It is the (natural or artificial) process of formation of solid crystals precipitating from a solution, melt or more rarely deposited directly

from a gas. It is also a chemical solid-liquid separation technique, in which mass transfer of a solute from the liquid solution to a pure solid crystalline phase occurs. It is the process by which a chemical is separated from solution as a high-purity, definitively shaped solid.

The crystallization process consists of two major events: Nucleation is the step where the solute molecules dispersed in the solvent start to gather into clusters The crystal growth is the subsequent growth of the nuclei that succeed in achieving the critical cluster size

Methods of crystallization includes; Solution Cooling (if solubility is dependent on temperature Solvent Evaporation (solubility is nearly independent on temperature) Adiabatic (combination of cooling and evaporation under vacuum) Chemical Reaction

Others includes: Anti-solvent/drown-out (addition of second solvent to reduce solubility) Changing the pH

Two major groups of applications: Crystal production (macroscopic crystal production and tiny crystal production) Purification ( improving and/or verifying purity of substance)

The nature of a crystallization process is governed by both thermodynamic and kinetic factors, which can make it highly variable and difficult to control. T(Sliquid Ssolid) > Hliquid Hsolid Gliquid < Gsolid It is easy to dissolve a perfect crystal than to grow again a new one from the resulting solution

a process that is conducted under vacuum. chosen when solubility of the solute is nearly independent of temperature.

There are four common types of evaporative crystallizers namely: Steam-heated Evaporators Forced-circulation Evaporative Crystallizers Oslo-crystal Evaporating Crystallizers Draft-tube Baffle Crystallizers

EVAPORATIVE CRYSTALLIZERS

a typical evaporator body used in evaporative crystallization is the short tube vertical type the type of most evaporator units a steam chest or calandria with a large central downcomer allows the magma to circulate through the tubes

downcomer Vertical tubes

EVAPORATIVE CRYSTALLIZERS

a circulating magma unit operated under reduced pressure for feeds where high rates of evaporation are required, where there are scaling compounds, where crystallization is achieved in inverted solubility solutions, or where the solution is of relatively high viscosity

most frequent use is in the continuous processing of such materials: NaCl (food or technical grade) KNO3 Na2 SO4, K2 SO4 NH4Cl Na2CO3H2O Citric acid

can be either single or multiple effects and the vapor recompression concept (either thermal or mechanical) is often applied. Usually, they operate from low vacuum to atmosphere pressure. used for high evaporation rates and when crystal size is not of the utmost importance or if crystal grows at a fair rate.

Features: Active volume Agitation Special design of the liquid vapor separation area Internal baffles Elutriation leg Internal scrubbing section

EVAPORATIVE CRYSTALLIZERS

also called classified-suspension crystallizer is the oldest design developed for the production of large, coarse crystals The classifying crystallization chamber is the lower part of the unit. The upper part is the liquor-vapor separation area

The basic design criteria are twofold: desupersaturation of the mother liquor by contact with the largest crystals present in the crystallization chamber keeping most of the crystals in suspension without contact by a stirring device, thus enabling the production of large crystals of narrow size distribution

Closed type

Open type

EVAPORATIVE CRYSTALLIZERS

DTB crystallizer by incorporating a steam-heated exchanger in the clear liquor recycle line. operate with a rather low supersaturation, which is sometimes a limitation to crystal growth, so that very large crystals can be produced only by providing extensive and costly dissolving of fines.

includes a baffled area (settling zone), peripherical to the active volume for processes exhibiting a moderate evaporation rate Contains elutriation leg

A. Capable of producing large singular crystals. B. Longer operating cycles. C. Lower operating costs. D. Minimum space requirements, single support elevation.

E. Adaptable to most corrosion resistant materials of construction. F. Can be easily instrument-controlled. G. Simplicity of operation, start-up and shutdown. H. Produces a narrow crystal size distribution for easier drying and less caking. I. The product size varies only slightly with large changes in production rate.

elutriation leg

A crystallizer where a solid phase crystalline material results from the reaction of two components, can often be performed more profitably than in a separate reactor. Can operate conventional evaporative type crystallizer Reactive crystallization can also be performed in a forced circulation type crystallizer where the reactants are mixed in the circulation piping.

-Crystallizer in which a warm saturated solution is fed to a lagged, closed vessel maintained under vacuum. The solution evaporates and cools adiabatically, resulting in crystallization.

-is widely used in chemical industry for suspending solids in liquids. - Flow pattern may be upward or downward.
Swenson draft-tube baffled (DTB) crystallizer
-A vacuum unit capable of producing large crystals of narrow size distribution . -Has a low speed propeller agitator -The baffle forms an annular space in which agitation effect is absent.

Swenson Draft tube Baffled Crystallizer

Messo turbulence crystallizer

-is another draft tube

agitated unit. - Circulation is effected by the variable speed agitator. -Two liquor flow circuits are created by concentric pipe. -Outer injection tube -Guide Tube

-it operates in which mass of crystals is suspended in an upward flowing stream of liquor.

Oslo Crystallizer Unit -is a fluidized bed agitated crystallizer in which the gentle action minimizes secondary nucleation allows large crystals to grow.

Standard Messo Multistage Vacuum Crystallizer

-provides a number of cooling stages in one vessel. - Hot feedstock is sucked into the first compartment which is operated at the highest pressure and temperature.

Tank Crystallizer
-includes cooling of hot saturated solution in open tanks. After a long period of time the mother liquor is drained and the crystals removed. -High labor costs -Tank is cooled by coils or a jacket and a agitator used to improve heat transfer rate.

Non Agitated Vessel

-the simplest type of cooling crystallizer, a form of tank crystallizer -because of slow cooling, large interlocked crystals are usually obtained

Agitated Vessel
-The installation of an agitator in an open-tank crystallizer generally results in smaller, more uniform crystals and reduced batch time.

Large Agitated Cooling Crystallizer

-has an upper conical section which slows down the upward velocity of liquor and prevents the crystalline product from being swept out with the spent liquor.

Trough Crystallizer
The Wulff-Bock crystallizer Swenson Walker Crystallizer

-Frequently crystallizing crystallizer.

referred cradle

to or

as the rocking

-is a trough crystallizer with internal agitation and a cooling system.

Oslo-Crystal Cooling Surface

-It has a feature where a concentrated solution, which is continuously cycled through the crystallizer, is supersaturated in one part of the apparatus, and the saturation solution is conveyed to another part, where it is gently released into a mass of growing crystals.

Direct Contact Cooling Surface -is effected by blowing air into a

hot crystallizing solution.

Cerny Direct Coolant Crystallizer -A continuous crystallizer which has been used for the large scale production of calcium nitrate tetrahydrate, wherein aqueous feedstock enters at the top of crystallizer at 25 C and flows counter currently to the immiscible coolant droplets.