Constant pattern

Fig. 13. Schematic diagram showing (a) approach to constant pattern behavior for a system with a favorable isotherm and (b) approach to proportionate pattern behavior for a system with an unfavorable isotherm, jy axis cj qlj q,----------------------- < q,-- From ref. 7.

The distance requited to approach the constant pattern limit decreases as the mass transfer resistance decreases and the nonlinearity of the equihbrium isotherm increases. However, when the isotherm is highly favorable, as in many adsorption processes, this distance may be very small, a few centimeters to perhaps a meter. 

Length of Unused Bed. The constant pattern approximation provides the basis for a very useful and widely used design method based on... 

Under constant pattern conditions the LUB is independent of column length although, of course, it depends on other process variables. The procedure is therefore to determine the LUB in a small laboratory or pilot-scale column packed with the same adsorbent and operated under the same flow conditions. The length of column needed can then be found simply by adding the LUB to the length calculated from equiUbrium considerations, assuming a shock concentration front. 

Favorable and unfavorable equihbrium isotherms are normally defined, as in Figure 11, with respect to an increase in sorbate concentration. This is, of course, appropriate for an adsorption process, but if one is considering regeneration of a saturated column (desorption), the situation is reversed. An isotherm which is favorable for adsorption is unfavorable for desorption and vice versa. In most adsorption processes the adsorbent is selected to provide a favorable adsorption isotherm, so the adsorption step shows constant pattern behavior and proportionate pattern behavior is encountered in the desorption step. 

Adsorption Dynamics. An outline of approaches that have been taken to model mass-transfer rates in adsorbents has been given (see Adsorption). Detailed reviews of the extensive Hterature on the interrelated topics of modeling of mass-transfer rate processes in fixed-bed adsorbers, bed concentration profiles, and breakthrough curves include references 16 and 26. The related simple design concepts of WES, WUB, and LUB for constant-pattern adsorption are discussed later. 

Most dynamic adsorption data are obtained in the form of outlet concentrations as a function of time as shown in Figure 18a. The area iebai measures the removal of the adsorbate, as would the stoichiometric area idcai, and is used to calculate equiUbrium loading. For constant pattern adsorption, the breakthrough time and the stoichiometric time ( g), are used to calculate LUB as (1 — (107). This LUB concept is commonly used... 

Constant pattern and related analyses Gives asymptotic transition shapes and upper bound on MTZ Deep bed with fully developed transition... 

FIG. 16-2 Limiting fixed-bed behavior simple wave for unfavorable isotherm (top), square-root spreading for linear isotherm (middle), and constant pattern for favorable isotherm (bottom). [From LeVan in Rodtigues et al. (eds.), Adsorption Science and Technology, Kluwer Academic Publishers, Dotdtecht, The Nethedands, 1989 reptinted withpeimission.]... 

Alternate driving force approximations, item 2B in Table 16-12, for solid diffusion, and item 3B in Table 16-12, for pore diffusion, provide somewhat more accurate results in constant pattern packed-bed calculations with pore or solid diffusion controlling for constant separation factor systems. 

Local equihbrium theory also pertains to adsorption with axial dispersion, since this mechanism does not disallow existence of equilibrium between stationary and fluid phases across the cross section of the bed [Rhee et al., Chem. Eng. ScL, 26, 1571 (1971)]. It is discussed below in further detail from the standpoint of the constant pattern. 

With a favorable isotherm and a mass-transfer resistance or axial dispersion, a transition approaches a constant pattern, which is an asymptotic shape beyond which the wave will not spread. The wave is said to be self-sharpening. (If a wave is initially broader than the constant pattern, it will sharpen to approach the constant pattern.) Thus, for an initially uniformly loaded oed, the constant pattern gives the maximum breadth of the MTZ. As bed length is increased, the constant pattern will occupy an increasingly smaller fraction of the bed. (Square-root spreading for a linear isotherm gives this same qualitative result.)... 

In constant pattern analysis, equations are transformed into a new coordinate system that moves with the wave. Variables are changed from (, Ti) to — Ti, Ti). The new variable — Ti is equal to zero at the stoichiometric center of the wave. Equation (16-130) for a bed... 

The constant pattern is approached as the T, dependence in this eqna-tton disappears. Thus, discarding the derivative with respect to T, and integrating, using the condition that and approach zero as Nit, — Ti) oo [or approach unity as N — Ti) gives simply... 

TABLE 16-13 Constant Pattern Solutions for Constant Separation Factor Isotherm (R < 1)... 

Mechanism N Dimensionless rate equation Constant pattern Refs. 

After eliminating /if or cf using the adsorption isotherm, Eq. (16-140) can be integrated directly to obtain the constant pattern. 

Constant pattern solutions for the individual mechanisms and constant separation factor isotherm are given in Table 16-13. The solutions all nave the expected dependence on R—the more favorable the isotherm, the sharper the profile. 

Figure 16-27 compares the various constant pattern solutions for R = 0.5. The curves are of a similar shape. The solution for reaction kinetics is perfectly symmetrical. The cui ves for the axial dispersion fluid-phase concentration profile and the linear driving force approximation are identical except that the latter occurs one transfer unit further down the bed. The cui ve for external mass transfer is exactly that for the linear driving force approximation turned upside down [i.e., rotated 180° about cf= nf = 0.5, N — Ti) = 0]. The hnear driving force approximation provides a good approximation for both pore diffusion and surface diffusion. 

Breakthrough Behavior for Axial Dispersion Breakthrough behavior for adsorption with axial dispersion in a deep bed is not adequately described by the constant pattern profile for this mechanism. Equation (16-128), the partial different equation of the second order Ficldan model, requires two boundaiy conditions for its solution. The constant pattern pertains to a bed of infinite depth—in obtaining the solution we apply the downstream boundaiy condition cf 0 as oo. Breakthrough behavior presumes the existence of... 

Extensions Existence, uniqueness, and stabihty criteria have been developed for the constant pattern [Cooney and Lightfoot, Jnd. 

The rectangular isotherm has received special attention. For this, many of the constant patterns are developed fuUy at the bed inlet, as shown for external mass transfer [Klotz, Chem. Rev.s., 39, 241 (1946)], pore diffusion [Vermeulen, Adv. Chem. Eng., 2, 147 (1958) Hall et al., Jnd. Eng. Chem. Fundam., 5, 212 (1966)], the linear driving force approximation [Cooper, Jnd. Eng. Chem. Fundam., 4, 308 (1965)], reaction kinetics [Hiester and Vermeulen, Chem. Eng. Progre.s.s, 48, 505 (1952) Bohart and Adams, J. Amei Chem. Soc., 42, 523 (1920)], and axial dispersion [Coppola and LeVan, Chem. Eng. ScL, 38, 991 (1983)]. 

Treatments of constant pattern behavior have been carried out for multicomponent adsorption [Vermeulen, Adv. in Chem. Eng., 2, 147 (1958) Vermeulen et., Ruthven, gen. refs. Rhee and Amundson, Chem. Eng. ScL, 29, 2049 (1974) Cooney and Lightfoot, Jnd. Eng. Chem. Fundam., 5, 25 (1966) Cooney and Strusi, Jnd. Eng. Chem. Fundam., 11, 123 (1972) Bradley and Sweed, AJChE Symp. Ser. No. 152, 71, 59 (1975)]. The behavior is such that coexisting compositions advance through the bed together at a uniform rate this is the coherence concept of Helfferich and coworkers [gen. refs.]. 

The constant pattern concept has also been extended to circumstances with nonplug flows, with various degrees of rigor, including flow profiles in tubes [Sartory, Jnd. Eng. Chem. Fundam., 17, 97 (1978) Tereck et al., Jnd. Eng. Chem. Res., 26, 1222 (1987)], wall effects [Vortmeyer and Michael, Chem. Eng. ScL, 40, 2135 (1985)], channeling [LeVan and Vermeulen in Myers and Belfort (eds.). Fundamentals of Adsorption, Engineering Foundation, New York (1984), pp. 305-314, AJChE Symp. Ser No. 233, 80, 34 (1984)], networks [Aviles and LeVan, Chem. Eng. Sci., 46, 1935 (1991)], and general structures of constant cross section [RudisiU and LeVan, Jnd. Eng. Chem. Res., 29, 1054 (1991)]. 

The solution gives all of the expected asymptotic behaviors for large N—the proportionate pattern spreading of the simple wave if R > 1, the constant pattern if R < 1, and square root spreading for R = 1. 

Parallel arrays of microtubules are found in the axoneme of cilia and flagella of eukaryotic cells, and these are of constant pattern throughout the phylogenetic scale. 

VHiereas the previous case revealed temperature and conversion profiles propagating with almost constant velocity ("constant-pattern profiles"), the next case shows oscillatory behavior of the filtration combustion process for parameters a = 1.0, p = 0.08, y = 0.05, 6 = 1.0, (A) = 100.0, L =50.0 and 8 = -10.0. Figure 3a... 

The asymptotic behavior of transitions under the influence of mass-transfer resistances in long, deep beds is important. The three basic asymptotic forms are shown in Fig. 16-2. With an unfavorable isotherm, the breadth of the transition becomes proportional to the depth of bed it has passed through. For the linear isotherm, the breadth becomes proportional to the square root of the depth. For the favorable isotherm, the transition approaches a constant breadth called a constant pattern. 

With a favorable isotherm and a mass-transfer resistance or axial dispersion, a transition approaches a constant pattern, which is an asymptotic... 

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