Geoffrey Widdison

1656 Sunnyside Avenue

Salt Lake City, Utah, 84105
Dr. Terry Ring
Department of Chemical Engineering
University of Utah
Salt Lake City, Utah, 84102

Dear Dr. Ring,

On October 18, 2005, you assigned the members of project group E the task of
operating the distillation column located in the MEB Senior Lab. We were asked to use
the column to separate a water-isopropanol mixture under conditions of total reflux, as
well as under continuous feed with a reflux ratio of twice the minimum. We were asked
to determine the efficiency of each tray, and to make recommendations for the operation
of the column.
We determined that measured efficiency rates within the column varied widely
within the column and from one set of operating conditions to another. The minimum
reflux ratio was found to be 1.11. The average efficiency of the column was found to be
approximately 31.1% under total reflux conditions and 23.84% with a reflux ratio twice
the minimum. The values of individual trays, however, ranged from near 100% to
approximately 1%. While this may be partly due to defects and variation within the
column, it seems important to reexamine the methods used to measure composition at
each tray.
The lack of a vapor sampling port on each tray inhibited the data range we were
able to gather, installation of additional vapor ports could increase the accuracy of models
developed for the separation process. Syringes that form better connections with the
liquid sampling ports could also facilitate the testing process.
Examination of the separation data leads us to conclude that the ninth tray is at or
near the optimal feed location for most operating conditions, though additional testing
may be desired to confirm this. The range of conditions we used are near to those used to
separate a number of mixtures. The information on tray and column efficiency, and the
related information concerning column capacity and flow rates make it possible for a
wide variety of separations to be modeled, the reaction of this specific column to be
predicted.

Sincerely,

Geoffrey Widdison
OPERATION OF A BUBBLE-CAP CONTINUOUS DISTILLATION COLUMN

By
Geoffrey Widdison

Project No. 2M

Projects Laboratory I

Assigned: October 18, 2005

Due: November 15, 2005

Submitted: November 16, 2005

Project Team Members for Group E:

Brandon Grimm

Stanley Holbrook

Geoffrey Widdison

Geoffrey Widdison

2
 INTRODUCTION

According to Seader (1998), distillation processes are a major component of

chemical processing with a great deal of scientific and economic significance. A large

amount of industrial distillation takes place in staged columns. Each stage consists of a

tray designed to contact rising vapor with descending liquid, which increases the vapor

composition of the more volatile component. This process allows the separation of a

wide variety of mixtures into separate species.

The relationship between the configuration of a distillation column and the degree

of separation achieved can be predicted using a combination of theoretical and

empirically derived models. Since complete equilibrium is rarely achieved in any stage

in distillation processes, experimental data must be gathered in order to determine the

efficiency of the column.

By collecting and analyzing samples from different stages, the efficiency of the

distillation operation can be calculated. These calculations can be used to confirm the

mathematical model for the distillation operation, and modify it for the specific

equipment being used.

3
 THEORY

The mathematical basis for staged distillation columns is well established and

presented in a number of texts. The following treatment is adapted from Seaders (1998).

The separation dynamics are most heavily dependent on the vapor pressures of the

species in the column. The more volatile component is also known as the light key, the

less volatile component is also known as the heavy key. For a two-component

separation:

α=KL/KH. (1)

KL= PL/P. (2)

KH= PH/P. (3)

All symbols are defined in the nomenclature section at the end of the text. By Raoult’s

law, this means that relative volatility can be described in terms of mole fractions in the

liquid and vapor phases.

yL / x y L (1  x L )
  L
 . (4)
yH / x H x L (1  y L )

This can be rearranged to give

(xL)
y  . (5)
L
1  x L (  1)

The traditional approach to modeling distillation processes is known as the McCabe-

Thiele approach. This model requires making the following assumptions:

¨ That the relative volatility is constant over the temperature range in the column.

¨ That the components have equal and constant molar enthalpy.

¨ That enthalpy changes and heat of mixing are negligible.

¨ That the pressure is uniform within the column.

4
 These assumptions allow equations to be derived relating flow rates to molar

compositions in each stage of the column. The column is divided into a stripping section,

in which the more volatile component is selectively driven into the vapor phase, and the

rectification section, in which the less volatile component is selectively condensed. In

each section, the liquid and vapor compositions can be related to flow rates.

Rectification section:

Vn+1yn+1=Lnxn+DxD. (6)

yn+1=(Ln/ Vn+1)+(D/ Vn+1) xD. (7)

Where the stages are numbered consecutively, beginning with the top stage.

L/V=R/(R+1). (8)

 R   1 
yn   x   x . (9)
 R  1 n  R  1 D

Stripping section:

yn=(Ln/Vn)xn-(Bn/Vn)xB. (10)

VB=V/B (11)

L V  B V  1
  B . (12)
V V VB

VB  1  1 
yn    xn   x . (13)
 VB  VB  B

Given equilibrium data for the components of the distillation, these equations can

be used to model the stages graphically, as shown in Figure 1.

5
 Figure 1. Sample McCabe-Thiele diagram. Each step indicates a theoretical stage
going to complete equilibrium. The calculations are shown for the rectification
section only. Reprinted from Seader (1998).

Because true vapor-liquid equilibrium is unlikely to be achieved on each stage,

this method must be adapted in order to properly model the distillation system. A widely

used method for this is known as Murphree Efficiency.

 y n  y n 1 
E    , (14)
M V
 y n *  y n 1 

where y* used in this equation is derived from experimentally measured liquid-

phase composition values. The Murphree Efficiency can be used to alter the equilibrium

line in the Mcabe-Thiele graph. This adapted graph can be used to more accurately

predict the separation under different conditions of feed composition and reflux ratios.

6
 APPARATUS AND PROCEDURE

The primary piece of equipment used was the distillation column located in the

Merrill Engineering Building on the University of Utah campus. The top of the column,

control system and condenser were located in room 3290 on the third floor. The column

extended directly downward to the second floor, where the reboiler and bottoms storage

tank were located. The feed tank and pump, as well as the distillate storage tank were

located on the first floor, directly below the column.

The distillation column contained 12 bubble cap trays spaced at 11” intervals. The

trays were numbered in descending order, with the top tray designated tray 1. Each tray

had a diameter of approximately 14” and contained 18 bubble-caps. The bubble-caps

were 3” in diameter with square openings. The total column height was 145”. A full

schematic can be found in Appendix C.

Figure 2. Illustration of a bubble cap. Reprinted from Seader (1998)

7
 The column design allowed for variation in the feed point, but for the purposes of

our experiments it remained stationary above tray 9. T-type thermocouples were

positioned inside each tray with digital readouts to the control computer. Each tray was

equipped with a sample port for the liquid phase. Sample ports for the vapor phase were

located on even-number trays only. Additional sample ports were available to sample

liquid from the feed, distillate and bottoms. Orifice plate meters equipped with digital

pressure gauges were used to measure flow rate of the feed, reflux, distillate and bottoms.

A computer equipped with Opto 22 control software was used to alter valve

positions to control feed, distillate and reflux flow rates, as well as the flow of steam to

the reboiler, and the flow of cooling water to the condenser. The software also received

and reported data from the thermocouples and flow meters.

Composition analysis was done with two pieces of equipment. A Mettler/Par

DMA46 densitometer (SN: 451038) was used to calculate sample densities. A Reichert-

Jung ABBE Mark II digital refractometer (SN: 10952-9) was used to measure refractive

indices of samples. Assuming binary mixtures at every point, these measurements allow

the composition to be calculated. The correlations between densitometer and

refractometer data and composition were developed by creating and testing standards

with known volumetric compositions. These compositions were then converted to mole

fractions. For details, see Appendix A.

The column was first operated at total reflux. The pump was used to mix the

feed, then a sample of the feed was taken prior to distillation. Approximately 17.5

gallons of feedstock was introduced into the column, and then the valve was closed and

the pump shut down. The steam flow valve was opened until the steam flow rate was

0.456 kg/min, which required manual adjustment of the valves. The flow rate of the

8
cooling water was set at 50% of capacity using the computer control system, which

corresponded to a flow-meter reading of 136.8 kg/min. The temperature profile within

the column was monitored until the temperatures stabilized. When the temperatures no

longer changed significantly, the column was assumed to be at steady state.

A syringe with a plastic connection hose was used to extract a liquid sample from

each the top six trays. A glass syringe with a stainless steel needle was used to sample

the vapor from trays 2, 4 and 6. Samples of the distillate and bottoms were also taken.

All of these samples were saved and tested for refractive index. The samples with

sufficient volume to allow a densitometer reading were tested for density as well. Once

the samples were taken, the steam was shut down, and valves were opened to drain the

bottoms, the distillate, and any remaining fluid in the column into the feed tank. Once

the column had cooled below 70°C, the cooling fluid was shut off, and the valves were

closed.

Due to time constraints, only the top six trays were tested in this fashion on the

first distillation run. The column was subsequently started and brought to steady state

using the same procedure previously described, with a new sample of the feed taken

before running the column. Once the column was at steady state, liquid samples were

taken from trays 6 through 12, as well as the distillate and bottoms. Vapor samples were

taken from trays 8, 10 and 12. As before, all of these samples were tested for refractive

index, and as many as had sufficient volume were tested for density. The column was

shut down as previously described.

The feedstock analysis allowed the calculation of inlet composition. This

composition was used to graphically determine the minimum reflux ratio for a distillate

product of 60 mol% isopropanol. Given this data, it was calculated that 69% of the

9
distillate needed to be recycled for the column to run at twice the minimum reflux (see

Appendix D). The column was once again brought to steady state using the previously

described process. Once steady state was reached, the feed pump was turned on and the

valve was opened until the flow-meter reported a flow rate of 4.4 kg/min. The bottoms

valve on the column was immediately opened to release fluid at a similar flow rate, and

the reflux settings were changed to recycle 69% of the distillate.

Rotameters which reported the flow rates of the feed and the bottoms were

monitored and valves were adjusted to maintain a similar flow rate from each.

Additionally, the fluid level in the reboiler was observed, and any significant changes

were compensated for by adjustment of the flow rates of the feed and the bottoms.

As in previous experiments, the temperature profile of the column was watched.

When the profile no longer changed significantly, the column was assumed to be at

steady state. Liquid samples were taken from each tray, and vapor samples were taken

from the even numbered trays, using the methods previously mentioned. The samples

were tested for refractive index and density, and the compositions of the vapor and liquid

at each tested point was calculated.

Using known vapor-liquid equilibrium data for water-isopropanol systems and the

experimental data, the efficiency of each tray was estimated. These efficiencies, which

reflect the specific characteristics of the column, could then be used to predict the

behavior of other distillation systems run on the same equipment.

10
 RESULTS AND DISCUSSION

The calculated mole fraction in each tray was as follows:

Table 1: Liquid and vapor compositions from the first run of the distillation column
under conditions of total reflux. Given in mole fractions of isopropanol in water.
Calculated from density and refractive index data.
Tray Liquid Composition Vapor Composition
1 0.55±0.015
2 0.42±0.015 0.45±0.015
3 0.33±0.015
4 Error 0.41±0.015
5 0.33±0.015
6 0.04±0.015 0.39±0.015
7 0.00±0.015
Feed 0.027±0.015

Table 2: Liquid and vapor compositions from the second run of the distillation column
under conditions of total reflux. Given in mole fractions of isopropanol in water.
Calculated from density and refractive index data.
Tray Liquid Composition Vapor Composition
6 0.496±0.015 0.612±0.015
7 0.383±0.015
8 0.374±0.015 0.524±0.015
9 0.091±0.015
10 0.027±0.015 0.505±0.015
11 0.016±0.015
12 0.020±0.015 0.103±0.015
Bottoms 0.014±0.015
Feed 0.027±0.015

11
Table 3: Liquid and vapor compositions from the distillation column with a reflux ratio
of 2.22. Given in mole fractions of isopropanol in water. Calculated from density and
refractive index data.
Tray Liquid Vapor
Composition Composition
1 Error
2 0.603±0.015 0.225±0.015
3 0.573±0.015
4 0.549±0.015 0.232±0.015
5 0.504±0.015
6 0.450±0.015 0.160±0.015
7 0.028±0.015
8 0.026±0.015 0.121±0.015
9 0.025±0.015
10 0.022±0.015 0.092±0.015
11 0.020±0.015
12 0.018±0.015 0.070±0.015
Feed 0.023±0.015
Bottoms 0.017±0.015

The error points indicate samples that became tainted or otherwise inaccurate due

to mistakes in the sampling or handling process. Further experimentation is necessary to

determine the steady-state compositions at these points. Because the distillate (the liquid

from tray 1) was improperly sampled, and because the composition at tray 2 is near the

isopropanol-water azeotrope, it is assumed that the distillate for the partial reflux

operation is near the composition of the tray 2 liquid.

Because vapor samples could not be taken from every tray, the Murphree vapor

efficiency for each tray could not be calculated. Therefore, the liquid composition at

each point was used, with published vapor-liquid equilibrium data (Perry’s, 1999) to

create a McCabe-Thiele graph for the process. From this graph, efficiency for each tray

was be estimated.

12
Figure 3: Representation of liquid composition on trays 1 through 6 of the
distillation column at conditions of total reflux, plotted against graph of
vapor-liquid equilibria for the isopropanol-water system.

Figure 4: Representation of liquid composition on trays 7 through 10 of

the distillation column at conditions of total reflux, plotted against graph
of vapor-liquid equilibria for the isopropanol-water system.

13
Figure 5: Representation of liquid composition on trays 9 through 12 of the
distillation column at conditions of total reflux, plotted against a partial graph of
vapor-liquid equilibria for the isopropanol-water system.

Figure 6: Representation of liquid composition on trays 1 through 7 of the

distillation column with a reflux ratio of 2.22, plotted against a partial graph of
vapor-liquid equilibria for the isopropanol-water system.

14
 Figure 7: Representation of liquid composition on trays 7 through 10 of the
distillation column with a reflux ratio of 2.22, plotted against a partial graph of
vapor-liquid equilibria for the isopropanol-water system.

The efficiency of each stage under each set of conditions can be approximated

graphically using an inverse lever-arm technique. A perpendicular line connecting the

operating line to the equilibrium line is drawn for each step. The length of the line below

the step divided by the length of the line overall is taken to be the stage efficiency. Since

these are estimates, it is difficult to quantify the error margins.

Table 4: Efficiency of each distillation column tray under conditions of total and partial
reflux. Values were estimated graphically.
Tray Total Reflux Partial Reflux
1 20.00% -
2 30.40% 50.00%
3 5.76% 40.00%
4 - 38.90%
5 78.60% 27.30%
6 53.80% 100.00%
7 8.69% 1.00%
8 61.53% 1.00%
9 45.70% 1.00%
10 18.20% 1.00%
11 5.10% 1.00%
12 14.30% 1.00%

15
 There is a clear trend toward a heightened efficiency in trays 5 and 6 as compared

to the other trays. Under the partial reflux regime, most of the separation takes place in

tray 6. Under partial reflux, it is also evident that very little separation occurs on trays 7

through 12. Further testing is necessary to determine whether these phenomena occur

consistently in this column.

There is a clear difference in plate efficiencies between conditions of partial and

total reflux. While the precise reasons for this are unknown, the liquid and vapor flow

rates in each plate were notably lower than for the partial reflux conditions. It appears

that the differences in flow effect the performance of certain trays. This is a reasonable

conclusion, particularly if the flow rates are significantly below those assumed in the

column design.

16
 CONCLUSIONS AND RECOMMENDATIONS

The data gathered suggests that most of the separation processes are occurring on

a few trays, with the rest displaying little performance. An additional testing regime to

gather data over a wider variety of operating conditions may be of use.

Sample extraction proved to be a very challenging aspect of the experiment.

However, the process was much simpler under continuous feed conditions. Thus it is

likely that the difficulties experiences earlier where the result of too little fluid in the

column. Increasing the amount of feed used for total reflux from 17.5 gallons to 25

gallons might alleviate this problem considerably. It should be noted that, when

gathering samples from taps on the feed tank, tops line or bottoms line, the taps should be

purged before taking a sample. Failure to do so is a possible cause of errors in our data.

As was mentioned, additional testing is necessary to confirm the results gathering

in this experimental regime. Future tests could be facilitated by the installation of vapor

sampling ports on the odd-numbered trays. This would allow the Murphree vapor

efficiency of each tray to be calculated directly.

Preliminary data suggests that some of the trays, particularly trays 3 and 4 may be

operating at significantly lower than expected efficiency. If further experiments confirm

this conclusion, it may become necessary to inspect these trays for defects, damage or

signs of wear.

The end compositions show that a reasonable separation of the species in the feed

stock was effected. However, data concerning the steps within the process are not

consistent with what one would expect from the theory. Experimental data and defects

within the equipment are both potential causes of this inconsistency, and both should be

addressed in order to ensure accuracy in modeling this process.

17
 REFERENCES

Seader, J.D., Henley; Ernest J., Separation Process Principles, John Wiley & Sons,
Danvers, MA, p 359-387. (1998)

Perry, Robert H.; Green, Don W.Perry’s Chemical Engineer’s Handbook, McGraw-Hill
Professional, New York, NY. (1997)

18
 NOMENCLATURE

Symbol Definition Units

α Relative volatility
B Bottoms Flow Rate l/min
D Distillate Flow Rate l/min
EMV Murphree Vapor Efficiency
KH Fractional Pressure of Heavy Key
KL Fractional Pressure of Light Key
L Total Liquid Flow Rate in Column mol/min
Ln Liquid Flow Rate in Stage n mol/min
P Total Pressure in Column psi
PH Partial Pressure of Heavy Key psi
PL Partial Pressure of Light Key psi
R Recycle Ratio
RI Refractive Index
T Period of Vibration as Read by a Densitometer
V Total Vapor Flow Rate in Column mol/min
VB Boilup Ratio
Vn Vapor Flow Rate in Stage n mol/min
xB Mole Fraction of Light Key in Bottoms Product
xD Mole Fraction of Light Key in Distillate
xH Mole Fraction of Heavy Key in Liquid Phase
xL Mole Fraction of Light Key in Liquid Phase
yH Mole Fraction of Heavy Key in Vapor Phase
yL Mole Fraction of Light Key in Vapor Phase
y*n Equilibrium Mole Fraction of Light Key in Vapor
at Stage n, Based on Measured Liquid Composition

19
 APPENDIX A
Full Data

The standardization curves were developed from the following data.

Refractive Index
Composition (%) Run1 Run2 Run3 AVG (vol STDEV Mole % (IPA)
%)
0 1.3330 1.3327 1.3326 1.3328 0.0002 0.0000
10 1.3408 1.3401 1.3409 1.3406 0.0004 0.0255
20 1.3472 1.3477 1.3480 1.3476 0.0004 0.0557
30 1.3543 1.3541 1.3548 1.3544 0.0004 0.0918
40 1.3605 1.3608 1.3608 1.3607 0.0002 0.1359
50 1.3641 1.3649 1.3648 1.3646 0.0004 0.1909
60 1.3684 1.3691 1.3687 1.3687 0.0004 0.2614
70 1.3721 1.3723 1.3721 1.3722 0.0001 0.3550
80 1.3747 1.3747 1.3751 1.3748 0.0002 0.4855
90 1.3767 1.3763 1.3763 1.3764 0.0002 0.6798
100 1.3767 1.3764 1.3764 1.3765 0.0002 1.0000

Density
Composition (vol%) T1 T2 T3 Ave St Dev Density (IPA) Mole % (IPA)
0 5.7023 5.7024 5.7023 5.7023 0.0001 0.9980 0.0000
10 5.6839 5.6840 5.6859 5.6846 0.0011 0.9837 0.0255
20 5.6712 5.6712 5.6716 5.6713 0.0002 0.9731 0.0557
30 5.6533 5.6533 5.6535 5.6534 0.0001 0.9587 0.0918
40 5.6287 5.6286 5.6258 5.6277 0.0016 0.9383 0.1359
50 5.6018 5.6016 5.6020 5.6018 0.0002 0.9178 0.1909
60 5.5723 5.5722 5.5711 5.5719 0.0007 0.8942 0.2614
70 5.5405 5.5403 5.5359 5.5389 0.0026 0.8683 0.3550
80 5.5054 5.5047 5.5058 5.5053 0.0006 0.8421 0.4855
90 5.4702 5.4702 5.4698 5.4701 0.0002 0.8148 0.6798
100 5.4270 5.4271 5.4270 5.4270 0.0001 0.7817 1.0000

From these data sets, empirical correlations were found to relate instrument
measurements to composition

Refractive Index:

xL =(RI110.47)*(10-15.617)

Densitometer:

xL = -101.92*T3+291.13*T2-279.46*T+90.244

20
 Refractive Index vs Mol% IPA

1.3800 1.0500
1.3750
1.0000
1.3700
1.3650
Refractive Index

0.9500
1.3600
RI
1.3550 0.9000
Densitometer
1.3500
0.8500
1.3450
1.3400
0.8000
1.3350
1.3300 0.7500
0.0000 0.2000 0.4000 0.6000 0.8000 1.0000
Mol% IPA

Figure A1. Refractive indices and densities of standard mixtures of isopropanol and
water, plotted against mole fraction of isopropanol.

These correlations were then used to determine the composition of samples taken
from the distillation column.

21
Continuous Feed Conditions

Table A1. Densitometer periods and refractive indices for liquid and vapor samples taken
from the distillation column operating with a reflux ratio of 2.22.
Tray RI of Liquid RI of Vapor Period of Liquid Period of Vapor
1 5.5643
5.5643
5.5639
2 5.4860 5.4798
5.4860 5.4798
5.4859 5.4796
3 5.4923
5.4923
5.4922
4 5.4974 5.4893
5.4972 5.4893
5.4971 5.4892
5 5.5072
5.5072
5.5072
6 5.5198 5.5559
5.5197 5.5558
5.5197 5.5558
7 1.3412
1.3409
1.3408
8 1.3404 1.3417
1.3405 1.3415
1.3403 1.3416
9 1.3403
1.3401
1.3400
10 1.3393 1.3407
1.3395 1.3406
1.3392 1.3404
11 1.3388
1.3390
1.3391
12 1.3384 1.3401
1.3384 1.3400
1.3383 1.3400
Bottoms 1.3374
1.3377
1.3375
Feed 1.3397
1.3396
1.3395

22
Total Reflux Conditions

Table A2. Refractive indices for liquid and vapor samples taken from the distillation
column operating operating at total reflux.
Tray RI of Liquid RI of Vapor
1 1.3752
1.3751
1.3756
2 1.3740 1.3744
1.3734 1.3748
1.3739 1.3750
3 1.3716
1.3712
1.3715
4 1.3640 1.3735
1.3640 1.3736
1.3641 1.3736
5 1.3723
1.3704
1.3712
6 1.3433 1.3727
1.3445 1.3728
1.3424 1.3732
7 1.3332
1.3339
1.3339

Table A3. Refractive indices for liquid and vapor samples taken from the distillation
column operating operating at total reflux.
Tray RI of Liquid RI of Vapor
6 1.3760 1.3759
1.3760 1.3760
1.3761 1.3758
7 1.3729
1.3729
1.3727
8 1.3725 1.3750
1.3724 1.3751
1.3727 1.3752
9 1.3553
1.3549
1.3549
10 1.3402 1.3751
1.3401 1.3747
1.3400 1.3748
11 1.3340
1.3341
1.3343
12 1.3364 1.3564
1.3372 1.3564
1.3368 1.3553

23
 APPENDIX B

Error calculations

The standard deviation for the refractometer was 0.0004. Since the highest

refractive index used in this testing regime is 1.375, we can calculate the margin of error

as

ΔxL =(1.3750110.47)*(10-15.617)-( 1.3754110.47)*(10-15.617)=0.015.

This is the margin of error for all compositions determined by refractometry.

24
 APPENDIX C
Equipment Schematics

Figure A1. Schematic of the distillation column used in this experiment.

25
 APPENDIX D
Calculations

The calculations for minimum reflux are based upon the graphical “pinch point”

analysis, as developed in Seader (1998). The feed stock was calculated to be 2.7 mol%

isopropanol, and this was assumed to be a saturated liquid, therefore, a vertical line

connected this point to the equilibrium line. The distillation point was assumed to be 60

mol% isopropanol, this point on the equilibrium line was identified. The line drawn

between these two points indicates a rectification section with an infinite number of steps.

Thus:

R m in
S lo p e  . (A1)
R m in  1

S lo p e
R  . (A2)
m in
1  S lo p e

The slope was measured to be 0.525.

0 .5 2 5
R m in   1 .1 0 . (A3)
0 .4 7 5

Therefore, twice the minimum reflux ratio is 2*1.10=2.20.

L L
2 .2 0   . (A4)
D 1  L

2 .2 0
L   0 .6 9 .
1  2 .2 0
(A5)

Thus, the reflux valves must be set to recycle 69% of the distillate in order to produce a

reflux ratio of twice the minimum.

26