropore of MOR (micropore filling) as well as the electrostatic interaction in MOR on NO adsorption. The NO molecules adsorb irreversibly and fill up the micropore of MOR at 201 K, above the critical temperature of NO, regardless of the kind of cation species. The NO adsorption takes place even at 273 K. In the adsorption at 273 K, the strength of electrostatic field formed by cation sites affects the adsorptivity and the order of saturation amount of adsorption (V _s) corresponds to that of the electrostatic field strength. EPR results show that NO molecules strongly interact with cation sites in MOR and disproponation reaction of NO take place on CaM.     

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.     

Optimum isotherm equation and thermodynamic interpretation for aqueous 1,1,2-trichloroethene adsorption isotherms on three adsorbents

Aqueous 1,1,2-trichloroethene (TCE) adsorption isotherms were obtained on Ambersorb^1® 563 and 572 adsorbents and Filtrasorb^2® 400 granular activated carbon (GAC). The data for Ambersorb 563 adsorbent covers TCE concentrations from 0.0009 to 600 mg/L. The data for each adsorbent was fit to 15 isotherm equations to determine an optimum equation.The best equation for the TCE adsorption isotherms is the Dubinin-Astakov (DA) isotherm. The DA isotherm coefficients were used to estimate the TCE micropore volume and the adsorption potential distribution. For each adsorbent, the TCE micropore volume is equivalent to the N₂ porosimetry micropore volume. The mean adsorption potential is 18.8, 13.0, and 8.9 kJ/mol, with coefficients of variation of 0.37, 0.53, and 0.67, for Ambersorb 563 and 572 adsorbents and Filtrasorb 400 GAC, respectively. Thus, Ambersorb 563 adsorbent has the most energetic and most homogeneous adsorption volume, while Filtrasorb 400 GAC has the least energetic and most heterogeneous adsorption volume. For these reasons, Ambersorb 563 adsorbent has the highest TCE capacity at low concentrations, whereas Filtrasorb 400 GAC has the highest TCE capacity at high concentrations. The performance of Ambersorb 572 adsorbent is generally intermediate to the other two adsorbents.     

Adsorption behavior of organic halides on zeolites

The adsorption behavior and the differential heat of adsorption of chloroform were measured on various types of zeolite (faujasite, ZSM-5 and mordenite) with different Si/Al ratios. The results reveal that saturated adsorption is almost proportional to the micropore volume and is independent of the micropore structure or the Si/Al ratio. However, initial heat of adsorption was the highest (90 kJ mol⁻¹) on the mordenite with low Si/Al ratio, while low on the faujasite with high Si/Al ratio or ZSM-5 (50 kJ mol⁻¹). Change in initial heat of adsorption with Si/Al ratio is small for faujasite or mordenite and large for ZSM-5. For the comparison, trichloroethylene adsorption behavior of zeolite was also investigated. Saturated adsorption of trichloroethylene was almost constant for all types of zeolite, while the faujasite with high Si/Al ratio exhibited an adsorption isotherm of type V in BDDT (Brunauer, Deming, Deming and Teller) classification. The tendencies of heat of immersion are similar to the results of the initial heat of adsorption.     

磁性活性炭的制备及其对KMn04的吸附性能

采用浸渍氮气保护焙烧法,以自制碳酸锶、氯化铁和工业活性炭为原料,制备了介孔磁性活性炭．采用红外光谱、N2吸附、X光衍射、振动样品磁强计等手段和以吸附KMnO4作为探针实验,表征了样品的性质和吸附性能．结果表明,磁性活性炭是具有较高微孔率的介孔磁性材料,其微孔率为45．74％．该材料的饱和磁化强度为19．6emu／g,矫顽力为239．7Oe,易于吸附后的磁分离,且具有一定的抗退磁能力．对KMnO4的吸附探针实验表明其吸附本质为物理吸附．Freundlich吸附等温式可描述KMnO4在磁性活性炭上的吸附平衡,准二级动力学方程是描述KMnO4在磁性活性炭上吸附的最佳吸附动力学模型．本研究有望为特种废水处理剂提供新型功能性材料．     

沥青基球状活性炭气相吸脱附行为研究

本文利用热重法研究了一系列沥青基球状活性炭对蒸汽及正已烷蒸汽的动态吸脱附曲线。结果表明,PSAC对苯蒸汽的吸附及再生性能优良。随吸附温度的降低、比表面积的增大、总孔容及微孔容的增大,PSAC对苯蒸汽的吸附容量增大。PSAC对正已烷的吸附速度大于对苯蒸汽的吸附速度,但其对正已烷的平衡吸附容量小于对苯蒸汽的平衡吸附容量。     

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。     

Low-temperature adsorption/storage of hydrogen on FAU, MFI, and MOR zeolites with various Si/Al ratios: effect of electrostatic fields and pore structures

Several zeolites, such as faujasite, mordenite, and ZSM-5, with various aluminum contents have been used to analyze the effect of aluminum or cation concentration (strength of electrostatic field) on hydrogen adsorption at low temperature. Irrespective of the zeolite structure, the adsorption capacity, isosteric heat of adsorption (-DeltaHads), surface coverage, and micropore occupancy increase with increasing aluminum content of a zeolite. Zeolites with a higher amount of aluminum favorably adsorb hydrogen at relatively low pressures. For zeolites with similar aluminum contents, the adsorption capacity, isosteric heat of adsorption, surface coverage, and micropore occupancy are in the order of mordenite>ZSM-5>faujasite, probably due to differing pore sizes and the presence or absence of pore intersections. This work demonstrates that zeolites with strong electrostatic fields and narrow pores without intersections are beneficial for high hydrogen uptake.     

甲烷在富纳米孔炭质吸附剂上的吸附

分析了以石油焦为原料采用复合活化工艺制备的吸附剂的孔结构特性。发现吸附剂微孔含量在90%以上并且主要集中于1 nm～2 nm之间，是富含纳米孔的吸附材料。甲烷在此吸附剂上的吸附研究表明，在25 ℃，3.5 MPa的条件下，甲烷质量吸附量超过14.0%；有效体积吸附量超过120?V/V(吸附甲烷的体积/容器的体积)。甲烷在富纳米孔炭质吸附剂上的等温吸附曲线表明，吸附类型属于Ⅰ类吸附，符合微孔填充理论；等压吸附曲线表明，低温有利于体积吸附量的增加；吸附剂中水分的增加对吸附有不利的影响。     

Determination of the micropore volume distribution function of activated carbons by gas adsorption

A new method for the determination of the micropore volume distribution function of activated carbons is presented. It is based on the treatment of pure gas adsorption isotherms by a theoretical model derived from the Hill-de Boer theory. Adsorption data (isotherms and heat curves) for carbon dioxide, ethane and ethylene on activated carbon (F30/470 CHEMVIRON CARBON) have been provided by a thermobalance coupled to a calorimeter (TG-DSC 111 SETARAM) at different temperatures (233, 273, 303 and 323 K) for pressures up to 100 kPa. Adsorption isotherms of carbon dioxide and ethane at 303 and 323 K have been used for the determination of the micropore volume distribution function of the activated carbon of interest. The knowledge of its structure has then allowed the simulation of adsorption isotherms and heats for the same adsorbates at the same temperatures as those experimentally studied. Similar calculations have been conducted for ethylene. Whatever the adsorbate (carbon dioxide and ethane used for the determination of the micropore volume distribution function or ethylene), the mean deviation between experimental and calculated isotherms does not exceed 4% at quasicritical and supercritical temperatures (303 and 323 K). In the same temperature conditions, discrepancies between calculation and experiment reach about 10% for adsorption heats. For both isotherms and heats, large discrepancies appear at low temperature (233 and 273 K). This method allows the determination of the micropore volume distribution function of activated carbons. The validity of the results is insured using several isotherms of several adsorbates and taking into account the calorimetric effect of the phenomenon. That is the reason why this method can also be seen as a new possible model for pure gas adsorption data prediction. This paper also presents a brief summary of the state of the art in this field.     

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.     

Diffusion Mechanism of Carbon Dioxide in Zeolite 4A and CaX Pellets

The adsorption kinetics and equilibria of CO₂ in commercial zeolite 4A and CaX pellets were theoretically and experimentally studied by a gravimetric method in the range of 273–313 K and 0.0–0.8 atm. The diffusion mechanism of an adsorbate into a pellet is composed of micropore and macropore diffusion due to the bidisperse structure of the pellet. When one diffusion mechanism played a more important role than the other in determining the overall diffusion rate, the diffusion rate was estimated by the nonisothermal monodisperse diffusion model (NMDM). However, when the combined effects of both mechanisms controlled the overall adsorption kinetics, the experimental uptake was analyzed by the nonisothermal bidisperse diffusion model (NBDM). The CO₂ diffusion in zeolite 4A pellets was controlled by micropore diffusion within the experimental pressure and temperature ranges. However, both macropore and micropore diffusion contributed to CO₂ diffusion in the zeolite CaX pellet. The overall CO₂ diffusion rate in zeolite CaX became faster as pressure increased mainly due to its highly favorable isotherm in the zeolite CaX. The micropore diffusion time constant of CO₂ in the zeolite CaX pellet was approximately one hundred times greater than that in the zeolite 4A pellet. In addition, the activation energy of micropore diffusion of CO₂ diffusion in the zeolite CaX pellet was smaller than that in the zeolite 4A pellet. In this study, the dimensionless parameter, , indicating the relative importance of macropore and micropore diffusion, was modified to consider non-zero coverage as an initial condition for each step in the gravimetric method. When is greater than 100, the overall adsorption rate is controlled by macropore diffusion. However, in cases where is less than 0.1, micropore diffusion is the dominant mechanism in the overall adsorption rate. In the case of a system with between these values, both macropore and micropore diffusion contributed to the overall diffusion rate.     

气固吸附等温线的研究进展

综述了近些年来在气固吸附理论研究领域对吸附等温线的研究进展。论述了从早期的BDDT的5种类型吸附等温线，到IUPAC的6种类型吸附等温线，再到基于Ono-kondo晶格模型的Gibbs吸附分类的5种类型吸附等温线．讨论了与各种类型吸附等温线类型相对应的吸附机理，并对滞留回环现象进行了解释和分析。     

甲苯在多级孔丝光沸石上的吸附平衡和吸附动力学

为了考察多级孔丝光沸石中介孔的存在对丝光沸石吸附平衡和动力学的影响,选择甲苯分子作为探针分子,对其在具有不同介孔孔隙度的多级孔丝光沸石上的吸附等温线和吸附动力学曲线进行了测试。结果表明,甲苯在多级孔丝光沸石上的吸附等温线可以很好地用双位Toth吸附模型进行描述,由拟合参数以及亨利常数（K_H）和初始吸附热（Q_st）的计算得知,相对于微孔丝光沸石,介孔的引入增大了甲苯在丝光沸石内的吸附量,但减弱了甲苯与沸石表面的相互作用力;另外,甲苯在多级孔沸石表现出高的吸附速率,并随介孔孔隙度的增加而增大,反映了沸石内介孔的存在可有效促进沸石的传质能力。