Distillation Report

By Group 13: Nordiyanah Ahmad Ali, Nordalilah Ahmad Ali, Alice To (z3252159)

1. Abstract
In this experiment, a batch separation of a binary liquid mixture of ethanol and water is attained by the application of heat, with a vapour containing a higher concentration of ethanol (the component of higher volatility) being evolved and subsequently condensed and collected as a liquid distillate product. The experiment aimed to optimise distillate productivity through optimisation of packing material and condenser cooling rate to control temperature. Distillate productivity was assessed using a productivity equation which accounted for both e volume and purity of the distillate. The distillate productivity obtained in this experiment was 255.85, which is 19.17% of the maximum possible productivity.

2. Introduction and Theory

Distillation is a process involving the separation of liquids with different volatilities by means of vaporisation and condensation and is commonly employed in industry [1]. The three main techniques of distillation are rectification, flash distillation, and differential distillation. In recent years, there has been an increased emphasis on obtaining the highest purity distillate at minimal cost which has driven research on the effect of different distillation techniques [C&R: 542]. This report is a documentation of our attempts to optimise distillation using the batch rectification method by producing the highest quantity of high purity distillate possible. The aim of this experiment was to separate 1% vol ethanol in water mixture to obtain the best possible mole separation and volume of distillate. It is important to note that the purity of our distillate is limited to 89.5% mol due to the azeotropic nature of the ethanol/ water mixture. It was found that this limitation could be overcome through the addition of an entrainer such as benzene to the mixture which will volatise water (a highly polar molecule) to greater extent than it volatilises ethanol (a moderately polar molecule) and a virtually pure ethanol product may be obtained (C&R: 476). However, benzene was not available to us during the experiment so our purity was contrained to that of the azeotrope. Two vital concepts needed to study distillation include height of equivalent equilibrium plate (HETP) and number of stages. Although HETP has no theoretical basis, there are several empirical correlations which can be employed for its calculation, such as: the McCabe-Thiele method, the Fenske-Underwood-Gilliland method, and Murchs Correlation. The McCabe-Thiele method involves the plot of an x-y diagram to construct an equilibrium curve. On the same diagram, the operating line (with slope=L/V) is drawn. For constant reflux composition, the slope is 1 which is a 45 line. The number of stages can then be determined by stepping: constructing a vertical line from distillate composition to the operating line, extending the line horizontally to the equilibrium curve, and then vertically to the operating line to form a triangle. Stepping is repeated until boiler composition is reached or exceed, with each triangle represents a stage. The Fenske-Underwood-Gilliland method involves the use of relative volatility to calculate the number of stages: ( ) [ ] ( ) ( ) ( ) Where is the relative volatility, Top is the relative volatility at the condenser and Bottom is the relative volatility at the boiler. For both McCabe Thiele and Fenske-Underwood-Gilliland methods, HETP is calculated thus:

Another method for calculating

is Murchs Correlation:

Where, , , is the packing constant, is the diameter of column, is the column height, volatility, is the liquid viscosity, and is the density of the liquid g dm .

is the relative

3. Equipment and Method

3.1 Description of Equipment
The materials used in this experiment includes a batch distillation unit which is made up of a distillation column, a condenser, a reservoir, and a heating system, water coolant, 500mL of 6mm polypropylene Raschig ring packing, and a 10L ethanol-water solution (1% ethanol by volume). The batch distillation unit is connected as per Figure 1. The solution is fed into the reservoir where the heating system supplies heat to the solution, causing it to vapourise. As the vapour flows upwards through the distillation unit, it comes in contact with the packings inside the column, which increases contact surface area and provides a moderate pressure drop, which assists in the purification of ethanol composition. The resultant vapour then condenses in the condenser to form the distillate. Measurement of condenser and boiler temperatures were obtained from thermometers and the flowrate of cooling water was determined using a 1L measuring cylinder and a stopwatch.

3.2 Operational Strategy

Setup and operating of the distillation unit can be found was performed as described in the Project Brief (Le-Clech, P., 2010: 5). Once the heating element has been turned on, the unit was allowed to reach steady state before beginning the distillation process. Steady state was assumed to be reached when the condenser temperature stabilised, which was determined by observation of the condenser thermometer to occur after 50 minutes after turning on the heating element. There are two main modes of operation for batch rectification: constant reflux ratio and constant distillate composition. The first method requires a constant monitoring of cooling water flow whilst the latter requires constant monitoring of distillate composition. Since a composition sensor was not readily available thus, the first operation mode (constant reflux) was adopted. Hence, the key operating strategy adopted was constant reflux ratio. Heat was transferred from the ethanol enriched 3 -1 vapour to the coolant. As the coolant flow rate was kept constant (62.5 cm s ), the amount of heat transferred at any given time should also be constant, As a result, the condenser temperature was kept roughly constant, yielding a constant distillate rate and thus a constant reflux ratio.

4. Summary of Results and Calculations

Table I: Volume and quality of distillate recovered Volume of Distillate/ L 0.052 Mole Percentage of Ethanol/ % 73.48 Distillate Productivity 255.61 Table II: Summary of HETP calculated Method Number of Stages (N) McCabe-Thiele Fenske-Underwood-Gilliland Industrial Value 4.84 4.09 2.95

HETP/ cm 3.65 4.32 6.0

% Error 39.2% 28.0% 0%

Process Variables Condenser temperature range during distillation: 78.5-79.8C Boiler temperature range during distillation: 95.9-98.7C Median cooling water flow: 0.0625 L/s Productivity value: 255.85 For more detailed results and calculations, see Appendices.

5. Discussion and Conclusion

5.1 Productivity
The two values required to calculate the distillate productivity are mole percentage and volume of the distillate which 3 were found to be 0.735 and 52cm respectively, thus, giving 255.85 as the distillate productivity. As means to support the aim of maximising the value of distillate productivity, a greater importance was placed on obtaining a large volume of distillate. This is due to the more profound effect the distillate volume has on the productivity. The experimental productivity was 19.17% of the maximum productivity (maximum productivity= 1334.93, see Appendix B).

5.2 Comparison of HETP Calculations

Vapour is richer in the more volatile component, ethanol, as it progresses through the column [Coulson and Richardson]. HETP or height equivalent of a theoretical plate refers to the height in which the enrichment of ethanol by one equilibrium step occurs. The McCabe-Thiele diagram and Fenske-Underwood-Gilliland (FUG) methods were employed to find the number of stages and thus the respective HETP values. The former method produced 4.84 as the number of stages and 3.65cm for HETP value, whilst the latter 4.09 and 4.32 cm. An increase in the number of stages is preferred as more stages leads to a higher mole fraction of ethanol in the resulting distillate. However, the FUG method is considered to be more reliable as it takes into account not only the physical and chemical properties of the fluid but also the interactions between liquid and vapour (e.g. relative volatility). Another option which was not explored fully was Murchs correlation, which takes even more fluid mechanic properties, i.e. liquid viscosity and mass velocity of vapor and packing properties, into account. However, due to the unavailability of data for packing properties, a HETP value using Murchs correlation was unable to be calculated and thus was not considered in this report. The industrial HETP value for small diameter column should equal to the column diameter of the plant [Frank]. Thus, for this experiment, the HETP value should then be 6cm, since the column diameter is 6cm. The FUG method was found to obtain a more accurate HETP value than the Mc-Cabe Thiele method (28.0% error compared to 39.2% error). The higher accuracy of the FUG method was expected, as it relies on less assumptions that the Mc-Cabe Thiele method, which are (no liquid holdup, heat of vaporisation of feed components are equal, negligible heat transfer [Perry]). Murchs correlation wouldve likely produced an even more accurate value, due to the additional information used in the correlation.

5.3 Comparison of Packing Options

One of the factors that affect ethanol composition in distillate is the type of packing used in the column. The packing 3 selected was 500mL of 6mm polypropylene Raschig rings, but two other options were also available: 250cm of 6 mm protruded metal packing or 50 pieces of 25 mm polypropylene Pall rings (see Appendix E). The protruded metal packing has self-wetting properties as well as the greatest surface area of the three (see table V in Appendix E) and are commonly used in the industrial column. The metallic nature of the packing corresponds to high thermal conductivity which will lessen the operators control over condenser temperatures and thus vaporization and condensation, potentially causing flooding of the column.

The 50 Pall ring provided was determined to occupy approximately 245cm as opposed to 500cm of Raschig ring packings. Since both packings are made using the same material, the higher volume of the two is favoured as greater volume leads to greater packing height, allowing more purified distillate to form. Also, to minimise channelling of liquid, the nominal diameter of packing should be less than one-eighth of the column diameter (Seader & Henley: 198), which was calculated to be 7.5mm. Considering these factors, the 6mm polypropylene Raschig ring was chosen. Increasing packing volume will result in increased distillate purity. However, this will also lead to an increase amount of time vapour spends in the column, and thus minimise the potential distillate volume produced in a given time. Due to time constraints, no extra packing was purchased. This decision was made based on the volume of distillate produced in the trial lab (approx. 50mL).

5.4 Limitations and Constraints

The main limitations and constraints encountered during course of this experiment was the coolant flow. Due to unforeseen circumstances such as weather and piping structure in lab, the coolant flowrate used in the actual lab was significantly lower than cooling water flow during the trial lab. The maximum measured flowrate from the trial lab was 3 -1 3 -1 3 -1 72.5 cm s and the maximum flowrate of 62.5 cm s for the actual lab. The flowrate used in the trial lab, 56.2 cm s allowed sufficient heat transfer which reduced the condenser temperature to 76.5C. However, although the maximum flowrate possible was used for the actual lab, the condenser temperature did not decrease beyond 78.6C. This was 1.6C above the desired temperature suggesting insufficient heat transfer. As heat did not transfer at a satisfactory rate, heat continues to build up inside the column thus affecting the condenser temperature. As a result of the high condenser temperature, the composition of ethanol also significantly decreased thus minimising the potential volume of distillate. The coolant used in this experiment was tap water. As such, the valve controlling the flowrate is an ordinary water tap valve which is difficult to control as slight adjustments can have a significant effect on the flowrate. The flowrate was fairly constant throughout the experiment (see Appendix A), thus, there was no need to adjust the flowrate. Ethanol-water is an azeotropic mixture and cannot be separated beyond 89.5% mole of ethanol. In order to overcome this problem, a recommendation is to allow the addition of a material separation agent such as benzene as it forms an azeotrope with a lower boiling point than ethanol. However, the introduction of a third material means that additional subsequent separation becomes necessary, increasing the cost of operation.

6. Conclusions and Recommendations

The batch rectification unit was operated under constant reflux ratio and the distillate productivity was found to be 255.61. The HETP values were calculated using McCabe-Thiele and FUG and found to be 3.65cm and 4.32cm respectively, which deviated 39.2% and 28.0% respectively from the literature value of 6cm. It is recommended in future experiments to increase distillation time to improve volume, to add additional volumes of 6mm polyprolyene Raschig rings to the column, which will improve distillate purity, and to add a material separation agent such as benzene. These alterations will result in higher productivity. Mark Estimate: 89

Bibliography
1. 2. 3. Horobin, W., 2003, Distillation- How it Works: Science and Technology. B. P. Limited. 5 edition th Perry, R.H., Green, D.W., 1997, Perrys Chemical Engineering Handbook, 7 Edition, McGraw-Hill, Chapter 2, pg 91-112 th Aylward, G., Findlay, T., 2002, SI Chemical Data, 5 Edition, John Wiley and Sons Australia, Ltd., Chapter 4, pg. 5-13, Chapter 31 pg. 151
th

7. Appendices
7.1 Appendix A: Table of Process Variables
Table III: Process Variables with Time

Boiler Temp (C) Condenser Temp (C) Distillate Volume (mL) 0 22.8 22 0 5 23.3 22.1 0 10 23.6 22.3 0 15 23.9 22.4 0 20 24.3 22.4 0 25 30 22.4 0 30 78.1 22.5 0 45 83.5 20.3 0 40 98 81 0 45 97.3 79.3 0 50 97.3 78.6 2 55 97 78.6 4 60 97.1 78.5 8 65 96.7 78.5 9.5 70 97.4 78.6 10 75 97.3 78.6 10.5 80 95.9 78.6 11 85 97.3 78.6 11 90 96 78.6 11 95 96.4 78.6 11.5 100 97.5 78.6 12 105 97.6 78.6 12.5 110 98.1 78.9 14.5 115 98.6 78.9 21.5 120 98.6 79 28.5 125 98 79.1 37.5 130 98.3 79 38.5 135 98.7 79.8 38.5 140 98.4 79.8 38.5 145 98.1 79.8 38.5 150 98.5 79.8 38.5 155 98.6 79.8 38.5 160 98.6 79.4 40.2 165 98.4 79.4 46.4 170 98.3 79 52 Total volume of distillate collected: 52mL Condenser temperature range during distillation: 78.5-79.8C Boiler temperature range during distillation: 95.9-98.7C Median cooling water flow: 0.0625 L/s

Time (min)

Flowrate (L/s) 0 0 0 0 0 0 0 0 0 0.0625 0.0625 0.0625 0.0625 0.0625 0.0625 0.0667 0.0500 0.0455 0.0357 0.0370 0.0278 0.0526 0.0526 0.0526 0.0526 0.0278

7.1 Appendix B: Productivity Calculations

Distillate Productivity Calculations Assuming ,

The relative molecular mass, Mr :

Assuming the temperature of the solution at the time of analysis is also room temperature, which is taken to be 25C, similar calculations are done for the distillate obtained. In this experiment, the distillate obtained was 90% ethanol by volume. Thus taking a basis of 100mL:

( ) ( )

From lab results: Volume of distillate= =0.052mL Mole fraction of ethanol in distillate= ( Maximum Productivity Calculations From data [insert reference]: Mole fraction of ethanol in distillate= Taking a basis of 100 moles: ) ( )

Assuming all ethanol in original mixture is in the distillate: ( ( ) ) ( )

7.2 Appendix C: HETP Calculations

Reboiler Calculation

Therefore,

McCabe-Thiele Diagram Method

Figure 1: McCabe-Thiele Diagram for Ethanol/Water System

1.00 0.90 0.80 0.70 0.60 yA 0.50 0.40 0.30 0.20 0.10 0.00 0.00 0.10 0.20 0.30 0.40 0.50 xA 0.60 0.70 0.80 0.90 1.00 Equilibrium Curve Operating Line Stages

In order to calculate HETP, the packing height is also required: ( )

From, the above diagram: No. of stages for Mc-Cabe Thiele method= 4.84 Thus: for Mc-Cabe hiele method

Table IV: Summary of Calculated Mc-Cabe Thiele Data

V/dm-3

m/g

n/mol

xD

xB

Ethanol Water

0.09 0.01

70.65 9.97

1.53 0.553

0.735 0.265

0.00165 0.9983

Fenske-Underwood-Gillilands Equation Diy, write down where you got your numbers highlighted from maybe? Looking good though! ( Similarly,
( ) ( )

) (

( [

)( ( (

) ] ) [ ( ( ( ) ) ] ) ( )

No. of stages for FUG method= 4.09 or method

7.3 Appendix D: Error Calculations

| | | |

Absolute error for temperature measurements = 0.05C

7.4 Appendix E: Packing Properties

Table V: Surface Area of Packings

Packing 6mm Protruded Metal Packing 6mm Polypropylene Raschig Ring 25mm Polypropylene Pall Ring Volume of Pall Packing

Surface area (m2/m3) 1120 320 421

) ( )