State-of-the-Art Technologies For Separation of Azeotropic Mixtures

Separation & Purification Reviews
ISSN: 1542-2119 (Print) 1542-2127 (Online) Journal homepage: www.tandfonline.com/journals/lspr20
State-of-the-Art Technologies for Separation of

Azeotropic Mixtures
Taha Mahdi, Arshad Ahmad, Mohamad Mahmoud Nasef & Adnan Ripin
To cite this article: Taha Mahdi, Arshad Ahmad, Mohamad Mahmoud Nasef & Adnan Ripin
(2015) State-of-the-Art Technologies for Separation of Azeotropic Mixtures, Separation &
Purification Reviews, 44:4, 308-330, DOI: 10.1080/15422119.2014.963607
To link to this article: https://doi.org/10.1080/15422119.2014.963607
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Separation & Purification Reviews, 44: 308–330, 2015
Copyright © Taylor & Francis Group, LLC
ISSN: 1542-2119 print / 1542-2127 online
DOI: 10.1080/15422119.2014.963607
State-of-the-Art Technologies for Separation of

Azeotropic Mixtures
Taha Mahdi,1 Arshad Ahmad,1,2 Mohamad Mahmoud Nasef,2,3
and Adnan Ripin1,2
1
Faculty of Chemical Engineering, Universiti Teknologi Malaysia, Johor Bahru, Malaysia
2
Institute of Hydrogen Economy, Energy Research Alliance, Universiti Teknologi Malaysia, Johor
Bahru, Malaysia
3
Malaysia–Japan International Institute of Technology, Universiti Teknologi Malaysia, Kuala
Lumpur, Malaysia
Azeotropic separation technologies have been classified broadly into two major categories, i.e.,
distillation and membrane processes. Because normal distillation has limitations for azeotropic
mixtures, enhancements have been proposed that either introduce a third component serv-
ing as an entrainer in extractive and azeotropic distillation processes or apply a pressure
swing distillation system. Among the membrane processes, pervaporation was reported to
be most promising for azeotropic separations. More recently, an approach known as process
intensification has been proposed for combining multiple processes into single units such as a
dividing wall distillation column or exploiting sonication phenomena to break an azeotrope in
an ultrasonic distillation system. This article reviews the state-of-the-art technologies covering
all the separation techniques mentioned here. Existing techniques are appraised, and technol-
ogy gaps are identified. Based on these insights, areas for further development are suggested,
aiming at satisfying the process objectives by inherently safer, environmentally benign and
economically more attractive techniques.
Keywords: Azeotropic mixtures, intensified processes, pervaporation, separation technologies,

special distillation processes
INTRODUCTION processes in chemical process industries (2). Nevertheless,

because distillation offers many processing advantages and
The separation of liquid mixtures is an important task is well understood, it remains the preferred process whenever
in the process industry, and much research has been car- possible.
ried out to meet the requirements of the industry. Of all Distillation is, however, limited in its use when the mix-
available liquid separation techniques, distillation stands as tures to be separated exhibit complex phenomena. An exam-
the most widely applied technique. Distillation is typically ple of these situations is when the mixtures involved form
achieved in columns of various sizes with heights rang- azeotropes, a point at which the vapor phase has the same
ing from 6 to 60 meters and diameters that range between composition as a liquid phase. There are two types of
0.65 and 6 meters (1). Despite its widespread use, distilla- azeotropic systems: i) a minimum boiling azeotropic sys-
tion consumes large amounts of energy that are estimated to tem and ii) a maximum boiling azeotropic system. For such
be more than 95% of the total energy used for separation systems, a higher purity product beyond the azeotrope point
cannot be achieved using a conventional distillation pro-
cess. Therefore, alternative methods have been developed to
Received 31 July 2013, Accepted 9 August 2014. satisfy the separation requirement.
Address correspondence to Arshad Ahmad, Institute of Hydrogen
Figure 1 shows some of the currently available technolo-
Economy, Energy Research Alliance, Universiti Teknologi Malaysia, 81310
Johor Bahru, Malaysia. E-mail: [email protected] gies for separation of azeotropic mixtures, which can be
AZEOTROPIC SEPARATION TECHNOLOGIES 309
Separation
Processes of
Azeotropes
Process Distillation Membrane

Intensification Processes Processes
Pressure swing Extraction Azeotropic

Distillation Distillation Distillation
Pervaporation
Conventional
Liquid Salt Liquid Techniques
and salt
Hyperbranched Ionic liquids

polymer Frictional Membrane
Diffusion Distillation
Dividing Microwave
Wall Column Enhance
Process
Ultrasonic Sweeping
Air gap Vacuum
Enhance gas
Process Emerging
Techniques Direct
contact
FIGURE 1 Schematic diagram of various techniques for separation of azeotropic mixtures.
classified into three main categories: i) enhanced distilla- aim of intensification is to optimize capital, energy, envi-
tion, ii) membrane processes and iii) process intensification. ronmental and safety benefits by radical reduction of the
The first category involves enhancement of the distillation physical size of the plant. This technology includes dividing
process by modifying the process conditions and configu- wall column, microwave and ultrasonic techniques. The for-
rations. These modifications include extractive distillation, mer introduces changes in column internals, whereas the two
azeotropic distillation, and pressure swing distillation. The latter techniques employ microwave and sonication effects to
second category involves utilization of membrane separa- alter the thermodynamic properties of the mixture.
tion technologies such as the pervaporation process. The Due to the importance of the subject, there have been
pervaporation process is advantageous as it offers low energy several review articles in various journals and chapters
consumption and better safety and is more environmen- in books dealing with the separation of azeotropic mix-
tally friendly than conventional processes. Nevertheless, the tures, elaborating their fundamental theories and applica-
pervaporation process is still limited in terms of applications tions. For example, the work of Widagdo and Seider (3)
because it is yet to be proven in large scale applications. concentrated on methods used for analyses, entrainer selec-
Another class of process intensification consists of the devel- tion, column design and control of azeotropic distillation.
opment of novel apparatuses and techniques, compared to Lei et al. (4) discussed various combinations of extractive
the present state-of-art in the chemical process industry. The distillation and other separation processes. Li et al. (5)
310 T. MAHDI ET AL.
addressed the entrainer selection and proposed a mathemati- activity coefficient of various compounds in different ways,
cal model for the process. Huong et al. (6) published a review thus affecting the relative volatility of the mixture, thus
on extractive distillation for biorefining of hemicelluloses enabling the new three-part mixture to be separated by
and added chemicals from fermentation hydrolysates. More normal distillation (12).
recently, Pereiro et al. (7) reviewed methods utilizing ionic
liquids as azeotrope breakers and compared the performance Rules of Entrainer Selection
of the new system with conventional extractive distillation.
Similarly, Villaluenga and Mohammadi (8) reviewed the The entrainers to be used in the azeotropic and extractive dis-
performance of the membrane pervaporation process for tillation processes are chosen based on selectivity. Typically,
separation of benzene and cyclohexane mixtures. The appli- solvents considered are ranked based on their potential to
cations of pervaporation and vapor permeation in envi- affect the relative volatility of the components, and the sol-
ronmental protection were reviewed by Kujawski (9) The vent that gives the highest relative volatility and the lowest
scientific and technological factors governing the separation operating costs is selected (13). The relative volatility of sep-
of organic mixtures by pervaporation were also reviewed by aration of a given mixture of key components i and j occurs
Smitha et al. (10). Despite the significant number of review in two phases (vapor-liquid) at equilibrium, as illustrated in
articles, a comprehensive coverage that addresses the over- Eq. (1):
all technologies is not available and has therefore become
the motivation for this article. Here, a comprehensive review yi γi Poi
x
of the available technologies is provided with elaboration αij = y i = (1)
j
xj γj Poj
of advantages and disadvantages of each method. Based on
these insights, technological gaps are identified and future
work is recommended with special emphasis on develop- Here, xi and yi are the molar fractions in the liquid and vapor
ing processes that are more energy efficient, environmentally phase of component (i), respectively. The parameter γ i is
benign and inherently safe. the activity coefficient, and Pi ◦ is the vapor pressure of the
pure component. In some cases, for large changes in operat-
ing pressure and temperature, the value of α ij is significantly
ENHANCEMENT OF DISTILLATION PROCESS affected, and the azeotrope is eliminated (4). For small tem-
FOR SEPARATION OF AZEOTROPIC perature changes, the ratio of Pi ◦ /Pj ◦ is almost constant, and
MIXTURES the relative volatility can only be affected by introducing a
solvent that changes the ratio γ i / γ j . This ratio, in the pres-
Separation of azeotropic mixtures can be achieved by ence of the solvent, is called selectivity, Sij , as shown in
enhancing the separation mechanisms involved in the distil- Eq. (2):
lation process to overcome its limitations. The most common
strategy is to introduce a third component to alter the ther- γi
Sij = (2)
modynamic equilibrium. By choosing a suitable candidate γj s
component, along with the determination of thermodynamic
properties such as residue curve maps, optimal values of There are several other constraints to be considered in choos-
distillation parameters such as the entrainer amount, reflux ing the entrainers. These constraints include the requirement
ratio and boiler duty and the number of stages can be fixed that the entrainer should have a boiling point significantly
(11), setting the foundation of the azeotropic and extractive different from the other components to facilitate an easier
distillation processes. Another approach to enhance the dis- separation in the second column. Moreover, the entrainer
tillation is to manipulate the operating pressure as in the case selection should also consider safety, environmental effect,
of pressure swing distillation. corrosiveness, costs and availability (14).
Ewell et al. (15) studied the relationship between
hydrogen bonding and azeotrope formation and classified
Distillation Processes Using an Entrainer
entrainers into groups according to their molecular interac-
Azeotropic and extractive distillation processes have the tions. These authors also developed guidelines to identify
same common features that basically consist of two distil- chemical classes suitable as entrainers for heteroazeotropic
lation columns to separate compounds with close boiling and extractive distillations. Based on these guidelines, Berg
points or mixtures that form azeotropes. This separation is (16) classifies organic and inorganic mixtures by making use
normally accomplished by adding a third component known of the molecular structure to identify promising entrainers
as an entrainer as a separating agent, to increase the rel- and suggests that the successful entrainers for extractive
ative volatility and alter the vapor liquid equilibrium data distillation should be highly hydrogen-bonded liquids (e.g.,
of the components that are the most difficult to separate. water, amino alcohols, amides, phenols alcohols and organic
Added in the liquid phase, the new component alters the acids). Although it is impossible to choose the best entrainer
entirely through experimental work, a large number of com- use of a decanter at the top of the azeotropic distillation col-
putation approaches appear to fit the purpose. These methods umn can be considered as a homogeneous mixture, and at the
include the Pierotti-Deal-Derr method, the Parachor method, same time, the liquid composition on a tray or a section of the
the Weimer-Prausnitz method and computer-aided molecular packing is replaced by the overall liquid composition (19).
design (CAMD). Among these methods, CAMD is the most Relative volatility is an important physical quantity as
recent and preferred method (17). it reflects the influence of the entrainer on the vapor-liquid
equilibrium (20). In the case of heterogeneous azeotropic
Azeotropic Distillation Process distillation, the entrainer and the two components i and j
being separated form three phases on trays of the column,
Azeotropic distillation can be defined as a distillation in
(i.e., vapor-liquid-liquid) and two liquid phases in equilib-
which a relatively small amount of the added entrainer forms
rium with a vapor phase. For the three-phase equilibrium,
an azeotrope with one or more of the components in the
the solubility of components i and j in the upper liquid phase
feed based on differences in polarity (18). Most of the sol-
is denoted by xi l and xj l , respectively. The solubility of com-
vents are highly volatile compared to the components to be
ponents i and j in the lower liquid phase is denoted by xi ll and
separated so that the solvent is taken off from the overhead
xj ll , respectively, and the corresponding activity coefficients
of the column. Azeotropic distillation processes basically
are denoted by γ and in the upper and lower liquid phases,
utilize two columns. The first column serves as the main col-
respectively. The relative volatility of components i and j is
umn, and the second column is used for entrainer recovery.
related to the overall composition xi by Eq. (3):
In this process, an entrainer leaves the first column from the
column overhead with the lighter component, while the heav-

ies are collected as a bottom product. The entrainer and the γi Γi poi θi xiII − Xi Γj + Xi − xiI γj
lighter component are then fed to the second column to pro- αij = (3)
γj Γj poj θj xjII − Xj Γi + Xj − xjI γi
duce a high purity product at the bottom while the recovered
entrainer is recycled back to the first column.
Azeotropic distillation is usually classified into two where θ i and θj are correction factors for high pressure.
classes based on the type of mixtures to be separated: i) At low or moderate pressure, the values can be approximated
homogeneous and ii) heterogeneous azeotropic distillation as θ j = θ i ≈ 1. Eq. (3) represents the relative volatility of
(12), as illustrated in Figure 2. In the case of homoge- components i and j in a three-phase (vapor-liquid-liquid) at
neous process, phase split does not appear in the liquid equilibrium.
along the whole column, unlike the heterogeneous counter- The key feature of feasible heterogeneous azeotropic
part, in which the two liquid phases exist in some regions distillation is that entrainers and top tray vapor composi-
of a composition space. A decanter is used in heterogeneous tions are selected to generate liquid-liquid tie lines, which
azeotropic distillation to collect the condensed vapor from straddle at least one of the distillation boundaries divid-
the condenser and permits the separation of the two liquid ing the two regions containing the two components to be
phases. Commonly, these two liquids are the entrainer and separated. Heterogeneous azeotropic distillation is often pre-
the lighter component where the entrainer phase is refluxed ferred industrially over homogeneous azeotropic distillation
back to the column. The other phase is fed to the second due to the ease of recovery of the entrainer and the tran-
column where it is fractionated to remove the dissolved sition across a distillation boundary in the decanter (21).
entrainer. The case of heterogeneous mixtures without the However, heterogeneous azeotropic distillation suffers from
S S
S+A S+A
A+B
A+B
B A
A
B
(a) (b)
FIGURE 2 Schematic diagram of an azeotropic distillation, where A and B are light and heavy components of the feed mixture, respectively, S is an entrainer
component; a) homogeneous process and b) heterogeneous process.
312 T. MAHDI ET AL.
some disadvantages associated with the high degree of non- amount of entrainer is maintained on all plates in the tower
linearity, multiple steady states, distillation boundaries, long below its entry. Thus the solvent is removed from the bottom
transients, and heterogeneous liquid-liquid equilibrium, lim- of the tower. An extractive distillation process is more com-
iting the operating range of the system under different feed monly applied in the chemical and petrochemical industries
disturbances (22). Moreover, it is difficult to find a model than the azeotropic distillation (43). Figure 3a shows the
that represents both the vapor-liquid and liquid-liquid equi- principle of this technology, where components A and B are
librium data accurately for heterogeneous systems. Unstable fed to the first column that acts as an extractive column where
saddle azeotropes are also difficult to identify experimen- the solvent (S) is introduced at the top stage. In this process,
tally. Furthermore, the examinations based on the rate-based the lighter component (A) is withdrawn at the top of the first
model are necessary, but the studies with the rate-based column, while the solvent with other component exits at the
model for design and analysis of a heterogeneous azeotropic bottom. The bottom products of the first column are then fed
distillation process are quite insufficient (23). to the second column, in which the heavier component (B) is
Homogeneous and heterogeneous azeotropic distillation withdrawn at the top and the entrainer is separated from the
corresponds to the real state of the mixture, consisting of bottom and recycled back to the first column. The separation
the components to be separated as high purity products. in the second column is often easier because of the larger
Forming a homogeneous azeotrope neither means that the boiling point difference between the high-boiling entrainer
separation method becomes a homogeneous process nor that and the existing second component, and because the solvent
it is forming a heterogeneous azeotrope, because the separa- does not form an azeotrope with the second component.
tion method becomes heterogeneous while depending on the As highlighted in Table 2, extractive distillation is more
physical property of the entrainer used (24).). In addition, commonly used due to lower energy requirement and wider
for both types of azeotropic distillation, the entrainer must selection of entrainers (44). However, extractive distillation
be vaporized through the top of the column, thus consuming cannot produce highly pure product compared to azeotropic
much energy. Some of the recent studies on the application distillation because the solvent coming from the bottom of
of azeotropic distillation as a separation method are listed in the solvent-recovery column most likely contains impurities
Table 1. that may affect the separation process (45). Another draw-
back of the extractive distillation is the number of degrees
of freedom when compared with a simple distillation setup.
Extractive Distillation Process In a simple distillation setup, the degrees of freedom are
Extractive distillation involves a relatively nonvolatile the reflux ratios and the number of stages of the distillation
entrainer compared to the components to be separated. columns, while in extractive distillation, the entrainer type
Therefore, the entrainer is charged continuously near the and its flow rate comprise additional degrees of freedom
top of the fractionation column, so that an appreciably high (46).
TABLE 1
Summary of the latest azeotropic distillation cases with minimum–boiling binary azeotropes
Components to be separated (A+B) Type azeotropic distillation Entrainers Azeotrope B.P. ◦ C B wt% in azeotrope References
Cyclohexane + benzene Homogeneous Chlorobenzene 77.80 45.0 (25)

Ethanol + water Heterogeneous Cyclohexane 78.20 95.6 (26)
Ethanol + water Homogeneous Methanol 78.20 95.6 (27)
Acetic acid + water Heterogeneous Butyl acetate 76.60 3.0 (28)
Isopropanol + water Heterogeneous Benzene 80.40 87.8 (29)
Isopropanol + water Heterogeneous Benzene 80.40 87.8 (30)
Isopropanol + toluene Homogeneous Acetone 80.60 58.0 (19)
Acetone + heptanes Homogeneous Toluene — — (31)
Ethyl acetate + n-hexane Heterogeneous Acetone 64.80 65.7 (32)
Tetrahydrofuran + water Heterogeneous n-Pentane 65.00 95.0 (33)
Acetontrite + water Homogeneous butyl acetate 76.50 83.7 (34)
Acetone + heptane Homogeneous Benzene 55.60 93.5 (35)
Acetone + water Heterogeneous Toluene — — (36)
1,2Dichlor ethane + water Heterogeneous Chlorinated 72.00 80.5 (37)
Phenol + water Heterogeneous Toluene 99.76 97.8 (38)
Formic acid + water Heterogeneous Propyl Formate 107.10 77.5 (39)
Dichloromethane + acetone Heterogeneous Water — — (40)
Ethylene Diamine + water Heterogeneous Benzene 119.00 81.6 (40)
1,4-dioxane + water Heterogeneous Benzene 87.80 81.6 (41)
Isopropanol + ethanol Homogeneous 1,3-Dioxolane — — (42)
Ethyl acetate + ethanol Homogeneous Ethyl ether 71.80 69.0 (42)
B 6
A 5
2
1 3 4
A+B S+B
(a) (b)
FIGURE 3 Schematic diagram of an extractive distillation (5); a) double column process where A and B are light and heavy components of the feed mixture,
respectively; S is a solvent component; b) single column process with salt: 1 - feed stream, 2 - column of extractive distillation, 3 - equipment for salt recovery,
4 - bottom product, 5 - the salt recovered, 6 - reflux tank, and 7 - overhead product.
© Elsevier. Reprinted from (5) with permission from Elsevier. Permission to reuse must be obtained from the rightsholder.
TABLE 2
energy consumption. However, because the solvent can be
Comparison between azeotropic distillation and extractive distillation
recovered effectively under normal operating conditions, this
Azeotropic Extractive scheme remains a preferred choice in industry rather than
Parameters distillation distillation schemes using any other agents and attracts the interest of
Common use Less More
many researchers (34, 55, 58, 61, 63).
Energy consumption More Less
Solvent coming out Top Bottom (ii) Extractive distillation with solid salt
Purity of products More Less
Flexible selection of solvents Less More In this case, a separating agent in a form of a solid salt
is fed at the top of the column, dissolved into the liquid
phase, and recovered from the column by evaporation (65).
Some of the latest examples of the single liquid sol- A schematic diagram of this process is shown in Figure 3b.
vents commonly used in the extractive distillation tech- To suit the process requirements, the solid salt must be solu-
nique are listed in Table 3. Interested readers can compare ble in the feed components, nonvolatile and able to flow all
the entrainers used in practice with the rules of selecting the way down the column. The salt extracted from the bottom
entrainers. This table shows that there is a difference in the of the column is then recycled.
azeotropic percentile of the component and different boiling The so-called ‘‘salt effect in vapor-liquid equilibrium
points in an azeotropic mixture. (VLE)’’ refers to the ability of a solid salt that has been dis-
solved into a liquid phase consisting of two or more volatile
Types of Entrainers Used in Extractive Distillation. components to alter the composition of the equilibrium vapor
The selection of a separating agent influences the eco- without itself being present in the vapor. The feed component
nomics of the extractive distillation process. This separating in which the equilibrium vapor is enhanced is said to have
agent can be a liquid solvent, dissolved salt, mixture of liq- been ‘‘salted out’’ by the salt, while the other feed compo-
uid solvents, mixture of dissolved salts, ionic liquids and nent is ‘‘salted in.’’ This phenomenon can be described by
hyperbranched polymers. Based on the type of separat- the following equation, which is known as the Setschenow
ing agent, the extractive distillation process can be further equation and expresses the solubility of a nonelectrolyte in a
divided into five categories that will be discussed in the solid salt solution with a low salt concentration:
following subsections.
So
log = Ks C (4)
(i) Extractive distillation with a liquid solvent S
A schematic diagram of an extractive distillation with liq- Here, So is the solubility of the salt in pure solvent, S is
uid solvents is shown in Figure 3a. In this case, a high solvent the solubility of the salt in a salt solution of concentration C
ratio (i.e., mass ratio of solvent to feed) with values typi- (mol/L,), and Ks is the salting coefficient, which has a char-
cally in the range of 5 to 8 is used, thus leading to high acteristic value for a given salt-nonelectrolyte pair. A positive
314 T. MAHDI ET AL.
TABLE 3
Summary of the latest studies on extractive distillation for separation of azeotropic mixtures
Azeotrope B wt.% in
Mixtures of solvent (A + B) Entrainer Type B.Pt. ◦ C azeotrope Reference
Benzene + cyclohexan N,N-dimethyl acetamide Close-boiling and minimum-boiling 77.8 45.0 (47)
(DMAC) azeotropes
Tetrahydrofuran + water Propylene glycol Minimum-boiling azeotropes 65.0 95.0 (48)
Ethyl acetate + chloroform 2-Chloro-butane Maximum-boiling azeotropes — — (49)
Ethanol + water DMF Minimum-boiling azeotropes 78.2 95.6 (50)
Hexane + ethanol [mmim] [MeSO4 ] Minimum-boiling azeotropes 58.7 79.0 (51)
Isopropyl ether + acetone 3-Pentanone Minimum-boiling azeotropes 53.3 43.5 (52)
Propanone + di-isopropyl ether Putyl ether Minimum-boiling azeotropes 61.0 — (53)
Ethanol + water Ethylene glycol Minimum-boiling azeotropes 78.2 95.6 (54)
Ethyl acetate + ethanol Diethylene triamine Close-boiling and minimum-boiling 71.8 69.0 (55)
azeotropes
Acetone + methanol Water Minimum-boiling azeotropes 55.7 88.0 (26)
Methyl acetate + methanol Dimethylformamide Minimum-boiling azeotropes 119.0 81.6 (56)
Propylene + propane Acetonitrile Close boiling — — (57)
Acetonitrile + water Ethylene glycol Minimum-boiling azeotropes 76.5 83.7 (34)
C4 material/ 1,3-butadiene DMF Close boiling 126.0 45.0 (58)
Acetic acid + water Tributyl amine Minimum-boiling azeotropes 76.6 3.0 (59)
Di-n-propyl ether + n-propyl alcohol 2-Ethoxyethanol Minimum-boiling azeotropes 50.0 66.5 (60)
Chloroform + methanol Water Minimum-boiling azeotropes 53.5 13.0 (61)
Ethyl benzene + p-xylene 5-Methyl-2-hexanone Close boiling 136.1 60.0 (62)
Isobutyl alcohol + isobutyl acetate n-Butyl propionate Minimum-boiling azeotropes 107.4 55.0 (63)
Methyl acetate + cyclohexane Carbon tetrachloride Minimum-boiling azeotropes — — (64)
value of Ks , corresponds to salting out (So > S); if Ks , is neg- erosion and availability are considered. However, because
ative, salting in is observed (So < S). Species that lower the solid salts tend to cause corrosion in the equipment and decay
dielectric constant should be salted out by all electrolytes (4). easily at high temperatures, a narrow range of suitable solid
Solid salt is a more effective separating agent when com- salts is available for selection.
pared to the liquid agent, and requires a much smaller salt
ratio, thus leading to a high production capacity and a low (iv) Extractive distillation with ionic liquid
energy consumption (66). Furthermore, because solid salt
is not volatile, the product at the top of the column is free The use of ionic liquids (ILs) as separating agents in the
from salt impurities and is therefore more environmentally extractive distillation process is a recent strategy that has
friendly. However, when solid salt is used in industrial oper- been adopted and is often used in processes involving chem-
ation, dissolution, reuse and transport of the salt that has been ical reactions (68). This process has a configuration similar
introduced causes corrosion of equipment, thus limiting the to the configuration of extractive distillation with solid salt as
application of salt in the process industry (5). shown in Figure 3b. The features of this process include salts
consisting completely of ions, which are in the liquid state at
room temperature. The salts of ionic liquids therefore do not
(iii) Extractive distillation with the combination of liquid
need to be melted by an external heat source (69). The most
solvent and solid salt
outstanding reason for interest in these solvents is the negli-
The extractive distillation using a combination of liq- gible vapor pressure at room temperature (70), leading to a
uid solvent and solid salt has a configuration similar to the lower risk of worker exposure and minimal loss of solvent
system with liquid solvent as shown in Figure 3a. This pro- to the atmosphere. ILs can be tailored for a specific applica-
cess is advantageous due to the easier operation offered by tion by accurate selection of the cations and anions (71). ILs
the liquid solvent scheme and the high separation ability also have the advantages of liquid solvents in promoting high
offered by a solid salt scheme. This process is also suitable separation ability. ILs are also suitable for both polar and
for separating both polar and nonpolar systems. Lei et al. nonpolar solvent systems. In addition, extractive distillation
(67) examined the use of N, N-dimethylformamide (DMF) with the IL technique has the following advantages (72):
as a solvent to separate a C4 mixture. By adding a small
amount of solid salt to DMF, considerable improvement in 1. Absence of product impurities at the top of the column,
the relative volatilities of C4 was achieved. These authors because ionic liquids are not volatile.
also concluded that NaSCN and KSCN are among the best 2. Suitability for use over a wide temperature range from
salt additives when criteria such as relative volatilities, price, room temperature to above 300◦ C, which corresponds
to the typical operating conditions of extractive distil- azeotropic phase behavior and concluded that the use of
lation due to the inherently high volatility of ILs. hyperbranched polyesters provides cost savings compared
3. Suitability of ionic liquids for treatment with a wide to conventional separation processes. Comparing between
variety of materials including organic, inorganic and dendrimers and hyperbranched polymers, the tedious
even polymeric materials. and complex multistep synthesis of dendrimers results
4. Facile recovery and reuse of ionic liquids. in expensive products with limited use for large-scale
5. High stability of ionic liquids under the operating con- industrial applications. For many applications that do not
ditions of extractive distillation in terms of thermal and require structural perfection, hyperbranched polymers can
chemical conditions. circumvent this major drawback of dendrimers. Therefore,
a wide variety of applications, which originally seemed
Taking all of these features into account, the ILs are conceivable only for dendrimers, were investigated for the
considered good candidates for application as extracting sol- statistically branched hyperbranched polymers in the past
vents or entrainers in the separation of azeotropic mixtures, decade (83).
and ILs have demonstrated capabilities to separate many
mixtures (73, 74). However, despite the increase in pub-
Pressure Swing Distillation
lications addressing azeotropic separations with ILs, these
studies are limited to analysis of the liquid-liquid equilib- Pressure swing distillation (PSD) is a process alternative to
ria (75) and vapor-liquid equilibria (76) or simulation of the the broadly applied azeotropic and extractive distillations.
extractive distillation process with ILs (77). The principle of pressure swing distillation (PSD) is based
Extractive distillation with ILs also suffers from some dis- on the fact that a change in pressure can alter the relative
advantages such as the long time required to prepare the volatility of a liquid mixture, even for liquid mixtures with
ionic liquids and the high cost of synthesis of such spe- a close boiling point or those that form an azeotrope. If the
cialty components (5). The separation of viscous solutions operating pressure is increased, the azeotropic point shifts to
using this technique is very difficult to manage (7) and the lower composition values of the light component. The signif-
ILs demonstrate moisture sensitivity (72). Such disadvan- icant positive change in the azeotrope point and enlargement
tages have slowed down the application of this process in of the relative volatility of azeotropic mixtures allow the sep-
industry (5). aration to take place without any need for a separating agent.
Following the early work in 1928 by Lewis (84) and further
(v) Extractive distillation with hyperbranched polymers developments that followed (85–87). Table 4 shows some of
the recent studies on the separation of azeotropic mixtures
A class of highly branched polydisperse macromolecules using PSD.
with a treelike topology, with a large number of func- PSD can be operated in three different modes: i) contin-
tional groups, and three-dimensional polymers such as uous (3, 85), ii) batch (96), and iii) semicontinuous (97).
hyperbranched polymers (78) or dendrimers (79), have The dependence of the azeotropic concentration on the sys-
recently found a variety of applications in the field of chem- tem pressure is used for the separation of the mixture. If the
ical engineering. Most of the applications are related to the feed has a lower light component concentration than the
absence of chain entanglements and presence of a large num- azeotropic point, the feed is introduced into the low pressure
ber of functional groups within a molecule. Furthermore, (LP) column, otherwise the feed has to be fed into the high
the functional groups of hyperbranched polymers allow tun- pressure (HP) column.
ing of their thermal, rheological, and solution properties. Figure 4 illustrates the separation of a binary mixture with
This tuning provides the opportunity to design entrainers a homogeneous minimum-boiling azeotrope in a continuous
for a wide variety of applications (80, 81). Unlike the con- PSD. Because the feed stream F1, which is a combination of
ventional linear polymers, hyperbranched polymers not only the combination of the fresh feed F with the recovery stream
show a remarkable selectivity and capacity, but because of a D2, has a mole fraction of light component A greater than
lack of chain entanglements, also show a comparatively low the azeotropic point, F1 is fed into the low-pressure col-
solution and melt viscosity as well as an enormous thermal umn (LP). The objective of this column is to concentrate
stability (77). component B near an azeotropic point of the mixture and
Recently, Seiler et al. (77) suggested the use of to remove pure component A in the column bottom stream.
hyperbranched polymers as entrainers for extractive The azeotropic mixture D1 that leaves the top of the column
distillation for the separation of azeotropic mixtures. serves as the feed stream F2 to the second high-pressure (HP)
In another study, these authors studied the separation of the column to produce pure heavy component B in the bottom
tetrahydrofuran (THF)/water and ethanol/water mixtures stream. The remaining products are recycled from the top to
using different hyperbranched polyesters as entrainers be mixed with fresh feed F to the first column. Both columns
in extractive distillation (82). Their experimental results operate at different pressures that suit the intended separation
illustrated the potential of such entrainers in breaking the requirement.
316 T. MAHDI ET AL.
TABLE 4
Summary of the latest studies using pressure swing distillation for separation of azeotropes
System Type LP (bar) HP (bar) Process type Reference
Acetonitrile + water Minimum 1.013 2.78 Continuous (88)

Acetonitrile + water Minimum 1.013 3.02 Batch (89)
THF + water Minimum 1.013 7 Continuous (87)
THF + water Minimum 1.013 10 Semicontinuous (86)
Acetone + methanol Minimum 1.013 4 Continuous (90)
Acetone + methanol Minimum 1.013 10 Batch (91)
Ethyl acetate + ethanol Minimum 4 25 Continuous (92)
Ethyl acetate + ethanol Minimum 1 10 Batch (93)
Isobutyl acetate + isobutyl alcohol Minimum 0.2 1.013 Continuous (63)
Diamine-ethylene + water Maximum 1.013 8 Batch (94)
Ethanol + toluene Minimum 0.1 1.1 Batch (29)
di-n-propyl ether + n-propyl alcohol Minimum 0.3 1.01 Continuous (60)
Acetone + n-pentane Minimum 1.013 10 Batch (94)
Ethanol + water Minimum 1.013 10 Continuous (95)
In general, vapor-liquid equilibrium calculations can be where γi is the activity coefficient, and ∅i is the fugacity
divided into two types. The starting point for both is the coefficient (for more details, see (85).
equality of fugacities of a component (i) in the vapor and In a batch operation, only a single column is used for
liquid phases, as shown in Eq. (5). The two types differ in the separation. Component A is supposed to be the ultimate
the description of the component fugacities in the vapor (fi V ) product in a mixture consisting of components A and B. This
and liquid (fi l ) phases (87). process includes two steps: in the first step, the column is
initially charged with the feed mixture F into a bottom tank
fiv (T, P, yi ) = fil (T, P, xi ) (5) (for a regular batch) and operates at low pressure, as shown
in Figure 5. Component B is removed from the bottom of
The correlations of the first types involve a “two-model” the tower while a mixture close or equal to the azeotropic
approach: one model is used to estimate the vapor phase composition is accumulated at the top. This step runs until
(φi ) nonidealities, while another model is used for the liquid the target composition of component B is achieved in the
phase (γi ). The starting equations are bottom tank.
On completion, the process is switched over to the second
fi V (T, P, yi ) = ∅i yi P for the vapor phase (6a) step, in which the column is recharged with the azeotropic
mixture and is operated at high pressure. Thus, component
fi 1 (T, P, xi ) = γi xi Pi vap for the liquid phase (6b) A is obtained from the bottom while the mixture approaches
Pressure P1 Pressure P2
D1
B2 D2
P2
D2
T
F2
F2
F F1
P1
LP
D1 HP
B1 B1 B2
Pure B F F1 Pure A
composition Pure A Pure B
(a) (b)
FIGURE 4 Schematic diagram for continuous pressure-swing distillation: (a) pressure-sensitive, minimum-boiling azeotrope, and (b) column sequence (90).
© (1992) American Chemical Society. Reprinted with permission from (90). Permission to reuse must be obtained from the rightsholder.
First Step Second Step

S1
Azeotropic mixture T1 T2
Azeotropic mixture
S2 S3
Low pressure High pressure
T3 T4
A B
FIGURE 6 Schematic diagram for semicontinuous operation of Pressure

Feed (F) Feed (F) Swing distillation (86).
End of process End of process © (2000) American Chemical Society. Reprinted with permission from (86).
component B component A Permission to reuse must be obtained from the rightsholder.
FIGURE 5 Schematic diagram for regular batch operation of Pressure

Swing Distillation (89).
© Elsevier. Reprinted from (89) with permission from Elsevier. Permission T2. S1 has a zero flow rate. The operating mode is low
to reuse must be obtained from the rightsholder. pressure. Mode 2: S3 feeds the column. The overhead and
off-specification bottom product is fed to tank T1. S1 feeds
tank T1. The operating pressure is high. Product is fed to tank
the azeotropic composition at the top. If the initial feed T3 or tank T4 when the bottom composition exceeds high
concentration is higher than the azeotropic point, then the purity in A or B, respectively. The process switches between
first step becomes the high pressure step, and component A is modes when tank T1 or tank T2 is empty. In each mode, the
produced at the bottom. To provide high recovery, this cycle column has a fixed pressure, reflux and reboil ratio. Modes
may be repeated many times (89). 1 and 2 operate at low and high pressure, respectively (86).
More recently, a number of novel batch column config- Compared with continuous processing, semicontinuous
urations have been introduced. These novel batch column PSD has several advantages, including greater plant flexibil-
configurations include an inverted batch process for separa- ity and lower investment costs, because the product can be
tion of an acetonitrile/water mixture (89), a middle vessel obtained without the need for additional equipment. When
configuration for separation of the ternary azeotropic mix- semicontinuous operation is compared with batch PSD, the
ture of acetone, benzene, and chloroform (98) and multi- downtime due to liquid holdups is sharply reduced because
vessel design for separating a mixture of methanol–ethanol– the compositions near the top of the column approach the
propanol–butanol (99). azeotropic compositions in the distillate and consequently
In a semicontinuous operation, only a single distilla- do not vary greatly as the tower shifts between low- and
tion column is involved. However, the column operates high-pressure operation (86).
continuously or periodically. Liquid levels are maintained The minimum number of columns required for a given
on the trays or packing, a stream is fed continuously to separation can be calculated from Eq. (7), below (86):
the reboiler, and cooling water is fed continuously to the
condenser. The column operates in two modes, with tanks
T1 and T2 alternating as the feed source, and the distillate Ncol = NP + NB − 1 (7)
and bottoms products are also sent to alternate tanks, as
shown in Figure 6. Operation begins in mode 1, after startup, Here, Ncol is the minimum number of columns required,
during which on-specification products (nearly pure A as a Np is the number of pure component products, NB is the
bottoms product and distillate near the azeotrope at a low number of boundaries crossed for PSD (which does not
pressure) are achieved. T1 is recharged periodically with include boundaries that disappear as the pressure changes).
fresh feed from S1. The column operates continuously but For example, for an extractive distillation to separate a
not at a steady state. ternary mixture, NB is equal to unity and the number of
The column alternates between the modes defined as columns needed is 3 (Ncol = 3 +1– 1= 3). Consequently, it
follows: Mode 1: S2 feeds the column. The condensed over- is unlikely that PSD will be advantageous as the azeotropic
head and off-specification bottoms product is fed to tank point for homogeneous azeotropes may vanish as the
318 T. MAHDI ET AL.
pressure decreases to some extent. Thus NB = 0 and the Feed Retentate

column number is therefore reduced to 2 for PSD. Liquid
However, the PSD process has a number of disadvantages, Membrane
including a higher complexity of operation, resulting in the Vapor
need for more sophisticated automation and more complex
process control. There is also a gap in the experimental data
in the literature because industrial applications are seldom
published. In spite of the available theoretical knowledge
(85), reliable experimental studies are scarce, partly because Cooler Vacuum
the operation tends to be limited to atmospheric conditions
because operations under nonatmospheric conditions are dif-
ficult to establish and generation of such data is expensive
(100). This drawback limits the application of the PSD pro-
cess in industry. Among the limited applications reported is Permeate
the work of Knapp and Doherty (90) on the separation of
FIGURE 7 Schematic diagram of the pervaporation process.
tetrahydrofuran and water by continuous PSD.
on each side of the membrane. The retentate is the remain-

SEPARATION OF AZEOTROPIC MIXTURE
der of the feed leaving the membrane feed chamber, which
USING MEMBRANE TECHNOLOGY
did not permeate through the membrane (109). However, the
use of PV to break azeotropes is restricted because the mass
A higher energy requirement and a limited choice of
transportation through a thick dense polymer membrane is a
entrainers to be used in azeotropic and extractive distil-
slow process (110).
lation processes have led to the development of alterna-
The main advantages of PV separation technology are that
tive processes such as membrane-based processes (8, 101).
it is not limited by the vapor–liquid equilibrium because it is
Membrane processes may be regarded as “clean technology”
independent of relative volatilities. This property makes PV
due to the lower energy demand and the fact that mem-
a good alternative technique to separate azeotropic and close-
brane processes do not require the use of additional chem-
boiling point liquid-liquid mixtures (111). However, because
icals (102). Within this class of techniques, pervaporation
the feed mixtures are in direct contact with the surface
(PV) is most prominent (10, 103), and accounts for 3.6%
of the polymeric membranes, the feed mixtures affect the
of the total membrane separation applications in chemi-
swelling or shrinking of the membrane materials. Uragami
cal and petrochemical operations (104). Some of the PV
and coworkers (112) proposed an improvement to over-
applications in industry include removal of water from
come this disadvantage by vaporizing the feed solution and
organic solvents (e.g., dehydration of alcohols, ketones and
permeating it through the membrane. In this manner, the
esters) (105), removal of organic compounds from water
swelling or shrinking of the polymeric membrane can be pre-
(106), and separation of organic-organic azeotropes and
vented. A polymer with great affinity with one component in
isomers (107).
the feed is preferred for making PV membranes to obtain
higher selectivity. However, the membrane becomes swollen
if this affinity exceeds a certain level in a way that makes
Pervaporation (PV)
the membrane lose its integrity, thus necessitating higher
Pervaporation involves permeation of feed components selectivity.
through a membrane, followed by evaporation into the down- Aptel et al. (113) and Binning et al. (114) proposed that
stream in various rates. A schematic diagram of the PV the control of the membrane selectivity prevents the swollen
process is shown in Figure 7. PV separates the liquid feed fraction of the skin layer in a PV. Therefore, the choice of
mixture by partial vaporization through a dense nonporous the proper membrane material is a crucial factor for a spe-
membrane. The feed mixture is usually in direct contact with cific separation. In practice, separation by PV is achieved
one side of the oliophilic membrane, whereas permeate is with a small amount of feed mixture as a result of the
removed in a vapor state from the opposite side into a vac- low permeation rate and therefore a large surface area for
uum or sweeping gas and then condensed (108). The driving the membrane is needed. Increasing the membrane surface
force for the separation is the difference in the partial pres- area for a larger-scale application is required, and several
sures of the components on the two sides of the membrane, heat exchangers must be available to vaporize the perme-
and the driving force is not affected by the relative volatility ating component of the feed stream (110). The PV process
of the mixtures. This driving force for transport is the differ- is limited by the boiling point of the feed mixture and the
ence between the liquid feed/retentate and vapors permeated temperature sensitivity of the feed components (115).
Factor Influencing PV Performance The mass transfer in the PV process is also influenced
by the operating conditions, including the concentration and
The separation performance of the PV process is dependent
composition of the feed, the feed permeate pressure and the
on flux and selectivity. Flux is affected by the operating
temperature. This allows manipulation of the operating vari-
conditions, while selectivity involves a design decision. The
ables to suit the process constraints and to find the optimal
maximum separation potential is provided when a suitable
operating conditions for the maximum mass transfer.
membrane is selected. In a binary system, the selectivity
of a membrane is defined as the ratio of the concentrations
of components in the permeate to the concentrations of the Membrane Material Selection in PV Technology
components in the feed (116):
The work on membrane separations began in 1960 with a
ya wide range of membrane materials including dense met-
y
α = xb (8) als, zeolites, polymers, ceramics and biological materials.
a
xb The first manufactured polymeric membranes that found
applications for organic solvent dehydration (120), includ-
where α is the selectivity, and x and y are the concen- ing hydrophilic PV membranes, are still in use in the industry
trations of the components in the feed and the permeate, (121). Recently, ceramic membranes have also been used as
respectively. The a and b subscripts refer to the two com- selective barriers in PV (122). Such ceramic membranes are
ponents to be separated. The selectivity of a membrane is used in a wide range of applications, including separation of
strongly dependent on the membrane affinity for one (or mixtures in acid and alkaline environments, which require
more) component(s) of the feed and the diffusion of the high thermal and chemical stability (123).
permeating molecules through the membrane matrix. The The selection of the membrane polymeric materials for
expected selectivity of a membrane therefore decreases with PV applications depends on three important factors, includ-
the increase in the molecular size of the components (117). ing capacity of sorption, chemical resistance, and mechanical
The overall selectivity of a membrane can be computed by strength. To separate a liquid mixture by the PV process, one
multiplying the selectivity of sorption, α s , by the selectivity of the components of the feed solution must have good inter-
of diffusion, α D : action with the membrane materials to provide the swelling
needed. Table 5 summarizes the performance and design lim-
itations of the various membranes currently available for the
α = αs ∗ αD (9)
separation of azeotropic mixtures.
An efficient and economical membrane separation pro-
Flux is defined as the rate of permeation of the feed com- cess can be established by correctly choosing membrane
ponents through a unit area of the membrane at a unit time. materials with desirable qualities including high selectivity
Flux is governed by the mass transfer process described by and stability, good permeability, resistance to fouling, and
Fick’s law of diffusion, as defined by Eq. (10): lengthy lifetime (156). The PV permeability coefficient rep-
resents the product of the solution coefficient and the diffu-
dC sion coefficient. Fouling, which is generally caused by scale
J = −D (10)
dz formation rather than clogging or blocking of pores, poses
a challenge to the economy of the PV together with the
where J is the diffusion flux (mole/m·s), D is the diffusivity membrane life cycle.
(m2 /s), C is the concentration (mole/m3 ) and z is the posi-
tion [length] (m). The negative sign indicates that J is
positive when movement is down the gradient, i.e., the neg-
Frictional Diffusion
ative sign cancels the negative gradient along the direction
of positive flux. D is proportional to the squared velocity Frictional Diffusion (also called friction difference, FricDiff)
of the diffusing particles, and the value of D depends on is a separation technology based on differences of diffu-
the temperature, the viscosity of the fluid and the size of sivities in a mass separating sweep gas or vapor mixtures.
the particles according to the Stokes–Einstein relationship. A FricDiff module consists of flows of a target gas mix-
The driving force for the one-dimensional diffusion is the ture (feed side) and a mass separating agent (sweep side)
quantity −dC / dz that is the concentration gradient for ideal separated by a nonselective porous layer (barrier). FricDiff
mixtures. In chemical systems other than ideal solutions or has been shown to allow for the breaking of azeotropes
mixtures, the driving force for diffusion of each species is in mixtures (157, 158). Development of frictional diffu-
the gradient of the chemical potential of these species (118). sion (FricDiff) technology for azeotropic mixture separations
According to Fick’s law, the rate of transfer by diffusion is aims for increasing the energy-efficiency and reducing the
proportional to the concentration gradient in the area of the use of hazardous solvents in the separation section of a chem-
interface over which the diffusion takes place (119). ical process (159). As implied by the name, the separation
320 T. MAHDI ET AL.
TABLE 5
Summary of the latest studies of the pervaporation process for separation of azeotropic mixtures
Content of A
in feed Temperature Selectivity Flux
Binary mixtures (A/B) Membrane materials [wt. %] [◦ C] α A/B [Kg/m2 .h] Reference
Water/ethanol Phosphorylated chitosan 10.23–52.3 70 213 0.58 (124)

Water/1,4-dioxane Chitosan and Nylon-66 18 40 865 0.09045 (125)
Water/acetic acid Polymide-6 /PAA 8.7 15 82 0.005 (126)
Isopropanol/water Chitosan 87.5 70 472 0.39 (127)
Butanol/water Silicone rubber 0–8 30 45–65 <0.035 (128)
MTBE/water PDMS 2 50 280 1.2 (129)
Methanol/toluene Cellulose 5–90 45 1200 15 (130)
Methanol/ ETBE CAB PEG600DMA 20 40 21 1.4 (131)
Methanol/MTBE Poly(ether ether ketone) 1–87 30 254–3.2 0.015–0.113 (132)
Methanol/benzene PFSA on Teflon 31 45 9.6 100.28 (118)
Ethanol/cyclohexane Polyelectrolyte 12.1 50 106.7 8.7 (133)
Methanol/cyclohexane PAN-g-MA 5–80 50 <200 <80 (134)
Methanol/MTBE Chitosan with H2 SO4 20 25 9.3 1.5 (135)
Ethanol/ETBE PERVAP 2256 30 50–70 14.2 2.3 (136)
Benzene/cyclohexane LDPE 50 25 1.6 10.8 (137)
Toluene/cyclohexane PS and PAM 75 30 7.9 1400 (138)
Toluene/n-hexane Polyurethane 10–70 25 2.8-5.8 1.1-3.5 (139)
Toluene/n-octane Polyesterimide 50 50 70 10 (140)
Styrene/ethylbenzene Polyurethane 20–80 60 1.1–5.7 0.3–1.2 (141)
Ethanol/ethyl acetate Polydimethylsiloxane PDMS 60 30 3.61 1.397 (142)
Ethanol/cyclohexan Poly(vinyl pyrolidone) 25–100 54 7.5–47.4 0.05 (143)
Methanol/dimethyl carbonate Poly(acrylic acid)/poly (vinyl alcohol) 10–90 60 1–6 0.577 (144)
Methanol/methyl acetate Pervap 2255-30 30 60 − 7.4 (145)
Water/ethanol Sodium alginate 5.2–38.6 30 2182 0.035 (146)
Toluene/n-heptane MSE-modified 10 85 4.985 4.61 (147)
Dimethyl carbonate/methanol Hydrophobic nano-sillca/ polydimethylsiloxane 30 40 3.97 0.702 (148)
Toluene/iso-octane 3,5-Diaminobenzoic 50 100 90 − (149)
Methanol/MTBE Poly(lactic acid) 10 30–50 30 15 (150)
Methanol/dimethyl carbonate Chitosan 10 60 − 0.276 (151)
Methanol/toluene PVAHII 1.8–18.6 30 0.759-2.88 16-622 (152)
Methanol/TAME Poly(vinyl alcohol) 97 50 4 175 (153)
Water/ethyl acetate Polyvinyl alcohol 5.1 60 129 2.83∗ 10−4 (154)
Ethanol/ethyl acetate Na Y 30 130 27–82 2.9 (155)
principle that governs FricDiff is the membrane separation

method (160).
Figure 8 depicts the mechanism at the molecular level.
When considering the diffusion of molecules A and B
through a third species C, the smaller molecule A experi-
ences, in terms of diffusion, less hindrance from the so-called
sweep gas (counter gas) C than the larger molecule B, result-
ing in a higher diffusive velocity of A compared to B, which
can be exploited to achieve separation of the two gases. The
FricDiff apparatus consists of two channels that are separated
by a porous layer. The feed mixture A + B enters a side of the
device. The sweep gas C enters the other side. In this setup, a
FIGURE 8 Schematic presentation of the principle of the FricDiff sepa-
countercurrent flow pattern is chosen, but the concept works
ration technique (157).
for co-current flow patterns as well. If the pressure gradi- © Elsevier. Reprinted from (157) with permission from Elsevier. Permission
ent needed for convective flow through the channels can be to reuse must be obtained from the rightsholder.
neglected, FricDiff works both isothermally and isobarically
on both sides of porous barrier. The separation in FricDiff is
based on diffusional processes only (157). potential, which reduces to a gradient in the partial vapor
Similar to other membrane processes, the driving force pressure for ideal gases. However, the mechanism for
for mass transport in FricDiff is the gradient in the chemical separation between FricDiff and these membrane processes
is different. The separation principle in membrane separation the column and permeate as well as the retentate streams are
processes depends on the type of selective membrane that is fed back into the column. In Figures 9c and 9d, the mem-
used, while in the FricDiff process, separation is based on brane is located, respectively, on the head and bottom of
the difference in transport velocities of the components of the column performing the final product stream purification
the feed mixture in the sweep gas (161). (164).
Daviou et al. (165) carried out studies on the optimal
design of hybrid distillation pervaporation systems for the
Hybrid Process Distillation/Pervaporation separation of a methanol/methyl tert-butyl ether mixture.
The PV process alone is not sufficient to separate some of Their simulation results using rigorous models show that
the azeotropic mixtures. Thus, hybrid processes combining significant cost reduction can be achieved. Working on
distillation and membranes, known as membrane distilla- isopropanol–water and propylene–propane mixtures, Naidu
tion (MD), is highly attractive to overcome these limitations and Malik (166) illustrate the structural and parametric opti-
(162). Hybrid MD processes have drawn attention on various mization of a continuous hybrid distillation-pervaporation
occasions (30, 163). However, only a few studies deal with process with different configurations such as series, parallel,
optimization aspects of such a hybrid process with different and series-parallel arrangements of pervaporation modules
approaches. in the network. Their findings proved that the purity of
In the MD process, a liquid solution at a high temperature products can be obtained without violating the composi-
is brought into contact with one side of a porous hydrophobic tion constraints of products and the heat exchange policy
membrane that acts as a barrier to separate the warm solution that minimizes the required membrane area by increas-
(called the feed side) from the permeate in either a liquid or ing the flux through the membrane. Kookos (167) car-
a gaseous phase, which enters a cooling chamber called the ried out studies on optimal design of hybrid processes for
permeate side. The hydrophobic nature of the microporous membrane/distillation column using the structural and para-
membrane prevents liquids/solutions from entering its pores metric optimization procedures. The results proved that the
due to the surface tension forces. As a result, a fixed inter- economic potential for using hybrid systems is significant.
face is formed at the pore entrance. If the solution contains
at least one volatile component, the temperature difference at
the two ends of the pores produces a vapor pressure gradient PROCESS INTENSIFICATION
within the pores. By the driving force, the vapor molecules
of the volatile component that is produced by evaporation Process intensification is a process design approach that
from the feed solution at the vapor-liquid interface migrate leads to substantially smaller, cleaner, safer and more
from the feed side to the permeate side of the membrane. energy-efficient process technology (168). Within the realm
At the permeate side, the migrated molecules that depend of the separation processes discussed in this review, process
on the configuration of the membrane used are either con- intensification can be used to increase the functionality of the
densed or removed in a vapor form from the membrane process as in the case of the dividing wall distillation column,
module. Flowing this way, the solution from the feed side or process intensification can be used to introduce selected
is concentrated (5). process phenomena into the conventional separation (169).
MD is advantageous due to its low cost and low energy In the following sub-sections, some examples are illustrated.
consumption but suffers from some drawbacks such as low
permeate flux (compared to other separation processes, such
as RO), high susceptibility of the permeate flux to the con-
Dividing Wall Distillation Column
centration and temperature of the feed conditions due to the
concentration and temperature polarization phenomena. The When more than two products are to be obtained in a distil-
trapped air within the membrane also introduces a further lation process from a multicomponent feed, the number of
mass transfer resistance, which also limits the MD permeate columns required to isolate products at the specified quality
flux. The amount of heat lost by conduction is quite large is equal to the number of components. Accordingly, plants
(164). with multiple products require a large number of possible
A distillation column and a membrane module can gener- column sequences, and it is important to determine the opti-
ally be combined in various different configurations. Figure 9 mal number of separation columns in a sequence to reduce
(a-d) shows a schematic diagram for some configurations operation costs. To overcome such challenges, a distillation
for a membrane/distillation hybrid process. The membrane column with one longitudinal partition wall welded to the
module can be placed in the column feed stream as shown in column wall, known as a dividing wall column (DWC), is
Figure 9a, and this design is called parallel configuration. introduced to reduce the number of columns required. In this
A series configuration is also available and is considered case, the middle section of the vessel is split into two sec-
a special case of the more general solution (Figure 9b), in tions by inserting a vertical wall at an appropriate position
which the membrane feed stream is taken as a side draw from (170).
322 T. MAHDI ET AL.
D D
P P
F
F
B
B
W
a b
W
D
D
F
F
B
W
c d W
FIGURE 9 Schematic diagram for various configurations for a membrane/distillation hybrid process (164).
© Elsevier. Reprinted from (164) with permission from Elsevier. Permission to reuse must be obtained from the rightsholder.
DWC has found a great appeal in the chemical process being the lightest and C the heaviest. In the first half (pre-
industry because it offers significant energy saving along fractionator) of the DWC, a crude separation is carried out
with substantial capital and space reductions. These advan- between components A and C. Component A is concen-
tages can be further enhanced by using a recently introduced trated at the top of the second half (main column), and C
non-welded wall technology, which allows the use of mul- is concentrated at the bottom with component B distributed
tiple columns within a shell. Several reviews and research between the top and the bottom. A liquid from the top sec-
articles have been published on this topic, covering the tion refluxes to the top of both the pre-fractionator and the
design (171), simulation (172), control (144, 173), optimiza- main fractionator, while the vapor from the bottom section
tion (174) and applications of DWC (175, 176). However, similarly strips the bottom of the pre-fractionator and the
because this process defines a single operating pressure, the main fractionator. Under steady-state conditions, the DWC
boiling point in the reboiler becomes higher leading to a yields the lightest component (A) at the top of the column
higher pressure drop and a higher temperature difference and the heaviest component (C) at the bottom. The mid-
(177). dle component B is withdrawn at a selected stage of the
The separation of a ternary mixture of components A, main fractionator where its concentration is at a maximum
B and C by a DWC is illustrated in Figure 10, with A (175).
currently limited to a few applications such as extraction

(185), desorption (186) and drying (187).
In recent years, several studies have focused on under-
Liquid split
A standing of the microwave technology to enhance evapora-
tion and improve the performance of the distillation process,
and promising results have been reported (188). Altman
Dividing wall et al. (189) studied the effects of microwave on distilla-
tion of a binary system and concluded that the improve-
A+B+C B
ments offered by the microwave field occur only when
Prefractionation the microwave field interacts directly with the vapor–liquid
Main column
interface. On azeotropic mixtures, Gao et al. (190) studied
the separation of a benzene/ethanol system at 101.33 kPa
Vapor split under various operating conditions and concluded that the
azeotropic point is shifted upward from the standard curve
when a microwave field is introduced.
C The influence of a microwave field on the vapor–liquid
equilibrium varies based on the components involved due to
FIGURE 10 Schematic diagram for a dividing wall column. Adapted the variation in absorption of microwave energy. For exam-
from (175). ple, ethanol is a good microwave absorber, whereas benzene
© Elsevier. Reprinted from (175) with permission from Elsevier. Permission is a poor microwave absorber. Thus, for a benzene/ethanol
to reuse must be obtained from the rightsholder.
mixture, the OH groups of ethanol become rotationally
excited, and heat is generated, leading to an increase in the
overall internal energy of the ethanol molecule. The VLE is
The DWC technology can also be used in azeotropic sep-
shifted because the microwave energy dissipated rapidly into
arations (A-DWC) (178, 179), extractive distillation (180),
the ethanol, and the heat transfer rate between ethanol and
and even reactive distillation (181). However, industrial
benzene in the vapor–liquid interface is slower than the inter-
application for the separation of azeotropic mixtures is yet
action of the microwave field with ethanol (190). As a result,
to be realized, and publications are still more focused on
the vapor phase is richer in the high microwave irradiation
theoretical and simulation studies. For example, Briones-
absorption medium for the binary system, and the liquid
Ramírez et al. (182) report an Aspen-Plus simulation
phase is exactly the opposite, opening up opportunities for
of an A-DWC system for isopropanol-water–acetone and
exploiting microwave irradiation in overcoming azeotropic
isopropanol-water–methanol mixtures and obtain results
separation.
claiming energy savings of up to 50% compared to a system
with a two-column sequence.
Sun et al. (178) also carry out Aspen-Plus simula- Ultrasonic Enhanced Process
tion of A-DWC for an ethanol dehydration process with
cyclohexane as an entrainer. The results revealed that the The application of ultrasonic waves can be found in various
proposed A-DWC system managed to save 42.17% of the areas of application including biology, medicine, material
energy consumption and 35.18% of the overall annual forming, and the chemical industry (191, 192). In the process
operating costs, along with reduction in greenhouse gas industry, this sonication phenomenon has been exploited in
emissions. Kiss and David (183) used a DWC to enhance enhancing cleaning, separation and reaction processes (193,
the bioethanol dehydration in both extractive distillation 194). Heating, acoustic streaming and ultrasonic cavitation
and azeotropic distillation and obtained energy savings of are widely believed to be the main causes for the enhance-
10–20% for the novel process intensification alternatives ment (195). Recently, employment of the potential of the
based on DWC, while using fewer equipment units compared sonication phenomenon for the separation of liquid mixtures
to the conventional extractive and azeotropic distillation has been reported (196, 197).
configurations. Ultrasonic waves have also been found to be useful in
enhancing the distillation process, particularly for the sepa-
ration of azeotropic mixtures. Ripin et al. (198) and Mudalip
et al. (199) studied the effect of ultrasonic waves on the vapor
Microwave Enhanced Process
liquid equilibrium (VLE) using typical binary mixtures.
A microwave heating process is a molecular-level pro- These authors also found that ultrasonic waves can positively
cess that has gained substantial attention in academia and change the VLE and alter the relative volatility of azeotropic
industry, including chemical process applications. However, mixtures. The changes in the relative volatility and VLE data
while microwave technology has been introduced for reac- for the binary mixtures are caused by the cavitation activ-
tion intensification (184), its use in separation processes is ity during the transmission of ultrasonic waves in a liquid
324 T. MAHDI ET AL.
medium. When the ultrasonic intensity is increased, greater Considering the membrane separation technology routes,
energy enters the liquid medium, producing microbubbles, because the available surface area and durability play pivotal
and this effect is coupled with the creation of vacuum roles in process operability, research in these areas is likely
effects inside the liquid. Because sonication is a fast tran- to continue, as indicated by the increasing number of patents
sient process that occurs in microseconds, during this short and publications on this subject. The separation commu-
period, heat and mass transfer processes are very rapid. nity should either develop such processes for small-scale
Although the use of ultrasonic waves does not produce specialty applications or embark on the development of
significant net changes in the operating conditions of the hybrid processes to overcome the surface area limitations.
distillation process, use of ultrasonic waves does impact Process intensification is a fast growing approach in
the thermodynamics significantly by altering the VLE of the chemical process industry, offering a wide horizon of
the system. options. Because distillation is still considered the preferred
The main advantage of ultrasonic technology is the fact process, intensification of the distillation process through
that the azeotrope point can be eliminated by correctly a variety of frontier technologies should be explored. For
choosing the sonication parameters and other operating con- example, by applying sonication to the liquid mixture, the
ditions. The separation of azeotropic mixtures can be carried properties of the mixture can be altered, thus opening oppor-
out in a single column without the need for a separating tunities for further process development. Some recent studies
agent. The ultrasonic technology is therefore attractive from on ultrasonic distillation have been found to be promis-
the perspective of energy requirements and environmental ing and require additional efforts to formulate workable
protection. Because ultrasonic technology may also offer solutions for industrial applications. Further developments
a reduction in the equipment size as it reduces the sep- needed in this area include basic thermodynamic studies and
aration requirement by altering the VLE, the technology the development of process technology involving the formu-
also offers safety features. Although previous studies (198– lation of optimal design and operation strategies, the perfor-
200) have illustrated the success on a single-stage system, mance of safety and control studies and the development of
these studies are too sketchy, and the use of a complete complete system prototypes.
ultrasonic-assisted distillation system with the typical indus-
trial separation requirements is yet to be realized. A number
of issues must be addressed that include design, safety, CONCLUDING REMARKS
operability, control and efficiency.
This article provides a state-of-the-art-review on the con-
ventional and emerging technologies for the separation of
azeotropic mixtures. The research areas to be emphasized for
FUTURE WORK further development are also elucidated. Conventional sepa-
ration processes such as azeotropic and extractive distilla-
Research and development, along with knowledge genera- tions are observed to be the main technologies used at present
tion and its adaptation to the chemical process industry, will and in the near future, with opportunities for improvements
continue to be driven by individual interests or availability by introducing new entrainers with desirable properties.
of funding. Due to the importance of the chemical and petro- Similarly, while membrane processes offer good efficiency,
chemical industry to the world economy, studies on even simplicity of operation and low energy consumption, mem-
old technologies such as chemical separation continue to brane processes are limited by the surface area requirement
be relevant. Considering the separation of azeotropic mix- and thus may only be suitable for small-scale applica-
tures, various studies taking different approaches have been tions. To extend the applicability, hybrid processes com-
reported. However, more studies are needed to improve the bining membranes with other process technologies might
economic efficiency and ease of operation while ensuring be needed. For the frictional diffusion process, although
safety to personnel and the environment. it offers high thermodynamic efficiency and energy reduc-
Because pragmatic practitioners would prefer to stay with tion and is an inherently irreversible process, it suffers low
conventional processes because they are well-understood and selectivity and thus requires further improvement. Another
established, azeotropic and extractive distillations would still potential approach is to exploit the process intensification
be the main technologies used for large scale applications in concept in developing new separation techniques. Although
the near future. The search for “perfect” entrainers should some ideas have been implemented (including dividing
therefore be continued by examining existing options or wall column, microwave and ultrasonic assisted distillation),
synthesizing new ones aiming at entrainers that are effec- many issues remain unresolved and therefore require further
tive in separation, highly selective, energy efficient, and scrutiny.
environmentally friendly with minimal safety and health In summary, we can conclude that while some workable
hazards. In this regard, the use of ionic liquids (ILs) and solutions are readily available, the challenges are numerous,
hyperbranched polymers has shown promising potential. with a wide horizon of opportunities for improvement. The
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Separation & Purification Reviews

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State-of-the-Art Technologies for Separation of

Keywords: Azeotropic mixtures, intensified processes, pervaporation, separation technologies,

INTRODUCTION processes in chemical process industries (2). Nevertheless,

Process Distillation Membrane

Pressure swing Extraction Azeotropic

Hyperbranched Ionic liquids

FIGURE 1 Schematic diagram of various techniques for separation of azeotropic mixtures.

Cyclohexane + benzene Homogeneous Chlorobenzene 77.80 45.0 (25)

System Type LP (bar) HP (bar) Process type Reference

Acetonitrile + water Minimum 1.013 2.78 Continuous (88)

First Step Second Step

Low pressure High pressure

FIGURE 6 Schematic diagram for semicontinuous operation of Pressure

FIGURE 5 Schematic diagram for regular batch operation of Pressure

pressure decreases to some extent. Thus NB = 0 and the Feed Retentate

on each side of the membrane. The retentate is the remain-

Water/ethanol Phosphorylated chitosan 10.23–52.3 70 213 0.58 (124)

principle that governs FricDiff is the membrane separation

currently limited to a few applications such as extraction

search for better processes should be intensified to expedite REFERENCES

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