INSTRUCTIONAL MANUAL
BATCH CRYSTALLIZATION
INTRODUCTION
Crystallization is an important operation in processing as a method of both
purification and of providing crystalline materials in a desired size range. In a
crystal, the constituent molecules, ions or atoms are arranged in a regular
manner with the result that the crystal shape is independent of size and, if a
crystal grows, each of the faces develops in regular manner. The presence of
impurities will, however, usually result in the formation of an irregular crystal.
Generally large regular crystals are a guarantee of the purity of the material,
though a number of pairs of materials forms “mixed crystals”. In recent years,
techniques have been developed for growing perfect crystals, which are used
in the production of semiconductor devices, laser beams, and artificial gems.
In an energy-conscious environment, crystallization can offer substantial
savings as a method of separation when compared with distillation, even
though it is more costly to achieve cooling rather than heating. This is
attributed to the fact that the enthalpy of crystallization is much lower
compared to Enthalpy of vaporization.
The crystallization process consists essentially of two stages which generally
proceed simultaneously, but which can to some extent be independently
controlled. The first stage is the formation of small particles or nuclei, which
must exist in the solution before crystallization can start, and the second stage
is the growth of nuclei. If the number of nuclei can be controlled, the size of
the crystals ultimately formed may be regulated, and this forms one of the
most important features of the crystallization process.
Nuclei may form spontaneously if conditions are suitable, but in many cases
small seed crystals may be added and small quantities of impurities may also
act as nuclei. The rate of growth of a crystal in a solution is dependent on the
temperature and concentration of the liquid at the crystal face. These
conditions are not generally the same as those in the bulk of the solution
because a concentration gradient is necessary for the transfer of solute
towards the face, and a temperature gradient for the dissipation of the heat of
crystallization. The problem thus involves both heat and mass transfer, though
in most cases the heat transfer may be negligible; however, in the case of
melts, the problem is one of heat transfer alone.
YIELD OF CRYSTALS:
The yield of crystals produced by a given cooling may be estimated from the
concentration of the initial solution and the solubility at the final temperature,
allowing for any evaporation, by making solvent and solute balances as
follows:
For the solvent, usually water, the initial solvent present is equal to the sum of
the final solvent in the mother liquor, the water of crystallization within the
crystals and any water evaporated or:
w1 = w2 + y(R-1)/ R + w1E (1)
Where,
w1 and w2 are the initial and final masses of solvent in the liquor
y is the yield of crystals
R is the ratio (molecular weight of hydrate/ molecular weight of
anhydrous salt)
And E is the ratio (mass of solvent evaporated/ mass of solvent in the
initial solution)
For the solute:
w1c1 = w2c2 + y/ R (2)
Where,
c1 and c2 are the initial and final concentrations of the solution in the
terms of mass of anhydrous salt per unit mass of solvent.
From equation (1):
w2 = w1(1 – E) – y(R - 1)/ R (3)
And in equation (2)
w1c1 = c2 [w1(1 – E) – y(R - 1)/ R] + y/ R (4)
From which the yield,
y = Rw1[c1 – c2 (1 – E)]/ [1 – c2(R-1)] (5)
Broadly, crystallizers may be classified according to whether they are batch or
continuous in operation, and continuous crystallizers may be divided into
linear and stirred types which are referred to later. Crystallizers may also be
classified according to which the super saturation is achieved. In evaporative
crystallizers conditions are approximately isothermal, and super saturation is
achieved as a result of the removal of solvent. In cooling crystallizers, super
saturation results from lowering of the temperature of the solution, and this
can be affected either by means of exchange of sensible heat or by
evaporative cooling; in the latter case, there is a small loss of solvent.
Evaporative crystallization must of course be used where the solubility shows
little variation with temperature.
The main feature of the crystallizer is the method by which the size of the
product is regulated, and this is almost entirely dependent on the control of the
nucleation process. In general, slow cooling will result in the formation of
relatively few and large crystals because spontaneous nucleation is then
reduced, and rapid cooling will result in a high rare of nucleation and a number
of sizes of crystal. Crystallizers are generally simple in construction, the only
moving part being agitators and the scrapers, which are used to keep the heat
transfer surface free of solids.
The simplest and cheapest type of crystallizer consists of an open tank,
which can be used either as an evaporative or as a cooling crystallizer. In
small scale of batch processing, such crystallizers are quire convenient
because of their low first cost, simplicity of operation and flexibility. They are
too wasteful of labor and give too uneven product to be attractive for large
scale continuous processing
BATCH TYPE TANK CRYSTALLIZER EXPERIMENTAL
MANUAL
AIM:
To study the yield of crystals of Sodium Sulfate (Na2SO4) from its saturated
solution using open tank type agitated batch crystallizer.
PROCEDURE:
Take about 3-4 liter of DM water in the crystallizer and 40 liter of tap water
in the hot/ cold water supply tank.
Switch ON the power supply to the unit.
Switch ON the pump and start circulating the water from the tank in to the
jacket at fixed value using the rotameter. The exit water from the jacket
shall be recycled back to the water supply tank.
Set the temperature of the crystallizer content using the front panel of the
Temperature Indicator-Controller (TIC) to the desired value.
After achieving temperature of water in the crystallizer in the range of
desired value, slowly start adding the solid to be crystallized and allow it to
dissolve completely.
Add the total amount of solid as calculated from its solubility curve.
Maintain the solution at this temperature for about 5-10 minutes with
continuous stirring.
Now set the temperature value of the crystallizer on the TIC to the value
corresponding to the value at which the crystallization is to be carried out.
(If the crystallization temperature is above the cooling water available in the
laboratory by 5 C then no ice addition is required. However, if this
temperature is below 5 C than the cooling water temperature available, ice
addition to the water supply tank is essential.) The cooling shall be
achieved in the slowest possible manner to limit the nucleation rate and to
have better crystal growth.
As we set the temperature to a new value which is lower compared to the
initial value, the heater will be switched off automatically and because of
inevitable losses the temperature of the hot water circulating in the jacket
will come down slowly.
Reduce the rate of circulation of hot water in the jacket and maintain it in
the range of about 1.5-2.0 LPM and start draining the water coming out of
the jacket.
Add the cooling water available in the laboratory at the same rate to the
water supply tank to make up the loss of water in the water supply tank.
After sometime all the hot water will be drained out of the supply
completely and only the cooling water will be circulating in the jacket. Now
start recycling the exit water from the jacket back to the water supply tank.
(Alternatively, if the set temperature is higher than 5 C compared to the
cooling water temperature, heater is switched on during this procedure,
stop adding cooing water to the water supply tank and start recirculating
the exit water from the jacket back to the water supply tank.)
If ice addition is required to bring down the temperature of the Crystallizer
obtained by the cooling water alone, slowly add finely crushed ice to the
water supply tank so that the temperature of the crystallizer do not go
below the set value.
After 10-15 minutes stop circulation of the cold water and drain the water
from the crystallizer using drain valve.
Filter and then weigh the water and crystals collected. Collect the crystals
from the crystallizer. Dry them and weigh.
OBSERVATION:
Initial weight of water taken (w1) = _____ gm
Initial weight of Na2so4 added (m1) = _____ gm
Temperature at which dissolution takes place = _____ C
Final weight of Na2so4 collected (m2) = _____ gm
Final Cooling Temperature = _____ C
CALCULATION:
% Yield of crystals = (m2 /Solubility at exp. Temp.) * 100
From solubility data (At 600C) = 47.5 gm/100 ml water
So, ___ gm Na2so4 can not be recovered from solution at 100c
For experiment
= ___*___/100
= ___ gm. Na2so4 loss
Yield of crystal = Wt. of Na2so4 obtained as crystals
Wt. of Na2so4 initially taken in feed
= _____ %
RESULT:
Yield of crystals = _____ %
SAMPLE CALCULATIONS
OBSERVATION:
Initial weight of water taken (w1) = 3000 gm
Initial weight of Na2so4 added (m1) = 2000 gm
Temperature at which dissolution takes place = 60 C
Final weight of Na2so4 collected (m2) = 900 gm
Final Cooling Temperature = 10 C
CALCULATION:
% Yield of crystals = (m2 /Solubility at exp. Temp.) * 100
From solubility data (At 600C) =47.5 gm/100 ml water
So, 8 gm Na2so4 cannot be recovered from solution at 10 0C
For experiment
= 8 * 3000 / 100
= 240 gm. Na2so4 loss
Yield of crystal = Wt. of Na2so4 obtained as crystals
Wt. of Na2so4 initially taken in feed
= 900 / [2000-240] * 100
= 51.10%
RESULT:
Yield of crystals = 51.10%
Solubility Curve of Na2SO4 in Water with Temperature
SOLUBILITY CURVES FOR VARIOUS CHEMICALS:
FLOW DIAGRAM
