Showing papers in "Adsorption-journal of The International Adsorption Society in 1995"

Sensitivity of PSA process performance to input variables

Abstract: Mathematical models for pressure swing adsorption (PSA) processes essentially require the simultaneous solutions of mass, heat and momentum balance equations for each step of the process using appropriate boundary conditions for the steps. The key model input variables needed for estimating the separation performance of the process are the multicomponent adsorption equilibria, kinetics and heats of adsorption for the system of interest. A very detailed model of an adiabatic Skarstrom PSA cycle for production of high purity methane from a ethylene-methane bulk mixture is developed to study the sensitivity of the process performance to the input variables. The adsorption equilibria are described by the heterogeneous Toth model which accounts for variations of isosteric heats of adsorption of the components with adsorbate loading. A linear driving force model is used to describe the kinetics. The study shows that small errors in the heats of adsorption of the components can severely alter the overall performance of the process (methane recovery and productivity). The adsorptive mass transfer coefficients of the components also must be known fairly accurately in order to obtain precise separation performance.

Physisorption of alcohols and water vapour by MCM-41, a model mesoporous adsorbent

Abstract: Adsorption isotherms of methanol, ethanol, propan-1-ol, butan-1-ol and water vapour have been determined on MCM-41, a model mesoporous adsorbent. The isotherms of the alcohols are all of Type IV, whereas the water isotherm is of Type V in the IUPAC classification. Each adsorption isotherm exhibits a sharp step, indicative of capillary condensation within a narrow distribution of mesopores. The isotherms are reversible in the monolayer-multilayer region, but distinctive hysteresis loops are associated with the condensation-evaporation cycle. The area within the loop is dependent on the adsorptive, increasing in scale from methanol to butan-1-ol and water. It is evident that the large internal surface of MCM-41 is somewhat hydrophobic and that its mesopore structure is remarkably uniform and stable.

Monolayer cuprous chloride dispersed on pillared clays for olefin-paraffin separations by π-complexation

Abstract: New adsorbents containing cuprous chloride dispersed on pillared interlayered clays (PILC) have been prepared and studied for olefin-paraffin separations. High surface-area PILC's were synthesized with different metal oxide (Al2O3, Fe2O3, TiO2 and ZrO2) as the intercalating pillars. Cuprous chloride was dispersed in a submonolayer form on these PILC's. Pure-component isotherms were measured for C2H4, C2H6, C3H6 and C3H8 at 25°C and 60°C. All sorbents exhibited high C2H4/C2H6 and C3H6/C3H8 ratios with significantly high amounts of olefins adsorbed. The best sorbent was CuCl/TiO2-PILC which showed a C2H4/C2H6 ratio of 5.3 and C3H6/C3H8=2.9 at 25°C. In all cases, olefins adsorbed by π-complexation with Cu(I) ion, reflected by heats of adsorption in the range 10.7–13.7 kcal/mol, as compared to 4.8–6.9 kcal/mol for the physical adsorption of the paraffins. The π-complexation was fully reversible, limited only by the rates of pore diffusion. Diffusion of C2's was rapid while for C3's the diffusion reached 60% completion in approximately 6 min. Comparing these results with those of CuCl/γ-Al2O3, the olefin/paraffin adsorption ratios were not as high as those of the later. However, the olefin isotherms on the PILC-supported CuCl displayed the desirable feature of having a steeper portion above the knee of the isotherm (the knee occurred at below 0.1 atm). This was a useful feature for separation because it yielded a larger working capacity. The steeper isotherm was attributed to a higher degree of energy heterogeneity as the PILC contained both surfaces of pillars and clay layers as opposed to only γ-Al2O3.

Determination of transport coefficients in microporous solids

Abstract: Macroscopic transient methods are reviewed with respect to their applicability to the investigation of molecular transport in microporous sorption systems. Various levels of sophistication of data evaluation for nonequilibrium sorption results obtained by means of batch methods are identified and characterised. Special attention is paid to the characterisation ofFickian (intracrystalline) diffusion as well as to the identification and quantification of additional rate mechanisms that, in general, may simultaneously occur in molecular sieve systems. A state-of-art determination of transport coefficients is exemplified for the systems benzene/microporous gallosilicate of MFI-type, n-hexane/silicalite-I and p-ethyltoluene/ZSM-5. Their sorption rate behaviour can be understood either byFickian diffusion or byFickian diffusion and intracrystalline molecular immobilisation/mobilisation and surface barrier penetration, respectively. To analyse complex sorption rate patterns in microporous systems, the method oftotal curve fitting with full parameter region consideration becomes mandatory.

A simulation model of a high-capacity methane adsorptive storage system

Abstract: A two-dimensional model is developed to describe the hydrodynamics, heat transfer and adsorption phenomena associated with the adsorptive storage of natural gas (NG) in cylindrical reservoirs. Intraparticle and film resistances to both heat and mass transfer are neglected. In the momentum equation, Ergun's law is considered locally valid and is extended to two dimensions. These assumptions are fully justified in the paper. Numerical results are presented concerning the pressurization and blowdown of an ultra-lightweight 50 litre cylinder, commercially available for the storage of compressed NG, if it were filled with an activated carbon having a good adsorptive storage capacity. A simple formula is also proposed to predict the filling times for fast charges. The predicted temperature changes in the packed-bed are in good agreement with those reported in the literature for an experimental charge/discharge.

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

Abstract: Aqueous 1,1,2-trichloroethene (TCE) adsorption isotherms were obtained on Ambersorb1® 563 and 572 adsorbents and Filtrasorb2® 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.

Activity coefficients of adsorbed mixtures

Abstract: Experimental and simulated data for adsorption of gas mixtures on energetically heterogeneous surfaces like activated carbon and zeolites exhibit negative deviations from ideality. The deviations are large in some cases, with activity coefficients at infinite dilution equal to 0.1 or less. Similar molecules form ideal mixtures, but molecules of different size or polarity are nonideal. Equations for bulk liquid mixtures (Wilson, Margules, etc.) do not apply to isobars for adsorbed mixtures. A two-constant equation for activity coefficients as a function of composition and spreading pressure is in good agreement with theory, simulation, and experiment.

Adsorption of gas mixtures on solid surfaces, theory and computer simulation

Abstract: A treatment of the thermodynamics of mixed gas adsorption is presented in which the gas-solid interface is three dimensional. Such a treatment yields an additional term as compared to two dimensional approaches. This additional term has significant consequences for the derivation of adsorbed solution theories, particularly at higher temperatures. Results are presented for a Grand Canonical Monte Carlo study of a model methane-ethane mixture in a carbonaceous slit pore. Comparison of single component and mixture results provides an unambiguous means of testing theories of adsorbed solutions and bears out the thermodynamic treatment presented in the previous section of the paper.

Controlled gas adsorption properties of various pillared clays

Abstract: Microporous pillared clays (PILC) were prepared by the intercalation of montmorillonite with particles of titania (Ti-PILC), zirconia (Zr-PILC), alumina (Al-PILC), iron oxide (Fe-PILC) and mixed lanthania/alumina (LaAl-PILC). Nitrogen adsorption isotherms (77 K) and XRD data provided information on the porosity, surface area, micropore volume and interlayer distance of these samples. The surface area varied between 198 and 266 m2/g for Ti- and Fe-PILC, respectively. The titania pillared clay had also the highest micropore volume (0.142 cc/g) and interlayer spacing (16–20 A), compared to the Zr-PILC, which had the smallest spacing between the layers (max, 4 A). Despite this fact, Zr-PILC always showed a high adsorption capacity for gases such as N2, O2, Ar or CO2, due to its high adsorption field in the very small micropores. From gas adsorption experiments on these various PILCs, it became clear that their adsorption properties depend on the pillars in three ways: (i) the pillar height, (ii) the distribution of the pillars between the clay layers and (iii) the nature of the pillaring species. The incorporation of other elements in the pillars leads to specific adsorption sites in the pores. This was demonstrated by the preparation of mixed Fe/Cr and Fe/Zr pillared clays. Compared to the parent Fe-PILC, the incorporation of chromium and zirconium in the iron oxide pillars had a positive influence on the adsorption capacity. Also the modification of a PILC with cations increases both capacity and selectivity for gases. This was confirmed by the increased adsorption of N2, O2 and CO2 at 273 K on a Sr2+ exchanged Al-PILC.

Predicting isotherms in micropores for different molecules and temperatures from a known isotherm by improved Horvath-Kawazoe equations

Abstract: Our improved Horvath-Kawazoe (H-K) equations (by considering the isotherm nonlinearity) for three pore geometries are first summarized. These equations apply to adsorption in microporous materials at subcritical temperatures. From a known isotherm at a given temperature, these equations are used to predict isotherms of the same adsorbate molecules at other temperatures, and also to predict isotherms for other adsorbate molecules at the same (or any subcritical) temperature. A reasonable agreement is obtained between predictions and experimental data. Since the H-K formulation only involves dispersion forces, it underpredicts for gas-solid systems in which other forces also exist. The N2-zeolite system is one of these systems.

Displacement chromatography of proteins using low molecular weight displacers

Abstract: A method for the purification of proteins by displacement chromatography on ion exchange media using molecular weight displacers is disclosed. Several classes of low molecular weight, charged species are exemplified, including aminoacids, peptides, antibiotics and dendrimeric polymers. Novel compounds useful as displacers are dendrimers of formula (I), wherein R1 is lower alkyl, n is 2 to 6, and X is a common counter anion and similar dendritic polymers based thereon.

Production of oxygen enriched air by rapid pressure swing adsorption

Abstract: A novel rapid pressure swing adsorption (RPSA) process is described for production of 25–50% oxygen enriched air. The embodiment consists of one or more pairs of adsorbent layers contained in a single adsorption vessel. The layers undergo simultaneous pressurization-adsorption and simultaneous depressurization-purge steps. A total cycle time of 6–20 seconds is used. The process yields a very large specific oxygen production rate and a reasonable oxygen recovery for production of 20–50 mole% oxygen enriched gas.

Density of He adsorbed in micropores at 4.2K

Abstract: The density of He adsorbed in the cylindrical micropores of zeolites NaY and KL has been determined by He adsorption at 4.2K. He adsorption isotherms were then compared with N2 adsorption isotherms at 77K. Crystallographic considerations of the micropore volumes gave the density of the He adsorbed layer, which is necessary for assessment of ultramicroporosity of less-crystalline microporous solids, such as activated carbons. The determined density of He adsorbed in the cylindrical micropores of the zeolite was in the range 0.22 to 0.26 gml−1, greater than that of He adsorbed on a flat surface (0.202 gml−1). A value for the density of He between 0.20 to 0.22 gml−1 is recommended for evaluation of ultramicroporosity of a slit-shaped microporous system such as activated carbon.

Waste heat driven solid sorption coolers containing heat pipes for thermo control

Abstract: This paper provides a focus on the R&D of solid sorption coolers and heat pumps made in the Luikov Heat & Mass Transfer Institute (CIS Countries Association “Heat Pipes”) under Thermacore, Inc. Agreement. Commercial and space applications of sorbent systems offer an attractive alternative to compression systems and liquid sorption systems for cooling, heating and air conditioning. MgA zeolites solid sorption systems are analyzed. Some new results are presented. Solid sorption heat pump technology utilizing heat pipe heat recovery with a condensing/evaporating refrigerant holds considerable promise for bivariant (space and domestic) applications due to the variable temperature and variable load capabilities of such machines.

Separation of a binary gas mixture by pressure swing adsorption: Comparison of different PSA cycles

Abstract: Gas separation of a binary gas mixture by various pressure swing adsorption (PSA) cycles was studied by a numerical simulation in order to provide a guidance in selecting PSA cycles. PSA cycles considered in this study are 3, 4-step cycles for production of only one component and a cycle with pressure equalization for production of a light component. 4 and 5-step cycles for simultaneous production of both components of a binary gas mixture are also considered. Separation of a CH4/CO2 gas mixture with zeolite 5A was chosen as a case study. Performances of cycles were examined and compared in view of purity, recovery and productivity. Their relative advantages were discussed. Inclusion of a purging step to a 3-step cycle for production of only one component improves a cycle performance. Further performance improvement of a cycle for production of a light component can be achieved by employing pressure equalization. Sircar's 4-step cycle with a recycle of effluent shows the best performance in view of purity and recovery among cycles for simultaneous production of both components.

Adsorptive separation by thermal parametric pumping part II: Experimental study of the purification of aqueous phenolic solutions at pilot scale

Abstract: In this work scale-up concerns in adsorptive parametric pumping operation in recuperative mode are studied An experimental study of the purification of wastewater containing 100 ppm of phenol using a polymeric adsorbent (Duolite ES861-Rohm and Haas, France) is reported A completely automated pilot plant (column and ancillary equipment, product receivers, sampling, collector and analytical devices) is described The plant is computer controlled enabling automatic data acquisition for temperature, pressure and flowrate

Adsorptive separation by thermal parametric pumping part I: Modeling and simulation

Abstract: A detailed model for the recuperative parametric pumping is presented. The model includes intraparticle mass transfer resistance, axial diffusion and non-linear equilibrium represented by Langmuir equation. The sensitivity studies shows that process performance strongly increases when cycle time increases and φB/φT ratio and particle size decreases. It also shows that bottom and top dead volumes do not influence much the process performance. Evolution of the histories of concentrations and temperatures, the bed performance from cycle to cycle and the bed dynamics at the cyclic steady state have been discussed.

Theory of Measurement of Gas-Adsorption Equilibria by Rotational Oscillations*

Abstract: The gas adsorbed on the inner surface of a highly porous material like activated carbon or zeolite can be measured by slow damped oscillations of a torsional pendulum. The physical principles and the theory of this method are outlined. Formulas are given relating the increase in mass due to adsorption to changes of the frequency and the logarithmic decrement of slow, damped rotational oscillations of the pendulum. Preliminary measurements of gas adsorption equilibria of nitrogen on activated carbon show that the ratio of the mass adsorbedm, to the mass of the adsorbentms, can be determined by this method with mean absolute error δ|m/ms|≤0.04%.

Interpretation of water isotherm hysteresis for an activated charcoal using stochastic pore networks

Abstract: Water vapor adsorption equilibria on activated carbons typically exhibit hysteresis. The size and shape of the hysteresis loop which separates the adsorption and desorption branches is a strong function of the pore size and interconnectivity of the pores. Neither conventional pore filling models nor statistical thermodynamics approaches provide a means for predicting the extent of hysteresis from only adsorption measurements. This work uses the Kelvin Equation in conjunction with the structural concept of a stochastic pore network to describe measured water isotherms on BPL carbon. Using a pore segment distribution function determined from the adsorption branch, it is shown that totally random assemblies underestimate the extent of hysteresis. It is possible, however, to closely fit the measured BPL-water hysteresis loop using a patchy heterogeneity in which a proportion of the larger pores are preferentially located on the exterior, mid-range pores are concentrated in a sub-surface layer and some large pores form shielded voids behind much smaller pores.

Radial Flow Rapid Pressure Swing Adsorption

Abstract: A new PSA process has been proposed and experimentally verified. This process was operated with a radial flow geometry under a cycle time less than 30 seconds. It has been showed that enriched oxygen could be produced when air was fed inward. The same system showed virtually no separation effect if the feed direction was reversed. The change of separation efficiency upon flow reversal was most significant when small adsorbent particles were employed. A o 200×75 mm annular packing with 3 µm particles of zeolite 5A was able to produce 60% purity oxygen from air. The effect of flow direction on system performance confirmed the importance of flow resistance distribution. In radial flow geometry, most of the flow resistance was located near the center of the disk. The relative small pressure gradient at the feed end enabled a better absorbent utilization during the inward feed step, and a more effective desorption during the vent step. The same principle could be extended to other geometric configurations.

Adsoprtion and adsorptive separations: A bibliographical update (1992–1993)

Abstract: This article provides a bibliographic listing of published journal papers concerned with adsorptive separations during 1992–1993. The references are taken from the 40 most important chemical engineering journals. This paper provides an update to the literature as provided in previous bibliographic papers [1, 2]. These previous papers also included membrane-type separations, however due to the number of papers and the diversity of membrane and associated processes, this material is to be published separately [3]. Other bibliographic papers covering the more traditional unit operations, e.g. distillation [4], and equilibrium-staged separations in general [5, 6] have been published. Liquid-liquid extraction [7] is the subject of a separate bibliography (for 1992–1993), due to the number of publications on this topic. A bibliography detailing supercritical extraction from 1980–1993 is also to be published separately due to the current interest in this relatively new technology [8]. A complete bibliography of the chemical engineering journal literature from 1967–1993 has been published by the author [9–12]. An earlier bibliography [13] provides access to the literature prior to 1967.

Effect of pore size distribution on the surface diffusivity in activated carbon: Hybrid Dubinin-Langmuir isotherm

Abstract: The concentration dependence of the observed surface diffusivity for activated carbon due to the pore size distribution is theoretically investigated. The mathematical model is derived based on the assumption of a local hybrid adsorption isotherm (proposed recently by Shethna and Bhatia, 1994) and a local surface diffusive flux for a particular pore of half widthr. Using those local quantities and assuming a Gamma pore size distribution, the observed surface diffusivity is obtained. This observed surface diffusivity was found to increase rapidly with loading if the chemical potential is the driving force for surface flow. Furthermore, this observed surface diffusivity,D/D(0), was found to be the same as the Darken thermodynamic correction factor, using only the macroscopic isotherm information. This indicates that the thermodynamic correction factor contains information on the averaging of the surface heterogeneity.

Measurement of the diffusivity of benzene in microporous silica by quasi-elastic neutron scattering and NMR pulsed-field gradient technique

Abstract: The diffusivity of benzene in a microporous silica powder has been measured by neutron scattering and NMR techniques. The measurements have been performed on un-supported silica but the powder has the same characteristics as the active layer of a real membrane. Self-diffusion coefficients of the order of 10−10 m2s−1 are found at 300 K by both techniques so that the model of Knudsen diffusion is not valid for benzene in this microporous material. Due to the presence of small pores, the diffusion of benzene in the membrane-material approaches the diffusion regime usually observed in zeolites. Furthermore, the diffusivity of benzene follows an Arrhenius law with an activation energy of 11 kJ mol−1.

Effect of variable feed concentration on the performance of a pressure swing adsorption process

Abstract: Effects of variable feed composition on the performance of a pressure swing adsorption process are analyzed by simulation. Two scenarios are considered. The first, “increasing impurity,” case considers low impurity concentration in the feed followed by high impurity concentration in the feed. The second, “decreasing impurity,” case considers high impurity concentration in the feed followed by low impurity concentration in the feed. These results are compared against a case which has an impurity concentration in the feed at an average of the high and the low impurity concentrations. Simulations show that the increasing impurity scenario is expected to perform better, and the decreasing impurity scenario is expected to perform worse than the average feed concentration case.

Differential pressure-jump method for routine measurement of sorption kinetics

Abstract: A sensitive pressure-jump method has been developed for the measurement and characterization of material transport in porous solids. The apparatus is automatically operated and the data evaluation is performed by means of numerical methods based on the Crank-Nicholson procedure. As an example, the sorption ofn-butane and ethene in spherical mesoporous silica gel pellets has been studied. In this way, it is possible to obtain uptake curves and in case of known particle shape to derive values for effective diffusion coefficients. From the pressure and temperature dependence ofDe, information on the transport mechanism by means of Knudsen and surface diffusion can be obtained as well as the tortuosity factor characterizing the pore network.