超临界甲烷在高表面活性炭上的吸附测量及其理论分析

实验测定了0～10 MPa,233～333 K (20 K间隔)范围内超临界甲烷在高表面活性炭上的吸/脱附等温线,确定了此物理吸附过程的可逆性,并从实验数据计算出吸附热为16.5 kJ/mol.　建立了描述具有最大点的吸附等温线模型,其总体偏差为±2%.　模型保持了特征吸附能恒定的性质,方程指数亦反映了吸附剂的微孔分布特征,模型参数给出了超临界甲烷的吸附相密度.　将超临界吸附极限态引入等温线模型中,经典的吸附理论亦可解释超临界吸附现象.     

K2CO3活化煤矸石制备活性炭吸附剂

用Ｋ２ＣＯ３化学活化煤矸石制备适用于废水处理的活性炭吸附剂．考察了活化条件对产物的比表面、孔体积及灰分的影响．增加了前处理和后处理步骤以改善产物的性能．最佳条件下获得的活性炭吸附剂ＢＥＴ比表面达１２３６ｍ２／ｇ，孔体积０．６７９ｃｍ３／ｇ．所制得的吸附剂表面是疏水性的，对水溶液中的酚类污染物有良好的吸附性能．     

六硅Y沸石的研制及性能

ＬｉＮａＹ沸石经ＳｉＣｌ４气相同晶脱铝补硅后制得系列高硅铝比,高结晶度的Ｙ沸石,用低温氮吸附法,救是样品对Ｎ２的吸附－－脱附等温线,从而计算其比表面和孔体积,并采用ＢＪＨ模型计算孔径分布。用真空重量法测定了四种Ｃ６化合物（正己烷,２,３－二甲基丁烷、苯、环己烷）的吸附等温线,探讨吸附量与吸附物的性能（极性、几何构型）,吸附量一吸附剂脱铝深度的关系,从而得到,经ＳｉＣｌ４同晶取代后Ｙ沸石的孔结构和表     

交联聚苯乙烯型多孔吸附剂的中孔性质研究

采用77K温度下的氮气吸附方法,测定了经悬浮聚合制备的不同交联度的交联聚苯乙烯多孔吸附剂的吸附/脱附等温线.根据BET吸附模型计算了比表面,由吸附量计算了总的孔体积,由孔体积和比表面计算出平均孔径,并依据脱附等温线采用BJH方法计算孔径分布.结果表明,交联度对交联聚苯乙烯多孔吸附剂的孔结构均具有显著影响.随着交联聚苯乙烯多孔吸附剂的交联度升高,其孔径变小,比表面增大,而且低交联度吸附剂的中孔接近圆柱形,高交联吸附剂的中孔形状接近“墨水瓶”形.显然,交联度对孔性质的影响与孔结构在交联聚苯乙烯多孔吸附剂制备和后处理过程中的稳定性密切相关.交联度低时,初期形成的小孔不能保持稳定,在后续聚合及后处理过程中合并为大孔,结果造成低交联吸附剂大孔径、低比表面的现象.通过对孔径分布的研究,揭示了不同吸附剂在中孔范围内的孔特征,并对其形成机制进行了分析.     

油气吸附分离过程的研究

本文以油气回收的吸附剂筛选为出发点。研究了93号汽油在不同系列吸附剂上的吸附、脱附性能,以及活性炭微孔结构对吸附性能的影响,并与美国类似吸附剂作了比较。结果表明：所用吸附剂的吸附容量自欺欺人优于一般市售活性炭,可望应用于国内炼油厂,加油站和油田的油气吸附回收利用。     

酸性溶液中β-苯胺基苯丙酮在铁上的吸脱附行为

用极化曲线法研究了０．５ｍｏｌ·Ｌ－１硫酸溶液中β－苯胺基苯丙酮（ＰＡＰ）在铁－溶液界面的吸脱附行为及Ｃｌ－,Ｉ－的影响．结果表明,ＰＡＰ的吸附遵循Ｆｌｏｒｙ－Ｈｕｇｇｎｓ等温式;在较正的极化电位区出现阳极脱附现象．讨论了两种粒子联合吸附方式与浓度的关系,提出可根据吸附粒子的脱附电位与其浓度关系来推断联合吸附的理论模型     

超声场下苯酚吸附相平衡和均相催化剂氧化降解实验研究

测定了常规条件和超声场条件下苯酚在活性炭上的吸附等温线,并研究了超声再生活性炭和均相催化剂氧化降解苯酚实验.研究结果表明,超声场作用下苯酚在活性炭上的吸附等温线降低,平衡吸附量减少,被脱附下来的苯酚及时被Cu2 和Fe3 型催化剂氧化降解,吸附剂得到更彻底再生,避免了二次污染,而且再生后的活性炭均具有较高的二次吸附能力,对于处理低浓度含酚废水具有实际意义.     

甲烷在石墨化热解碳黑和活性炭上的吸附

为研究影响碳基吸附剂吸附超临界温度气体的主要因素,选择石墨化热解碳黑BP280和Ajax活性炭,分析超临界温度高压甲烷在其上的吸附平衡。应用容积法,在压力0~20.5 MPa、温度253 K~313 K测定甲烷的吸附平衡数据,并由等量吸附线标绘和亨利定律常数确定等量吸附热。引入通用吸附等温方程,再由方程的Langmuir标绘确定最大吸附容量,进而通过方程的线性化计算吸附平衡态中甲烷分子的作用能。结果表明,甲烷在两种吸附剂上的最大吸附容量均随温度而变化,并都小于液态甲烷的密度;甲烷在碳黑和活性炭上的等量吸附热分别为11.9 kJ/mol~12.5 kJ/mol和17.5 kJ/mol~22.5 kJ/mol,体现了两种吸附剂不同的表面能量分布;甲烷分子间作用能随吸附量的变化特点反映了超临界温度甲烷以类似于压缩气体状态聚集的特点和吸附剂结构上的差异。碳基吸附剂的比表面积和微孔容积是影响其储存甲烷容量的重要因素。     

热重分析技术测定二苯并呋喃在活性炭上的吸附相平衡

以吸附动力学为基础,建立了热重分析技术测定难挥发性有机物吸附等温线的方法.通过热重分析实验测定了不同升温速率下二苯并呋喃从Norit RB1和Chemviton BPL活性炭上脱附速率曲线,及对应的脱附峰温度.运用所提出的方法,对二苯并呋喃在Norit RB1和ChemvironBPL活性炭上的Langmuir吸附等温线方程进行了估算.估算结果与静态吸附实验测定结果相比,误差不超过10%.     

高硅Y沸石的研制及性能——Ⅱ.沸石孔结构及吸附性能

LiNaY沸石经SiCl₄气相同晶脱铝补硅后制得系列高硅铝比、高结晶度的Y沸石,用低温氮吸附法,求得样品对N₂的吸附—脱附等温线,从而计算其比表面和孔体积,并采用BJH模型计算孔径分布。用真空重量法测定了四种C₆化合物(正己烷,2,3-二甲基丁烷、苯、环己烷)的吸附等温线,探讨吸附量与吸附物的性能(极性、几何构型)、吸附量与吸附剂脱铝深度的关系。从而得到,经SiCl₄同晶取代后Y沸石的孔结构和表面性质与脱铝深度的关系。     

Contribution to the evaluation of density of methane adsorbed on activated carbon

The adsorption isotherms of N(2) at -196 degrees C, CO(2) at 0 degrees C, and CH(4) at 25 degrees C on 35 activated carbons with a wide range of micropore volumes and pore size distributions have been compared to evaluate the density of adsorbed methane. Results indicate that methane is adsorbed in the micropores of the activated carbon with a density that is a function of the carbon porosity because methane is packed more compactly in narrow than in wide micropores. An experimental procedure is proposed to evaluate the density in both types of micropores as a function of pressure. Its application to these porous carbons indicates that density of adsorbed methane increases rapidly with pressure on narrow micropores, the increase becoming slower above 1.5 MPa. The value reached at 3 MPa is 0.21 g/cm(3), near that estimated as the limiting value, 0.23 g/cm(3). Density in wide micropores is low, 0.09 g/cm(3) at 3 MPa, but it continuously increases with pressure.     

磷酸铝吸附除水中氟的研究

采用静态吸附法研究了比表面为308m2/g的无定形磷酸铝吸附除氟性能,研究了接触时间、pH值、吸附剂量等对吸附的影响。结果表明,磷酸铝吸附除氟高效、迅速,30min内可以接近最大吸附量。对含氟50mg/g的溶液,优化条件下的最大除氟率约93%。研究了吸附与溶液pH的关系,得到了优化pH值并解释了吸附机理。吸附的最佳pH值约为5.5。用拟二级动力学方程描述了吸附速率并计算了速率常数。用Langmuir方程拟合了吸附等温线,计算的饱和吸附量为53.5mg/g。吸附剂量对分配系数的影响表明吸附剂表面是不均匀的。     

Measurement and theoretical analysis of the adsorption of supercritical methane on superactivated carbon

Adsorption/desorption isotherms of supercritical methane on superactivated carbon have been measured in the range of 0-10 MPa and 233-333 K (20 K interval). The reversibility of the physical adsorption process is acknowledged. The heat of adsorption of 16.5 kJ/mol is determined from the isotherms, and a new modeling strategy for isotherms with maximum is presented. The model yields fits to the experimental isotherms with precision of ?%, maintaining the constancy of the characteristic energy of adsorption. The exponent of the model equation expresses the pore size distribution feature of the adsorbent. The density of the supercritical adsor-bate is evaluated as a parameter of the model. It is shown that the conventional isotherm theory works too at supercritical condition if the limit state of supercritical adsorption is introduced into isotherm modeling.     

Hypothetical high-surface-area carbons with exceptional hydrogen storage capacities: open carbon frameworks

A class of high-surface-area carbon hypothetical structures has been investigated that goes beyond the traditional model of parallel graphene sheets hosting layers of physisorbed hydrogen in slit-shaped pores of variable width. The investigation focuses on structures with locally planar units (unbounded or bounded fragments of graphene sheets), and variable ratios of in-plane to edge atoms. Adsorption of molecular hydrogen on these structures was studied by performing grand canonical Monte Carlo simulations with appropriately chosen adsorbent-adsorbate interaction potentials. The interaction models were tested by comparing simulated adsorption isotherms with experimental isotherms on a high-performance activated carbon with well-defined pore structure (approximately bimodal pore-size distribution), and remarkable agreement between computed and experimental isotherms was obtained, both for gravimetric excess adsorption and for gravimetric storage capacity. From this analysis and the simulations performed on the new structures, a rich spectrum of relationships between structural characteristics of carbons and ensuing hydrogen adsorption (structure-function relationships) emerges: (i) Storage capacities higher than in slit-shaped pores can be obtained by fragmentation/truncation of graphene sheets, which creates surface areas exceeding of 2600 m(2)/g, the maximum surface area for infinite graphene sheets, carried mainly by edge sites; we call the resulting structures open carbon frameworks (OCF). (ii) For OCFs with a ratio of in-plane to edge sites ≈1 and surface areas 3800-6500 m(2)/g, we found record maximum excess adsorption of 75-85 g of H(2)/kg of C at 77 K and record storage capacity of 100-260 g of H(2)/kg of C at 77 K and 100 bar. (iii) The adsorption in structures having large specific surface area built from small polycyclic aromatic hydrocarbons cannot be further increased because their energy of adsorption is low. (iv) Additional increase of hydrogen uptake could potentially be achieved by chemical substitution and/or intercalation of OCF structures, in order to increase the energy of adsorption. We conclude that OCF structures, if synthesized, will give hydrogen uptake at the level required for mobile applications. The conclusions define the physical limits of hydrogen adsorption in carbon-based porous structures.     

Effect of carbon nanofiber functionalization on the adsorption properties of volatile organic compounds

The effect of the chemical activation, using HNO3, of a commercial carbon nanofiber (CNF) on its surface chemistry and adsorption properties is studied in this work. The adsorption of different alkanes (linear and cyclic), aromatic compounds and chlorohydrocarbons on both the parent and the oxidized CNF were compared. Temperature-programmed desorption results, in agreement with X-ray photoelectron spectroscopy experiments, reveal the existence of oxygen groups on the surface of the treated CNF. Capacity of adsorption was derived from the adsorption isotherms, whereas thermodynamic properties (enthalpy of adsorption, surface free energy characteristics) have been determined from chromatographic retention data. Both the capacity and the strength of adsorption decrease after the oxidant treatment of the carbon nanofibers, although in the case of chlorinated compounds the specific component of the surface energy shows an important increase. For n-alkanes and cyclic compounds, it was demonstrated that the presence of oxygen surface groups does not affect their interaction, the morphology of the surface being the key parameter. The oxidation of the nanofiber leads to steric limitations of the adsorption. In the adsorption of aromatic compounds, these limitations are compensated by the nucleophilic interactions between the aromatic ring and surface oxygenated groups, leading to similar performances of both materials. The absence of nucleophilic groups in the chlorinated compounds hinders their adsorption on the activated nanofibers.     

Influence of KMnO4 oxidation on the electrochemical performance of pitch-based activated carbons

In this work, activated carbons (ACs) are obtained from petroleum pitch by the combination of a chemical treatment with different potassium permanganate (KMnO₄) amounts, i.e., 0, 0.5, 1.0, and 2.0 g, and a chemical activation with KOH at a constant KOH/pitch ratio of 3/1. The effects of the chemical activating agent on the surface morphology and porosity are evaluated with scanning electron microscopy and N₂ adsorption isotherms at 77 K, respectively. The specific surface area of the pitch-based ACs is increased with increasing the amount of KMnO₄ pre-treatment and showed the highest value of 2,334 m² g^?1 at 2 g of KMnO₄ amount. The electrochemical performance of AC electrodes is examined by cyclic voltammetry and galvanostatic charge/discharge characteristics in 6 M KOH electrolyte. Among the prepared ACs, 2.0 K-ACs possesses a specific capacitance as high as 237 F g^?1 and showed excellent electrochemical performance due to its suitable porous structure and low interface resistance.     

氢在A、X及ZSM-5型沸石上的高压物理吸附

The hydrogen adsorption properties and uptake capacities of the A, X and ZSM-5 types of zeolites were investigated at temperatures of 77, 195 and 293 K and pressures up to 7MPa, using a conventional volumetric adsorption apparatus. All hydrogen adsorption isotherms were basically type I, but the maximum in isotherm,a unique feature of supercritical adsorption, was observed at high pressures of 2-5 MPa at 77 K. The isosteric heats of adsorption were determined from the isotherms and the factors that influence their variations were discussed. Different types of zeolites exhibited remarkably different hydrogen uptake, based on both the framework structure and the nature of the cations present. The highest gravimetric storage capacity of 2.55wt% was obtained for NaX-type zeolite at 4 MPa and 77 K. In CaA, NaX and ZSM-5 types of zeolites,hydrogen uptakes were proportional to the specific surface areas, which were associated with the available void volumes of the zeolites. A threshold in hydrogen adsorption observed in NaA and KA was attributed to a pore blocking effect by large cations in KA. A ratio of the kinetic diameter of adsorbate to the effective opening diameter of zeolite was used to judge the blocking effect for physisorption.     

氮气和氧气在膜表面和狭缝孔内平衡吸附的分子模拟

采用巨正则系综的MonteCarlo方法(GCMC)模拟常温(T=303K)下,氮气和氧气在具有狭缝状膜孔的碳膜内的吸附.气体分子之间、气体分子与膜原子之间的相互作用均采用Shifted-Lennard-Jones势能模型.研究了303K和10MPa下,不同膜厚度和膜孔宽度时氧气在膜面和膜孔内的密度分布以及303K和压力从1MPa到10MPa变化时,氮气和氧气在狭缝膜孔内超额吸附等温线.实验结果表明,膜孔端口效应显著,膜厚和膜孔宽度对孔内吸附影响较大,而膜构型对膜面吸附影响显著.     

Organization of complex monolayers by matrix controlled adsorption

Complex monolayers can be organized at the air | water interface by adsorption of a water-soluble, negatively charged porphyrin dye from the aqueous subphase to a matrix monolayer containing positively charged head groups at the surface of the solution. The organization of the complex monolayer depends on the composition of the matrix monolayer which controls the molecular interactions with the dissolved porphyrin. Surface pressure versus area isotherms in combination with measurement of the enhanced light reflection from the interface in the presence of the porphyrin provides information on the packing and orientation of the chromophores. In an optimal situation, the surface density of the positively charged head groups matches the surface density of the negative charges in the densely packed porphyrins attached to the matrix monolayer, and neutral molecules in the monolayer occupy the free space to provide a dense packing of the matrix.     

活化和表面改性对碳纳米管超级电容器性能的影响

用KOH为活化剂对碳纳米管（CNTs）进行活化；用浓硝酸为氧化剂对活化CNTs进行表面改性.通过TEM、BET和IR对经过活化和表面改性的CNTs进行了分析,并运用循环伏安和恒流充放电测试研究了活化和表面改性对CNTs超级电容器性能的影响.结果表明,通过活化使CNTs的比表面积增大,从而使其比电容从未活化时的43 F•g－1提高到73 F•g－1；通过表面改性引进赝电容,使电容器的比电容进一步提高到94 F•g－1.