Professional Documents
Culture Documents
Understanding
Crystallization and
Crystallizers
This article offers qualitative insight into the
Ketan D. Samant
Lionel O’Young
basic mechanisms of crystallization and the
ClearWaterBay Technology, Inc. principles of crystallizer operation,
and the ways in which these concepts relate
to the various crystallizer configurations
in industrial use today.
C
rystallization is an important separation process in the The region between the solubility curve and the limit of sta-
production of commodity and specialty chemicals. bility (the dashed line) is called the metastable zone. In this
Several different types and configurations of continu- region, nucleation sites are necessary to initiate the formation
ous crystallizers have been developed for these applications. of a solid phase from a supersaturated liquid. Theoretically, if
The design and operation of an industrial crystallizer are one could suppress all nucleation sites, the liquid could exist
optimized based upon the conditions needed for: as a stable supersaturated liquid even though it would not be
• producing larger and more uniform crystals of the in equilibrium.
desired product Beyond the metastable zone boundary, however, the pres-
• reducing the formation of agglomerates ence of nucleation sites is not a requirement for the formation
• 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.
Stable
Let’s first consider how various crystallization mecha- Zone
nisms affect these objectives. le
tab
Thermodynamics. Figure 1 illustrates the general thermo- e tas ne
Temperature
M Zo
dynamic phase behavior of a solute-solvent system and the
concepts of thermodynamic equilibrium and thermodynamic
Unstable
stability for solid-liquid systems. Solubility Zone
The solid line is the solubility curve, which represents Curve
thermodynamic equilibrium between the liquid and solid
Stability
phases. Any liquid with a composition and temperature above Limit
the solubility curve exists as stable unsaturated liquid.
Any liquid with a composition and temperature below the
Solute Composition
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. ■ Figure 1. Solid-liquid phase behavior is characterized by
thermodynamic equilibrium and thermodynamic stability.
ML P,M SP
determine the residence time provided.
Unstable The suspension in the active crystallization volume may
Zone exhibit varying degrees of mixedness. At one extreme, it may
be completely mixed in terms of compositions, solids con-
Solute Composition tents, and particle sizes. At the other extreme, it may be fully
■ Figure 2. Control of supersaturation generation. classified, with clear liquid at the top and progressively larger
solids concentrations and particle sizes below. The choice of
fied using solubility curves and phase diagrams (3, 6). the degree of mixedness is usually a direct consequence of
In most cases, supersaturation is generated by a decrease the mechanism used for control of supersaturation generation.
in temperature and/or decrease in solvent composition. There
are three mechanisms for creating supersaturation:
• Cooling (typically by surface cooling, or in some cases Control of supersaturation generation
by direct contact with a refrigerant) generates supersaturation Figure 2 shows schematically the operation of a simple
through a decrease in temperature. This mechanism is best cooling crystallizer. Supersaturation is generated by cooling
suited for systems in which the solubility of the crystallizing the fresh feed stream (stream FF), resulting in a stream that is
component decreases steeply or moderately with decreasing (arbitrarily) designated stream M. Stream M is sent to the
temperature. It is not suited for systems with flat or inverted crystallizer tank, which provides the active volume for reliev-
solubility-temperature relationships. ing the supersaturation. Inside the crystallizer tank and in the
• Evaporation generates supersaturation through a decrease product stream (stream P), the liquid-phase composition is
in solvent composition, which is achieved when heat is added represented by ML and the solids composition by SP.
to evaporate the solvent. It is the only mechanism that can be Both nucleation and growth are driven by the amount of
used where the solubility of the crystallizing component either supersaturation (the composition difference between ML and
increases with decreasing temperature or remains essentially the solubility curve at the crystallizer temperature) in the
unchanged. For such systems, supersaturation can be generated active volume. If sufficient residence time is provided, the
far more effectively by decreasing the solvent composition. For liquid phase ML will be within the metastable zone, and the
systems with steep or moderate solubility, the other two mech- supersaturation will be low. However, the crystallizer tank
anisms are better options than evaporation. does not generate supersaturation — it simply provides the
• Adiabatic evaporative cooling generates supersatura- mechanism, i.e., the active crystallization zone, to relieve it.
tion through adiabatic solvent evaporation. Rather than Supersaturation is generated by cooling the fresh feed
adding heat to the system, it relies on both a decrease in sol- stream (from FF to M). But as shown in Figure 2, stream M
vent composition and a decrease in temperature brought lies in the unstable zone. As a result, nucleation occurs spon-
about by the adiabatic evaporation. As with surface or taneously, generating a large number of small particles inside
direct-contact cooling, this mechanism is best used when the cooler even before stream M reaches the crystallizer tank.
the solubility of the crystallizing component decreases mod- This is undesirable, and it implies that the supersaturation
erately or steeply with decreasing temperature. Adiabatic generation needs to be controlled so that stream M is also in
evaporative cooling may not be appropriate when the bub- the metastable zone.
ble point temperature decreases very slowly with pressure; Figure 2 also illustrates two ways in which such control
in such cases, even high vacuums cannot bring about a suf- can be exercised:
ficient reduction in temperature. • the temperature can be reduced only to T*, at which
The solubility characteristics of the crystallizing compo- point the cooled stream M* lies on the limit of stability curve
nent dictate what mechanisms are needed for creating super- • the amount of solvent can be increased such that the
saturation. Criteria such as cost, operability and compatibility operating temperature is the limit of stability for the new
with crystallizer configurations should be used to further fresh feed stream FF*.
refine the selection. In most applications, the width of the metastable zone,
Temperature
Temperature
M P SP M P,M' SP
Unstable Unstable
Zone Zone
■ Figure 3. In liquor recirculation, liquid is removed from the active ■ Figure 4. In magma recirculation, a mixed stream containing liquid
volume without entraining any crystals and is recirculated. and crystals is removed from the active volume and is recirculated.
which is very narrow, is not known. As a result, the restric- streams, and points L′ and M′ represent the total composi-
tions on temperature and amount of solvent required in these tions (including the solids). Note that here, too, the liquid
methods are quite severe. Both methods are highly undesir- portion of the recirculating stream (points L and M) lies
able because they adversely affect product recovery — higher inside the metastable zone.
temperature and higher solvent content mean lower recovery. From a material balance point of view, magma recircula-
The only other option is recirculation. This involves tion accomplishes the same objectives as liquor recirculation.
removing a stream from the active crystallization volume, However, from an operational point of view, there are two
mixing it with the fresh feed, and then sending the combined key differences between liquor and magma recirculation.
stream through the supersaturation generator and back to the The first concerns the presence of solids at the site of
active crystallization volume. Two types of recirculation supersaturation generation. In liquor recirculation, no solids
mechanisms may be used: are present, whereas in magma recirculation, solids are pres-
• liquor recirculation, which involves recirculating only the ent. In essence, liquor recirculation creates a stable supersatu-
liquid (or mother liquor) from the active crystallization volume rated liquid and brings it into contact with growing crystals;
• magma recirculation, wherein the slurry from the active magma recirculation brings growing crystals into contact
crystallization volume is recirculated. with a liquid that becomes supersaturated. Therefore, the par-
Figure 3 shows the operation of a cooling crystallizer with ticle size distributions resulting from liquor and magma recir-
liquor recirculation. It is assumed that a liquid stream (which culation will be different. If the liquor-recirculation liquid can
has a composition corresponding to ML) can be removed from be maintained in the stable supersaturated condition before it
the active volume. This stream is mixed with fresh feed stream comes into contact with growing crystals, it will generally
FF to form stream L prior to the generation of supersaturation produce larger crystals.
by cooling. The location of stream L on the temperature vs. The second difference relates to the degree of mixedness
composition plot is such that the cooled stream M lies inside of the active crystallization volume required. Liquor recircu-
the metastable zone. There are no changes to operating temper- lation relies on being able to maintain fluidized classification
ature, feed composition or residence time. Thus, in this config- in the active volume. The recirculation stream is drawn from
uration, recirculation helps avoid high supersaturations at the the top of the active volume, which contains clear liquid, and
point of supersaturation generation without affecting the recov- the supersaturated liquid is returned from the bottom upward
ery of crystallized product. so that larger crystals are in contact with higher supersatura-
For liquor recirculation, it is assumed that only the mother tions. Magma recirculation, on the other hand, does not
liquor is recirculated while the crystals remain in the active require product classification.
volume. As a result, streams L and M are supersaturated, but The ability to maintain a classified suspension in the
stable, liquids. active crystallization volume is very sensitive to changes in
If the suspension in the active volume is mixed, it is not operating conditions, especially to changes in the recircula-
possible to recirculate only the liquor. The recirculation flow, tion rate. Liquor recirculation can easily turn into magma
known as magma, will include crystals as well. Operation recirculation in response to minor changes in operating con-
with magma recirculaton is depicted in Figure 4. Points L and ditions. Therefore, from an operability point of view, magma
M represent the liquid compositions of the recirculating recirculation is preferred.
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
As noted earlier, it is very difficult to reliably estimate volume, dissolution of these particles, and the return of the
or predict the width of the metastable zone for industrial resulting solution back to the crystallizer. The fines are nei-
crystallizers, although laboratory experiments do offer use- ther allowed to grow in the active crystallizer volume nor
ful, but limited, insights. Thus, in both liquid and magma leave with the product slurry. These restrictions promote the
recirculation (see Figures 3 and 4), streams L and M are formation of larger, more-uniform particles, which makes this
typically kept as close to ML as possible by using high mechanism highly desirable.
recirculation rates. Classified product removal involves the selective removal
of only particles larger than a certain size (or size range) in
Optional auxiliary mechanisms the product slurry, which retains the smaller particles in the
Manipulation of particle sizes is useful for producing larg- active crystallizer volume and promotes larger particle sizes.
er and more-uniform particles. It also makes it possible for This mechanism is desirable, but optional.
the process to adapt to changes in operating conditions. Fines Table 1 summarizes the conditions under which each
dissolution and product classification are two auxiliary mech- operating mechanism should and should not be considered.
anisms that are used to manipulate particle sizes. The following sections describe the important crystallizer
Fines dissolution involves removal of particles smaller configurations in industrial use today and the mechanisms
than a certain size (or size range) from the active crystallizer they employ.
Draft-tube crystallizers
Fresh
Draft-tube (DT) and draft-tube-baffle (DTB) crystallizers Recirculation Feed
Loop
are similar, except that DT units have no baffle. DTB and DT
crystallizers:
Recirculation
• use direct-contact cooling, evaporation or adiabatic evap- Pump
orative cooling to generate supersaturation
• provide a mixed suspension as the active volume for ■ Figure 5. A forced-circulation crystallizer can employ evaporation
relieving the supersaturation (as shown here) or adiabatic evaporative cooling (without the heat
exchanger) to generate supersaturation.
Vapor to Vapor to
Vapor Condenser/
Condenser
Vacuum System
Agitator
Assembly
Mother Liquor
with Fines Mother Liquor
Skirt Mother Liquor with Fines
Baffle with Fines
Settling ∞
Zone ∞ Dissolution
Draft Steam Liquid
Tube Inlet Fresh
Feed Fresh
∞ Active Feed
Volume
Feed
Inlet a c
Dissolution
Product Condensate Tank
Discharge Outlet
Fines Dissolution
and Recirculation Loop
Elutriation Vapor to Refrigerant Vapor
Liquid Condenser/ to Condenser
Vacuum System
■ Figure 6. Draft-tube-baffle crystallizers (above) can
employ various options(right): (a) evaporation, (b) adia-
batic evaporative cooling with feed addition for fines Mother Liquor Mother Liquor
dissolution, (c) adiabatic evaporative cooling with a with Fines with Fines
fines dissolution tank, or (d) direct-contact cooling.
Refrigerant
In either the DTB or DT configuration, ∞ ∞
the draft tube serves as the magma recircula-
Fresh Fresh
tion leg, and the area outside the draft tube Feed Feed
as the mixed-suspension active crystalliza-
tion area. The feed is introduced into the b d
base of the crystallizer and is directed
upward into the draft tube flow. The agitator
induces the flow, circulating the liquor and crystals from When evaporation is the mechanism for supersaturation
the bottom of the unit to the top liquid surface. The draft generation, the feed and the draw-off are passed through a
tube and the agitator arrangement thus act as an internal shell-and-tube heat exchanger (Figure 6a). The heat exchang-
magma-recirculation loop (as shown by the arrows in er acts as both a heat source and a fines dissolver. When adia-
Figure 6). It maintains large recirculation rates at extreme- batic evaporative cooling is used, fines dissolution is accom-
ly low heads (compared with external recirculation) and plished either by mixing with dilute feed (Figure 6b) or by
continually brings growing crystals from the active crys- mixing with mother liquor or solvent in a separate dissolution
tallization volume to the vapor-liquid interface, where the tank (Figure 6c). These two options are also used when
supersaturation is generated. This internal recirculation supersaturation is generated by direct-contact cooling, in
significantly reduces attrition and crystal breakage com- which case the refrigerant is added separately to the base of
pared to external magma recirculation via recirculation the crystallizer (Figure 6d). Note that the fines dissolution
loops and pumps. loop does not constitute the recirculation mechanism —recir-
The settling zone provided by the skirt baffle is key in culation is provided internally as discussed above.
bringing about fines removal. A stream is continuously drawn Because DT crystallizers do not have the skirt baffle, they
off from the top of the settling zone. This induces an upward cannot provide for fines dissolution. In these units, fresh feed
flow into the settling zone. Fines below a certain size, whose is added directly to the crystallizer.
free settling rate is lower than the upward flow, stay in this
zone and are removed in the draw-off. The draw-off then Surface-cooled crystallizers
consists mostly of mother liquor with a small amount of Surface-cooled (SC) and surface-cooled-baffle (SCB)
fines. It is mixed with the fresh feed and sent back to the crystallizers are the same except for the absence of a baffle in
crystallizer after the fines are completely dissolved. the SC units. SCB and SC crystallizers:
Vapor to
Condenser
Suspension
Vaporizer Tank
Recirculation
Loop
Steam Product
Outlet Recirculation
Discharge Loop
Fresh Recirculation Coolant
Feed Pump Outlet
a Recirculation Pump b
■ Figure 8. A classified-suspension, or Oslo, crystallizer can employ (a) evaporation, adiabatic evaporative cooling (not shown), or (b) surface cooling.
metastable zone and remains stable and near the solubility limit. Summing up
The liquid from the vaporizer flows down into the suspen- Table 2 summarizes the operating mechanisms
sion tank through a downcomer that extends to near the bot- employed in the various crystallizer configurations. This
tom of the tank. The suspension tank provides the active summary, along with the guidance regarding operating
crystallization volume in the form of fluidized classification mechanisms provided in Table 1, provides insights for
of growing crystals. The classification ensures that the super- selecting the appropriate crystallizer design.
saturated liquid coming from the downcomer comes into con- These configurations are the most commonly used in
tact with the larger crystals first. It also ensures that near the industrial practice. Several other modifications and combi-
top of the active volume, the liquid is sufficiently clear and nations employing the basic operating mechanisms dis-
can be withdrawn for liquor recirculation. In some cases, weir cussed here are used for specific applications. Regardless
baffles are included to promote liquor recirculation. of the configuration, engineers designing and operating a
These configurations have built-in mechanisms for fines continuous crystallizer for a specific application should
dissolution and classified product removal. If the liquor pay attention to the following:
drawn from the top of the suspension tank contains fines, the • The residence time provided for the liquid phase
addition of heat (in case of evaporation) or feed (in case of should be enough to ensure low supersaturation in the
adiabatic evaporative cooling) dissolves the fines. The prod- active crystallization volume.
uct slurry is taken off near the bottom of the suspension tank. • The impact of possible changes to the residence time
Classification inside the tank ensures classified product due to future changes in operating conditions should be
removal. As a result, additional provisions for fines dissolu- taken into account.
tion and classified product removal are usually not needed. • Changes in operating conditions that may bring about
Figure 8b shows the Oslo configuration that uses surface significant changes in the residence time should be avoided.
cooling for supersaturation generation. This system also has a • The recirculation rate should be high enough to control
classified suspension tank. However, it uses a shell-and-tube the generation of supersaturation. As a rule of thumb: when
heat exchanger instead of a vaporizer to generate supersatura- surface cooling is used, the temperature drop in the heat
tion. This is similar to the SCB/SC configurations. However, exchanger should be limited to about 1–2°C; when evapora-
unlike the SCB/SC design, it uses liquor recirculation. tion is used, the temperature increase in the heat exchanger
In all Oslo configurations, liquor recirculation ensures that should be limited to about 1–5°C; and when direct-contact
there will be no (or minimal) attrition and crystal breakage. cooling or adiabatic evaporative cooling is used, the tempera-
However, as noted earlier, the ability to maintain a classified ture drop at the vapor-liquid interface should be about 1–5°C.
suspension is sensitive to changes in the recirculation rate. • The recirculation rate should also be compatible
Supersaturation Generation
Cooling — ✔Direct-contact ✔Direct-contact ✔Surface ✔Surface ✔Surface
Evaporation ✔ ✔ ✔ — — ✔
Adiabatic Evaporative Cooling ✔ ✔ ✔ — — ✔
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