Determination of the adsorption volume and surface of carbon adsorbents with developed mesoporosity

The isotherms of excess adsorption of CH₄ (atP=0.001–160 MPa), SF₆ (atP=0.001–2.4 MPa), and C₆H₆ (atP=0.0001–0.1 MPa) on carbon adsorbents—microporous carbons CMS and FAS with developed mesoporosity and graphitized soot—were measured in the 298–408 K temperature region. Calculation of the isotherms of absolute adsorption of the total content of these substances requires knowledge of the adsorption volume, which was determined by different methods: by the Dubinin—Radushkevich equation; by the experimental isotherm of excess adsorption and the equation of absolute adsorption; by the method using the intersection of nonlinear isosteres of excess adsorption and isosteres of absolute adsorption; by the comparative plot of values of the excess C₆H₆ adsorption Γ_FAS—Γ_soor; by the method using the difference of molecular radii of adsorptives and the surface of the specific adsorbent; and by the calculation of the adsorption layer thickness using the FHH equation for mesoporous systems. The results of determination of the adsorption volume for microporous systems of these carbons agree well with each other and with the passport data for the adsorbents. Analysis of the results revealed the peculiarity of the sulfur hexafluoride adsorption related to the formation of associates on the surface of the carbon adsorbents. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 688–696, April, 2000.     

Adsorption phenomena at high pressures and temperatures 5. Heats of excess and total adsorption of krypton on zeolite NaA

Thermodynamic principles for the calculation of differential heats of excess and absolute adsorption were considered. A set of isosteres of excess adsorption of krypton on zeolite NaA are presented, from which the coverage and temperature dependences of the heats of excess adsorption are calculated and analyzed. The reasons for infinitely high values of the excess heats at finite values of adsorption are discussed. The problems of recalculation of the excess adsorption to absolute adsorption are considered.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1946–1950, August, 1996.     

超临界甲烷在活性炭上的吸附平衡分析

为分析由吸附平衡时的热力参数确定吸附量、吸附模型和等量吸附热精度的影响因素,选择在温度268.15~338.15 K和压力0~13.5 MPa测试的甲烷在Ajax活性炭上的吸附平衡数据,通过引入甲烷分子可进入活性炭吸附空间内的容积和可以不考虑甲烷在孔内吸附的临界孔宽的概念,依据甲烷在吸附平衡前后的总量守恒,确定甲烷在吸附池内的总量、绝对吸附量和过剩吸附量三者之间的关系式。结果表明,在引入吸附质分子可进入吸附空间内的容积和临界孔宽后,经由活性炭的孔径分布(PSD),可以准确计算甲烷在活性炭上的过剩吸附量;应用实验数据非线性回归Toth方程参数后,可由Gibbs关于吸附的定义确定甲烷在活性炭上的绝对吸附量。比较结果时发现,由于未考虑本体相中甲烷分子对吸附甲烷分子的影响,采用过剩吸附量的等量吸附线标绘确定的等量吸附热数值偏高,工程应用时应由绝对吸附量来确定等量吸附热。     

Comparison of molecular simulation of adsorption with experiment

Experimental measurements of adsorption yield the surface excess. The Gibbs surface excess is the actual or absolute amount of gas contained in the pores less the amount of gas that would be present in the pores in the absence of gas-solid intermolecular forces. Molecular simulation of adsorption yields the absolute amount adsorbed. Comparison of simulated adsorption isotherms and heats of adsorption with experiment requires a conversion from absolute to excess variables. Molecular simulations of adsorption of methane in slit pores at room temperature show large differences between absolute and excess adsorption. The difference between absolute and excess adsorption may be ignored when the pore volume of the adsorbent is negligible compared to the adsorption second virial coefficient (VB _1s ).     

Comparative analysis of methods for determination of structural characteristics of carbon adsorbents

Experimental data on the equilibrium adsorption of sulfur hexafluoride, methane, carbon dioxide, and benzene on carbon adsorbents of different porosity obtained in a wide pressure range at 298–408 K were analyzed. The adsorption volumes, surface areas, and sizes of slit-shaped pores of the carbons were determined using several independent methods. A method for determination of the adsorption volume from the experimental isotherm of excessive adsorption of gases and the total content equation was proposed. The resulting values are similar to the adsorption volumes calculated from the data for vapors. A new method for the calculation of the adsorbent surface area is described. The method is based on the dependence of the adsorption volume of adsorbent pores on the effective size of adsorbate molecules. A possibility to determine the average size of narrow slit-shaped carbon pores from the difference of the initial heats of adsorption of the gas under study on the carbon black and porous carbon adsorbent is considered. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2219–2227, October, 2005.     

Adsorption phenomena at high pressures and temperatures 4. Isotherms of excess and absolute adsorption of Kr on NaA zeolite

The problem of conversion of an isotherm of excess adsorption measured experimentally into values of the total amount of the adsorbate (absolute adsorption) has been formulated. Five isotherms of excess adsorption of krypton on NaA zeolite were measured (at 334–500 K) at equilibrium pressures of -160 MPa. The corresponding isotherms of the total amount were calculated and the temperature dependences of the parameters of an equation describing the isotherms of excess adsorption were identified. It was shown that at high temperatures and pressures, krypton atoms diffuse into the -cavities of the NaA zeolite.For Part 3, seeRuss. Chem. Bull., 1996, 45, 534 (Engl. Transl.).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1138–1142, May, 1996.     

New method for the determination of adsorption space volume for sorbents with an arbitrary porous structure from excess gas adsorption isotherm measurements

A new method for the determination of adsorption space volume has been proposed, which is applicable to adsorbents with an arbitrary porous structure, including nonporous adsorbents with open surfaces. The method is based on the use of an experimental excess adsorption isotherm measured over a wide range of pressures in the equilibrium gaseous phase (as a rule up to 100–150 MPa) and the absolute adsorption isotherm equation with unspecified parameters in the most general form, given by statistical physics. The method has been tested for a number of adsorption systems, and it has been found that the result was always unambiguous, correct, and stable in the sense of input data.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2381–2385, December, 1995.     

Mesoporous Fluorinated Metal–Organic Frameworks with Exceptional Adsorption of Fluorocarbons and CFCs

Two mesoporous fluorinated metal–organic frameworks (MOFs) were synthesized from extensively fluorinated tritopic carboxylate‐ and tetrazolate‐based ligands. The tetrazolate‐based framework MOFF‐5 has an accessible surface area of 2445 m² g^?1, the highest among fluorinated MOFs. Crystals of MOFF‐5 adsorb hydrocarbons, fluorocarbons, and chlorofluorocarbons (CFCs)—the latter two being ozone‐depleting substances and potent greenhouse species—with weight capacities of up to 225 %. The material exhibits an apparent preference for the adsorption of non‐spherical molecules, binding unusually low amounts of both tetrafluoromethane and sulfur hexafluoride.     

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。     

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.     

CO2 laser-induced interaction between sulfur hexafluoride and carbon disulfide

Interaction between carbon disulfide and sulfur hexafluoride is excited by cw CO₂ laser radiation and has been investigated for different ratios over a pressure range from 3.1 to 34.6 kPa. The reaction yields sulfur tetrafluoride, sulfur, carbon, thiocarbonyl fluoride, tetrafluoromethane and hexafluoroethane, the ratio of these latter products is dependent on the partial pressure of sulfur hexafluoride in the initial CS₂-SF₆ mixture. Interaction is considered to include both the SF₆-sensitized decomposition of carbon disulfide and reaction between sulfur hexafluoride and carbon disulfide.     

Comparison of molecular simulation of adsorption with experiment

Experimental measurements of adsorption yield the surface excess. The Gibbs surface excess is the actual or absolute amount of gas contained in the pores less the amount of gas that would be present in the pores in the absence of gas-solid intermolecular forces. Molecular simulation of adsorption yields the absolute amount adsorbed. Comparison of simulated adsorption isotherms and heats of adsorption with experiment requires a conversion from absolute to excess variables. Molecular simulations of adsorption of methane in slit pores at room temperature show large differences between absolute and excess adsorption. The difference between absolute and excess adsorption may be ignored when the pore volume of the adsorbent is negligible compared to the adsorption second virial coefficient (V?B _1s ).     

Gas chromatographic investigations of the adsorption of n-octane on the surface of sulfur

Summary From the adsorption isotherms of n-octane on the surface of sulfur at 29.8°C and 40.6°C some thermodynamic functions were determined. On the basis of these data the structure of the adsorbed layer of n-octane is postulated. The molecular interactions and adsorption mechanism are also discussed. It is stated that both quasi-liquid and quasi-sold layers may be formed on the surface of sulfur depending on the surface coverage with n-octane.     

Determination of Absolute Gas Adsorption Isotherms by Combined Calorimetric and Dielectric Measurements

A new method to determine absolute masses of gas adsorbed on the external and internal surfaces of a porous solid is proposed. It consists on a combination of calorimetric and dielectric measurements. These lead to the enthalpy and the dielectric polarization of the adsorbed phase from which by purely thermodynamic calculations the absolute mass adsorbed can be determined without using the so-called helium volume hypothesis nor any other equivalent assumption.As example adsorption of subcritical carbon dioxide (CO₂) on zeolite (Degussa DAY) at 298 K and pressures up to 0,4 MPa is considered. As expected data of absolute masses adsorbed are always somewhat larger than the corresponding Gibbs excess masses calculated from both volumetric and gravimetric measurements via the helium volume of the zeolite.     

Sulfur hexafluoride as a mobile phase for supercritical fluid chromatography

Summary The capabilities of sulfur hexafluoride as a mobile phase for supercritical-fluid chromatography are investigated. An evaluation of its overall utility on the basis of separations of standard aromatic hydrocarbon odel mixtures performed on a variety of bonded-phase, packed columns with UV detection is presented. The dependence of separation performance upon operational parameters is also examined. A comparative evaluation of the chroamtographic properties of supercitrical sulfur hexafluoride and those of supercritical carbon dioxide is developed from these separations under corresponding supercritical state conditions.     

Correlation between excess adsorption data measured for solvent mixture/adsorbent systems and RM values obtained for different solutes chromatographed in binary mobile phases

This paper concerns the application of excess adsorption isotherms, measured for solvent mixture/adsorbent systems, to the characterization of TLC data. For this purpose the excess adsorption isotherms for three liquid mixtures: cyclohexane/ benzene, benzene/acetone, and carbon tetrachloride/ethyl acetate on silica gel at 20°C have been measured. These mixtures have been used as binary mobile phases in TLC measurements. It has been shown for a given solute in binary mobile phase that the quantity R_M is a simple function of the excess adsorption. Parameters of this function have been used to characterize chromatographic systems with binary mobile phases.     

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。     

低温一步法活性炭基脱硫剂的制备与评价

以木屑为原料,在低温条件下一步法制得活性炭基吸附剂,考察了吸附剂制备条件和液-固、气-固吸附条件对吸附剂脱硫性能的影响。结果表明,吸附剂的最佳制备条件为,浸渍液与木屑质量比为1：1,浸渍液中硝酸质量分率为30%、吸附剂表面NiO负载量为5%,常温下浸渍24 h,400℃焙烧3 h。该吸附剂在0.2 g吸附剂/10 mL模拟油、温度为40℃及时间为5 h的液-固吸附脱硫的条件下,脱硫率为28.36%,吸附四次后饱和吸附硫容量可达2.34 mgS/g;在气-固吸附温度为250℃、空速为6.3 h^-1的条件下,饱和吸附硫容量为2.37 mgS/g;高温气-固吸附脱硫对吸附剂的影响表明,与脱硫前相比,吸附剂在比表面积、总孔体积、微孔体积均有明显提高,这说明气-固吸附脱硫过程同时实现了活性炭的扩孔活化。甲苯溶剂再生实验表明,经五次再生后吸附剂的再生性能均可达90%以上。