Simulation of Conventional, Reactive and Divided Wall Distillation

Column for the Production of MTBE (Methyl-Tert-Butyl-Ether)

through Aspen Plus
Abstract
Distillation is one of the most important separation processes due to the complexity involved,
the energy required and the vast applicability in chemical industries. Over the years a number
of new technologies have been evolved so as to optimize the distillation process. Divided wall
distillation column (DWC) and Reactive distillation column (RDC) are two such technologies
which have brought about a drastic change not only in the production quantity and quality but
has also improved the energy efficiency, cost redundancy and thus has proven to be an allround feasible technology especially in petroleum petrochemical and pharmaceutical
industries. The recent development of simulation technologies is one of the main reason that
these distillation technologies evolved and got utilized in industries so effectively. ASPEN plus
is one such modelling and simulation package that is used for optimizing any unit operation or
process. In this study, ASPEN plus was used to optimize the production of Methyl-Tert-butylEther (MTBE) which is used in the gasoline to raise its octane number and is used as an
oxygenate, using a conventional, DWC and RDC technologies. Simulations were run for
different reflux ratio, feed location, number of stages, operating pressures and temperatures
and the process was optimized for each of the three columns. The study led to the conclusion
that the production of MTBE was found to be the best in DWC also the amount of energy
required for the reboiler for heating was much less for DWC as compared the other two. The
purity of the product is best seen in the DWC column and also the number of stages required
is less as compared to the RDC and the conventional column. The heat load on reboiler is less
on the DWC column as compared the other two. Thus DWC is more efficient in terms of energy
consumption and require less number of stages and this leads to reduced operating costs and
higher product quality. The rate of the production of the MTBE is higher in the DWC column
as compared to the RDC and the conventional distillation column. There is no need of extra
distillation column in the DWC as in conventional distillation column and this leads to lesser
heat required in the reboiler.

Contents
Abstract ...................................................................................................................................... 1
1.

2.

3.

Introduction: ....................................................................................................................... 5
1.1.

Heat Pump Assisted Distillation Column ................................................................... 6

1.2.

Reactive Distillation Column ...................................................................................... 9

1.3.

Divided Wall Distillation Column ............................................................................ 13

Literature Survey ............................................................................................................. 16

2.1.

Introduction ............................................................................................................... 16

2.2.

Heat Pump Assisted Distillation Column ................................................................. 17

2.3.

Reactive Distillation Column .................................................................................... 22

2.4.

Divided Wall Distillation Column ............................................................................ 24

Modelling and Simulation................................................................................................ 27

3.1.

Introduction ............................................................................................................... 27

3.2.

Design of Reactive Distillation Column ................................................................... 28

Phase Equilibrium ............................................................................................................ 29

Summation Equation........................................................................................................ 30
Kinetic Modelling ............................................................................................................ 30
3.3.

Design of Divided Wall Distillation Column ............................................................ 32

3.4.

Sequence of Steps Followed for Modelling in ASPEN Plus .................................... 36

Feed Specifications: ......................................................................................................... 38

4.

Results and Discussion .................................................................................................... 44

4.1.

Conventional distillation column .............................................................................. 44

4.2.

Reactive distillation column ...................................................................................... 46

4.3.

Divided wall distillation column ............................................................................... 49

Conclusion and Recommendations .......................................................................................... 52

References ................................................................................................................................ 53

Figure 1.1. Schematic Representation of the Vapour Recompressed Batch Distillation (VRBD)
Column. A.K Jana (2013). ......................................................................................................... 6
Figure 1.2: A Closed-System Configuration of a Combined Overall Heat Pump System and
Intermediate Exchangers. A.K Jana et al. (2013). ..................................................................... 7
Figure 1.3. Schematic Representation of the HIDiC Column. Taylor R. et al (2012). .............. 8
Figure 1.4: Schematic Representation of the Mechanical Heat pump Assisted Distillation
Schemes. Krishna R (2012). ...................................................................................................... 9
Figure 1.5: Reactive Distillation Column Consisting of Three Sections: (a) Reactifying Section
(b) Reactive Section (c) Stripping Section. R. Baur et al. (2000) ............................................ 11
Figure 1.6: Prominent Approaches for Conceptual Design of RD. Vinay Amte et al. (2012) 12
Figure 1.7: Separation and Purification Technology. O. Yildrim et al (2011) ........................ 13
Figure 1.8: Different Position and Shape of Dividing Wall. Separation and Purification
Technology. O. Yildrim et al. (2013). ..................................................................................... 14
Figure 1.9 Basics Types of Dividing Wall. Fractioning Apparatus and Method of Fraction. D.A
Monro (2010). .......................................................................................................................... 14
Figure 1.10. Dividing Wall Columns for the separation of four components mixture. Omer
Yildrim et al (2011). ................................................................................................................ 14
Figure 2.1 Heat Pump Assisted Vapor Recompressed RD Column With Intermediate Reboiler.
Amiya K Jana (2013). .............................................................................................................. 18
Figure 2.2. Schematic Representation of the Double Stage Vapour Recompression RD Column
with Double Intermediate Reboiler. A. K. Jana (2013). .......................................................... 19
Figure 3.1. Schematic Representation of reactive Distillation Column. Muhamad Nazri Murat
et al. (2003). ............................................................................................................................. 28
Figure 3.2. Algorithms for Solving Reactive Distillation Simulation. M.N. Murat et al. (2003).
.................................................................................................................................................. 31
Figure 3.3. Schematic Representation of the DWC column using Petlyk column. Michael A. et
al. (2013). ................................................................................................................................. 35
Figure 3.4. Flowsheet for the Production of MTBE using ASPEN PLUS Software in Reactive
Distillation Column.................................................................................................................. 36
Figure 3.5. Conventional Route for the Production of MTBE Using ASPEN PLUS Software
.................................................................................................................................................. 36
Figure 3.6. Flowsheet for the production of MTBE Using ASPEN PLUS in Divided Wall
Distillation................................................................................................................................ 37
Figure 3.7 Selection of Components for the Production of MTBE. ........................................ 42
Figure 3.8. Flowsheet Showing Kinetic of the Reaction Using ASPEN PLUS ...................... 43
Figure 4.1. Product purity with changing reflux ratio for conventional distillation ................ 44
Figure 4.2. Reboiler duty with changing reflux ratio for conventional distillation ................. 44
Figure 4.3. Production rate with changing number of stages .................................................. 45
Figure 4.4. Reboiler heat duty with changing number of stages for conventional distillation 45
Figure 4.5. Temperature with changing number of stages for conventional distillation ......... 46
Figure 4.6. Product purity with changing reflux ratio ............................................................. 46
Figure 4.7. Reboiler duty with changing reflux ratio............................................................... 47
Figure 4.8. Production rate with changing number of stages .................................................. 48
Figure 4.9. Reboiler heat duty with changing number of stages ............................................. 48
Figure 4.10. Temperature with changing number of stages..................................................... 49
Figure 4.11. Product purity with changing reflux ratio ........................................................... 49
Figure 4.12. Reboiler duty with changing reflux ratio............................................................. 50
Figure 4.13. Production rate with number of stages ................................................................ 50
Figure 4.14. Reboiler heat duty with changing number of stages ........................................... 51
Figure 4.15. Temperature with changing number of stages..................................................... 51

List of Tables
Table 3.1. Input Specifications of Methanol Feed ................................................................... 38
Table 3.2. Input Specifications of Iso Butylene Feed .............................................................. 38
Table 3.3. Stoichiometry of reactants ...................................................................................... 40
Table 3.4. Stoichiometry of products ....................................................................................... 40
Table 3.5. Stoichiometry of reactants ...................................................................................... 40
Table 3.6. Stoichiometry of products ....................................................................................... 40

1. Introduction:
The global energy consumption is rising continuously because of modernization and
motorization of the world. Our fossil fuels meet eighty percent of our energy demand and as a
result of this the rate of formation of fossil fuels is continuously decreasing. Uncontrolled
utilization of the fossil fuels also leads to many negative effects to the environment such as
increasing global warming, floods, water scarcity, ozone layer depletion and different types of
pollution. Time duration between the formation and utilization of the fossil fuels is less because
of huge energy demand in the present time. To meet this huge energy demand, need arises to
search new renewable sources of energy and energy efficient equipments [1].
Distillation is the most widely used separation process in the chemical and pharmaceutical
industries which utilises about forty percent of the energy used in the separation process. In
distillation column most of the energy got wasted in the condenser and reboiler section.
Reboiler section requires heat for converting the reactant mixture into vapour and when this
vapour mixture goes into the condenser then the amount of energy which is utilised by the
reboiler is released by the condenser which is wasted [4]. When this heat goes to atmosphere
then it cause many environmental pollution and green house emission. Therefore it becomes
necessary to couple the condenser with the reboiler to reutilize the heat which is wasted by the
condenser into the atmosphere.
Humphrey has shown that the separation process in United State consists of 40000 distillation
columns in operation which is used for the 90 percent separation of the product and their
purification. The investment made on this distillation is reported to be about at least 8*109 US
Dollar. The fact that led the scholar to research in distillation field is that the distillation use
huge amount of energy for the evaporation of the reactant mixture. Half of the heat which is
supplied to the distillation column is ended in the reboiler column and the same amount of
energy is released at the top at a very low temperature [8]. The energy which is freed at the top
of the column is not used in heat integration but is released in the atmosphere as a waste which
causes several environmental problems. Mix and co-workers in the United State of America
has shown practically that 3% of the total energy is used in the separation process in distillation
column from very early years and this has not shown any changes in this amount of energy.
According to recent data of the US DOE (Department of Energy) from 1995 distillation
columns consume 2.87*1018 (2.87 million TJ) a year which is equal to a continuous power
supply of 91 GW or to a 54 million tonnes of crude oil. Therefore saving of 1% of energy in
distillation column would be tremendous in this age of energy crisis [9].

In distillation column, there are many ways by which we can save energy such as by reducing
reflux ratio, multiple effect distillation, lateral line heat transfer distillation, heat pump
distillation and many more. If we compare all these factor of energy saving then we find that
the heat pump distillation is identified as most of energy saving factor. Heat pump assisted
distillation column integrates the condenser and reboiler section of the distillation column and
construct a unique configuration. Heat pump assisted distillation column not only save the heat
that is wasted in the atmosphere but also protect the atmosphere from harmful effect of the gas
emission such as carbon dioxide, sulphur dioxide and nitrogen. Gas separation process requires
multi-component distillation and consume very high amount of energy. If we take the mixture
of propylene and propane and want to separate propylene gas at a very high purity greater than
99% then for this, we will have to increase the reflux ratio so that the purity of the desired gas
could increase. If reflux ratio is large then it also require huge amount of energy consumption
that it accounts for about 40% to 50% of the entire device and at the same time condenser
require a lot of water for the cooling of the distillate. Therefore if we want to avoid wastage of
energy in conventional distillation column then we can replace this distillation column with the
heat pump assisted distillation column [10, 11, and 12].
1.1. Heat Pump Assisted Distillation Column

Figure 1.1. Schematic Representation of the Vapour Recompressed Batch Distillation

(VRBD) Column. A.K Jana (2013).

In conventional distillation column, more than one distillation column is required for the
separation and purification of the product. In this arrangement, mixing of the reactants take
place in one column and then reaction takes place in another whole single column. Further
purification of the product is carried out in another single column and stripping of the unwanted
product takes place in other column. In this way conventional distillation column requires more
than one distillation column to complete its whole process. This whole arrangement requires
greater capital cost and huge amount of energy. Therefore increasing capital cost and the huge
amount of energy led the researchers to discover the energy efficient technology in this time of
energy crisis and hence need arises to save this wasted heat and reutilize this heat again in the
distillation column to carry out further process.

Figure 1.2: A Closed-System Configuration of a Combined Overall Heat Pump System and
Intermediate Exchangers. A.K Jana et al. (2013).
After the oil crisis in 1970, researchers switch to the advancement of the distillation process. It
has been observed that in the separation process the major energy consumed equipment are
reboiler, condenser and compressor. In this condition, heat integration technique plays an
important role and led the researcher to work in this field. Various heat integration techniques
are available but heat pump integration technique is more efficient and interesting.
It is because heat pump assisted distillation column consumes less energy to separate a mixture
as compared to conventional distillation column. In this arrangement heat pump is coupled
with the reboiler and condenser of the distillation column. The amount of heat which is wasted
in the condenser during the condensation of the product is reutilized through heat pump coupled
with it. Since heat pump works in two ways that is as heating as well as cooling media. Heat

pump takes the heat at low pressure from the condenser and releases this heat to the reboiler at
high pressure and utilizes this heat to heat the feed to convert it into the vapour mixture [1].

Figure 1.3. Schematic Representation of the HIDiC Column. Taylor R. et al (2012).

Heat pump can be coupled with the distillation column, works in two ways that is, as a
mechanical and absorption heat pump. In mechanical heat pump, we do not use overhead
condenser and bottom reboiler and the vapour leaving the top tray is compressed to a very high
pressure as a result of this its temperature increase and is used to heat the bottom liquid to
convert it into vapour or the bottom liquid is passed through a pressure reducing valve and its
temperature gets reduce and the liquid become cold. Further this cold liquid is used to cool the
overhead vapour. While absorption heat pump uses a closed separate loop fluid system to
transfer the heat from condenser to reboiler [1].
The separation process which is difficult to carry out then in this condition mechanical heat
pump is used. Fonyo et al. have practically found that while using distillation column with heat
pump require less heat and reduced capital cost in all the case in the separation of c4 splitter as
compared to the conventional distillation column.
Mechanical heat pump is of recompression types and driven by the electric power. Based on
the concept which is known in early 1950s Null has given three basic schemes of coupling the
mechanical heat pump with the distillation column, namely direct vapour recompression,
bottom flashing and external recompression. It is clear from the Fig. 1.4 that all three schemes
of mechanical heat pump consists of expansion valve and compressor so that the temperature

of the rejected heat can be increased or decreased to heat the bottom liquid or to cool the bottom
head product.

Figure 1.4: Schematic Representation of the Mechanical Heat pump Assisted Distillation
Schemes. Krishna R (2012).
In the direct vapour recompression, the overhead vapour is compressed to a very high pressure
so that the temperature of its latent heat increases and this heat is utilized to heat the liquid of
the bottom. Further, the condensate leaving the reboiler is flashed across a throttle valve at the
top column pressure for receiving the reflux and distillate. In the bottom flashing, the pressure
of the bottom liquid is raised corresponding to the temperature of the saturated distillate and is
used as a cooling media in the overhead condenser. When the bottom product acts as a good
refrigerant then then the botton flashing arrangement in the distillation column makes a suitable
choice which increases the thermal efficiency of the distillation column. While on the other
hand, when the heat pump is coupled in between the top condenser and the bottom reboiler
then this type of arrangement is termed as external vapour recompression using some sort of
working fluid known as a closed system. These three arrangements especially works on that
condition where the boiling point of the product mixture is very close and in this situation these
arrangements show a good potential in the reduction of the heat requirement in the distillation
column for the separation process [1, 13].
1.2. Reactive Distillation Column
In reactive distillation column, the reaction and the separation of the product takes place in the
same distillation column. Reactive distillation column gives higher conversion, product
selectivity and energy savings with less investments and operating costs as compared to
conventional distillation column. However, there are various hurdles in the implementation of
RDC column such as complex design, difficult scale-up and advanced process control. The

most important process that utilizes the concept of RD is esterifications, trans-esterification

and etherification in which the chemical equilibrium plays an important role in the limitation
of the maximum reactant conversion. Efficient performance of the RD processes depend upon
the reliable process design, properly selected column internals, feed locations, catalyst choice
and sufficient understanding of the process behaviour. Hence the efficient design of RD
processes requires reliable and accurate models that make the process engineer to importantly
decrease the expensive and time consuming experimental work [14, 15, 16, 17, 18, 19, 20, 21
and 22].
Reactive Distillation process requires more than one component so it is a multi-component
process and occurs in a multiphase fluid system. As a result of this multi-component
thermodynamic and diffusional coupling in the phases and in the interface are accompanied by
complex hydrodynamics and complex chemical reactions. Therefore an adequate description
of RD processes requires specially developed mathematical models that are capable of covering
column hydrodynamics, mass and heat transfer resistances and reaction kinetics. Detailed
reviews on the fundamentals of the different types of modelling developed for RD processes
provided an overview of possible modelling approaches for RD processes. Each model are
different in their complexities to describe the mass transfer between the gas and liquid phase,
chemicals reactions and hydrodynamics. The models which require mass transfer are of
basically two types available in the literature that is the equilibrium-stage model and the nonequilibrium-stage model. The non-equilibrium-stage model considers the mass transfer
between the vapour and liquid phase while the equilibrium stage model assume thermodynamic
equilibrium between the two phases [22, 23 and 24].
The selectivity of a reaction gets improve at a greater extent especially when an intermediate
product desired in the series or combination of series and parallel reactions in the reactive
distillation. In reactive distillation process, the rate of side reactions can be reduced while
removing one of the products from the reaction mixture or maintaining low concentration of
one of the reactant. In reactive distillation process, there are several adjustable designs and
operating parameters, therefore it becomes easy to identify a suitable RD configuration for the
desired performance.
Several methods have been given in the past to consider the need of the RD process. As shown
in Fig. 1.5 the conceptual design methodology for RD can be classified into three main groups:
(a) Evolutionary or heuristic approach, (b) Graphical Approach and (c) Optimization based
approach. Among all of these methodologies, attainable region approach, which is best suited
technique for the conventional reactor network is further applied to reactive separation. In the

previous work, Attainable region approach method was used to determine a suitable RD
configuration or a network of RD and conventional reactors and giving the desired selectivity
for a general multi-reaction system of azeotropic or non-azeotropic vapour liquid equilibrium
[26, 27, 28 and 29].
When the inert components are present in the series reaction system, then its concentration
does not show any effect in the selectivity factor of the desired product. However, the
composition profile in the RD column is affected by the presence of the inert components and
therefore the suitable design of the RD column depends upon the relative volatility of the inert
component. Hence it becomes compulsory to accept different strategy for obtaining a RD
configuration for a desired performance. However complexities occur in the RD process
because of the non-ideality of the components and the interaction between them and the
intricate hydrodynamics and transport phenomenon in the column. Till today, the design,
control and simulation of the reactive distillation process highly dependent on empirical
correlations due to the lack of comprehensive understanding of the process. To simulate the
reactive distillation process, two types of model have been developed in the literature that is
equilibrium stage model and non-equilibrium stage model. Equilibrium stage model considers
that the vapour composition which is leaving the top stage of the column is in equilibrium with
the liquid composition on the stage. On the other hand non-equilibrium model is based on the
fact that it is a rate based model for conventional distillation. Better simulation results are
obtained in the non-equilibrium model, however, it is difficult to solve this model and it is not
easy to get the transport parameters [25, 30 and 31].

Figure 1.5: Reactive Distillation Column Consisting of Three Sections: (a) Reactifying
Section (b) Reactive Section (c) Stripping Section. R. Baur et al. (2000)

Figure 1.6: Prominent Approaches for Conceptual Design of RD. Vinay Amte et al. (2012)

1.3. Divided Wall Distillation Column

Divided wall column is the integration of more than one column into a single column in which
the separation of more than one component can be carried out in a efficient manner and a lot
of energy can be saved by avoiding extra distillation column as in conventional method Fig.
1.7. Because of a number of design parameters, it had been very difficult to simulate, design
and built divided wall columns for many years. The first implementation of divided wall
column in the industry took place in 1985 by BASF SE. Since 1985, the number of application
of DWCs has increased more than hundred in 2010. According to Schultz et al. the divided
wall distillation column will become a standard distillation column in the next 50 years [32,
33, 34 and 35]. The DWC configuration which is more common for the separation of three
components is patented by Wright et al. which is shown in Fig. 1.9a, 1.9b and 1.9c. In Fig.
1.9a, the feed and the dividing wall are placed at the middle of the distillation column. The
divided wall is located at the lowermost part of the column and the feed has been placed at the
upper portion of the column in the Fig. 9b and this configuration is patented by the Monro et
al and first implemented in 2004. This configuration is termed as split shell column with
common overhead section and divided bottom section, while on the other hand, the
configuration shown in the Fig. 9c is known as split shell column with divided overhead section
and common bottoms section. Further, the DWC column can be classified on the basis of the
position of the divided wall towards the wall of the column from the centre of the main column
as shown in Fig. 8a and also the divided wall can be positioned diagonally as shown in Fig. 8b
and 8c.

Figure 1.7: Separation and Purification Technology. O. Yildrim et al (2011)

Figure 1.8: Different Position and Shape of Dividing Wall. Separation and Purification
Technology. O. Yildrim et al. (2013).

Figure 1.9 Basics Types of Dividing Wall. Fractioning Apparatus and Method of Fraction.
D.A Monro (2010).

Figure 1.10. Dividing Wall Columns for the separation of four components mixture. Omer
Yildrim et al (2011).

The DWC column can also be implemented for the separation of three or four components
depending on the number divided wall column inserted into the main distillation column as
shown in the Fig. 1.10.
In the configuration shown in Fig. 1.6a called Kaibel column, the separation is done with one
divided wall inserted into the main column and the product are separated at the right side of
the main distillation column. Kaibel et al. has stated that the DWC configuration that consists
of only one divided wall is thermally inefficient and the thermal efficiency can be improved by
inserting more divided wall in the main column as shown in Fig. 10b which is known as Sargent
Arrangement. However, no industrial application has been noticed till now in the industry [35,
36, 37, 38, 39, 40, 41, and 42]. If a desired and efficient heat and mass transfer is to be achieved
then a proper selection of columns internal is necessary and only then the desired purity of the
product is achieved. Different kinds of packing or trays are used with the divided wall columns
to insert the DWC with the main column in a desired manner. The way of selection criteria for
the optimal column internals for divided wall columns are same as done in the conventional
distillation column. The DWCs which are applied in the industry, are mostly employed
structured packing to obtain the desired purity of the product. Most industry of the world such
as BASF SE are employed packed columns and other industries such as Koch Glitsch and
CEPSA refinery employ trays in the divided wall column [43 and 44]. The construction of
divided wall is different for tray and packed columns but generally the construction of DWC
is easy and the divided wall that is inserted in the main column provides strength and stability
to the main column. The manufacture of packed DWC is not easy and the task of inserting
divided wall into the main column is very difficult. When the divided wall is inserted into the
main column then it must be insured that the dividing walls do not touch packing columns
otherwise, it would result in excessive liquid flow and consequently affect the separation
according to Kaibel et al. Now-a-days Julius Montz GmbH and BASF SE has developed the
non-welded wall technology, with the help of which the designing of the columns became much
simpler. Other advantage of the non-welded wall technology includes that the divided wall can
be installed in a much simpler and precise way. Another benefit includes less manpower, lower
weight, fast revamping of conventional columns, simpler and cheaper. The first non-welded
wall has been implemented in mid-1990 and the number of divided wall column produced by
the Montz GmbH reached around 85 in 2009 [39 and 45] .

2. Literature Survey
2.1. Introduction
Distillation Column is among the major energy consuming units in food, chemical,
petrochemical and refining industries. Almost all the separation process are carried out through
the distillation. However, distillation process is very costly and consumes a lot of energy even
then it is employed in major industries for the separation process. It is because, distillation
column is found to be very effective in case of controllability and operation. A lot of energy is
required to carry out the distillation process and energy wastes takes place in the condenser of
the distillation column which is equal to the energy consumed in the reboiler column of the
column. This led the researcher to work in this field and lay the foundation of heat assisted
distillation column, reactive distillation column and divided wall distillation column. Although,
these concepts are not new and is known from very past but due to lack of modern technology
and awareness, this cannot be carried out, but as the energy crisis took place due to uncontrolled
use of fossil fuels, industrialization and urbanization, the researcher started manufacturing
energy efficient equipments.
If we talk about the conventional distillation column then we find that a lot of energy is wasted
in this column and this waste of energy cause severe environmental problem. These
environmental problems not harmful only to the living beings but also cause the natural
hazardous such as Tsunami, floods and earthquake. To reduce this waste of energy and
environmental problem, a heat pump is coupled with the conventional distillation column
which works on the principle that it takes heat at lower temperature and delivers the heat at
high temperature. When the condensation process takes place in the condenser then a lot of
energy is released in the atmosphere at low temperature. This released energy is taken by the
heat pump at low temperature and it is delivered at the higher temperature to the reboiler
column of the distillation column. In this way, much amount of energy is saved and reutilized
in the reboiler section. In reactive distillation column, both the reaction and the separation of
the product takes place simultaneously and there is no need of extra distillation column for the
reaction and the separation of the product. In divided wall distillation column, a divided wall
is inserted at the centre of the main column and this configuration is known as DWC column.
In this column more than three components can be separated at a time by avoiding the extra
required distillation column. A lot of research works have been carried out in these fields by
different researcher which are explained below.

2.2. Heat Pump Assisted Distillation Column

The integrated distillation column shown in Fig. 3 shows the combination of the vapour
recompression and diabetic operation that will be supposed a backbone in the separation
technology in the near future. Nakaiwa et al. has shown an outstanding configurations of the
HIDiC column who carried out a bench-scale experimental tests for separating the binary
mixture of benzene and toluene, it has been shown that the consumption of energy can be
reduced more than 40% in the separation of the benzene and toluene from the mixture of the
benzene-toluene. Further, Horiuchi et al. implemented the HIDiC column in the pilot plant at
zero reflux ratio and found that there is a saving of more than 50% of energy requirement.
Now-a-days, several small and industrial-scale projects of HIDiC column are going to start in
Japan and in the Netherlands [46, 47, 48, 49, 50 and 51].
In heat Integrated Distillation Column, the rate of vapour flow from top to bottom decreases in
the rectifier section and it increases when the vapour flows from bottom to top of the stripper
section. Generally, the rate of vapour inflow in the compressor of the HIDiC column is much
more than that of a vapour recompression column and it also requires a comparatively large
compression ratio. Although, if a small vapour flow is maintained through the compressor of
the HIDiC column, even then it can provide benefits to the vapour recompression column and
if the compression ratio is large then it has a negative effect on the compressor power
requirement. It has been known from the past that requirement of the electric power for
operating the compressor is several times more expensive than the thermal energy used to run
the reboiler as well as the condenser. If we compare the vapour recompression column and
HIDiC column then it is found that the HIDiC column can gain better economic benefits even
then if the compression ratio is less [52]. Earlier, it was highly suggested to implement the
HIDiC column than the vapour recompression column, it is because, the HIDiC column is
cheaper and more economical [53]. Vapour recompression column can be only implemented
when the temperature difference between the overhead and bottom of the column is usually
small. Although, as time proceeded then we realized that there is no thermally efficient
distillation column that are always energy efficient [54]. Flower and Jackson introduced a heat
exchanger in the vapour recompression column for boosting the thermodynamic efficiency
[55].

Figure 2.1 Heat Pump Assisted Vapor Recompressed RD Column With Intermediate
Reboiler. Amiya K Jana (2013).
Implementation of heat heat exchanger in regular distillation column is proved to be very
beneficial particularly when there is a huge difference between the boiling points of the
components to be separated. Luyben has designed his own conventional distillation column for
separating the components which have a wide range of boiling points which lowered the annual
cost of up to 6.6%. Jane and Mane have optimized the VRC system consisting of the
intermediate reboiler in which the total reflux has been taken and the multiple feed is used in
the reactive distillation column which is shown in Fig. 2.1. For the separation of ethyleneGlycol, for whom the difference in boiling is much more, this VRC system is best suited as
compared to the conventional distillation column and saves the energy of about 46.2% and
payback period of about 2.7 year. Further Jane and Mane assumed that it is better to use
compressed overhead vapour in the intermediate reboiler as a heating medium and in the
bottom reboiler steam is used. The same work has been by the Flower and Jackson. I has been

concluded that in VRC configuration, the thermal efficiency and cost benefits is better for all
types of mixtures, whether they have close boiling point or there is a maximum difference in
the boiling of the components of the mixture as compared to the conventional distillation
column [56, 57 and 55].

Figure 2.2. Schematic Representation of the Double Stage Vapour Recompression RD

Column with Double Intermediate Reboiler. A. K. Jana (2013).
Recently, Kumar et al. have built and did the analysis of different type of heat pump
arrangements with intermediate reboiler using the VRC arrangements. This column is

implemented for the production of ethyl-tert-butyl-ether using the RD arrangements to show

the application of VRC system using intermediate reboiler in which the components of the
mixture have wide range of difference in their boiling points. The double stage vapour
recompression column which is shown in Fig. 2.2 which has a various practical application and
have shown the total energy saving of 50.6% and payback period of 3.23 year. Shenvi et al.
gave their contribution on the development of the multi-stage vapour recompression
configuration by using intermediate heat exchangers for a binary distillation column. Various
other alternative scheme of VRC column has been developed for the comparative study of the
VRC column with the heat pump assisted distillation column. At last, they came on the
conclusion that the heat integration distillation configuration consist of the single heat
integration scheme is not always energy efficient. Agrawal and his co-workers have proposed
some guidelines for an economically optimal distribution of intermediate heat exchangers
arrangement which are proved to be very suitable in determining the configuration and how to
couple the heat pump with the conventional distillation column for the transfer of wasted heat
into the reboiler [58, 59, 60 and 61].
In spite of the effective results in heat integrated distillation column, even then there is
industrial application of this column in plant scale because of its complex design and structure.
One of the most important reasons lies in the coupling of the heat exchangers along the height
of the column. It is still a big problem in the equipment process design, however, it is noticed
by the several research groups that if the location of the heat transfer is reduced to a smaller
number then there is as a negligible effect on the economic performance of the column.
Harwardt and Marquqrdt have practically shown that the cost optimal HIDiC designs need only
a few heat exchange locations. They have also suggested that it is better to use a single heat
exchanger in the HIDiC configuration which gives the same arrangement as the direct VRC
scheme gives. Therefore, for the implementation of the HIDiC column in the industrial scale,
it becomes compulsory to recognize its design that makes the heat integrated system similar to
the VRC column [62, 63, 64 and 65]. The most important approach for enhancing the
thermodynamic efficiency of several industrial processes is to minimize the wastes of heat and
if energy is wasted then recover every possible source of waste heat and turn it into useful
products. It is a matter of great concern that during the operation of HIDiC rectifier at an
elevated pressure, the difference in temperature between the rectifier top vapour and stripper
bottom liquid may be positive and if, it is negative then the magnitude of the negativity is
negligible. Therefore, the HIDiC column can be further intensified by introducing the VRC
scheme. In Fig. 2.2, it has been shown that in this intensified configuration a small amount of

thermal driving force is maintained by using a second compressor for the optimal use of latent
heat of rectifier top vapour for the reboiling of bottom liquid. The first combination of internal
and external thermal integrations of the integrated HIDiC configuration is first given by Mane
and Jana. This system is first implemented for the fractionation of an equimolar
benzene/toluene mixture. In comparison with the general heat integrated distillation column
which shows 19.9% energy savings and a payback period of 6.75 year, the integrated HIDiC
configuration enhance the efficiency of energy utilization up to 61.12% and cost savings of
upto 11.45% [66].
Further Shenvi et al. have given the same concept as given by Mane A and Jana AK but Shanvi
et al. discussed the thermal coupling between the overhead vapour of rectifier and bottom liquid
of the stripper in which, internally, there is no exchange of heat. For the implementation of this
configuration, there is no need to operate the entire rectifier at high pressure. When the two
column runs, the pressure between them remains same and only that vapour which is required
for reflux and boilup needs to be compressed. This type of operation prohibits the compression
of the whole vapour that flows through the rectifier. In real sense, this type of combination is
capable of saving more energy than the simple HIDiC equivalent column. The two forms of
internally HIDiC column have been further extended for the fractionation of a multi-component
hydrocarbon system by Kiran et al. Their concept is mainly based on the use of the number of
compressors. It has been seen that the integrated HIDiC column with single and double
compressor scheme appears to be more superior and energy efficient than the general HIDiC
and conventional heat integrated distillation column in terms of energy consumption and
economic evaluation. In the integrated HIDiC column which consists of single compressor
scheme, the top rectifier is operated at high pressure so that s desired thermal driving force is
maintained between the top rectifier and the bottom stripper. If the integrated HIDiC column
consists of second compressor that is double compressor system then there is no need of
operating the top rectifier at high pressure and the desired thermal driving force is obtained
between the top rectifier and bottom stripper. Integrated HIDiC column with double
compressor is highly efficient and gives maximum energy savings of 59.15% and a payback
period of 3.44 year. Integrated HIDiC column with single compressor is possible only when
there is a positive thermal driving force between source and heat sink and for making the
thermal driving force positive, the compression ratio must be enhanced. Practically, the
intensified structure of the distillation column may not always be proved to be a cost effective
and energy efficient as compared to the simple distillation column. Bjorn et al. have shown that
for obtaining the higher thermal efficiency and energy saving, it is necessary to couple the

distillation with the heat integrated system, theoretically it is possible, but practically, it is
unattainable and the simple distillation plays a better role in this condition. Although, simple
distillation column is not up to the desired mark in terms of thermal efficiency and energy
saving but practically, it is being operated in the refinery and other industries for the separation
process [61, 67 and 68].
2.3. Reactive Distillation Column
The design and optimization of reactive distillation column has received a much attention due
to its compact size, efficient separation capacity and operational advantages obtained from this
column. The main speciality of this column lies in its structure of making it capable for carrying
out the reaction and separation of the product simultaneously in a single unit which results into
simpler and intensified processes with less recycle streams and decreasing waste handling and
consequently lower investments and operating costs [69]. Reactive distillation column offers
higher reaction rate and selectivity; prevent the performance of zoetropes, less energy
consumption and solvent usage. In spite of all these advantages, the reactive distillation column
has limited commercial applications; it is because of the control performance and the
complexity in the operation of the reactive distillation column. Enough design strategies and
methods are available for the suitable design of the reactive distillation column; even then, it
is not implemented in the industry in pilot scale and are not feasible in the environment of the
application [70]. Till now, strong shortcut methods have been given for the modelling of nonreactive separation which involves homogeneous and heterogeneous azeotropic multicomponent mixtures. These methods require tray to tray calculations and pinch technique or
hybrid approaches [71]. In reactive distillation column, both reaction and separation takes place
simultaneously, because of this fact, a lot of numerical problems are arisen in the modelling,
design and optimization of the reactive distillation column. Composition Variables are not
suitable for the modelling of the reactive distillation column; it is because, dimensionally, these
variables are not match with the degree of freedom given by the Gibbs phase rule for reactive
systems. Therefore, keeping this fact in mind, composition variables are transformed which
have been used to simplify the modelling of the reactive distillation column. These approaches
are based on the transformation of the physical compositions and its main profit is that the
chemical and physical equilibrium is similar to an equilibrium model [71, 72 and 73].
A lot of researchers are trying to develop strong and feasible approaches for the design of
reactive column for multicomponent mixtures. For example, boundary value method is
extended by the Barbosa and Doherty for the desired design of the reactive distillation column

which involves reactions at equilibrium. Further, design methods have been given with the
kinetic control which provide detailed analysis and design of reactive distillation processes [75
and 76]. Dragomir and Jobson further extended graphical design methodology made for nonhybrid systems to hybrid systems by implying mass and energy balance which is optimized on
the basis of equipment cost for the available configurations [77]. Jantharasuk et al. has given
the approach which is based on the element and coupled with a driving force diagram which is
further implemented for the design of the reactive distillation column consisting of the multielement systems. This configuration is limited only to the equivalent binary element system
[78].
Since the past decades, a lot of research has been carried out and several papers have been
published related to the reliability of the RD processes and column design. The computational
and the reactive residue analysis curve are used to analyse the coupling between reactions and
vapour liquid equilibrium [79]. Reactive distillation process also requires the McCabe and
Thiele and the Ponchon Savarit method but these methods are limited to binary separation only
[80]. Mass and heat balance are applied for computing the composition and temperature profile
inside the column and to evaluate the configuration of the process in terms of the number of
stages and the location of the feed [81]. Barbosa and Doherty worked on the procedure to
develop and design the whole reactive distillation column for the systems which involve the
instantaneous chemical equilibria [82]. Further, Espinosa et al. applied this approach to hybrid
processes which involve pure stripping section [83]. Okasinski and Doherty, Buzad and
Doherty used the same concept to study the effects of the kinetics on the configuration of the
process [84 and 85].
Mahajani and Kolah gave a model which is based upon the film theory which pay attention
into the axial dispersion that is produced in the packed columns [86]. At last, Ciric and Gu, and
Gumus and Ciric introduced a method which is based upon the MINLP optimization [87 and
88]. When the breathing methods are extended for the design of the reactor such as the
attainable region method then these ideas are taken from the existing research and are given by
Glasser et al [89]. No orderly and reliable procedures have been proposed which combines
achievability analysis, synthesis and design of reactive distillation column. Considering this
complexity of the problem, graphical analysis is proposed which restricts its use to reactive
systems with a degree of freedom less than 3. This chronological and hierarchical approach is
based on some methods encountered in the literature. It gives a great help in selecting the step
necessary for the design of the reactive distillation column. The principal steps which are
required for the efficient design of the reactive distillation column in terms of feasibility

analysis, synthesis and design are number of theoretical stages, location and the length of the
reactive zone, location and number of feed plates, reflux ratios and heat duties. The software
which is developed for the design of the reactive distillation column and for the feasibility
analysis of this column is given by Meyer et al. It produces the whole reactive residue curves
maps for the RD system in which the degrees of freedom is less than or equal to two and
produce the results by itself with distillation boundaries. The reactive residue curve map is only
suitable for the feasibility analysis of the whole reactive distillation column [81].
2.4. Divided Wall Distillation Column
The increase in worldwide energy demand led the researcher to work for the alternative sources
of energy which meets the modern energy crisis. Natural gas has filled a huge gap of energy
demand because of its cleaner combustion and less flue gas emission into the atmosphere [90].
Natural gas consists of different types of gases which are harmful to the living organisms as
well as environment such as carbon dioxide, hydrogen sulphide, carbon disulphide, mercaptans
and minute quantity of carbonyl sulphide. Therefore, from safety purpose, the removal of these
harmful gases has been become essential in this time of energy crisis. Separation of these gases
include series operation of distillation column and this results in greater capital investment and
a huge amount of energy is required to carry out this type of separation. Hence, to avoid this
system of huge energy consumption, heat integrated and highly thermally efficient distillation
column such as thermally coupled distillation column, divided distillation column [91].
The middle section of the divided wall distillation column of a single shell is split into two
sections and a wall strip is inserted into the middle of the column in the appropriate position
[92]. Divided Wall Distillation Column has the capacity of separating more than one
component in a single distillation column and hence, it achieved a greater attention in the
chemical industry for the separation process and saves both energy and capital. Sangal et al.
have shown that the theoretical study confirms the energy saving of at least 30% as compared
to the conventional distillation column [93]. The DWC technology is not confined to ternary
separation only but it can also carry out azeotropic separations and reactive distillation [94].
Innat et al., Sangal et al., and Wu et al., have conducted a lot of research related to the extractive
divided wall column in which, the process is totally different from the process of the
conventional distillation column [93, 95 and 96]. A third component is added in the extractive
divided wall column and a make-up stream is required for the solvent loss but in the recent
study, the solvent is made up of the mixture of the propane and the heavier components in
which the solvent is similar to the light key component. Convergence problem is occurred due

to this feature of the divided wall system. In recent studies, there is no water in the solvent
stream and also the solvent does not possess the corrosive behaviour as compared to the
conventional distillation column. To reduce the energy requirements and the number of trays
in the extractive distillation process for the separation purpose, HYSIS 3.1 is first examined to
use the divided wall column using top wall configuration [97].
There is a mixture in which three components are present that is A, B and C, in which the A is
the lightest component and C is the heaviest component. In Fig. 13a, it has been shown that
how these three components are separated through direct sequence of two distillation columns.
In the mixture, where B is the major component and the split between B and C is much simple
as split between A and C and the thermal efficiency of this type of configuration is enhanced
which is shown in Fig. 13b. The concentration of B in the first column tends to be maximising
at a tray which is near to the bottom. On trays which are below that tray which is near to the
bottom, the concentration of the heaviest component continues to increase and the
concentration of the component B starts decreasing on each additional tray which is towards
the bottom of the column. For separating the in a desired amount and at a maximum purity, a
large quantity of energy is used and this huge amount of energy utilization leads to the low
thermal efficiency of the distillation column. The configuration which is shown in Fig. 13b
does not possess such a complex problem of remixing which occurs in direct sequence
distillation column and this combination is known as Petlyk column and carry out the sharp
split between the components A and C in the first column and facilitate the B to distribute in
equal amount between A and C. The smaller prefractionation column of the Petlyk
configuration separate the entire A and a small quantity of B while the bottom column separates
the entire quantity of C and the remaining amount of B. Therefore, the upper section of the
Petlyk configuration performs the A/B separation and the bottom section carry the separation
of B and C. The fraction of the B which is separated in the overhead section of the
prefactionation column can be adjusted in such a way that the remixing does not take place
during the design phase as happens in the direct sequence column. This has resulted in the
decreasing of the thermal inefficiency as seen in the direct sequence column and results in a
energy saving of about 30% for a typical design and can reach up to 50% to 60% in case of
conventional distillation column [98, 99, 100 and 101].
It has been seen in Fig. 13b that the Petlyk column is thermally coupled, it means that the
vapour and liquid which remains unused and got wasted is used to provide vapour and liquid
to the prefactionation column. This type of arrangement consists of only one condenser and
one reboiler and both these columns are attached to the second column of the Petlyk

arrangement. It is because, the Petlyk column consists of very few number of the distillation
column so the total capital costs is less as compared to the conventional distillation column. If
the prefractionation column is integrated in a single shell which is the main column and further
the column is reduced into much compact distillation column called the divided wall distillation
column which is shown in Fig. 13c. There is a negligible heat transfer across the dividing wall
column and also the divided wall column is equivalent to the Petlyk column. There is a saving
of 30% capital cost in the divided wall column as compared to the conventional distillation
column [100 and 101].
The feasibility of the divided wall column in the industry depends upon the thermodynamic
properties, composition of the stream to be separated and the product requirements. Further,
product purity, feed composition, relative volatility and revamp possibilities decides whether
the divided wall column is suitable for the particular separation or not. The purity of the middle
product is greater in the divided wall distillation column as compared to conventional column.
Therefore, divided wall distillation column is given preference in the particular separation. If
the sufficient purity of the middle product is not required then the side draw column is sufficient
for this type of separation. If in this case, a divided wall column is applied, it is because, it
requires less column and hence minimum capital cost and less energy as compared to the simple
side draw column. Divided wall column is more advantageous in those cases where the
composition of one of the component is 60% to 70%.

3. Modelling and Simulation

3.1. Introduction
ASPEN PLUS is an industry based market leading process modelling tool for conceptual
design, optimization and performance monitoring for the chemical, polymer, speciality
chemical, metals and minerals and coal power industries. ASPEN PLUS software helps in
extending steady-state simulation to dynamic simulation for safety and controllability studies,
sizing relief values and optimization transition start-up and shutdown policies. Properties
analysis which are required during simulation are properties are properties of pure components
and mixtures that is enthalpy, density viscosity, heat capacity etc. Parameters estimation which
are required for property models are UNIFAC method which is used for binary parameters and
Joback method for boiling points.
Process simulation equipment which are required during simulation are pump, compressor,
different types of distillation column and reactors, valve, tank, heat exchanger, CSTR, PFR,
extraction column, absorber, filter, crystallizer etc. ASPEN PLUS software is employed for
mass and energy balances, physical chemistry, chemical engineering thermodynamics,
chemical reaction engineering, unit operations, process design and process control. It uses a
mathematical model to predict the performance of the process. This information can then be
used in an iterative fashion to optimize the design. This accurate modelling of thermodynamic
properties are particularly important in the separation of non-ideal mixtures and ASPEN PLUS
has a large data of regressed parameters. It can handle very complex process including multiple
column separation systems, chemical reactors, distillation of chemically reactive compounds
and even electrolyte solutions like mineral acids and NaOH solutions.
MTBE is an organic compound with molecular formula (CH3)3COCH3 and IUPAC
nomenclature 2-methoxy 2-methyl propane. It is a volatile flammable and colourless liquid that
is sparingly soluble in water. It is an gasoline additive used as an oxygenate to raise the octane
number. MTBE is manufactured via the chemical reaction of methanol and isobutylene.
Methanol is derived from naturel gas and isobutylene is derive from butane obtained from
crude oil or natural gas. MTBE is mostly used as a fuel for gasoline engines. It is one of a group
of chemicals commonly known as oxygenates because they raise the oxygen content of
gasoline. In the US it has been used in gasoline at low levels since 1979 to replace tetraethyl
lead and to increase its octane rating helping prevent engine knocking. Oxygenates help
gasoline burn more completely reducing tailpipe emissions from pre 1984 motor vehicles

dilutes or displaces gasoline components such as aromatics and sulphur and optimize the
oxidation during combustion.
3.2. Design of Reactive Distillation Column
For the modelling of the reactive distillation column, it has been assumed that the distillation
column operates at the adiabatic condition and the reaction is carried out in the liquid phase.
Each stage is considered as a perfectly mixed continuous stirred tank reactor (CSTR). Further,
the vapour and liquid are in phase equilibrium in which there is a negligible heat of mixing of
liquid and vapour mixture at any stage of the distillation column. There is no vapour hold up
in any stage of the distillation column. For the simplification of the modelling complexities,
there is no hydrodynamic effects in the modelling work which has been presented. This include
mass and energy balances, vapour liquid equilibrium model and summation equation.

Figure 3.1. Schematic Representation of reactive Distillation Column. Muhamad Nazri Murat
et al. (2003).
The overall material balance for equilibrium stage j;

Fj L j 1 Vj 1 jR j L j Vj

(3.1)

Unsteady state component i material balance;

Hj

dx j ,i

( Z j ,i X j 1,i L j 1 Y j 1,iV j 1 ) ( X j ,i L j Y j ,iV j ) j (Vr ,i rj ,r )

dt

(3.2)

r 1

Here, J is the number of stage, I is the number of component, R is the specific reaction number.
The derived material can be better understood under the following definitions
H j is the liquid holdup on stage j which is defined as the molar quantity of liquid mixture that

is being held on the stage j at a certain level.

R is the total numbers of moles which is generated or disappear through reaction on stage j.
In r j , r ,r is the rate of reaction r on stage j. Term j decides whether the reaction occurs or not.
If the reaction occurs then the value of j is one otherwise it is zero. It means there is no
reaction.
Symbols Z j ,i , Y j ,i , X j ,i represents the component i mole fractions of feed flow Fj, liquid flow
Lj and vapour flow Vj on stage j and all are in moles.
The term Vr,i is the stoichiometric coefficient of component i for reaction r.
Energy balance

F j z j ,i h jf,i h jL,i L j 1 x j 1,i h Lj 1,i h Lj ,i V j 1 y j 1,i hVj 1,i h Lj ,i

c

i 1

jW j H
R

r 1

R
j ,r

i 1

i 1

V j x j ,i h h
c

j ,r

i 1

V
j ,i

L
j ,i

J / s

(3.3)

Here, hL is the partial molar enthalpy of liquid in J/mol, hv is the partial molar enthalpy of
vapour in J/mol, HR is the heat of reaction in j/mol, W is the weight of catalyst in kg.
Phase Equilibrium

p0
Y
X
P

(3.4)

For making the entire fugacity coefficient to unity for the system, it is necessary to assume the
vapour phase to be ideal. The activity coefficient which characterises liquid phase non
ideality are calculated from the UNIFAC method. Antoine equation is used to calculate the
saturated vapour pressure P0 and the total pressure P.

Summation Equation
c

X
i 1

j ,i

Y
i 1

j ,i

1.0 (For liquid phase)

(3.5)

1.0 (For vapour phase)

(3.6)

Kinetic Modelling
The main reaction between the methanol and isobutylene for the production of the methyl tert
butyl ether is represented as follows:
CH 3OH CH 3 2C CH 2
CH 3 3 COCH 3MeOH
Methanol

IB

(3.7)

MTBE

a
aMTBE
in mol/s
Rate Wq K f IB
2
aMeOH K eq aMeOH

(3.8)

Where W is the weight of the catalyst in kg and q is the quantity of acid group on the resin per
unit mass. Kf is the forward rate constant and is given by the following equation.
11110
K f 3.67x1012 exp
in mol/(s eqv)
T

(3.9)

The equilibrium constant is given by the equation:

Keq 284 exp f T

(3.10)

And
1 1
T
f T A1 A2 ln A3[T T0 ] A4 [T 2 T0 2 ] A5 [T 3 T03 ] A6 [T 4 T0 4 ]
T T0
T0
(3.11)

Figure 3.2. Algorithms for Solving Reactive Distillation Simulation. M.N. Murat et al.
(2003).

3.3. Design of Divided Wall Distillation Column

The design of the divided wall column can be carried out under the following headings:
i.

Design of the prefactionator (section I).

ii.

Design of the main column.

iii.

Minimum reflux ratio for section II.

iv.

Minimum reflux ratio for section III.

v.

Selection of the dominant section for the main column.

vi.

Determination of compositions for interconnecting streams.

Design of the prefactionator: In the prefactionator column, the recoveries of light and heavy
component are considered that is rA and rC. For the recovery of the product in three component
mixture, the Underwood equation plays an important role.
3

i xi , f
1 qI
I

i 1

c 2 I B 1I A

(3.12)

And the minimum reflux ratio can be obtained from the following equation
3 F j i
LImin= maxj LI min max j i i ri .
i 1 i j

(3.13)

Underwoods method is used for the calculation of the products from the section I and their
compositions and the minimum reflux ratio. Gillilands equation is used to calculate the
number of stages for the given of the reflux ratio while the Kirkbrides equation is used to
determine the feed tray location.
Design of the main column: The main column is comprised of the section II and the section II.
The separation of the light and the intermediate component takes place in the section II and the
heavy component is sent into the bottom of the section II. The separation between the heavy
and the intermediate component takes place in the section III and the light component goes
completely into the upper portion of the section III. If it has been realised that each section of
the main column possess minimum flow requirement then the section which has the highest
value provides overall minimum requirement of the flow.
Minimum reflux ratio for section II: Section II consists of the saturated vapour feed (V I) and a
saturated liquid as a side withdrawal (LI). These streams belong to the same tray of the main

column. Here, the minimum reflux ratio can be determined with the help of the Underwoods
method even the compositions of the VI and LI are not known. Glinos and Malone (1985) has
given their own method for the calculation of the minimum reflux ratio with side rectifiers. The
section II of the DWC arrangement which is shown in Fig. 15 is similar to DWC arrangement
configured by the Glinos and Malone (1985). Further, they have given that the interconnecting
flows can be presented in terms of an equivalent feed stream with a superheated thermal
condition.
qD I

LI
RI
I
I
V L

(3.14)

Underwoods method can be applied with the help of this equation for the calculation of the
minimum reflux ratio in section II of the DWC arrangement.
Minimum reflux ratio for section III: This section comprises of the saturated liquid feed ( LI )
and a saturated vapour side product ( V I ). Here also the similar method is applied for the
calculation of the minimum reflux ratio as in the case of the section II of the DWC arrangement.
Further, the thermal condition which applied here is different from the previous one and is
given as:
qwI

LI
.
LI V I

(3.15)

Equivalent feed streams can be used for the estimation of the thermal condition with the help
of this equation. Further, Carlberg and Westerberg implemented these equations in the analysis
of the temperature heat diagrams of the thermally coupled distillation systems.
Selection of the dominant section for the main column: After the calculation of the minimum
reflux ratios in the section I and section II of the DWC arrangement in the Fig. 3.15, the
operating value is selected for the DWC arrangement and is given by the equation:
LIII min s D I q D i

Rmin max
D

(3.16)

And
LII min

Rmin max
D

(3.17)

These two equations are equivalent to the equations which are reported by Nikolaides and
Malone (1987). Further, these equations are simplified as:
Rmin

LII min

Rmin

(3.18)

LIII min s D I q D i
D

(3.19)

Further the design value for R above the minimum value can be set and hence for the main
column, the internal liquid flow rates are:
LII = RDII
LIII = LII + DIqDI - S

(3.20)
(3.21)

Gilliland and Kirkbrides equations are used for the determination of the number of the ideal
trays and the location of the feed trays in the section II and III of the DWC arrangement shown
in Fig. 15.
Determination of compositions for interconnecting streams:
If the system consists of the two component mixture that is if the feed saturated liquid or vapour
then the composition of the feed stage is equal to the feed composition. On the other hand, if
the feed is sub-cooled, superheated or partially vaporized then the composition of the feed in
the stage is not equal to the feed composition. The operating line and the feed line give the
composition of the equivalent feed streams on solving. The compositions of the saturated
streams which are equivalent to the non-saturated feed can be determined in the multicomponent systems. In DWC arrangement, the composition of the feed stream corresponds to
the composition of the interconnecting streams. Hence, the feed line and the operating line are
used for the determination of feed compositions of the interconnecting streams.

Figure 3.3. Schematic Representation of the DWC column using Petlyk column. Michael A.
et al. (2013).
q
x
xi D
Yi
q 1
q 1

x
R
Yi
xi D
R 1
R 1

(3.22)
(3.23)

On combining these equations we can get,

Xi
Yi

Z i R 1 xD q 1
Rq

Rz i qxD
Rq

(3.24)
(3.25)

The above equations give an idea for the determination of the compositions of the
interconnecting streams in terms of the reflux ratio and the feed composition.

3.4. Sequence of Steps Followed for Modelling in ASPEN Plus

Figure 3.4. Flowsheet for the Production of MTBE using ASPEN PLUS Software in Reactive Distillation Column

Figure 3.5. Conventional Route for the Production of MTBE Using ASPEN PLUS Software

Figure 3.6. Flowsheet for the production of MTBE Using ASPEN PLUS in Divided Wall Distillation.

Feed Specifications:
Methanol
Table 3.1. Input Specifications of Methanol Feed
Temp.
320K

Pressure
1atm

Total Flow Rate

711.3

Mole Fraction
0.64

Isobutylene
Table 3.2. Input Specifications of Iso Butylene Feed
Temp.
350K

Pressure
1atm

Pump
Discharge pressure 11.7 atm
Control volume 1
Outlet pressure 11.5 atm
Valid Phases Liquid only

Compressor
Type Isentropic
Discharge pressure 11.5 atm
Control Volume 2
Outlet pressure 10.8
Valid Phases Liquid only
Control Volume 3
Outlet pressure 11.3 atm
Valid phases Liquid only

Distillation Column Specification

Calculation type Equilibrium
Number of stages 17
Condenser Type Total
Reboiler type Kettle
Valid phases Vapour liquid
Convergence Strongly non-ideal liquid
Operating conditions
Bottom rate 640.8 Kmol/h

Total Flow Rate

1965.8

Mole Fraction
0.36

Reflux ratio - 7
Stream specifications
Product stream 1
Vapour feed Stage 11
Liquid feed - Stage 10
Product stream 2
Distillate - Stage 1
Bottom - Stage 17
Pressure
Stage 1 or condenser pressure - 11 atm
Pressure drop for rest of the column - 0.5 atm

Reactions
Starting stage - 4
Ending stage - 16
Reaction ID - R1

Sizing and rating specifications

Packing section
Starting stage - 2
Ending stage - 16
Type - Raschig
Packing characteristics
Vendor - Raschig
Material - Standard
Section diameter - 6 meter
Dimensional - 35mm
HETP - 1
Basic convergence
Algorithms non-ideal
Maximum iterations 200

Methods

Initialization method - standard

Damping level - none
Liquid-liquid phase splitting method - Gibbs

Solids handling - overall

Salt precipitation handling - include
Stoichiometric specification
Reaction name 1
Type - kinetic

Reactants
Table 3.3. Stoichiometry of reactants
Components Coefficients Exponent
MeOH
-1
-1
IB
-1
1

Products
Table 3.4. Stoichiometry of products
Components Coefficients Exponent
MTBE
1
-

Reaction name 2
Type kinetic

Reactants
Table 3.5. Stoichiometry of reactants
Components Coefficients Exponent
MTBE
-1
1

Products
Table 3.6. Stoichiometry of products
Components Coefficients Exponent
MeOH
1
2
IB
1
Kinetics
MeOH + IB = MTBE
Reacting phase Liquid
Power law kinetic expression
If T0 is specified then

E 1

T RT T T
Kinetic Factor = k e 0
T0

(3.26)

If T0 is not specified then

n

Kinetic factor = kT e

RT

(3.27)

Here,
K = 3.67e+12
n=0
E = 92440
Basis mole fraction
MTBE = MeOH + IB
Power law kinetic factors are same as for the above reaction and only the value of the
k, n and E are changed.
K = 2.67e+12
N=0
E = 134554 in kj/mol
T0 = 0
Basis mole fraction.

Figure 3.7 Selection of Components for the Production of MTBE.

Figure 3.8. Flowsheet Showing Kinetic of the Reaction Using ASPEN PLUS

4. Results and Discussion

4.1. Conventional distillation column
Effect of reflux ratio on product quality: In this column, there is no much effect of reflux
ratio on product quality. On increasing the reflux ratio, there is a little increase in the
quality of the MTBE and on further increase of the reflux ratio the product quality becomes
constant.
0.8
0.75

Product

0.7
0.65

0.6
0.55

Distillate

0.5

MTBE

0.45
1

Reflux Ratio
Figure 4.1. Product purity with changing reflux ratio for conventional distillation
At reflux ratio of 5, the product quality of MTBE is 68% which is the bottom product.
Figure 4.2 shows the effect of reflux ratio on reboiler duty. In conventional distillation column,
there is a sharp increase in the reboiler duty on increasing the reflux ratio. It is because, in this
column more than one separate column is required for the desired separation.

Reboiler Duty (kW)

2500000
2000000
1500000
1000000
500000
0
1

Reflux Ratio
Figure 4.2. Reboiler duty with changing reflux ratio for conventional distillation

On increasing the reflux ratio up to 5, the heat load on reboiler duty increases upto 2600000
kW.
If the reflux ratio is further increased then there is no significant effect of the reflux on reboiler
duty is seen.
Figure 4.3 shows the effect of the number of the stages on the production rate of the product.
This figure tells that how the production rate changes on varying the number of stages. On
increasing the number of the stages, there is no significant increase in the bottom product. The
bottom product increases at a very slow rate.

MTBE

1200

Top Product

Prooduction Rate
(kmol/hr)

1400

1000
800
600
400

200
0
14

19

24

29

34

39

44

49

Number of Stages
Figure 4.3. Production rate with changing number of stages
At the stage of 40, the production rate of the top product is minimum and the bottom product
is maximum. Therefore the optimum number of the stage is 40.
Number of Stages
10

20

30

40

50

Reboiler Heat Duty

(mmkol/h)

-36
-38
-40
-42
-44
-46
-48
-50

Figure 4.4. Reboiler heat duty with changing number of stages for conventional distillation

Figure 4.4 shows the effect of number of stages on reboiler heat duty: In conventional
distillation column
There is a linear relationship between the reboiler heat duty and the number of stages as seen
in the above figure. The reboiler heat duty increases up to -47 at the stage number of 45.
Figure 4.5 shows effect of number of stages on temperature: There is almost a linear
relationship between the number of stages and the temperature in case of conventional
distillation.

Temperature (C)

330
280
230
180
130
80
30
0

10

15

20

25

30

Number of stages
Figure 4.5. Temperature with changing number of stages for conventional distillation
On increasing the number of stages, the temperature at the same rate and it is 330 degree
celcious at the stage number of 25 as reported in the literature.
4.2. Reactive distillation column
0.95
0.9

Product

0.85
0.8
0.75

Distillate

0.7

MTBE

0.65
0.6
1

Reflux Ratio
Figure 4.6. Product purity with changing reflux ratio

Effect of reflux ratio on product purity: The variation of product purity is shown in the Fig. .
The purity of the main product MTBE increase to a greater extent on increasing the reflux ratio
whereas the purity of the side and bottom product is less as compared to the purity of the
MTBE. At reflux ratio of 7, the purity of the top product increases up to 90%.
Figure 4.7 shows effect of reflux ratio on reboiler duty. The effect of reflux ratio on reboiler
duty is explained as follows. On increasing the refllux ratio, heat load on reboiler increases to
a greater extent as compared to the divided wall column.

Reboiler Duty (kW)

2500000
2000000
1500000
1000000
500000
0
1

Reflux Ratio
Figure 4.7. Reboiler duty with changing reflux ratio

On increasing the reflux ratio of 5, the reboiler duty becomes 2700000 kW.
Effect of the number of stages on the amount of the product: This figure shows that how the
amount of the product varies on varying the number of stages. On increasing the number of
stages, the production rate of the top product decreases while that of the bottom product
increases. The bottom product that is MTBE being less volatile so it is stripped from the bottom
of the RDC column.

Production Rate (kmol/hr)

1600
1400
1200
1000
800
600
400

MTBE

200

Top Product

0
10

20

30
Number of Stages

40

50

Figure 4.8. Production rate with changing number of stages

On stage number 30, the production of the top product is minimum and the production of the
bottom product that is the desired product MTBE is maximum, so the optimum stage is 30.
Figure 4.9 shows effect of number of stages on reboiler heat duty. On increasing the number
of stages, the reboiler heat duty increases but on further increase of number of stages, the
reboiler heat duty becomes constant. Therefore at stage number 45, the reboiler heat duty is 44 mmkcal/h.
Number of Stages

Reboiler Heat Duty (mmkcal/h)

10

20

30

40

50

-36
-38
-40
-42
-44

-46
-48
-50

Figure 4.9. Reboiler heat duty with changing number of stages

Figure 4.10 shows effect of number stages on the temperature. In RDC column, there is not a
steep rise in temperature on increasing the number of stages. It is because in RDC column, the

reaction and the separation process takes simultaneously. There is a temperature rise of 230
degree Celsius at the stage number of 25 as reported in the literature.

Temperature (C)

330
280
230
180
130
80
30
0

10

15

20

25

30

Number of stages
Figure 4.10. Temperature with changing number of stages
4.3. Divided wall distillation column
Figure 4.11 shows effect of reflux ratio on product. On increasing reflux ratio, the product
quality increases, it is because when the reflux comes in contact with the vapour coming
towards the upper portion of the column then the mass transfer between the vapour and the
reflux takes place as a result of this the concentration of the vapour to be condensed increases
and hence the product quality increases.

Product

0.9

Distillate
MTBE
0.8
1

Reflux Ratio
Figure 4.11. Product purity with changing reflux ratio
Especially the quality of the desired product that is MTBE increases rapidly on increasing the
reflux ratio but on further increase in reflux ratio, the product quality becomes constant because
the condition of total reflux is reached.

Figure 4.12 shows effect of reflux ratio on reboiler duty. In case of DWC column, the load on
reboiler increases as the reflux ratio increases. It happens because the reflux remains in the
form of condensed liquid and when this liquid goes back into the column then it require extra
heat to convert into the vapour form.

Reboiler Duty (kW)

2500000
2000000
1500000

1000000
500000
0
1

3
4
Reflux Ratio

Figure 4.12. Reboiler duty with changing reflux ratio

Figure 4.13 shows effect of the number of stages on the amount of the product. This figure
explains that the amount of the top product is decreasing on increasing the number of the stages
and the amount of the bottom product is increasing. At the stage number 20, the top product is
minimum and the bottom product is maximum.
1400

Prooduction Rate
(kmol/hr)

1200
1000
800
600
400

MTBE

200
0
10

20

30

40

50

Number of Stages
Figure 4.13. Production rate with number of stages
On further increasing the number of stages, the production rate of both that is the top
product and the bottom becomes constant. Therefore the optimum number of stage is
20.

Number of Stages
10

20

30

40

50

Reboiler Heat Duty

(mmkcal/h)

-36
-38
-40
-42
-44
-46
-48
-50

Figure 4.14. Reboiler heat duty with changing number of stages

Figure 4.14 shows effect of number of stages on reboiler heat duty. In DWC column, firstly
the reboiler heat duty increases on increasing the number of stages but for the further increase
of the number of stages, the reboiler heat duty becomes constant and at the stage number of 45,
the reboiler heat duty is -40 mmkcal/h.
Figure 4.15 shows effect of number of stages on temperature: In this column, given figure tells
that how the temperature changes on increasing the number of stages. There in much increase
in temperature on increasing the number of stages.

Temperature (C)

330

280
230
180
130
80
30
0

10

15

20

25

30

Number of stages
Figure 4.15. Temperature with changing number of stages
The rise in temperature is not steep in case of DWC column it is because all the separation
process takes place in one shell only. There is a temperature rise of 250 degree Celsius at the
stage number of 25.

Conclusion and Recommendations

Simulation and steady state behavior and production of the MTBE is carried out in the
conventional distillation column, reactive distillation column and the divided wall distillation
column. Results were obtained in terms of the product purity, product production rate, reboiler
heat duty, temperature and pressure effect on the product streams and effect of reflux ratio and
number of stages on the distillate and bottom product.
1.

The product purity increases with increase in the reflux ratio in case of the CD, RDC and
DWC column. In case of conventional distillation, there is no much effect of reflux ratio
on product quality that is on reflux ratio of 5.5, the product quality is 60% while in case
of RDC and DWC distillation, the product quality is 90% and 98% at reflux ratio of 5.5.

2.

In case of conventional distillation the load on the reboiler is 2800000 kW at reflux ratio
of 5.5 but in case of RDC and DWC column the reboiler duty is 2500000 kW and 2300000
kW at reflux ratio of 5.5.

3.

The number of stages have a huge effect on the production rate of the product. In case of
conventional distillation, the production rate of the desired is maximum that is 400 kmol/h
at the stage of 30 and the rate of the top product is minimum at that stage. In case of RDC
distillation column, the production rate of the desired bottom product is 600 kmol/h at the
stage number of 30. While in case of DWC column it is 700 kmol/h at the same stage.
Thus the DWC column is better among the other two.

4.

The reboiler duty increases linearly with the number of stages in case of conventional
column that is at stage number 45, the reboiler heat duty is -47 mmkcal/h. While in case
of RDC and DWC column, it is -44 and -40 mmkcal/h at the stage number of 45.

5.

In case of conventional column there is a steep rise in temperature on increasing the

number of stages. In case of RDC and DWC there in much increase in temperature with
the number of stages. The temperature rises up to 280 and 250 degree Celsius at stage
number of 25 while temperature rises up to 330 degree Celsius at the stage number of 25
in case of conventional column.

References
1. Amiya K. Jana, Advances in Heat Pump Assisted Distillation Column, Energy and
Process Engineering Laboratory, Department of Chemical Engineering, Indian
Institute of Technology Kharagpur 2013, India.
2. Daniel Staak et al, Dividing Wall Column For Industrial Multipurpose Use, Lonza
Chemical R&D, Visp, Switzerland 2013.
3. Omer Yildirim et al, Dividing Column In Chemical Process Industries: A Review
On Current Activities. University Of Paderborn, Faculty Of Mechanical
Engineering, Chair Of Fluid Process Engineering, Pohlweg 55, D-33098 Paderborn
Germany
4. Z. FONYO AND N. BENKO, Comparison Of Various Heat Pump Assisted
Distillation Configurations, Department Of Chemical Engineering, Technical
University Of Budapest, Budapest, Hungary.
5. Eduardo diez, Paul Langston, Gabriel Ovejero, M. Dolores Romero, Economic
Feasibility of Heat Pumps in Distillation to Reduce Energy Use, School of Chemical
and Environmental Engineering, The University of Nottingham, University park,
Nottingham NG7 2RD, UK Group De Catalisis y Procesos de Separacion (CyPS),
Departamento de Inginiena Qumica, Facultad de C.C. Quimicas, Universidad
Complutense de Madrid Avda, Complutense s\n, 28040 Madrid Spain.
6. G.P. Quadri, Use of Heat Pump for p-p splitter, Hydrocarbon Processing 60 (1981)
147-151.
7. Z. Fonyo, R. Kurrat, D.W.T. Rippin, I. Meszaros, Comparative Analysis of Various
Heat Pump Scheme Applied to C4 Splitters, Computers and Chemical Engineering
19 (1995) S1-S6.
8. J. Humphrey, Separation processes: playing a critical role, Chem. Eng. Progr. 91
(10) (1995) 3141.
9. T. Mix, J. Dweck, M. Weinverg, R. Armstrong, Energy conservation in distillation,
chemical Engineering Programme 74(4) (1978) 49.
10. Wang Ping, Xie Changfang, Xu Shiming, Ge Yulin, School of Energy and Power
Engineering, Dalian University of Technology Dalian, China, Design Institute of
Jinzhou CNPC Northeast petrochemical Engineering Company limited, Jinzhou,
China.

11. Rivera-Ortega P, Picon-Nunenz M, Torres-Reyes E. Thermal Integration of Heat

Pumping System in Distillation columns [J]. Applied Thermal Engineering, 1999,
19(8):819-929.
12. James G G., Jensen M K., Domanski P A., Experimental Transient Performance of
a Heat Pump Equipped With a Distillation Column [J]. Intrnational Journal of
Refrigeration, 2007, 30(3):499-505.
13. Null HR. Heat Pumps in Distillation. Chemical Engineering Programme
1976;73:58-64.
14. Tobias Kellera,*, Andrjez Goraka,b,2012, TU Dortmand University, Department of
Biochemical and Chemical Engineering, Laboratory of Fluid Separarions, EmillFigge-Trasse 70, D-44227 Dortmund, Germanya, Lodz Technical University,
Department of Environmental and Process Engineering, Lodz, Poland.
15. Harmsen, G.J. (2007). Reactive Distillation. The Front-runner of Industrial Process
Intensification. Chemical Engineering and Processing, 46, 774-780.
16. Shoenmakers, H., and Bessling, B. (2003). Reactive and Catalytic Distillation from
an Industrial Perspective. Chemical Engineering and Processing, 42, 145-155.
17. Georgiadis, M.C., Schenk, M., Pistikopoulos, E.N., and Gani, R. (2002). The
Interactions of Design, Control and Operability in Reactive Distillation Systems.
Computers and Chemical Engineering, 26, 735-746.
18. Sundmacher, K., and Hoffmann, U. (1996). Development of a New Catalytic
Distillation Process for Fuel Ethers via a Detailed Non-equilibrium model.
Chemical Engineering Science, 51, 2359-2368.
19. Agreda, V.H., Partin, L.R., and Heise, W.H., (1990). High Purity Methyl-acetate
via Reactive Distillation. Chemical Engineering Process, 86, 40-46.
20. Steinigewege, S., and Gmehling, J. (2004). TransestrificationProcesses By
Combination of Reactive Distillation and Pervaporation. Chemical Engineering and
Processing, 43, 447-456.
21. Schmitt, M., Hasse, H., Althaus, K., Schoenmakers, H., Goetze, L., and Moritz, P.
(2004). Synthesis of n-hexyl Acetate by Reactive Distillation. Chemical
Engineering and Processing, 43, 397-409.
22. Mohl, K.-D., Kienle, A., Gilles, E.-D., Rapmund, P., Sundmacher, K., and
Hoffmann, U. (1999). Steady-State Multiplicities in Reactive Distillation Columns
for the Production Fuel Ethers MTBE and TAME. Chemical Engineering and
Journal, 72, 1029-1043.

23. Ramzan, N., Faheem, M., Gani, R., and Witt, W. (2010). Multiple Steady-State
Detection in a Packed-bed Reactive Distillation Column Using Bifurcation
Analysis. Computers and Chemical Engineering, 43, 460-466.
24. Kenig, E.Y., and Gorak, A. (2007). Modelling of Reactive Distillation. In F. Keil
(Ed.), Modelling of Process Intensification (pp. 323-364). Weimheim:, Viley-VCH.
25. Taylor, R., and Krishna, R. (2000). Modelling Reactive Distillation. Chemical
Engineering Science, 55, 5183-5229.
26. Vinay Amte, Sri Harsha Nistala, Sanjay M. Mahajani, Ranjan K. Malik*.
Department of Chemical Engineering, IIT-Bombay, Mumbai 40079, India.
27. Glasser, D., Hildebrandlt, D., and Crowe, C. (1987). A Geometry Approach to
Steady Flow Reactors: the Attainable Region and Optimization in Concentration
Space. Industrial and Engineering Chemistry Research, 26, 1803-1810.
28. Nisoli, A., Manole, M.F., and Doherty, M.F. (1997). Attainable regions for Reaction
with Separarion. AIChE Journal, 43(2), 374-386.
29. Agarwal, V., Thotla, S., and Mahajani, S.M. (2008a). Attainable Regions of
Reactive Distillation. Part-II. Single Reactant Non-azeotropic Systems. Chemical
Engineering Science, 63, 2946-2965.
30. Jingjun Liu, Bolun Yang, Shiqing Lu, Chunhai Yi*. Department of Chemical
Engineering, State Key Laboratory of Multiphase Flow in Power Engineering,
Xian Jiaotong University, Xian, Shaanxi, 710049, PR China.
31. R. Krishnamurthy, R. Taylor, A Non-equilibrium Stage Model of Multi-component
Separation Processes. 3. The Influence of Unequal component efficiencies in
process design problems, AIChE Journal. 31 (1985) 1975-1985.
32. Omer Yildrima, Anton A. Kissb, Eugeny Y. Keniga,*. Dividing Wall Columns in
Chemical Process Industry.

University of Paderborn, Faculty of Mechanical

Engineering, Chair of Fluid Process Engineering, Pohlweg 55, D-33098 Paderborn,

Germany.

Akzo Nobel Research, Development and Innovation, Process

Technology Expert Capability Group, Velperweg 76, 6824 BM, Arnhem, The
Netherlands.
33. G. Kaibel, Distillation Columns with Longitudinal Subdivision, Chemical
Engineering Technology 59 (1987) 533.
34. G. Parkinson, Dividing-Wall Columns Find Greater Appeal, Chemical Engineering
Programme. 103 (2007) 8-11.

35. J. Harmsen, Process Intensification in the Petrochemicals Industry: Drivers and

Hurdles for Commercial Implementation, Chemical Engineering Process, Process
Intensification 49 (2010) 70-73.
36. R.O. Wright, Fractionation Appararus, US Patent No. 2471134 (1949).
37. N. Asprion, G. Kaibel, Dividing Wall Columns: Fundamentals and Recent
Advances, Chemical Engineering Processes, Process Intensification 49 (2010) 139146.
38. D.A. Monro, Fractionating Appararus and Method of Fractionation, US patent No.
2134882 (1938).
39. B. Kaibel, H. Jansen, E. Zich, Z. Olujic. Unfixed Dividing Wall Technology for
Packed and Tray Distillation Columns, Distillation and Absorption 2006, IChemE,
London, England, 2006. Pp. 252-266.
40. M.A. Schultz, D.E. OBrien, R.K. Hoehn, C.P. Luebke, D.G. Stewart, Innovative
Flowschemes Using Divided Wall Columns, In 16th European Symposium of
Computer Aided Process Engineering Elsevier, Garmisch-Partenkirchen, Germany,
(2006), pp. 695-700.
41. J. Strandberg, S. Skogestad, Stabilizing Operation of a 4-Product Integrated Kaibel
Column, Distillation and Absorption 2006, IChemE, London, England, (2006), pp.
638-647.
42. A.C. Christiansen, S. Skogestad, K. Lien, Complex Distillation Arrangements,
Extending the Petlyuk Ideas, Computational Chemical Engineering, 21 (1997)
S237-S242.
43. M. Jobson, Dividing Wall Distillation Comes of Age, The Chemical Engineering
766 (2005), 30-31.
44. Z. Olujic, B. Kaibel, H. Jansen, T. Reitfort, E. Zich, G. Frey, Distillation column
Internals/Configurations For Process Intensification, Chemical Biochemical
Engineering. Q. ( 2003) 301-309.
45. I. Dejanovic, L. Matijasevic, Z. Olujic, Dividing Wall Column- A breakthrough
towards

sustainable

distilling,

Chemical

Engineering

Process,

Process

Intensification 49 (2010) 559-580.

46. Olujic Z, Jodecke M, Shilkin A, Schuch G, Kaibel B. Equipment Improvement
Trends in Distillation. Chemical Engineering Process, 2009; 48: 1089-104.

47. Olujic Z, Fakhri F, de Rijke A, De Graauw J, Jansens Pj. Internal Heat Integration,
The key to an Energy-conserving Distillation Column, J Chem Technol Biotechnol
2003;78:241-8.
48. Nakaiwa M, Huang K, Endo A, Ohmori T, Akiya T, Takamatsu T, Internally Heat
Integrated Distillation Columns, A Review, Trans Inst Chem Engrs 2003;81:16277.
49. Horiuchi K, Yanagimoto K, Kataoka K, Nakaiwa M, Iwakabe K, Matsuda K.
Energy Saving Characteristics of the Internally Heat Integrated Distillation Column
Pilot Plant For Multi-component Petroleum Distillation. J Chem Eng Jpn
2008;41:771-8.
50. Jana AK, Heat Integrated Distillation Operation. Applied Energy 2010;87:1477-94.
51. Naito K, Nakaiwa M, Huang K, Endo A, Aso k, Nakanishi T et al. Operation of a
Bench-scale Ideal Heat Integrated Distillation Column. An Experimental Study.
Computational Chemical Engineering, 2000;24:495-9.
52. Olujic Z, Sun L, de Rijke A, Jansens Pj. Conceptual Design of an Internally Heat
Integrated Propylene-Propane Splitter. Energy 2006;31:3083-96.
53. Fonyo Z, Benko N. Comparison of Various Heat Pump Assisted Distillation
Configurations. Trans Inst Chem Engrs, 1998;76:348-60.
54. Annakou O, Mizsey P. Rigorous Investigation Heat Pump Assisted Distillation.
Heat Recovery Syst CHP 1995;15:241-7.
55. Flower JR, Jackson R. Energy Requirements in the Separation of Mixtures By
Distillation. Trans Inst Chem Engrs. 1964;42:T249-58.
56. Luyben WL. Design and Control of Distillation Columns with Intermediate
Reboilers. Ind Eng Chem Res 2004;43:8244-50.
57. Jana AK, Mane A. Heat Pump Assisted Reactive Distillation, Wide Boiling
Mixture. AIChE J 2011;57:3233-7.
58. Kumar V, Kiran B, Jana AK. A novel Multi-stage Vapor Recompression Reactive
Distillation with Intermediate Reboilers. AIChE J (2013).
59. Agrawal R, Herron DM. Efficient Use of an Intermediate Reboiler or Condenser in
a Binary Distillation. AIChE J 1998;44:1303-15.
60. Agrawal R, Herron DM. Intermediate Reboiler and Condenser Arrangement For
Binary Distillation Columns. AIChE J 1998;44:1316-24.

61. Shenvi AA, Herron DM, Agrawal R. Energy Efficiency Limitations of the
Conventional Heat Integrated Distillation Column Configuration For Binary
Distillation Column. Ind Eng Chem Res 2011;50:119-30.
62. Harwardt A, Marquardt W. Heat Integrated Distillation Columns: Vapour
Recompression or Internal Heat Integration. AIChE J 2012;58:3740-50.
63. Chen H, Huang K, Wang S. A novel simplified configuration for an ideal heat
integrated distillation column. Sep Purif Technol 2010;73:230-42.

64. Huang k, Chen H, Wang S. A design simplification of the ideal heat integrated
distillation column. In de Haan AB, Kooijman h, Gorak A Editors. Distillation and
Absorption, Eindhoven, The Netherlands; 2010, p, 55-60.
65. Suphanit B. Optimal Heat Distribution in the Internally Heat Integrated Distillation
Column. Energy 2011;36:4171-81.
66. Mane A, Jana AK. A New Intensified Heat Integration in Distillation Column. Ind
Eng Chem Res 2010;49:9534-41.
67. Kiran B, Jana AK, Samanta AN. A Novel Intensified Heat Integration in Multicomponent Distillation. Energy 2012;41:443-53.
68. Bjorn I, Gren U, Strom K. A study of a Heat Pump Distillation Column System.
Chemical Engineering Process 1991;29:185-91.
69. Taylor R, Krishna R, 2000. Modelling Reactive Distillation. Chemical Engineering
Science. 55, 5183.
70. Kraemer K, Harwardt A, Skiborowski M, Mitra S, Marquardt W, 2011. Shortcut
Based Design of Multicomponent Heteroazeotropic Distillation. Chemical
Engineering Research Design. 89, 1168.
71. Bruggermann S, Muaquardt W, 2010. Conceptual Design of Distillation Processes
For Mixtures With Distillation Boundaries. II: Optimization of Recycle Policies.
AIChE J, 57, 1540.
72. Ung S, Doherty M.F. 1995. Vapor-liquid Phase Equilibrium in Systems With
Multiple Chemical Reactions. Chemical Engineering Science. 50,23.
73. Seider W.D., Widadgo D., 1996. Multiphase Equilibria of Reactive Systems. Fluid
Phase Equilibrium. 123, 283.
74. Wasylkiewicz K.S., Ung S. Global Phase Stability Analysis For Heterogeneous
Reactive Mixtures and Calculation of Reactive Liquid-Liquid Equilibria. Fluid
Phase Equilibria. 175, 253.

75. Sanchez-Daza O., Perez-Cisneros E., Gani R., Bek-Pedersen E., 2003. Graphical
and Stage to Stage Methods for Reactive Distillation Column Design. AIChE J. 49,
2822.
76. Barbosa D., Doherty M.F., 1998. Design and Minimum Reflux Calculations For
Single Feed Multicomponent Reactive Distillation columns.
77. Dragomir R.M., Jobson M., 2005. Conceptual Design of Single Feed Hybrid
Reactive Distillation Columns. Chemical Engineering Science. 60,4377.
78. Jantharasuk A., Gani R., Gorak A., Assabumrungrat S., 2011. Methodology For
Design and Analysis of Reactive Distillation Involving Multi-element Systems.
Chemical Engineering Research Design. 89, 1295.
79. Barbosa D. And Doherty M.F., 1987b. A New Set of Composition Variables For
the Representation of Reactive Phase Diagrams, Proc R Soc Lond A413:459-464.
80. Lee J.W., Hauan S., Lien K.M. and Westerberg A.W., 2000a. A Graphical Method
for Designing Reactive Distillation Columns I. The Ponchon Savarit Diagram. Pro
R Soc London, 456, 1953.
81. R. Thery, X.M. Meyer*, X. Joulia. Preliminary Design of Reactive Distillation
Column.
82. Barbosa D. And Doherty M.F., 1987c. Design and Minimum Reflux Calculations
for Double Feed Multi-component Reactive Distillation Column, Chemical
Engineering Science, 43(7):1523-1537.
83. Espinosa J., Aguirre P. And Perez G., 1996. Some Aspects in the Design of Multicomponent Reactive Distillation Columns With a Reactive core, Mixtures
Containing Inerts. Ind Eng Chem Res, 35:4537-4549.
84. Okasinski M.J. and Doherty M.F., 1998. Design Method For Kinetically Controlled,
Staged Reactive Distillation Columns, Ind Eng Chem Res, 37(7):2821-2834.
85. Buzad D. And Doherty M.F., 1994. New tools For the Design of Kinetically
Controlled Reactive Distillation Columns . Comput Chem Eng, 18(suppl), S1-S13.
86. Mahajani S. And Kolah A.K., 1996. Some Design Aspects of Reactive Distillation
Columns. Ind Eng Chem Res 35(12): 4587-4596.
87. Ciric A.R. and Gu D., 1994. Synthesis of Non-equilibrium Reactive Distillation By
MINLP Optimization. Ame Inst Chem Eng Jour, 40(9): 1479-1487.
88. Gumus Z.H., Ciric A.R., 1997. Reaction Distillation Column Design With VapourLiquid Equilibria, Comput Chem Eng, 21(supplement): S983-S988.

89. Glasser D., Hildebrandt D. And Crowe C., 1987. A Geometric Approach to Steady
Flow Reactors, the Attainable Region and Optimization in Concentration Space, Ind
Eng Chem Res, 26: 1803-1810.
90. Affadala H.E., Al-Musleh E., 2009. Proceedings of the First Annual Gas Processing
Symposium, Quatar.
91.

Yildrim O, Kiss A.A., Kenig E.Y., 2011. Dividing Wall Columns in Chemical
Process Industry. A Review on Current Activities. Separation and Purification
Technology, 80, 403-417.

92.

Bravo-Bravo C., Segovia-Hernandez J.G., Guttierrez Antonia C., Duran A.L.,

Bonilla-Petriciolet A., Briones-Ramirez A., 2010. Extractive Dividing Wall
Column, Design and Optimization. Ind. Eng. Chem. Res., 49, 3672-3688.

93.

Sangal V.K., Kumar V., Mishra I.M., 2012. Optimization of Structural and
Operational Variables For Energy Efficiency of a Divided Wall Distillation
Column. Computational Chemical Engineering, 40, 33-40.

94.

Kiss A.A., Suszwalak D.J.-P.C., 2012b. Innovative Di-methyl ether synthesis

in a reactive dividing wall column. Computational Chemical Engineering. 38,
74-81.

95.

Ignat R.M., Kiss A.A., 2012. Integrated Bioethanol separation and dehydration
in a non extractive DWC. Chem. Eng. Trans. 29, 619-624.

96.

Wu Y.C., Hen-Chia P., Chien I.-L., 2013. Critical Assessment of the Energy
Saving Potential of an Extractive Dividing Wall Column. Ind. Eng. Chem. Res.
52, 5384-5399.

97.

Yadollah Tavana,*, Shahrokh Shahhosseinib, Seyyed hossein Hosseinic. Design

and Simulation of Ethane Recovery Process in an Extractive Dividing Wall
Column. a National Iranian Gas Company, Tehran, Iran, b Process Simulation
and Control Research Laboratory, School of Chemical Engineering, Iran
University of Science and Technology, P.O. Box 16765-163, Narmak, Tehran,
Iran,

Chemical Engineering Department, Faculty of Engineering, Ilam

University, 69315-516, Ilam, Iran.

98.

Becker H. Et al., 2001. Partitioned Distillation Columns. Why, when and how.
Chemical Engineering 108(1). P.P. 68-74.

99.

Triantafyllou C., and R. Smith., 1992. The Design and Optimization of Fully
Thermally Coupled Distillation Columns. Trans. IChemE, 70, Part A. PP. 118132.

100.

Petlyk F.B. et al., 1965. Thermodynamically Optimal Method for Separaring

Multi-component Mixtures. Int. Chem. Eng., 5, PP. 555-561.

101.

Michael A. Schultz, Douglas G. Stewart, James M. Harris, Steven P.

Rosenblum, Mohammed S. Shakur and Dennis E. OBrien., 2002. Reduce Costs
With Dividing Wall.

102.

Sudibyo; Murat, M.N.; Aziz, N., "Simulation studies of Methyl Tert-butyl Ether
production in reactive distillation," Control System, Computing and
Engineering (ICCSCE), 2011 IEEE International Conference on , vol., no.,
pp.369,374, 25-27 Nov. 2011.