ABSTRACT Crystallization is a unit operation process used to separate pure solutes or solids from the aqueous solution.

The objective of this experiment is to demonstrate the batch crystallization utilizing the cooling method. In this experiment a saturated sugar solution is used as the feed to minimize the time taken for the crystallization to occur. A Solteq crystallization unit is used as the batch crystallizer. As the initial step, all valves should be ensured that they are closed except the ventilation valve V15. The product vessel B2 should be checked that it is empty of liquid and properly connected to valve V5 at the circulation line. The prepared feed solution was poured into the 10 L feed/reaction vessel R1 through the charge port. The temperature drop in the feed/reaction vessel R1 was observed until it has reached a constant value. Temperature value was recorded at every 15 minute intervals. 100-150mL product slurry was being collected and consequently filtered. The crystallized solids on the filter paper were dried and the weight was measured. As for the results, the cooling temperature drops gradually where the vessel temperature decreases but the products yield increases. From the result analysis a conclusion was made that the longer the time, the lower the cooling and vessel temperature, as a result, the more crystals are formed. From the experiment, we just get maximum of 3.28% yield. This shows that the rest of the solutes are impurities. There are some recommendations which an experimenter must ensure includes ensuring the system in good conditions to run an experiment. It has to be ensured that the filtration method has been done wisely by pouring the solution slowly so that it doesnt stick to the filtration pipe and produce a lower yield.

CHAPTER 1 1.1 INTRODUCTION Crystallization is a technique which chemists use to purify solid compounds. It is one of the fundamental procedures each chemist must master to become proficient in the laboratory. Crystallization is based on the principles of solubility: compounds (solutes) tend to be more soluble in hot liquids (solvents) than they are in cold liquids. If a saturated hot solution is allowed to cool, the solute is no longer soluble in the solvent and forms crystals of pure compound. Impurities are excluded from the growing crystals and the pure solid crystals can be separated from the dissolved impurities by filtration. This simplified scientific description of crystallization does not give a realistic picture of how the process is accomplished in the laboratory. Rather, successful crystallization relies on a blend of science and art; its success depends more on experimentation, observation, imagination, and skill than on mathematical and physical predictions. Understanding the process of crystallization in itself will not make a student a master crystallizer; rather, this understanding must be combined with laboratory practice to gain proficiency in this technique. 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. These stable clusters constitute the nuclei. However, when the clusters are not stable, they redissolve. The crystal growth is the subsequent growth of the nuclei that succeed in achieving the critical cluster size. Whichever the form of the crystallizer to achieve an effective process control it is important to control the retention time and the crystal mass, to obtain the optimum conditions in terms of crystal specific surface and the fastest possible growth.
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1.2 LITERATURE REVIEW Glynn (1990) states that a 12.2L draft tube jacketed crystallizer was used (see Fig. 1). It is made of glass and equipped with an agitator; a thermocouple and an electrical conductivity cell. Details of the experimental set up and procedure are described elsewhere. Aqueous solution of potassium alum, saturated at 35C, was cooled to 20C with an initial super saturation of Ci=5103 kg-hydrate/kg-free water, where the initial super saturation is the super saturation at the start of cooling. Natural and controlled cooling modes were examined (see Fig. 2). In the former mode, temperature was lowered by circulating a constant temperature coolant of 20C through the jacket. Solution temperature falls rapidly at the beginning, while later to the end, it drops slowly. In the latter mode, however, it is lowered slowly in the early stage and then rapidly to the end with the intention of suppressing secondary nucleation. This controlled cooling curve employed was determined according to the literature. The temperature was lowered along with the determined curve by controlling coolant temperature. The termination temperature was 20C. Agitation speed was maintained at 400 min 1 for all the experiments to ensure homogeneous crystal suspensions. Seeding was made at the start of a batch. Product crystals were separated by filtration from suspension withdrawn from the bottom of the crystallizer and sieved to obtain CSDs after air-drying. The super saturation was determined on-line through electric conductivity and temperature measurements by a technique developed by Hlozny et al.

Fig.1: Experimental apparatus

Fig. 2: Controlled and natural cooling modes employed

Recrystallized crystals were used as seeds after sieving. The mean size of the seeds used was 41.5, 165 and 327.5 m. The average size was calculated from the two adjacent sieve openings. This average size can be approximated to the mean mass size because of the narrow size distribution. The seeds having size of 41.5 m were added without washing because they were too small, while the other size seeds were introduced after washing with a slightly under saturated potassium alum solution at room temperature. (Stanley, 2006)

CHAPTER 2 2.1 OBJECTIVE Demonstrating the batch crystallization process utilizing the cooling method where the feed was inserted into the batch crystallizer through the pumping since no flow rates are considered and the cooling temperature was used to produce the crystals where they are no more soluble in the solution.

2.2 METHODOLOGY Earliest, all valves were closed except the ventilation valve V15. The product vessel B2 was checked so that it was empty of liquid and properly connected to valve V5 at the circulation line. The 800 mL of sugar solution that to be crystallized was prepared by adding 400 g sugar into it to produce a 500 g/L concentrated solution. Then, the vacuum pump P3 was switched on for the sugar solution to enter the reaction vessel R1. The stirrer M1 was switched on and the speed was adjusted to mid-range. The thermostat T2 was switched on and the cooling temperature was set up to -20C and also the timer was started by using stop watch. The temperature drop in the reaction vessel R1 was observed until it has reached a constant value. Then, the temperature value was recorded at every 15 minutes interval. After 15 minutes, the timer and the stirrer M1 were stopped. The newly formed crystals were allowed to settle to the bottom of the reaction vessel R1. A beaker was placed below the R1 and valve V1 was opened to collect 50 mL of product slurry. Then, the slurry solution was poured through a filter paper so that the crystallized solid will obtain. After that, the steps were repeated for each 15 minutes to obtain three other values to study the relationship between the temperature and the mass of the crystal obtained. The solid was dried by putting it in an oven. Lastly, the weight of solid collected was measured.

CHAPTER 3 3.1 RESULT Solute Solvent = Sugar = Water

Stirrer Speed = 548m/s Initial volume of feed solution = 1 liter Initial solute concentration = 500 g/L

Time (min)

Cooling

Vessel

Collected

Amount of Crystal crystals (g)

Yield

temperature temperature slurry (C) (C) volume (mL)

concentration (%) (g/L)

15 30 45 60

5.0 4.9 4.5 3.9

15.4 12.4 11.6 11.2

50 50 50 50

0.7581 0.7741 0.7798 0.8201

15.162 15.482 15.996 16.402

3.03 3.10 3.20 3.28

3.1.1 Calculation Mass of filter paper: 1.0098g Mass of filter paper + amount of crystals: 1.7679g Amount of crystals= (1.7679-1.0098) g=0.7581g Crystal concentrations= (0.7581/0.005)g/L = 15.162g/L Yield = the actual amount of crystal divided by the solute concentration x 100%.

For time= 15min, the yield =

For time =30 min, the yield=

For time =45min, the yield=

For time= 60min, the yield=

3.2 DISCUSSION

6 cooling temperature (C) 5 4 3 2 1 0 0.75 0.76 0.77 0.78 0.79 0.8 0.81 0.82 0.83 amounts of crystals(g)

From the result above, we can make a conclusion that, the longer the time, the lower the cooling and vessel temperature, as a result, the more the crystals are formed. The yield will be a maximum, because the assumption has to be made that the final mother liquor in contact with the deposited crystals will be just saturated. Mother liquor is the part of a solution that is left over after crystallization. It is encountered in chemical processes including sugar refining. The yield will refer only to the quantity of pure crystals deposited from the solution, but the actual yield of solid material may be slightly higher than that calculated, because crystals masses invariably retain some mother liquor even after filtration. When the crystals are dried they become coated with a layer of material that is frequently of a lower grade than that in the bulk of the crystals.

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CHAPTER 4 4.1 CONCLUSION The data presented in this report shows more crystals will be formed with the decreasing of cooling temperature (cooler). When the solution is cold, the solute is no longer soluble in the solvent and forms crystals of pure compound. The yield is a maximum quantity of pure crystals deposited on the solution. From the experiment, we just get maximum 3.28% of yield only.

4.2 RECOMMENDATIONS There are some recommendation which is an experimenter must ensure that the system in good conditions to run an experiment. If there are any minor error occurs, it can affect the results obtained. Other than that, you can directly ask the instructor if you have any question. And lastly, do not run the experiment by your own. After we finish the experiment, make sure all the systems are in original condition. It also has to be ensured that the filtration method has been done wisely by pouring the solution slowly so that it doesnt stick to the filtration pipe and produce a lower yield. A lower cooling temperature can be used to obtain a higher yield of crystals.

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CHAPTER 5 5.1 REFERENCES 5.1.1 Websites 1) Retrieved from http://en.wikipedia.org/wiki/Crystallization 2) Retrieved from http://www.ipe.ethz.ch/laboratories/spl/research/crystallization/project04 3) Retrieved from http://us.mt.com/us/en/home/applications/L1_AutoChem_Applications/ L2_Crystallization/Batch_Crystallization.html 5.1.2 Book Geankoplis, C. J. (2003). Transport Processes and Separation Process Principles: Includes Unit Operations. New Jersey: Pearson Education International. 5.1.3 Journal Glynn P. D. & Reardon E. J. (1990). Solid-solution aqueous-solution equilibria: thermodynamic theory and representation". American Journal Science, 290, 164201. Stanley S. J. (2006). Tomographic Imaging during Reactive Precipitation: Mixing with | Chemical Reaction. Chemical Engineering Science, 61 (23), pp 78507863.

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APPENDICES Appendix A: Formulae Used in the Calculation

Percentage yield =

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