PROJECT INTERNSHIP REPORT

CHALLENGES ASSOCIATED WITH

SEPARATION OF HCl-WATER AZEOTROPE
IN COPPER CHLORINE
THERMOCHEMICAL HYDROGEN
GENERATION CYCLE
(A CASE STUDY)

24th July 2015

SUBMITTED BY,
MOHAMMED FAYAZUDDIN.
1

Project Internship Report

On

CHALLENGES ASSOCIATED WITH SEPARATION OF HCl-WATER

AZEOTROPE IN COPPER - CHLORINE THERMOCHEMICAL
HYDROGEN GENERATION CYCLE - A CASE STUDY

by

Mohammed Fayazuddin
B.Tech 3rd year (Chemical Engineering),
Rajiv Gandhi Institute of Petroleum Technology,
Rae Bareli (July 2015)

Under the supervision of

Dr. D Parvatalu,
Project manager, Hydrogen project,
OEC, panvel.

In fulfilment of requirement of project intern for 3rd year B.Tech in Chemical engineering at
RGIPT,
Raebareli(U.P)

CERTIFICATE
I hereby certify that the project internship report titled Challenges Associated with
Separation of HCl - Water Azeotrope in Copper-Chlorine Thermochemical Hydrogen
Generation Cycle A Case Study has been carried out successful by him in the ONGC
Energy Centre, Panvel. Mr. Mohammed Fayazuddin has worked on this topic as Summer
Internship trainee under my guidance from 18th May 2015 to 24th July 2015.

Signature

Research Supervisor : Dr. D. Parvatalu, Project Manager, Hydrogen Project, OEC, Panvel
Affiliation

: ONGC ENERGY CENTRE, Panvel, Maharashtra, India.

Date

Acknowledgement
It has been an immense pleasure and truly enriching experience doing my vocational training
at ONGC Energy Center, Panvel, Navi Mumbai in their Hydrogen Project.
I would first like to thank Dr. B. Bhargava, Director General, ONGC Energy Centre, Mr. C.
Tandi, ED-HOI-IEOT, Panvel and Mr. Puneet Kishore, GM(P) - Head-TRU, OEC for
allowing me to pursue my summer training at OEC, Panvel. I take this opportunity with
much pleasure to thank all the people who have helped me through the course of my journey
as an intern
I take this opportunity to express my profound gratitude and deep regards to my guide and
mentor Dr. D. Parvatalu Project Manager, Hydrogen project, OEC, Panvel for his exemplary
guidance, monitoring and constant encouragement throughout the course of this thesis. He
has been the driving force behind the completion of this project. I express my gratitude to Dr.
S. Banerjee for his valuable guidance and technical advice during the course of my work.
I would like to express my gratitude to Mrs. Bina Prasad, Head ASU, OEC for giving me this
opportunity to undertake this summer internship.
I would like to thank Ms. Kamini Sivakumar, Sr. Project Fellow, OEC, Panvel for her
assistance. I would like to thank OEC for this opportunity to work with them and giving me
a first-hand experience of separation techniques and software applications involved in
Hydrogen production through thermochemical cycles.

INDEX
1.0 INTRODUCTION

2.0 OBJECTIVE

3.0 APPROACH

4.0

MAJOR SEPARATION ISSUES RELATED TO CU-Cl CYCLE

5.0

SEPARATION TECHNIQUES FOR AZEOTROPE MIXTURE

6.0 RESIDUE /DISTILLATION CURVE ANALYSIS OF SYSTEMS FORMING

AZEOTROPE
7.0 SEPARATION OF H2(g)/HCl(g) GASEOUS MIXTURE
8.0

PRESSURE SWING DISTILLATION

9.0

SIMULATIONS CARRIED OUT TO DETERMINE PHASE BEHAVIOUR

9
14
15

AND AZEOTROPIC COMPOSITION OF HCL-WATER

16

10.0 SIMULATIONS CARRIED OUT TO DETERMINE PHASE BEHAVIOUR

AND AZEOTROPIC COMPOSITION OF HCL-WATER

17

10.1 CASE STUDY 1 : APPLICATION OF PRESSURE SWING

DISTILLATION TO HCL WATER SYSTEM

17

10.2 CASE STUDY-2 : SIMULATION STUDY OF PRESSURE SWING

23

11.0 DISTILLATION COLUMNS OPERATING AT 0.01ATM AND 10 ATM

26

12.0 CONCLUSION

27

14.0 BIBILOGRAPHY

27

1. INTRODUCTION:
5

Hydrogen is clean energy carrier and promising alternative to the conventional fossil fuel. It
has a highest energy per unit mass of 120MJ/kg .To obtain similar amount of energy would
require 2.5 kg of natural gas, 2.75kg of oil and 3.7-4.5kg of coal. The most widely used
method for production of hydrogen is steam methane reforming process, produces CO and
CO2 which are greenhouse gases. Other sustainable and green methods have been developed
in the near past, one of which is production of H 2 by thermochemical water splitting cycles.
These cycles are promising water splitting alternatives that can be linked with Solar or
nuclear heat source to thermally decompose H2O through a series of intermediate reactions
and have the potential for large scale hydrogen generation. Several thermochemical cycles are
reported in the past but very few have been pursued in view of their merits as appear
promising to develop in near future. Iodine-Sulfur cycle and Copper Chlorine cycles are the
best examples. These are being developed by ONGC Energy Centre in collaboration with
several national R&D institutions of repute. One of the most promising thermochemical
cycle is the Copper Chlorine (Cu-Cl) cycle and have been widely researched worldwide.
The

Cu-Cl

thermochemical

cycle:

The CopperChlorine

cycle (CuCl

cycle)

is

thermochemical cycle (Figure 1) for the production of hydrogen. The CuCl cycle is a
hybrid process that employs both thermochemical and electrolysis steps. It has a maximum
temperature requirement of about 530o C.
The CuCl cycle involves chemical reactions for water splitting, whose net reaction
decomposes water into hydrogen and oxygen. All other chemicals are recycled. The CuCl
process can be linked with nuclear plants or other heat sources such as solar and industrial
waste heat to potentially achieve higher efficiencies, lower environmental impact and lower
costs of hydrogen production than any other conventional technology (Orhan et al., 2010).
Advantages of the CopperChlorine cycle include lower operating temperature, the ability to
use low-grade waste heat to improve energy efficiency, and potentially lower cost materials.
In comparison with other thermochemical cycles, the CuCl process requires relatively low
temperatures of up to 530C. Another significant merit of this cycle is a relatively low
voltage (thus low electrical energy expenditure) that is required for the electrochemical step
(0.6 to 1.0 V). The overall efficiency of the CuCl cycle has been estimated to be just over
43%, excluding the additional potential gains of utilizing waste heat in the cycle.

Figure 1. Four stage Cu-Cl cycle

During hydrolysis reaction step of the Cu-Cl thermochemical cycle for hydrogen generation,
excess steam is required for maximum conversion of Cupric Chloride. The unreacted steam
and product HCl forms an azeotropic mixture at the product end. Here complete separation
of HCl and water is not possible by conventional distillation alone because of formation of
HCl/water azeotrope. The present work aims to find a feasible solution to this important
problem.
2. OBJECTIVE
The main objective of the work was to perform Simulation Studies utilising CHEMCAD
simulation software for separation of HCl-water azeotrope in the hydrolysis reaction step of
the Copper Chlorine cycle.
3. APPROACH
Simulation studies by application of pressure swing distillation using CHEMCAD
Simulation Software for separation of HCl and water from HCl/water azeotrope produced in
the hydrolysis step of the Cu-Cl cycle.

4. MAJOR SEPARATION ISSUES RELATED TO CU-Cl CYCLE:

Hydrogen generation reaction: The separation of mixture of product H2(g) and unreacted

HCl(g).
Disproportionation Reaction: During electrolysis reaction there is formation of cupper

powder. These copper powder need to be separated from electrolytic solution.

Hydrolysis Reaction: During hydrolysis reaction excess steam is required for maximum
conversion of cupric chloride. The unreacted steam and product HCl forming the
azeotropic mixture at the product end. The complete separation of HCl/water is not
possible by conventional distillation alone because of azeotrope. Pressure swing
distillation may solve this separation problem.

4.1

H2O/HCl azeotrope separation:

Water and HCl form a maximum boiling azeotrope at 1 atmpressure as shown in H 2O/HCl
phase diagram (Figure 2). This means that the boiling point of azeotrope is higher than both
water and HCl. Maximum boiling azeotrope are quite uncommon in nature. They have
negative deviations from ideal behaviourwhich means that its activity coefficient i is
negative. The reason for this non ideality is that the hydrogen bonding interaction associated
with the H2O and HCl.is depicted below.

Figure 2.H2O/HCl Azeotrope separation with temperature

5.0

SEPARATION TECHNIQUES FOR AZEOTROPE MIXTURE:

5.1

Extractive distillation:

Here a large amount of relatively highboiling solvent is used to alter liquid phase activity
coefficients so that relative volatility of key components becomes more favourable for
separation. Solvent enters the column a few trays below the top, and exits from the bottom
without forming azeotrope. If the Column feed is an azeotrope, the solvent breaks it.
5.2

Salt distillation:

It's a variation of extractive distillation in which relative volatility of key components is

altered by adding to the top reflux asuitable, non-volatile ionic salt which stays in the liquid
phase as it separates as it passes down the column.
5.3

Pressure Swing Distillation:

It separates a mixture that forms a pressure sensitive azeotrope, by utilizing two columns at
different pressures. By changing the pressure the phase diagram, and the azeotropic
composition changes which helps in crossing the initial azeotropic composition for obtaining
higher purity.The pressure variation is oscillatory, meaning we increase,decrease and again
increase so on.
5.4

Homogenous Azeotropic Distillation:

It's a method of separating a mixture by adding an entrainer that forms a homogenous

minimum or maximum boiling azeotrope with fee component(s).Where the entrainer added
depends on whether the azeotrope is removed from top or bottom of the column.
5.5

Heterogeneous Azeotropic Distillation:

A minimum boiling azeotrope is formed by the entrainer. The azeotrope splits into 2 liquid
phases inthe over head condenser. One liquid phase is sent back as reflux; the other is sent to
another separation step or is a product.
5.6

Reactive Distillation:

A chemical that reacts selectively with one or more feed constituents is added, and the
reaction product is then distilled from the non-reacting components. This reaction is later
reversed to recover the separating agent and reacting component. Reactive distillation also
refers to chemical reaction and distillation conducted simultaneously in the same apparatus.
6.0

RESIDUE / DISTILLATION CURVE ANALYSIS OF SYSTEMS FORMING

AZEOTROPE:
For ordinary multicomponent distillation,the determination of feasible distillation sequences,
design of distillation column is pretty straightforward, whereas enhanced methods of
9

separation for azeotropes are fairly complicated and the determination of feasible distillation
design and column design is substantially more difficult. Many a time rigorous calculations
fail because of non idealities of liquid solution. For making the analysis simple a very
important tool is of graphical techniques developed by Doherty and co-workers (Doherty et
al,.) and by Stichmlair and co-workers. These graphical techniques are described as follows.
6.1

Residue Curve:

When an entrainer is added to a binary mixture forming an azeotrope the result is a ternary
mixture, so it is very important to consider the phase equilibrium for predicting the possible
overhead and bottoms composition. Triangular diagrams are often used to describe
equilibrium for ternary mixtures. One of the most important aspects of ternary diagrams is the
residue curves (Figure 3-5). These curves represent liquid residue composition as a function
of time as a result of a simple batch distillation of a ternary mixture. They are derived
mathematically as a result of component mass balance done around the still, assuming that
the liquid is perfectly mixed and is at its bubble point. The equation (1) governing the residue
curve is as follows.

dxi
dw
( yi xi )
dt
Wdt

.......... (1)

Where, xi: mole fraction of a component

i : W moles of a perfectly mixed liquid residue in the still
yi: mole fraction of component i in the vapour leaving the still instantaneously which
is in equilibrium with xi.
The results of this equation when plotted on a triangular graph form residue curves because
the plot follows with time the liquid residue composition in the still. Note that we are not
plotting vapour composition in the plotting of residue curve. A collection of the residue
curves at a fixed pressure is called a residue curve map. Plotting the residue curve by hand is
a tedious and a laborious task which requires a lot of time.Residue curve can be draw easily
by using process simulators such as aspen plus or CHEMCAD..
A residue curve map has the following characteristics:
(1).

The direction in which the arrow points starts indicates the initial composition in the
still to the final composition as time progresses.Arrow starts from a low boiling
component or an azeotropeto the higher boiling component or an azeotrope.

10

(2)

There can be distillation boundaries in some cases which a residue curve cannot cross.
The distillation boundary itself is a residue curve dividing the ternary plot into 2
regions. These boundaries are thermodynamic in nature

Some important terminology in residue curve analysis:

Node: Residue curves begin and end at nodes.
Stable node: The component or azeotrope with the highest boiling point in the region. All the
residue curves in the region point to (terminate) at this point.
Unstable node: The component or azeotrope with the lowest boiling point in the region
Saddle Residue curves move toward and then away from saddles. Pure components and
azeotrope which have a boiling point between thestable and unstable nodes are saddles

Figure 3

11

Figure 4

Figure 5

12

6.2

Distillation Curves:

An alternative representation for distillation on a ternary diagram is a distillation curve for

continuous, rather than batch, distillation. The curve is most readily determined for total
reflux. The sequence of liquid-phase compositions, which corresponds to the operating line at
totalreflux, is plotted on a triangular diagram (Figure 6). Distillation curve maps can be
arbitrarily directed to increasing or decreasing temperatures. Inthe former case, they closely
approximate residue curve maps.The mathematical governing relations for distillation curve
are

xi , j 1 yi , j
...............(2)
this is the equation of the operating line in a distillation column (both rectification and
stripping section) at total reflux.

yi , j Ki , j xi , j
..................(3)
this is the equilibrium relationship between the vapour and liquid leaving a tray. To solve
these equations an initial assumtion of x i,1 is made and by using above equations in succesion
xi,2 , xi,3 ... etc can be determined . Plotting a distillation curve also is a laborious task but
takes lesser effort and time when compared to residue curve.

13

Figure 6.Ttriangular diagram

It is found that residue curve maps and distillation curve map of a ternary system are
approximately coincident, so one can be used in place of another (interchangeably).
7.0

PRODUCT OF COMPOSITION REGIONS AND FEASIBLITY ANALYSIS:

Residue-curve maps and distillation-curve maps are used to make preliminary estimates of
regions of feasible product compositions for distillation of non-ideal ternary mixtures. The
product regions are determined by superimposing a column material balance line on the curve
map diagram.If a straight line is drawn that connects distillate and bottoms compositions, that
line must pass through the feed composition at some intermediate point to satisfy overall and
componentmaterial balances. For such a material balance line, the distillate and bottoms
compositions must lie on the same distillation (residue) curve.
For azeotropic systems, where distillation boundaries are present, a feasible product region
canbe found for each distillation region.
8.0

SEPARATION OF H2(g)/HCl(g)GASEOUS MIXTURE:

14

The most common method for separating a mixture of gas is by absorption or adsorption
either in tray towers or packed towers.The other methods also include membrane separation
and use of molecular sieves.
8.1

Separation by Absorption methods:

Absorption methods(physical and chemical): Absorption methods are gas-liquid separations

where absorbents (Water) are used to remove soluble (HCl gas) components from H 2/HCl
mixture. The equipment consists of an adsorption column in which soluble components are
trapped in an absorbent in which the absorbed components are released at a lower pressure or
high temperature. There are two types of absorption mainly physical and chemical.
(1) Physical absorption: In this process the solubility of gaseous components generally obeys
Henry's law, are mostly applied to separations of H 2 from feed gas. The advantage of this
is that regeneration of absorbents is very easy and product hydrogen of this leaving the
absorption column is near the feed pressure.
(2) Chemical absorption: This process is suitable for complete removal of specific impurities
from crude hydrogen and recovery of H 2 from that at its relatively low pressure or low
concentration in comparison with Physical absorption. This chemical absorption method
is used mainly for separation of acidic substances such as H2S,HCN,carbonyl sulphide,
HCl from raw H2 gas. Hot alkaline or amine solutions are used as the absorbing agents to
remove the acidic impurities.
8.2

Separation by Adsorption methods:

Adsorption separation methods utilize the preferential adsorption of some constituent species
other than hydrogen mainly due to difference in adsorption equilibrium. Representative
adsorbents are silica gel, activated carbon, activated aluminium and molecular sieves. Most
separation units are operated in dual mode and molecular sieves. Most separation units are
operated in dual mode of adsorption by passing the feed hydrogen gas and regeneration by
means of heating, pressure reduction, gas purge or a combination of these methods. In 1960's
a new separation technology, the so called "pressure swing adsorption PSA process" (Sircar et
al) was developed. A PSA unit consists of 4-12 columns containing specific adsorbents. The
columns are connected through valves in order to perform pressurisation and depressurisation
by sophisticated charge and discharge of H2 gases. Each column is operated in sequential
cycle ,which consists of adsorption of impurities, equilibriation of pressures ,desorption of
impurities, purge of impurities and pressurisation.PSA offers several features in H 2 in a
product gas and other constituents in a purge gas, separation to highly pure hydrogen at a
moderate hydrogen recovery, product hydrogen pressure is near the feed pressure , minor
15

influence on the design of the separation unit and the purity and recovery of product H 2 by
variations in comparison in feed hydrogen and low operating cost. Owing to these advantages
PSA process of various types are widespread for recovery of H2.
8.3

Separation by membrane separation process:

Here a membrane acts as a semi-permeable barrier and separation occurs by the membrane
controlling the rate of movement of various molecules between two liquid phases, two gas
phases or liquid and a gas phase. The two fluid phases are usually miscible and the membrane
barrier prevents actual, ordinary hydrodynamic flow.
Membrane process for H2/HCl is gas diffusion where the rates of gas diffusion depend on the
pore sizes and the molecular weights. We may have molecular,transition and Knudsen
diffusion region depending on the relative pore and gas molecule. The type of membrane
used for gas separation is flat membranes and spiral wound membranes.
9.0

PRESSURE SWING DISTILLATION:

If a binary azeotrope disappears at some pressure, or changes composition by 5 mol% or

more over a moderate range of pressure, consideration should be given to using two ordinary
distillation columns operating in series at different pressures. This process is referred to as
pressure-swing distillation. Knapp and Doherty list pressure-sensitive, binary azeotropes,
mainly from the compilation of Horsley. The effect of pressure on temperature and
composition of two minimum-boiling azeotropes is shown in Figure 10.The mole fraction of
ethanol in the ethanolwater azeotrope increases from 0.8943 at 760 torr to more than 0.9835
at90 torr. Not shown in Figure b is that the azeotrope disappears at below 70 torr. A more
dramatic change in composition with pressure is seen in for the ethanolbenzene system,
which forms a minimum-boiling azeotrope at 44.8 mol% ethanol and 1 atm. Applications of
pressures wing distillation, first noted by Lewis in a 1928 patent, include separations of the
minimum-boiling azeotrope of tetrahydrofuranwater and maximum-boiling azeotropes of
hydrochloric acidwater and formic acidwater. Van Winkle describes a minimum-boiling
azeotrope for A and B, with the Tyx curves shown in Figure 7.As the pressure decreases
from P2 to P1, the azeotropic composition moves toward a smaller percentage of A. An
operable pressure-swing sequence is shown in Figure b. The total feed, F1, to Column 1,
operating at lower pressureP1, is the sum of fresh feed, F, which is richer in A than the
azeotrope, and recycled distillate, D2, whose composition is close to that of the azeotrope at
pressure P2. D2 and, consequently,F1 are both richer in A than the azeotrope at P1. The
bottoms, B1, leaving Column 1 is almost pure A. Distillate,D1, which is slightly richer in A
16

than the azeotrope but less rich in A than the azeotrope at P2, is fed to Column 2, where the
bottoms, B2, is almost pure B. Robinson and Gilliland discuss the separation of ethanol and
water, where the fresh feed is less rich in ethanol than the azeotrope. For that case, products
are still removed as bottoms, but nearly pure B is taken from the first column and A from the
second. Pressure-swing distillation can also be used to separate less-common maximumboiling binary azeotropes. A sequence is shown in Figure10c, where both products are
withdrawn as distillates, rather than as bottoms. In this case, the azeotrope becomes richer in
A as pressure is decreased.

Figure 7. Different methods of azeotropic pressure swing operations

10.0

SIMULATIONS CARRIED OUT TO DETERMINE PHASE BEHAVIOUR

AND AZEOTROPIC COMPOSITION OF HCL-WATER

10.1

Case Study 1: Application of pressure swing distillation to HCl water system

After some trials of binary phase diagram of HCL-water system at different pressures, it was
found that the system is pressure sensitive, so we can carry out pressure swing distillation for
separation of the mixture. As cited in literature (Seaderhenley) that for economic feasibility of
pressure swing distillation the 2 columns should be operated at pressures such that there is at
17

least 4-5 mol% shift in azeotropic composition. Such possible values of pressures were
estimated by many trials on CHEMCAD6.3software and it found that 1atm and 20atm are 2
such pressure values. Another set of values were 0.01atm and 10atm. The phase diagrams
plotted by the software are shown below for 1atm and 20atm using thermodynamic setting (K
value) as PPAQ.
As we can see that at 1atm the azeotropic composition is 0.11 and it changes by 0.04 (4mol
%) to 0.07 at 20atm, thus now it's possible to design the pressure swing distillation operation
for such pressure values. An attempt to design pressure swing distillation was made on the
process simulator chemcad6.3 and was carried out successfully, the flow sheet and screen
shots were taken for reference.

Figure 8 Variation of mole fraction of HCl/water with temperature at 1 atm

18

1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
Hydrogen Chloride Vapor Mole Fraction
0

Hydrogen Chloride Liquid Mole Fraction

Figure 9. Equilibrium curve for HCl/water at 0.01 atm

Figure 10. Variation of mole fraction of HCl/water with temperature at 20 atm

19

Figure 11. Equilibrium curve for HCl/water at 20 atm

Sequencing of the Pressure-Swing Distillation Process by simulation:
Figure 12 shows the pressure-swing sequence for the separation of HCl from water. The feed
enters the low pressure distillation column at 1 atm and the distillate of this column has a
composition that approaches the azeotropic concentration. This distillate is the feed stream to
the high pressure column at 20 atm. Generally the distillate of second column has a
composition that is similar to the feed composition and it is recycled to mix with the feed to
first column. High purity HCl is produced as a distillate stream from the second column.
The number of stages is very temperature sensitive for azeotropic distillation. For first
column (as shown in Figure13).it is very sensitive at around 106 C. For second column as
shown inFigure 14 it is sensitive at 178 C

20

Figure 12.HCl/water pressure swing azeotropic at1 and 20atm for HCl/water system

Figure 13.Variation of stages with temperature at 1 atm for HCl/water system

21

Figure 14.Variation of stages with temperature at 20 atm for HCl/water system

During simulation for separation of HCl/water azeotrope, first column was kept at 1 atm
while seconds at 20atm pressure. The other specifications of individual stream are shown
below in Table No 2.

Stream

Temperature

Pressure

Total Flow Rate

Wt. fraction

Wt. fraction

No
1

(C)
107

(atm)
1

(kmol/hr)
100

of HCl
0.05

of HCl
0.95

102.69

59.80

0.067

0.99

106.96

40.19

0.114

0.88

30.84

20

0.04

200.95

20

40.157

0.11

0.89

Table No. 2 Stream specifications for HCl/water pressure swing isotropic at1 and 20atm
It was observed from Table XXX that the bottom outlet of the first stream achieve the
azeotropic composition and in second column it get separated. For first column the 30 stages

22

were used with 14th plate as feed plate while for second column the 30 stages were used with
7th stage as feed stage.
10.2

Case Study-2: Simulation study of pressure swing distillation columns operating

at 0.01atm and 10 atm

The reason for doing this simulation was that the earlier simulation the value used for the 2 nd
distillation column used a value of 20 atm which is on the higher side and such value may not
be easily achieved so a reasonable amount of 10 atm was chosen and to create a difference of
5 mol% in the azeotropic composition the value ofpressure for the 1 stcolumn was found
suitable was 0.01 atm. Similar to the earlier case study simulations was carried out for many
input specifications and the following results are for the case in which the simulation
converged.

Figure 15HCl/water pressure swing azeotropic at0.1 and 10atm for HCl/water system

23

Figure 16. Variation of mole fraction of HCl/water with temperature at 0.01 atm

Figure 17. Equilibrium curve for HCl/water at 0.01 atm

24

Figure 18. Variation of mole fraction of HCl/water with temperature at 10 atm

Figure 19. Equilibrium curve for HCl/water at 10 atm

Stream

Temperature

Pressure

Total Flow Rate

Wt. fraction

Wt. fraction

No
1

(C)
12.00

(atm)
0.01

(kmol/hr)
100

of HCl
0.05

of HCl
0.95

7.40

0.01

61.73

16.69

0.01

38.27

0.13

0.87

-26.09

10

0.038

172.61

10

38.23

0.13

0.87

Table No. 3. Stream specifications for HCl/water pressure swing azeotropic at 0.1 and 10atm
25

11.0

COST ESTIMATION FOR THE PRESSURE SWING SEPARATION:

Cost estimation by considering tray column of carbon steel material. Column diameter and
height were considered at 1.25 m and 10 m respectively. Thickness of the column at top and
bottom was fixed at 0.158 cm and 0.23 cm respectively. The trey spacing was fixed at 0.61 m.
The Fixed head carbon steel condenser and reboiler having 92.21 m2 and 41.95m2 surface
area respectively, designed for 5 atm pressure used. The total purchase cost is estimated to be
$ 169458.1 ( $79230.4 for distillation column +$90227.7 for condenser and reboiler)
12.0

CONCLUSION:

Although there are many techniques are reported for carrying out separation of azeotropes,
designing of all of them is not easy with the help of a process simulator especially those
techniques which involve addition of third component as calculations become tedious and the
simulator (CHEMCAD) was unable to converge even after several trials, so pressure swing
distillation of HCL-water was chosen and an attempt was made to design and carry out cost
estimation of both the distillation columns.
The highlight of using pressure swing distillation for the separation of HCL-water azeotrope
was that there was no 3rd component (entrainer) used due to which the additional cost of
entrainer was avoided and also the simulations were able to converge in the case of pressure
swing distillation as addition of a 3rd component complicates the mathematics and
attainability of a converging solution.
In the present study, it was found that distillation columns operating at 1atm and 20atm along
with above shown specifications made the calculations converge and HCl and water were
obtained as almost pure products. In the second case study the pressures chosen were 0.01atm
and 10atm and the top products were pure HCl and water.
While80.4% of HCl was recovered in the case 1 of 1atm and 20atm , in case 2 at 0.1atm and
10atm it was found to be 76.6%. So we can see that the fraction of HCl recovered is slightly
higher in case 1.
The cost of 1st distillation was found to be $90227 and 2nd column was found to be $79230.4
and the specifications for height, diameter etc., were taken which were most commonly used
in any chemical industry.

26

13.0

BIBILOGRAPHY:

1. Doherty, M. F., and Malone, M. F. (2001), Conceptual Design of Distillation System. New
York: McGraw-Hill, Inc.
2. Sircar, S., and Golden, T.C. (2000), Purification of hydrogen by pressure swing adsorption,
Separation Science and Technology, 35(5), 667.
3. Seader, J. D., and Henley, Ernest J. (1998), Separation Process Principles. New York:
Wiley.
4. Progress of International Program on Hydrogen Production with the Copper Chlorine
cycle
5. Naterer G.F., Suppiah S., Stolberg L., Lewis M., Wang Z., Rosen M.A., Dincer I., Gabriel
K., Odukoya A., Secnik E,. Easton E.B., and Papangelakis V. (2015), Progress in
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