Article No : b03_01

Separation Processes, Introduction

C. JUDSON KING, University of California, Berkeley CA 94 720, United States

1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . 405 6. Selection of a Separation Process. . . . .... .. 409

2. Definitions . . . . . . . . . . . . . . . . . . . . . . . . . . . 406 7. Factors Influencing Phase Equilibria . .... .. 410
3. Process Configurations. . . . . . . . . . . . . . . . . . 406 8. Sources of Equilibrium Data . . . . . . . .... .. 411
4. Separation Principles . . . . . . . . . . . . . . . . . . . 408 References . . . . . . . . . . . . . . . . . . . . . .... .. 411
5. Advantages and Disadvantages of Different
Separation Methods . . . . . . . . . . . . . . . . . . . . 408

1. Introduction Mineral Sorting

Magnetic Separation
Separation processes are used to convert feed Electrostatic Separation
mixtures into two or more products differing in Gravity Concentration
composition. Unit operations treated in the first Dense-Medium Separation
part of this volume deal primarily with diffusion- Flotation
al separation processes suitable for feeds that are
homogeneous mixtures: Separation processes constitute more than
half of the total equipment investment for the
Evaporation chemical and fuel industries. They are also
Distillation, 1. Fundamentals widely used in pharmaceutical and food indus-
Sublimation tries, in beneficiation of mineral ores and
Liquid–Liquid Extraction recovery of metals, in processing effluents,
Absorption, 1. Fundamentals and in a diverse array of other industries.
Adsorption Separation processes may have a number of
Process-Scale Chromatography purposes, which can be loosely categorized as
Biochemical Separations follows:

These contrast with mechanical separation of 1. Purification: Removal of impurities, thereby

heterogeneous mixtures, in which the product enabling a desirable substance to be obtained
phases are already present on a microscale. These at a higher level of purity; e.g., refining of
are discussed in the following articles: sugar and treatment of drinking water.
2. Concentration or Recovery: Increasing the
Filtration, 1. Fundamentals concentration of a desired substance in solu-
Centrifuges, Filtering tion, usually by removal of a substantial frac-
Centrifuges, Sedimenting tion of solvent; e.g., production of fruit juice
Hydrocyclones concentrates and recovery of metal values
Sedimentation from effluents.
Dust Separation 3. Fractionation: Separation of desired sub-
Screening stances from one another; e.g., primary distil-
Elutriation lation of crude oil and chromatographic
Air Classifying separations.

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: 10.1002/14356007.b03_01
406 Separation Processes, Introduction
The first two categories imply separation of a
small amount of one substance from a large
amount of another. The desired products are the
major and minor constituents, respectively, in the
first and second processes.
2. Definitions
Most separation processes are based on the prin-
ciple that different phases of matter have differ-
ent compositions at equilibrium. Examples are
vapor and liquid phases in distillation, and im-
miscible liquid phases in liquid – liquid extrac-
tion. These processes achieve separation by al-
lowing the phases to proceed toward equilibrium,
hence the name equilibration processes.
Another category, known as rate-governed
processes, achieves separation by means of
differences in rates of transport of different
species through a medium or barrier. Here the
products are probably fully miscible with the
feed; the separation would be destroyed by
remixing them. Examples are ultrafiltration and
gaseous diffusion.
A separating agent is added to achieve sepa-
ration. In equilibration processes, this agent
serves to create the second phase. The separating
agent takes the form of energy or matter. Ex-
amples of energy separating agents are reboiler
heat, which forms the vapor in distillation, and
chilling or refrigeration, which causes ice to form
in freeze concentration processes. Examples of
mass separating agents are an absorbent used to
separate gases and an ion-exchange resin used to
desalt water. Typically, most of the utilities costs
for a separation process are associated with the
separating agent, e.g., the cost of steam to drive
the reboiler of a distillation column or the cost of
regenerating a mass separating agent for reuse.
Economics and environmental restrictions usu-
ally dictate that a mass separating agent should be
regenerated and reused. A separation process
based upon a mass separating agent thereby
requires a second, subsequent separation process.
The degree of separation achieved between
two substances in different products relates to the
separation factor between them. For equilibra-
tion processes, the separation factor aij is usually
defined as the ratio of the partition coefficients
(Ki and Kj) of the two species between the two
phases at equilibrium (aij ¼ Ki/Kj). The con-
Vol. 32
stants Ki and Kj are the partition coefficients of
species i and j, which are defined as the concen-
tration of a particular species in phase 2 divided
by that in phase 1. Any concentration units may
be used for Ki and Kj in either phase, provided the
same units are used for both species in a given
phase. Phases 1 and 2 are usually chosen so that
aij is greater than unity.
3. Process Configurations
Often, the species being separated is separated
to an insufficient degree by a simple equilibra-
tion or by a single passage through a barrier. In
these cases, the degree of separation between
species can be improved by staging or counter-
currency. Examples of each are shown in Fig-
ure 1. By sending the product from one con-
tacting or stage to another and appropriately
recycling intermediate products to previous
stages (Fig. 1 A), the degree of separation be-
tween species in the ultimate products can be
improved considerably. For a distillation oper-
ated at total reflux (infinitesimal feed and prod-
uct flow), the separation factor for products from
a single equilibrium stage is aij, as already
noted, whereas that from N equilibrium stages
joined countercurrently is aN ij (the Fenske equa-
tion) (! Distillation, 1. Fundamentals).
Continuous countercurrent contacting can be
used to accomplish the same effect, as shown in
Figure 1 B. Here, two phases flow countercur-
rent to each other through an open material such
as a structured packing, which serves to create
interface for mass transfer between phases. The
action is analogous to that of a countercurrent
heat exchanger, where the exit temperature of the
hot stream can be lower than the exit temperature
of the cold stream. Sometimes contactors are
built with elements of both discretely staged and
continuous countercurrent contacting, for exam-
ple, rotating disk contactors used for liquid –
liquid extraction (! Liquid–Liquid Extraction).
Another way of improving the degree of
separation achievable in a simple contacting is
the chromatographic mode. Here a mobile phase
flows along a thin, stationary phase (! Process-
Scale Chromatography).
The thinness of the stationary phase provides
rapid rates of mass transfer, giving the effect of
many stages or ‘‘transfer units’’ per unit length of
Vol. 32 Separation Processes, Introduction 407

Figure 1. Staging and countercurrency

A) Staged mixer – settler system for solvent extraction; B) Continuous countercurrent extractor

the stationary phase. In elution chromatography,

components of a mixture injected as a pulse at the
inlet end of the contactor proceed along the
stationary phase at different rates, determined
by the different equilibrium distributions be-
tween phases, and emanate as a succession of
isolated peaks (Fig. 2). Field-flow fractionations
are rate-governed processes operated in an anal-
ogous, elution-chromatographic mode.
A continuous staged or countercurrent con-
tactor provides high feed capacity but generates
only two products of high purity. (Intermediate
products, or sidestreams, of lesser purity can also
be present.) The elution-chromatography mode
can separate a complex mixture into many pure
peaks or products, but its inherent capacity is low
because the feed is injected intermittently as
pulses.
When a solid feed is used (e.g., leaching of
Figure 2. Typical output from a gas or liquid chromatograph
roast and ground coffee to form coffee extract; (peak height, as sensed by any of various detection methods,
! Liquid–Solid Extraction) or a solid mass vs. elution time)
408 Separation Processes, Introduction
separating agent is employed (e.g., an adsorbent;
! Adsorption), movement of the solids should
generally be avoided because attrition and unde-
sirable mixing may result. Fixed-bed processes
are commonly used (e.g., the home water soft-
ener filled with ion-exchange resin or a bed of
activated alumina for drying air) when a solid
feed or mass separating agent is used. A regen-
erated fixed-bed separation can handle a substan-
tial feed rate but in its simplest form provides
only one highly purified product, the initial ef-
fluent, before a second component leaves the bed.
Among the more notable innovations in industri-
al separation during the past few decades have
been effective ways of simulating countercur-
rency with fixed beds.
Yet another fundamentally different approach
to separation involves migration of different
species to equilibrium positions within a gradient
field. One example is isoelectric focusing. These
processes are inherently slow but can give se-
parations that are not possible by other means.
4. Separation Principles
For a feed of any particlular phase condition, an
equilibration separation process can be based
upon formation of, or contact with, any immisci-
ble second phase of matter. For a liquid feed, the
second phase may be a gas (stripping), an im-
miscible liquid (extraction), or a solid (crystalli-
zation, adsorption). Equilibration may be with
the bulk of the second phase or with a surface.
Surface-based separation processes include ad-
sorption, as well as foam, bubble, and emulsion
fractionation (! Flotation).
For rate-governed processes, differences in
any form of transport can be exploited. These
include rates of permeation through a solid mem-
brane (! Membranes and Membrane Separation
Processes, 1. Principles), Knudsen diffusion in a
porous medium (as used for separation of urani-
um isotopes in UF6; ! Isotopes, Natural), ther-
mal diffusion, electrophoresis, or pressure
diffusion.
Often, two separation principles used in con-
cert can operate synergistically. Examples are the
use of cross fields for rate-governed separation
and the enhancement of relative volatility in a
distillation by adding a substance that modifies
the equilibrium between phases, as done in azeo-
Vol. 32
tropic and extractive distillation (! Distillation,
1. Fundamentals).
5. Advantages and Disadvantages of
Different Separation Methods
When the same separation factors can be at-
tained, equilibration processes using energy sep-
arating agents tend to be less costly than those
using a mass separating agent, because of the
need for circulating and regenerating the mass
separating agent or else disposing of and repla-
cing it. Similarly, when staging or countercur-
rency is needed, equilibration processes tend to
be more attractive economically than rate-gov-
erned processes that give an equivalent separa-
tion factor, because equipment and energy can be
utilized more efficiently in the former.
Separation processes involving a solid phase
can suffer drawbacks associated with low or
vanishingly small transport rates in the solid
phase and with the desirability of keeping the
solid phase stationary.
Certain methods of separation are better suit-
ed for certain ranges of feed concentration. In
particular, fixed-bed operations are most effec-
tive for removing relatively dilute solutes, since
the diluteness necessitates less bed volume and
less frequent regeneration. Thus, adsorption and
ion-exchange processes tend to be used to recov-
er solutes from relatively dilute feeds or to re-
move impurities. Along this spectrum of feed
concentration, extraction (with liquids) and ab-
sorption (with gases) are usually considered for a
middle range of concentration, because the sol-
vent flow rate required tends to be relatively
independent of the feed solute concentration.
Operational upper limits on feed solute concen-
tration can come from the need to keep liquid
phases immiscible in extraction or to avoid too
large a percentage decrease of the flow rate of the
feed phase. Distillation works well over a wide
range of feed concentrations but can experience
low stage efficiencies at very low solute
concentrations.
Membrane Separation can provide high se-
lectivity for removing or concentrating (ultrafil-
tration) high molecular mass or macromolecular
solutes, for removing salts from water or concen-
trating them (reverse osmosis, electrodialysis),
Vol. 32
and for fractionating solutes of high and low
molecular mass (dialysis); (for further informa-
tion, see ! Membranes and Membrane Sepa-
ration Processes, 1. Principles). Economical,
high-capacity membranes that effectively
remove polar organic solutes of lower molecular
mass have yet to be developed, but are an area of
research. The solute throughput capacity and
selectivity provided by membranes can be en-
hanced by impregnation of the membrane with
an appropriate extractant (solid-supported liq-
uid membranes, facilitated transport). Mem-
brane processes are best suited for low molar
solute concentrations, because providing the
driving force for transport across the membrane
is otherwise difficult and expensive.
Cost and Scaleup. Different methods of sep-
aration have inherently different costs. An in-
verse relationship tends to exist between the
value of the product and the scale of production.
For high-value substances produced on a small
scale, a much wider range of separation techni-
ques can be considered than for substances of
lower value. Often the cost or value of a sub-
stance is influenced strongly by the difficulty of
separation; therefore, for a high-value substance,
utilization of a newer or less common means of
separation may be necessary in order to perform
the desired separation at all. Furthermore, certain
separation processes (e.g., distillation, extrac-
tion) can be scaled up more readily than others.
Those methods that rely on very thin phases or
thin flow channels (chromatography), laminar
flow (field-flow processes), or ready dissipation
of heat (electrophoresis) are particularly difficult
to scale up to large capacities.
Thermosensitive Product. In many cases, the
feed or products are sensitive to thermal degra-
dation, contamination, or changes due to a
change in the chemical environment, such as
denaturation of proteins. These constraints are
particularly common in the food and pharmaceu-
tical industries. Here, methods of separation that
avoid these problems will have an advantage. To
avoid thermal degradation, low temperatures and
short residence times should be used. Processes
that avoid heating the feed (extraction, sorption,
crystallization, etc.) are advantageous; if vapori-
zation must be used, operation under vacuum is
helpful. Concerns about contamination and
Separation Processes, Introduction 409
chemical environment limit the types of mass
separating agents that can be used. For instance,
in bioprocessing, many solvents have toxic ef-
fects, so precipitation and the use of solid sor-
bents are relatively advantageous. Similarly, pro-
teins may denature if they are taken into a
nonaqueous phase.
Processes Involving Reversible Chemical Re-
actions. Most industrial separations are carried
out by processes that do not involve chemical
reactions, because of the consumption of re-
agents required to accomplish the reaction, the
cost of reagents needed to regenerate the original
desired substance, and the need to dispose of
unwanted reaction products. However, chemical
complexation or association reactions (donor –
acceptor, chelation, clathration, etc.) are much
more readily reversible and can be used advan-
tageously in separations to increase the selectivi-
ty among solutes or the capacity for a desired
solute. Reversible chemical interactions can be
implemented in extraction; sorption; ion ex-
change; azeotropic and extractive distillation;
impregnated membranes; and foam, bubble, and
emulsion fractionation. Finally, the common
processes for concentrating a solute in solution
by removal of solvent (evaporation, reverse os-
mosis, ultrafiltration, freeze concentration) incur
expense in proportion to the amount of solvent
that must be removed. Extraction or sorption of
the solute(s) of interest can lead to concentration
as well, because only a limited amount of the
solvent will accompany the solute into or onto the
extractant or sorbent. Reversible chemical inter-
actions can be used effectively here as well.
6. Selection of a Separation Process
In seeking one or more appropriate methods of
separating a particular mixture, the first consid-
eration is the size of the separation factor likely
to be attained by different methods of separation.
Differences in volatility (distillation, evapora-
tion, stripping), solubility (crystallization, ex-
traction, absorption), charge-to-mass ratio (ion
exchange, electrophoresis), molecular size and
shape (adsorption with molecular sieves, crys-
tallization, gel permeation, clathration, dialysis),
and chemical reactivity can all be used for
separations.
410 Separation Processes, Introduction
Next, whether ordinary or extreme conditions
(very high or low pressure, very high or low
temperature, etc.) are needed to obtain attractive
separation factors must be determined. Methods
that require excessive temperature – time com-
binations or result in contamination or chemical
change may be ruled out by the nature of the feed
or product. Also, as already noted, the value of
the substance and the desired scale of operation
can determine the number and types of alterna-
tives to be considered, because of the varying
cost of different separation methods and their
suitability for scaleup. Finally, a very practical
consideration is the amount of previous experi-
ence with a particular process.
Among near equals, distillation has an advan-
tage because it avoids solids, it is easy to stage
and scale up, and a vast backlog of experience
exists. Rate-governed processes are usually con-
sidered seriously only when the desired separa-
tion can be achieved in a single stage. Separation
of uranium isotopes by gaseous diffusion is a
notable exception to this generalization, howev-
er. With processes utilizing a mass separating
agent, ease of regeneration becomes a dominant
factor. Finally, as already noted, fixed-bed pro-
cesses gain a compensating advantage when
substances at relatively low concentration are to
be removed.
7. Factors Influencing Phase
Equilibria
Several general factors influence phase equilibria
and can be utilized in the logic of selecting
processes and choosing mass separating agents.
A generalized equilibration separation process
may be regarded as having a source (feed) phase
and a second, receiving phase. For the solute(s) of
interest to move in the desired direction, the
chemical potential of the solute in the receiving
phase must be less than that in the source phase.
The partition coefficient Ki for a solute be-
tween two bulk phases is independent of solute
concentration when ideal solutions exist in both
phases or, in most instances, when the solute is
very dilute in both phases. The partition coeffi-
cient is simply the ratio of the activity coefficient
in the source phase to that in the receiving phase,
if the activity coefficients and the partition coef-
ficient are based upon the same concentration
Vol. 32
units (moles or mass per volume, weight fraction,
etc.). If preferential interactions occur between
solute and solvent [defined as the major compo-
nent(s)] in either phase, the distribution of the
component toward that phase will be enhanced.
Similarly, if less affinity exists between solute
and solvent molecules than between solvent mo-
lecules themselves, the solute will be driven
toward the other phase.
The values of Ki for many phase-distribution
processes are dominated by the nonidealities in
one of the two phases. This is particularly true for
processes that remove nonpolar or low-polarity
solutes from aqueous solution in which the aque-
ous phase is highly nonideal (very large activity
coefficients) and the receiving phase is much
more nearly ideal. Thus relationships among
many organic compounds based upon a single
set of chemical parameters related to dispersion
forces, polarity and polarizability, and acidity
and basicity, serve to correlate such seemingly
diverse partitioning properties as solubility in
water [2], adsorption from water onto activated
carbon [3], and extraction from water into 1-
octanol [4]. All of these situations are dominated
by aqueous-phase nonidealities.
Dimerization or Polymerization of the sol-
ute, or formation of solute molecules into mi-
celles in one of the phases, serves to increase the
distribution (i.e., increase Ki) of the solute in that
phase at higher solute concentrations.
Another common equilibrium feature is the
saturation of a phase. In adsorption processes,
the finite amount of solid surface area present
provides an upper limit on the amount of solute
that can be taken up within the capacity of the
selective layer adjacent to the surface. The same
is true of gas – liquid surface capacity in foam or
bubble fractionation. In these cases, the partition
coefficient toward the surface phase decreases as
saturation is approached. This is another reason
why surface-based separation processes are more
useful when the solute to be removed is present in
low concentration.
A similar situation exists where chemical
reactions are involved (e.g., ion exchange, re-
versible chemical complexation). The reactant in
the receiving phase has a limited capacity, in that
the stoichiometry of the underlying reaction(s)
cannot be exceeded. Thus, a solvent phase con-
taining a reactive organic extractant of molecular
Vol. 32
mass 400 at 40 wt % in an organic diluent can at
most take up 5 wt % of a solute of molecular
mass 50, with which the extractant forms a 1 : 1
complex. Complexation of additional solute mo-
lecules with a reactant molecule engenders addi-
tional uptake.
8. Sources of Equilibrium Data
Many measurements of phase-equilibrium prop-
erties exist, but they are widely scattered in the
literature. For a particular system, a search of
Chemical Abstracts may be the most useful
approach. Complications of data are given in
[5–8] for vapor – liquid equilibria; [9] for liq-
uid–liquid equilibria; [10] and [11] for solubili-
ties of gases and solids in liquids; [12] and [13]
for bulk solid – liquid equilibria; and [14] for
phase diagrams in general.
Methods for Prediction, Correlation, and In-
terpretation of vapor–liquid and liquid – liquid
phase equilibria are treated in [15] and summa-
rized in [16]. Prominent among these is the
UNIFAC method, described for vapor – liquid
equilibria in [17] and for liquid – liquid equi-
libria, in a more general context, in [18] and
[19]. This method is suitable for mixtures with
moderate degrees of nonideality but cannot yet
be extended to situations involving simulta-
neous strong, specific chemical interactions. For
further information, see ! Estimation of Phys-
ical Properties.
References
General References
1 C. J. King: Separation Processes, 2nd ed., McGraw-Hill,
New York 1980. R. W. Rousseau (ed.): Handbook of
Separation Process Technology, Wiley, New York 1987.
P. A. Schweitzer (ed.): Handbook of Separation Techni-
ques for Chemical Engineers, McGraw-Hill, New York
1979.
Specific References
2 R. W. Taft, M. H. Abraham, R. M. Doherty, M. J. Kamlet,
Nature (London) 313 (1985) 384.
Separation Processes, Introduction 411
3 M. J. Kamlet, R. M. Doherty, M. H. Abraham, R. W. Taft,
Carbon 23 (1985) 549.
4 R. W. Taft, M. H. Abraham, G. R. Famini, R. M. Doherty,
et al., J. Pharm. Sci. 74 (1985) 807.
5 I. Wichterle, J. Linek, E. Hala (eds.): Vapor-Liquid Equi-
librium Data Bibliography, Elsevier, Amsterdam 1973
Suppl. 1, 1976. Suppl. 2, 1979. Suppl. 3, 1982. Suppl. 4,
1985.
6 M. Hirata, S. Ohe, K. Nagahama: Computer Aided Book of
Vapor-Liquid Equilibria, Elsevier, Amsterdam 1975.
7 J. Gmehling, U. Onken, et. al.: Vapor-Liquid Equilibrium
Data Collection, vol. 1, 1 a, 2abcd, 3, 4, 5, 6abc,7, 8,
Dechema, Frankfurt 1977 ff.
8 H. Knapp, R. D€oring, L. Oellrich, U. Pl€ockner, J. M.
Prausnitz: Vapor-Liquid Equilibria for Mixtures of Low-
Boiling Substances, Chemistry Data Ser., vol. 6, De-
chema, Frankfurt 1982.
9 J. Wisniak, A. Tamir: Liquid-Liquid Equilibrium and
Extraction, 2 vols., Elsevier, Amsterdam 1980 – 1981
Suppl. 1, 1985.
10 J. Wisniak, M. Herskowitz: Solubility of Gases and Solids,
2 vols., Elsevier, Amsterdam 1984.
11 A. Seidell, W. F. Linke: Solubilities of Inorganic and
Metal-Organic Compounds, Van Nostrand, New York
1958.
12 J. Timmermanns: The Physico-chemical Constants of
Binary Systems, Interscience, New York 1959 – 1960.
13 H. Stephen, T. Stephen (eds.): Solubilities of Inorganic
and Organic Compounds, Pergamon, New York 1964.
14 J. Wisniak: Phase Diagrams, 2 vols., Elsevier, Amster-
dam 1981.
15 J. M. Prausnitz, R. N. Lichtenthaler, E. Gomes de Aze-
vedo: Molecular Thermodynamics of Fluid-Phase Equi-
libria, 2nd ed., Prentice-Hall, Englewood Cliffs NJ 1986.
16 R. C. Reid, J. M. Prausnitz, T. K. Sherwood: Properties of
Gases and Liquids, 3rd ed., McGraw-Hill, New York
1977.
17 A. Fredenslund, J. Gmehling, P. Rasmussen: Vapor-Liq-
uid Equilibria Using UNIFAC, Elsevier, Amsterdam
1977.
18 J. M. Sørensen, T. Magnussen, P. Rasmussen, A. Fre-
denslund, Fluid Phase Equilib. 2 (1979) 297; 3 (1979) 47;
4 (1980) 151.
19 T. Magnussen, P. Rasmussen, A. Fredenslund, Ind. Eng.
Chem. Process Des. Dev. 20 (1981) 331.
Further Reading
J. D. Seader, E. J. Henley: Separation Process Principles, 2nd
ed., Wiley, Hoboken, NJ 2006.
P. C. Wankat: Separation Process Engineering, 2nd ed.,
Prentice Hall, Upper Saddle River, NJ 2007.