8

Crystallization

Thierry Hombourger

Crystallization is the process whereby a solvent-solute system’s thermody-

namic properties are modified so as to precipitate at least part of the solute in
solid form. It is seldom used in the oil industry today, but in contrast it is
widely used in inorganic chemistry and high added value organic chemistry.
The petrochemical industry resorts to crystallization in some special cases.
The reason for this relative unpopularity is related to a number of downsides
(sometimes considerable energy costs, operations that are difficult to handle,
high investments, high maintenance costs). However, in certain special cases
this type of operation proves to be well suited to the purpose. In this connec-
tion, dewaxing of lubricant cuts will be developed in detail in Chapter 9. In
addition, phenomena related to the presence of paraffins in crudes and
petroleum cuts are easier to control if the specific features of the crystalliza-
tion process are taken into account. For instance, the behavior of paraffinic
crudes during pipeline transportation can be assessed more accurately, the
problems that crop up can be overcome and original solutions can be found.
Likewise, compliance with diesel oil specifications (cloud point, pour point,
cold filter plugging point) is easier if the action of additives is better under-
stood, whether to lower the crystallization threshold or to modify the crystal
structure.
We are going to examine the basic principles that govern crystallization in
this chapter and this will entail discussing the following points:
Solid-liquid equilibrium conditions for solute-solvent mixtures.
The importance of equilibrium deviations (metastability, supersatura-
tion).
Crystallization kinetics (nucleation, growth).
Crystal morphology.
Precautions needed to get properly shaped, non-agglomerated crystals
with satisfactory size distribution.
458 Chapter 8. CRYSTALLIZATION

We in no way claim to cover the very vast domain going from crystallogra-
phy to the operation of all types of industrial crystallizers in this chapter. The
reader can refer to excellent works such as those by Mullin (1972) or Rousseau
(1987) for the theoretical part, and by Banforth (1965) for industrial applica-
tions. Lastly, the Ullmann encyclopedia provides an overview of the crystalline
state as well as genesis and growth of crystals and crystallization in general.

8.1 SolidpLiquid Equilibria. Equilibrium Deviations

In Chapter 2 the principles related to determination and utilization of solid-liq-
uid equilibria were discussed in depth. It was pointed out that thermodynamic
equilibria sometimes take time to become established and that care must be
taken not to interpret an intermediate, unfinished, apparently stable state,
termed "metastable" (see Section 2.3.1), as actually being stable.
If we consider a system in equilibrium and proceed to modify conditions
(dilution, cooling, evaporation, concentration, addition of an anti-solvent,
etc.), we create an imbalance. The difference between the initial position and
the final one (corresponding to a new state of equilibrium) generates a driving
force. Its action will attempt to reduce the perceived imbalance as quickly as
possible in order to approach a new equilibrium position. This driving force is
"supersaturation". Its importance is overriding as we will see all along the
series of steps that end with the establishment of a crystallized whole.
If the concentration of a solute in the liquid phase is represented on a graph
versus temperature, the result is a diagram like the one presented in Figure 8.1.
Curve I is the true equilibrium curve, as it comes from the laws of thermo-
dynamics (see Chapter 2). Curve I1 delimits a metastable zone, which is
defined as the region where there can be no spontaneous appearance of seed
crystals, even after a very long time has elapsed. The imprecision in the term
"very long" time means that the border delimiting the metastable zone can not
be defined exactly: curve I1 is drawn in a dotted line. Beyond curve I1 sponta-
neous generation is possible: this zone is sometimes called "labile" zone.
Supersaturation can be defined by comparing the actual concentration of the
solute prevailing in the liquid phase, C, to the concentration that would prevail
if the liquid phase were in equilibrium with the solid phase, C*. Several expres-
sions of supersaturation are possible: C/C*, C - C*, (C - C*)/C*. Sometimes
supersaturation is even defined by (T - T*) for a given concentration: here it
would be better to use the term "subcooling".
Moving across the metastability boundary therefore involves establishing
a minimum supersaturation.

8.2 First Step in the Crystallization Process:

Nucleation
The formation of seed crystals in a solution is the initial step in crystallization.
It is called nucleation.
 Chapter 8 CRYSJALLIZAJION 459

C'

T T*

Metastability and supersaturation. Curve I: mother liquor/crystals equilibrium

curve. Curve 11: metastability boundary curve.

The following can be distinguished:

Primary nucleation:
- homogeneous: spontaneous formation of seeds in a clear liquid,
- heterogeneous: spontaneous formation in a liquid containing impuri-
ties that may initiate seed formation.
Primary nucleation is an indispensable step, and should be monitored
carefully so that there are not too many or too few seeds. As mentioned
earlier, it can occur only beyond the metastability zone.
Secondary nucleation: formation of seeds in a mother liquor already con-
taining growing crystals. Secondary nucleation continues all throughout
the crystallization process. It conditions to a large extent the crystal size
distribution.
460 ChaDter 8. CRYSTALLIZATION

8.2.1 Kinetics of Primary Nucleation

The rate of homogeneous primary nucleation complies with the following
basic theoretical equation (Mullin, 1972):

with:
1 dn,
- - number of seeds formed per unit of time and per unit of volume
dt of mother liquor. Let us point out that seeds are made up of
molecules and not moles, and this explains the presence of K, the
Boltzmann constant, instead of R, the ideal gas constant.' For
example, a crystal nucleus of ice contains up to 100 molecules of
water
A preexponential constant (s-l.m-9
M mass of the molecule of solute (kg)
Y interfacial tension between crystals and solution (N/m)
T absolute temperature (K)
P density of the solute in the solid phase (assumed to be identical
to the density in the solution phase) (kg/m3)
C/C* ratio of the actual and equilibrium concentrations
Equation 8.1 shows the influence of supersaturation on how quickly the
first crystals appear or, in other terms, on the time required to see the first
crystals appear once a given supersaturation is established. By way of illus-
tration, Table 8.1 indicates the influence of the C/C*ratio on the time required
to produce the first crystals, T, (induction period) by making T = Vdt/dnl, A = 1
and 16ny 3 M 2/ 3p2 ( K Q=~10.

c/c* z
1 W

2 35 years
3 1 hour
4 3 minutes
5 45 seconds
- Table
8.1 Induction period before the First crys-
tals appear.

1. H = Avogadro number = 6.023.1023(mol-'); K= 1.380.10-23J/K R = 8.314 J/(mol.K).

 Chapter 8. CRYSTALLIZATION 461

It can be noted that Eq. 8.1 disregards the metastability limit, since it is not
taken into account in the theory. Additionally, this equation, which is based on
the evaluation of excess Gibbs energy associated with the formation of a solid
crystalline compound, and therefore purely thermodynamic in nature, does
not take into account the mobility of nucleus precursor clusters. As a result, it
can not account for the influence of temperature in a satisfactory way, in par-
ticular because of the sometimes very wide variation in viscosity. In fact, in all
types of nucleation, the nucleation velocity reaches (or is thought to reach) a
maximum when the relevant temperature domain is scanned.
Equation 8.1 mainly involves homogeneous primary nucleation, even
though attempts have been made to use it in a modified form for heteroge-
neous primary nucleation.
For the practical needs of crystallizer design calculations and modelling, it
is more convenient to use empirical formulas that have been proven by long
experience.
By combining homogeneous and heterogeneous primary nucleation, the
nucleation rate can be represented by an empirical expression of the following
type:
-V1 -dn,
dt
= kVl(C- P ) . l

with v1 usually ranging between 1 and 2, and k,, the constant of primary nucle-
ation generation.
kvl and v1 depend on the physical properties of the system and on hydro-
dynamic conditions.

8.2.2 Kinetics of Secondary Nucleation

In the presence of crystals of the same type as that of the future nuclei (or of
isomorphic nature), which is generally the case in industrial crystallizers, sec-
ondary nucleation occurs, caused:
either by contact between existing crystals;
or by contact between crystals and walls, internals or the agitation sys-
tem.
The secondary nucleation rate can be expressed by:

-V1 -dn2 = kv2 (C- P)"2 (8.3)

dt
k,, rises with the mass concentration of crystals in the slurry2and with the
agitation intensity of the system
k,, falls when the viscosity increases, when the temperature is lowered for
example

2. The generic term of slurry refers to a suspension of solid particles in a liquid. The
expression has been commonly adopted and is found in several refining areas such as cat-
alytic cracking.
462 Chapter 8. CRYSTALLIZATION

8.2.3 Seeding (Tertiary Nucleation)

Lastly, we could speak of tertiary nucleation referring to the possibility of
seeding the mother liquor with microcrystals of the same nature (or isomor-
phic) as the future crystals. In this case of course, the rate of tertiary nucle-
ation is the same as the rate of seed introduction. The technique is sometimes
used to shorten the germination induction period. It also helps moderate ini-
tial supersaturation better by preventing the nuclei from proliferating anar-
chically when crystallization is beginning. However, there are other ways of
triggering lazy germination, such as temporary gas bubbling, sudden agitation,
scraping the walls, etc. for example.

8.2.4 Measuring Nucleation Rates

Primary and secondary nucleation rates can be determined experimentally in
the laboratory by measuring the width of the metastability zone and also the
duration of the induction period. The major difficulty of course consists in
having a solution that is representative of the one that will be processed indus-
trially, impurities included.

8.3 Second Step in Crystallization: Crystal Growth

Once a stable nucleus has been generated in a supersaturated solution it can
grow. In simplified terms the growth process can be considered to occur in two
stages:
transfer of solute molecules from the solution to the crystals;
orderly deposit on the crystals’ surface.
We are going to examine two extreme cases where the process is governed
by one or the other of the limiting factors, then consider a combination of the
two.
The growth rate will be expressed by dr/dt, r being the radius of the sphere
equivalent to the crystal during growth. This is therefore a linear velocity,
expressed in meters per second3and is applicable to all of the crystals present
in the slurry of course, whatever their size. Consequently, the increase in the
crystal mass in the slurry will be the result of integrating all of them.

3. It would also be possible to express t h e rate of crystal growth by the mass increase
dmldt. The relation which links dmldt and drldt is the following:
drn dr
- = 4nr2 pc -
dt dt
with pc the density of the crystals.
 Chapter 8. CRYSTALLIZATION 463

8.3.1 Crystal Growth Rate Governed by Mass Transfer

Let us consider a particle with a radius r submerged in the virtually immobile
mother liquor. The concentration gradient is limited to the thickness of the
film in contact with the crystal. Since growth is assumed to be controlled only
by mass transfer, the concentration which prevails on the surface of the crys-
tal is equal to the concentration at equilibrium C" (Fig. 8.2A). The mass flow
per particle is written:

NM= k A M ( C - C * ) (8.4)
with:
N solute flow (mol/s)
M solute molar mass (kg/mol)
k mass transfer coefficient (m/s)
A interfacial area = 4n9 (m2>
C solute concentration in the solution (mol/m3)
but:
dm dr
NM = - = 4n r2pc -
dt dt
p, being the density of the crystals (mol/m3).
Consequently, we have:
dr
4n r2pc- = k 4n r2M(C- C*) (8.5)
dt
Here this is the case where Sh = kd/D = 2 (see Chapter 3). From this we get
the expression of growth rate, equal to the transfer rate:

It can be noted that the linear velocity is inversely proportional to the

radius. The smaller the crystal, the higher the velocity.
However, if we consider the mass deposit rate dmldt:
dm dr 4x:rDM
- = 4n r2pc - = 4n r2pc
dt dt
we end up with the opposite conclusion: the mass deposit rate increases with
the size of the crystal.
It is therefore very important to specify exactly which rate we are talking
about.
It can also be noted that the rate is here proportional to (C - C*).
In a simplified way the following will be written:
464 Chapter 8. CRYSTALLlZATlON

8
\
I
I
Mother liquor
I
:;
# I

c, = C'
.* .
.

rto Lengrn 1
I ,
I ,
,
I
I
, Concentration profile
I ,

L around a crystal during

growth. A. Rate con-
trolled by mass trans-
fer. B. Rate controlled
C by both mass transfer
C, and orderly crystal
C* deposit.

C : Mother liquor concentration.

C' : Concentration at equilibrium.
C, : Surface concentration.
6 : Thickness of diffusion film.

The Sherwood number could of course be higher than 2 if the agitation

intensity increases in the vicinity of the grains, and because of this the trans-
fer coefficient k could be greater than DM/rp,. It has, however, been observed
that this gain is usually insignificant and that it is relatively difficult to disre-
gard the mass transfer limitation, whether in diffusion (virtually immobile
medium) or in convection (agitated medium).
 Chapter 8. CRYSTALLIZATION 465

8.3.2 Growth Rate Controlled by Molecule Integration

in the Crystal Lattice
The electron microscope has been used to show the growth of a crystal, layer
after layer, according to a well determined order. Crystal growth takes place on
sites where the cohesion energy between crystals and free molecules is the
greatest. Generally speaking, growth is faster along higher level lattice planes.
As for the case we are more particularly dealing with, that of long paraffins,
growth is fastest on the lateral faces. Paraffins can crystallize in mono- or
multi-layers, where the zigzag chains are parallel to one another, with methyl
end groups belonging to planes parallel or perpendicular to the axes. This con-
struction mechanism leads to shapes such as pyramids (Fig. 8.3). If there are
inclusions or dislocations, growth may then be in a spiral whose single layer
does not need the addition of any new seeds (Fig. 8.4).
When crystal growth is controlled by molecule integration in the crystal
lattice, the growth rate can generally be expressed by:

(2) integration
- kintegration (C - C*Y
with i ranging between 1 and 2 and kintegrationdependent on r via a complex
(8.9)

function that is variable from one case to another.

8.3.3 Growth Rate Controlled by Both Mass Transfer

and Integration in the Lattice
If the two processes are both limiting, the concentration profile looks like the
one indicated in Figure 8.2B and the following can be written:
dr
-dt
= kt(C- CJ = k;(Cs - C*)i (8.10)

CS is the surface concentration (C* < C, < C)

(C- Ca is the driving force for transfer and (C,- C*) is the driving force
for integration
In the special case where i = 1, the following can be written:
dr
- = K ( C - C*) (8.1 1)
dt
1 1 1
with: - --
K
-
k,
+ -ki (8.12)

but this is an accidental case.

Accordingly, whatever the limiting process, crystal growth rate is once
again seen to depend highly on supersaturation.
Even though the expressions for:

and (e)
dt integration
466 Chapter 8. CRYSTALLIZATION

z
CH3 CH, CH3
/ / /

CH3 CH3 CH3

Figure
8.3 Pyramid shaped crystal growth.

Figure I

1'
Spiral shaped crystal
growth.

I
 Chapter 8. CRYSTALLIZATION 467

are very similar, it is sometimes possible to determine which one is limiting by

examining the variation in growth rate with temperature. In fact, k,,the mass
transfer coefficient, varies very little with temperature (apparent activation
energy approximately a few kJ/mol). Meanwhile k ,which can be considered as
a constant of chemical reaction rate, exhibits high activation energy (several
tens of kJ/mol).
It is also possible to follow a variation in the mechanism versus tempera-
ture. Orderly deposit is limiting at low temperature, whereas deposit becomes
very rapid at high temperature and transfer consequently becomes limiting in
this case.
Figure 8.5 illustrates this situation. The equation below is written:
dr - - Eapparent
- - kapparent(C- C*) = k" exp (C- C*) (8.13)
dt RT
from which the following is taken:
d In kapparent =-- Eapparent
(8.14)
d(l/T) R
In an attempt to reduce the influence of transfer, the degree of agitation of
the system can be increased as mentioned earlier. In this way k, increases and
therefore the overall growth rate rises. However, this procedure is not very
effective, it may even be pointless, because a transfer limitation causes very
few disadvantages. It can even be detrimental because it allows secondary

-
'apparent
Slope =
/ ~

Rate limited
by mass
transfer

: controlled
: by orderly deposit

1IT

Figure
8.5 Variation in the growth rate with temperature.
468 Chapter 8. CRYSTALLIZATION

nucleation to develop, which is not advisable in continuous industrial crystal-

lizers where the aim is size distribution as narrow as possible to facilitate fil-
tering, washing and purification operations later on.

8.4 Crystal Agglomeration

The problems related to agglomeration of crystals with each other and their
incrustation on crystallizer and filter walls and internals are seldom dealt with
in the literature. It is, however, a critical issue for those who manage and main-
tain the units. Generally speaking, slight and well controlled supersaturation,
slow and regular agitation with continuous scraping of walls, along with regu-
lar input to filter feed chutes are sufficient to prevent this type of trouble.

8.5 Crystal Morphology

Crystals can seldom be obtained with perfect shapes corresponding to their
basic crystal system. As mentioned earlier, the presence of impurities can pro-
mote nucleation, but the same impurities or others can upset crystal growth.
Growth takes place at different rates on the different exposed faces of crystals
(this distinction was not taken into account in the section devoted to crystal
growth as the growth process was considered from a general standpoint). It is
obvious that if certain impurities are adsorbed preferentially on one of the
faces, it will hinder the growth of this face and cause an often spectacular mod-
ification in crystal morphology. The solvent used as a crystallization aid has a
similar influence. Naphthalene crystallizes in a needle shape in cyclohexane
and in a platelet shape in methanol. In the presence of a large amount of impu-
rities all the faces will be attacked and the result will be a crystal with a com-
pletely different shape from what is normally obtained. A few per cent of biuret
in urea makes the crystal go from needle shape to platelet shape.
Rapid cooling of the solution causes needle shape growth preferentially
(the needle shape lends itself better to dissipating the heat produced by crys-
tallization). Inversely, very slow cooling promotes the formation of well struc-
tured crystals.

8.6 Influence of Crystal Shape on Filtration

(Case of mParaffins)
Our study will be confined to n-paraffins separated by crystallization-filtration
from lube oil fractions by means of the solvent dewaxing process described in
Chapter 9. The petroleum cuts in dewaxing unit feed are cooled in the pres-
ence of a selective solvent and the paraffins precipitate out. The filtration step
is generally the bottleneck of this type of unit and it is important to know the
effects of crystallization on the filtration operation.
 Chapter 8. CRYSTALLIZATION 469

8.6.1 Macroscopic Measurement

of Paraffin Cake Filterability
In 1983 Giorgio and Kern in collaboration with, and with the support of, Total
undertook an indepth study of the behavior of paraffin crystals during filtra-
tion. In the followingsection we have borrowed extensively from their results
and interpretation.
The crystallization of n-paraffins in the presence of a solvent, then their fil-
tration is simulated in the laboratory. The volume of filtrate collected from a
filter of known area during a given time under a constant differential pressure
is measured. The experiment is run with a sequence of n-paraffins with 32,36
and 40 carbon atoms and an equimass mixture.
The experiments are conducted as follows: a known amount of noncrys-
tallizable oil made up of a mixture of saturated hydrocarbons with less than 20
carbon atoms and a known amount of an equivolume mixture of MEK and
toluene are added to a known amount of crystallizable n-paraffin at 60°C. This
mixture is then cooled at a rate of 4°C a minute to -23°C while being agitated
so that all the heavy paraffins precipitate out. Filtration is performed at -20°C
under constant differential pressure. The volume of filtrate collected is mea-
sured versus time only after the cake has reached a uniform thickness.
The results obtained are presented in Figure 8.6 with the ratio of elapsed
time t over cumulative filtrate volume V on the abscissas, and the cumulative
filtrate volume V divided by two times the square of the filter area S on the
ordinates. Straight lines are obtained whose slope is:
V2
F= -
2S2t

Fis defined as "filterability" and is expressed in m2/s. Its inverse is filtration

resistance.
It can be seen that filterability for a given experiment is a constant. There
is therefore proportionality between the cumulative amount of filtrate and the
square root of elapsed time. F decreases going from C,, to C,o. The most strik-
ing fact is that filterability is the lowest for the equimass mixture C,, +
c36 c40*
It can also be seen that filterability is proportional to differential pressure
and inversely proportional to filtrate viscosity and to volume crystal content
of the slurry.
Giorgio and Kern distinguished the external features of the process, i.e. the
pressure differential AP, the filtrate viscosity p and the crystal content in the
suspension W, as well as the intrinsic features concerning the cake itself. They
established the relation below based on a laminar flow law for fluids in a
porous medium:

(8.15)
470 Chapter B. CRYSJALL~ZAJ~ON

with intrinsic filterability cp defined by:

(8.16)

with:
f filterability (m2/s)
cp intrinsic filterability (m2>
S area of the filtering surface (m2>
At’ differential pressure (Pa)
p filtrate viscosity (Pas)
W ratio of crystal volume to filtrate volume
E porosity of paraffin cake
0 average pore cross section (m?
z pore tortuosity (ratio of length to height, i.e. cake thickness)

AP = 2.78.104 Pa = 0.278 bar

fi = 1.54.10-3 Pa.s
f v/2s2 (m-’’
w
T =
= 4.1.10-3 (vol/vol)
-20°C
* O I With crystallization aid S= 12.56.10-4 td

-
Figure
8.6 Filtration curves at constant differential pressure. lRe curve with an adjuvant
is common to all n-paraffinsand to their equimass mixture.

8.6.2 Measuring Cake Porosity

The concept of cake porosity is particularly important in a crystallization-fil-
tration process for it conditions how thick and compact the cake is as well as
the impurity retention ratio (in the case examined here, impurities are repre-
sented by the dewaxed oil).
 Chapter 8. CRYSTALLIZATION 471

By weighing the different cakes recovered from the experiments described

earlier, before and after eliminating the solvent that impregnates them, the
porosity E can easily be determined. Porosity values are listed in Table 8.2.
Porosity is seen to be very high in all cases.

Intrinsic Average Average

Filterability fi filterability cp Porosity E diagonal d thickness e volume &e
n-paraffins
(m2/s) 10-13 (m2) (' 0*05)
10-6 (m) (m) 10- 1* (m3)
2.51 0.88 47 0.8
1.02 0.85 27 0.5
0.68 0.84 24 0.3
0.34 0.92 11 3

Results of filtration experiments with paraffincakes.

LYI
8.6.3 Crystal Morphology and Cake Texture
We have just examined the impact of the crystallization operation's external
variables on filtration (pressure differential applied, area of the filtering sur-
face, crystal content of the slurry, filtrate viscosity, temperature, etc.), as well
as the primary characteristics of the paraffin cake (thickness, porosity). Now
we need to look into how crystal morphology and cake crystal texture can
influence intrinsic filterability.
The crystals obtained for the n-paraffins examined and for their equimass
mixture are observed to be thin platelets, built according to the orthorhombic
system. Let us simply note that the equimass mixture platelets are thicker by
an order of magnitude than the pure n-paraffin platelets (Table 8.2).
Figure 8.7 presents bar charts with the values of the longest diagonal d of
the platelet faces. The highly monodisperse feature of the equimass mixture
platelets will be noted in particular. The average values of these diagonals
have been listed in Table 8.2, as well as those of the platelet volumes d2e as a
reminder.
As for the way the platelets are oriented with respect to the filtering sur-
face, they are observed to be preferentially parallel to the surface with an aver-
age angular dispersion of less than 20" in all instances. This result must of
course be related to the operating conditions used: it is not sure that the same
behavior would be observed if the solvent were changed for example.
Developing their interpretation further, Giorgio and Kern conclude that the
value of intrinsic filterability is related not only to porosity, here not very selec-
tive, but also to crystal morphology, in particular anisotropy, characterized by
the ratio d/e.It is also related to the cake texture, in particular the angular dis-
persion. These factors are not independent, since the texture is conditioned by
morphology and the porosity is related to texture. The authors believe that for
472 Chapter 8. CRYSTALLlZaTlON

20 -
10 - I = 24 Clm
dmean

-
Figure
8.7 Bar charts with values for diagonals d.

the same crystals with average porosity and volume, intrinsic filterability
increases with anisotropy d/e: platelets (d/e > 100) exhibit better intrinsic fil-
terability than needles (d/e < l). Additionally, intrinsic filterability decreases
when angular dispersion increases and this is particularly significant for
platelets. Platelets lined up flat along the filtration plane exhibit better intrin-
sic filterability than those that are randomly oriented. This is true to such an
extent that intrinsic filterability for random platelets can become lower than
for needles with the same average volume, whatever their angular dispersion.

8.6.4 Filter Aids

Substances called filter aids were developed in order to improve filterability
by modifying crystallization. Giorgio and Kern completed their series of exper-
iments by implementing an alkylacrylate copolymer (in this instance Shell
 Chapter 8. CRYSTALLIZATION 473

Dewaxing Aid 1615), with a dosage of 40 ppm in relation to the feed to be

dewaxed, for the four cases examined earlier. Remarkably, filterability not only
increased, but adding this substance also made all the results more uniform.
Examination of isolated crystals shows no alteration in their morphology, but
in contrast the texture has completely been transformed: the crystals in the
form of orthorhombic miniplatelets (d 4 1 pm) are organized in the shape of
hollow cones which are closed at the apex and open at the base (Fig. 8.8). The
cones exhibited an angle of 60°, a height of 25 p n and a wall thickness of 2 to
3 pm. They are preferentially arranged with the apex downward and upward,
with their axes perpendicular to the filtering surface. Angular dispersion is
very low, as shown in Figure 8.8. The concept of pores can be considered as
somewhat unrealistic in this case and some difficulty can also be imagined
when the mother liquor is due to be eliminated from the cones by washing...
It should be noted that this type of adjuvant is not the only one that yields this
particular texture. If heptane is used as a diluting agent instead of the MEK-
toluene mixture, cones are also produced, but made up in this instance of mon-
oclinic miniplatelets.
No satisfactory explanation has as yet been found for the formation of
these cones, which occur early on in the crystallization process, probably in
the very first stages of crystal growth.

Configuration o f paraF
fin cones in a cake

.- .-
formed with a filter aid.

8.7 Reminder of Precautions Recommended

to Succeed with a Crystallization0Filtration
Operation
The preceding section clearly shows that crystallization operations, especially
on an industrial scale, require a good deal of know-how if both quality and
yield of the separated products are to be maintained.
A few simple principles should imperatively be complied with:
Use the driving force provided by supersaturation with circumspection.
Generally speaking, low supersaturation is preferable as discussed ear-
lier, even though it weighs somewhat heavily on productivity.
474 Chapter 8. &YSJALLlZAJlON

The choice of an appropriate solvent is often crucial. It regulates viscos-

ity and also governs nucleation, orients crystallization and reduces reten-
tion of mother liquor by crystals. If a mixture of solvents is used, the
components’ dosage must be controlled all throughout the process.
Any solvent addition during crystallization must be done carefully, with-
out any thermal shocks. It should not be forgotten that dilution causes
temporary desaturation at the injection point, followed by a supersatu-
ration peak if the diluent is very cold, with all the consequences that this
entails.
A great deal of attention should be paid to the formation of the initial
cake. Too great a drop in pressure can generate a highly compact initial
layer which keeps the filter from working normally. It is advisable to
increase AP very gradually.
Moderate agitation should always be sought. Agitation can be advanta-
geously combined with light, continuous scraping of the walls.
The cooling rate affects crystal morphology. Rapid cooling causes crys-
tals to grow needle shaped preferentially. Inversely, very slow cooling
promotes the formation of large well structured crystals, thereby facili-
tating the filtration operation that usually follows the crystallization
operation in an industrial process.
The use of filter aids causes crystals to cluster together in orderly cones,
thereby allowing the filtration proceed at a faster rate.

8.8 Crystallization Techniques

All crystallization processes consist of one or more crystallizers as such and
one or more mother liquor-crystal separators.
The crystallizer is a horizontal or vertical vessel equipped with an agitation
system, wall scrapers and a heat exchanger. The heat exchanger provides
either negative calories when crystallization is obtained by cooling the mother
liquor, or calories when it is obtained by evaporation, usually under vacuum
conditions, of the mother liquor.
The separator can be the crystallizer itself in batch operations, or it can be
distinct: filter press, rotary filter, continuous settler, centrifuge, etc. There is a
detailed description in Chapter 9 of the use of a multipurpose rotary filter: for
separation, draining off the mother liquor, washing, purification, partially dry-
ing and collecting the cake.
As for any chemical engineering operation using an equilibrium between
phases, contacting can take place in one single stage, multiple stages, or
preferably in a continuous countercurrent if the recovery yield and purity are
to be enhanced in the crystallized product. The fact that a solid phase is
involved of course complicates the system exceptionally in comparison to
other operations such as distillation, absorption or extraction.
 Chapter 8. CRYSJALLlZAJlON 475

It would be beyond the scope of this volume to describe the different crys-
tallization processes in detail, especially since present-day applications of
crystallization in the oil refining industry do not justify a thorough analysis
here.

8.9 Crystal Purification Techniques

The oil industry usually confines purification of crystals to washing the cake
and gradually replacing the mother liquor with diluent which is then evapo-
rated. However, there are more sophisticated purification techniques which
are used when purity of up to 99% or even 99.9%is sought. This is the case for
example for the paraxylene produced by crystallization from aromatic C8 cuts
that we will describe briefly by way of illustration (Fig. 8.9).

Crystals
from -.
filter
Height Recycle to
filter or to last 4i-
ation stage

Crystal bed
level controller
(optic probe or
other device)

Condensate purge
Temperature
Purified
product

Figure
8.9 Diagram o f a melter-purifier.
@: Samples taken to check the melting point periodically (13.26"Cfor pure
476 Chapter 8. CRYSTALLIZATION

The filtering surface is scraped continuously so as to keep a constant filter

cake thickness. The scraper sends the crystals down a chute into an empty
vertical receptacle (the ‘‘melter’~), with a fine mesh horizontal screen in the
lower part where the crystals accumulate up to a specified level. A heat
exchanger is placed under the screen and its heating fluid flow rate is con-
trolled by the system that regulates the crystal level in the melter.
The product is drawn off from the bottom under purity control: the bottom
temperature must be as close as possible to the melting point of the pure prod-
uct. The liquid reflux circulates countercurrently with the crystals, exits the
upper part of the melter and is recycled to the last crystallization stage or to
an appropriate section of the filter. The melter is started up with a total reflux
and the product is drawn off gradually. Different variations on this technique
have been designed, such as the Philips pulse column melter or the one equip
ping Brodie purifiers (Mullin, in: (Illman’s Encyclopedia of Chemical
Technology).
The system does not basically differ from other fractionation separation
operations, such as distillation. In particular, the concepts of minimum reflux
ratio (with an infinite number of trays) and of minimum number of trays (with
an infinite reflux ratio) still hold perfectly true.