Adsorption system

The complexity of the dynamic behavior of an adsorption column is directly related to the number of components and the nature of the operation (isothermal or adiabatic) since these factors determine the number of transitions or mass transfer zones. It is therefore convenient to elassify systems, in order of increasing complexity, according to the following scheme. 

The additional complexity which can arise in a limited range of compositions due to selectivity reversal is discussed in Section 9.4. 

Numerical solutions to the coupled heat and mass balance equations have been obtained for both isothermal and adiabatic two- and three-transition systems but for more complex systems only equilibrium theory solutions have so far been obtained. In the application of equilibrium theory a considerable simplification becomes possible if axial dispersion is neglected and the plug flow assumption has therefore been widely adopted. Under plug flow conditions the differential mass and heat balance equations assume the hyperbolic form of the kinematic wave equations and solutions may be obtained in a straightforward manner by the method of characteristics. In a numerical simulation the inclusion of axial dispersion causes no real problem. Indeed, since axial dispersion tends to smooth the concentration profiles the numerical solution may become somewhat easier when the axial dispersion terra is included. Nevertheless, the great majority of numerical solutions obtained so far have assumed plug flow. 

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The Unction of this chapter is to summarize some of the general approaches to the determination of the physical and chemical state in both of the types of adsorption systems described. 

Electron Spin Resonance Spectroscopy. Several ESR studies have been reported for adsorption systems [85-90]. ESR signals are strong enough to allow the detection of quite small amounts of unpaired electrons, and the shape of the signal can, in the case of adsorbed transition metal ions, give an indication of the geometry of the adsorption site. Ref. 91 provides a contemporary example of the use of ESR and of electron spin echo modulation (ESEM) to locate the environment of Cu(II) relative to in a microporous aluminophosphate molecular sieve. 

As stated in the introduction to the previous chapter, adsorption is described phenomenologically in terms of an empirical adsorption function n = f(P, T) where n is the amount adsorbed. As a matter of experimental convenience, one usually determines the adsorption isotherm n = fr(P), in a detailed study, this is done for several temperatures. Figure XVII-1 displays some of the extensive data of Drain and Morrison [1]. It is fairly common in physical adsorption systems for the low-pressure data to suggest that a limiting adsorption is being reached, as in Fig. XVII-la, but for continued further adsorption to occur at pressures approaching the saturation or condensation pressure (which would be close to 1 atm for N2 at 75 K), as in Fig. XVII-Ih. 

Below the critical temperature of the adsorbate, adsorption is generally multilayer in type, and the presence of pores may have the effect not only of limiting the possible number of layers of adsorbate (see Eq. XVII-65) but also of introducing capillary condensation phenomena. A wide range of porous adsorbents is now involved and usually having a broad distribution of pore sizes and shapes, unlike the zeolites. The most general characteristic of such adsorption systems is that of hysteresis as illustrated in Fig. XVII-27 and, more gener-... 

An adsorption system follows Eq. XVII-79 in the form lnv = B-(l/n)lnln(P /P) with n - 2.75 and B = 3.2. Assuming now that you are presented with data that fall on the curve defined by this equation, calculate the corresponding BET vm and c values. 

Still another type of adsorption system is that in which either a proton transfer occurs between the adsorbent site and the adsorbate or a Lewis acid-base type of reaction occurs. An important group of solids having acid sites is that of the various silica-aluminas, widely used as cracking catalysts. The sites center on surface aluminum ions but could be either proton donor (Brpnsted acid) or Lewis acid in type. The type of site can be distinguished by infrared spectroscopy, since an adsorbed base, such as ammonia or pyridine, should be either in the ammonium or pyridinium ion form or in coordinated form. The type of data obtainable is illustrated in Fig. XVIII-20, which shows a portion of the infrared spectrum of pyridine adsorbed on a Mo(IV)-Al203 catalyst. In the presence of some surface water both Lewis and Brpnsted types of adsorbed pyridine are seen, as marked in the figure. Thus the features at 1450 and 1620 cm are attributed to pyridine bound to Lewis acid sites, while those at 1540... 

Figure Bl.25.12 illustrates the two scattering modes for a hypothetical adsorption system consisting of an atom on a metal [3]. The stretch vibration of the atom perpendicular to the surface is accompanied by a change m dipole moment the bending mode parallel to the surface is not. As explained above, the EELS spectrum of electrons scattered in the specular direction detects only the dipole-active vibration. The more isotropically scattered electrons, however, undergo impact scattering and excite both vibrational modes. Note that the comparison of EELS spectra recorded in specular and off-specular direction yields infomiation about the orientation of an adsorbed molecule.

The term heat of adsorption has been defined in a number of different ways. Unfortunately, the initial and final states of the adsorption system and the conditions under which the exchange of heat takes place have not always been adequately defined. As in all applications of thermodynamics, it is essential that the experimental data refer to a system which has reached equilibrium. 

A characteristic feature of a Type IV isotherm is its hysteresis loop. The exact shape of the loop varies from one adsorption system to another, but, as indicated in Fig. 3.1, the amount adsorbed is always greater at any given relative pressure along the desorption branch FJD than along the adsorption branch DEF. The loop is reproducible provided that the desorption run is started from a point beyond F which marks the upper limit of the loop. 

A recently developed drying appHcation for zeoHtes is the prevention of corrosion in mufflers (52,55). Internal corrosion in mufflers is caused primarily by the condensation of water and acid as the system cools. A unique UOP zeoHte adsorption system takes advantage of the natural thermal cycling of an automotive exhaust system to desorb the water and acid precursors. 

Most adsorption systems use stationary-bed adsorbers. However, efforts have been made over the years to develop moving-bed adsorption processes in which the adsorbent is moved from an adsorption chamber to another chamber for regeneration, with countercurrent contacting of gases with the adsorbents in each chamber. Union Oil s Hypersorption Process (90) is an example. However, this process proved uneconomical, primarily because of excessive losses resulting from adsorbent attrition. 

Process Concepts. Hybrid systems involving gas-phase adsorption coupled with catalytic processes and with other separations processes (especially distillation and membrane systems) will be developed to take advantage of the unique features of each. The roles of adsorption systems will be to efficiently achieve very high degrees of purification to lower fouUng contaminant concentrations to very low levels in front of membrane and other separations processes or to provide unique separations of azeotropes, close-boiling isomers, and temperature-sensitive or reactive compounds. 

Design Methods. Improvements ia the ability to predict multicomponent equilibrium and mass-transfer rate performance will allow significant improvements ia the design of new adsorption systems and ia the energy efficiency of existing systems. 

Adsorption systems employing molecular sieves are available for feed gases having low acid gas concentrations. Another option is based on the use of polymeric, semipermeable membranes which rely on the higher solubiHties and diffusion rates of carbon dioxide and hydrogen sulfide in the polymeric material relative to methane for membrane selectivity and separation of the various constituents. Membrane units have been designed that are effective at small and medium flow rates for the bulk removal of carbon dioxide. 

Fig. 1. Iron oxide process where Kl represents the iron oxide sorbent bed ( ), the adsorption system and (-...

Other types of regenerators designed for specific adsorption systems may use solvents and chemicals to remove susceptible adsorbates (51), steam or heated inert gas to recover volatile organic solvents (52), and biological systems in which organics adsorbed on the activated carbon during water treatment are continuously degraded (53). 

Reaction kinetics at phase houndaiies. Rates of adsorption and desorption in porous adsorbents are generally controlled by mass transfer within the pore network rather than by the kinetics of sorption at the surface. Exceptions are the cases of chemisorption and affinity-adsorption systems used for biological separations, where the kinetics of bond formation can be exceedingly slow. 

The phenomenological aspects of diffusional mass transfer in adsorption systems can be described in terms of Fick s law ... 

This expression can be used to describe both pore and solid diffusion so long as the driving force is expressed in terms of the appropriate concentrations. Although the driving force should be more correctly expressed in terms of chemical potentials, Eq. (16-63) provides a qualitatively and quantitatively correct representation of adsorption systems so long as the diffusivity is allowed to be a function of the adsorbate concentration. The diffusivity will be constant only for a thermodynamically ideal system, which is only an adequate approximation for a limited number of adsorption systems. 

Cycle Control Valves are the heart of cycle control for cyclic adsorption systems. These on/off valves switch flows among beds so... 

Continuous Countercurrent Systems Most adsorption systems use fixed-bed adsorbers. However, if the fluid to be separated and that used for desorption can be countercurrently contacted by a moving bed of the adsorbent, there are significant efficiencies to be realized. Because the adsorbent leaves the adsorption section essentially in equilibrium with the feed composition, the inefficiency of the... 

Adsorption-Control Equipment If a gas stream must be treated for a short period, nsnally only one adsorption unit is necessary, provided, of course, that a sufficient time interval is available between adsorption cycles to permit regeneration. However, this is usually not the case. Since an nninternipted flow of treated gas is often required, it is necessary to employ one or more units capable of operating in this fashion. The units are designed to handle gas flows without interruption and are charac terized by their mode of contact, either staged or continuous. By far the most common type of adsorption system used to remove an objectionable pollutant from a gas stream consists of a number of fixed-bed units operating in such a sequence that the gas flow remains nninternipted. A two- or three-bed system is nsn ly... 

Industrial adsorption systems are engineered so that they operate in the region before the breakpoint and are continually regenerated by units. 

Fig, 29-13, Adsorption system shown schematically in Fig. 29-13. Source The British Ceca Company, Ltd. 

Many gas streams can be deodorized by using solid adsorption systems to remove the odor before the stream is released to the atmosphere. Such procedures are often both effective and economical. 

Because of this heat generation, when adsorption takes place in a fixed bed with a gas phase flowing through the bed, the adsorption becomes a non-isothermal, non-adiabatic, non-equilibrium time and position dependent process. The following set of equations defines the mass and energy balances for this dynamic adsorption system [30,31] ... 

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