Exp 2: CRYSTALLIZATION OF BIOPRODUCTS CSB 30103

OBJECTIVES:

 To perform batch crystallization process utilizing the evaporation method.

 To examine the rate of evaporation and crystallization in a batch process.

 To determine the effect of circulation flow rate and heating rate on the
evaporative crystallization processes.

INTRODUCTION

Batch evaporative crystallization

Crystallization is the process by which a chemical is separated from solution as a high-

purity, definitively shaped solid. A crystal may be defined as a solid composed of atoms
arranged in an orderly, repetitive array. The infer-atomic distances in a crystal of any
definite material are constant and characteristic of that material. Crystals are, in short,
high-purity products with consistent shape and size, good appearance, high bulk density
and good handling characteristics. Because the pattern or arrangement of the atoms is
repeated in all directions, there are definite limitations on the shapes which crystals may

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Exp 2: CRYSTALLIZATION OF BIOPRODUCTS CSB 30103

assume. For each chemical compound, there are unique physical properties differentiating
that material from others, so the formation of a crystalline material from its solution, or
mother liquor, is accompanied by unique growth and nucleation characteristics. While
crystallization is a unit operation embracing well known concepts of heat and mass
transfer, it is nevertheless strongly influenced by the individual characteristics of each

material handled. Therefore, each crystallization plant requires many unique features
based upon well established general principles. Each application must be evaluated on an
individual basis to achieve optimum results. The mechanical design of the crystallizer has
a significant influence on the nucleation rate due to contact nucleation (that which is
caused by contact of the crystals with each other and with the pump impeller, or
propeller. when suspended in a supersaturated solution). This phenomenon yields varying
rates of nucleation in scale up, and differences in the nucleation rates when the same
equipment is used with different materials.

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Exp 2: CRYSTALLIZATION OF BIOPRODUCTS CSB 30103

OPERATING PROCEDURES:

4.2 General Start-Up Procedures for Evaporation Crystallization

1. All valves are ensured closed except the ventilation valve V12.

2. The product vessel B2 is checked empty of liquid.

3. 10 L of saturated salt solution was prepared by dissolving the appropriate amount

of salt in water.

4. The saturated salt solution was poured into the crystallizer vessel B1 through
valve V10 until the liquid overflows at the conical inlet. Valve V10 was closed.

5. The remaining solution was poured into the feed/reaction vessel R1 through the
charge point.

6. The stirrer M1 was switched and adjusted the speed to mid-range.

7. The crystallizer pump P1 was switched on and the circulation flow rate was set to
200 L/hr. The liquid solution was observed flowing from the crystallizer vessel
B1 through the pump to the heat exchanger W1 and then overflowing at the
conical inlet back to the crystallizer vessel.

8. The cooling water was turned on by opening valves V14 and V15.

9. The thermostat T1 was ensured contain sufficient heat transfer fluid while
thermostat T2 contains sufficient water and was refilled as necessary.

10. Both thermostat T1 and T2 were switched on. The temperature of T1 (containing
thermal-oil fluid) was set to 110 °C and thermostat T2 (containing glycol-water)
was set to 80 °C. The pump speed was set for both thermostats to a value of 8.

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Exp 2: CRYSTALLIZATION OF BIOPRODUCTS CSB 30103

11. Valve V12 was closed to operate the crystallization under vacuum. The vacuum
pump P3 was switched on and pressure was set at 0.3 bars on the controller.

12. The temperature rise in the feed/reaction vessel was observed until it has reached
a constant value.

13. The circulation line was allowed to heat up until boiling and evaporation occurs
and condensate starts to appear in the condensate vessel B4.

14. The units now were ready for experiments.

4.3 General Start-Up Procedures for Batch Cooling Crystallization

1. All valves were ensured closed except the ventilation valve V7.

2. About 10 L saturated oxalic acid solution was prepared by dissolving the

appropriate amount of oxalic acid in clean water.

3. The oxalic acid solution was poured into the feed/reaction vessel R1 through the
charge port.

4. The stirrer M1 was switched and adjusted the speed to mid-range.

5. The thermostat T2 was ensured contain glycol-water and was refilled as

necessary.

6. Thermostat T2 was switched on. The temperature of thermostat T2 was set to 60

°C.

7. The temperature rise in the feed/reaction vessel was observed until it has reached
a constant value.

8. The appropriate amount of oxalic acid was added into the feed/reaction vessel R1
through the charge port and let it dissolved. Saturated oxalic acid should remain in
60 °C temperature. Solubility data of oxalic acid was referred.

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Exp 2: CRYSTALLIZATION OF BIOPRODUCTS CSB 30103

9. The circulation line was allowed to cool down.

10. The units now were ready for experiments.

4.5 Product Collection

1. The product vessel B2 was empty.

2. If the unit operating at atmospheric pressure, valve V6 was opened and let the
slurry solution flow from the circulation line into the product vessel.

3. If the unit operating under vacuum, vent valve V7 and V8 were slowly opened to
released the vacuum.

4. Valve V6 was opened to collect the required amount of slurry solution and valve
V6 was closed.

5. The quick removable connections were opened carefully at product vessel B2 and
the vessel was removed. The slurry solution was poured into a collection bottle.

6. The product vessel was cleaned before placing it back into the unit.

7. From the collection bottle, the slurry solution was poured through the filter to
obtain the crystallized solid. The solid was dried by putting it under the sun or in
an oven.

4.6 Draining Condensate

1. If the unit operating at atmospheric pressure, valve V13 was opened to drain the
condensate vessel B3.

2. If the unit operating under vacuum, the vessel was isolated from the vacuum
system by closing valve V11.

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Exp 2: CRYSTALLIZATION OF BIOPRODUCTS CSB 30103

3. Vent valve V12 was opened slowly to release the vacuum.

4. Valve V13 was opened to fully drain the vessel. Valve V13 was closed.

5. Vent valve V12 was closed and valve V11 was opened slowly to return the
condensate vessel B3 to vacuum.

4.4 General Shut-Down Procedures

1. The temperature set point was reduced for both thermostat T1 and T2 to below
room temperature and the liquid in the thermostats was allowed to cool down to
room temperature.

2. The cooling water was keep running through condensers W2 and W3.

3. The stirrer M1 was switched off and dosing pump P2.

4. The circulation flow rate of pump P1 was set to 200 L/hr and the liquid was
allowed to cool down to room temperature.

5. The circulation pump P1 was turned off.

6. Valves V14 and V15 were closed to stop the cooling water flow.

7. The quick removable connections were opened carefully at product vessel B2 and
the vessel was removed. Any remaining liquid or solid residue was discarded and
cleaned in the vessel.

8. The sampling bottle B5 was removed and valve V5 was opened to drain all liquid
from the circulation line.

9. A hose was attached to valve V9 to clean the solid residue in the circulation line
and the pipeline was flushed with tap water. Valve V5 and V6 were drained
through water.

10. The condensate vessel B4 was drained by opening valve V13.

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Exp 2: CRYSTALLIZATION OF BIOPRODUCTS CSB 30103

11. If required, the liquid in the feed/reaction vessel were drained by opening valves
V1, V2 and V3.

12. The product vessel B2 and sampling bottle B5 were placed back into the unit.
Valves V5 and V6 were closed.

EXPERIMENT PROCEDURES:

1. The general start-up procedures were performed as described in Section 4.2. For
batch crystallization, thermostat T2 need not be switched on.

2. The circulation flow rate, vacuum pressure and the temperature of thermostat T1
were set to a suitable value. The feed solution was ensured boil at the specified
temperature and pressure.

3. The circulation line was allowed to heat up until boiling and evaporation occurs
and condensate starts to appear in the condensate vessel B3. The timer was
started.

4. The circulation flow rate and inlet/outlet temperatures were recorded of both feed
solution and thermal fluid through the heat exchanger W1.

5. The formation of crystals was observed in the circulation line. Once crystals start
to appear, the timer was stopped and the time duration was recorded.

6. The amount of condensate was measured accumulated in condensate vessel B3

and the condensate vessel was drained. Section 4.6 was referred. The timer was
restarted.

7. The following steps were performed at every 15 minute intervals:

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Exp 2: CRYSTALLIZATION OF BIOPRODUCTS CSB 30103

i. The circulation flow rate and inlet/outlet temperatures were recorded of

both slurry solution and thermal fluid through the heat exchanger W1.

ii. The amount of condensate was measured accumulated in vessel B3.

iii. The condensate vessel B3 was drained by opening valve V13. Section 4.6
was referred.

8. Step 7 above was carried out until the liquid level in the crystallizer vessel B1 has
dropped to about halfway below the conical inlet.

9. The total time taken was recorded for the crystallization process.

10. About 2 L of product slurry was collected from the circulation line as explained in
Section 4.5.

11. The amount of crystals obtained and the crystal concentration were determined in
the crystallizer at the end of the batch process.

12. The entire experiment was repeated by varying the circulation flow rate, vacuum
pressure and heating rate (temperature at thermostat T1).

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Exp 2: CRYSTALLIZATION OF BIOPRODUCTS CSB 30103

RESULTS

Panel No/Unit
FI301 FI302 PIL201 TI101 TI102 TI103 TI104 TI105 TI106
Time L/hr L/hr °C °C °C °C °C °C °C
9.50 am 665 798 0.301 58.8 77.3 25.2 26.7 107.3 101.0

10.20 am 480 801 0.301 58.8 74.9 26.5 27.0 107.5 100.8
10.50 am 550 805 0.301 58.5 75.2 26.8 27.5 107.7 101.1
11.20 am 405 806 0.301 58.2 75.9 27.0 27.7 107.8 101.2
11.50 am 361 805 0.302 58.9 76.4 27.3 27.9 107.8 101.4
12.20 pm 301 802 0.300 62.4 77.0 27.6 28.3 107.8 101.6
12.50 pm 301 808 0.297 61.9 75.5 28.0 28.8 107.9 101.7
1.20 pm 290 806 0.306 67.4 77.4 28.3 29.0 107.9 101.7
1.50 pm 284 807 0.302 66.6 77.7 28.6 29.2 107.9 101.8
2.20 pm 276 805 0.302 64.1 77.7 28.9 29.4 107.9 101.7

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Exp 2: CRYSTALLIZATION OF BIOPRODUCTS CSB 30103

Amount of Salt water that used = 6 Liter

Weight of crystal + container = 529.09 g

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Exp 2: CRYSTALLIZATION OF BIOPRODUCTS CSB 30103

DISCUSSION

Crystallization processes are usually carried out in agitated mixing tanks (Wachi and
Jones, 1995). Conditions of mixing in crystallizers with internal circulation forced by
mechanical stirrer significantly influence the final size of product crystals (Mersmann,
1999) and their characteristics. High levels of supersaturation around crystallization
points in the mixer due to a cooling surface, evaporative interference and or liquid
reactants contact lead to an inhomogeneous solution and non-uniform mixing especially
in fast precipitation systems. This causes very strong effects of homogeneous nucleation
and possibly inhibits the growth of crystalline nuclei. Imperfect mixing conditions are
generally observed in most industrial crystallizers. They are caused by supersaturation
phenomena, which create crystals of small final sizes, making downstream operations
such as filtration difficult and inefficient (Mersmann, 1994). Moreover, the content of
solution in the cake after filtration is too high, which lowers the quality of crystals
considerably. This necessity complicates the filtration technology, raises costs of
production and does not guarantee the expected specification of produced crystals.

Crystallisation is a separation and purification process, used in the production of a wide

range of materials. It involves the formation of one or more solid phases from a liquid
phase or amorphous solid phase. Crystallisation is one of the older unit operations in the
chemical industry and it differs from most unit operations because of the presence of a
solid product. The main advantages of crystallisation are a high purity in one process
step, a low level of energy consumption and relatively mild process conditions. Although
crystallisation is widely used it is still not well understood. This is a disadvantage and
problems in terms of product quality and process operation is frequently encountered.
One of these problems related to product quality requirements is an excess of fine
particles, resulting in bad filterability. Applications of crystallisation can be found in
producing inorganic materials such as potassium chloride (fertiliser), organic materials
such as paraxylene (raw material for polyester). An enormous number of and diversity in
crystallisation processes is found in the pharmaceutical, organic fine chemical and dye
industries.

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Exp 2: CRYSTALLIZATION OF BIOPRODUCTS CSB 30103

Among the crystallization mechanism that influences the crystal population discussed
above. Nucleation is the formation of new crystalline material. The driving force for
nucleation is supersaturation, which is defined as the difference in chemical potential
between the solid and the liquid phase. A distinction is made between two mechanisms of
formation of new crystalline material, known as primary nucleation and secondary
nucleation. The formation of new crystalline material from a clear liquid is called
primary nucleation. This type of nucleation can be subdivided in heterogeneous and
homogeneous nucleation. In heterogeneous nucleation, the liquid contains microscopic
foreign particles such as dust or dirt and the primary nucleation takes place on these
particles. In homogeneous nucleation, these foreign particles are absent and primary
nucleation occurs as a result of local fluctuations of concentration in the liquid. In
practice, the liquid will always contain small particles and heterogeneous nucleation is far
more likely to occur than homogeneous nucleation. The formation of new nuclei at the
surface of parent crystalline material is referred to as ‘birth’ or secondary nucleation. The
main source of parent material in the liquid is attrition. Attrition is the discontinuous
separation of very small particles from a parent crystal due to collisions of the parent
crystal with the impeller in the pump, the vessel wall and other crystals. Whereas primary
nucleation requires a very high level of supersaturation, secondary nucleation occurs at a
moderate level. The next step in the crystallisation process is the growth of the small
sized particles formed during nucleation. In the absence of agglomeration and breakage,
growth, together with nucleation, determines the final particle size distribution of the
crystal population. The driving force for crystal growth is again supersaturation. Crystal
growth is a process of mass transfer, surface integration and heat transfer. The mass
transfer step involves the diffusion of growth units such as ions, atoms or molecules
towards the crystal surface. Next, orientation and adsorption of the growth unit takes
place in the surface integration step. Heat transfer occurs simultaneously with both steps
and is usually not rate-limiting apart from melt crystallisation. In general crystals have
different growth rates at different surfaces, referring to the increase in length per time of a
surface in the direction normal to that specific surface. However, a single linear growth
rate of the characteristic crystal length is often used. Dissolution of crystals takes place

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Exp 2: CRYSTALLIZATION OF BIOPRODUCTS CSB 30103

when the solution is under saturated. Dissolution is not quite the opposite of growth as it
does not require the surface integration step and the rate-limiting step is therefore mass
transfer away from the crystal surface. Therefore, when the dissolution takes place,
crystals are easily rounded off as its corners and edges are the regions where mass
transfer is least rate limiting. Attrition and breakage are both a result of crystal collisions
with the pump, the vessel wall or other crystals. The impact of these collisions can result
in increased internal crystal stress. The stress will accumulate with repeated collisions,
ultimately leading to crystal fracture. The distinction between attrition and breakage is
made by the size of the particles after the original crystal has fractured. Breakage is
referred to as the separation of a crystal into two or more similar sized crystals. The
separation of a crystal into one slightly smaller crystal and many much smaller fragments
is named attrition. The amount of impact energy required for breakage is considerably
more than for attrition. As stated before in the part on secondary nucleation, attrition is a
main source for parent material from which new crystals are born. The mass formed by
the cementation of individual particles is referred to as agglomerate. For agglomeration to
take place, first of all two or more crystals have to collide. When these crystals are held
together by interparticle forces, such as Van der Waals, electrostatic and steric forces,
they form a mass called an aggregate. Growth between the crystals in the aggregate is the
final cementation step, resulting in agglomerate. In solution crystallisation processes,
agglomeration is usually an undesired phenomenon as the agglomerates can entrap
mother liquid. Mother liquor inclusions can result in caking behavior downstream the
crystallization process or during storage. Caking means the inclusions fracture and the
contained mother liquid comes out, cementing multiple crystals together as the solvent
evaporates and the supersaturated mother liquor crystallizes. This gives considerable
problems in product storage and processing.

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Exp 2: CRYSTALLIZATION OF BIOPRODUCTS CSB 30103

CONCLUSION

As conclusion, to get the better sizing of crystallization products, these parameters of

mechanism should be controlled during the process. For applications involving relatively
small amounts of material it is often convenient to use a batch crystallizer. Another
reason to make use of a batch process is when losses must be kept to a minimum, usually
when expensive materials are involved. Batch operation also has useful applications
where the cooling range is very wide, such as in handling material whose initial feed
concentration corresponds to relatively high pressure and whose final mother liquor
temperature corresponds to room temperature or significantly lower. In such systems the
use of batch crystallization avoids the shock introduced to the system in continuous
equipment by mixing high-temperature feed solutions with relatively low-temperature
mother liquor.

REFERENCES

 http://sundoc.bibliothek.uni-halle.de/diss-online/02/03H046/t4.pdf

 Whiting Equipment Canada Inc. Swenson Crystallization Equipment

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Exp 2: CRYSTALLIZATION OF BIOPRODUCTS CSB 30103

APPENDIX

CRYSTAL FORM

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