关于氢在活性炭上高压吸附特性的实验研究

利用研制的大容量超级低温恒温槽,以20K为步长,首次在298K至77K,0到7MPa的大范围内系统地研究了氢在活性炭上的吸附特性。采用容积法测定了氢在AX-21活性炭上的一组吸/脱附等温线。通过将该组数据拟合到描述I-型等温线的诸理论模型,发现Dubinin-Astakhov方程在整个实验范围内与实验数据较好地吻合。由非线性回归定出的参数值,使该方程可以±4％的误差预测吸附量。根据该模型作出了三维吸附面,并解析地计算出等量吸附热。除低压部分外,计算值与实验值符合良好。最后讨论了D-A方程在超临界领域遇到的问题。     

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.     

疏水界面上标准蛋白质吸附等温线的研究

测定了几种具有代表性的标准蛋白质在疏水色谱填料上的吸附等温线.除溶菌酶和牛血清白蛋白的吸附近似呈线性外,细胞色素-c、肌红蛋白、胰岛素、α-淀粉酶和卵清蛋白均呈凸型吸附.用Langmuir、计量置换吸附模型(SDM-A)、BET和Jovanovic吸附模型对这些蛋白的吸附等温线拟合后发现,SDM-A关系式能够良好描述这7种蛋白的吸附,Langmuir关系仅能较好地描述后5种蛋白质的吸附.而Jovanovic和BET关系式对上述两类蛋白质吸附的描述欠妥.实验发现对于不同盐浓度条件下卵清蛋白的吸附,用SDM-A和Langmuir公式拟合所得的参数与盐浓度之间呈现出一定的规律性.     

吸附等温线的插值方法的研究

关于用函数形式确切地描述吸附等温线已有不少研究.沈中和等认为,难于找到适合各种形状吸附等温线的理想函数形式,建议采用线性插值.但线性插值显然会使计算结果带来额外偏差.Buchner等和Zingales等曾提出用函数平滑或拟合整个吸附等温线,但此法受所选函数形式的限制并存在拟合误差,无法如实描绘某些吸附等     

SAPO-34上甲醇及二甲醚吸附等温线及吸附热测量与分析(英文)

在25,60和100°C下分别测定了甲醇及二甲醚在SAPO-34分子筛上的吸附等温线,同时用微量热法测定了微分吸附热与覆盖率的关系曲线(量热线),提出了吸附数据需要利用双吸附位Langmuir方程拟合,并获取了相应的吸附参数.对比测得的吸附等温线与量热线发现,在一定压力下,当甲醇及二甲醚在SAPO-34上达到一定吸附量后,随着吸附质分压增加,量热线快速下降,而吸附等温线显示出吸附量仍然继续增加.由此推断,在SAPO-34分子筛上存在两种吸附位——常规吸附位及弱吸附位,其中弱吸附位在高分压下继续吸附.如缺乏量热数据提供的常规吸附位饱和吸附量数据,对吸附等温线进行单吸附位拟合获取吸附参数极易导致错误结果,尤其是当吸附质分压较高时.建议采用双吸附位Langmuir方程,参照量热线提供的常规吸附位的饱和吸附量,通过拟合可以获得两种吸附位的吸附参数.     

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。     

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.     

气体临界温度以上吸附平衡的预测研究

Experimental adsorption isotherms of CH4 and N2 higher than critical temperatures on K02 activated carbon were measured with the volumetric method The pressure and temperature ranges were 0～12 MPa and 273～333 K respectively. A model, which took into account the adsorbate properties above critical temperatures and the adsorbent surface heterogeneity by pore size distribution, was proposed in this paper to predict the equilibrium data only using one adsorption isotherm. The gamma distribution was adopted to express the pore size distribution of the activated carbon, and the adsorption potential was calculated bythe 10-4-3 equation for slit shape micro pores. The relationships between the adsorbate density, the saturated adsorption amount and the equilibrium temperature have been discussed in detail. Through this method, the experimental adsorption data of CH4 and N2 were compared with the prediction equilibria. The study illustrates that the predicting method could present the adsorption equilibria accurately in the whole research range. And the mean relative deviations of the prediction of CH4 and N2 are only about 1.9% and 2.9%. This proves that the analyses of the adsorbate properties are reasonable. Inaddition, the model was applied to calculating the equilibrium data of various supercritical adsorption systems published in literatures. Despite different adsorbents and equilibriaconditions, the investigation results demonstrate that the suggested model performs well in predicting the gases adsorption equilibrium data with all mean relatived eviations less than 6.8%. Therefore, the model could be utilized to calculate the gases adsorption equilibrium data above critical temperatures in a wide range.     

复合吸附剂SiO2·xH2O·yCaCl2的水蒸气吸附等温线

配制了一种由粗孔球形硅胶和氯化钙组成的新型复合吸附剂SiO2·xH2O·yCaCl2,测得了4个不同氯化钙含量的复合吸附剂样品(氯化钙质量分数分别为0.130,0.2733,0.384和0.510)、CaCl2和粗孔球形硅胶在25℃、35℃及45℃的水蒸气吸附等温线。实验结果表明,复合吸附剂的平衡吸水量随CaCl2质量分数增加而增加,最大可达到粗孔球形硅胶的10倍。用Dubinin-Astakhov方程回归测得的等温线,求得相应的参数。     

应用吸附势理论研究氢在沸石上的超临界吸附

针对吸附势理论描述气体超临界吸附所面临的问题, 采用经验方法求取了临界温度以上且较宽的压力范围内氢在微孔沸石上吸附的虚拟饱和蒸汽压和该吸附体系的亲合势系数茁i,j, 并通过对ln(W/W0)与(着i,j/茁i,j) (W,W0分别为吸附相体积及吸附剂的饱和吸附容量, 着i,j为吸附势)的相关性分析得到了一般吸附函数的表达式. 研究结果表明, 茁i,j与吸附热qi,j具有线性关系, 因此可将吸附热作为一般吸附函数的参数应用于吸附势理论的研究. 利用一般吸附函数对本实验条件下的吸附数据的拟合分析证实该函数可较好地表述氢在微孔沸石上的超临界吸附.     

Multicomponent Adsorption of Pesticides onto Activated Carbon Fibers

The adsorption equilibria of pesticides and metabolites (atrazine, deethylatrazine, deisopropylatrazine and simazine) are studied onto activated carbon fibers –ACF– with a broad pore size distribution (32% mesopore volume, 68% micropore volume). Mono-and multi-component isotherms have been determined for low concentrations, from 0.23×10⁻⁶ to 9.52×10⁻⁶ mol L⁻¹. Single solute isotherms, modeled by Freundlich and Langmuir models, tend to prove the influence of the adsorbate's solubility in the adsorption capacity of activated carbon fibers. Binary solute isotherms confirm the strong influence of pesticide solubility on the competitive adsorption mechanism: the competition is higher in the case of adsorbates of different solubilities (atrazine and DEA or DIA for example). Multicomponent experimental data were modeled by extended Langmuir-based equations and the Ideal Adsorbed Solution theory. Whereas the first ones failed to model accurately binary adsorption due to restrictive hypothesis, the IAS model showed a good agreement between experimental and predicted data. It emphasised also the difficulty in satisfying the hypothesis of the model in the case of highly adsorbed compounds. Finally, the simultaneous adsorption of atrazine and NOM (in a natural water, DOC = 18.2 mg L⁻¹) shows no adsorption competition effects between natural organic matter and atrazine. This is due to the presence of secondary micropores (0.8–2 nm) and mesopores in the ACF, which limit a pore blockage phenomenon by NOM.     

超临界状态下炭基材料的储氢

评介了目前各种储氢方法,指出了炭基材料作为储氢材料的优势,综述了近年来纳米炭材料在储氢方面的进展,详细探讨了超临界状态下氢气在纳米孔隙中的吸附机理,并在此基础上提出了研究中的问题及进一步的研究方向。     

On the Correct Use of the Dubinin-Astakhov Equation to Study the Mixed-Gas Adsorption Equilibria

This paper presents the possibilities of Integral Equation (IE) approach to study the mixed-gas adsorption equilibria. As a result, the generalizations of Dubinin-Astakhov equation for the case of mixed-gas adsorption are presented. These new equations are examined using a few adsorption systems recently published in literature.     

Adsorption of Carbon Dioxide on Activated Carbon

The adsorption of CO2 on a raw activated carbon A and three modified activated carbon samples B, C, and D at temperatures ranging from 303 to 333 K and the thermodynamics of adsorption have been investigated using a vacuum adsorption apparatus in order to obtain more information about the effect of CO2 on removal of organic sulfur-containing compounds in industrial gases. The active ingredients impregnated in the carbon samples show significant influence on the adsorption for CO2 and its volumes adsorbed on modified carbon samples B, C, and D are all larger than that on the raw carbon sample A. On the other hand, the physical parameters such as surface area, pore volume, and micropore volume of carbon samples show no influence on the adsorbed amount of CO2. The Dubinin-Radushkevich (D-R) equation was the best model for fitting the adsorption data on carbon samples A and B, while the Preundlich equation was the best fit for the adsorption on carbon samples C and D. The isosteric heats of adsorption on carbon samples A, B, C, and D derived from the adsorption isotherms using the Clapeyron equation decreased slightly increasing surface loading. The heat of adsorption lay between 10.5 and 28.4 kJ/mol, with the carbon sample D having the highest value at all surface coverages that were studied. The observed entropy change associated with the adsorption for the carbon samples A, B, and C (above the surface coverage of 7 ml/g) was lower than the theoretical value for mobile adsorption. However, it was higher than the theoretical value for mobile adsorption but lower than the theoretical value for localized adsorption for carbon sample D.     

Estimation of Adsorption Capacity for Dissociating and Non Dissociating Aromatic Compounds on Activated Carbon with Different Models

The process of adsorption of two dissociating and two non-dissociating aromatic compounds from dilute aqueous solutions on an untreated commercially available activated carbon (B.D.H.) was investigated systematically. All adsorption experiments were carried out in pH controlled aqueous solutions. The experimental isotherms were fitted into four different models (Langmuir homogenous Models, Langmuir binary Model, Langmuir-Freundlich single model and Langmuir-Freundlich double model). Variation of the model parameters with the solution pH was studied and used to gain further insight into the adsorption process. The relationship between the model parameters and the solution pH and pK_a was used to predict the adsorption capacity in molecular and ionic form of solutes in other solution.A relationship was sought to predict the effect of pH on the adsorption systems and for estimating the maximum adsorption capacity of carbon at any pH where the solute is ionized reasonably well.N₂ and CO₂ adsorption were used to characterize the carbon. X-ray Photoelectron Spectroscopy (XPS) measurement was used for surface elemental analysis of the activated carbon.     

氢气在A和X型沸石上超临界吸附的格子密度函数模型

采用基于三维Ono-Kondo方程的格子密度函数理论(LDFT)模型模拟了氢气在A和X型微孔沸石上的超临界吸附等温线. 根据沸石孔的尺寸和形状, LDFT模型将氢分子在孔中的吸附位分布近似为简单立方、面心立方和体心立方的团簇结构. 模拟结果表明, LDFT模型可有效地用于描述氢气在A和X型沸石上的单层或多层超临界吸附行为. 模拟所得的吸附等温线与实验测定结果吻合. 特别是, LDFT模型中的氢-沸石作用势能参数的准确性得到了Lennard-Jones(12-6)势能方法的有效验证. 因此, LDFT模型被用于预测了更宽温度和压力范围内氢气在X沸石上的超临界吸附.     

Use of Quantitative Structure Activity Relationship Methods in Predicting Activated Carbon Adsorption Isotherms for Hazardous Air Pollutants

Abstract

A quantitative structure activity relationship (QSAR) approach is presented to predict gas phase activated carbon adsorption capacities and isotherms for several organic chemicals and their binary mixtures. F,x peri menial adsorption data reported in the literature for various binary mixtures on two di ercnt carbons were used to validate this predictive approach. The QSAR-predicted and experimental adsorption capacities for di erent chemical mixtures of small apolar hydrocarbons at di erent temperatures on two di erent carbons under a range of total pressures and gas phase compositions agreed well with r₂ = 0.85 for a total of 338 data points.     

高比表面活性碳微球分离H2中少量CO2

以实验数据为依据, 结合双Langmuir模型研究了用高比表面活性碳微球材料分离H2中少量CO2的行为. 在实验中, 用高精度的IGA-003重力吸附仪测定了温度为298、273 和268 K, 压力在0-1.8 MPa范围内CO2、H2及n(CO2):n(H2)=1:9混合物在活性碳微球中的吸附等温线. 比较不同吸附模型的计算结果与实验数据, 结果表明, 双Langmuir模型与实验结果拟合得较好; 而且通过结合理想吸附溶液理论, 该模型可以准确地计算不同的混合物体系(包括H2-CO2体系)的吸附量和吸附选择性. 利用该模型求解了不同温度下各组分的分吸附量, 得到了CO2的吸附选择性;在268 K和1.7 MPa下, CO2的吸附选择性可达到73.4, 表明活性碳微球是一种优秀的吸附H2中少量CO2的材料.     

Studies on the Physical Adsorption Equilibria of Gases on Porous Solids over a Wide Temperature Range Spanning the Critical Region—Adsorption on Microporous Activated Carbon

Adsorption equilibria of nitrogen and methane on microporous ( < 2 nm) activated carbon were measured for a wide temperature range (103‐298 K) spanning the critical region. Information relating to Henry constants, the isosteric heat of adsorption, and the amount of limiting adsorption were evaluated. All isotherms show type‐I features for both sub‐ and supercritical temperatures. A new isotherm equation and a consideration for the importance of the effect of the adsorbed phase volume allow this kind of isotherms to be modeled satisfactorily. The model parameter of the saturated amount of absolute adsorption (n⁰_t) equals the limiting adsorption amount (n^itm), leaving the physical meaning of the latter clarified, and the exponent parameter (q) proves to be an appropriate index of surface heterogeneity.     

Adsorption of Phenolic Compounds from Water on Activated Carbon: Prediction of Multicomponent Equilibrium Isotherms using Single-Component Data

Batch-type experiments were carried out to obtain equilibrium isotherms for the adsorption of phenol and m-cresol in aqueous solutions on activated carbon. Single solute systems, at 20 and 40^∘C, were tested for Langmuir, Freundlich and Sips adsorption isotherms in the range of concentrations up to 200 mg/L. Equilibrium data were more closely followed by the Freundlich and Sips equations for all cases. Adsorption isotherms for bisolute systems at 20^∘C, with two different initial concentrations of phenol and m-cresol, were predicted solely on the basis of single solute equilibrium parameters by using the equations of Butler and Ockrent and the IAS theory. The best agreement with the experimental loading values was afforded with the IAS theory based on Sips isotherm for pure compounds. However, this theory is found to be not able to predict with success the binary isotherms in this work where significant displacement of one solute by the other is observed. Chemical interactions in the adsorbed phase, estimated by a modified Butler–Ockrent model, can be responsible for this lack of success of the conventional IAS theory. The predictions based on the IAS theory are compared with the results of some empirical models.