15

ADSORPTION AND ION EXCHANGE

eparation of the components of a fluid can be

S
In ion exchange equipment, cations or anions from the
effected by contacting them with a solid that has a fluid deposit in the solid and displace equivalent amounts of
preferential attraction for some of them. Such other ions from the solid. Suitable solids are not necessarily
processes are quantitatively significant when the porous; the ions are able to diffuse through the solid material.
specific surfaces of the solids are measured in hundreds of A typical exchange is that of H or OH - ions from the solid
+

m*/g. Suitable materials are masses of numerous fine pores for some undesirable ions in the solution, such as Ca or
++

that were generated by expulsion of volatile substances. The SO;-. Eventually all of the ions in the solid are replaced, but
most important adsorbents are activated carbon, prepared by the activity is restored by contacting the exhausted solid with
partial volatilizationor combustion of a carbonaceous body, a high concentration of the desired ion, for example, a strong
and activated alumina, silica gel, and molecular sieves which acid to replace lost hydrogen ions.
are all formed by expulsion of water vapor from a solid. The For economic reasons, saturated adsorbents and
starting material for silica gel is a coagulated silicic acid and exhausted ion exchangers must be regenerated. Most
that for molecular sieves is hydrated aluminum silicate commonly, saturation and regeneration are performed
crystals that end up as porous crystal structures. Porous alternately and intermittently, but equipment can be devised
glasses made by leaching with alkai have some application in in which these processes are accomplished continuously by
chromatography. Physical properties of common adsorbents countercurrent movement of the solid and fluid streams. Only
are listed in Tables 15.1 and 15.2. Representative a few such operations have proved economically feasible. The
manufacturing processes are represented on Figure 15.1. UOP and Toray processes for liquid adsorption are not true
The amount of adsorption is limited by the available continuous processes but are effectively such.
surface and pore volume, and depends also on the chemical Desorption is accomplished by elevating the
natures of the fluid and solid. The rate of adsorption also temperature, or reducing the pressure, or by washing with a
depends on the amount of exposed surface but, in addition, suitable reagent. The desorbed material may be recovered as
on the rate of diffusion to the external surface and through valuable product in concentrated form or as a waste in easily
the pores of the solid for accessing the internal surface which disposable form. Adsorbent carbons used for water treating
comprises the bulk of the surface. Diffusion rates depend on often must be regenerated by ignition in a furnace. Relatively
temperature and differences in concentration or partial small amounts of adsorbents that are difficult to regenerate
pressures. The smaller the particle size, the greater is the are simply discarded.
utilization of the internal surface, but also the greater the
pressure drop for flow of bulk fluid through a mass of the
particles.

15.1. ADSORPTION EQUILIBRIA data are presented in graphical form only (LB IV 4/b, 1972, pp.
121-187). The effect of temperature also is correlated by a theory of
The amount of adsorbate that can be held depends on the
Polanyi, whereby all data of a particular system fall on the same
concentration or partial pressure and temperature, on the chemical
curve; Figure 15.4 is an example. For isothermal data, a
nature of the fluid, and on the nature, specific surface, method of
combination of the Freundlich and Langmuir equations was
preparation, and regeneration history of the solid. For single
developed by Yon and Turnock (Chem. Eng. Prog. Symposium
adsorbable components of gases, the relations between amount
Series 117, 67, 1971):
adsorbed and the partial pressure have been classified into the six
types shown in Figure 15.2. Many common systems conform to
Type I, for example, some of the curves of Figure 15.3. Adsorption w = kP"/(l+ kP"). (15.3)
data are not highly reproducible because small contents of
impurities and the history of the adsorbent have strong influences
on their behavior. Individuals of multicomponent mixtures compete for the
One of the simplest equations relating amount of adsorption limited space on the adsorbent. Equilibrium curves of binary
and pressure with some range of applicability is that of Freundlich, mixtures, when plotted as x vs. y diagrams, resemble those of
vapor-liquid mixtures, either for gases (Fig. 15.5) or liquids (Fig.
w =UP" (15.1) 15.6). The shapes of adsorption curves of binary mixtures, Figure
15.7, are varied; the total adsorptions of the components of the
and its generalization for the effect of temperature pairs of Figure 15.7 would be more nearly constant over the whole
range of compositions in terms of liquid volume fractions rather
than the mol fractions shown.
w=aP"exp(-b/T). (15.2) Higher molecular weight members of homologous series adsorb
preferentially on some adsorbents. The desorption data of Figure
The exponent n usually is less than unity. Both gas and liquid 15.8 attest to this, the hydrogen coming off first and the pentane
adsorption data are fitted by the Freundlich isotherm. Many liquid last. In practical cases it is not always feasible to allow sufficient
data are fitted thus in a compilation of Landolt-Bornstein (11/3, time for complete removal of heavy constituents so that the capacity
Numerical Data and Functional Relationships in Science and of regenerated adsorbent becomes less than that of fresh, as Figure
Technology, Springer, New York, 1956, pp. 525-528), but their gas 15.9 indicates. Repeated regeneration causes gradual deterioration

495
TABLE 15.1. Physical Properties of Adsorbents

External
Effective Bulk Void External Specific Reactivation
Particle Mesh Diameter Density Fraction Surface Heat Tempera! ure
Form* Size D1,, ft. p b , Lb/cu.ft. F, a, sq.ft. C,, Btullb O F O F Examples

Activated Carbon ... P 4x6 0.0128 30 0.34 310 0.25 20@-1000 Columbia L
P 6x8 0.0092 30 0.34 446 I, *I

P 8 X 10 0.0064 30 0.34 645 I* .,

G 4 x 10 0.0110 30 0.40 460 0.25 ., I,
Pittsburgh BPL
G 6 X 16 0.0062 30 0.40 720 ,I I.

G 4 X 10 0.0105 28 0.44 450 ,I I ,

Witco 256
Silica Gel.. . ... . . ... G 3x8 0.0127 45 0.35 230 0.22 250-450 Davison 03
G 6 X 16 0.0062 45 0.35 720 II 1,

S 4x8 0.0130 50 0.36 300 0.25 300-450 Mobil Sorbead R

Activated Alumina.. G 4x8 0.0130 52 0.25 380 0.22 350-600 Alcoa Type F
G 8 X 14 0.0058 52 0.25 480 ,I *I I. ,* I,

G 14x28 0.0027 54 0.25 970 I. ,I I, I, I.

S (1/4*) 0.0208 52 0.30 200 0.22 350-1000 Alcoa Type H

S (1/8") 0.0104 54 0.30 400 *# It I. I. ,.
Molecular Sieves.. . G 14 x 28 0.0027 30 0.25 970 0.23 300-600 Davison. Linda
P
P
(1/16')
(1/8")
0.0060
0.0104
45
45
0.34
0.34
650
400
I.

P. ..
.I

S 4x8 0.0109 45 0.37 347 #I .I

I.
8 X 12 0.0067 45 0.37 565 I,
S
' P = pellets; G = granules; S = spheroids
(Fair, 1969).

Na Na I Z[(A102)lZ(Si0,)121 8-ring 3.8 Desiccant. CO, removal

(obstructed) from natural gas
Ca Ca,N a,[( AlO,) I ,( SOz)I ,] 8-ring 4.4 Linear paraffin
A (free) separation. Air
separation
K K I z[(AIOz)lz(Si0z)I 21 8-ring 2.9 Drying of cracked gas

Mordenite ( Ag
H
Age[(A10~)dSi02)41
Hd(A102)dSi0z).d
12-ring 7.0 I and Kr removal from
nuclear ~ f f - g a s e s ' ~ ~ - ~ )

Silicali te - (SiO,), IO-ring 6.0 Removal of organics

from water
ZSMJ Na Na3[(A102)dSiO~k31 IO-ring 6.0 Xylene separatiod3')

"Also K-BaX.
(Ruthven, 1984).

496
 15.2. ION EXCHANGE EQUILIBRIA 497
TABLE 15.2-(continued)
(b) Typical Properties of Union Carbide Type X Molecular Sieves

Ncniiiiinl piirv hilk I Irill ld IGpiililiriiiiii

Basic diaiiieter, density, adsorption (mu), HtO capacity, Molecules Molecules
type angstroms Available form Ib/ft3 B t d h HtO %wt adsorbed excluded Applications
3A 3 Powder 30 1800 23 Molecules with an Molecules with The preferred molemlar sieve
$bin pellets 44 20 effective diameter an effective adsorbent for the commerical
%-in pellets 44 20 < 3 A, including diameter > 3 &
., dehydration of unsaturated
HIO and NH, e.g., ethane hydrocarbon streams such as
cracked gas, propylene,
butadiene, and acetylene. It is
also used for drying polar liquids
such as methanol and ethanol.
4A 4 Powder 30 1800 28.5 Molecules with an Molecules with The preferred molecular sieve
$bin pellets 45 22 effective diameter an effedive adsorbent hor static dehydration in
%-in pellets 45 22 e 4 A, including diameter > 4 A, a closed gas or liquid system. It is
8 x 12beads 45 22 ethanol, HIS, CQ, e.g., propane used as a static desiccant in
4~8beads 45 22 SO,, CH,, Gk household refrigeration systems;
1 4 x 30mesh 44 22 and C H , in packaging of drugs, electronic
components and perishable
chemicals; and as a water
scavenger in paint and plastic
systems. Also used commercially
in drying saturated hydrocamon
ctrparnr.

5A 5 Powder 30 1800 2a Molecules with an Molecules with Separates normal p&s from
%-in pellets 43 21.5 effective diameter an effective branchedchain and cyclic
%-in pellets 43 21.5 < 5 A, including n- diameter > 5 A, hydrocarbons through a selective
C,H,OH,t n- e.g., is0 adsorption process.
C,H,,,t CH. to compounds and
GHa R-12 all +carbon rings
lox 8 Powder 30 1800 36 Is0 paraffins and Di-n-butylamine Aromatic hydrocarbon separation.
' b i n pellets 36 28 olefins, CH,, and larger
%-in pellets 36 28 molecules with an
effective diameter
<8A
-
13X 10 Powder 30 1800 36 Molecules with an Molecules with Used commercially for general
%-in pellets 38 28.5 effective diameter an effective gas drying, air plant feed
%-in pellets 38 28.5 < 10 A diameter > 10 A, purification (simultaneous
8 x l2beads 42 28.5 e.g., (CF,),N removal of H,O and CQ), and
4 x 8 beads 42 28.5 liquid hydrocarbon and natural
14 x 30 mesh 38 28.5 gas sweetening (HIS and
mercaptan removal).

(Kovach, 1978).

of adsorbent; Figure 15.10 reports this for a molecular sieve that necessarily develop. These are of the same order of magnitude
operation. as heats of condensation. Some data are in Figure 15.4
Representation and generalization of adsorption equilibria of
binary and higher mixtures by equation is desirable, but less 15.2. ION EXCHANGE EQUILIBRIA
progress has been made for such systems than for vapor-liquid or
liquid-liquid equilibria. The Yon and Turnock equations (1971) Ion exchange is a chemical process that can be represented by a
applied to components 1 and 2 of binary mixtures are stoichiometric equation, for example, when ion A in solution
replaces ion B in the solid phase,
(15.4)
(15.5) +
A (solution) B (solid) eA (solid) + B (solution) (15.7)
or
(15.6)
A + B / A + B, (15.8)
They have been found useful as an empirical correlation
method for adsorption on molecular sieves [Maurer, Am. Chem. where the overstrike designates a component in the solid phase.
SOC. Symp. Ser. l35, 73 (1980)l. Other attempts at prediction or
The equilibrium constant is called the selectivity, designated by
correlation of multicomponent adsorption data are reviewed by KAB,
Ruthven (1984). In general, however, multicomponent equilibria
are not well correlatable in general form so that design of (15.9)
equipment is best based on direct laboratory data with the exact (15.10)
mixture and the exact adsorbent at anticipated pressure and = [&]/[A]
temperature. (15.11)
I-x, 1-XA '

Adsorption processes are sensitive to temperature, as the data

of Figures 15.3, 15.5, and 15.11 show. Thus practical adsorption The last equation relates the mol fractions of the ion originally in
processes are complicated by the substantial heats of adsorption the solution at equilibrium in the liquid (xA) and solid ( x i ) phases.
 Calcium Wash
r- chloride r- water

Sodium
aluminate

Sodium
silicate -
Crystallization
tank

Screen
(a)

I Spenrchar I
Treatment with HCI
to remove lime
I I

Washing
with water

adsorbed materials
NaOH solution
I , 1 I Boilingwith Na,CO,
I
or NaOH solution
8
SDrav
1 Washing with
dilute HCI I
Retort or kiln burning at
750 deg. F with regulated air

-
supply - selective oxidation of
impurities

Cooling

I Screening of
revivified char I
Dust Hydrogel
Coarse

(b) (C)

Figure 15.1. Processes for making adsorbents. (a) Flowsketch of a process for making molecular sieve adsorbents. (b) Process for
reactivation of bone char. (c) Silica gel by the BASF process. The gel is formed and solidifies in air from sodium silicate and
sulfuric acid, then is washed free of sodium sulfate with water (Ullmann, Encyclopedia of Chemical Technology, Verlag Chemie,
Weinheim, Germany).

498
 15.2. ION EXCHANGE EQUILIBRIA 499

Pressure
0.02m
0.0 1.o
RT In (Po/P) (kcal/gmol)
2.0

Figure 15.4. Polanyi characteristic curve for effect of temperature

on adsorption of n-butane on silica gel [AI-Sahhat et al., Ind. Eng.
Figure 15.2. Types of adsorption isotherms: (I) monomolecular Chem. Process. Des. Dev. 20, 658 (1981)l.
layer; (I1 and 111) multimolecular layers; (IV and V) multimolecular
layers and condensation in pores; (VI) phase transition of a
monomolecular layer on the surface (after Brunauer, Physical
Adsorption, Princeton Univ. Press, 1945). and the equilibrium constant or selectivity is given by

(C/C)KDB= x;xfi/x&~~ (15.14)

The residual mol fraction in the liquid phase corresponding to a = (xfi/xD)[(l - xD)/(1 - Xfi)]', (15.15)
given mol fraction or degree of saturation in the solid phase is
where C and are the total concentrations of the two kinds of ions
in the solution and in the solid, respectively.

Approximate values of the selectivity of various ions are shown in

Table 15.3; for a particular pair, K,, is the ratio of tabulated values
for each.
When the exchanged ion D is divalent, the reaction is

D + 2B S D + 2B, (15.13)

Mol fraction of first-named in adsorbate

Figure 15.5. Adsorption of binary mixtures: (1) ethane + ethylene.

Type 4A MS 25"C, 250 Torr; (2) ethane + ethylene. Type 4A MS,
Pressure, Torr 2 5 T , 730Torr; (3) ethane+ethylene. Type 4A MS, 75"C,
+
730 Torr; (4) carbon dioxide hydrogen sulfide. Type 5A MS,
Figure 15.3. Effects of temperature, pressure, and kind of adsorbent +
27"C, 760 Torr; (5) n-pentane n-hexane, type 5A MS, 100°C,
on the amount of ethane adsorbed: (1) activated carbon at 25°C; (2) 760 Torr; (6) ethane + ethylene, silica gel, 25"C, 760 Torr; (7)
type 4A molecular sieve (MS) at 0°C; (3) type 5A MS at 25°C; (4) ethane + ethylene, Columbia G carbon, 25T, 760 Torr; (8)
type 4A MS at 25°C; (5) type 4A MS at 75°C; (6) silica gel at 25°C; +
acetylene ethylene. Type 4A MS, 3 1 T , 740 Torr. (Data from
(7) type 4A MS at 150°C. (Data from Union Carbide Corp.) Union Carbide Corp.)
 500 ADSORPTION AND ION EXCHANGE

5 -

I 1 1 1 1
0 10 20 3.0 40 50

0 I c (mmolelg anhydrous zeolite)

Mol fraction of first-named in liquid
Figure 15.8. Variation of isosteric heat of adsorption with coverage
Figure 15.6. Binary liquid adsorption equilibria on X-Y diagrams: showing the difference in trends between polar and nonpolar
(1) toluene+iso-octane on silica gel (Eagle and Scott, 1950); (2) sorbates. nC4H,,-5A (data of Schirmer et al.); CF4-NaX,
toluene + iso-octane on charcoal (Eagle and Scott, 1950); (3) SF,-NaX (data of Barrer and Reucroft); C0,-NaX, (data of
ethylene dichloride + benzene on boehmite (Kipling); (4) ethylene Huang and Zwiebel), NH,-SA (data of Schirmer et al.); H,O-LiX,
dichloride + benzene on charcoal (Kipling). (Kidina in Proceedings
~- -,\. NaX, and CsX, (data of Avgul et al.). (Ruthven, Sep Purification
of the Second International Congress of Surface Activity. (19575, Methods 5(2), 189 (1976))
Vol. III, p . 462.)

Example 15.1 is concerned with such an exchange and

regeneration process.

15.3. ADSORPTION BEHAVIOR IN PACKED BEDS

Adsorption is performed most commonly in fixed vertical beds of
porous granular adsorbents. Flow of adsorbing fluid usually is down
through the bed, that of regenerant usually is upward. Moving and
fluidized beds have only a limited application in the field.
If the time is sufficient, the adsorbent nearer the inlet of the
fluid becomes saturated at the prevailing inlet fluid concentration
but a concentration gradient develops beyond the saturation zone.
Figure 5.12 depicts this behavior. The region of falling concen-
tration is called the mass transfer zone (MTZ). The gradient is
called the adsorption wave front and is usually S-shaped. When
its leading edge reaches the exit, breakthrough is said to have been
attained. Practically, the breakthrough is not regarded as
necessarily at zero concentration but at some low value such as 1%
or 5% of the inlet that is acceptable in the effluent. A hypothetical
position, to the left of which in Figure 15.12(b) the average
adsorbate content equals the saturation value, is called the
stoichiometric front. The distance between this position and the exit
of the bed is called the length of unused bed (LUB). The
exhaustion time is attained when the effluent concentration becomes
the same as that of the inlet, or some practical high percentage of it,
such as 95 or 99%.
Mol fraction of chloroform or benzene in liquid
The shape of the adsorption front, the width of the MTZ, and
the profile of the effluent concentration depend on the nature of the
Figure 15.7. Adsorption of liquid mixtures on charcoal. Chloro- adsorption isotherm and the rate of mass transfer. Practical bed
form + acetone and benzene + ethanol. The ordinate gives the
amount of each individual substance that is adsorbed, the depths may be expressed as multiples of MTZ, values of 5-10
abscissa the mol fraction of chloroform (mixed with acetone) or multiples being economically feasible. Systems that have linear
the mol fraction of benzene (mixed with ethanol). (Data adsorption isotherms develop constant MTZs whereas MTZs of
gathered by Kipling. Adsorption from Solutions of Non- convex ones (such as Type I of Figure 15.1) become narrower, and
Electrolytes, 1965). those of concave systems become wider as they progress through
 15.3. ADSORPTION BEHAVIOR IN PACKED BEDS 501

I I

Y
Time on stream

1
c
-
c
zn
.-C
-
-al3
L
al
C
8
.
3
3
‘8
.3
3
0 0
0 lime after breakthrough
Mass transfer front
Stoichiometric front

(b)

Figure 15.9. Concentrations in adsorption beds as a function of position and of effluent as a function of time. (a)
Progress of a stable mass transfer front through an adsorption bed and of the effluent concentration (Lukchis,
1973). (b) The mass transfer zone (MTZ), the length of unused bed (LUB), stoichiometric front, and profile of
effluent concentration after breakthrough.

the bed. The last types are called unfavorable isotherms; C/C,, in terms of a time parameter T, at a number of values of a
separations in such cases usually are accomplished more parameter Z‘, which involves the bed length Z. In Example 15.2,
economically by some other kind of process. The narrower the this chart is used to find the concentration profile of the effluent, the
MTZ, the greater the degree of utilization of the bed. break and exhaustion times, and the % utilization of the adsor-
The rate of mass transfer from fluid to solid in a bed of porous bent bed. In this case, the model affords a fair comparison with
granular adsorbent is made up of several factors in series: experimental data.
Many investigations have been conducted of the mass transfer
1. Diffusion to the external surface. coefficient at the external surfaces of particles and of other
2. Deposition on the surface. diffusional mechanisms. Some of the correlations are discussed in
3. Diffusion in the pores. Chapters 13 and 17. A model developed by Rosen [Znd. Eng.
4. Diffusion along the surface. Chem. 46, 1590 (1954)l takes into account both external film and
pore diffusional resistance to mass transfer together with a linear
Various combination of shapes of isotherms and mass transfer isotherm. A numerical example is worked out by Hines and
factors have been taken into account by solutions of the problem in Maddox (1985, p. 485).
the literature. One of the simpler cases was adopted by Hougen and In the model developed by Thomas [ J . Am. Chem. SOC. 66,
Marshall (1947, see Figure 15.13), who took a linear isotherm and 1664 (1944)], the controlling mechanism is the surface kinetics
diffusion to the external surface as controlling the rate. They represented by the Langmuir isotherm. Extensions of this work by
developed the solution in analytical form, of which several Vermeulen et al. (1984) incorporate external surface and pore
approximations that are easier to use are mentioned for instance by diffusional resistances.
Vermeulen et al. (1984, p. 16.28). A graphical form of the solution No comprehensive comparisons of the several models with each
appears in Figure 15.13. This shows the effluent concentration ratio, other and with experimental data appear to have been published.
502 ADSORPTION AND ION EXCHANGE

TABLE 15.3. Gas Phase Adsorption Cycles, Steam

Requirements, and Operating Parameters
.8
3
3
(a) Typical Cycle Times in Hours for Adsorber Operation

High Pressure Organic Solvent

Distance Gas Dryer Recovery Unit
~~ ~~~ ~~ ~~~

(1) At end of adsorption.

A B A B
Onstrearn ................. 24 24 2.00 1.00
r Depressure/purge.. ....... 2 1 ..........
Hotgas .................... 10 13 ..........
Steam.. ...................... ... 0.75 0.67
Hot gas ....................... ... 0.33 .....
Cold gas ................... 5 8 0.42 0.33
Distance Pressure/standby.. ....... 7 2 0.50 .....
(2) At end of regeneration. - - - -
24 24 2.00 1.00
(Fair, 1969).
(b) Steam/Solvent Ratios and Amount of Adsorbate for a
Coconut-Shell Carbon 6-12 Mesh, 1200 m2/g
24

Distance 22
(3) Useful capacity of cycle.
20

18
Figure 15.10. Incomplete regeneration of adsorbent bed by a
thermal-swing cycle. 16
s
z l4
oi
tij 12
2
2 10
2 8

0
0 I 2 3 4 5
Pounds of steam per pound of solvent
(Kovach, 1979).

(c) Typical Operating Parameters for Gas Phase Adsorption

Range Design
~~ ~~~ ~~

Superficial gas velocity 20 to 50 c d s 40 c d s

(40to 100 fUmin) (80Wmin)
Adsorbent bed depth 3 to 10 MTZ 5 MTZ
Adsorption time 0.5 to 8 h 4h
Temperature -200 to 50°C
Inlet concentration
Adsorption base 100 to 5OOO vppm
LEL base 40%
Adsorbent particle size 0.5 to 10 mm 4 t o 8 mm
Working charge 5 to 20% wt 10%
Temperature, "C Steam solvent ratio 2:l to 8:l 4:1
Adsorbent void volume 38 to 50% 45%
Steam regeneration temperature 105 to 110°C
Inert gas regenerant termperature 100 to 300°C
Figure 15.11. Effect of temperature on molecular sieve type SA, Regeneration time 'h adsorption time 1
silica gel and activated alumina at water vapor pressure, 13.3 kPa Number of adsorbers 1 to 6 2 to 3
(100 mm Hg). A, molecular sieve type SA; B, silica-type adsorbent;
C, alumina-type adsorbent. (Chinnd Cummings, 1978). (Kovach, 1979).
 15.3. ADSORPTION BEHAVIOR IN PACKED BEDS 503

EXAMPLE
15.1 its ion concentration is 2.23eq/L. Other values for the system
Application of Ion Exchange Selectivity Data remain at C = 1.2 eq/L and K,, = 0.15. Accordingly,
The SO; ion of an aqueous solution containing C-= 0.018 eq/L is to
be replaced with C1- ion from a resin with C = 1.2eq/L. The KDBC/C= 0.15(1.2)/2.23 = 0.0807
reaction is
and Eq. (15.15) becomes
SO;(solution) + 2Cl-(resin) Ft SOb(resin) + 2Cl-(solution),
D + 2B FtD 2B. + ~ 6 / ( 1 -~6)'= 0.0807~,/(1- x ~ ) ' .

From Table 15.3, the selectivity ratio K, = 0.15/1.0 = 0.15, and The values of x,,? in the liquid phase will be calculated for several
values in the resin. Those results will be used to find the minimum
KDBC/C= 0.15(1.2)/0.018 = 10. amount of regenerant solution needed for each degree of
regeneration
Then Eq. (15.15) becomes
xso?j
L regenerant/
XD/(l - X 6 ) 2 = lOX,/(l - X D ) 2 . In Resin In Solution L resin
For several values of mol fraction x, of SO; in solution, the 0.1 0.455 1.06
corresponding mol fractions x, in the resin are calculated and 0.05 0.319 1.60
0.01 0.102 5.22
tabulated:
Sample calculation for the last entry of the table: The
XSOZ
equivalents of SOT transferred from the resin to the solution are
In Solution In Resin
0.99(1.2) = 1.188 eq/L.
1 1
0.1 0.418
0.05 0.284
The minimum amount of solution needed for this regeneration is
0.01 0.0853

For regeneration of the resin, a 12% solution of NaCl will be used;

""' 5.22L solution/Liter.
0.102(2.23)
=

2 ethoxyethyl acetate

0 -

Proponone

0 5 10 15 20 25
L, in Desorption time, min

(a) (b)

Figure 15.12. Multicomponent mixtures, adsorption, and desorption. (a) Concentrations of the components of a ternary
mixture in continuous adsorption, as in a moving bed unit (Kovach, 1979). (b) Composition of a desorbed stream consisting
of several components as a function of time.
 504 ADSORPTION AND ION EXCHANGE
0.999
0.898 The most common method of regeneration is by purging the
0.995 bed with a hot gas. Operating temperatures are characteristic of the
0.99
0.98 adsorbent; suitable values at atmospheric pressure are shown in
0.95 Table 15.1. The exit temperature of the gas usually is about 50°F
0.9 higher than that of the end of the bed. Typical cycle times for
0.8
adsorption and regeneration and steam/adsorbent ratios are given
0.7 in Table 15.4. Effluent composition traces of a multicomponent
0.6
0.5 system are in Figure 15.9. Complete removal of adsorbate is not
2 0.4 always economically feasible, as suggested by Table 15.4(b). The
0 0.3
0.2
effect of incomplete removal on capacity is shown schematically by
0.1
Figure 15.10. Sufficient heat must be supplied to warm up the
0.05
adsorbent and the vessel, to provide heat of desorption and
0.02 enthalpy absorption of the adsorbate, and to provide for heat losses
0.01 to the surroundings. Table 15.4(c) suggests that regeneration times
0.005
o.m2 be about one-half the adsorption times. For large vessels, it may be
0.001 worthwhile to make the unsteady heating calculation by the general
methods applicable to regenerators, as presented, for instance, by
Figure 15.13. Dependence of the concentration ratio, C / C , of the Hausen (Heat Transfer in Counterjlow, Parallel Flow and Cross-
effluent from an adsorber on parameters of bed length and time; for flow, McGraw-Hill, New York, 1983).
the case of a linear isotherm, zero initial adsorbate content and Purging of the adsorbate with an inert gas at much reduced
constant inlet composition C, pressure is feasible in high pressure adsorption plants. The
adsorption of Example 15.2, for instance, is conducted at 55 atm, so
that regeneration could be accomplished at a pressure of only a few
2’ = ( K p / c u i ) Z , bed length parameter, atmospheres without heating. If the adsorbate is valuable, some
z = ( K p / K D p b ) ( t- Z/u,), time parameter, provision must be made for recovering it from the desorbing gas.
K D = q/C, coefficient of linear adsorption isotherm, Ignition of adsorbents in external furnaces is practiced to
ui= interstitial velocity in the bed, remove some high molecular weight materials that are difficult to
E = voidage of the bed, volatilize. This is done, for example, for reactivation of carbon from
2 = length of the bed, water treating for trace removal of impurities such as phenol.
Kp = mass transfer coefficient, (L3 fluid)/(L3 bed)(time). Caustic solution can convert the phenol into soluble sodium phenate
in readily disposable concentrated form as an alternate process for
(Hougen and Watson, Chemical Process Principles, Wiley, New regeneration.
York, 1947, p . 1086; Hougen and Marshall, Chem. Eng. Prog. 43, Displacement of the adsorbate with another substance that is in
197 (1947); Vermeulen et al., Chemical Engineers’ Handbook, turn displaced in process is practiced, for instance, in liquid phase
McGraw-Hill, New York, 1984, p . 16.29.) recovery of paraxylene from other C, aromatics. In the Sorbex
process, suitable desorbents are toluene and paradiethylbenzene.
This process is described later.

15.4. ADSORPTION DESIGN AND OPERATING PRACTICES

Moreover, they are all based on isothermal behavior and
approximations of adsorption isotherms and have not been applied When continuous operation is necessary, at least two adsorbers are
to multicomponent mixtures. The greatest value of these calculation employed, one on adsorption and the other alternately on
methods may lie in the prediction of effects of changes in basic data regeneration and cooling. In cases where breakthrough is especially
such as flow rates and slopes of adsorption isotherms after harmful, three vessels are used, one being regenerated, the other
experimental data have been measured of breakthroughs and two onstream with the more recently regenerated vessel down-
effluent concentration profiles. In a multicomponent system, each stream, as in Figure 15.16.
substance has a different breakthrough which is affected by the Beds usually are vertical; adsorbers 45 ft high and 8-10 ft dia
presence of the other substances. Experimental curves such as those are in use. When pressure drop must be minimized, as in the
of Figure 15.14 must be the basis for sizing an adsorber. recovery of solvents from atmospheric air, horizontal vessels with
Since taking samples of adsorbent from various positions in the shallow beds are in common use. Process gas flow most often is
bed for analysis is difficult, it is usual to deduce the shape of the downward and regenerant gas flow is upward to take advantage of
adsorption front and the width of the MTZ from the effluent counterflow effects. Upflow rates are at most about one-half the
concentration profile which may be monitored with a continuous fluidizing velocity of the particles. Vertical and horizontal types are
analyzer-recorder or by sampling. The overall width of the MTZ, represented on Figure 15.17.
A major feature of adsorber design is the support for the
for instance, is given in terms of the exhaustion and breakthrough
times and the superficial velocity as granular adsorbent, preferably one with a low pressure drop. The
combination of Figure 15.18(a) of grid, screens, and support beams
width = us(&- tb)/&. is inexpensive to fabricate and maintain, has a low heat capacity and
a low pressure drop. The construction of Figure 15.18(b) is suited to
REGENERATION adsorbers that must be dumped frequently. Supports of layers of
ceramic balls or gravel or anthracite, resting on the bottom of the
Adsorbents are restored to essentially their original condition for vessel, are suited to large vessels and when corrosion-resistant
reuse by desorption. Many hundreds of cycles usually are feasible, construction is required. Typical arrangements are shown in Figures
but eventually some degradation occurs, as in Figure 15.15 for 17.26 and 17.27. The successive layers increase in diameter by
instance, and the adsorbent must be discarded. factors of 2-4 up to l i n . or so. Holddown balls also may be
 15.4. ADSORPTION DESIGN AND OPERATING PRACTICES 505

EXAMPLE 15.2 kdp, z 1.731(52) 3.58

t=-t+-=- t+-
Adsorption of n-Hexane from a Natural Gas with STca Gel kga U,/E 206.4 11.4/0.35
Hexane is'to be recovered from a natural gas with silica gel.
= 0.4362 + 0.11 min.
Molecular weight of the gas is 17.85, the pressure is 55.4atm,
temperature is 94"F, and the content of n-hexane is 0.853 mol % or
0.0982 Ib/cuft. The bed is 43 in. deep and the superficial velocity is Values of t are read off Figure 15.13 and converted into values of t:
11.4ft/min. Other data are shown with the sketch:
C f c, c t(min)
0.01 40 17.56
0.0982 Ibkuft
I 0.05 45 19.74
0.1 50 21.92
0.2 53 23.23
0.4 60 26.28
0.6 65 28.46
0.8 73 31.95
ft/rnin 0.9 79 34.57
0.95 82 35.87
0.99 92 40.24
3.58 f l
The total amount adsorbed to the breakpoint, at C/CO= 0.01, per
sqft of bed cross section is

0.0982(11.4)(17.56) = 19.66 Ib/sqft cross section.

The saturation amount for the whole bed is

3.58(0.17)(52) = 31.65 lb/sqft cross section.

Accordingly,
Z = 3.58 ft, bed depth,
us= 11.4 ft/min, superficial velocity, utilization of bed = (19.66/31.65)(100%) = 62.1%.
0,= 0.01 ft, particle diameter,
The calculated concentration profile is compared in the figure with
a = 284 sqft/cuft, packing external surface, experimental data, Run 117, of McLeod and Campbell, SOC. Pet.
pb = 52 lb/cuft, bed density, Eng. J . , 166 (June 1966):
E = 0.35 bed voidage.

From these and physical property data, the Schmidt and Reynolds
numbers are calculated as 1 1 1 I I I
,. -
Y 1 - I

Sc = 1.87, Re = 644. -

The equation of Dwivedi and Upadhyay, Eq. (13.148), is 0.8-

applicable:
-

0.6 -

:. kg = 0.35(lL4
1.8 7 y 3
(0.0038 + 0.0301) = 0.7268 ft/min, t -
k,a = 0.7268(284) = 206.4cuft gas/(cuft solid)(min). .
0"
0 0.4 -
Saturation content of adsorbate is 0.17 Ib/lb solid. Accordingly,
the coefficient of the linear adsorption isotherm is -

k 0.17 Ib hexane/lb solid 0.2 -

- 0.0982 - 1'731 lb hexane/cuft gas'
-
Use the Hougen-Marshall chart (Fig. 15.13):

-
0 I I I I I I I
10 20 30 40 50
t, min
506 ADSORPTION AND ION EXCHANGE

n-Pentono LUB
0.75
tone rtoichiomotric front

n-Pontono concontrot ion

0.50 n-tbxono rtoichiomotric in food
-Hrxono concontrotion
in food

0.25 -Pentane t n-hoxono

odrorpvien section adsorption soction

0
20 25 30 35 40 45 50
Adsorption l i m e , Minutor

F w e 15.14. Breakthrough curves in the adsorption of a mixture of hydrocarbons with composition n-butane 0.4 mol %,
n-pentane 25.9, n-hexane 23.9 is0 and cyclic hydrocarbons 49.8 mol % (Lee, in Recent Advances in Separation Science,
CRC Press, Boca Raton, FL, 1972, Vol. II, pp. 75-110).

provided at the top to prevent disturbance of the top layer of Steam rates for regeneration of a particular adsorbent carbon
adsorbent by incoming high velocity gas or entrainment by are shown in Table 15.3(b). Steam/solvent ratios as high as 8
upflowing gases. When regeneration is by heating, a drawback of sometimes are necessary.
the ball support arrangement is their substantial heat capacity, Data for liquid phase adsorption are typified by water treating
which slows up the heating rate and subsequent cooling to process for removal of small but harmful amounts of impurities. Some
temperature. conditions are stated by Bernardin [Chern. Eng., (18 Oct. 1976)l.
Representative values and ranges of operating parameters Water flow rates are 5-l0gpm/sqft. When suspended solids are
are summarized in Table 15.3. Cycle times for some adsorptions present, the accumulation on the top of the bed is backwashed at
are adjusted to work shift length, usually multiples of 8 hr, with 15-20 gpm/sqft for 10-20 min/day. The adsorbent usually is not
valve adjustments made by hand. When cycle times are short, as regenerated in place but is removed and treated in a furnace.
for solvent recovery, automatic opening and closing of valves is Accordingly, a continuous operation is desirable, and one is
necessary. simulated by periodic removal of spent adsorbent from the bottom
of the vessel with a design like that of Figure 15.18(b) and
replenishing of fresh adsorbent at the top. The pulses of spent and
fresh carbon are 2-10% of the total bed. Height to diameter ratio in
such units is about 3.
A carbon adsorber for handling 100,OOOgal/day of water
consists of two vessels in series, each 10 ft dia by 11ft sidewall and
containing 20,OOOIb of activated carbon. Total organic carbon is
reduced from 650 mg/L to 25 mg/L, and phenol from 130 mg/L to
less than 0.1 mg/L.
The capacity of regeneration furnaces is selected so that they
operate 8O-W% of the time. In multiple-hearth furnaces the
loading is 70-80 Ib/(sqft)(day). In countercurrent direct fired rotary
kilns, a 6% volumetric loading is used with 45min at activation
temperature.
Details of the design and performance of other liquid phase
adsorptions such as the Sorbex processes are proprietary.

15.5. ION EXCHANGE DESIGN AND OPERATING

I
0
I
50
I
100 150
I I
200
I
250 I
PRACTICES
Ion exchange processes function by replacing undesirable ions of a
Cycle¶
liquid with ions such as H+ or OH- from a solid material in which
Figure 15.15. Capacity decline with service of a molecular sieve the ions are sufficiently mobile, usually some synthetic resin.
(plant data, Davbon Sieve 562). Flow, 8150 kg mol; pressure, Eventually the resin becomes exhausted and may be regenerated by
3600 kPa (36 atm); temperature, 15°C; water content, 96 kg/hr; contact with a small amount of solution with a high content of the
minimum cycle time, 24 hr. (Chiand Cummings, 1978). desired ion. Resins can be tailored to have selective affinities for
TABLE 15.4. Properties of Ion-ExchangeMaterials
(a) Physical Properties
Moisture Eachange capcity
Bulk wet content Swelling Maaimum

Material
shr'
particles
density
(drained).
k/L
(d?P).
wei&
due to
eachange.
5%
operating
temperature. f
OC
Operating
pH range
Dry.
equinknt/kg
wet.
equivaknt/L

Crtion cachmgcn: strongly acidic

P d y s ~ y m msulfonate
Homogencow (gel)resin S 120-190 0-14
4% nos-linked 0 75-0 85 64-70 10-12 50-55 I 2-1 6
6% cross-linked 0 7&0 86 58-65 8-10 4a54 13-1 8
aim cmr-linked 0 77-0 87 48-60 6-8 46-52 14-1 9
12% cross-linked o 78-0 as 44-48 5 4 4-4 I3 15-20
16%nos-linked 0 79-0 89 42-46 4 4 2-4 6 17-2 1
eCm cross-linked 0 80-0 90 40-45 3 30-42 1 8-20
Mocmpaour structure
10-12% cross-linked S 0 81 50-55 4-6 120-150 0-14 4550 15-19
Sulfauted phenolic rnln G 0 74-0 85 50-60 7 50-90 0-14 20-25 0 7-0 9
Sulfauted coal G
Cation eichan en weakly acidic
Acrylic ( p u g ) or methacrylic (pK 6)
Homogeneous (gel) resin S 0 70-0 75 45-50 20-80 120 4-14 8 3-10 33-40
M.CropoW S 0 67-0 74 50-55 10-100 120 -8 0 2 5-3 5
phcndic resin C 0 70-0 80 -50 10-25 6-65 0-14 25 10-14
Polystyrene phosphormte c. s 0 74 50-70 (40 120
75
3-14
3-14
66
29
30
07
Polystyrene aminodiacetate S 0 75 68-75 (100
Polystyrene amidoaime S -0 75 58 10 50 1-11 28 oao9
P d yrene thid S -0 75 45-50 60 1-13 -5 20
CdLSC
PhmptKmate F -7 0
Methylene carboxylate F, P. C -0 7
Crmtrasnd (Fe silicate) G 13 1-5 0 60 6-8 0 14 0 18
Zeolite (AI silicate) c 0 85-0 95 40-45 0 60 6-8 14 0 75
Zirconium tungstate G 115-1 25 -5 0 >I50 2-10 12 IO
Anion eachangm: strongly basic
P d yst y r r n c h x d
Trimethyl benzyl ammonium (type
1)
Homogeneous, 8% CL S 0 70 46-50 -20 60-80 0-14 3 4-3 8 13-1 5
;our. 11% CL S 0 67 57-60 15-20 60-80 0-14 34 IO
D E h T y d r o a yeth yl ammonium
(type 11)
Homogemour. 8% CL S 071 -42 15-20 40-80 0-14 3 8-4 0 12
Macroporous. 10% CL S 0 67 -55 12-15 40-0-80 0-14 38 I 1
Acrylic-bued
Hnnoarneour (gel)
Mac+ -
S
S
0 72
0 67
-
-60
70 -15
-12
40-80
40-80
0-14
0-14
-5 0
30-33
10-12
0 8-0 9
C~llUbbPud
Ethyl trimethyl ammonium F I00 4-10 0 62
Triethyl hydroaypropyl ammonium io0 4-10 0 57
Anion eachnngen: intermediite~ytasic
(pK 11)
Polystyrme-based
Epky-polyamine
S
S
0 75
0 72
- 50
-64
15-25
8-10
65
75
0-10
0-7
48
65
18
17
Anion eachangen: weakly basic (pK 9)
Aminopdystyrene
Hanoge-
Macrocarour
(gel) S
S
0 67
0 61
- 45
55-60
8-12
-25
100
100
0-7
0-9
55
49
18
12
Arrylic-b;wd amine
Hmagcnau (gel) S 0 72 -63 8-10 80 0-7 65 17
M.cro~+our ~ S 0 72 -68 12-15 60 0-9 50 I1
Crllulou-bued
Aminoethyl P 10
Diethyl a m i m t h y l P -0 9

'Shapes: C. cylindrical pellets; G. g r a m P. powder, S. icres

IWhen two temperatures are shown. th st applies to H Irm for cation or OH form for anion. eachanger. the m n d . to salt ion
NOTE To convert kilograms per liter to pounds per cubic d.multiply b; 6238 X I O t , O F = X "C 32+
(Chemical Engineers' Handbook, McGraw-Hill, New York, 1984; a larger table complete with trade names is in the 5th edition, 1973)

(b) Selectivity Scale for Cations on 8% Crosslinked Resin

Li+ 1.o ZnZ+ 3.5

H+ 1.3 coz+ 3.7
Na+ 2.0 cuz+ 3.8 I- 8 HCO; 0.4
NH: 2.6 Cd2+ 3.9 NO; 4 CH,COO- 0.2
K+
Rb+
cs+
2.9 BeZ+
Mn2+
Niz+
4.0
4.1
3.9
Br-
HSOT
NO;
3
::: / F-
OH-(Type I)
0.1
0.05-0.07

Ag+
UOf+
MgZ+
3.3 II
caz+
s1z+
Pb2+
Baz+
5.2
6.5
9.9
11.5
CN-
CI-
BrO;
OH-(Type 11)
1.3
k:
0.65
1 SO:-
c0:-
HP0:-
0.15
0.03
0.01

(Bonner and Smith, J. Phys. Chem. 61,1957, p. 326). (Bonner and Smith, J. Phys. Chem. 61,1957, p. 326).

507
508 ADSORPTION AND ION EXCHANGE

Feed in;^ = 10Process

psi gas

r - - - --- 7
~

I
The ranges of possible operating conditions that have been
stated are very broad, and averages cannot be depended upon. If
the proposed process is similar to known commercial technology, a
new design can be made with confidence. Otherwise laboratory
work must be performed. Experts claim that tests on columns
I 3 vessels, each 2.5 cm dia and 1m bed depth can be scaled up safely to commercial
Knockout 14 ft dia by 12.5 diameters. The laboratory work preferably is done with the same
drum
450 FI
I
I
f t TT and 100
cuft of dessicant
on an 8 hour
bed depth as in the commercial unit, but since the active exchange
zone occupies only a small part of a normal column height, the

oil
1L ---J
I cycle. exchange capacity will be roughly proportional to the bed height,
and tests with columns 1m high can be dependably scaled up. The
Water laboratory work will establish process flow rates, regenerant
Dry gas, -90 F dewpoint quantities and flow rates, rinsing operations, and even deterioration
450 Ibmol/hr of performance with repeated cycles.
20 atm Operating cycles for liquid contacting processes such as ion
exchange are somewhat more complex than those for gas adsorp-
Figure 15.16. A three-vessel drying system for a cracked light tion. They consist of these steps:
hydrocarbon stream. Valve operation usually is on automatic timer
control. Recycled process gas serves as regenerant. 1. Process stream flow for a proper period.
2. A rinse for recovering possibly valuable occluded process
solution.
particular kinds of ions, for instance, mercury, boron, ferrous iron, 3. A backwash to remove accumulated foreign solids from the top
or copper in the presence of iron. Physical properties of some of the bed and possibly to reclassify the particle size distribution.
commercial ion exchange resins are listed in Table 15.3 together 4. The flow of regenerant for a proper period.
with their ion exchange capacities. The most commonly used sizes 5. Rinse to remove occluded regenerant.
are -20+50 mesh (0.8-0.3mm) and -40+80 mesh (0.4-
0.18 mm). As complex a cyclic process as this may demand cycle times of
Rates of ion exchange processes are affected by diffusional more than a few hours. Very high ion concentrations or high
resistances of ions into and out of the solid particles as well as volumetric rates may require batteries of vessels and automatic
resistance to external surface diffusion. The particles are not really switching of the several streams, or continuously operating equip-
solid since their volume expands by 50% or more by imbibition of ment. Several continuous ion exchange plants are being operated
water. For monovalent exchanges in strongly ionized resins, half successfully. The equipment of Figure 15.20 employs pulsed transfer
times with intraparticle diffusion controlling are measured in of solid between exchange and regenerant zones as often as every
seconds or minutes. For film diffusion, half times range from a few 4min to every 20 or 30min. Attrition of the resin may require
minutes with 0.1N solutions up to several hours with 0.001N replacement of as much as 30% of the resin each year in water
solutions. Film diffusion rates also vary inversely with particle conditioning applications.
diameter. A rough rule is that film diffusion is the controlling Fluidized bed units such as the multistage unit of Figure 15.20
mechanism when concentrations are below 0.1-l.ON, which is the suffer from some loss of efficiency because the intense mixing
situation in many commercial instances. Then the design methods eliminates axial concentration gradients. They do have the merit,
can be same as for conventional adsorbers. however, of not being bothered by the presence of foreign solid
Ion exchange materials have equilibrium exchange capacities of particles.
about 5 meq/g or 2.27 g eq/lb. The percentage of equilibrium The economic break between fixed bed and continuous
exchange that can be achieved practically depends on contact time, operation has been estimated as ion concentrations of 0.5N, or flow
the concentration of the solution, and the selectivity or equilibrium rates above 300gpm, or when three or more parallel beds are
constant of the particular system. The latter factor is discussed in required to maintain continuous operation. The original application
Section 15.2 with a numerical example. of continuous ion exchange was to treatment of radioactive wastes,
Commercial columns range up to 6 m dia and bed heights from but some installations of ordinary water treating have been made.
1 to 6 m, most commonly 1-3 m. Freeboard of 50-100% is provided Resin requirements for two extremes of ion concentration are
to accommodate bed expansion when regenerant flow is upward. analyzed in Example 15.3. The high concentration stream clearly is
The liquid must be distributed and withdrawn uniformly over the a candidate for continuous ion exchange.
cross section. Perforated spiders like those of Figure 15.19 are
suitable. The usual support for the bed of resin is a bed of gravel or
layers of ceramic balls of graded sizes as in Figure 17.27. Balls ELECTRODIALYSIS
sometimes are placed on top of the bed to aid in distribution or to
prevent disturbance of the top level. Since the specific volume of In this process, dissolved electrolytes are removed by application of
the material can change 50% or more as a result of water electromotive force across a battery of semipermeable membranes
absorption and ion-ion exchange, the distributor must be located constructed from cation and anion exchange resins. The cation
well above the initial charge level of fresh resin. membrane passes only cations and the anion membrane only
Liquid flow rates may range from 1 to 12 gpm/sqft, commonly anions. The two kinds of membranes are stacked alternately and
6-8gpm/sqft. When the concentration of the exchange ion is less separated about 1mm by sheets of plastic mesh that are still
than 50meq/L, flow rates are in the range of 15-80 bed volumes provided with flow passages. When the membranes and spacers are
(BV)/hr. For demineralizing water with low mineral content, rates compressed together, holes in the corners form appropriate
as high as 400 BV/hr are used. Regenerant flow rates are kept low, conduits for inflow and outflow. Membranes are 0.15-0.6 mm thick.
in the range of 0.5-5.0BV/hr, in order to allow attainment of A commercial stack may contain several hundred compartments or
equilibrium with minimum amounts of solution. pairs of membranes in parallel. A schematic of a stack assembly is
 Spent
regeneration

"T

Regeneration

-Product

Hinged head
(a)

Gas
out
A

(b)
Figure 15.17. Two designs of fixed bed gas adsorbers. (a) Vertical bed with balls on top for
hold-down and distribution of feed (Johnson, Chem. Eng. 79, 87 (27 Now 1972)]. (b)
Horizontal fixed bed for low pressure drop operation [Treybal, Mass Transfer Operations,
McGraw-Hill, New York, 1980; Logan, U.S.Pat. 2,180,712 (1939)l.

509
 510 ADSORPTION AND ION EXCHANGE
Feed, Like many other specialities, electrodialysis plants are
’ \- ,Screw clamps purchased as complete packages from a few available suppliers.
,/‘,Segmental Membrane replacement is about 10% per year. Even with
/ /’ clamp prefiltering the feed, cleaning of membranes may be required at
1‘ 1’ ’Compressible intervals of a few months. The comparative economics of
.’ ,/ /’ gasket electrodialysis for desalting brackish waters is discussed by Belfort
(1984): for lower salinities, electrodialysis and reverse osmosis
:’2--4-mesh screen
are competitive, but for higher ones electrodialysis is inferior.
Electrodialysis has a number of important unique applications, for
removal of high contents of minerals from foods and pharmaceuti-
cals, for recovery of radioactive and other substances from dilute
solutions, in electro-oxidation reduction processes and others.

15.6. PRODUCTION SCALE CHROMATOGRAPHY

t Detail
Product When a mixture of two substances is charged to a chromatographic
(a)
column, one of them may be held more strongly than the other.
Elution with an inert fluid will remove the more lightly held
Feed,
substance first, then the other. Separations even between very
similar substances can be very sharp. Figure 15.22(a) is an example
of a chromatogram. Only fluid-solid chromatography is an
adsorptive process, but gas-liquid and liquid-liquid are used more
frequently since liquids with suitable absorption properties are
easier to find than solid adsorbents. The active sorbent is a
high-boiling solvent deposited on a finely divided inert solid carrier.
The process is one of absorption, but the behavior is much like that
of adsorption. The principal application is to chemical analysis.
Relative retention times on various sorbents are key data which are
extensively tabulated, for instance in Meites (Handbook of
Analytical Chemistry, McGraw-Hill, New York, 1963).
Chromatographic separations are necessarily intermittent with
alternate injections and elutions, although a measure of continuity
I
‘-Hinged head can be achieved with an assembly of several units, or with suitably
Detail
sized surge tanks. A process flowsketch appears in Figure 15.22(b).
(b) Information on production scale chromatography is provided by
Figure 15.18. Two types of supports for adsorbent beds [Johnston, Conder (1973). Only separations difficult to achieve by other means
Chem. Eng., (27Nou. 1972)]. See also Figures 17.23 and 17.24. (a) are economical with chromatography.
Common type of flat screen support. (b) Conical-type of support Individual drums are provided for each product fraction. A
suited to frequent removal of adsorbent. detector monitors the separation and provides signals for controlling
the injection and collection sequence. The operation of partial
condensers for the dilute eluted streams presents challenges because
in Figure 15.21. Properties of commercially produced membranes of aerosol formations. When a valuable carrier such as nitrogen is
are in Table 15.5 and performance data are in Table 15.6. used, it must be cleaned up and recycled.
Membranes may be manufactured by mixing powdered ion A 1968 estimate of the cost breakdown for a plant with a
exchange resin with a solution of binder polymer and pouring the column 4 ft dia by 15 ft high and a throughput of 200-920 tons/yr
heated mixture under pressure onto a plastic mesh or cloth. The has been converted to a percentage basis in Table 15.7 because of
concentration of the ion exchanger is normally 50-70%. They are its age. The costs are said to not vary greatly with throughput or the
chiefly copolymers of styrene and divinylbenzene, sulfonated with nature of the separation, although this analysis has been made
sulfuric acid for introduction of the cation exchange group. specifically for the separation of CY- and /3-pinenes. The temperature
Standard cell sizes are up to 30 by 45in. In an individual was 165°C and the solvent was Carbowax 20M. The design was
stack the compartments are in parallel, but several stacks in series based on data in a 4in. dia column which had a capacity of
are employed to achieve a high degree of ion exchange. The 200-1500 mL/hr.
ion exchange membrane is not depleted and does not need Some of the materials for which chromatographic separation
regeneration. The mechanism is that an entering cation under the should be considered are essential oils, terpenoids, steroids, alka-
influence of an emf replaces an H+ ion from the resin and H+ from loids, pharmaceuticals, metal chelates, isotopes, and close-boiling
solution on the opposite face of membrane replaces the migrating isomers. For easy separations, vacuum distillation, liquid-liquid
cation. extraction, and fractional crystallization are less expensive.
Table 15.6 shows that pressures drops may be as high as
9OOpsi. Flow rates in a single stage are about 1gal/(hr)(sqft of 15.7. EQUIPMENT AND PROCESSES
available membrane surface). The process is distinguished by very
low power requirements: the desalination of sea water, for instance, Adsorbents are made in pellet form by extrusion or pressing or in
consumes 11-12 kWh/1000 gal. One stage effects a reduction of granular form by crushing and classification of larger masses or in
about 50% in salt content, so several stages in series are used for spherical or globular form by precipitation in an inert gaseous or
high performance. A flow sketch of a three-stage electrodialysis liquid medium. Typical processes for some adsorbent preparations
plant is in Figure 15.21(c). are represented in Figure 15.1. The BASF process of Figure 15.l(c)