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Adsorption: Journal of the International Adsorption Society (v.9, #1)
Equation of State for Adsorption of Gases and Their Mixtures in Porous Materials by Alan L. Myers (pp. 9-16).
Desorption functions (G, H, S) are useful for adsorbent characterization, phase equilibria, and enthalpy and entropy balances. Adsorption isotherms, enthalpy, and entropy are temperature and pressure derivatives of the free energy, so that G(T, P) is an adsorption equation-of-state which contains complete thermodynamic information about the system. The free energy of desorption is the minimum isothermal work necessary to regenerate the adsorbent. The free energy of desorption also determines the selectivity of an adsorbent for different gases. The ideal enthalpy of desorption for a mixture (H = ∑ i n i h° i ) is a simple function of the enthalpies of desorption for the individual components. Sample calculations of the free energy, enthalpy, and entropy desorption functions are provided for pure components and mixtures.
Keywords: adsorption; gas; mixture; micropore; enthalpy; entropy
Gibbs Dividing Surface and Helium Adsorption by Sasidhar Gumma; Orhan Talu (pp. 17-28).
All adsorption data is based on the definition of Gibbs dividing surface, which is a purely mathematical transformation. Adsorption measurements in microporous solids necessitate experimental determination of the dividing surface. An international protocol does not exist on how to perform this important measurement. Commonly, helium is assumed not to adsorb and used as a probe molecule for this measurement. Each experimentalist chooses an arbitrary set of conditions, often without even disclosing them, which adds to the confusion in adsorption literature. Here, a self-consistent method for the analysis of helium data is proposed which does not assume non-adsorbing helium. The method is compared to others using the extensive set of helium/silicalite data. The Gibbs dividing surface and hence the helium isotherms at all temperatures are determined.
Keywords: adsorption equilibrium; helium adsorption; Gibbs dividing surface; silicalite; pore volume measurement
Measurement of Diffusion in Zeolites—A Never Ending Challenge? by Jörg Kärger (pp. 29-35).
A review is given on the main problems associated with the determination and interpretation of molecular diffusion in zeolites. It is shown that the diffusivities may most decisively depend on the relevant space and time scales of observation, as well as on the physical state under which the measurements are carried out. Special emphasis is given to the microscopic techniques and their most recent evidence on the existence of transport resistances distributed over the intracrystalline space.
Keywords: zeolites; diffusion; diffusion measurement; equilibrium techniques; microscopic techniques; anomalous diffusion
Frequency Response Method for Measuring Mass Transfer Rates in Adsorbents via Pressure Perturbation by Brian K. Sward; M. Douglas LeVan (pp. 37-54).
A new apparatus for the measurement of equilibria and dynamics for gas-phase adsorption systems is utilized to examine the adsorption of carbon dioxide on BPL activated carbon. The apparatus has a flow-through configuration. For dynamics, with constant inlet flow, pressure within the adsorbent-containing section is varied sinusoidally, and the time-dependent outlet flow rate is measured to determine an amplitude ratio and phase lag. Studies are made of temperature effects and particle size effects. Results are compared with several mathematical models. Frequency response data show that the BPL system follows surface (or micropore) diffusion kinetics. The rate of adsorption for the activated carbon is found to be only weakly dependent on the bulk particle size.
Keywords: frequence response; surface diffusion; micropore diffusion; dynamics; rate; kinetics
Adsorption Calculations Using the Film Model Approximation for Intraparticle Mass Transfer by Giorgio Carta (pp. 55-65).
An approximate rate equation based on a film-model representation of diffusional mass transfer has been developed to describe the kinetics of multicomponent adsorption. The model describes mass transfer as a pseudo-steady state diffusion process through a flat film of thickness equal to one fifth of the particle radius. The flux relationships are integrated across the film yielding analytical expressions for the rate of mass transfer in a multicomponent adsorption system. The usefulness of the film model approximation is tested by carrying out calculations for three different practical adsorption systems: the adsorption of n-pentane and n-heptane mixtures on NaCaA zeolite discussed by Marutovsky and Bülow (1987); the adsorption of air in molecular sieve RS-10 discussed by Farooq et al. (1993); and the separation of air in a kinetically-controlled nitrogen PSA process discussed by Farooq and Ruthven (1990) and Sundaram and Yang (1998). In each case, the film model approximation predicts the expected trends accounting for the coupling of diffusion fluxes in the adsorbed phase.
Keywords: multicomponent adsorption; coupled diffusion; linear driving force approximation; pressure swing adsorption
Thermal-Adsorptive Concentration by Gopalan Natarajan; Phillip C. Wankat (pp. 67-76).
Methods for concentrating dilute fluids using adsorption followed by partial thermal regeneration were studied using the simulation package ADSIM. The systems studied were NaCl in liquid water on Amberlite XD-2 resin and benzene vapor in nitrogen on activated carbon. Cycles studied included counter-current regeneration with pure hot fluid, co-current regeneration with pure hot fluid, a new process called Hot Feed Addition (HFA) consisting of co-current regeneration with pure hot fluid followed by hot feed, and cycling zone adsorption (co-current alternating hot and cold feeds with no pure regeneration fluid). The optimum system depends upon the conditions of the system and the value function chosen to evaluate the systems. For example, for benzene in nitrogen with hot regeneration gas at 467.4 K, cycling zone adsorption used no carrier gas, had the most concentrated benzene stream and a very pure nitrogen product, but the energy use was greater than the other processes. For liquid systems counter-current operation could produce the purest product, but regenerant requirements were high. With slightly lower purity requirements HFA reduced solvent usage and increased the concentration of the concentrated waste stream. For the liquid system all processes used approximately 3% or less of the energy that would be required for evaporation.
Keywords: adsorption; cycling zone adsorption; thermal-swing adsorption
Influence of the Presence of CO2 in the Feed of an Indirect Heating TSA Process for VOC Removal by M. Clausse; J. Bonjour; F. Meunier (pp. 77-85).
This work deals with an experimental study of an indirect temperature swing adsorption process for VOC removal from air or for gas purification. A 1 m long and 70 mm diameter column with an internal heat exchanger has been filled with Ambersorb 600 carbonaceous adsorbent. This column is equipped with sensors to measure temperature at several points inside the bed, as well as the inlet and outlet gas concentration, pressure, temperature and mass flow. In a first step, CO2 or ethane/dry nitrogen mixtures were used to simulate a single VOC in air, with different concentrations (350 ppm, 1% and 10%). As a first results very effective gas purification was obtained and an advantage of this process is the high pollutant concentration during the regeneration phase. Experiments were performed with various ethane/CO2 mixtures. The influence of the presence of CO2 on the ethane concentration breakthrough curves and on the ethane concentration during regeneration is reported. The IAS theory was used, as a first approach, to predict the adsorbed pollutants amount. Relatively good prediction is obtained with a maximum error in the order of 10%. An energy balance study is reported as well.
Keywords: indirect TSA; VOC removal; CO2 ; multicomponent
Landfill Gas: From Rubbish to Resource by Kent S. Knaebel; Herbert E. Reinhold (pp. 87-94).
The prospects of using landfill gas (LFG) as a high-grade fuel in the immediate future, in view of environmental regulations, the Kyoto Protocols, and energy prices, are discussed. Adsorption cycles suggested in the late 1980s by Sircar and co-workers for treating LFG are reviewed: one produced CO2-free methane and the other produced both CO2-free methane and methane-free CO2. Neither of those could be used to produce pipeline quality gas from LFG, due to contaminants such as nitrogen. Two new three-stage flowsheets are discussed as a means to separate pipeline-grade methane from LFG. One is a hybrid membrane—PSA system. The other is a TSA—PSA system. The third stage of both of these systems is crucial to obtaining pipeline quality gas, i.e., a PSA unit to extract the nitrogen and other light gases from methane. A novel PSA cycle is suggested and explained in terms of: a model by which the recovery, power requirements, and adsorbent bed size can be estimated.
Keywords: pressure swing adsorption; purification; bulk separation; environmental application
Carbon Whisker Membrane by Yuan-Yao Li; Sang-Dae Bae; Takeshi Nomura; Akiyoshi Sakoda; Motoyuki Suzuki (pp. 95-98).
We report a recent developed membrane called carbon whisker membrane (CWM). The CWMs consist of a tubular ceramic membrane covered by a layer of carbon film and carbon whiskers formed on the surface of the carbon film. Hydrocarbons such as methane and a modified chemical vapor deposition apparatus were employed for fabricating uniformed CWMs. Because of the unique feature of the CWMs, the filtration performance of the CWMs was investigated and it was found that the CWMs possess a function of anti-attachment of particles and/or biomaterials on the membranes so that the permeate flux and the cleaning process of the membrane can be improved.
Keywords: carbon whiskers; vapor grown carbon fibers; membrane separation