Selectivity membrane performance

In modeling and simulating MR, Pd-based membranes are selected in this chapter to exploit their very high selectivity and because their development is at a pre-commercial status. For typical Pd-based selective membrane performance. 

Advantages to Membrane Separation This subsertion covers the commercially important membrane applications. AU except electrodialysis are pressure driven. All except pervaporation involve no phase change. All tend to be inherently low-energy consumers in the-oiy if not in practice. They operate by a different mechanism than do other separation methods, so they have a unique profile of strengths and weaknesses. In some cases they provide unusual sharpness of separation, but in most cases they perform a separation at lower cost, provide more valuable products, and do so with fewer undesirable side effects than older separations methods. The membrane interposes a new phase between feed and product. It controls the transfer of mass between feed and product. It is a kinetic, not an equihbrium process. In a separation, a membrane will be selective because it passes some components much more rapidly than others. Many membranes are veiy selective. Membrane separations are often simpler than the alternatives. 

The explicit mathematical treatment for such stationary-state situations at certain ion-selective membranes was performed by Iljuschenko and Mirkin 106). As the publication is in Russian and in a not widely distributed journal, their work will be cited in the appendix. The authors obtain an equation (s. (34) on page 28) similar to the one developed by Eisenman et al. 6) for glass membranes using the three-segment potential approach. However, the mobilities used in the stationary-state treatment are those which describe the ion migration in an electric field through a diffusion layer at the phase boundary. A diffusion process through the entire membrane with constant ion mobilities does not have to be assumed. The non-Nernstian behavior of extremely thin layers (i.e., ISFET) can therefore also be described, as well as the role of an electron transfer at solid-state membranes. 

The preferred choice of a water-selective membrane up to now has been hydrophilic membranes because of their high water affinity. However, recently Kuhn et al. reported an all-silica DDR membrane for dehydration of ethanol and methanol with high fluxes (up to 20kg m h ) and high selectivities (H20/ethanol 1500 and H20/methanol 70 at 373 K) in pervaporation operation. The separation is based on molecular sieving with water fluxes comparable to well-performing hydrophilic membranes [51]. 

Hybrid membranes composed of poly(vinyl alcohol) (PVA) and tetraethylorthosilicate (TEOS), synthetised via hydrolysis and a co-condensation reaction for the pervaporation separation of water-isopropanol mixtures has also been reported [32], These hybrid membranes show a significant improvement in the membrane performance for water-isopropanol mixture separation. The separation factor increased drastically upon increasing the crosslinking (TEOS) density due to a reduction of free volume and increased chain stiffness. However, the separation factor decreased drastically when PVA was crosslinked with the highest amount of TEOS (mass ratio of TEOS to PVA is 2 1). The highest separation selectivity is found to be 900 for PVA TEOS (1.5 1 w/w) at 30°C. For all membranes, the selectivity decreased drastically up to 20 mass % of water in the feed and then remained almost constant beyond 20 mass %, signifying that the separation selectivity is much influenced at lower composition of water in the feed. 

When the membrane performs only a separation function and has no catalytic activity, two membrane properties arc of importance, the permeability and the selectivity which is given by the separation factor. In combination with a given reaction, two process parameters are of importance, the ratio of the permeation rate to the reaction rate for the faster permeating component (c.g. a reaction product such as hydrogen in a dehydrogenation reaction) and the separation factors (permselectivities) of all the other components (in particular those of the reactants) relative to the faster permeating gas. These permselectivities can be expressed as the ratios of the permeation rates of... 

The membrane performance for separations is characterized by the flux of a feed component across the membrane. This flux can be expressed as a quantity called the permeability (P), which is a pressure- and thickness-normalized flux of a given component. The separation of a feed mixture is achieved by a membrane material that permits a faster permeation rate for one component (i.e., higher permeability) over that of another component. The efficiency of the membrane in enriching a component over another component in the permeate stream can be expressed as a quantity called selectivity or separation factor. Selectivity (0 can be defined as the ratio of the permeabilities of the feed components across the membrane (i.e., a/b = Ta/Tb, where A and B are the two components). The permeability and selectivity of a membrane are material properties of the membrane material itself, and thus these properties are ideally constant with feed pressure, flow rate and other process conditions. However, permeability and selectivity are both temperature-dependent... 

Symmetrical placement of the ion-selective membrane is typical for the conventional ISE. It helped us to define the operating principles of these sensors and most important, to highlight the importance of the interfaces. Although such electrodes are fundamentally sound and proven to be useful in practice, the future belongs to the miniaturized ion sensors. The reason for this is basic there is neither surface area nor size restriction implied in the Nernst or in the Nikolskij-Eisenman equations. Moreover, multivariate analysis (Chapter 10) enhances the information content in chemical sensing. It is predicated by the miniaturization of individual sensors. The miniaturization has led to the development of potentiometric sensors with solid internal contact. They include Coated Wire Electrodes (CWE), hybrid ion sensors, and ion-sensitive field-effect transistors. The internal contact can be a conductor, semiconductor, or even an insulator. The price to be paid for the convenience of these sensors is in the more restrictive design parameters. These must be followed in order to obtain sensors with performance comparable to the conventional symmetrical ion-selective electrodes. 

The two types of placement of ion-selective membrane are schematically shown in Fig. 6.16a and b. If designed correctly, they will perform the same sensing... 

Conducting polymers have been studied as potentiometric ion sensors for almost two decades and new sensors are continuously developed. The analytical performance of solid-state ion sensors with conducting polymers as ion-to-electron transducer (solid-contact ISEs) has been significantly improved over the last few years. Of particular interest is the large improvement of the detection limit of such solid-contact ISEs down to the nanomolar level. Further optimization of the solid contacts as well as the ion-selective membranes will most certainly extend the range of practical applications. 

Several factors contribute to the successful fabrication of a high-performance membrane module. First, membrane materials with the appropriate chemical, mechanical and permeation properties must be selected this choice is very process-specific. However, once the membrane material has been selected, the technology required to fabricate this material into a robust, thin, defect-free membrane and then to package the membrane into an efficient, economical, high-surface-area module is similar for all membrane processes. Therefore, this chapter focuses on methods of forming membranes and membrane modules. The criteria used to select membrane materials for specific processes are described in the chapters covering each application. 

The layer of solution immediately adjacent to the membrane surface becomes depleted in the permeating solute on the feed side of the membrane and enriched in this component on the permeate side. Equivalent gradients also form for the other component. This concentration polarization reduces the permeating component s concentration difference across the membrane, thereby lowering its flux and the membrane selectivity. The importance of concentration polarization depends on the membrane separation process. Concentration polarization can significantly affect membrane performance in reverse osmosis, but it is usually well controlled in industrial systems. On the other hand, membrane performance in ultrafiltration, electrodialysis, and some pervaporation processes is seriously affected by concentration polarization. 

This is called the membrane-selectivity-limited region, in which the membrane performance is determined only by the membrane selectivity and is independent of the pressure ratio. There is, of course, an intermediate region between these two limiting cases, in which both the pressure ratio and the membrane selectivity affect the membrane system performance. These three regions are illustrated in Figure 8.13, in which the calculated permeate concentration ( , ) is plotted versus pressure ratio pressure ratio of 1, feed pressure equal to the permeate pressure, no separation is achieved by the membrane. As the difference between the feed and permeate pressure increases,... 

Equation (9.11) identifies the three factors that determine the performance of a pervaporation system. The first factor, pevAp, is the vapor-liquid equilibrium, determined mainly by the feed liquid composition and temperature the second is the membrane selectivity, G-men, an intrinsic permeability property of the membrane material and the third includes the feed and permeate vapor pressures, reflecting the effect of operating parameters on membrane performance. This equation is, in fact, the pervaporation equivalent of Equation (8.19) that describes gas separation in Chapter 8. 

Composite membranes combine two or more different materials with different characteristics to obtain optimal membrane performance. Basically, the preparation involves (i) preparation of porous support that is usually made by a phase-separation process (cf. Section 2.4.2), and (ii) deposition of a selective barrier layer on this porous... 

Because most of the established membrane polymers can not meet all the performance requirements for a membrane dedicated to a particular application, membrane modifications are gaining rapidly increasing importance. Membrane modification is aimed either to minimize undesired interactions, which reduce membrane performance (e.g., membrane fouling), or to introduce additional interactions (e.g., affinity, responsive or catalytic properties) for improving the selectivity or creating an entirely novel separation function [3]. Three general approaches can be distinguished ... 

A wide variety of polymeric membranes with different barrier properties is already available, many of them in various formats and with various dedicated specifications. The ongoing development in the field is very dynamic and focused on further increasing barrier selectivities (if possible at maximum transmembrane fluxes) and/ or improving membrane stability in order to broaden the applicability. This tailoring of membrane performance is done via various routes controlled macro-molecular synthesis (with a focus on functional polymeric architectures), development of advanced polymer blends or mixed-matrix materials, preparation of novel composite membranes and selective surface modification are the most important trends. Advanced functional polymer membranes such as stimuli-responsive [54] or molecularly imprinted polymer (MIP) membranes [55] are examples of the development of another dimension in that field. On that basis, it is expected that polymeric membranes will play a major role in process intensification in many different fields. 

These observations have several practical consequences for membrane processes where the selective layers are as thin as or even thinner than the low end of the range studied here. First, it is clear that use of thick film data to design or select membrane materials only gives a rough approximation of the performance that might be realized in practice. Second, because the absolute permeability of a thin film may be severalfold different than the bulk permeability, use of the latter type of data to estimate skin thickness from flux observations on asymmetric or composite membranes structures is also a very approximate method. Finally, these data indicate that one could expect... 

Figure 9.5 Hydrogen-selective membrane combining steps 1 + 2 + 3 in precombustion decarbonization. Starting from synthesis gas, for example, after gasification of coal, step 2 + 3 may be combined in the membrane unit. After WCS, the membrane unit may perform step 3, only.

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