CHAPTER 2 : DRYING AND CRYSTALLIZATION 1

2.0 DRYING AND CRYSTALLIZATION

Objective:
This topic provides the general principles of drying, the factors
influencing drying rate as well as the classification and selection of a
suitable dryer for a process. This topic covers a crystallization theory,
the factors that influencing the rate of crystal growth and the
crystallization equipment.

2.1 Drying Process

In general, drying a solid means the relatively small amounts of water or other liquid from the
solid material to reduce the content of residual liquid to an acceptably low value.
Evaporation refers to removal of relatively large amounts of water as vapor from material at
its boiling point. Commonly, liquid content of a dried substance varies from product to
product; example dried table salt contains about 0.5% water and dried coal 4%. The product
contains no liquid called bone dry. Drying is relatively reduction in liquid content from an
initial value to some acceptable final value.

Purposes of drying

i) Prevent microorganisms that cause food spoilage and decay cannot grow and
multiply in the absence of water. Then, the material can be stored for extended
period of time. Application: drying or dehydration of biological materials, especially
food is used as a preservation technique.

ii) Drying material is smaller than wet material and can reduce space, reduce packing
size and make solid handling easier.

iii) Drying is usually the final processing step before packaging and makes many
materials, such as soap and powders and dyestuffs, more suitable for handling.

Methods of drying
A major division:

1. Adiabatic (Direct dryers)

◼ Dryers in which the solid is directly exposed to a hot gas(usually air)
◼ In adiabatic dryers the solids are exposed to the gas in the following ways:
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a) Cross circulation drying - Hot gas blown across a surface of a bed or slab of solids
or cross one or both faces of a continuous sheet or film static bed of solids.

b) Through circulation drying –. Hot gas is blown through a bed of coarse granular
solid that are supported on a screen. The velocity is kept low to avoid any
entrainment of solid particles.

c) Solid are showered down ward through a slowly moving gas stream

d) Gas passes through the solid at a velocity sufficient to fluidize the bed.

e) The solid are all entrained in a high velocity gas stream and are pneumatically
conveyed from mixing device to a mechanical separator

2. Non adiabatic (Indirect dryers)

◼ Dryers in which heat is transferred to the solid from an external medium such as
condensing steam, usually through the metal surface with which the surface contact.
◼ Example: dryers heated by electric, radiant or microwave energy.
◼ In non-adiabatic dryers, the solids are exposed to the hot surface or other source of heat.

a) Solids are spread over a stationary or slowly moving horizontal surface and
“cooked” until dry. The surface may be heated electrically or by a heat
transfer fluid such as steam or hot water.

b) Solids are moved over a heated surface, usually cylindrically, by an agitator or

a screw or paddle conveyer.

c) Solids slide by gravity over an inclined heated surface or are carried upward
with the surface for a time and then slide to a new location. (Rotary dryer)

3. Combination adiabatic and non adiabatic drying: direct-indirect dryers

2.2 Rates of Drying

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By referring to figure below, the moisture content XT typically falls as shown by line A and line B
is drying rate; it is horizontal for much of its length, indicating that the drying rate is constant;
later it curves downward and eventually, when the material has come to its equilibrium moisture
content, reaches zero.

Figure 2.1: Typical plots of total moisture content/Grain temperature and drying rate vs
drying time

Drying periods and implications optimal drying

There are three different drying periods which will occur consecutively in time:
• I. Preheating period (drying rate is almost 0):
When wet material is exposed to hot air, initially only a very slight change in moisture
content is observed. This happens because all the heat provided in the drying air is
used to heat up the material to the drying temperature.

• II. Constant-rate period (drying rate is constant in time):

Once the material is at the drying temperature, water starts to evaporate from the
surface of the material. During this period, all the heat from the drying air is used to
evaporate surface moisture and the amount of moisture removed from the material is
constant in time. It is therefore called the constant-rate period. During this period,
material temperature is constant as well.
Effect of process variables on Constant Rate Period: air velocity, gas humidity, gas
temperature and thickness of solid being dried.

• III. Falling-rate period (drying rate declines over time):

As time passes, it takes more time for internal moisture to appear at the surface, and
evaporation of water is no longer constant in time. As a result, drying rate will decline,
and some of the heat from the drying air will heat up the material.
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Figure 2.2 : Typical drying-rate curve for constant drying condition(a) plot of data as a
free moisture versus time, (b) rate of drying curve as rate versus free moisture content.

In the beginning, the solid is usually at a colder temperature than its ultimate temperature, and
the evaporation rate will increase. Eventually at point B the surface temperature rises to its
 CHAPTER 2 : DRYING AND CRYSTALLIZATION 6

equilibrium value. Alternatively, if the solid is quite hot to start with, the rate may start at point
A`. this initial unsteady state adjustment period is usually quite short and it is often ignored in
the analysis of times of drying. From point B to C, the line is straight, and hence the slope and
rate are constant during this period. At point C, the drying rate starts to decrease in the falling
rate period until it reaches point D. At point D the rate of drying falls even more rapidly, until it
reaches point E. in some material being dried, the region CD may be rising completely or it may
constitute all the falling-rate period.

Example 1: Time of Drying from Drying Curve

A solid with Ls/A = 21.5kg/m2 whose drying curve is represented by figure a) is to be dried from
a free moisture content X1 = 0.38 kgH2O/kg dry solid to X2 = 0.25 kgH2O/kg dry solid. Estimate
the time required.

Solution.
From figure a), X1 = 0.38, t1 is read off as 1.28h. For X2 = 0.25, t2 = 3.08h. Hence, the time
required is
t = t2 - t1 = 3.08 – 1.28 = 1.80h

Example 2 : Time of Drying from Rate of Drying Curve

Repeat Example 1 but use Equation below:
R = - Ls dX
A dt _________________(1)
where R = drying rate in kgH2O/h.m2 or lbmH2O/h.ft2
Ls = dry solid used in kg or lbm
A = exposed surface area for drying in m2 or ft2

Solution
From figure b), Rc = 1.51 kgH2O/h.m2
R = - Ls dX ………………… equation 1
A dt
Then to find time, from equation (1)
t = Ls__ ( X1 – X2 )
ARc
= 21.5 ( 0.38 – 0.25 ) = 1.85h
1.51

2.3 Drying Equipment

General Consideration – there are some general guidelines for selecting a dryer.
1. Batch or continuous process – batch (150 – 200kg/h) ;continuous (greater than 1 – 2
tons/h)
2. Thermally sensitive materials must be dried in optimum condition.
3. Fragile crystals must be handled gently as in tray dryer or tower dryer.
4. The dryer must operate reliably, safely and economically.
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Tower Dryers –to dry solids and pastes

◼ A series of circular trays mounted one
above the other on a central rotating shaft
are spread with solid feed.
◼ Solid feed dropped on the topmost tray is
exposed to a stream of hot air or gas that
passes across the tray. The solid is then
scraped off and dropped to the tray below.
◼ It travels in this way through the dryer,
discharging as dry product from the
bottom of the tower. The flow of solids and
gas may be either parallel or
countercurrent.
◼ Batch system

Rotary Dryer - to dry solids and pastes

◼ A rotary dryer consists revolving
cylindrical shell, which is rotated and
usually slightly inclined toward the outlet.
◼ The granular solids are fed at the high
end, F and move through the shell as it
rotates.
◼ Rotary dryer are heated by direct contact
of gas with the solids, by hot gas passing
through an external jacket, or by steam
condensing in a set of longitudinal tubes
mounted on the inner surface of the shell.
◼ Continuous system

Spray Dryer – to dry solutions or slurries

◼ In a spray dryer, a liquid or slurry solution
is sprayed into a hot gas stream in form of
a mist of fine droplets.
◼ The water is rapidly vaporized from the
droplets, leaving particles of dry solid
which are separated from the gas stream.
The flow of the gas and liquid in the spray
chamber may be countercurrent, co
current or combination.
◼ The fine droplets are formed from the
liquid feed by spray nozzles or high speed
rotating spray disks inside a cylindrical
chamber.
◼ The dried solid leave at the bottom of the
chamber through the screw conveyer.
◼ The exhaust gases flow through the
cyclone separator to remove any fine.
◼ The particles produced are usually light
and quite porous.
◼ Continuous system
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Thin Film Dryer - to dry solutions and

slurries
◼ This equipment is to dry liquid or slurry
into dry and free flowing solids.
◼ Built in two section;
i) vertical agitated evaporator dryer
- here most of the liquid is removed from
the feed, and partially wet solid is
discharged to the second section
ii) horizontal dryer – the residual liquid
content of the material from the first section
is reduced to the desired value.
◼ The thermal efficiency is high, and there is
little loss of solids, since little or no gas to
be drawn through the unit.
◼ Relatively expensive and limited in heat
transfer area.
◼ Continuous system

Drum Dryer - to dry solutions and slurries

◼ A drum dryer consists of a one or more
heated metal roll, on the outside of which
a thin layer of liquid or slurry is evaporated
to dryness.
◼ The final dry is a thin layer of dry material
then is scared off by doctor blades into
conveyers below, which is revolving
slowly.
◼ Vapor hood is to collect and remove
vaporized moisture.
◼ This equipment is suitable for handling
slurries or pastes of solids in fine
suspension and for solutions.

Screen Conveyer Dryer - to dry solids and

pastes
- this equipment can accept s liquid or a
slurry feed and produce a free-flowing
solid product.
- built in two section, i) vertical agitated
evaporator-dryer. ii) horizontal dryer.
- the thermal efficiency of thin-film dryer
is high and there is little loss of solids
- expensive and limited in heat transfer
area.
- useful in removing and recovering
solvents from solid products.

2.4 Crystallization
 CHAPTER 2 : DRYING AND CRYSTALLIZATION 9

Crystallization is the process of formation of solid crystals precipitating from a solution,

melt or more rarely deposited directly from a gas. Crystallization can also refer to the
solid-liquid separation and purification technique in which mass transfer occurs from the
liquid solution to a pure solid crystalline phase. An important example is in the production
of sucrose from sugar beet, where the sucrose is crystallized out from an aqueous
solution. Crystallization is therefore an aspect of precipitation, obtained through a
variation of the solubility conditions of the solute in the solvent, as compared to
precipitation due to chemical reaction.

Process
The crystallization process consists of two major events, nucleation and crystal growth.
Nucleation is the step where the solute molecules dispersed in the solvent start to gather
into clusters, on the nanometer scale (elevating solute concentration in a small region),
that become stable under the current operating conditions. These stable clusters
constitute the nuclei. However, when the clusters are not stable, they redissolve.
Therefore, the clusters need to reach a critical size in order to become stable nuclei.
Such critical size is dictated by the operating conditions such as temperature and
supersaturation. It is at the stage of nucleation that the atoms arrange in a defined and
periodic manner that defines the crystal structure. The crystal growth is the subsequent
growth of the nuclei that succeed in achieving the critical cluster size.

Nucleation and growth continue to occur simultaneously while the supersaturation

exists. Supersaturation is the driving force of the crystallization, hence the rate of
nucleation and growth is driven by the existing supersaturation in the solution.
Depending upon the conditions, either nucleation or growth may be predominant over
the other, and as a result, crystals with different sizes and shapes are obtained (control
of crystal size and shape constitutes one of the main challenges in industrial
manufacturing, such as for pharmaceuticals). Once the supersaturation is exhausted, the
solid–liquid system reaches equilibrium and the crystallization is complete, unless the
operating conditions are modified from equilibrium so as to supersaturate the solution
again.

Many compounds have the ability to crystallize with different crystal structures, a
phenomenon called polymorphism. Each polymorph is in fact a different thermodynamic
solid state and crystal polymorphs of the same compound exhibit different physical
properties, such as dissolution rate, shape and melting point. For this reason,
polymorphism is of major importance in industrial manufacture of crystalline products.
Crystals are grown in many shapes, which are dependent upon downstream processing
or final product requirements. Crystal shapes can include cubic, tetragonal,
orthorhombic, hexagonal, monoclinic, triclinic, and trigonal. In order for crystallization to
take place a solution must be "supersaturated". Supersaturation refers to a state in which
the liquid (solvent) contains more dissolved solids (solute) than can ordinarily be
accommodated at that temperature.

As with any separation method, equilibrium plays an important role. Below is a general
solubility curve for a solid that forms hydrate (a compound that has one or more water
molecules attached) as it cools.
 CHAPTER 2 : DRYING AND CRYSTALLIZATION 10

In Figure 1, X may be any solid that can form hydrates such as Na2S2O3. The number of
hydrate molecules shown in Figure 1 is strictly arbitrary and will vary for each substance.

So how do you grow crystals? Let's consider an example that is fairly easy to envision.
Take a pot of boiling water and add table salt while stirring to make a water-salt solution.
Continue adding salt until no more salt will dissolve in the solution (this is a saturated
solution). Now add one final teaspoon of salt. The salt that will not dissolve will help the
first step in crystallization begin. This first step is called "nucleation" or primary
nucleation. The salt resting at the bottom of the pot will provide a site for nucleation to
occur.

Crystallization separates a product from a liquid feedstream, often in extremely pure

form, by cooling the feedstream or adding precipitants which lower the solubility of the
desired product so that it forms crystals.
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. However, there are instances when
impurities incorporate into the lattice, hence, decreasing the level of purity of the final
crystal product. Also, in some cases, the solvent may incorporate into the lattice forming
a solvate. In addition, the solvent may be 'trapped' (in liquid state) within the crystal
formed, and this phenomenon is known as inclusion.
 CHAPTER 2 : DRYING AND CRYSTALLIZATION 11

Figure 3: Solubilities of Several Solids

For crystallization (see also recrystallization) to occur from a solution it must be

supersaturated. This means that the solution has to contain more solute entities
(molecules or ions) dissolved than it would contain under the equilibrium (saturated
solution).
In an industrial setting, the solute-solvent mixture is commonly referred to as the
"mother liquor".
Each method of achieving supersaturation has its own benefits. The four most common
methods of reaching supersaturation in industrial processes are:

1.Cooling (with some exceptions) - solution cooling ;For cooling and evaporative
crystallization, supersaturation can be generated near a
heat transfer surface and usually at moderate rates.
2.Solvent Evaporation
3. Chemical Reaction - change in pH being the most common methods used in industrial
practice. A chemical reaction can be used to alter the dissolved
solid to decrease its solubility in the solvent, thus working toward
supersaturation.
4. Drowning - addition of a second solvent to reduce the solubility of the solute
(technique known as antisolvent or drown-out). Drowning describes the
addition of a nonsolvent to the solution which decreases the solubility of
the solid. Drowning or reactive crystallization allows for localized, rapid
crystallization where the mixing mechanism can exert significant influence
on the product characteristics

Progression of crystallization

Primary nucleation is the first step in crystallization. Simply defined, it's the growth of a
new crystal A. On an industrial scale, a large supersaturation driving force is necessary
to initiate primary nucleation. Usually, the instantaneous formation of many nuclei can be
observed "crashing out" of the solution. You can think of the supersaturation driving force
 CHAPTER 2 : DRYING AND CRYSTALLIZATION 12

as being created by a combination of high solute concentration and rapid cooling. In the
salt example, cooling will be gradual so we need to provide a "seed" for the crystals to
grow on. In continuous crystallization, once primary nucleation has begun, the crystal
size distribution begins to take shape. Think about our salty water, as you look at Figure
2 describing the progression of crystallization.

Figure 2: Progression of Crystallization

The second chief mechanism in crystallization is called secondary nucleation. In this

phase of crystallization, crystal growth is initiated with contact. The contact can be
between the solution and other crystals, a mixer blade, a pipe and a vessel wall. This
phase of crystallization occurs at lower supersaturation (than primary nucleation) where
crystal growth is optimal. Secondary nucleation requires "seeds" or existing crystals
to perpetuate crystal growth. In our salt example, we bypassed primary nucleation
by "seeding" the solution with a final teaspoon of salt. Secondary nucleation can
be thought of as the workhorse of crystallization.

Again, no complete theory is available to model secondary nucleation and it's behavior
can only be anticipated by experimentation. Mathematic relationships do exist to
correlate experimental data. However, correlating experimental data to model
crystallization is time consuming and often considered extreme for batch operations, but
can easily be justified for continuous processes where larger capital expenditures are
necessary. For batch operations, only preliminary data measurements are truly
necessary.

We've discussed how crystallization occurs once supersaturation is reached, but how do
we reach supersaturation? We have already covered one such method in our salt
crystallization example. Since the solubility of salt in water decreases with decreasing
temperature, as the solution cools, its saturation increases until it reaches
supersaturation and crystallization begins (Figure 3). Cooling is one of the four most
common methods of achieving supersaturation. It should be noted that cooling will only
help reach supersaturation in systems where solubility and temperature are directly
related. Although this is nearly always the case, there are exceptions.

Crystallization in nature
 CHAPTER 2 : DRYING AND CRYSTALLIZATION 13

Figure 3.
• Snow flakes formation;
• Honey crystallization (nearly all types of honey crystallize).

Crystal production
From a material industry perspective:
• Macroscopic crystal production: for supply the demand of natural-like crystals
with methods that "accelerate time-scale" for massive production and/or
perfection.
o Ionic crystal production;
o Covalent crystal production.
• Tiny size crystals:
o Powder, sand and smaller sizes: using methods for powder and controlled
(nanotechnology fruits) forms.
▪ Mass-production: on chemical industry, like salt-powder production.
▪ Sample production: small production of tiny crystals for material
characterization. Controlled recrystallization is an important method to supply
unusual crystals, that are needed to reveal the molecular structure and nuclear
forces inside a typical molecule of a crystal. Many techniques, like X-ray
crystallography and NMR spectroscopy, are widely used in chemistry and
biochemistry to determine the structures of an immense variety of molecules,
including inorganic compounds and bio-macromolecules.
o Thin film production.

Purification
Used to improve (obtaining very pure substance) and/or verify their purity.
 CHAPTER 2 : DRYING AND CRYSTALLIZATION 14

Equipment for Crystallization

Crystallization is a chemical solid-liquid separation technique, in which mass transfer of a
solute from the liquid solution to a pure solid crystalline phase occurs, consisting of two
major events, nucleation and crystal growth. The first requirement of any crystallizers is
to create a supersaturated solution, because crystallization cannot occur without
supersaturating. A classification of crystallizing equipment can be made based on the
methods used to bring about saturation as follows:
1) supersaturation produced by cooling the solution with negligible evaporation-tank
and batch-type crystallizers.
2) supersaturation produced by evaporation of the solvent with little or no cooling-
evaporator-crystallizers and crystallizing evaporators
3) supersaturation by combined cooling and evaporation in adiabatic evaporator-
vacuum crytallizer.

1.Tank Crystallizers This is probably the oldest and most

2.Scraped Surface Crystallizers
basic method of crystallization. In fact,
the "pot of salt water" is a good
example of tank crystallization. Hot,
saturated solutions are allowed to cool
in open tanks. After crystallization, the
mother liquor is drained and the
crystals are collected. Controlling
nucleation and the size of the crystals
is difficult. The crystallization is
essentially just "allowed to happen".
Heat transfer coils and agitation can be
used. Labor costs are high, thus this
type of crystallization is typically used
only in the fine chemical or
pharmaceutical industries where the
product value and preservation can
justify the high operating costs.
An example may be the Swenson-
Walker crystallizer consisting of a
trough about 2 feet wide with a semi-
circular bottom. The outside is jacketed
with cooling coils and an agitator blade
gently passes close to the trough wall
removing crystals that grow on the
vessel wall.
The shell surface of the cylinder type
jacket tank is working as a cooling
surface and it is continuously scraped
by a scraper, so it keeps stable heat-
transfer modulus for a long time. In
addition, a double propeller and draft
tube enable the complete mixing to
obtain fine crystals.
 CHAPTER 2 : DRYING AND CRYSTALLIZATION 15

This crystallizer is more suitable for

materials apt to adhere to the cooling
surface, in comparison with the
element type.

3.Circulating-liquid Evaporator Crystallizers Just as the name implies, these

crystallizers combine crystallization and
evaporation, thus the driving forces
toward supersaturation. The circulating
liquid is forced through the tubeside of
a steam heater. The heated liquid flows
into the vapor space of the
crystallization vessel. Here, flash
evaporation occurs, reducing the
amount of solvent in the solution
(increasing solute concentration), thus
driving the mother liquor towards
supersaturation. The supersaturated
liquor flows down through a tube, then
up through a fluidized area of crystals
and liquor where crystallization takes
place via secondary nucleation. Larger
product crystals are withdrawn while
the liquor is recycled, mixed with the
feed, and reheated.
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4.Circulating-magma Vacuum Crystallizers In this type of crystallizer, the

crystal/solution mixture (magma) is
circulated out of the vessel body. The
magma is heated gently and mixed
back into the vessel. A vacuum in the
vapor space causes boiling at the
surface of the liquid. The evaporation
causes crystallization and the crystals
are drawn off near the bottom of the
vessel body.