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Perry’s Chemical Engineer’s Handbook: Adsorption and Ion Exchange


Adsorption and ion exchange share so many common features in regard to application in batch and fixed-bed processes that they can be grouped together as sorption for a unified treatment. These processes involve the transfer and resulting distribution of one or more solutes between a fluid phase and particles. The partitioning of a single solute between fluid and sorbed phases or the selectivity of a sorbent toward multiple solutes makes it possible to separate solutes from a bulk fluid phase or from one another.
This section treats batch and fixed-bed operations and reviews process cycles and equipment. As the processes indicate, fixed-bed operation with the sorbent in granule, bead, or pellet form is the predominant way of conducting sorption separations and purifications. Although the fixed-bed mode is highly useful, its analysis is complex. Therefore, fixed beds including chromatographic separations are given primary attention here with respect to both interpretation and prediction.

Adsorption involves, in general, the accumulation (or depletion) of solute molecules at an interface (including gas-liquid interfaces, as in foam fractionation, and liquid-liquid interfaces, as in detergency). Here we consider only gas-solid and liquid-solid interfaces, with solute distributed selectively between the fluid and solid phases. The accumulation per unit surface area is small; thus, highly porous solids with very large internal area per unit volume are preferred. Adsorbent surfaces are often physically and/or chemically heterogeneous, and bonding energies may vary widely from one site to another. We seek to promote physical adsorption or physisorption, which involves van der Waals forces (as in vapor condensation), and retard chemical adsorption or chemisorption, which involves chemical bonding (and often dissociation, as in catalysis). The former is well suited for a regenerable process, while the latter generally destroys the capacity of the adsorbent.
Adsorbents are natural or synthetic materials of amorphous or microcrystalline structure. Those used on a large scale, in order of sales volume, are activated carbon, molecular sieves, silica gel, and activated alumina [Keller et al., gen. refs.]. Ion exchange usually occurs throughout a polymeric solid, the solid being of gel-type, which dissolves some fluid-phase solvent, or truly porous. In ion exchange, ions of positive charge in some cases (cations) and negative charge in others (anions) from the fluid (usually an aqueous solution) replace dissimilar ions of the same charge initially in the solid. The ion exchanger contains permanently bound functional groups of opposite charge-type (or, in special cases, notably weak-base exchangers act as if they do). Cation-exchange resins generally contain bound sulfonic acid groups; less commonly, these groups are carboxylic, phosphonic, phosphinic, and so on. Anionic resins involve quaternary ammonium groups (strongly basic) or other amino groups (weakly basic).
Most ion exchangers in large-scale use are based on synthetic resins—either preformed and then chemically reacted, as for polystyrene, or formed from active monomers (olefinic acids, amines, or phenols). Natural zeolites were the first ion exchangers, and both natural and synthetic zeolites are in use today.
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