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Cover Story

Confronting
Crystallization Issues
Reliable information about industrial crystallization can be difficult to find and to apply to new
situations. The work process outlined here will help engineers approach crystallization challenges

P
Brooke Albin and roject and plant engi-
Charles Moyers neers frequently face
MATRIC issues with crystal-
lization processes,
but often possess little prior
experience to address them.
IN BRIEF In probing for answers, engi-
INVESTIGATE SYSTEM neers often discover that reli-
BASICS able prediction of equipment
WHAT CAN BE LEARNED
capacities from machine ge-
IN THE LABORATORY? ometry and physical proper-
ties of liquids and solids is
ACCURATE PHASE- improbable, and that most
EQUILIBRIUM DATA of the literature describing
SELECTION OF A crystallization and separation
CRYSTALLIZATION equipment is confusing. They
SCHEME are also likely to find that fea-
LABORATORY
sibility and scaleup correla-
CRYSTALLIZATION TESTS tions are based primarily on
empirical know-how devel-
CRYSTAL MORPHOLOGY oped by crystallization equip-

PILOT PLANT TESTING ment users and manufactur-


ers. Given that, how should
TROUBLESHOOTING
engineers proceed toward
CLOSING THOUGHTS obtaining a reliable and eco-
nomic solution to their current
cystallization problem?
Using the work process
outlined in this article can help
guide engineers in approach-
ing crystallization process
problems. This includes devel-
oping a strong understanding FIGURE 1. Particle morphology is an important parameter
of the systems solubility data, for crystallization processes
conducting laboratory tests to
gain hands-on experience with a material needs, distillation is usually considered first.
and setting up a pilot-scale system. However, distillation may not be practical
because of azeotrope formation, low relative
Investigate system basics volatilities of the components to be separated
It is important to first understand why crystal- or other reasons. Sometimes, materials are
lization could be an appropriate separation unstable at high temperatures, which might
method and which types of crystallization prohibit using distillation. Crystallization is a
are available. For separation or purification good fit for some of these applications.
30 CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM NOVEMBER 2017
Crystallization is used industrially to create
a particulate solid phase (product), which
is recovered and purified by washing and
drying. Sometimes the solid product is a
waste product, but more often, the product
is a valuable commodity. Crystallization falls
into two main categories: solution crystalli-
zation and crystallization from the melt (also
referred to as fractional crystallization).
Solution crystallization implies that material
is crystallized from a mixture containing a
solvent. Crystals are formed by either con-
centrating the desired component by solvent
evaporation or cooling or both, and the solid
phase is typically formed at a temperature
well below its freezing point. In melt crystalli-
zation, crystals are generated by cooling the
solution, and are recovered at temperatures
near the pure component freezing point. The
melt crystallization product is recovered as a
liquid, and particulate solids processing can
largely be avoided. This can be helpful if the
product is preferred in liquid form.

What can be learned in the laboratory?


When evaluating the feasibility of crystalli-
zation as a separation technique for a new
process, small-scale testing can provide
valuable insight. Significant development
work can be accomplished in the labora-
tory at this early stage. Using solubility in-
formation, a basic process scheme can be
proposed and tested. Often, through this
work, the type of crystallization technique
to be used, as well as operating conditions, well as deal with potential solids handling FIGURE 2. Laboratory-scale
are defined. Furthermore, the number of issues in small-scale equipment. Moreover, testing of crystallization pro-
cesses can give investigators
crystallization stages required and an ap- good qualitative observations can be ob- valuable information about
propriate solid-liquid separation technique tained by working with smaller equipment. how to address problems at
can all be determined at laboratory scale. For example, using glass crystallizers, which larger scales
Conducting small-scale crystallization tests are readily available for laboratory-scale
also allows a first look at crystal morphol- work, can provide a real advantage. Also at
ogy (Figure 1) and particle size distribution, this scale, the cost of raw materials is much
and provides a framework for estimating lower. Downtime can be minimized, since,
product purity and yield. in many cases, the commercial process can
In addition, in existing commercial crystal- continue to operate while improvements are
lization processes, sometimes troubleshoot- being made independently. Figure 2 shows a
ing is needed to resolve an issue, or re-design laboratory crystallizer unit.
is needed due to changes to the process,
such as increasing production capacity or Accurate phase-equilibrium data
switching to a new feedstock with different Regardless of what may be the specific
types or concentrations of impurities. Typi- focus or objective of the development or
cally, for these scenarios, there becomes a troubleshooting work involving crystalliza-
need for either increased yield, quality or ca- tion, reliable solubility data are essential. Ob-
pacity for the crystallization operation. taining accurate solubility curves or phase
For existing processes, it often makes diagrams is a critical first step. Theoretical
sense to do off-line testing at smaller scale. freezing curves can be generated using the
This enables the investigators to gain a Vant Hoff equation, if the pure component
deeper understanding of problems, since it melting point and heat of crystallization are
is usually simpler to change conditions as known [Equation (1)].

CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM NOVEMBER 2017 31


Cover Story
20.0 a pure sample of component A or B will
crystallize. At the eutectic point, both com-
10.0 ponents will crystallize together at the given
composition, such that separation (or purifi-
Desired
0.0 cation) is not possible. This point represents
Freezing temperature (C)

component A

urv
e the conditions at which the maximum yield
c Undesired
-10.0 can be achieved.
rium component B
u ilib Consider a scenario where the solution
eq Solidus line
-20.0 uid is cooled. As the solution is cooled to 0C,
d-liq Liquid + solid A
Soli solids begin to form, and the solution com-
-30.0 position shifts accordingly to become less
Liquid + solid B
concentrated in component A. Thus, fur-
-40.0 ther cooling is necessary to continue crys-
Solid A + solid B tallization. As the temperature is lowered,
-50.0 pure crystals of component A will theoreti-
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 Mass fraction A
1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 Mass fraction B
cally form until the solution is cooled to its
Eutectic point eutectic point, shown at 40C in the figure.
80% feed
2:1 B:A From this curve, given the starting composi-
FIGURE 3. The phase diagram Vant Hoff Equation: tion and the final temperature, the theoreti-
shown here presents solid- cal product yield and the remaining solution
liquid equilibrium data for
a two-component eutectic (1) (known as mother liquor) composition can
system be calculated.
Where x2 is the solubility mass fraction, Hf Using the same example, say the final
is the crystal heat of formation, R is the gas crystallizer temperature is 35C. After solids
constant, T is saturation temperature, and removal is complete, the remaining mother
TM is the melting point temperature. liquor still contains about 40 wt.% of com-
With this approach, freezing temperature ponent A, and 60% component B. The theo-
versus concentration is plotted to construct retical product yield for this case is found by
a phase diagram. While theoretical solubil- doing a material balance, which simplifies to
ity curves can be calculated, it is preferred the following Equation (2), where x1 is the
to ascertain the solubility of the system ex- feed mass fraction of component A, y1 is the
perimentally. At the least, it is recommended feed mass fraction of component B, x2 is the
that several data points from the calculated final mass fraction of component A, and y2 is
curve be verified in the laboratory, since real- the final mass fraction of component B.
ity often differs from what is calculated theo-
retically, or even from what is reported in the % yield = [(x1 (x2 y1)/y2 )]/x1 100 (2)
scientific literature.
A good approximation of solubility can be For the given example, the resulting yield of
determined quite easily in the laboratory. It is component A is calculated to be 83.3%.
essential to have a reliable temperature mea- For this type of two-component system,
surement device and an accurate method for the data are used to compute a chart that
quantifying the composition of the solution. combines product yield and total solids in
First, a slurry of the solids suspended in so- suspension (TSS) as a function of tempera-
lution is prepared and held at a stable tem- ture and initial feed concentration. The chart
perature for a length of time sufficient for it to organizes the overall material balance for the
equilibrate. Then, a sample of the saturated system and serves as a basis for preliminary
mother liquor is taken while either filtering out evaluation of product yield as a function of
solids, or after allowing them to settle. The process variables. Development and use of
saturated solution is analyzed to determine this chart narrows the choices available for
its equilibrium composition. A curve can be zones of probable operation and also pro-
generated by repeating the procedure over a vides guidance regarding necessary staging
range of temperatures. of the process. A typical yield chart is pre-
The phase diagram depicted in Figure 3 sented in Figure 4.
shows solid-liquid equilibrium data for a bi- This has proven to be a valuable tool for
nary (two-component) eutectic system. The quickly estimating the yield that can be ob-
freeze curve indicates the temperature at tained with a given feed concentration and
which a solid begins to crystallize from a so- operating temperature. The value for TSS is
lution with the corresponding composition. also included for consideration, since there
It shows the range of conditions at which is a practical upper limit that should be ob-
32 CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM NOVEMBER 2017
100

90
50% feed

80 60% feed

70 70% feed
60% TSS 80% feed

PROCESS
Products yield, %

60
50% TSS 90% feed
50
95% feed

PLANTS FOR
40% TSS
40
30% TSS
30
20 % TSS
20

10

0
-40 -30 -20 -10 0 10.0
Saturation temperature, oC
FIGURE 4. This yield chart shows yield as a function of crystallizer temperature and total solids in sus-
pension (TSS)
served in order to end up with a nent A). This becomes the feed for
slurry stream that is manageable stage two. Since its saturation point
and can be pumped and transferred is 10C, cooling below this point
without plugging. The operating TSS will trigger the formation of solids.
is usually the highest TSS with which The final temperature will be 30C,
the equipment can comfortably op- which corresponds to the maximum
erate. This level often ranges from 40% TSS. Approximately 60% of the
30 to 40% TSS. product contained in the stage-two
For the example above, wherein feed is recovered in this step (that is,
the feed contains 80% of the de- 60% of the remaining 50% from step
sired product, component A, and one is recovered), bringing the over-
20% of the undesired component all yield to about 80%.
B, a maximum of ~87% yield can 3. The third stage is necessary for
be obtained. To reach this maxi- obtaining the maximum yield, which
mum, cooling to 40C is necessary. will be reached at just above the eu-
However, if cooling were completed tectic point (40C). Often, it is not
in only one step, the slurry den- worth approaching conditions too
sity would be exceedingly high. At near the eutectic, where impurities Hydrogenation
greater than 60% TSS, it is unlikely are more likely to solidify.
that this slurry could be processed. It is important to note that, often, Solids blending / drying
Thus, splitting the process into mul- systems do not behave according to
tiple steps is probably required. theory. For instance, the solid-liquid Pharma, food, cosmetics
To reach the maximum yield, but equilibrium state may not be easily
limit slurry density to less than or achieved by simply cooling to equi- Finechemicals
equal to 40%, it will be necessary to librium temperature. The region of
have three stages of crystallization, conditions where a solution is stable
as follows: below its equilibrium line is referred
1. In the first stage, 80% feed is to as the metastable zone. When op-
cooled from its initial temperature erating in the metastable region, the
to roughly 10C. Crystals begin to solution is supersaturated, but crys- Your fast lane to
form at 0C and continue to build tals do not form. For a system with a advanced mixing technology:
up until they reach 40% TSS as the large metastable zone, considerable
solution is cooled to 10C. Nearly sub-cooling or seeding (the addition Phone: +1 201 825 4684
50% yield is achieved in the first of fine crystals as nucleation points) Ext.: 205
stage. The crystals are removed via will likely be necessary to trigger nu- usa@ekato.com
an appropriate solid-liquid separa- cleation of the dissolved solute.
tion step and the mother liquor con-
tinues to the next stage. Crystallization scheme selection
2. In stage two, the mother liquor Selecting the operating mode for www.ekato.com
from the previous stage contains crystallization is dictated by labora-
roughly 65% solute (desired compo- tory evaluation and desired product
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CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM NOVEMBER 2017 33


Cover Story
lization is used when a very low operating
temperature is required in order to achieve
good product yields or due to reactivity or
degradation at higher temperatures.
In addition, evaporative cooling (also
known as vacuum cooling or vacuum crys-
tallization), a hybrid process that achieves
cooling by evaporation at sub-atmospheric
pressure, can be considered when solubility
has a moderate dependence on tempera-
ture. It offers the advantage of low oper-
ating temperatures relative to evaporative
crystallization, while avoiding fouling on
cold surfaces.
Melt crystallization is a less common and
more specialized technique that is capable
of producing extremely high product purity,
and it can be useful when a liquid product is
acceptable. When melt crystallization is pos-
sible, it offers the benefit that solids handling
operations can be avoided, and the associ-
ated separation and drying equipment is not
necessary. One limitation is that the product
must be able to be handled at its melting
point. If a material is either unstable at its
melting point or its melting point temperature
is very high or very low, such that process-
ing at that temperature is impractical, melt
crystallization is not a possible solution. An
example of a laboratory melt crystallizer is
presented in Figure 5.

Laboratory crystallization tests


Once a recovery chart has been assessed
FIGURE 5. The equipment form. However, determining whether to use and a preliminary crystallization scheme has
shown here is a laboratory- evaporation, cooling, or some combination been selected, actual crystallization tests can
scale falling-film melt crystal-
lizer of both can often be accomplished even be carried out in the laboratory using authen-
before testing begins. The phase diagram tic or synthetic process solution. These tests
and yield charts can prove quite useful in se- are used to verify that the scheme and condi-
lecting a preliminary crystallization scheme. tions that were selected are appropriate and
Studying the phase diagram is a good place will provide valuable practical experience re-
to start. When solubility is not significantly garding processing of the given feed stream.
affected by changes in temperature, evap- During crystallization tests, both ease of
orative crystallization is a likely candidate. nucleation and crystal growth are observed,
Most commonly, commercial crystallization which helps to determine a practical cooling
processes incorporate evaporative crystal- or evaporation rate. Cooling or evaporation
lization, and often, multi-effect evaporation must be approached so that solidification
or vapor recompression is utilized to reduce occurs slowly enough to grow crystals of
energy demand. adequate size and purity. Either cooling or
Conversely, cooling crystallization can be evaporating too aggressively can lead to fine
effective when the solid-liquid equilibrium crystals crashing out of solution or encrusta-
is strongly dependent on temperature. Al- tion on cold or hot surfaces due to localized
though cooling crystallization is simpler, it is high supersaturation. Suitable crystallizer
associated with more fouling problems due residence times can be estimated based on
to formation of encrustations on cold sur- the time needed for sufficient crystal growth.
faces and is often avoided. Yet, sometimes Solid product is recovered by some means
cooling crystallization is necessary, such as of solid-liquid separation. Laboratory-scale
for processing materials with very high boil- pressure filters and basket centrifuges are
ing points. In other cases, cooling crystal- available, and are convenient for these early
34 CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM NOVEMBER 2017
studies. Product purity is measured by an
appropriate analytical method, such as gas
chromatography (GC) or high-pressure liquid
chromatography (HPLC), and yield can be
calculated. Particle shape (habit) can be de-
termined using microscopy, and a number of
analytical methods are available for perform-
ing particle size analysis. One simple method
for measuring particle size distribution uses
a sonic sifter to separate product crystals
based on their ability to pass through a stack
of sieves with gradually decreasing screen
size (known as sieve analysis). The average
size and mass for each group of particles is
determined, and the data are plotted for a
visual representation of crystal size.
Typically, it is premature to do product-
purity studies at this stage, but conducting
product recovery and washing tests are use-
ful for understanding how easily desired yield for removing residual mother liquor from a FIGURE 6. This photomicro-
and purity can be obtained. solid crystalline product. By incorporating a graph image shows crystal
platelets in various stages of
In practice, crystals that are recovered few sequential wash steps, the bulk of the growth
from the mother liquor are rarely 100% pure. mother liquor can be effectively removed.
Impurities are expected to be present due Nonetheless, washing must be optimized to
to occlusions (when impurities are physically improve purity with a minimal loss of yield,
trapped inside the crystal lattice), inclusions since some dissolution of crystals will cer-
(when impurities are incorporated into the tainly occur.
crystal structure), and due to imperfect solid- During this step in testing, recommenda-
liquid separation. Any solid-liquid separation tions can also be made regarding seeding.
technique will leave behind some amount of Sometimes nucleation for solid formation
impurity-containing mother liquor. In some can be achieved solely by controlling tem-
cases, adjusting the solid-liquid separation perature. In other situations, seeding may
technique can result in better removal of im- be required, and even agitation can play a
purities, giving a better outcome. Another role. Seeding is often necessary when the
common option is to perform washing of metastable zone is large, such that the so-
the crystals. Washing is a standard method lution endures significant supersaturation

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Cover Story
before nucleation. An appropriate seeding studying crystal shape and size. An exam-
technique can prevent large amounts of fine ple of a photomicrograph of a crystal prod-
crystals from crashing out of solution, versus uct sample taken with a light microscope is
growing fewer larger crystals that are easier shown in Figure 6. With this tool, engineers
to filter and transport. Often this must be can track the appearance of crystals with
done carefully so that crystals begin to form response to changing process variables.
and grow in such a way as to produce the Observation with a microscope can reveal
desired crystal size. changes in habit that result from the pres-
ence of various impurities. It allows compari-
Crystal morphology son of crystals before and after washing to
Crystal morphology is an aspect of crys- see any notable improvements. In addition, it
tallization that can have a major impact on provides a look at crystal breakage (attrition)
processing. Moreover, it is not a variable that that could result from processing.
is easily manipulated. Usually for industrial
processes employing crystallization, there Pilot plant testing
is little concern with specific morphology as Pilot-scale operation also serves an impor-
long as the particles filter well (without exces- tant purpose in the development of a new
sive plugging) and can be transferred easily. process, and is a good tool for troubleshoot-
However, when certain crystal shapes, such ing. A crystallization pilot plant minimizes risk
as needles, are present, serious handling of scaleup by using equipment that is geo-
problems can occur. In these instances, metrically similar to commercial equipment,
filters can blind off quickly, and settling of and is used to obtain reliable engineering
particles may be slow. Needle-shaped crys- design data. Process recycles are often in-
tals may also be more prone to breakage. corporated at pilot scale, and this can be
When crystal morphology hinders operation, extremely important in refining the material
production capacity may be significantly af- balance and verifying the crystalline product
fected, and downstream processing often purity that can be achieved. Furthermore, pi-
must be modified to compensate for slower lot-scale crystallizers are able to accommo-
and less efficient solid-liquid separation. date production of larger quantities of prod-

When presented with any crystallization problem, it is important to begin with a strong
understanding of the systems solubility data. Careful assessment of solubility curves
and yield charts . . . can provide valuable insight into the root cause of an issue, as well
as potential solutions

Crystal size is also a concern, but offers uct material to use for market testing and
more possibilities for control. With an ap- development. Testing of scalable solid-liquid
propriate seeding technique, a reasonable separation and drying equipment is often
cooling rate, and adequate residence time, conveniently conducted in the pilot unit.
a manageable crystal-size distribution can
often be attained. Process optimization
Attrition of crystals is known to occur, and There are three primary objectives in com-
can be a particular challenge for some frag- mercial crystallization processes: achieving
ile solid materials. When crystal breakage is product purity, yield and capacity. While it
severe, particle size can decrease to such is desirable to maximize each of these vari-
an extent that solid-liquid separation is im- ables, in reality, when one of these is pushed
pacted. In this case, measures to improve too far, the other variables will be negatively
handling procedures are necessary. Attri- impacted. Thus, prioritization is necessary to
tion can be mitigated by using a moderate develop a crystallization process with an op-
flowrate and a pump design that is suited for timum balance among these elements.
gently handling slurries. When these controls In cases where higher purity (better quality)
are unable to produce the desired size, spe- is desired, multiple methods can be investi-
cialized crystallizer designs intended to grow gated as potential routes for improvement.
large crystals can be tested by collaborating Sometimes, (as mentioned above), a better
with crystallizer equipment vendors. solid-liquid separation is needed, to sepa-
A simple light microscope is useful for rate the impurity-containing mother liquor
36 CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM NOVEMBER 2017
away from a solid product. Other later stage. In either case, following
times, this can be accomplished by the work process outlined in this ar-
changing the solid-liquid separation ticle is an effective way to approach
technique. A new type of centrifuge the matter.
or filter may be beneficial. Adjusting When presented with any crystal-
the washing procedure might give lization problem, it is important to
rise to incremental improvements as begin with a strong understanding of
well. In still other cases, the crystals the systems solubility data. Careful
are small, and growing larger crys- assessment of solubility curves and
tals can help improve solid-liquid yield charts, as covered in this article,
separation. Yet another factor influ- can provide valuable insight into the
encing purity is the rate of crystalliza- root cause of an issue as well as po-
tion. In general, slower crystallization tential solutions before proceeding
yields a better quality product. When to experimental testing. Laboratory
all else fails to produce the target tests provide the basis to work out
purity, recrystallization of a first stage the fundamental design and operat-
product could be a solution. ing conditions of the system. There
When a higher yield is needed, the is no substitute for gaining hands-on
approach might also include grow- experience in working with a specific
ing larger crystals or selecting an- material and directly observing the
other solid-liquid separation device crystallization process. This often re-
to decrease the loss of solids. Incor- veals characteristics that can impact
porating recycle streams might also processing, but are subtle and might
be a way to increase overall yields, not be appreciated otherwise.
since the product contained in the Once the basic process design
saturated mother liquor has another has been established and opera-
opportunity to undergo crystalliza- tion is reasonably well-understood,
tion. For certain systems, concen- a pilot plant is recommended to de-
trating the crystallizer feed or cooling fine recycle schemes and to gather
to a lower temperature might be an scaleup data before finally imple-
option to improve yields, but when menting at commercial scale. n
slurry density (solids in suspension) Edited by Scott Jenkins
becomes too high, solids handling
issues can be a challenge. It may be Authors
necessary to add an additional crys- Brooke Albin is a project man-
tallizer stage to manage the higher ager at MATRIC (Mid-Atlantic
Technology, Research and Inno-
mass of solids. vative Center; 1740 Union Car-
For boosting production capacity, bide Drive, South Charleston, WV
more effective heat transfer is usu- 25303; Email: brooke.albin@
matricinnovates.com; Website:
ally the answer. This allows the crys- www.matricinnovates.com). In
tallizer to accommodate a higher this role, she is responsible for
the coordination and execution of
feedrate, which in turn, decreases research and development (R&D) activities for numer-
the residence time. As a result, par- ous clients. She has 10 years of experience in develop-
ticle size may decrease, and purity ment of new processes to produce chemicals from
biofeedstocks, and has specialized skills in the area of
follows suit. Thus, increasing capac- solids handling and crystallization. She received her
ity must be approached with regard B.A. in chemistry and B.S. in biology from Alderson-
to the proper balance of capacity Broaddus College, and earned her M.S. in chemical
engineering at West Virginia University.
versus yield and purity. However,
engineers can attempt to compen-
Charles Moyers is a senior engi-
sate by improving washing or solid- neering scientist at MATRIC (Mid-
liquid separation, or both. Atlantic Technology, Research
and Innovative Center; same ad-
dresss as above; Email: charles.
Closing thoughts moyers@matricinnovates.com;
It is more efficient to make the effort Website: www.matricinnovates.
to understand an issue and solve com). He is a fellow of AIChE and
has co-taught several AIChE edu-
problems early in process develop- cation courses, including Indus-
ment than after a poor design is in trial Crystallization, Liquid-Solid Separation, and Dry-
ing. He holds a B.S. from Virginia Tech, an M.S. from
place. Nonetheless, in many situ- West Virginia University and a Ph.D. from the University
ations, issues must be solved at a of Delaware, all in chemical engineering.
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CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM NOVEMBER 2017 37

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