Adsorption

Department Editor: Kate Torzewski

uccessful adsorber design requires information about certain adsorbent properties, including: adsorbent densities and void fractions; isotherms or other equilibrium data; and data on mass-transfer kinetics and fixed-bed dynamics. Here, these adsorbent properties are explained, along with corresponding equations.

NOMENCLATURE

1 Aj 1+ ij = 1 Ai 1+

(7)

A B C dp DAB Deff F i j jD k l L n* Re Sc t xi yi s

Kinetics Data
Kinetics data describe the intraparticle mass-transfer resistance and control the cycle time of a fixed-bed adsorption process. Fast kinetics, or a high rate of diffusion, occur when the effluent concentration remains level until the adsorbent is almost saturated, then rises sharply. Slow kinetics, on the other hand, occur when the effluent concentration begins fluctuating soon after adsorption starts. The effect of slow diffusion can be overcome by adding adsorbent at the product end, or by increasing the cycle time. It is also possible to use small particles. Intraparticle diffusion is characterized by an effective diffusivity Deff, which equals DAB/. Dimensionless time is expressed as Deff t/l 2, which allows the determination of the fractional change (during adsorption or regeneration), as shown below.

Densities anD voiD Fractions

Three densities are relevant: bulk, particle and solid. There are four pertinent void fractions, three corresponding to the three densities, and one representing the overall void fraction in the bed of adsorbent (e). These terms are related in the following way:

= (1 ) S

B = (1 B ) P = (1 B ) (1 P ) S

(1)

Bulk density is the mass of adsorbent in a given volume. Particle density is the mass of adsorbent per volume occupied by the particle. Solid density is the mass of the adsorbent per volume occupied by the particle, but with the pores volume deducted.

equilibrium Data
Adsorption-equilibrium data are usually gathered at a fixed temperature and plotted or tabulated as isotherms: adsorbent capacity (loading) versus fluid-phase concentration (or partial pressure, for gases and vapors). Below are three equilibrium equations for isotherm data. Henrys Law:

(8) This equation shows that, when searching for an effective adsorbent, it is usually safe to choose one having a large diffusivity, a small diameter, or both.

n* = AC
Langmuir Isotherm:

(2)

Henrys law coefficient empirical coefficient Concentration (subscripts: 0, initial; f, final; i, instantaneous) particle diameter adsorbate diffusivity in the liquid effective diffusivity fractional conversion assigned to strongly adsorbed component assigned to less strongly adsorbed component Colburn-Chilton j-factor fluid-to-particle mass transfer coefficient particle radius (for a sphere or cylinder), or half-thickness (for a rectangular solid) bed length adsorbent loading Reynolds number Schmidt number elapsed time mole fraction in fluid phase mole fraction in adsorbed phase selectivity, 1<<infinity selectivity, 0<<1 void fraction (subscripts: B, bulk; P, particle; S, solid) fluid viscosity fluid density (subscripts: B, bulk; P, particle; S, solid) tortuosity superficial velocity particle shape factor

n* =

AC 1 + BC

(3)

FixeD-beD Dynamics
Interstitial mass transfer in fixed beds, primarily fluid-to-particle transfer, can be related to the fluid, adsorbent and system properties via either of two equations, depending on the value of the systems Reynolds number. (9) For 10<Re<2,500, use Equation (10), where Sc equals /DAB.

Freundlich Isotherm:

n* = AC B

(4)

Henrys Law is the simplest isotherm, while the Langmuir Isotherm takes surface coverage into account, and the Freundlich Isotherm is the result of fitting isotherm data to a linear equation on log-log coordinates. In situations that involve multiple adsorbate components in the feed, the concept of selectivity comes into play. Selectivity, and in the three equations below, is the ratio of the capacity of an adsorbent for one component to its capacity for another.

The particle shape factor, , is 1.0 for beads, 0.91 for pellets and 0.86 for flakes. i is the ratio of particle interfacial area to volume, which equals 6(1 )dP. Another major factor in bed dynamics is pressure drop. Most adsorbers are designed to operate with relatively low pressure drop, because large particles are used whenever possible and the velocity is typically low, to allow equilibration of the fluid with the adsorbent. The pressure drop in a fixed bed is represented by the Ergun Equation, below.

P
(10)

jD = ( k s ) Sc0.667 = 1.17 Re0.415

2 1 B 1 B s = 150 + 175 3 gc dp B L Re
(12)

ij =

yi y j xi x j

For lower flowrates, corresponding to values of a modified Reynolds number, Re, of below 50, use Equation (11).

References

(5) (6)

jD = 0.91 Re'0.51

(11) (11a)

ij = Ai A j

1. Knaebel, K., The Basics of Adsorber Design, Chem. Eng., April 1999, pp. 92101. 2. Knaebel, K., For Your Next Separation, Consider Adsorption, Chem. Eng., November 1995, pp. 99102. 3. Masel, R.I., Principles of Adsorption and Reaction on Solid Surfaces, Wiley-Interscience, New York, 1996.