Selective adsorption-surface diffusion

The adsorption-surface diffusion-desorption mechanism of transport through the SSF membrane can simultaneously provide high separation selectivity between H2 and the impurities of the PSA waste gas and high flux for the impurities even when the gas pressure in the high-pressure side of the membrane is low to moderate (3-5 atm). 

FIGURE 8.1 Molecular-level overview of a catalytic chemical reaction. Selected elementary-like steps of the CO oxidation reaction CO adsorption, surface diffusion of CO, the TS of the C0 +0 surface reaction, the COj desorption, and various adsorbed species. 

Integration of a H2 PSA process with an adsorbent membrane can meet this goal [23, 24]. A nano-porous carbon adsorbent membrane called Selective Surface Flow (SSF) membrane which selectively permeates CO2, CO and CH4 from their mixtures with H2 by an adsorption- surface diffusion-desorption transport mechanism may be employed for this purpose. The SSF membrane can produce an enriched H2 gas stream from a H2 PSA waste gas, which can then be recycled as feed to the PSA process for increasing the over-all H2 recovery. The membrane is prepared by controlled carbonization of poly-vinyledene chloride supported on a macro-porous alumina tube. The membrane pore diameters are between 6 -7 A, and its thickness is - 1-2 pm [25]. 

Surface-selective flow membranes made of nanoporous carbon, which is a variation of molecular sieving membranes, were developed by Rao et al. (1992) and Rao and Sircar (1993). The membrane can be produced by coating poly(vinylidene chloride) on the inside of a macroporous alumina tube followed by carbonization to form a thin membrane layer. The mechanism of separation is by adsorption-surface-diffusion-desorption. Certain gas components in the feed are selectively adsorbed, permeated through the membrane by surface diffusion, and desorbed at the low-pressure side of the membrane. This type of membrane was used to separate H2 from a mixture of H2 and CO2 (Sircar and Rao, 2000), and their main advantage is that the product hydrogen is at the high-pressure side eliminating the need for recompression. The membrane, however, is not industrially viable because of its low overall separation selectivity. In addition, since the separation mechanism involves physical adsorption, operation at low temperatures is required. 

The effect of surface diffusion on the selectivity of the catalytic reaction A - B -y C has been examined [129]. The authors suggest that the sites of a-phase (assumed to be round) are uniformly distributed over the jS-phase. Reaction A -> B takes place only on the a-phase, whereas B — C occurs only on the /f-phase. Substance B formed on the a-phase is transferred to the /i-phase due either to surface diffusion or adsorption-desorption processes. 

Selective surface diffusion is governed by a selective adsorption of the larger (nonideal) components on the pore surface. The critical temperature, 7), of a gas will thus indicate which component in a mixmre is more easily condensable. The gas with the highest T will most likely be the fastest permeating component where a selective surface flow can take place. Eor a mixed gas an additional increase in selectivity may be achieved if the adsorbed layer now covering the internal pore walls restricts the free pore entrance so that the smaller nonadsorbed molecules cannot pass through. 

The use of an evanescent wave to excite fluorophores selectively near a solid-fluid interface is the basis of the technique total internal reflection fluorescence (TIRF). It can be used to study theadsorption kinetics of fluorophores onto a solid surface, and for the determination of orientational order and dynamics in adsorption layers and Langmuir-Blodgett films. TIRF microscopy (TIRFM) may be combined with FRAP ind FCS measurements to yield information about surface diffusion rates and the formation of surface aggregates. 

The free aperture of the main 100 channels in Y-type zeolite is 0.74 nm [7] and is much larger than the diameter of CO2 and N2 molecules. If the concentrations of CO2 and N2 in the micropores of the Y-type zeolite membrane are equal to those in the outside gas phase, these molecules permeate through the membrane at a low CO2/N2 selectivity. However, this was not the case. Carbon dioxide molecules adsorbed on the outside of the membrane migrate into micropores by surface diffusion. Nitrogen molecules, which are not adsorptive, penetrate into micropores by translation-collision mechanism from the outside gas phase. 

Aside from the potential of diffusion for producing a broad dispersive background, it would also be expected to alter the composition of the gases detected in surface methods. Starobinetz (1983) notes that not only can diffusion affect composition, but two additional processes have a similar effect. These are chromatographic separation and selective adsorption. 

Ma et al. (1996) and Whitley et al. (1993) have provided methods to decide if effects such as pore and surface diffusion or adsorption kinetics have to be considered in a model. Their approach is based on the qualitative assessment of breakthrough curves, which are the result of a step input for different feed concentrations and flow rates. When the physical parameters are known or can be estimated, the value of dimensionless parameters defined in these publications may be used to select a model. 

Kaczmarski et al. used a similar model for the calculation of the band profiles of the enantiomers of 1-indanol on a chiral phase in HPLC [29,57]. These authors ignored the external mass transfer and assumed that local equilibrium takes place for each component between the pore surface and the stagnant fluid phase in the macropores (infinite fast kinetics of adsorption-desorption). They also assumed that surface diffusion contribution is much faster than pore diffusion and neglected pore diffusion entirely. Instead of the single file Maxwell-Stefan diffusion, these authors used the generalized Maxwell-Stefan diffusion (see Chapter 5).The calculation (see below) requires first the selection of equations to calculate the surface molecular flux [29,57,58],... 

Selective surface adsorption with surface diffusion... 

Photochemistry on solid surfaces has unveiled the important role of sufaces as reactant media. Solid surfaces work as acids or bases sensitizers or quenchers reaction space for size-specific reactions seed crystals for epitaxial growth etc. Thus, the molecule-surface interaction enhances or reduces photoabsorption, reaction rates, and selectivities. Since there are a lot of parameters for surface reactions, such as adsorption, desorption, diffusion, nucleation etc., it has been difficult to control the photochemistry on solid surfaces. Recently, as it becomes possible to characterize the surface conditions with techniques of ESCA, SIMS, and STM and also to use new light sources, new research field appears as Surface Photochemisty ". 

On the basis of a differential equation Ivanov (1977) described all stages of thin liquid film evolution. He distinguished the effects of Marangoni-Gibbs and of surface viscosity. Additionally, the substantial effects of surface diffusion and slow adsorption (barrier or kinetic controlled mechanisms) are taken into consideration. A selection of basic equations can be find in Chapter 4. 

The repulsive forces arise from the electromagnetic interactions of the charged layer surrounding the particles, the so-called electrical double layer. On the surface of the particles, a charged layer may be formed due to selective adsorption of ions. This part of the double layer is immobile and consists of tightly adsorbed ions in direct contact with the particle surface. In the solution adjacent to the particle, a second layer, in which the ions are more diffusely distributed, penetrates into the liquid. This part of the double layer is termed the diffusion layer. The extent of this diffusion layer depends on the electrolyte concentration increasing electrolyte concentration causes this diffuse double layer to shrink closer in to the particle, so that the electrostatic potential falls off more quickly with distance. The process by which the particles are stabilized by the repulsive forces of the electrical double layers is known as electrostatic stabilization. 

However, the two-sink model as well as other existing adsorption (sink) models do not seem to be able to describe the strong asymmetry between the adsorption/desorption of VOCs on/from indoor surface materials (the desorption process is much slower than the adsorption process). Diffusion combined with internal adsorption is assumed to be capable of explaining the observed asymmetry. Diffusion mechanisms have been considered to play a role in interactions of VOCs with indoor sinks. Dunn and Chen (1993) proposed and tested three unified, diffusion-limited mathematical models to account for such interactions. The phrase unified relates to the ability of the model to predict both the ad/absorption and desorption phases. This is a very important aspect of modeling test chamber kinetics because in actual applications of chamber studies to indoor air quality (lAQ), we will never be able to predict when we will be in an accumulation or decay phase, so that the same model must apply to both. Development of such models is underway by different research groups. An excellent reference, in which the theoretical bases of most of the recently developed sorption models are reviewed, is the paper by Axley and Lorenzetti (1993). The authors proposed four generic families of models formulated as mass transport modules that can be combined with existing lAQ models. These models include processes such as equilibrium adsorption, boundary layer diffusion, porous adsorbent diffusion transport, and conveetion-diffusion transport. In their paper, the authors present applications of these models and propose criteria for selection of models that are based on the boundary layer/conduction heat transfer problem. 

As a consequence of the selective adsorption of ions with a higher affinity for the stationary phase than their counterions electrostatic theories assume the formation of a surface potential between the bulk mobile phase and stationary phase. The adsorbed ions constitute a charged surface, to which is attracted a diffuse double layer of strongly and weakly bound oppositely charged ions equivalent in number to the adsorbed surface charges to maintain electrical neutrality. Because of repulsion effects the adsorbed ions are expected to be spaced evenly over the stationary phase surface and at a concentration that leaves the properties of the stationary phase largely unaltered except for its electrostatic potential. The transfer of solutes from the bulk mobile phase to the... 

General rate models (GRM) are the most detailed continuous models considered in this book. In addition to axial dispersion, they incorporate a minimum of tvi o other parameters describing mass transport effects. These two parameters may combine mass transfer in the liquid film and inside the pores as well as surface diffusion and adsorption kinetics in various kinds. Only a small representative selection of the abundance of different models suggested is given here in order to provide an overview. Alternatives not considered can be easily derived in a straightforward manner. 

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