Crystallization

Definition:
Crystallization is the (natural or artificial) process where a solid forms where the atoms
or molecules are highly organized in a structure known as a crystal[1]. Crystallization is
also a chemical solidliquid separation technique, in which mass transfer of a solute
from the liquid solution to a pure solid crystalline phase occurs. In chemical
engineering crystallization occurs in a crystallizer. Crystallization is therefore related to
precipitation, although the result is not amorphous or disordered, but a crystal.[1]

Figure 1: Schematic drawing of the crystallizer (a).

Process principles:
The crystallization process consists of two major events, nucleation and crystal
growth which are driven by thermodynamic properties as well as chemical properties[2].
In crystal growth Nucleation is the step where the solute molecules or atoms dispersed
in the solvent start to gather into clusters, on the microscopic scale (elevating solute
concentration in a small region) [2], that become stable under the current operating
conditions. These stable clusters constitute the nuclei. Therefore, the clusters need to
reach a critical size in order to become stable nuclei. Such critical size is dictated by
many different factors (temperature, supersaturation, etc.)[2]. It is at the stage of
nucleation that the atoms or molecules arrange in a defined and periodic manner that
defines the crystal structure note that "crystal structure" is a special term that refers

to the relative arrangement of the atoms or molecules, not the macroscopic properties
of the crystal (size and shape), although those are a result of the internal crystal
structure[3].
The crystal growth is the subsequent size increase of the nuclei that succeed in
achieving the critical cluster size. Crystal growth is a dynamic process occurring in
equilibrium where solute molecules or atoms precipitate out of solution, and dissolve
back into solution[3]. Supersaturation is one of the driving forces of crystallization, as
the solubility of a species is an equilibrium process quantified by Ksp. Depending upon
the conditions, either nucleation or growth may be predominant over the other, dictating
crystal size[3].

Concept of crystallization:
There are three concepts which distinguish the modern crystallization. There are:
removal of excess nuclei or fines, circulation of the growing crystals to the zone where
supersaturation is being produced, and maintenance of high magma density in
circulation[2]. These factors are considered here in relation to a continuous crystallizer
which produces supersaturation by vacuum cooling, rather than by evaporation as in the
usual salt evaporation[2]. The design, known as the draft tube and baffle type, is used to
produce crystals up to about 16 mesh of a number of commonly crystallized materials.

Types of crystallization equipment:

Forced-circulation
Forced-circulation crystallization is the most widely used crystallization
method

in

industry.

Forced-circulation

crystallizers,

are

evaporative

crystallizers[3]. They create a super-saturated solution by evaporating the

solvent of a saturated solution. The solute of this supersaturated solution
then cools, forming crystals. These types of crystallizers are classified as

mixed-suspension, mixed-product-removal (MSMPR) crystallizers[3]. The key

assumption of an MSMPR crystallizer is that the slurry is perfectly mixed and
uniform throughout the system.

Draft tube baffle

Draft tube baffle crystallizers are used to control crystal size and
characteristics.
Draft

Tube

Baffle

(DTB)

crystallizers,

are

used

in

applications

in

which

excessive nucleation occurs. Small, unwanted crystals, called fines, are removed
from larger particles using gravitational settling and recycled through the
crystallizer again, resulting in maximum crystal recovery and larger crystals [5].

Surface-cooled
Surface-cooled crystallizers combine a draft tube baffle crystallizer body with
a heat exchanger. Slurry is drawn from the crystallizer body and then cooled
before being pumped back into the crystallizer body[5]. Crystallizers such as
these are the most useful for operations in which the solution's boiling point
is extremely high, or when such low temperatures are required that
evaporation by vacuum is not possible.

Surface-cooled
Surface-cooled crystallizers combine a draft tube baffle crystallizer body with
a heat exchanger. Slurry is drawn from the crystallizer body and then cooled
before being pumped back into the crystallizer body. Crystallizers such as
these are the most useful for operations in which the solution's boiling point
is extremely high, or when such low temperatures are required that
evaporation by vacuum is not possible[5].

Scraped surface
Scraped surface crystallizers such as the one shown below are used as low
energy, low cost means of crystallization for small scale operations. They are
used primarly for the crystallization of melts[5].

Application of crystallization
Artificial crystallization includes two major groups of applications: crystal production and
purification.
Crystal production
From the perspective of the materials industry:
To meet the demand for crystals that simulate natural crystals, there are methods that
accelerate the rate of production and crystal perfection. They include ionic crystal
production and covalent crystal production[1].

Examples of the mass production of crystalline materials include:

"Powder salt for food" industry.

Silicon crystal wafer production.

Production of sucrose from sugar beet, where the sucrose is crystallized out of
aqueous solution.

Purification
Well-formed crystals are expected to be pure because each molecule or ion must fit
perfectly into the lattice as it leaves the solution. Impurities would normally not fit as well
in the lattice, and thus remain in solution preferentially. Hence, molecular recognition is
the principle of purification in crystallization[1]. However, there are instances when

impurities are incorporated into the lattice, thus decreasing the level of purity of the final
crystalline product. Also, in some cases, the solvent may be incorporated into the lattice,
forming a solvate. In some cases, the solvent may be 'trapped' in the liquid state within
the crystal, forming what are known as inclusions[1].

Reference:
1. https://www.ethz.ch/content/dam/ethz/special-interest/mavt/processengineering/separation-processes-laboratory-dam/documents/practica
%20in%20process%20engineering%202/crystallization.pdf
2. Tavare, N.S. (1995). Industrial Crystallization Plenum Press, New York
3. McCabe
&
Smith
(2000). Unit
Operations
of
Chemical
Engineering' McGraw-Hill, New York
4. H. B. Caldwell, Ind. Eng. Chem., 1961, 53 (2), pp 115118, Feb 1961
5. http://encyclopedia.che.engin.umich.edu/Pages/SeparationsChemical/Crys
tallizers/Crystallizers.html