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Solid/Liquid Separations

28 www.aiche.org/cep October 2006 CEP


C
rystallization is an important separation process in the
production of commodity and specialty chemicals.
Several different types and configurations of continu-
ous crystallizers have been developed for these applications.
The design and operation of an industrial crystallizer are
optimized based upon the conditions needed for:
producing larger and more uniform crystals of the
desired product
reducing the formation of agglomerates
reducing the amount of liquid impurities included in
each crystal
reducing the amount of liquid impurities included in
crystal agglomerates
reducing the liquid retained by the crystal cake after
solid-liquid separation and washing.
Lets first consider how various crystallization mecha-
nisms affect these objectives.
Thermodynamics. Figure 1 illustrates the general thermo-
dynamic phase behavior of a solute-solvent system and the
concepts of thermodynamic equilibrium and thermodynamic
stability for solid-liquid systems.
The solid line is the solubility curve, which represents
thermodynamic equilibrium between the liquid and solid
phases. Any liquid with a composition and temperature above
the solubility curve exists as stable unsaturated liquid.
Any liquid with a composition and temperature below the
solubility curve is not in thermodynamic equilibrium with
respect to formation of a solid phase i.e., it is supersaturat-
ed. However, it is not always thermodynamically unstable.
The region between the solubility curve and the limit of sta-
bility (the dashed line) is called the metastable zone. In this
region, nucleation sites are necessary to initiate the formation
of a solid phase from a supersaturated liquid. Theoretically, if
one could suppress all nucleation sites, the liquid could exist
as a stable supersaturated liquid even though it would not be
in equilibrium.
Beyond the metastable zone boundary, however, the pres-
ence of nucleation sites is not a requirement for the formation
This article offers qualitative insight into the
basic mechanisms of crystallization and the
principles of crystallizer operation,
and the ways in which these concepts relate
to the various crystallizer configurations
in industrial use today.
Ketan D. Samant
Lionel OYoung
ClearWaterBay Technology, Inc.
Understanding
Crystallization and
Crystallizers
Solute Composition
Solubility
Curve
Stability
Limit
T
e
m
p
e
r
a
t
u
r
e
Stable
Zone
Unstable
Zone
M
e
t
a
s
t
a
b
le
Z
o
n
e
I Figure 1. Solid-liquid phase behavior is characterized by
thermodynamic equilibrium and thermodynamic stability.
CEP October 2006 www.aiche.org/cep 29
of a solid phase. This is the unstable region, in which any
supersaturated liquid is neither stable nor in equilibrium and
therefore is subject to spontaneous nucleation and the forma-
tion of a solid phase.
Clearly, an industrial crystallizer must operate below the
solubility curve in order to produce a solid phase. However,
since the objective is to avoid the creation of a large number
of small particles, the crystallizer must not be operated in the
unstable zone; rather its operation must be restricted to the
metastable zone.
Nucleation and growth. Material transfer from the liquid
phase to the solid phase occurs via two mechanisms that go
hand in hand nucleation and growth. Growth refers to
deposition of solid material on existing crystals, while nucle-
ation refers to formation of new crystals (which subsequently
grow). The number of crystals and their sizes in any industri-
al operation will depend primarily on these two mechanisms.
In the metastable zone, nucleation and growth can take
place through several mechanisms, and their rates, in general,
can be considered directly related to the degree of supersatura-
tion (1, 2). The particle size distribution in an industrial crystal-
lizer depends on the relative rates of nucleation and growth and
on how they relate to the rate of product removal (which
depends on residence time). In general:
promoting growth over nucleation leads to small num-
bers of more-uniform crystals
promoting both material transfer mechanisms over prod-
uct removal leads to larger crystals
lower supersaturations promote growth over nucleation
higher residence times promote both nucleation and
growth over product removal.
Agglomeration. Particle sizes in industrial crystallizers
may also be affected by agglomeration and breakage.
Agglomerates form when growing crystals (of the same size
or of different sizes) collide with each other in a perfectly
inelastic way i.e., the particles stick together to form a
new particle. Agglomeration will be more extensive if there
are more particles, which increases the probability of colli-
sion, or if the colliding particles tend to stick together.
In general, agglomeration is associated with higher supersat-
uration, and even operation in the unstable zone conditions
that result in the formation of large numbers of small particles.
To minimize agglomeration, supersaturation should be limited.
Liquid inclusion in individual crystals. There are several
mechanisms by which liquid gets trapped inside growing crys-
tals. Although there are no universally accepted theories, higher
growth rates are considered to increase the amount of liquid
included in individual crystals. Higher supersaturation results
in higher growth rates, and thus is a condition that typically
increases the amount of liquid impurities in individual crystals.
Liquid inclusion in crystal agglomerates. Liquid gets
trapped between colliding particles during agglomeration.
Here, too, there are no universally accepted theories, but it is
safe to assume that the amount of trapped liquid increases with
increased agglomeration. Thus, higher supersaturation results
in larger volumes of liquid trapped in crystal agglomerates.
Liquid impurities outside the crystals. Typically, in indus-
trial operations, the amount of liquid retained outside the
crystals is much larger than the amount of liquid trapped
within the crystals. Downstream of the crystallizer, the crys-
tals are first separated from the mother liquor during the
solid-liquid separation step, and then the liquid retained by
the crystal cake is removed during the washing step.
The residual liquid content in the crystal cake after this
solid-liquid separation is, in general, inversely proportional to
the square root of the mean crystal particle size (assuming all
other things are the same). The smaller the particles in the
crystal cake, the more liquid the cake will retain after the
same solid-liquid separation operation. As a result, the
amount of wash liquid required to achieve the same washing
efficiency will also be higher for cakes containing small parti-
cles than for cakes with larger particles.
Larger crystals, therefore, are desired. Lower supersatura-
tions and higher residence times in the crystallizer are benefi-
cial for the solid-liquid separation as well.
Crystallizer operating mechanisms
For any continuous crystallization application, industrial
crystallizers should be designed to operate in the metastable
zone, at lower supersaturations, and with higher residence
times, in order to meet the stated objectives. This section
describes the mechanisms of crystallizer operation.
Every continuous industrial crystallizer must have:
a mechanism to generate supersaturation
a mechanism to relieve the supersaturation
a mechanism to control supersaturation generation.
In addition, to manage product crystal size, it is useful for
the crystallizer to have:
a mechanism for fines dissolution
a mechanism for removing classified product.
Different crystallizer configurations employ different
choices for these mechanisms. Knowledge of these choices
and the operating principles behind them will guide the selec-
tion and design of the most suitable configuration for new
installations, as well as troubleshooting and improving the
operation of existing systems.
Generating supersaturation
The mechanisms for generating supersaturation rely on
the changes in solubility of the crystallizing component as
a function of temperature and composition. Such changes
are measured through solubility experiments and quanti-
30 www.aiche.org/cep October 2006 CEP
fied using solubility curves and phase diagrams (3, 6).
In most cases, supersaturation is generated by a decrease
in temperature and/or decrease in solvent composition. There
are three mechanisms for creating supersaturation:
Cooling (typically by surface cooling, or in some cases
by direct contact with a refrigerant) generates supersaturation
through a decrease in temperature. This mechanism is best
suited for systems in which the solubility of the crystallizing
component decreases steeply or moderately with decreasing
temperature. It is not suited for systems with flat or inverted
solubility-temperature relationships.
Evaporation generates supersaturation through a decrease
in solvent composition, which is achieved when heat is added
to evaporate the solvent. It is the only mechanism that can be
used where the solubility of the crystallizing component either
increases with decreasing temperature or remains essentially
unchanged. For such systems, supersaturation can be generated
far more effectively by decreasing the solvent composition. For
systems with steep or moderate solubility, the other two mech-
anisms are better options than evaporation.
Adiabatic evaporative cooling generates supersatura-
tion through adiabatic solvent evaporation. Rather than
adding heat to the system, it relies on both a decrease in sol-
vent composition and a decrease in temperature brought
about by the adiabatic evaporation. As with surface or
direct-contact cooling, this mechanism is best used when
the solubility of the crystallizing component decreases mod-
erately or steeply with decreasing temperature. Adiabatic
evaporative cooling may not be appropriate when the bub-
ble point temperature decreases very slowly with pressure;
in such cases, even high vacuums cannot bring about a suf-
ficient reduction in temperature.
The solubility characteristics of the crystallizing compo-
nent dictate what mechanisms are needed for creating super-
saturation. Criteria such as cost, operability and compatibility
with crystallizer configurations should be used to further
refine the selection.
Relieving the supersaturation
In all crystallizers, the mechanism for relieving the super-
saturation is simply the existence of an active crystallization
volume. This volume contains a suspension of growing crys-
tals. The input to this active crystallization volume is the
supersaturated liquid or slurry, and the output is the product
slurry. The input and output rates and the active volume
determine the residence time provided.
The suspension in the active crystallization volume may
exhibit varying degrees of mixedness. At one extreme, it may
be completely mixed in terms of compositions, solids con-
tents, and particle sizes. At the other extreme, it may be fully
classified, with clear liquid at the top and progressively larger
solids concentrations and particle sizes below. The choice of
the degree of mixedness is usually a direct consequence of
the mechanism used for control of supersaturation generation.
Control of supersaturation generation
Figure 2 shows schematically the operation of a simple
cooling crystallizer. Supersaturation is generated by cooling
the fresh feed stream (stream FF), resulting in a stream that is
(arbitrarily) designated stream M. Stream M is sent to the
crystallizer tank, which provides the active volume for reliev-
ing the supersaturation. Inside the crystallizer tank and in the
product stream (stream P), the liquid-phase composition is
represented by ML and the solids composition by SP.
Both nucleation and growth are driven by the amount of
supersaturation (the composition difference between ML and
the solubility curve at the crystallizer temperature) in the
active volume. If sufficient residence time is provided, the
liquid phase ML will be within the metastable zone, and the
supersaturation will be low. However, the crystallizer tank
does not generate supersaturation it simply provides the
mechanism, i.e., the active crystallization zone, to relieve it.
Supersaturation is generated by cooling the fresh feed
stream (from FF to M). But as shown in Figure 2, stream M
lies in the unstable zone. As a result, nucleation occurs spon-
taneously, generating a large number of small particles inside
the cooler even before stream M reaches the crystallizer tank.
This is undesirable, and it implies that the supersaturation
generation needs to be controlled so that stream M is also in
the metastable zone.
Figure 2 also illustrates two ways in which such control
can be exercised:
the temperature can be reduced only to T*, at which
point the cooled stream M* lies on the limit of stability curve
the amount of solvent can be increased such that the
operating temperature is the limit of stability for the new
fresh feed stream FF*.
In most applications, the width of the metastable zone,
Solid/Liquid Separations
I Figure 2. Control of supersaturation generation.
FF
M
P
ML
SP Cooler
Solute Composition
T
e
m
p
e
r
a
t
u
r
e
ML P,M SP
Unstable
Zone
Metastable
Zone
FF* FF
T*
M*
Active
Volume
CEP October 2006 www.aiche.org/cep 31
which is very narrow, is not known. As a result, the restric-
tions on temperature and amount of solvent required in these
methods are quite severe. Both methods are highly undesir-
able because they adversely affect product recovery higher
temperature and higher solvent content mean lower recovery.
The only other option is recirculation. This involves
removing a stream from the active crystallization volume,
mixing it with the fresh feed, and then sending the combined
stream through the supersaturation generator and back to the
active crystallization volume. Two types of recirculation
mechanisms may be used:
liquor recirculation, which involves recirculating only the
liquid (or mother liquor) from the active crystallization volume
magma recirculation, wherein the slurry from the active
crystallization volume is recirculated.
Figure 3 shows the operation of a cooling crystallizer with
liquor recirculation. It is assumed that a liquid stream (which
has a composition corresponding to ML) can be removed from
the active volume. This stream is mixed with fresh feed stream
FF to form stream Lprior to the generation of supersaturation
by cooling. The location of stream Lon the temperature vs.
composition plot is such that the cooled stream M lies inside
the metastable zone. There are no changes to operating temper-
ature, feed composition or residence time. Thus, in this config-
uration, recirculation helps avoid high supersaturations at the
point of supersaturation generation without affecting the recov-
ery of crystallized product.
For liquor recirculation, it is assumed that only the mother
liquor is recirculated while the crystals remain in the active
volume. As a result, streams Land M are supersaturated, but
stable, liquids.
If the suspension in the active volume is mixed, it is not
possible to recirculate only the liquor. The recirculation flow,
known as magma, will include crystals as well. Operation
with magma recirculaton is depicted in Figure 4. Points L and
M represent the liquid compositions of the recirculating
streams, and points L and M represent the total composi-
tions (including the solids). Note that here, too, the liquid
portion of the recirculating stream (points L and M) lies
inside the metastable zone.
From a material balance point of view, magma recircula-
tion accomplishes the same objectives as liquor recirculation.
However, from an operational point of view, there are two
key differences between liquor and magma recirculation.
The first concerns the presence of solids at the site of
supersaturation generation. In liquor recirculation, no solids
are present, whereas in magma recirculation, solids are pres-
ent. In essence, liquor recirculation creates a stable supersatu-
rated liquid and brings it into contact with growing crystals;
magma recirculation brings growing crystals into contact
with a liquid that becomes supersaturated. Therefore, the par-
ticle size distributions resulting from liquor and magma recir-
culation will be different. If the liquor-recirculation liquid can
be maintained in the stable supersaturated condition before it
comes into contact with growing crystals, it will generally
produce larger crystals.
The second difference relates to the degree of mixedness
of the active crystallization volume required. Liquor recircu-
lation relies on being able to maintain fluidized classification
in the active volume. The recirculation stream is drawn from
the top of the active volume, which contains clear liquid, and
the supersaturated liquid is returned from the bottom upward
so that larger crystals are in contact with higher supersatura-
tions. Magma recirculation, on the other hand, does not
require product classification.
The ability to maintain a classified suspension in the
active crystallization volume is very sensitive to changes in
operating conditions, especially to changes in the recircula-
tion rate. Liquor recirculation can easily turn into magma
recirculation in response to minor changes in operating con-
ditions. Therefore, from an operability point of view, magma
recirculation is preferred.
I Figure 3. In liquor recirculation, liquid is removed from the active
volume without entraining any crystals and is recirculated.
M
P
ML
SP
Active
Volume
FF
ML
L
M P SP
Unstable
Zone
Metastable
Zone
FF
L
Cooler
Solute Composition
T
e
m
p
e
r
a
t
u
r
e
I Figure 4. In magma recirculation, a mixed stream containing liquid
and crystals is removed from the active volume and is recirculated.
P
ML
SP
Active
Volume
FF
Cooler
Solute Composition
T
e
m
p
e
r
a
t
u
r
e
FF
ML
L
M
L'
P,M' SP
Unstable
Zone
Metastable
Zone
M,M'
L,L'
32 www.aiche.org/cep October 2006 CEP
As noted earlier, it is very difficult to reliably estimate
or predict the width of the metastable zone for industrial
crystallizers, although laboratory experiments do offer use-
ful, but limited, insights. Thus, in both liquid and magma
recirculation (see Figures 3 and 4), streams L and M are
typically kept as close to ML as possible by using high
recirculation rates.
Optional auxiliary mechanisms
Manipulation of particle sizes is useful for producing larg-
er and more-uniform particles. It also makes it possible for
the process to adapt to changes in operating conditions. Fines
dissolution and product classification are two auxiliary mech-
anisms that are used to manipulate particle sizes.
Fines dissolution involves removal of particles smaller
than a certain size (or size range) from the active crystallizer
volume, dissolution of these particles, and the return of the
resulting solution back to the crystallizer. The fines are nei-
ther allowed to grow in the active crystallizer volume nor
leave with the product slurry. These restrictions promote the
formation of larger, more-uniform particles, which makes this
mechanism highly desirable.
Classified product removal involves the selective removal
of only particles larger than a certain size (or size range) in
the product slurry, which retains the smaller particles in the
active crystallizer volume and promotes larger particle sizes.
This mechanism is desirable, but optional.
Table 1 summarizes the conditions under which each
operating mechanism should and should not be considered.
The following sections describe the important crystallizer
configurations in industrial use today and the mechanisms
they employ.
Solid/Liquid Separations
Table 1. Choosing a crystallization operating mechanism.
Mechanism Should Be Considered When Should Not Be Considered When
Supersaturation Generation
Cooling The solubility of the crystallizing component The solubility of the crystallizing component stays flat
decreases steeply to moderately with or increases with decreasing temperature
decreasing temperature
Very low crystallization temperatures are required
(direct-contact cooling should be considered)
Evaporation The solubility of the crystallizing component stays The solubility of the crystallizing component decreases
flat or increases with decreasing temperature steeply to moderately with decreasing temperature
Adiabatic The solubility of the crystallizing component The solubility of the crystallizing component stays flat
Evaporative decreases steeply to moderately with decreasing or increases with decreasing temperature
Cooling temperature The bubble point temperature decreases very slowly
with pressure
Relieving the Supersaturation
Mixed Magma recirculation is the mechanism of choice Liquor recirculation is the mechanism of choice for
Suspension for control of supersaturation generation control of supersaturation generation
Classified Liquor recirculation is the mechanism of choice Magma recirculation is the mechanism of choice for
Suspension for control of supersaturation generation control of supersaturation generation
Control of Supersaturation Generation
Magma The goal is to bring growing crystals into Attrition and crystal breakage in the recirculation flow
Recirculation contact with liquid that becomes supersaturated is to be avoided
It is not possible or desired to maintain a
classified suspension
Liquor The goal is to have no crystals present when Frequent changes and upsets in the operating
Recirculation supersaturation is created, and then to bring conditions are likely to upset the classified suspension
the stable supersaturated liquid into contact
with the growing crystals
A classified suspension can be and is maintained
in the active crystallization volume
Particle-Size Manipulation
Fines Additional control over particle size distribution These mechanisms are likely to interfere with the
Dissolution is desired active crystallization volume
and Classified Crystals smaller than a certain size range and
Product greater than a certain size range can be removed
Removal without affecting the active crystallization volume
CEP October 2006 www.aiche.org/cep 33
Forced-circulation crystallizers
Forced-circulation (FC) crystallizers:
use evaporation or adiabatic evaporative cooling to gen-
erate supersaturation
provide a mixed suspension as the active volume for
relieving the supersaturation
employ magma recirculation to control supersaturation
generation
do not provide a mechanism for fines dissolution
can, in some cases, provide a mechanism for classified
product removal.
Figure 5 illustrates a forced-circulation crystallizer. The
equipment consists of a closed vessel with a conical bottom.
Recirculation is provided by the recirculation piping and
pump. The recirculating magma is fed to the vessel tangen-
tially, below the vapor-liquid interface. The feed is added to
the recirculation piping ahead of the recirculation pump. The
product slurry is withdrawn from the recirculation piping
after the crystallizer outlet and before the feed inlet.
When supersaturation is generated by evaporation, as
shown here, the recirculating magma is passed through a
shell-and-tube heat exchanger. This heat source is omitted
from systems using adiabatic evaporative cooling.
Supersaturation is generated at the vapor-liquid interface.
In both mechanisms (evaporation and adiabatic evaporative
cooling), the recirculating magma creates local temperature
and composition changes at the interface upon entering the
vessel. These changes lead to solvent evaporation at the inter-
face and subsequent generation of supersaturation. The rest of
the vessel, containing the swirling mass of mixed suspension,
provides the active volume for relieving this supersaturation
and also provides the material for magma recirculation.
Forced-circulation crystallizers generally do not have a
mechanism for fines dissolution. In some cases, classified prod-
uct removal is achieved by employing an elutriation leg, which
is located at the bottom of the conical part of the vessel. The
elutriation fluid, which is essentially a small amount of the
mother liquor, flows upward through the leg. This flow prevents
crystals below a certain size, whose free settling rate in the elu-
triation leg is less than the upward flow, from being withdrawn
with the product slurry. The product slurry is drawn from the
elutriation leg instead of the recirculation piping.
Draft-tube crystallizers
Draft-tube (DT) and draft-tube-baffle (DTB) crystallizers
are similar, except that DT units have no baffle. DTB and DT
crystallizers:
use direct-contact cooling, evaporation or adiabatic evap-
orative cooling to generate supersaturation
provide a mixed suspension as the active volume for
relieving the supersaturation
employ internal magma recirculation to control supersat-
uration generation
usually provide a mechanism for classified product
removal
provide a mechanism for fines dissolution when a baffle
is present (DTB configurations; DT configurations do not
provide a mechanism for fines dissolution).
The basic DTB crystallizer is shown in Figure 6. Aclosed
vessel contains an internal skirt baffle positioned so that it
provides a partitioned settling zone. Inside the baffle is a ver-
tical draft tube, centered by support vanes. Aslowly rotating
agitator is located concentrically at the bottom of the draft
tube. An elutriation leg is usually fitted to the bottom of the
cone to provide classified product removal. The feed inlet is
located at the base of the bottom cone and is directed into the
draft tube. The settling zone provides an outlet for the mother
liquor. The elutriation leg has an inlet for the elutriation liquid
and an outlet for the product slurry.
Any of the three supersaturation-generation mechanisms
may be employed in a DTB crystallizer. However, with cool-
ing, only direct-contact cooling with a refrigerant may be used.
In all cases, supersaturation is generated at the vapor-liquid
interface as a result of local temperature and composition
changes that lead to solvent (or refrigerant) evaporation.
Fresh
Feed
Product
Discharge
Vapor to
Condenser
Active
Volume
Steam
Inlet
Conden-
sate
Outlet
Heat
Exchanger
(omitted
from
systems
using
Adiabatic
Evaporative
Cooling)
Recirculation
Pump
Recirculation
Loop
Tangential
Feed Entry
I Figure 5. A forced-circulation crystallizer can employ evaporation
(as shown here) or adiabatic evaporative cooling (without the heat
exchanger) to generate supersaturation.
34 www.aiche.org/cep October 2006 CEP
In either the DTB or DT configuration,
the draft tube serves as the magma recircula-
tion leg, and the area outside the draft tube
as the mixed-suspension active crystalliza-
tion area. The feed is introduced into the
base of the crystallizer and is directed
upward into the draft tube flow. The agitator
induces the flow, circulating the liquor and crystals from
the bottom of the unit to the top liquid surface. The draft
tube and the agitator arrangement thus act as an internal
magma-recirculation loop (as shown by the arrows in
Figure 6). It maintains large recirculation rates at extreme-
ly low heads (compared with external recirculation) and
continually brings growing crystals from the active crys-
tallization volume to the vapor-liquid interface, where the
supersaturation is generated. This internal recirculation
significantly reduces attrition and crystal breakage com-
pared to external magma recirculation via recirculation
loops and pumps.
The settling zone provided by the skirt baffle is key in
bringing about fines removal. Astream is continuously drawn
off from the top of the settling zone. This induces an upward
flow into the settling zone. Fines below a certain size, whose
free settling rate is lower than the upward flow, stay in this
zone and are removed in the draw-off. The draw-off then
consists mostly of mother liquor with a small amount of
fines. It is mixed with the fresh feed and sent back to the
crystallizer after the fines are completely dissolved.
When evaporation is the mechanism for supersaturation
generation, the feed and the draw-off are passed through a
shell-and-tube heat exchanger (Figure 6a). The heat exchang-
er acts as both a heat source and a fines dissolver. When adia-
batic evaporative cooling is used, fines dissolution is accom-
plished either by mixing with dilute feed (Figure 6b) or by
mixing with mother liquor or solvent in a separate dissolution
tank (Figure 6c). These two options are also used when
supersaturation is generated by direct-contact cooling, in
which case the refrigerant is added separately to the base of
the crystallizer (Figure 6d). Note that the fines dissolution
loop does not constitute the recirculation mechanism recir-
culation is provided internally as discussed above.
Because DT crystallizers do not have the skirt baffle, they
cannot provide for fines dissolution. In these units, fresh feed
is added directly to the crystallizer.
Surface-cooled crystallizers
Surface-cooled (SC) and surface-cooled-baffle (SCB)
crystallizers are the same except for the absence of a baffle in
the SC units. SCB and SC crystallizers:
Solid/Liquid Separations

Product
Discharge
Active
Volume
Settling
Zone
Feed
Inlet
Vapor
Skirt
Baffle
Draft
Tube
Agitator
Assembly
Elutriation
Liquid
Mother Liquor
with Fines
Fines Dissolution
and Recirculation Loop

Vapor to
Condenser
Steam
Inlet
Condensate
Outlet
Mother Liquor
with Fines
Fresh
Feed

Mother Liquor
with Fines
Fresh
Feed
Vapor to
Condenser/
Vacuum System

Dissolution
Tank
Dissolution
Liquid
Vapor to
Condenser/
Vacuum System
Mother Liquor
with Fines
Fresh
Feed

Refrigerant
Fresh
Feed
Mother Liquor
with Fines
Refrigerant Vapor
to Condenser
a
b
c
d
I Figure 6. Draft-tube-baffle crystallizers (above) can
employ various options(right): (a) evaporation, (b) adia-
batic evaporative cooling with feed addition for fines
dissolution, (c) adiabatic evaporative cooling with a
fines dissolution tank, or (d) direct-contact cooling.
CEP October 2006 www.aiche.org/cep 35
use only surface cooling to generate
supersaturation
provide a mixed suspension as the active
volume for relieving the supersaturation
employ magma recirculation to control
supersaturation generation
do not provide a mechanism for classi-
fied product removal
provide a mechanism for fines dissolu-
tion when a baffle is present (SCB configu-
rations; SC configurations do not provide a
mechanism for fines dissolution).
Figure 7 illustrates a common SCB con-
figuration. It consists of a shell-and-tube
heat exchanger, a vessel with an internal
skirt baffle, and a recirculation pump. The
baffle is positioned so that it acts as a parti-
tion between a settling zone and the active
crystallization volume. The feed inlet is
located on the recirculation pipe just prior
to the recirculation pump. The settling zone
outside the baffle provides an outlet for the
mother liquor. The recirculating magma is
returned to the crystallizer vessel through a
central tube extending into the active crystallization volume.
The operation of this crystallizer corresponds to the
schematic in Figure 4. The desired supersaturation is generat-
ed by cooling the mixed stream formed by the fresh feed and
the recirculating slurry in the tubes of the shell-and-tube heat
exchanger. The heat exchange surface is the coldest part of
the process and is prone to solids build-up. The heat exchang-
er is therefore operated such that the temperature difference
between the tube-side and the shell-side typically does not
exceed 510C.
The recirculation pump and the external recirculation loop
provide the magma recirculation. The recirculation rates are suf-
ficiently high to ensure that the supersaturation generated in the
heat exchanger is low. Returning the recirculating slurry
through a central tube extending into the baffled volume ensures
thorough mixing inside the active crystallization volume.
Fines dissolution in an SCB crystallizer works in much
the same way as in a DTB crystallizer. Astream is continu-
ously drawn off from the top of the settling zone created by
the baffle. This draw-off induces an upward flow into the set-
tling zone. Fines below a certain size (whose free settling rate
is less than the upward flow) stay in this zone and are
removed in the draw-off. The fines are usually dissolved in a
separate dissolution tank and sent back to the crystallizer.
Because the SC configuration does not have a skirt baffle,
it lacks a fines dissolution mechanism. It is similar to the
SCB configuration in all other respects.
Classified-suspension crystallizers
Also known as Oslo crystallizers, classified-suspension
crystallizers:
use surface cooling, evaporation or adiabatic evaporative
cooling to generate supersaturation
provide a classified suspension as the active volume for
relieving the supersaturation
employ liquor recirculation to control supersaturation
generation
provide a built-in mechanism for fines dissolution
provide a built-in mechanism for classified product
removal.
Figure 8a depicts the Oslo configuration that uses evapo-
ration to generate supersaturation. It consists of a suspension
tank and a vaporizer. Recirculation is provided by recircula-
tion piping and a pump. The recirculating liquor is fed to the
vaporizer. Fresh feed is added to the recirculation leg ahead
of the recirculation pump, and the product slurry is taken off
near the bottom of the suspension tank.
When evaporation is used to generate supersaturation, the
recirculating liquor is passed through a shell-and-tube heat
exchanger (as illustrated). When adiabatic evaporative cooling
is used, the heat exchanger is omitted (this version is not
shown). In both mechanisms, evaporation of solvent from the
recirculating liquor entering the vaporizer generates the super-
saturation. The liquor recirculation rate is high enough to ensure
that the supersaturated liquid in the vaporizer stays in the
I Figure 7. A surface-cooled baffle crystallizer uses an external heat-exchange surface to
generate supersaturation by cooling.
Dissolution Tank
Fresh Feed
Coolant
Outlet
Coolant
Inlet
Product
Discharge
Active
Volume
Dissolution
Liquid
Dissolved Fines Recirculation
Recirculation
Pump
Recirculation
Loop
Central
Feed
Tube
Settling
Zone
Cooler
Skirt
Baffle
Mother Liquor
with Fines
36 www.aiche.org/cep October 2006 CEP
metastable zone and remains stable and near the solubility limit.
The liquid from the vaporizer flows down into the suspen-
sion tank through a downcomer that extends to near the bot-
tom of the tank. The suspension tank provides the active
crystallization volume in the form of fluidized classification
of growing crystals. The classification ensures that the super-
saturated liquid coming from the downcomer comes into con-
tact with the larger crystals first. It also ensures that near the
top of the active volume, the liquid is sufficiently clear and
can be withdrawn for liquor recirculation. In some cases, weir
baffles are included to promote liquor recirculation.
These configurations have built-in mechanisms for fines
dissolution and classified product removal. If the liquor
drawn from the top of the suspension tank contains fines, the
addition of heat (in case of evaporation) or feed (in case of
adiabatic evaporative cooling) dissolves the fines. The prod-
uct slurry is taken off near the bottom of the suspension tank.
Classification inside the tank ensures classified product
removal. As a result, additional provisions for fines dissolu-
tion and classified product removal are usually not needed.
Figure 8b shows the Oslo configuration that uses surface
cooling for supersaturation generation. This system also has a
classified suspension tank. However, it uses a shell-and-tube
heat exchanger instead of a vaporizer to generate supersatura-
tion. This is similar to the SCB/SC configurations. However,
unlike the SCB/SC design, it uses liquor recirculation.
In all Oslo configurations, liquor recirculation ensures that
there will be no (or minimal) attrition and crystal breakage.
However, as noted earlier, the ability to maintain a classified
suspension is sensitive to changes in the recirculation rate.
Summing up
Table 2 summarizes the operating mechanisms
employed in the various crystallizer configurations. This
summary, along with the guidance regarding operating
mechanisms provided in Table 1, provides insights for
selecting the appropriate crystallizer design.
These configurations are the most commonly used in
industrial practice. Several other modifications and combi-
nations employing the basic operating mechanisms dis-
cussed here are used for specific applications. Regardless
of the configuration, engineers designing and operating a
continuous crystallizer for a specific application should
pay attention to the following:
The residence time provided for the liquid phase
should be enough to ensure low supersaturation in the
active crystallization volume.
The impact of possible changes to the residence time
due to future changes in operating conditions should be
taken into account.
Changes in operating conditions that may bring about
significant changes in the residence time should be avoided.
The recirculation rate should be high enough to control
the generation of supersaturation. As a rule of thumb: when
surface cooling is used, the temperature drop in the heat
exchanger should be limited to about 12C; when evapora-
tion is used, the temperature increase in the heat exchanger
should be limited to about 15C; and when direct-contact
cooling or adiabatic evaporative cooling is used, the tempera-
ture drop at the vapor-liquid interface should be about 15C.
The recirculation rate should also be compatible
Solid/Liquid Separations
I Figure 8. A classified-suspension, or Oslo, crystallizer can employ (a) evaporation, adiabatic evaporative cooling (not shown), or (b) surface cooling.
Steam
Inlet
Steam
Outlet
Product
Discharge
Fresh
Feed
Recirculation Pump
Vaporizer
Suspension
Tank
Classified Bed
Active Volume
Vapor to
Condenser
Recirculation
Loop
Weir
Baffles
Heat
Exchanger
(omitted
from
systems
using
Adiabatic
Evaporative
Cooling)
a
Suspension
Tank
Classified Bed
Active Volume
Product
Discharge
Recirculation
Loop
Fresh
Feed
Recirculation
Pump
Coolant
Inlet
Coolant
Outlet
Cooler
b
CEP October 2006 www.aiche.org/cep 37
with the degree of mixedness required to sustain the
recirculation type.
When magma recirculation is used, the recirculation
rates and equipment should not cause severe attrition and
crystal breakage.
When liquor recirculation is used, future changes in
operating conditions that may impact the ability to main-
tain a classified suspension should be evaluated.
When liquor recirculation is used, changes in operat-
ing conditions that may lead to mixed suspension and
change to magma recirculation should be avoided.
Both capital and operating costs must be considered
when designing a crystallizer for a particular application.
In general, rankings based on capital costs, from highest to
lowest, are DTB/DT, Oslo, FC, SCB/SC. This is only a
rough rule of thumb, however, as capital costs depend on
the actual design specifications for the application. In gen-
eral, the operating costs for industrial crystallizers domi-
nate the process economics.
The total cost for the crystallizer that gives higher-qual-
ity product and trouble-free operation over a long period
of time is much lower than for a crystallizer that requires
less capital but produces poorer-quality product and
requires frequent maintenance and cleaning.
It is our hope that the descriptions and insights provided
in this article will be useful for chemical engineers dealing
with continuous crystallization-based processes. The discus-
sion here is by no means comprehensive. Additional details
related to crystallization mechanisms, crystallizer design,
operational issues and auxiliary equipment are found
in sources such as Refs. 16.
Literature Cited
1. Bennett, R. C., Crystallizer Selection and Design, in
Handbook of Industrial Crystallization, 2nd edition,
Myerson, A. S., ed., Butterworth-Heinemann, Boston, MA,
pp. 115140 (2002).
2. Mullin, J. W., Crystallization, 4th edition, Elsevier
Butterworth-Heinemann, Boston, MA (2001).
3. Kwok, K. S., et al., Experimental Determination of Solid-
Liquid Equilibrium Phase Diagrams for Crystallization-
Based Process Synhesis, Ind. Eng. Chem. Res., 44, pp.
37883798 (2005).
4. Bamforth, A. W., Industrial Crystallization, The
Macmillan Co., New York, NY (1966).
5. Jancic, S. J., and P. A. M. Grootscholten, Industrial
Crystallization, University Press, Delft, The Netherlands (1984).
6. Wibowo, C., L. OYoung, and K. M. Ng, Streamlining
Crystallization Process Design, Chem. Eng. Progress, 100
(1), pp. 3039 (Jan. 2004).
KETAN D. SAMANT is a senior engineer and founding member at
ClearWaterBay Technology, Inc. (CWB Tech, 20311 Valley Blvd., Suite C,
Walnut, CA 91789; Phone: (909) 595-8928; Fax: (909) 595-8928; E-mail:
ketan@cwbtech.com). He also acts as product manager for SLEEK, CWB
Techs process-development tool for crystallization. In this role, he is
involved in various technology initiatives and consulting projects dealing
with the synthesis, design and operation of crystallizers and
crystallization-based processes. He received a BTech (Honors) from the
Indian Institute of Technology, Kharagpur, and a PhD from the Univ. of
Massachusetts Amherst, both in chemical engineering.
LIONEL OYOUNG is president and co-founder of CWB Tech (E-mail:
lionel@cwbtech.com). He has more than 15 years of experience in process
synthesis and development in the petrochemical, fine chemicals and
pharmaceuticals industries, and he holds patents for various
petrochemical processes. He earned both BS and PhD degrees in
chemical engineering from the Univ. of Manchester Institute of Science
and Technology (UMIST; Manchester, U.K.) and is a member of AIChE.
CEP
Table 2. Commonly used crystallizer configurations.
Forced- Draft-Tube Surface-Cooled
Mechanism Circulation Baffle Draft Tube Baffle Surface-Cooled Oslo
Supersaturation Generation
Cooling Direct-contact Direct-contact Surface Surface Surface
Evaporation
Adiabatic Evaporative Cooling
Relieving the Supersaturation
Mixed Suspension
Classified Suspension
Control of Supersaturation Generation
Magma Recirculation Internal Internal
Liquor Recirculation
Particle-Size Manipulation
Fines Type based on Type based on Internal
Dissolution supersaturation generation supersaturation generation
Classified Product With With With Internal
Removal elutriation leg elutriation leg elutriation leg