The Effect of Energy Input on the Efficiencies of a Corning 20-liter Distillation Unit

First report of Project #1 10/14/2011 Group B Arvind Ravichandran Ganesh Swaminathan Christian Parrish Colleen Quinlan

Abstract
After acquiring an old plant from Quack pharmaceuticals, WasteNot Chemicals found drums filled with dye mixtures in other volatile components. As the pure dyes had a greater market value, WasteNot Chemicals wanted to extract these valuable dyes using a distillation column. Hence, they required our team to evaluate and recommend operating conditions for the Corning 20-liter Distillation unit, a pilot-scale batch distillation column. Our team sought to determine the best energy input to run the column, such that it would be most efficient in terms of cost and energy. To this end, we ran the column using a water and ethanol mixture, without producing any distillate i.e. total reflux. We took samples from each stage and used the refractometer to measure its refractive index. Prior to this, we set up a standard curve to correlate refractive index of the sample to the ethanol composition of the sample. By computing the composition of ethanol at each stage using the standard curve, our team conducted a McCabe Thiele analysis. Through this analysis we determined the overall and individual tray efficiencies (Murphree vapor efficiency) of the column at three different energy inputs: 1.6 kW, 2.0 kW and 2.4 kW. This showed us how much, in general, the column deviated from theory and enabled us to determine the condition and performance of each tray. We discovered that the column performed best at the 1.6 kW energy input, where it had an overall efficiency of 0.469. We specified that the trays 3 and 5 were performing relatively poorly compared to other trays at various energy inputs, by using the Murphree vapor efficiency. We also specified conditions that should be avoided so as to prevent the improper functioning of certain stages of the distillation column known as weeping and flooding. Since the column efficiencies that we computed is applicable to all systems, with our analysis and framework for future experiments, WasteNot Chemicals can purify their dyes dissolved in any solvent.

Table of Contents

ABSTRACT DEFINITION OF SYMBOLS INTRODUCTION BACKGROUND EXPERIMENTAL METHODS RESULTS DISCUSSION CONCLUSION AND RECOMMENDATIONS LITERATURE CITED

1 3 4 4 13 18 25 28 29

Definition of Symbols
P T F N xA yA L V Eo EMV %wt %mol Pressure (atm) Temperature (K) degrees of freedom Number of phases Number of different components Molar composition of component A in the liquid phase Molar composition of component A in the vapor phase Liquid flowrate (kg/s) Vapor flowrate (kg/s) Overall efficiency Murphree vapor efficiency Weight fraction Mole fraction

Introduction
This project was carried out to measure the efficiency of the Cornell 20liter Distillation Unit. Upon acquiring an old plant from Quack pharmaceuticals, WasteNot Chemicals discovered many drums filled with dye mixtures in other volatile components. However, these dyes were dissolved in either ethanol and water or methanol and water or 1-propanol and water or benzene and toluene. Since the pure dyes had a greater market value, WasteNot Chemicals wanted to extract these valuable dyes from the volatile solvents using a distillation column. To this end, we used the Cornell 20-liter Distillation Unit. As the column did not have any documentation explaining its features, our team conducted experiments to understand the unit and evaluate the conditions to operate the column. Specifically, we analyzed how the overall efficiency of the unit and the efficiencies of each tray varied with the power input. Using this information, we defined the optimum power input for operation and provided recommendation on the performance of each tray.

Background
Phase Behavior
In our distillation process we analyze the interaction between the liquid and the vapor phase. We define a phase as a homogeneous region of matter.1 When a vapor and a liquid are in contact with each other, liquid molecules continually vaporize, while vapor molecules continually condense. When two chemical species, such as ethanol and water, are present in a mixture they will condense and vaporize at different rates. At equilibrium, the temperatures, pressures and fractions (mass or mole fraction) of the vapor and liquid phases cease to change.2 This is known as vapor-liquid equilibrium (VLE). Note that the equilibrium can only be reached, when the system is at steady state. For a system at steady state, quantities related to the process are time invariant. Hence, in our experiment when we observe constant temperature and

composition over time, we can estimate that the system has reached steady state and is also in equilibrium. It is possible to determine the state of a pure homogenous fluid when two intensive thermodynamic properties are set at specific values. This is expressed in the Gibbs phase rule.3 (See Equation 1.)

F = 2 + N
In Equation 1, F is the degrees of freedom,

[Equation 1]

is the number of phases and N is

the number of components in the system. According to Equation 1, for a two phase, two-component system, we will have two degrees of freedom. Hence, specifying temperature and pressure we can obtain the composition of ethanol and water at equilibrium. This is known as VLE data and it can be represented graphically through means of a temperature-composition diagram at a specified pressure. (See Figure 1.)

Figure 1: The vapor-liquid equilibrium mixture of ethanol and water at 1 atm. There are two
graphs, of which, one is temperature vs. xEth (liquid), and the other is temperature vs. yEth (above). These curves represent the saturated liquid and the saturated vapor lines. Any point below the saturated liquid curve represents a subcooled liquid and any point above the saturated vapor curve represents a superheated vapor. Points between the two saturation curves represent streams consisting of both liquid and vapor.
1

The isotherm shown in Figure 1 is called a tie line. For a system at equilibrium, the liquid to vapor ratio can be determined using the lever rule, given by Equation 2.

nl v = nv l

[Equation 2]

In Equation 2, nl and nv are the number of moles of liquid and vapor respectively. l and v represent the length of the segments of the tie line as shown in Figure 1.

Dynamics of Distillation
When a liquid mixture of a certain composition in the pot is heated it boils and produces vapor. (Denoted by a in Figure 2.) This vapor, denoted by b, is in equilibrium with the mixture at the pot. It enters the stage above it. Due to a lower temperature at this stage, the vapor condenses into a liquid, denoted by c. The liquid becomes richer in the more volatile component of the original mixture, as can be seen in Figure 2. This process continues on, giving an enriched mixture of the volatile component in the distillate and an enriched mixture of the less volatile component in the still pot. However, proceeding further brings the system to point d where the condensed vapor results in a distillate that has the same composition as the solution in the pot. Such a distillate is known as an azeotrope.4 After this point, further separation is no longer possible, and the solution boils at a constant temperature. For the ethanol-water mixture, Figure 1 shows that the saturated liquid and vapor curves merge at a certain temperature. This is known as the minimum-boiling azeotrope i.e., the liquid and vapor are of exactly the same composition at a mole fraction ethanol of 0.8943.4

Figure 2: Temperature-composition diagram. This illustrates a minimum boiling point azeotrope. The mixture in the pot, denoted by a, is heated and it boils to produce vapor. This vapor, denoted by b, is in equilibrium with the mixture at the pot. It enters the stage above it. The temperature at this stage is lower than that of the pot, due to a lack of energy input at this stage. The vapor condenses into a liquid, denoted by c. The liquid becomes richer in the more volatile component of the original mixture.
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McCabe Thiele Analysis

The McCabe-Thiele diagram is very useful in the analysis of fluid dynamics in a distillation column. The diagram is a plot of the vapor phase composition against the liquid phase composition of the more volatile component (ethanol in our project). It includes the VLE plot and the operating line. The operating line relates liquid and vapor flows between trays, also known as passing streams. The operating line is derived from a mass balance. (See Figure 3.) For the batch distillation case, the equation of the operating line can be obtained by solving a total mass balance and a component balance across 2 stages. This is expressed in Equation 3.

y j+1 =

L L x j + (1 )x d V V

[Equation 3]

In Equation 3, yj+1 is the composition of ethanol in the vapor phase in the stage below the jth stage. xj and xd are the compositions of the ethanol in the liquid phase in the jth stage and the vapor composition in the distillate respectively.1 (See Figure 4A.) The reflux ratio of a column is the ratio of the amount of condensate being refluxed to the amount being withdrawn as product. It is given by L/V in Equation 3. At total reflux, L/V = 1. The operating line reduces to the y = x line.1 (See Figure 3.) Note that the vapor from the (j+1)th stage and the liquid from the jth are called passing streams. L and V are the flow rates of the mixture through the downcomers and bubble caps respectively. L and V remain constant throughout the column, and that this equation implies a critical assumption.

Figure 3: McCabe Thiele Diagram showing the VLE line, x = y line and the operating line. The operating line is defined by Equation 3 and has a non-zero reflux ratio. At total reflux, the operating line is given by the y = x line.

This analysis is conducted with the assumption of Constant Molal Overflow (CMO)1. CMO consists of the following: The molar heats of vaporization of the feed components are equal For every mole of liquid vaporized, a mole of vapor is condensed Heat effects such as heats of solution and heat transfer to and from the distillation column are negligible.

Characteristics of a Distillation Column

The distillation column that was used in the project contained 6 stages. These stages enable the liquid and vapor phases of the mixture to interact and approach equilibrium at different, decreasing temperatures, up the column. A theoretical plate or stage is a hypothetical zone or stage in which the liquid and vapor phases establish equilibrium with each other. Any physical device that provides good contact between the vapor and liquid phases present in the distillation columns constitutes a plate or tray. Since an actual, physical plate is rarely a 100% efficient equilibrium stage, the number of actual plates is more than the required theoretical plates.6 (See Equation 4.) The flow of the vapor into stages above is made possible through bubble caps. (See Figure 6.) These are caps with slots or holes that enable the vapor to bubble through them1. Downcomers, enable the mixture in the liquid phase to flow downwards to the stage below. (See Figure 7.) The bubble caps and downcomers are essential for the distribution of the mixture between stages and to attain a state close to equilibrium for the purpose of effective separation.1

Efficiencies
To compare the performance of an actual stage to an equilibrium stage, we use the measure of efficiency.1 For the purpose of this project we will be using the concepts of overall efficiency and the Murphree vapor efficiency. The overall efficiency,

Eo , is

given by Equation 4, where

N equil

is the

number of theoretical plates required for the separation and number of stages required.

N actual

is the actual

Eo =

N equil N actual

[Equation 4]

The overall efficiency lumps together everything that happens in the column.1 The number of actual equilibrium stages is determined through the plotting of the pseudo-equilibrium curve. (See Figure 4B.) Stage efficiencies are defined for each stage and may vary from stage to stage. The Murphree vapor efficiency is defined as given in Equation 5.

E MV =

y j y j+1 y* y j+1 j
x j . (See Figure 3A.)

[Equation 5]

In Equation 4, y j is the vapor mole fraction in tray j, in equilibrium with actual liquid mole fraction

y* is the vapor mole fraction j

Figure 4: Murphree efficiency, (A) stage nomenclature, (B) McCabe-Thiele diagram for EMV.

Graphically, Murphree vapor efficiency can be calculated by taking the ratio of the distance from the operating line to the pseudo-equilibrium curve and the

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operating line and the equilibrium curve. (See Figure 4B.) This is given by Equation 6 as shown in Figure 4B.

E MV =
Flooding

AB AC

[Equation 6]

as flooding.7 When the vapor rising up the column is of great enough pressure to cause liquid hold-up the liquid in the stage cannot flow through the downcomer to the stage below and it is collected.

When liquid is held-up in the column, or in a particular stage, it is known

Refractometry
To fulfill the objective of the project, we had to take the composition of the mixtures at the various stages of the distillation column. For this, we used a refractometer. We can determine the concentration of the solution by determining the refractive index (RI) of the solution. The RI of a medium is the ratio of the speed of light traveling in that medium to the speed of light traveling in a vacuum.9 Since, this ratio is directly affected by the polarity of a medium, with increasing ethanol composition, the polarity and the RI of the mixture increases.10 However, temperature also affects the RI of a solution significantly.11 (See Figure 5.)

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Figure 5: Plot of refractive index, n, against T. The change in refractive index with temperature is roughly constant with increasing ethanol concentration. And between the 22.5C to 27.5C the refractive index of 11.91mol% water drops from 1.363 to 1.361.
11

Our team had to necessarily monitor the temperature of the readings in order to obtain reliable results. This relationship means that through the measurement of the RI of the solution, the composition of ethanol in the mixture can be back calculated, through the use of a standard curve. We obtained the standard curve through the measurement of RI of known mass compositions of ethanol in water. However, this relationship between composition and RI is not always a one-to-one mapping. (See Figure 6.) Note that the difference in RI is smaller at the 0.3 to 1 mole fraction region compared to the 0 to 0.2 mole fraction region.

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Figure 6: Plot of the refractive index of a water-ethanol mixture against ethanol mole fraction at 25C (from literature).
12

Note that beyond a certain composition (around 70 mol%),

12

the RI decreases with increasing water concentration. Also, the differences in RI are small beyond the 0.4 mole fraction region, relative to the 0 to 0.2 mole fraction region.

Note that the difference in RI is smaller at the 0.3 to 1 mole fraction region compared to the 0 to 0.2 mole fraction region.

Experimental Materials and Methods

Distillation Column
We used a bubble cap version of the Corning 20-liter Distillation Unit with six identical plates, each holding a single 3-inch bubble cap in the project. A schematic of the distillation column is shown below. (See Figure 5.)

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Figure 7: A Schematic of the Distillation Column used in the experiments. Note that the placement of thermocouples at each stage. There were also sampling taps present at each stage but are not represented in the schematic.

In the bubble-cap there is a riser, or weir, around each hole in the tray. A cap with slots or holes is placed over this riser, and the vapor bubbles through these holes. A photograph of the bubble-cap is shown. (See Figure 6.)

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Figure 8: A photograph of the bubble-cap in the Cornell Distillation Unit

A photograph of the downcomer in the column used is shown. (See Figure 7.)

Figure 9: A photograph of the downcomer in the Cornell Distillation Unit.

The still (boiling pot) was a 20-liter reboiler vessel fitted with a 2.4 kW electric heating mantle with three separate heating bands. We adjusted them to vary the energy inputs into the boiling pot.

Choice of ethanol-water mixture

In comparison to the other mixtures, we chose the ethanol-water mixture for this pilot project due to concerns over safety and cost. Our reasons for not using the other mixtures are explained below. (See Table 1.)
Table 1: Reasons why other mixtures were not chosen

Mixtures Methanol+water 1-Propanol+water Benzene+Toluene

Safety issue Poisonous, methanol is known to cause blindness Propanol is inflammable Both chemicals are known to be highly carcinogenic 15

Column Initializing
We mixed 10 liters of an ethanol-water mixture at 4.5 mole%, 1.6 liters of pure ethanol and 0.82 liters of pure water and charged the reboiler vessel with this mixture. We determined the ethanol-water mixture to be approximately 7 mole%. We made sure that the liquid level was above the top heating band, and approximately half of the 20 liter pot was filled with the still. Sample calculations of the still-pot composition are provided in Appendix A. We switched off the reflux divider and at start up only provided a 2kW heat input using the potter and the middle heater and we turned the powerstat to the zero position. We obtained the temperatures that we monitored through the thermocouples located at each stage, the boiler pot and the distillate. (See Figure 7.)

Flooding
During the running of the experiment, we observed flooding on the third stage of the column. At start up, the energy input was at maximum. We saw vigorous bubbling at this stage prior to flooding. The decrease in power input had little effect on the bubbling, and we observed liquid rise to nearly three quarters up the stage. The potter temperature was at 89.6C and the temperature at the third stage was 82.0C. We shut off the power input at the pot, and the column was allowed to cool down. We turned the column back on, when all the excess liquid in the stage had drained out.

Taking measurements
We started a timer at the start up of the column and recorded temperature at approximately five to ten minute intervals for the duration of the experiment. We operated the column at a total of three different power inputs: 1.2, 2, and the maximum power input of 2.4kW. We collected liquid samples from each stage after ensuring that steady state was reached after each change of the power setting. We determined that 16

the column had reached steady state by observing that the temperature readings remained fairly constant. We tried to obtain three different samples for each power setting to ensure that the readings were accurate. We also made sure that the 1.5 ml Eppendorf tubes were filled up completely so that the composition of the sample would stay constant until measurements were taken at the refractometer. We believed that some of the mixture in the liquid phase would evaporate and cause inaccuracies if the tubes were not filled up completely. We also ensured that we avoided taking readings too often, because this would lead to a decrease in the volume of fluid in a stage, and thus manifest as a disturbance in the steady state of the system. We ensured that the valves were open for a short time to get rid of residual liquid, before beginning sampling.

Refractometry
We used the Reichert AR6 Series refractometer to measure the composition of ethanol in the samples. We measured the RI of each sample only once. We set up the water bath at 25C and performed a one-point calibration with water. After cleaning the prism surface with a Kim wipe, we placed samples on the surface and took RI measurements. To prepare a standard curve, we prepared samples at different compositions by mass of ethanol. We prepared samples of composition by mass from 5% to 60%, at steps of roughly 5%. Upon plotting their RI against the composition by mole of ethanol, we obtained the standard curve. (See Figure 10.)

Dilution
To obtain accurate RI readings that would tolerate small inaccuracies in ethanol composition, we carried out a 1:3 dilution with water for all our samples. This ensured that the measured ethanol composition was in a viable region between 0 and 30 mole% as described in Figure 6. Beyond 40 mole% we

17

observe in both Figure 6 and Figure 10 that large differences in composition only leads to small changes in RI. Moreover, we immersed the samples in a water bath at 25C to ensure that the temperature of the samples were constant before their RI was measured. (See Figure 5.)

Safety
Although the chemicals that we worked with were not very harmful, it was critical to take certain safety precautions. We wore nitrile gloves when we handled the column or the ethanol-water mixture. We wore safety goggles at all times when the experiment was conducted to prevent splashes of harmful chemicals from entering the eye. We also took precautions when climbing the ladder to observe the column, so as to not knock over thermocouples that were sometimes in the way. We also did not make any contact with the still-pot during the experiment.

Results
The purpose of the project was to calculate the overall efficiency and individual tray efficiencies of the column. We did this by determining how much the column deviated from theoretical equilibrium conditions. Using this we determined the best heat input to operate the column.

Calibration Curve
The calibration curve for the refractometer was essential in our analysis of the column because we used it to calculate the composition of the mixtures from the various RI values. (See Figure 10.) We prepared three samples at each weight fraction of ethanol and measured the RI of each of them. We took the average of these RI values and used them to prepare Curve 2 on Figure 10. Unlike those of Curve 2, the points on Curve 1 represent single data points at different weight fractions from Curve 2. We appended it in Figure 10 for completion. 18

1.37000 1.36500 1.36000

Refractive Index

1.35500 1.35000 1.34500 1.34000 1.33500 1.33000 1.32500 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 y = -0.058x2 + 0.087x + 1.331 R = 0.998

Curve 1 Curve 2

weight fraction of ethanol

Figure 10: Standard Curve for Refractometry. Curve 1 contains single data points at different weight fractions from Curve 2. Curve 1 is plotted here because of the remarkable correlation with Curve 2 and to complete the missing data points that Curve 2 didnt cover. Curve 2 represents the average of three data points. The solid curve is fitted only with the points on Curve 2. The 2 2 equation of the Curve 2 is y = -0.0592x + 0.0875x + 1.3314 and the R value of the fit is 0.9994. We will use this equation to compute compositions of our samples.

The error bars in Figure 10 are very small and are not visible because the average standard deviation of the three points for the many weight fractions was approximately around 0.000126.

Determination of sample composition

We computed the composition of the samples using the formula given in Figure 10, once the RI was measured. However, to ensure that the data points fell in the 1.33 to 1.35 region, we carried out 1:3 dilutions on the samples. We back calculated the original composition of the mixture using literature values of density for the dilute mixtures at 25C. We performed a sample calculation of this in Appendix B. 19

McCabe Thiele Analysis

In the McCabe Thiele Analysis for our system at total reflux, L/V from Equation 3 is equal to 1. Hence, we obtain Equation 7.

y j+1 = x j

[Equation 7]

In other words, the ethanol composition liquid in a particular stage has the same composition as the ethanol composition in vapor in the stage below it. This means that the passing streams have the same compositions. Also the operating line is given by the y=x line. (See Figure 3.) Using this knowledge, we found out the respective vapor compositions in each stage, because this was just equal to the liquid composition in the downcomer on that stage. (See Figure 4A.) Analyzing the liquid sample from stage j gave us the mole fraction of ethanol in the liquid phase, xj. (See Table 2.) To obtain the pseudo-equilibrium curve, we corresponded x1 and y1, where y1= x2. Hence we got the point (0.30926, 0.42942). Similarly, by doing this for the other values we obtained 6 points to plot a best-fit line, which gave us the pseudo-equilibrium curve. (Figure 11.) We were able to use the distillate composition to begin stepping off stages and finally end at the bottoms composition.
Table 2: Composition of ethanol by mole fraction for 1.2kW power input. The x1 and y1 values correspond, x2 and y2 values correspond and so forth. These points are used to generate the pseudo equilibrium curve in Figure 11.

x 1 2 3 4 5 6 D

Sample A 0.18605 0.27073 0.34029 0.33025 0.57918 0.72011 0.66401

Sample B 0.36844 0.51517 0.56359 0.60945 0.72470 0.63432 0.86615

Sample C 0.37329 0.50236 0.57950 0.62742 0.62108 0.63050 0.63915

Average 0.30926 0.42942 0.49446 0.52237 0.64165 0.66165 0.72310

Std Dev 0.10673 0.13758 0.13375 0.16663 0.07491 0.05067 0.12451

Std Error 0.06162 0.07943 0.07722 0.09620 0.04325 0.02925 0.07188

y 0 1 2 3 4 5 6

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1.2

mol fraction ethanol in vapor

0.8

0.6

Equilibrium Line

0.4

0.2

Pseudo- Equilibrium Line

0 0.2 0.4 0.6 0.8 1 1.2

0 -0.2 -0.2

mol fraction ethanol in liquid

Figure 11: McCabe Thiele diagram for 1.2kW power input. The equilibrium line is the line above with equation: y = 305.9x - 345.0x + 193.3x - 56.40x + 8.501x. And quadratic best fit for the pseudo equilibrium line is below with equation: y = 12.24x - 8.803x + 3.190x and R = 0.978. Three samples were taken from each tray within approximately 7-minute time intervals to obtain the six points giving the pseudo equilibrium line. The line that steps off the pseudo equilibrium curve shows the actual step off giving six stages. Using the bottoms and distillate composition obtained from the analysis, the equilibrium step off is constructed. This gives the number of equilibrium stages to be three.
3 2 2 5 4 3 2

In Figure 11, the still-pot concentration can be determined by stepping down to the corresponding xeth from the tray closest to the still. For the 1.2kW power input, we found that the still-pot composition of ethanol by mole was about 0.35 from Figure 11. Similarly, we used readings from the 2kW power input experiment to populate Table 3.

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Table 3: Composition of ethanol by mole fraction for 2kW power input. Points obtained from this table are used to generate the pseudo equilibrium curve in Figure 12.

x 1 2 3 4 5 6 7

Sample A 0.35337 0.52549 0.51286 1.40830 0.60820 0.62577 0.89990

Sample B 0.32365 0.47243 0.62108 0.68167 1.20095 0.74107 0.17702

Sample C 0.35727 0.44985 0.84421 0.18234 0.96660 1.36409 0.64894

average 0.34477 0.48259 0.65938 0.75743 0.92525 0.91031 0.57528

std dev 0.01839 0.03883 0.16896 0.61648 0.29853 0.39719 0.36703

std error 0.01062 0.02242 0.09755 0.35593 0.17236 0.22932 0.21190

y 0 1 2 3 4 5 6

Like the 1.6 kW input, we used the same analysis to plot the pseudo-equilibrium curve and performed the McCabe Thiele Analysis. (See Figure 12.)
1.2

mole fraction ethanol in vapor

0.8

0.6

Equilibrium Line

Pseudo- Equilibrium Line

0.4

0.2

0 -0.2 -0.2 0 0.2 0.4 0.6 0.8 1 1.2

mole fraction ethanol in liquid

Figure 12: McCabe Thiele Diagram for 2kW power input. The equation of the equilibrium curve is identical to that in Figure 11. The pseudo-equilibrium curve in the figure has the equation: y = 1.15x - 0.497x + 1.494x with an R =0.549. There are 2 equilibrium stages and 6 actual stages. 3 samples were taken from each tray within approximately 7-minute time intervals to obtain the 6 points seen above.
3 2 2

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Only two samples were obtained for the 2.4 kW power input. (See Table 4.)
Table 4: Composition of ethanol by mole fraction for 2.4kW power input. Points obtained from this table are used to generate the pseudo equilibrium curve in Figure 13.

x 1 2 3 4 5 6 7

Sample A 0.34523 0.45745 0.54240 0.56410 0.61922 1.03144 0.63241

Sample B 0.39659 0.68167 0.52398 0.60820 0.71107 0.72701 0.74825

average 0.37091 0.56956 0.53319 0.58615 0.66514 0.87922 0.69033

std dev 0.03632 0.15855 0.01303 0.03118 0.06495 0.21526 0.08191

std error 0.02097 0.09154 0.00752 0.01800 0.03750 0.12428 0.04729

y 0 1 2 3 4 5 6

Plotting the points as per before we obtain the following McCabe Thiele graph. (See Figure 13.)
1.2

1 mole fraction ethanol in vapor

0.8 0.6 Equilibrium Line

0.4

0.2

Pseudo- Equilibrium Line

0 -0.2 -0.2 0 0.2 0.4 0.6 0.8 1 1.2

mole fraction ethanol in liquid

Figure 13: McCabe Thiele Diagram for 2.4kW (maximum power input). The equation of the 2 2 pseudo equilibrium curve is given by: y = - 0.352x + 1.556x with R =0.305. For this power input, we only took two samples from each tray at an approximate 7-minute time interval.

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Efficiency
We calculated the Murphree efficiency of each stage using the composition of the sample points and Equation 6. The technique described in Figure 4B was used for each of the three cases for all six stages. Our final evaluation of the efficiency of each stage at different power inputs is as follows in Table 5.
Table 5: Table of Murphree efficiency for each stage at different power inputs. This is our final evaluation of the efficiency of each stage at different power inputs is as follows in Table 3.

Stages

1 2 3 4 5 6

1.2 0.539 0.516 0.176 0.641 0.304 1.084

Power input (kW) 2.0 0.568 1.037 1.702 3.819 0.180 8.982

2.4 0.863 -0.328 0.388 0.795 3.871 -9.053

With the distillate composition and the still-pot composition, the number of equilibrium stages required was graphically determined from Figure 11 to 13. For instance, from Figure 11, we know that for the 1.2kW input we have 2 complete equilibrium stages and a 0.815 fraction appears at the end. Hence, the total number of equilibrium stages is calculated to be 2.815. Since we knew that the actual number of stages is six, using Equation 4, we calculated the overall efficiency of the column at each power input, Eo, to be 0.469. We carried out the same analysis for the other two cases. (See Table 6.)
Table 6: Table showing Eo values at different power inputs. This is our final evaluation of the overall efficiency of the column for different power inputs.

Power input (kW) 1.2 2.0 2.4

Equilibrium Stages 2.815 1.686 2.683

Actual Stages 6 6 6

Eo 0.469 0.281 0.447

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Discussion
Our analysis suggested that there is no apparent correlation between power input and the overall and tray efficiencies of the column. However, it must be noted that at 1.2kW, the column operates at the best overall efficiency compared to the other two power inputs.

Significance of efficiencies
With the understanding that the overall efficiency lumps together everything that happens in the column, we could better appreciate the results that we obtained from the experiment. The hydrodynamic flow properties such as viscosity and gas flow rate affect the flow regime in the column. The mass transfer rate, which is affected by the diffusivity, in turn affects efficiency.1 Hence, by finding out which power input had the best efficiency, we took into account the many different variables that affect the dynamics of the distillation unit. Moreover, the tray efficiency told us how each tray performed at different power inputs. A recurring pattern of low tray efficiency at a particular tray would have pointed out that something was faulty with the stage, possibly with the bubble caps or the downcomers. Ultimately, by carrying out this analysis of the column, our team wanted to point out which stages were faulty using stage efficiency data and also specify the best power input to run the column based on overall stage efficiency. We also sought to notice conditions, which caused flooding and weeping so that they can be avoided in the future.

Data Analysis
Tray 3 and tray 5 have been in general exhibiting lower tray efficiencies compared to other trays. For the 1.2 kW and 2.4 kW energy inputs, tray 3 has been exhibiting some of the lowest efficiencies. For the 1.2 kW and 2 kW energy input, tray 5 has been showing low tray efficiencies.

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From the overall efficiency data, we can see that the column exhibits best overall efficiency at the 1.2 kW energy input. However, the 2.4 kW energy input the Eo is only 4.7% smaller than that at the 1.2 kW energy input. It must be noted that the standard curve for the refractometeter proved to be reproducible and reliable. Moreover, these results also corresponded closely to literature values12. This meant that the ethanol compositions that we had obtained through the use of the refractometer were reliable. We also noticed flooding during sustained levels of very high power input at start up. The column should be closely monitored during and shortly after start up. The power input should be turned down or switched off completely when signs of vigorous bubbling are observed to avoid flooding. The results that we computed for the Murphree tray efficiencies do not follow a pattern as we had expected. Certain trays did not show a consistent pattern of performance, and the efficiencies continually varied for each tray for the different energy inputs. In some cases, unfeasible efficiencies were computed. For instance, an efficiency of -9.053 was calculated for tray 6 for the 2.4 kW energy input and some values were above 1. This was because we used the raw measured composition values from each tray (instead of using the pseudo-equilibrium curve) and compared it with the equilibrium data. Although this was done to present a representative analysis of the column, we had measured unfeasible composition values in many cases. Namely, we computed a Murphree vapor tray efficiency to be greater than 1 whenever the measured ethanol composition was greater than that of the equilibrium curve. Similarly, we found it difficult to compute an accurate overall efficiency because we had to fit the pseudo-equilibrium curve based on the measured ethanol composition data. Since, some of the measured data does not conform to the theoretical bounds of the system, it is difficult to rely on them to obtain accurate values of efficiency. We believe that the propagation of error in the readings of our samples was due to both systematic and random errors. During the dilution process, it was difficult to avoid vaporization of the sample during pipetting. Furthermore, 26

some of the sample could have also vaporized after we placed the sample in th refractometer and waited for the temperature to equilibrate to 25C. Vaporization of the volatile liquids would lead to unrepresentative and inaccurate values of composition. We determined that the column had reached steady state through the observation of the temperature from the thermocouples. During equilibrium, we expected the composition of the three samples at each power input to be fairly equal if the column had reached steady state. However, even after accounting for random errors, the composition varied largely between each of our three samples for the same energy input. This can be seen for the 2.0 kW energy input at the third tray. (See Table 4.) Between samples A, B and C the composition varied between 0.51286 and 0.62108 and 0.84421. The consistent occurrence of such a significant difference in many of the trays for the energy input suggests that the column had not reached steady state. Hence, using temperature fluctuations to gauge the onset of steady state was not entirely successful. There were also the possibility of random errors occurring due to RI differences due to temperature variation, vaporization of the sample within the Eppendorf tube upon collection and inaccuracies in pipettes that need to be accounted for in our findings. Hence, these errors have propagated in our final efficiency computations. Our team would have obtained more accurate data if we could observe and analyze the data before moving onto further sampling. For instance, we could have used the sample compositions to determine the onset of steady state instead of temperature fluctuations. We would have preferred to take more samples per power input and wait for a longer time for the column to reach steady state, but were constrained with a lack of time. We would have also liked to carry out the experiment at a more power inputs to see exactly if there is a correlation between column efficiency and power input.

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Conclusion and Recommendations

Our team aimed to evaluate the efficiencies of the unknown pilot distillation column. We were meant to analyze the column and provide WasteNot Chemicals with conditions to separate some valuable dyes from volatile component mixtures. Through the experiments with the column, our team could not conclusively specify the best power input necessary for such a distillation process. However, we were able to determine that adjusting the power input had a significant impact on the pseudo-equilibrium curve for the column, and that the efficiency of the column was definitely affected by the power input. To a certain degree, we were able to show that the most efficient power input was at 1.2kW, since that power input obtained a maximum Eo value of 0.469. Moreover, we also pointed out that trays 3 and 5 in the distillation column might have carried a problem as we observed from our computation of the Murphree vapor tray efficiency. We had also set up a viable framework for future experimentation on evaluating the performance of each tray in the distillation column. To move further with this goal and to completely understand the column, we recommend running the column at many different power inputs. Furthermore, running the column at different reflux ratios would give further information about the column and would help in the determination of the best reflux ratio for a distillation process. Ultimately, with further experiments on this column, we will be able to provide specific details on power input and tray performance critical in the separation of the dyes desired by WasteNot Chemicals.

28

Literature cited
1

Wankat, Phillip C. Separation process Engineering. Prentice Hall, 2007 Smith, J. M., and Ness H. C. Van. Introduction to Chemical Engineering

Thermodynamics. New York: McGraw-Hill, 1975. Print.

3

Enrico Fermi, Thermodynamics, 1956. Chang, Raymond Physical Chemistry for the Chemical and Biological Sciences,

2000
5

Figure reprinted from Chang, Raymond Phase Equilibria of Two-Component

Systems. Physical Chemistry for the Chemical and Biological Sciences, 2000, 226, Figure 7.14(a)
6

Kister, Henry Z. Distillation Design (1st ed.) McGraw-Hill. 1992 Emerson Process Management. "Distillation Column Flooding Diagnostics With

Intelligent Differential Pressure Transmitter." http://www.emersonprocess.com

8

reprinted from Wankat, Phillip C. "Efficiencies" Separation Process Engineering.

Prentice Hall, 2007, 134, Figure 4-27.

9

Walker, Jearl, Halliday/Resnick Fundamentals of Physics. 2009 Hanson lab techniques, Refractometry

10

<http://www2.ups.edu/faculty/hanson/labtechniques/refractometry/interpret.htm>
11

Jimnez Riobo, R.J. (Instituto de Ciencia de Materiales de Madrid (C.S.I.C.),

Campus de Cantoblanco, Madrid E-28049, Spain); Philipp, M.; Ramos, M.A.; Krger, J.K., European Physical Journal E, v 30, n 1, p 19-26, September 2009 29

12

Belda, R (Department of Thermodynamics, Faculty of Pharmacy, University of

Valencia, 46100 - Burjassot, Valencia, Spain); Herraez, J.V.; Diez, O. Source: Physics and Chemistry of Liquids, v 43, n 1, p 91-101, February 2005

30

Appendix A
Sample calculation to compute initial still concentration
To compute the initial still concentration, we followed the regime below. (See Table 7.) We start off with an excess mixture of weight fraction 0.1315 of ethanol. Note that in the calculation in Table 7, we use an approximation that the density of the mixture (983.035 g/L) can be used to determine the mass of Ethanol in the mixture.
Table 7

Mixture Volume (L) Density (g/L) Total Mass (g) Ethanol Mass Composition Ethanol Mass (g) Water Mass (g) Ethanol Mol Composition 12 983.035 11796.42 0.1315 1551.23 10245.19 0.055934

Pure Ethanol 0.875 788.08 689.57 1.0000 689.57 0 1

Final Mixture 12.875

0.1795 2240.80 10245.19 0.0788

Sample calculation to back calculate original composition

We obtain a sample and 0.5 ml of the sample is added to 1 ml of water to dilute it. We run the sample in the refractometer and obtain a RI value of 1.34895 at 25C. Using the standard curve, we obtain the weight fraction of ethanol to be 0.239. From Perrys Handbook, after interpolation between 23 and 24% mole fraction, we obtain the density of such a mixture at 25C to be 0.9597 g/ml. Density of water at the temperature is 0.9971 g/ml.

31

Thus, Total mass of diluted mixture Mass of water added = 1.5ml x 0.9597 g/ml = 1 ml x 0.9971 g/ml

Original weight fraction =

Hence, original weight fraction = 0.778

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Appendix B
Data from the Lab Notebook: RI at 1.2 kW
1.2kW Sample A 1 2 3 4 5 6 D Sample B 1 2 3 4 5 6 D Sample C 1 2 3 4 5 6 D Refractive Indicies Undiluted 1:3 Dilution 1.34563 1.35075 1.35432 1.35384 1.35645 1.34895 1.35645 1.35038 1.35631 1.34986 Refractive Indicies 1:2 Dilution 1:3 Dilution 1.35153 1.35448 1.35521 1.35582 1.35616 1.35042 1.34956 1.35150 Refractive Indicies 1:2 Dilution 1:3 Dilution 1.35165 1.35427 1.35543 1.35604 1.34942 1.34952 1.34961 Respective %wt ethanol Undiluted 1:3 Dilution 0.18604709 0.18604709 0.270733124 0.270733124 0.340286277 0.340286277 0.330245386 0.330245386 0.388293784 0.239322104 0.388293784 0.26410675 0.384938454 0.254947305 Respective %wt ethanol 1:2 Dilution 1:3 Dilution 0.285018975 0.343689908 0.35960623 0.373437229 0.381378387 0.264818651 0.249741001 0.284461217 Respective %wt ethanol Undiluted 1:3 Dilution 0.287256893 0.339228584 0.364535561 0.378555648 0.247330258 0.249051007 0.250604865

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RI at 2.0 kW
2.0 kW Sample A 1 2 3 4 5 6 D Sample B 1 2 3 4 5 6 D Sample C 1 2 3 4 5 6 D Refractive Index 1:3 Dilution 1.34543 1.34828 1.34811 1.35397 1.34928 1.34947 1.35172 Refractive Index 1:3 Dilution 1.34479 1.34753 1.34942 1.35003 1.35324 1.35056 1.34061 Refractive Index 1:3 Dilution 1.34551 1.34718 1.35135 1.34080 1.35212 1.35383 1.34971 Respective %wt ethanol 1:3 Dilution 0.183000741 0.228123192 0.225320507 0.332940278 0.244931277 0.248189879 0.28856748 Respective %wt ethanol 1:3 Dilution 0.173362664 0.215871397 0.247330258 0.257922553 0.318030911 0.267318764 0.114058963 Respective %wt ethanol 1:3 Dilution 0.184217273 0.210251033 0.281682631 0.116631986 0.296130939 0.330038822 0.252337191

RI at 2.4kW
Respective %wt ethanol 2.4kW Refractive Index Sample A 1:3 Dilution 1:3 Dilution 0.180424407 1 1.34526

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2 3 4 5 6 D Sample B 1 2 3 4 5 6 D

1.34730 1.34850 1.34877 1.34940 1.35247 1.34954 Refractive Index 1:3 Dilution 1.34627 1.35003 1.34826 1.34928 1.35030 1.35044 1.35062

0.212171261 0.231773182 0.236288933 0.246986831 0.302856542 0.249395883 Respective %wt ethanol 1:3 Dilution 0.195910219 0.257922553 0.227792667 0.244931277 0.262686141 0.265175002 0.268394307

100 90 80 70 Temperature (C) 60 50 40 30 20 10 0 0 50 100 150 200 250 Time (mins)

Pot 1 2 3 4 5 6 vapor

Graph showing Temperature change in different stages with respect to time.

35