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cRYSTALLIZATION
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DESCRIBE the basic
principles and
applications of
crystallization process.
CALCULATE the yields,
material and energy
balance in crystallization.
OUTLINES
Basic principles
and applications
of crystallization
process.
CALCULATION of
yields, material
and energy
balance in
crystallization.
CRYSTALLIZATION
Process of producing crystals from a
homogeneous phase which is obtained from a
solution.
Capable of producing bioproducts at very high
purity and considered to be a polishing step and a
purification step
Two different application of crystallization:
i.
ii.
COMPARISON OF CRYSTALLIZATION
AND PRECIPITATION
Description
Crystallization
Precipitation
Solubility
Relative
supersaturation
Low
High
Ill-defined
Large
Small
Nucleation
mechanism
Secondary
Primary
Nucleation rate
Low
High
Growth Rate
Wide Range
Low
Controllability
Controllable
Difficult to control
CRYSTALLIZATION FROM
SUPERSATURATED SOLUTIONS OF
SODIUM ACETATE
Source:
Source: Shakhashiri,
Shakhashiri, B.Z.
B.Z. Chemical
Chemical Demonstrations:
Demonstrations: A
A
Handbook
Handbook for
for Teachers
Teachers of
of Chemistry
Chemistry
CRYSTALLIZATION PRINCIPLES
Crystals
POLYHEDRONS SHAPE
TABULAR
Book-like (tablets) that are thicker than platy
but not as longated as bladed. Wulfenite
forms crystals that are a good example of
tabular crystals.
PRISMATIC
One of the most common of crystal habits.
Prismatic crystals are "pencil-like", elongated
crystals that are thicker than needles (see
acicular). Indicolite (a variety of elbaite) forms
good examples of prismatic crystals.
ACICULAR
Long and needle-like, thinner than
prismatic but thicker than fibrous. Natrolite
crystals can be good examples of acicular
crystals.
CRYSTALS GROW
IN 2 STEPS:
1.
1.
2.
2.
Nucleation
Nucleation -- first
first
aggregation.
aggregation.
Growth.
Growth.
Thermodynamically
Thermodynamically
distinct
distinct
Want
Want a
a few
few nuclei
nuclei to
to
grow
grow big
big
Use
Use thermodynamics
thermodynamics
to
to understand
understand the
the
required
required conditions
conditions
Crystallization
Principles
Nucleation
CRYSTALLIZATION
PRINCIPLES
kk11 :: rate
rate constant;
constant; M
MTT :: suspension
suspension density,
density, bb :: can
can
range
range up
up to
to 55 but
but has
has aa most
most probable
probable value
value of
of 2;
2;
j:j: ranges
ranges up
up to
to 1.5
1.5 with
with 11 being
being the
the most
most probable
probable value
value
Crystallization Principles
-
Nucleation
Crystallization Principles
PHASE DIAGRAMS
Protein concentration
Supersaturation
Precipitation zone
Nucleation zone
Solubility
curve
Metastable zone
Crystals grow, but
Nuclei form only
infinitely slowly
Under-saturation
(protein remains soluble; crystals dissolve)
an
pi
t
[p
re
ci
],
te
in
ro
[p
se
re
a
In
c
Protein concentration
t]
COURSE OF CRYSTALLIZATION
EXPERIMENT
Metastable
Start w/
soluble protein
(undersaturated
or metastable)
[Precipitatant]
Precipitation
Nucleates
here
Nucleation
Crystal grows
Sequesters protein
[protein] drops
Crystallization Principles
Crystal Growth
W:
W: mass
mass of
of crystals
crystals per
per volume
volume of
of solvent;
solvent;
A
A :: the
the surface
surface area
area of
of crystals
crystals per
per volume
volume of
of
solvent;
solvent;
kkGG :: overall
overall mass
mass transfer
transfer coefficient
coefficient (depends
(depends
on
on temperature,
temperature, crystal
crystal size,
size, hydrodynamic
hydrodynamic
conditions,
conditions, the
the presence
presence of
of impurities);
impurities);
gg :: usually
usually 00 and
and 2.5
2.5
CRYSTALLIZATION
PRINCIPLES
EXAMPLE 1
Yield of a Crystallization Process
EXAMPLE 1
Solution
The molecular weights are 106.0 for Na 2CO3, 180.2
for
10H20, and 286.2 for Na2CO3 10H2O. The process
flow diagram is shown in Fig. 3, with W being kg H 2O
evaporated, S kg solution (mother liquor), and C kg
crystals of Na2CO3 10H2O.Making a material balance
around the dashed line box for water for part
(a), where W = 0.
(13)
Example 1
Making a balance for Na2CO3,
(14)
EXAMPLE 2
Heat
Balance
Crystallization
in
EXAMPLE 2
Solution
Making a water balance and a balance for MgSO4
using equations similar to (13) and (14) in
Example 1, C = 616.9 kg MgSO47H2O crystals
and S = 1651.1 kg solution.
To make a heat balance, a datum of 293.2 K
(20C) will be used. The molecular weight
of MgSO47H20 is 246.49. The enthalpy of the
feed is H1:
Example 2
The heat of solution is -(13.31x10 3)/246.49 = -54.0 kJ/kg
crystals.
Then the heat of crystallization is -(-54.0) = +54.0 kJ/kg
crystals,
or 54.0(616.9) = 33312 kJ. This assumes that the value
at 291.2 K
is the same as at 293.2 K. The total heat absorbed, q,
is
Tank Crystallization
EQUIPMENT FOR
CRYSTALLIZATION
Circulating-liquid evaporatedcrstallizer
Supersaturation is generated by
evaporation.
Circulating liquid is drawn by the screw
pump down inside the tube side of
condensing steam heater
Heated liquid then flows into the
vapor space, where flash evaporation
occurs, giving some supersaturation.
The vapor leaving is condensed.
The supersaturated liquid flow down
the downflow tube and then up
through the bed fluidized and agitated
crystals, which are growing in size.
The living saturated liquid then goes
back as a recycle stream to the heater,
where it is joined by the entering feed.
The larger crystals settle out and a
slurry of crystals and mother liquor is
withdrawn as product.
Also called Oslo crystallizer.
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