[From DORAN]

In adsorption, the solute that is transferred from the fluid phase to the solid surface, where it is bound due to the action of

electrostatic or van der Waals or other binding forces, is termed the adsorbate; the solid to which the adsorbate binds is termed

the adsorbent. Adsorbents usually have a highly porous structure, being made up of fine internal pores that provide a very high

internal surface area (e.g. 450 - 1800 m2g-1 in activated carbon). Common adsorbents used in bioprocessing applications include

carbons, styrene-based resins, divinylbenzene or acrylamide polymers. They typically have void volumes of 30-50%

and pore diameters below 0.01 mm.

In an adsorption operation, the following sequence of stages is usually observed:

(i) adsorption solute is transferred from fluid to adsorbent followed by surface binding;

(ii) washing - any unadsorbed residual solute is removed;

(iii) desorption bound adsorbate is stripped out, commonly by elution with an appropriate solvent under a set of conditions

different from that which favor adsorption;

(iv) washing residual eluant is removed;

(v) regeneration of adsorbent.

Insofar as separation of the target solute biomolecule from associated impurities is concerned, note that while step (i) above

adsorption is the isolation step, step (iii) desorption is the recovery step. Eluant containing desorbed solute from this

latter step is subjected to further bioseparation operations for purification purposes.

Adsorbers may be of different configurations depending on the contacting pattern of the adsorbate and adsorbent phases, e.g.

fixed bed, moving bed, fluidized bed, stirred tank etc., of which fixed bed adsorbers (FBA), basically columns packed with

adsorbent particles, are most widely used probably due to their adsorption surface per unit volume being highest. Fig. 10.11

shows a typical dynamic profile of outflow (effluent) solute concentration from a FBA (the breakthrough curve) along with the

corresponding downward movement of the so-called adsorption zone the region of the adsorbent bed where the bulk of the

adsorption occurs at any given time. Feed containing solute (adsorbate) at concentration C Ai enters the column. Initially, adsorbent

at the top of the column rapidly binds most of the solute present in feed, hence effluent is almost solute-free. With continuing

feed flow, however, the top portion gradually becomes saturated with adsorbed solute (in equilibrium with liquid-phase

concentration CA1), and consequently the adsorption zone slowly moves down the column. Ultimately, as the breakpoint is

reached, the lower boundary of the adsorption zone comes in contact with the bottom of the bed (which, by now, is almost

completely saturated), and the concentration of solute in the outflow begins to increase substantially and quickly. As the

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adsorption zone passes through the bottom of the bed, no further adsorption of solute is possible, and the effluent concentration

increases to the inlet value.

The shape of the breakthrough curve greatly influences design and operation of fixed-bed adsorbers. Solute lost in the effluent is

given by the area under the breakthrough curve (Figure 10.12) between times t 3 (breakpoint) and t4 (when effluent solute

concentration equals that in the inlet). If adsorption is allowed to continue until the bed is completely saturated (and the effluent

concentration equals CAi), a significant amount of solute is wasted. To avert this eventuality, adsorption operations are usually

halted much earlier, at time t' (say), when the effluent concentration is quite low compared to C Ai. The price paid in the proeess is

that a fraction of the columns adsorbing capacity remains unutilized (shown as the shaded area in Fig. xx)

The overall rate of adsorption depends on two factors: the rate at which solute is transferred from liquid to solid by diffusional

mass-transfer mechanisms, and the rate of the actual adsorption or binding on the adsorbent surface. The resistances involved are

as follows:

(a) transfer of solute from bulk liquid to the liquid film/boundary layer around an adsorbent particle;

(b) diffusion through this film;

(c) pore diffusion that occurs in the fine internal pores of the adsorbent particle;

(d) adsorptive attachment to the internal pore surface;

(e) surface diffusion along the internal pore surfaces.

Steps (a) and (d) above are usually found to be relatively fast, so that they are seldom, if ever, rate-controlling. In contrast,

Step (b) constitutes the major external resistance to mass transfer, whereas steps (c) and (e) represent the major internal

resistances. Any or all of these steps can prove to be rate-limiting in a given situation.