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Table of Contents

1. Introduction.......................................................................................................... 1
2. Theory.................................................................................................................. 3
2.1. Determination of Vapor-Liquid Equilibrium Curve..........................................3
2.2. McCabe-Thiele (Graphical Method)................................................................5
2.3. Fenske Method............................................................................................... 8
2.4. Murphree Plate Efficiency.............................................................................. 9
2.5. Column (Overall) Efficiency..........................................................................13
3. Test Methods...................................................................................................... 14
3.1. Objectives.................................................................................................... 14
3.2. Assumptions and Expectations....................................................................14
3.2.1. Calibration............................................................................................. 14
3.2.2. Murphree Efficiency...............................................................................15
3.2.3. Fenske Equation.................................................................................... 15
3.2.4. McCabe-Thiele Method...........................................................................16
3.2.5. Overall Efficiency................................................................................... 17
3.2.6. Reflux Ratio........................................................................................... 17
3.2.7. Feed Location........................................................................................ 18
3.3. Apparatus.................................................................................................... 19
3.4. Procedure..................................................................................................... 23
4. Presentation and Discussion of Results..............................................................25
4.1. Batch Operation........................................................................................... 25
4.2. Continuous Operation.................................................................................. 31
5. Conclusions........................................................................................................ 34
6. Recommendations.............................................................................................. 35
7. References......................................................................................................... 36
8. Acknowledgements............................................................................................ 37
9. Nomenclature..................................................................................................... 38
10. Appendix......................................................................................................... 39
10.1. Sample Data............................................................................................. 39
10.2. Sample Calculations................................................................................. 46
10.3. Graphs and Tables...................................................................................... 5
FIGURE 1: BATCH DISTILLATION...................................................................................................... 1
FIGURE 2: CONTINUOUS DISTILLATION............................................................................................. 2
FIGURE 3: T-XY DIAGRAM.............................................................................................................. 5
FIGURE 4: MCCABE-THIELE GRAPH................................................................................................. 7
FIGURE 5: TEST APPARATUS......................................................................................................... 18
FIGURE 6: SCHEMATIC DIAGRAM OF ARMFIELD DISTILLATION COLUMNS.................................................19
FIGURE 7: DISTILLATE CONCENTRATION CHANGING AT UNSTEADY STATE BATCH OPERATING CONDITIONS....25
FIGURE 8: TEMPERATURE CHANGING WITH COMPOSITION GRAPH FOR BATCH 0.3 KW TRIAL....................28
FIGURE 9: TEMPERATURE CHANGING WITH COMPOSITION GRAPH FOR BATCH 0.4 KW TRIAL....................29
FIGURE 10: TRAY DIAGRAM......................................................................................................... 27
FIGURE 11: CALIBRATION CURVE FOR A REFRACTROMETER................................................................36
FIGURE 12: T-XY DIAGRAM FOR LITERATURE EQUILIBRIUM DATA.........................................................38
FIGURE 13: T-XY GRAPH INVERSED............................................................................................... 38
FIGURE 14: CONTINUOUS STEADY STATE P=0.4 KW FEED=MIDDLE R=2.3........................................55
FIGURE 15: 0.4 KW CONTINUOUS R=2.3 FEED=TOP TRIAL GRAPHICAL METHOD.................................59
FIGURE 16: 0.4 KW CONTINUOUS R=1.84 FEED=TOP TRIAL GRAPICAL METHOD................................57
FIGURE 17: 0.4 KW CONTINUOUS R=1.84 FEED=MIDDLE TRIAL GRAPICAL METHOD............................58
Y

TABLE 1: PRESSURE DROP CHANGING WITH BOIL-UP RATE................................................................22


TABLE 2: # OF THEORETICAL STAGES AND COLUMN EFFICIENCY VS BOIL-UP RATE.................................26
TABLE 3: MURPHREE TRAY EFFICIENCY..........................................................................................26
TABLE 4: EFFECT OF FEED LOCATION AND REFLUX RATIO ON PRODUCT...............................................29
TABLE 5: MURPHREE EFFICIENCY OF TRIAL 4..................................................................................29
TABLE 6: NUMBER OF STAGES FOR CONTINUOUS TRIALS...................................................................30
TABLE 7: REFRACTROMETER CALIBRATION DATA..............................................................................39
TABLE 14: ANTOINE COEFFICIENTS FOR MEOH-IPOH SYSTEM...........................................................37
TABLE 15: EQULIBRIUM DATA...................................................................................................... 37
TABLE 16: 0.3 KW BATCH TRIAL RAW DATA..................................................................................39
TABLE 17: BATCH 0.3 KW RAW DATA........................................................................................... 43
TABLE 18: BATCH 0.4 KW UNSTEADY STATE DATA..........................................................................40
TABLE 19: CONTINUOUS 0.4 KW TOP FEED R=2.3 RAW DATA.........................................................41
TABLE 20: CONTINUOUS 0.4 KW MIDDLE FEED R=2.3 RAW DATA....................................................41
TABLE 21: CONTINUOUS 0.4 KW TOP FEED R=1.84 RAW DATA.......................................................42
TABLE 22: CONTINUOUS 0.4 KW MIDDLE FEED R=1.84 RAW DATA..................................................42
TABLE 8: MCCABE-THIELE STEP COORDINATES................................................................................52
TABLE 9: 0.3 KW BATCH TRIAL FENSKE CALCULATIONS....................................................................52
TABLE 10:0.4 KW BATCH TRIAL FENSKE CALCULATIONS...................................................................53
TABLE 11: 0.3 KW BATCH MURPHREE PLATE EFFICIENCIES...............................................................56
TABLE 12: 0.4 KW BATCH MURPHREE PLATE EFFICIENCIES...............................................................56
TABLE 13: 0.4 KW CONTINUOUS R=2.3 FEED=MIDDLE TRIAL FENSKE CALCULATIONS..........................58
TABLE 14: 0.4 KW CONTINUOUS R=2.3 FEED=TOP TRIAL FENSKE CALCULATIONS...............................59
TABLE 15: 0.4 KW CONTINUOUS R=1.84 FEED=TOP TRIAL FENSKE CALCULATIONS.............................60
TABLE 16: 0.4 KW CONTINUOUS R=1.84 FEED=MIDDLE TRIAL FENSKE CALCULATIONS........................61
TABLE 17: 0.4 KW CONTINUOUS MURPHREE PLATE EFFICIENCIES (TRIAL 4).........................................62
1. Introduction
Distillation has been widely accepted for product separation, purification, and waste removal in chemical

process industries. It usually forms a key part of a chemical process, and is thus referred to as a unit

operation. In Canada, the oil sands use the columns extensively to produce different blends of products

for different clients. They are often the most or one of the most expensive components of any industrial

operation and can contribute to more than 50% of plant operating costs. The best way to reduce operation

cost is to improve their efficiency and operation via optimization and control. To achieve mentioned

improvements, thorough understanding of distillation principles and how distillation systems are designed

is essential. (Harris, 2013)

The distillation process can be performed in two ways:

Batch distillation: The mixture is added to the unit at the start of the distillation, distillate

fractions are taken out sequentially in time during the distillation, and the remaining bottoms

fraction is removed at the end. It is used in producing high-value and low-volume chemicals.

Moreover, it is also used in processes where small quantities of materials are to be handled in

irregularly or seasonally scheduled periods. It is implemented when the feed composition varies

widely from period to period or where completely different feed stocks have to be handled.

Potential applications include specialty chemical, biochemical, and pharmaceutical industries.


Figure 1: Batch Distillation
Continuous distillation: It is an ongoing separation in

which a mixture is continuously fed into the process and separated fractions are removed

continuously as output streams. In this way a stream of enriched methanol and a stream of

enriched isopropanol are obtained. Continuous distillation is used widely in the chemical process

industries where large quantities of liquids have to be distilled. Potential applications include

natural gas processing, petrochemical and bulk chemical industries.

Figure 2: Continuous Distillation

The Figures 1 and 2 shown above give a basic idea of Batch and Continuous Distillation. This experiment

deals with a methanol (MeOH) isopropanol (IPOH) mixture. Many topics, such as plate and column

efficiency, boil-up rate, reflux ratio, plate and column efficiencies, product purity, determination of

theoretical stages and reflux ratio will be explored, which makes it an excellent illustration of the

concepts covered in Staged Processes (ChE 3324).


2. Theory

2.1. Determination of Vapor-Liquid Equilibrium


Curve

The theoretical equilibrium model for MeOH-IPOH system at atmospheric pressure is determined

using Wilson and Antoine equations. The component 1 is MeOH and has boiling point of 64.7 C,

while component 2 is IPOH and has boiling point of 82.4 C. The activity coefficient of each

component is given by the following Wilson equations:

MeOH: ln 1 = - ln (R1) + x2(G12/R1 G12/R2) Equation 1: Wilson


Equation MeOH

IPOH: ln 2 = - ln (R2) + x1(G12/R1 G12/R2) Equation 2: Wilson


Equation IPOH

Where:

i =the activity coefficient. The activity coefficients theoretically account for the non-ideal

nature of the binary mixture.

xi = mole fraction of component i in the liquid phase

R1 = x1 + x2G12

R2 = x2 + x1G21

G12 and G21 are constants for this system with values of 1.689 and 0.5445 respectively.
The vapor composition is determined using Daltons and Raoults law. Equation 3 and 4 combine

Equations 1 and 2 as well as the activity coefficient in order to account for the ideal nature of the binary

mixture.

yiP = x1Pi*I Equation 3:


Daltons Law

P = P1*x11 + P2*x22 Equation 4:


Raoults Law

Where,

i = the mole fraction in the vapor phase

P = the total pressure

Pi* = the vapor pressure of i

xi = liquid mole fraction of component i

Vapor fractions of pure components are given as a function of temperature and given by the Antoine

equation. The Antoine equations for MeOH and IPOH with respective constants are as follows:

MeOH: log10 ( P1*) = 7.87863 1473.11/(T + 230.0) Equation 5: Antoine


Equation

IPOH: log10 ( P2*) = 6.66040 813.055/(T + 132.93) Equation 6: Antoine


Equition

Where:

P* = Vapor pressure (in mm Hg)

T = Temperature (in C)
By using the Wilson and Antoine equations shown above, a T-xy graph shown in Figure-3 was generated

and shown below. This model accounts for changing temperatures, but assumes constant pressure in every

tray and is not accurate. (Treybal)

Figure 3: T-xy Diagram

2.2. McCabe-Thiele (Graphical Method)

Graphical method is one of the most common calculation methods used for distillation columns. It

involves finding compositions and flows for the top (rectifying) and bottom (stripping) sections of the

column, and graphically determining the proper number of stages as well as the appropriate feed stage.

This graphical method is performed on a y-x (composition in vapor phase vs. composition in liquid phase)

equilibrium plot. The compositions of the distillate (x D) and bottoms (xB), are plotted on the graph, and

operating lines for the rectifying and stripping sections are derived from these conditions. The McCabe-

Thiele method can also be used when side-withdrawal is in use.

During batch distillation, the column in the laboratory operates at total reflux and the mass balance over
the column is:
L
y n= Equation 7: Batch Distillation
Vx n+1
Mass Balance

At steady state (constant temperatures), the molar liquid flow rate is equal to the molar vapor flow rate

everywhere in the column, so yn=xn+1. This should result in an operating line that is straight; co-incident

with the y=x line. Therefore, determining the theoretical number of plates is done by measuring the

steady-state compositions at the top and bottom of the column. For the purposes of this experiment,

MeOH is chosen as reference, Figure 3 summarizes the equilibrium data. (Geankoplis Christie John,

2003)

The equations used in McCabe-Thiele Method are as shown below.

q x
y= x f Equation 8: q-
q1 q1
line

Where:

heat required
heat
q= convert one mole of feed saturated vapor vaporize one mole of liquid saturated vapor

Equation 9: q value

x f = liquid mole fraction of feed

V b +1 x
Stripping Operating Line (SOL): y= x b Equation 10:
Vb Vb
SOL equation

Where:
V b= boil up ratio

x b =liquid mole fraction of bottom product

R x
Rectifying Operating Line: y= x d Equation 11:
R+1 R+1
ROL equation

Where:

R= reflux ratio

x d =liquid mole fraction of distillate product

The optimal feed tray is at the point where the q line, rectifying line, and stripping line meet. This pint is

called pinch point. This method is great for calculating the number of theoretical trays.

Equilibrium Curve
1.2
1
f(x) = - 0.67x^2 + 1.66x + 0.01
0.8 R = 1

y MeOH 0.6
0.4
0.2
0
0 0.2 0.4 0.6 0.8 1 1.2

x MeOH

Figure 4: McCabe-Thiele Graph


The basic McCabe-Thiele method assumes vapor-liquid equilibrium on each stage. Many chemical

engineers have invested major eorts in devising mechanical devices to promote the attainment of

equilibrium on the stage. However, this equilibrium is never obtained completely in practice and in many

situations the assumption of equilibrium is a poor one.

2.3. Fenske Method

The Fenske method (shortcut method) uses relative volatilities of MeOH and IPOH calculated from the

mole fraction of liquid and vapor at the first and last trays. It is used to calculate minimum number of

theoretical trays. The Fenske equation for theoretical number of stages is shown below in equation 5 and

6.

xD

N min =
(
ln
1x D
1x B

xB ) Equation 12:

ln avg
Fenske Equation

avg= T B Equation 13:

Average Volatility

Where:

Nmin = Minimum number of theoretical plates required at total reflux (including reboiler is plate)

xD = Distillate methanol mole fraction

xB = Bottom methanol mole fraction


avg = Average relative volatilities.

T = Relative volatility of more volatile component

B = Relative volatility of less volatile component

2.4. Murphree Plate Efficiency

The efficiency is introduced with the concept of Murphree plate efficiency. It is measure of the

efficiency of each individual tray. It can be calculated numerically by using the following equation:

y n y n1
M=
y n y n1 Equation 14:

Murphree Efficiency

Where:

yn vapor mole fraction for vapor leaving plate n

yn-1 vapor mole fraction for vapor leaving plate n-1

yn* vapor in equilibrium with liquid leaving plate n


2.5. Column (Overall) Efficiency

The overall plate efficiency for the column is found using the following formula:

Nt
0 ( ) = .100 Equation 15: Overall Efficiency
Na

Where:

Nt= number of theoretical (ideal) plates which can be calculated by different methods, ie. -Thiele

graphical analysis, Fenske equation etc.

Na = number of actual plates. Overall and Murphree efficiencies can be related by a simple

expression assuming linear selection involving phase equilibrium and uniform Murphree

efficiency across the column.


0 =
([
ln 1+ M ( mVL 1)])
Equation 16: Overall Efficiency using Murphree
mV
ln (
L )
Efficiency

Where:

m = slope of equilibrium line

3. Test Methods

3.1. Objectives

The objects of the experiment are:

To critically analyze experimental data during the experiment to verify expected trends and

validate assumptions.
To study the effects of different levels of heating to a batch and continuous distillation

operation.
To determine the theoretical and actual numbers of plates required for the column using

McCabe-Thiele Method and Fenske Method.


To calculate Murphree plate and overall efficiencies for the column under different heating

conditions.
To analyze factors that influence Murphree plate and column efficiencies.

3.2. Assumptions and Expectations

3.2.1. Calibration

The MeOH and IPOH used to form the calibration mixtures were 100% pure although the purest

sample of alcohol is slightly impure.


The composition of the alcohol or alcohol mixture to be measured did not change in composition

during testing. Small changes in composition would occur from exposure to atmospheric moisture

since both alcohols used are quite hygroscopic. Another variable affecting the composition of

alcohol sample is a change in composition due to the more rapid evaporation of the more volatile

component of the mixture when exposed to atmospheric conditions.

3.2.2. Murphree Efficiency

A key is assumption is that the Murphree Tray Efficiency (EM) is based on a semi-theoretical

models that assumes that the vapor between trays is well-mixed (uniform composition), that the

liquid in the down comers is well-mixed (uniform composition), and that the liquid on the tray is

well mixed and is of the same composition as the liquid in the down comer leaving the tray.
For an ideal tray, the vapor leaving is in equilibrium with the liquid leaving. This does not happen

in practice.
The binary Murphree efficiencies cannot be negative (although they can be greater than one).
Inclusion of the plate efficiencies lowers the equilibrium curve to the dashed line called Pseudo

Equilibrium Line. The steps in McCabe-Thiele method are ideally drawn between operating line

and Pseudo Equilibrium line.


In an ideal case for a binary system, the Murphree efficiency obtained for each component must

be the same.

3.2.3. Fenske Equation

This method is used to calculate minimum number of theoretical plates required at total reflux

(including the re-boiler plate).


The fist key assumption is that there might a wide gap between the volatilities of the heavies and

the lights. In such case there is a possibility for all the lights to be stored into one pseudo

component with the properties of the lights averaged on the basis of mole-fraction and then being

used as the light key. Similarly, all the heavies can be stored into a pseudo-component and then it

can be used as one heavy key.


The relative volatility of the light and the heavy keys is constant over the length of the column is

not that appropriate where the bubble point at the top of the column is quiet lower than that of the

bubble point which is in the bottom. So, it is not a reasonable approach to average the two values

of the alpha. In the so-called stabilizer columns after a flash drum the residual lights are purged

using the columns. It is quite evident through the difference in volatilities that the separation is

quite easy to acquire.

3.2.4. McCabe-Thiele Method

Both components have equal and constant molar enthalpies of vaporization (latent heats).quite

easy to acquire.
Sensible heat, CpT, is negligible compared to latent heat. Heat effects such as heat of solution

are negligible.
Column is insulated (no heat loss on each stage).
Column pressure is equal (thermodynamics can be done at a single pressure).
The molar heats of vaporization of the feed components are equal. If heats of solution and

transfer are considered, then all heats of solution calculations would need to be incorporated into

the McCabe-Thiele method.


For every mole of liquid vaporized, a mole of vapor is condensed. If it is not true, it means that a

chemical reaction is occurring due to activation energy being supplied (either thermally or some

other energy means). Possible chemical reaction would need to be calculated and added into the

equation for the McCabe-Thiele method.


Calculated number of steps is lower than actual number of steps.

3.2.5. Overall Efficiency

In an ideal case, the overall efficiency of the column is same as theoretical efficiency of the

column. Practically, the overall efficiency is less than theoretical efficiency.


It is predicted that the overall column efficiency would remain constant and then decrease with

increasing boil-up rate.

3.2.6. Reflux Ratio

An increase in reflux ratio would increase the concentration of MeOH in the top product and

simultaneously decrease the flow rate of top product. Increase in reflux ratio results in more

product being refluxed back to the column.


The most common way of improving the separation is to increase the reflux ratio. The use of

higher reflux ratio increases the pressure drop across the column and increases the re-boiler

temperature (using additional energy).


As top product as highest concentration of MeOH, refluxing it enriches the rising vapor in contact

by having mass and energy balance with falling liquid.


MeOH in falling liquid merges with vapor and thereby increases vapors concentration. Similarly

IPOH condenses from rising vapor and merges with liquid.


At reflux ratios below the minimum reflux ratios, there is lack of liquid flowing through the

column and column does not operate efficiently.


When designing columns, it is common to define the design reflux ratio as some multiple of the

theoretical minimum reflux. The cost optimum reflux ratio is typically in the 1.2 to 1.5 range

depending on energy costs, condenser coolant, and materials of construction. The rule of thumb

reported most often suggests that a reflux ratio of about 1.5 times the minimum is a good design

value. More reflux means higher re-boiler duty.


It may also be necessary to distinguish between returned reflux (the reflux stream flowing from

the accumulator to the column) and the effective reflux flowing down the column. This is a

concern if the reflux is sub-cooled. In this case, the effective reflux will consist of the returned

reflux plus whatever additional liquid is condensed when the cold liquid contacts vapor on the

reflux tray. It is probably best to use effective reflux in minimum reflux calculations.
At total reflux, we have high operating costs. At minimum reflux we have high capital costs. As

the reflux ratio increases, the number of trays and thus the capital cost of the column decreases.

3.2.7. Feed Location

The closer the feed tray is to the top of the column; higher is the concentration of light component

(MeOH) along with low temperature.


The closer the feed tray is to the bottom of the column; higher concentration of heavy component

(IPOH) along with higher temperatures.


The middle feed location is more efficient than top feed because adding liquid feed composition

of the top product will not have an enriching effect on the vapor rising in the upper trays.
3.3. Apparatus

The unit is a self-contained and fully instrumented distillation facility, suitable for practical laboratory

work relevant to the teaching of unit operations. The equipment employs galvanically isolated

intrinsically safe circuits and flameproof devices as appropriate, to enable safe distillation of standard test

binary mixtures such as methylcyclohexane-toluene, methyl alcohol-water, MeOH-IPOH etc.

The equipment consists of two interconnected units:

a. A floor standing Process Unit:


A 50mm diameter plate distillation column containing eight sieve plates and down comers.

Every plate includes a temperature sensor positioned to measure accurately the temperature

of the liquid on each plate. The sheaths of each plate temperature sensor are not more than 1.5

mm diameter, ensuring rapid dynamic response.


A 50mm packed column supplied as a separate item, but readily interchangeable with the

plate column by the user, for comparative studies of the two types of distillation column.
Electrically heated re-boiler of sufficient capacity for up to two hours of batch operation.

The re-boiler heater is protected against overheating and by a low level alarm.
An overhead condenser with cooling water flow measurement and adjustment.
A condensate collecting vessel, equipped with double overflow weirs and exit pipes to

enable separation of immiscible liquids.


A reflux return valve, solenoid operated, to provide for 0%-100% reflux, adjustable by

electrical signal.
A differential manometer connected to the top and bottom of the column, to monitor

column pressure drop.


A vacuum system with gauge to enable distillation studies at reduced pressures down to

200 mbar (abs).


Sampling points throughout the system for composition analyses.
Materials of construction for surfaces in contact with the process fluids are; glass,

stainless steel, PTFE or similar solvent-resistant materials.


Overall height of the process unit does not exceed 2.5 meters (8.2ft).
Lagging is provided, although it is possible to see at least one plate in operation with

distillation in progress.
Maximum operating temperature inside the column operation is at least 130 C.
Two 5 liter feed vessels, with rapid changeover to permit step changes in feed

composition to be made.
Peristaltic feed pump, range 0-0.25 liters/minute
Adjustable by voltage input variation to the pump motor controller.
Electrically heated re-boiler of sufficient capacity for one to two hours of batch operation,

but equipped with an internal overflow when continuous operation is required.


A bottoms product heat exchanger which may either be water cooled or used as a

(variable) feed pre-heater.


Alternative column feed points and the ability to vary the inlet feed temperature to the

column.
Dosing feed vessel, connected to the column for the continuous addition of a third liquid

component, which, together with the condensate phase separator vessel, enables the study

of azeotropic distillation.
b. Bench-mounted control console:
Monitoring and selectable display of at least 13 system temperatures, including those of

the liquid on each tray, the reboiler and across the condenser.
Monitoring, display and manual adjustment of:
The electrical power to the re-boiler heater.
The reflux ratio setting.
Figure 5: Test Apparatus
Figure 6: Schematic diagram of Armfield distillation columns

3.4. Procedure

The separation of MeOH from IPOH is performed using a distillation column with eight trays,

operating in a batch or continuous mode. Vapor and liquid samples are taken from each tray with

a syringe through the sample tray valves. The samples are cooled in small vials and

refractrometer readings are taken. A refractrometer calibration curve is created before running

the trials. Eleven solutions of methanol and isopropanol are mixed to simulate the mixture
composition at varying MeOH volume percentages. A refractrometer reading was taken for each

solution and the refractive index is plotted verses the molar percentage of MeOH. The trend line

equation is used to convert all the measured refractive indexes to mole percent; refer to Appendix

A for the calibration curve and data. (Wamsley, 2013)

In the Batch operation, to reach the steady state the total reflux is returned back to the column.

This changes the operation slope of both the enriching and stripping sections to match the ideal

y=x line. At steady state the theoretical number of stages, overall column efficiency and

individual tray efficiencies are calculated. To increase the boil-up rate, the column heat input is

increased. An additional trial is done to compare the steady to unsteady operation. Lastly, the

concentration of distillate is measured over time.

The pressure drop of the column is measured using a manometer 50-50 MeOH-IPOH solution.

Vapor flow rate controls the pressure drop in column. Trays are designed with sieve holes that

allow the vapor to flow up the column and contact the liquid sitting in the trays. The pressure

provided by vapor keeps the liquid from dropping through the sieve opening.

The procedure for continuous was similar to batch however the feed position and flow rates will

be altered with the intent of optimizing operation. The apparatus was setup in two configurations,

top or middle feed position. As necessary, in each feed mixture position, the reflux ratio was

varied from 1.2 to 1.5 times the minimum reflux ratio (R min) with re-boiler power supply of 4

KW set of all trials.


Following trials were taken:

Batch (Total Reflux); P=0.3 KW

Batch (Total Reflux); P=0.4 KW

Batch (Total Reflux); P=0.4 KW; Variation of distillate concentration with time

Continuous Steady State, P=0.4 KW;R=1.5Rmin=2.3;Feed:Middle

Continuous Steady State, P=0.4 KW;R=1.5Rmin=2.3;Feed:Top

Continuous Steady State, P=0.4 KW;R=1.2Rmin=1.84;Feed:Top

Continuous Steady State, P=0.4 KW;R=1.2Rmin=1.84;Feed:Middle

4. Presentation and Discussion of


Results

4.1. Batch Operation

The effects of boil-up rates and pressure drops were analyzed in the experiment. Theoretically, the

pressure drop was predicted to increase with the boil-up rate. Similar results are seen in Table 1 below
because liquid flows are normally very small in comparison to the vapor flows and thus the

resistance confronted by the vapor (measured in pressure drop) is very significant when the

vapor flow rate is increased beyond its design value. (Ni, 2012)

Table 1: Pressure Drop Changing with Boil-up Rate

Power Input Boil-up Rate Pressure Drop (kPa)

(kW) (ml/s)
0.3 0.1098 0.1161
0.4 0.1761 0.1316

The number of theoretic plates was found using the McCabe-Thiele and Fenske methods. Refer to

Appendix A and B for the coordinate data and sample calculation for the fraction proportion of the

step. The Fenske method uses the equation covered in the theory section to calculate the number of

theoretical stages. Table 2 below summarizes the theoretical number of stages and overall efficiency

of the boil-up rate changes. It was predicted that the overall column efficiency would remain constant

and then decrease with increasing boil-up rate. The McCabe-Thiele efficiency increased, while the

Fenske efficiency decreased. Further trials might need to be done to confirm the experimental trend.

The Fenske method follows the prediction closest by decreasing. Moreover, the Fenske method

includes one re-boiler plate and therefore actual number of stages is one less than theoretical number

of stages. As predicted, effective number of Fenske is lower than number of stages found by

McCabe-Thiele Method. Refer to Appendix B for sample calculations of the McCabe-Thiele and

Fenske methods.

Table 2: # of Theoretical Stages and Column Efficiency Vs Boil-up Rate

Power Input Boil-up Rate Number of Theoretical Stages Column Efficiency (%)

(kW) (mL/s) McCabe- Fenske McCabe- Fenske

Thiele Thiele
0.3 0.1098 3.409 4.043 42.61 50.53

0.4 0.1761 3.658 3.466 45.72 43.33

The efficiency of the individual plates was calculated using the Murphree equation introduced in the

theory section. Table 3 sows the calculated values changing with boil-up rate. Generally the individual

tray efficiencies correlate to the overall values found using McCabe-Thiele and Fenske methods.

Table 3: Murphree Tray Efficiency

Temperature (oC) Efficiency (%)


0.3 kW 0.4 kW 0.3 kW 0.4 kW
Plate
1 (Top) 65.4 65 -25.4 1442.4
2 65.3 65.1 33.3 -16.2
3 65.3 65.9 28.1 15.6
4 66.2 66 32.6 39.4
5 66.8 66.6 57.4 53.3
6 67.7 67.4 49.1 56.6
7 67.9 67.8 55.1 46.1
8 69.5 67.4

The results indicate that there is a trend towards increasing tray efficiency from the bottom to the top of

the column because the top column is exposed to concentrated liquid reflux flowing down the column. As

we move down the column, the liquid reflux becomes richer in IPOH.

The top 1 and 2 plates for the 0.3 kW and 0.4 kW trials respectively seem to be redundant because the

temperature is not changing and the efficiency values dont follow the general trend. As per predictions,

the Murphree efficiency cannot be negative and in most cases not above 1. The increase of boil-up rate

causes a decrease in number of the plates actually used in the separation. This irregularity is caused

because the reflux was returning to the column at temperatures below saturation temperature. For

safety reasons the total condenser was run with excess cooling water, which resulted in the liquid

being refluxed much below saturation temperature. The top tray was the tray most affected by
the below saturation temperature reflux flow from the total condenser above. Moreover, there

was less efficient mixing at the top tray, because it was the first tray to except the reflux flow

which in this case was not a steady stream but a cycling on-off flow. Flow over the trays

becomes more regular as liquid passes the first tray. Ideal mixing is an assumption for accurate

Murphree efficiency results.

This follows the prediction that number of theoretical plates decrease with the boil-up rate. All the batch

trials were done with total-reflux being returned to column, but normally there is a top product drawn off.

When the distillate is drawn off, the batch operating system becomes unsteady. To show the steady and

unsteady conditions data was gathered as column was transiting total reflux to unsteady state, shown in

Figure-7.

As predicted, the unsteady-state

operations will have a lower

distillate MeOH concentration. If

the trials were continued, the graph

would continue to drop until zero

MeOH was remaining in the

system and being produced in the


Figure 7: Distillate Concentration Changing at Unsteady
State Batch Operating Conditions distillate. (Perry H, 1999)

The experimental data was also compared to the literature equilibrium data using a T-xy graph, shown

below in Figure 8 and 9.

Figure 8: Temperature Changing with Composition Graph


for Batch 0.3 kW Trial
Figure 9: Temperature Changing with Composition Graph
for Batch 0.4 kW Trial

The 0.3 kW trial closely follows the literature data, but 0.4 kW has some variation. Generally, the vapor

curve is still above the liquid as in the equilibrium data. This was expected since no column or

sampling procedure is ideal. Vapor and liquid samples were not pure. The very nature of the

environment inside the distillation column obstructs obtaining pure samples since there are fine
liquid droplets or mist entrained or mixed in with the vapor above each tray. This is the major

reason behind data points being obtained between the theoretical bubble and dew point curves.

As expected, the column operation stays away from the ideal because of imperfect energy and

mass transfer caused due imperfect vapor-liquid mixing, non-ideal tray design and heat loss. The

column was insulated however there was heat loss due to outer surface cooling of the column

resulting in cooling of the vapor and liquid in contact with the inner surface through heat

transfer.

Distillation trays are designed best possible contact between the falling liquid and the rising

vapor, however perfect mixing is impossible to obtain even with the best designs. Sampling

location affects the accuracy of the results. As seen in the diagram below, the liquid flows

through a down comer from the tray above, across the tray and then down the opposite side

through another down comer. Vapor passes through the sieve tray through small perforations

creating a frothy mixture of vapor and liquid on the tray. (Perry H, 1999)

Figure 10: Tray Diagram


It is not until the liquid is leaving the tray that it is considered in equilibrium with the vapor

above the tray. The sampling ports on the Armfield distillation unit, used in the lab, are midway

between the two down comers. By careful liquid sampling where liquid flows off of each tray

and into the associated down comer greatest accuracy will be obtained.

4.2. Continuous Operation

The effects of feed location and reflux ratio on distillate and bottoms products were studied in this

experiment. The results of trials with varying feed location and reflux ratio is shown below in Table 4.

Table 4: Effect of Feed Location and Reflux Ratio on Product


As expected, the product purity increases with reflux ratio. An increase in reflux ratio has increased

the concentration of MeOH in the top product and simultaneously decreased the flow rate of top

product. Increase in reflux ratio resulted in more top product being refluxed back to the column. Since

a total condenser was used, top product composition was assumed to be the same as the composition

of the rising vapour above the top tray. The cost optimum reflux ratio is typically in the 1.2 to 1.5

range depending on energy costs, condenser coolant, and materials of construction. The results prove

that a reflux ratio of about 1.5 times the minimum reflux ratio is a good is appropriate for optimum

separation. (Seborg Dale, 2010)

It can be seen from the above table that as reflux ratio decreases there is a decrease in the

concentration of light component in the top product, as well as an increase in the concentration of

light component in the bottom product. This trend predictably shows that as reflux ratio decreases

below the minimum, product purity and percentage recovery are reduced as well. This is because for

efficient separation in a distillation column there must be counter current flow of liquid and vapour in

appropriately matched proportions and concentrations. Rising vapour interacts with the falling liquid

reflux and there is energy and mass transfer. If the energy and mass, which are both proportional to

the flow rates at a particular temperature, are not matched in correct proportion less than optimal

mass and energy transfer occurs in the column. Lastly, the cost optimum reflux ratio is typically in

the 1.2 to 1.5 range depending on energy costs, condenser coolant, and materials of construction. The

results prove that a reflux ratio of about 1.5 times the minimum reflux ratio is a good is appropriate

for optimum separation.

The efficiency of the individual plates was calculated using the Murphree equation introduced in the

theory section. Table 5 shows the calculated values changing with temperatures.

Table 5: Murphree Efficiency of Trial 4

Plate Temperature(in C) EM(%)


1 66 -3.04
2 66.4 51.5
3 66.6 28.6
4 68.3 66.82
5 70 46.86
6 70.3 66.64
7 70 41.29
8 70.6

The results indicate that there is a trend towards increasing tray efficiency from the bottom to the top of

the column because the top column is exposed to concentrated liquid reflux flowing down the column. As

we move down the column, the liquid reflux becomes richer in IPOH.

The top plate seems to be redundant because the temperature is not changing and the efficiency values

dont follow the general trend. As per predictions, the Murphree efficiency cannot be negative and in most

cases not above 1. This irregularity is caused because the reflux was returning to the column at

temperatures below saturation temperature. For safety reasons the total condenser was run with

excess cooling water, which resulted in the liquid being refluxed much below saturation

temperature. The top tray was the tray most affected by the below saturation temperature reflux

flow from the total condenser above. Moreover, there was less efficient mixing at the top tray,

because it was the first tray to except the reflux flow which in this case was not a steady stream

but a cycling on-off flow. Flow over the trays becomes more regular as liquid passes the first

tray. Ideal mixing is an assumption for accurate Murphree efficiency results. Murphree

efficiencies for trials were not calculated because only limited data points were collected due to

limited feed solution.

Table 6 summarizes the number of required stages for continuous trials calculated using

McCabe-Thiele and Fenske Method.

Table 6: Number of Stages for Continuous Trials

Trail No. McCabe-Thiele Stages Fenske Stages


4 (R=2.3,Middle) 12.30 5.70
5 (R=2.3, Top) 8.20 4.43
6 (1.84, Top) 4.02 2.73
7 (1.84, Middle) 4.39 2.86

As expected, the efficiency increases with increasing reflux ratio. Moreover, middle feed

location has better separation than top location. The reading for trial 4 derived using McCabe-

Thiele method is redundant because the theoretic number of stages are higher than actual number

of stages. This is not possible practically.

5. Conclusions
The pressure drop increased with boil up rate, likely because resistance confronted by the

vapor is very significant when the vapor flow rate is increased beyond its design value.
As expected, there is a decrease in theoretical number of stages with increasing boil-up

rate.
Steady state with total reflux has higher distillate MeOH concentration than unsteady

state. The concentration is predicted to decrease until no MeOH is left in the distillation

column.
Reflux ratio, boiler power input and feed location are key control variables for efficient

operation of distillation column.


Reflux ratio controls the purity and of the product. As reflux ratio decreases, there is a

decrease in the concentration of MeOH in the top product, as well as an increase in the

concentration of MeOH in the bottom product.


The product recovery is higher at higher reflux ratios. Proper reflux flow rate provides for

efficient mass and energy transfer between the vapor and liquid phases at each plate and

from the bottom to the top of the column.


A distillation column will always be close to equilibrium conditions, but never achieve it

due to imperfect mixing and non-ideal mass and energy transfer.


A middle feed tray location provides better performance than a top feed location.

6. Recommendations
No recommendations were requested.
7. References
Flick Ernest W. (1998). Industrial Solvent Handbook. New Jersey: Noyes Data
Corporation.

Geankoplis Christie John. (2003). Transport Process and Separation Process


Principles. New Jersey: Pearson.

Harris, A. (2013). Memorandum Report: Distillation Lab. Fredericton.

Hazazi, N. (2013). Memorandum Report: Distillation Lab. Fredericton.

McCabe W, T. E. (1925). Graphical Design of Fractionating Columns.

McCabe Warren L., S. J. (1993). Unit Operation in Chemical Engineering fifth.


Singapore: McGraw Hill.

Ni, Y. (2012). ChE 3314 Staged Processes Lecture Notes. Fredericton, Canada.

Perry H, R. G. (1999). Perry's Chemical Engineers Handbook. McGraw Hill.

Rhodes, M. (2008). Introduction to Particle Technology 2nd edition. West Sussex:


Wiley.

Seborg Dale. (2010). Continuous Distillation of a Binary Mixture. Santa Barbara:


Department of Chemical Engineering University of California.

Treybal, R. E. (n.d.). Mass Transfer Operations. McGraw Hill.

Wamsley, J. (2013). Memorandum Report: Distillation Lab. Fredericton.

Wiki. (2013, April 20). McCabe Theile method. Retrieved November 2, 2103, from
Wikipedia: http://en.wikipedia.org/wiki/McCabe%E2%80%93Thiele_method
8. Acknowledgements

The distillation experiment leading to this report would not have been successfully completed

without proper guidance of Professor Collins as well as teaching assistants Ms. Leila Behroozi

and Mr. Rogan Swift. The experiment and report were completed with untiring help of group

members Jenna Wamsley, Mr. Alexander Harris and Mr. Naif Hazazi. They worked diligently in

the lab and also prepared the preliminary calculation reports used to prepare this formal report. It

was a pleasure working with all of them.


9. Nomenclature
- Activity coefficient

M - Muphree efficiency

o - Overall efficiency

IPOH - Isopropyl Alcohol

L - Liquid

MeOH - Methanol

Nmin - Minimum number of plates

Nr - Actual number of plates

Nt - Theoretical number of plates

R - Reflux Ratio

Rmin - Minimum Reflux Ration

T -Temperature

VB - Boil up ratio

V -Vapor
xA -Mole fraction of MeOH in the liquid phase

xb -Liquid mole fraction of bottom product

xd - Liquid mole fraction of distillate product

xf - Liquid mole fraction of feed

y*A - Mole fraction of MeOH in vapor in equilibrium with liquid

yA - Mole fraction of methanol in the vapur phase

- Relative volatility

10. Appendix
10.1. Sample Data

Refractrometer Calibration Data and Curve

Table 7: Refractrometer Calibration Data

V V Vol % Mass Moles Mole% Refracti


(MeO (IPOH) ve
H) Index
ml Ml MeOH MeOH IPOH MeOH IPOH MeOH
0 10 0 0 7.86 0 0.1307 0 1.3736
82
1 9 10 0.7918 7.074 0.0247 0.1177 17.348 1.3711
05 04 03
2 8 20 1.5836 6.288 0.0494 0.1046 32.077 1.3656
1 26 13
3 7 30 2.3754 5.502 0.0741 0.0915 44.738 1.3612
15 47 72
4 6 40 3.1672 4.716 0.0988 0.0784 55.739 1.3561
21 69 58
5 5 50 3.959 3.93 0.1235 0.0653 65.386 1.3512
26 91 33
6 4 60 4.7508 3.144 0.1482 0.0523 73.914 1.3469
31 13 51
7 3 70 5.5426 2.358 0.1729 0.0392 81.507 1.3414
36 35 99
8 2 80 6.3344 1.572 0.1976 0.0261 88.312 1.3366
41 56 47
9 1 90 7.1262 0.786 0.2223 0.0130 94.444 1.3316
46 78 84
10 0 100 7.918 0 0.2470 0 100 1.3279
51

Figure 11: Calibration Curve for a Refractrometer Table 8: Antoine


Coefficients for MeOH-IPOH System

For Total Pressure P = 760 Torr (1 atm)


Antoine Equation Coefficients
Compound A B C G12 G21
7.878 1473. 0.544
Methanol 63 11 230 1.689 5
6.660 813.0 132.
2-propanol 4 55 93
Table 9: Equlibrium Data
Figure 12: T-xy Diagram for Literature Equilibrium Data
T-xy Graph Inversed
1.2

1
f(x) = 0x^2 - 0.12x
- 0x^2 + 6.89
+ 0.21x - 4.94
R = 1
0.8 Liquid
Polynomial (Liquid)
Mole Fraction of MeOH 0.6
Vapor
Polynomial (Vapor)
0.4

0.2

0
60 65 70 75 80 85

Temperature (in C)

Figure 13: T-xy Graph Inversed


Table 10: 0.3 kW Batch Trial Raw Data
Table 11: Batch 0.3 kW Raw Data

Table 12: Batch 0.4 kW Unsteady State Data


Table 13: Continuous 0.4 kW Top Feed R=2.3 Raw Data

Table 14: Continuous 0.4 kW Middle Feed R=2.3 Raw Data


Table 15: Continuous 0.4 kW Top Feed R=1.84 Raw Data

Table 16: Continuous 0.4 kW Middle Feed R=1.84 Raw Data


10.2. Sample Calculations
10.3. Graphs and Tables
Batch Trials

McCabe-Thiele Method Step Coordinates and Fenske Calculation

Table 17: McCabe-Thiele Step Coordinates

0.3 KW (Trial 1) 0.4 KW (Trial 2)


X Y x y
(xD,yD 0.959 0.959 0.963 0.963

)
(x1,yD) 0.91 0.959 0.917 0.962
(x1,y1) 0.91 0.91 0.917 0.917
(x2,y1) 0.813 0.91 0.825 0.917
(x2,y2) 0.813 0.813 0.825 0.825
(x3,y2) 0.667 0.813 0.681 0.824
(x3,y3) 0.667 0.667 0.681 0.681
***Estimated xB (Liquid Bottom Plate) = 0.753 *** Estimated xB (Liquid Bottom Plate) = 0.730

Table 18: 0.3 kW Batch Trial Fenske Calculations

0.3 Mole Fraction (Relative (Average) Number of Stages


Vapor Liquid
kW Volatility)
Tray 1 0.9662 0.939 1.575 1.6544 4.0427
Tray 8 0.8591 0.7709 1.7379
xD 0.9589
xB 0.753

Table 19:0.4 kW Batch Trial Fenske Calculations

0.4 Mole Fraction (Relative (Average) Number of Stages


Vapor Liquid
kW Volatility)
Tray 1 0.9537 0.9025 1.9061 1.9219 3.4633
Tray 8 0.8577 0.7481 1.9378
xD 0.963
xB 0.7302

Murphree Plate Efficiency

Table 20: 0.3 kW Batch Murphree Plate Efficiencies

Plate Temperature(in C) yn xn yn* EM(%)


1 65.4 0.9485 0.9212 0.9638 -25.37
2 65.3 0.9516 0.926 0.9658 33.34
3 65.3 0.9445 0.9059 0.9573 28.14
4 66.2 0.9394 0.907 0.9577 32.58
5 66.8 0.9306 0.8858 0.9482 57.39
6 67.7 0.907 0.8587 0.935 49.15
7 67.9 0.8799 0.8343 0.9169 51.11
8 69.5 0.08413 0.753 0.8753
Table 21: 0.4 kW Batch Murphree Plate Efficiencies

Plate Temperature(in C) yn xn yn* EM(%)


1 65 0.936 0.8847 0.9476 1442.4
2 65.1 0.9485 0.9523 0.9762 -16.18
3 65.9 0.9523 0.9445 0.9732 15.62
4 66 0.9485 0.9306 0.9677 39.37
5 66.6 0.936 0.9048 0.9568 53.35
6 67.4 0.9122 0.8664 0.9388 56.57
7 67.8 0.8775 0.8329 0.9215 46.07
8 67.4 0.8399 0.7302 0.8592

Continuous Trials

McCabe-Thiele Method Step Coordinates and Fenske Calculation

Continuous Steady State (P=0.4 kW)


Trial 4 Trial 5 Trial 6 Trial 7
Middle, R=2.3 Top, R=2.3 Top, R=1.84 Middle, R=1.84
X y X y x y x y
(xD,yD) 0.9386 0.9386 0.9589 0.9589 0.8953 0.8953 0.8842 0.8842
(x1,yD) 0.8659 0.9386 0.9097 0.9589 0.8556 0.8187 0.8456 0.8280
(x1,y1) 0.8659 0.8659 0.9097 0.9097 0.8556 0.8187 0.8456 0.8280
(x2,y1) 0.7402 0.8659 0.8115 0.9097 0.7402 0.7215 0.7512 0.7225
(x2,y2) 0.7402 0.7402 0.8115 0.8115 0.7402 0.7215 0.7512 0.7225
(x3,y2) 0.5773 0.7402 0.6639 0.8115 0.5773 0.5692 0.5783 0.5672
(x3,y3) 0.5773 0.5774 0.6639 0.6639 0.5773 0.5692 0.5783 0.5672
(x4,y3) 0.4131 0.5774 0.4959 0.6639 0.4231 0.4959 0.4231 0.4989
(x4,y4) 0.4131 0.4131 0.4959 0.4959 0.4231 0.4959 0.4231 0.4989
(x5,y4) 0.3423 0.4131 0.3423 0.4959 0.3428 0.3123 0.3421 0.3143
(x5,y5) 0.3423 0.3423 0.3423 0.3123 0.3428 0.3123 0.3421 0.3143
Figure 14: Continuous Steady State P=0.4 kW Feed=Middle R=2.3

Table 22: 0.4 kW Continuous R=2.3 Feed=Middle Trial Fenske Calculations

0.4 Mole Fraction (Relative (Average) Number of Stages


Vapor Liquid
kW Volatility)
Tray 1 0.9493 0.9350 1.30 1.70 5.70
Tray 8 0.8243 0.6797 2.21
xD 0.9563
xB 0.5197
Figure 15: 0.4 kW Continuous R=2.3 Feed=Top Trial Graphical Method

Table 23: 0.4 kW Continuous R=2.3 Feed=Top Trial Fenske Calculations

0.4 Mole Fraction (Relative (Average) Number of Stages


Vapor Liquid
kW Volatility)
Tray 1 0.8041 0.6995 1.76 1.81 4.43
Tray 8 0.8072 0.6936 1.85
xD 0.9589
xB 0.6298
Figure 16: 0.4 kW Continuous R=1.84 Feed=Top Trial Grapical Method

Table 24: 0.4 kW Continuous R=1.84 Feed=Top Trial Fenske Calculations

0.4 Mole Fraction (Relative (Average) Number of Stages


Vapor Liquid
kW Volatility)
Tray 1 0.8421 0.7187 2.09 1.99 2.73
Tray 8 0.8088 0.6896 1.90
xD 0.8953
xB 0.5649
Figure 17: 0.4 kW Continuous R=1.84 Feed=Middle Trial Grapical Method

Table 25: 0.4 kW Continuous R=1.84 Feed=Middle Trial Fenske Calculations

0.4 Mole Fraction (Relative (Average) Number of Stages


Vapor Liquid
kW Volatility)
Tray 1 0.9036 0.8659 1.45 1.81 2.86
Tray 8 0.8057 0.6468 2.26
xD 0.8842
xB 0.5810

Table 26: 0.4 kW Continuous Murphree Plate Efficiencies (Trial 4)

Plate Temperature(in C) yn xn yn* EM(%)


1 66 0.9315 0.9172 0.9622 -3.04
2 66.4 0.9324 0.9016 0.9554 51.5
3 66.6 0.908 0.8587 0.935 28.6
4 68.3 0.8972 0.8343 0.9223 66.82
5 70 0.8467 0.7374 0.864 46.86
6 70.3 0.8315 0.7007 0.8387 66.64
7 70 0.87 0.6912 0.8318 41.29
8 70.6 0.8064 0.6618 0.8098

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