STUDENT CONFERENCE

April 28th 2018, Pune, India.

SIMULATION AND ANALYSIS OF EFFECT OF REFLUX RATIO ON DISTILLATE AND RESIDUE

COMPOSITION IN A DISTILLATION COLUMN
Ashwin Acharya, Amit Tiwari, Narendra Gavali, Tanushree Bhattacharjee*
Chemical Engineering Department, Vishwakarma Institute of Technology, Pune, India.
E-mail Address: ashwin.r.acharya@gmail.com, amit.tiwari15@vit.edu,
narendra.gavali15@vit.edu, shreetanu123@gmail.com*

Abstract

Distillation columns have traditionally been simulated using a sequential simulation approach.
Modelling and simulating distillation columns are important enterprises. The models used for
distillation columns vary from the simple to the quite complex, depending on the nature of
assumptions.

This paper attempts to establish relationships between the effects reflux ratio and the amounts
of high key and low key components of multi-component system in distillate and residue. The
simulation is carried out with different values of reflux ratio, typically a product of Rm
(minimum reflux ratio) and a constant such that the constant ranges from 1.5-2.5, using ASPEN
PLUS. By inserting the Actual stages and the feed stage, we get the optimum desired result for
our multi-component system.

Introduction

We intend to do a process design for the synthesis of n-butanol on industrial scale. Guerbet
reaction is used for the industrial production of n-butanol.

Figure 1: Mechanism of Guerbet reaction

This reaction produces side products: 2-ethylhexanol, 2-ethylbutanol, n-hexanol, n-octanol and
water. Also unconverted ethanol is present in the process stream. Thus this stream needs to be
further treated upon so as to obtain pure n-butanol as product and ethanol to be fed back for
recycle.

Separation Processes plays a vital and major role in every chemical industry. Among various
separation process, distillation is most important and most energy intensive process for
chemical and petroleum industries. Distillation column is used for about 95% of liquid
separation and energy use from this process accounts for about 3% of worlds energy
consumption. To address this issue, new distillation structures have been considered and are
more energy efficient.

Process Description:-

The Project is based on Process designed for the production of N-butanol from Ethanol using
catalysts and pressurized hydrogen. The project aim is to design the profitable process for the
production of butanol by converting it from ethanol through Guerbet reactions with the aid of
catalyst. It involves various equipments and section which work on different pressure and
temperature conditions. More importantly it involves large process.

The process is divided into four key sections:

The first section (100) includes the reaction portion of the process, in which ethanol from
storage tank and a recycle stream are combined and react in the presence of Hydrogen to form
butanol and water.

In the second section (200), temperature and pressure changes are utilized to remove hydrogen
and recycle it back to the reactor.

Section three (300) uses a distillation column to separate the product butanol, with small
amounts of heavier alcohols, from the unreacted ethanol and the water byproduct.

Finally, this primarily water-ethanol system is separated in section four (400) using ethylene
glycol as an entrainer in order to purge water and recycle almost pure ethanol to the reactor.

Figure 3.1: Process Summary

This research paper is based on simulation and analysis of effect of reflux ratio on distillate and
residue composition in distillate column in section 300. Because the 300 distillate column used
to separate the product, mostly butanol with some ethanol butanol, ethyl hexanol, hexanol, and
octanol, from the water and some unreacted ethanol. Therefore, distillate column of section 300
is well simulate in ASPEN which are as follows:-

*Material and energy balance has been done for this process and the same has been reported in the
project report.

ASPEN Simulation

All the feed parameters, like composition, reflux ratio, number of stages, feed stage, temperature
and pressure conditions, etc., were provided to the simulator and results duly studied. We
found the minimum reflux ratio value and then varied the reflux ratio as the product of
minimum reflux and a constant which varied between 1.5 to 2.5.

Light key component is ethanol, heavy key component is n-butanol, light non key component is
water while heavy non-key component are 2-ethylhexanol, 2-ethylbutanol, n-octanol, n-hexanol,
ethylene glycol.

Figure 2: Schematic of Distillation column

*B2-Distillation column, S6-Feed, S7-Distillate, S8-Residue

Total feed: 1353.2587 kmol

xf Fxf (kmol)
Water 0.112246 151.8979
Ethanol 0.782914 1059.485
butanol 0.09991 135.2041
hydrogen 0 0
 2-
ethylhexanol 0.000952 1.288302
2-
ethylbutanol 0.001549 2.096198
n-hexanol 0.001213 1.641503
n-Octanol 0.001213 1.641503
ethylene
Glycol 0.00000196 0.002652
Total 0.99999896 1353.257
Table 1: Feed Composition

Minimum Reflux Ratio 0.190401

Theoretical stages 12
Feed stage 4
Stage Efficiency 60%
Actual stages 20
Actual Feed Stage 7
Temperature 30oC
Pressure 1.378 bar
Table 2: Simulation Parameters

These inputs were provided to the simulator, so the distillate and the residue composition and
enthalpy were obtained as result.

Reflux ratio:-

It is the ratio of flow rate of liquid has returned to the distillation column from the reflux drum
to the flow rate of the amount of distillate is removed.

R = L/D

Where, R is reflux ratio, L is liquid flow rate, D is flow rate of distillate.

Minimum Reflux Ratio:-

If the reflux ratio is reduced the slope of the operating line is reduced and the number of stages
required achieving for separation. Further reduction will increases infinite number of stages
because the slope line will become closer to operating line. This case is called a minimum reflux
ratio.

Rectifying or Enriching section:-

In this section of the column above the feed point, the concentration of the more volatile is
larger than in the feed. This means that the vapour is enriched or ‘purified’ by discarding the
less volatile component into the downflowing liquid. So the section of the column above the feed
tray is called rectifying or enriching section.

Total material balance: V = L + D

Component balance: V*y = L*x + D*xD

Energy balance: V*Hv = L*HL + D*HD

 Here, V and L are vapour and liquid flow rate in rectifying section, HV and HL are enthalpy of
vapour and liquid stream respectively. XD = mole fraction of mole volatile component in the
distillate and y and x are the mole fraction in vapour and liquid streams.

Following are the simulation results for rectifying section

Reflux Water Ethanol Butanol 2-ethyl 2-ethyl hexanol Octanol ethylene

Ratio hexanol butanol glycol
0.285602 151.8983 1052.13 7.348422 1.81E-05 0.00147563 0.000367 1.78E-06 5.78E-11
0.304642 151.8983 1052.917 6.561962 1.42E-05 0.00117385 0.00029 1.39E-06 4.36E-11
0.323682 151.8983 1053.62 5.859601 1.13E-05 0.000946666 0.000232 1.11E-06 3.35E-11
0.342722 151.8983 1054.244 5.23546 9.19E-06 0.000773066 0.000188 8.93E-07 2.61E-11
0.361762 151.8983 1054.797 4.682673 7.55E-06 0.000638524 0.000155 7.30E-07 2.08E-11
0.380802 151.8983 1055.285 4.194478 6.27E-06 0.000532945 0.000129 6.05E-07 1.67E-11
0.399842 151.8983 1055.716 3.76395 5.27E-06 0.000449099 0.000108 5.06E-07 1.36E-11
0.418882 151.8983 1056.095 3.384761 4.47E-06 0.000381846 9.17E-05 4.28E-07 1.13E-11
0.437922 151.8983 1057.036 2.44433 2.77E-06 0.000238613 5.69E-05 2.63E-07 6.51E-12
0.456962 151.8983 1056.725 2.755412 3.29E-06 0.000282492 6.75E-05 3.13E-07 7.91E-12
0.476003 151.8983 1056.985 2.495181 2.85E-06 0.000245575 5.86E-05 2.71E-07 6.73E-12
Table 3: Composition of distillate stream

Ethanol (kmol) Butanol (kmol)

1058 8
1057
1056 6
1055
Ethanol 4 Butanol
1054
(kmol) (kmol)
1053 2
1052
1051 0
0 0.2 0.4 0.6 0 0.2 0.4 0.6

Graph 1: Variation of ethanol w.r.t. Graph 2: Variation of butanol w.r.t.

reflux ratio variation reflux ratio variation
0.0016
0.0014
0.0012
n-hexanol
0.001
n-octanol
0.0008
2-ethylheaxanol
0.0006
2-ethylbutanol
0.0004
ethylene glycol
0.0002
0
0 0.1 0.2 0.3 0.4 0.5

Graph 3: Variation of other components w.r.t. reflux ratio variation

Reflux Ratio Enthalpy

(Cal/mol)
0.285602 -64896.8
0.304642 -64890.9
0.323682 -64885.7
0.342722 -64881
0.361762 -64876.8
0.380802 -64873.2
0.399842 -64869.9
0.418882 -64867.1
0.437922 -64860
0.456962 -64862.4
0.476003 -64860.4
Table 4: Enthalpy variation with respect to Reflux ratio

Enthalpy (Cal/mol)
-64855
-64860 0 0.1 0.2 0.3 0.4 0.5

-64865
-64870
-64875
Enthalpy (Cal/mol)
-64880
-64885
-64890
-64895
-64900

Graph 4: Variation of Enthalpy of distillate w.r.t. reflux ratio variation

 Stripping Section:-

In this section of the column below the feed tray , the more volatile component is removed or
stripped out of the liquid (by process of counterdiffusion, of course) to get a relatively pure
volatile component at the bottom. So this section is called the stripping section.

Total material balance: L’ = V’ +W

Component A balance: L’*x = V’*y + W*xw

Energy Balance: L’* H’L = V’*H’V + W*Hw

Here, L’ and V’ are the liquid and the vapour flow rate in stripping section respectively, H’L and
H’V are enthalpy of liquid and vapour respectively.

Following are the simulation results for stripping section

water Ethanol Butanol 2-ethyl 2-ethyl hexanol Octanol ethylene

Hexanol butanol glycol
0.285602 4.16E-05 7.358186 127.8561 1.285582 2.094728 1.641141 1.641506 0.0026524
0.304642 3.66E-05 6.571347 128.6425 1.285585 2.09503 1.641218 1.641506 0.0026524
0.323682 3.23E-05 5.868703 129.3449 1.285588 2.095257 1.641276 1.641507 0.0026524
0.342722 2.85E-05 5.244345 129.969 1.28559 2.095431 1.641319 1.641507 0.0026524
0.361762 2.52E-05 4.691392 130.5218 1.285592 2.095566 1.641353 1.641507 0.0026524
0.380802 2.24E-05 4.203067 131.01 1.285593 2.095671 1.641379 1.641507 0.0026524
0.399842 1.99E-05 3.772435 131.4405 1.285594 2.095755 1.6414 1.641507 0.0026524
0.418882 1.77E-05 3.393164 131.8197 1.285595 2.095822 1.641416 1.641507 0.0026524
0.437922 1.25E-05 2.452558 132.7602 1.285597 2.095965 1.641451 1.641508 0.0026524
0.456962 1.42E-05 2.763694 132.4491 1.285596 2.095922 1.64144 1.641507 0.0026524
0.476003 1.28E-05 2.503418 132.7093 1.285597 2.095959 1.641449 1.641508 0.0026524
Table 5: Composition of Residue Stream

Ethanol (kmol) Butanol (kmol)

8 134
6 132
4 Ethanol 130 Butanol
2 (kmol) 128 (kmol)

0 126
0 0.2 0.4 0.6 0 0.2 0.4 0.6

Graph 5: Variation of ethanol w.r.t. Graph 6: Variation of butanol w.r.t.

reflux ratio variation reflux ratio variation
2.5

2
n-hexanol
1.5 n-octanol
2-ethylhexanol
1
2-ethylbutanol
0.5 ethylene glycol

0
0 0.1 0.2 0.3 0.4 0.5

Graph 7: Variation of other components w.r.t. reflux ratio variation

Reflux Ratio Enthalpy

(Cal/mol)
0.285602 -73139.4
0.304642 -73171.8
0.323682 -73200.4
0.342722 -73225.6
0.361762 -73247.7
0.380802 -73267.1
0.399842 -73284
0.418882 -73298.9
0.437922 -73335.2
0.456962 -73323.2
0.476003 -73333.3
Table 6: Enthalpy variation with reflux ratio

Enthalpy (Cal/mol)
-73100
0 0.1 0.2 0.3 0.4 0.5
-73150

-73200
Enthalpy (Cal/mol)
-73250

-73300

-73350

Graph 8: Variation of enthalpy of residue w.r.t reflux ratio

Conclusion:-

 As the reflux ratio increases, in rectifying section the water composition remains
constant, while ethanol composition sharply increases and butanol composition
decreases, at the same time, composition of 2-ethylbutanol and hexanol also decreases.
There is no change in composition of remaining component.
 For same effect of increasing reflux ratio, in stripping section the water composition
decreases with small amount, ethanol composition decreases and the butanol
composition increases, while the composition of other component remains same.
 The enthalpy of rectifying section increases with increase in reflux ration, while for
stripping section its decreases for all components in multi-component system.

Acknowledgement

The project was supported by Dr. Tanushree Bhatcharjee, Dr. Gaytri Gawande. We thank our
guide Dr. Tanushree Bhatcharjee who provided insight and expertise that greatly assisted the
research, their pearls of wisdom with us during the course of research led us to make the great
project.

References

 Shawna Downing, Catherine Haak, Nader Jouzy & Kyle Sarnataro, Process Design for the
Production of N-Butanol from Ethanol, Department of Chemical & Biomolecular
Engineering,4-2014,University of Pennsylvania.
 Sabra Hanspal, The Guerbet Coupling of Ethanol into Butanol over Calcium
Hydroxyapatite Catalysts, University of Virginia.
 R.K.Sinnott, Coulson & Richardson’s Chemical Engineering Design,vol.6,Ed.3,Chemical
Engineering
 Robert E. Treybal, Mass transfer Operations
 B. Bhatt & S.B.Thakur, Stoichiometry,Ed.5
 B.K.Datta, Principles of Mass Transfer and Separation Processes
 https://webbook.nist.gov
 https://www.bnl.gov/magnets/staff/gupta/cryogenic-data-handbook/Section3.pdf