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120 IPCC Special Report on Carbon dioxide Capture and Storage treat the gaseous feed before CO2 separation in an adsorber. Operation at high temperature with other sorbents (see Section 3.3.3.4) can circumvent this requirement (Sircar and Golden, 2001). In many cases gases have to be also cooled and dried, which limits the attractiveness of PSA, TSA or ESA (electric swing adsorption) vis-à-vis capture by chemical absorption described in previous sections. The development of a new generation of materials that would efficiently adsorb CO2 will undoubtedly enhance the competitiveness of adsorptive separation in a flue gas application. 3.3.3.3 Membranes while the transfer of gas is not hindered. The overall process configuration in terms of unit operations would be very similar to a conventional chemical absorption/desorption process (see Figure 3.4). Membrane/solvent systems can be both used in the absorption as well as in the desorption step. Feron and Jansen (2002) and Falk-Pedersen et al. (1999) give examples of suitable membrane/solvent systems. Research and development efforts have also been reported in the area of facilitated transport membranes. Facilitated transport membranes rely on the formation of complexes or reversible chemical reactions of components present in a gas stream with compounds present in the membrane. These complexes or reaction products are then transported through the membrane. Although solution and diffusion still play a role in the transport mechanism, the essential element is the specific chemical interaction of a gas component with a compound in the membrane, the so-called carrier. Like other pressure driven membrane processes, the driving force for the separation comes from a difference in partial pressure of the component to be transported. An important class of facilitated transport membranes is the so-called supported liquid membrane in which the carrier is dissolved into a liquid contained in a membrane. For CO2 separations, carbonates, amines and molten salt hydrates have been suggested as carriers (Feron, 1992). Porous membranes and ion-exchange membranes have been employed as the support. Until now, supported liquid membranes have only been studied on a laboratory scale. Practical problems associated with supported liquid membranes are membrane stability and liquid volatility. Furthermore, the selectivity for a gas decreases with increasing partial pressure on the feed side. This is a result of saturation of the carrier in the liquid. Also, as the total feed pressure is increased, the permeation of unwanted components is increased. This also results in a decrease in selectivity. Finally, selectivity is also reduced by a reduction in membrane thickness. Recent development work has focused on the following technological options that are applicable to both CO2/N2 and CO2/H2 separations: • Amine-containing membranes (Teramoto et al., 1996); • Membranes containing potassium carbonate polymer gel Membrane processes are used commercially for CO2 removal from natural gas at high pressure and at high CO2 concentration (see Section 3.2.2). In flue gases, the low CO2 partial pressure difference provides a low driving force for gas separation. The removal of carbon dioxide using commercially available polymeric gas separation membranes results in higher energy penalties on the power generation efficiency compared to a standard chemical absorption process (Herzog et al., 1991, Van der Sluijs et al., 1992 and Feron, 1994). Also, the maximum percentage of CO2 removed is lower than for a standard chemical absorption processes. Improvements can be made if more selective membranes become available, such as facilitated membranes, described below. The membrane option currently receiving the most attention is a hybrid membrane – absorbent (or solvent) system. These systems are being developed for flue gas CO2 recovery. Membrane/solvent systems employ membranes to provide a very high surface area to volume ratio for mass exchange between a gas stream and a solvent resulting in a very compact system. This results in a membrane contactor system in which the membrane forms a gas permeable barrier between a liquid and a gaseous phase. In general, the membrane is not involved in the separation process. In the case of porous membranes, gaseous components diffuse through the pores and are absorbed by the liquid; in cases of non-porous membranes they dissolve in the membrane and diffuse through the membrane. The contact surface area between gas and liquid phase is maintained by the membrane and is independent of the gas and liquid flow rate. The selectivity of the partition is primarily determined by the absorbent (solvent). Absorption in the liquid phase is determined either by physical partition or by a chemical reaction. membranes (Okabe et al., 2003); • Membranes containing potassium carbonate-glycerol The advantages of membrane/solvent systems are avoidance of operational problems occurring in conventional solvent absorption systems (see Section 3.3.2.1) where gas and liquid flows are in direct contact. Operational problems avoided include foaming, flooding entrainment and channelling, and result in the free choice of the gas and liquid flow rates and a fixed interface for mass transfer in the membrane/solvent system. Furthermore, the use of compact membranes result in smaller equipment sizes with capital cost reductions. The choice of a suitable combination of solvent and membrane material is very important. The material characteristics should be such that the transfer of solvent through the membrane is avoided at operating pressure gradients of typically 50–100 kPa, (Kovvali and Sirkar, 2001). • Poly-electrolyte membranes (Quinn and Laciak, 1997); (Chen et al., 1999); • Dendrimer-containing membranes Facilitated transport membranes and other membranes can also be used in a preconcentration step prior to the liquefaction of CO2 (Mano et al., 2003). There are post-combustion systems being proposed that make use of regenerable solid sorbents to remove CO2 at relatively high temperatures. The use of high temperatures in the CO2 separation step has the potential to reduce efficiency penalties with respect to wet-absorption methods. In principle, they all 3.3.3.4 Solid sorbentsPDF Image | CARBON DIOXIDE CAPTURE AND STORAGE
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