See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/226247268

Bioethanol dehydration: State of the art

Article  in  Theoretical Foundations of Chemical Engineering · August 2010

DOI: 10.1134/S0040579510040342

CITATIONS READS
73 1,478

2 authors:

A. K. Frolkova Valentina М. Raeva

Moscow Technological University, Institute of Fine Chemical Technology Moscow State University of Fine Chemical Technology
69 PUBLICATIONS   280 CITATIONS    32 PUBLICATIONS   171 CITATIONS   

SEE PROFILE SEE PROFILE

All content following this page was uploaded by Valentina М. Raeva on 19 November 2014.

The user has requested enhancement of the downloaded file.

ISSN 00405795, Theoretical Foundations of Chemical Engineering, 2010, Vol. 44, No. 4, pp. 545–556. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © A.K. Frolkova, V.M. Raeva, 2009, published in Khimicheskaya Tekhnologiya, 2009, Vol. 10, No. 8, pp. 469–482.

ORGANIC
TECHNOLOGIES

Bioethanol Dehydration: State of the Art

A. K. Frolkova and V. M. Raeva
Moscow State Academy of Fine Chemical Technology, pr. Vernadskogo 86, Moscow, 119571 Russia
email: frolkova@mitht.ru, raeva@www.com.ru
Received February 24, 2009

Abstract—This article is a survey of the presentday methods of dehydration of ethanol resulting from fer
mentation processes. The existing separation techniques for water–ethanol mixtures of various compositions
are compared, and the conditions under which each particular technique is preferable are formulated.

Key words: bioethanol dehydration, dehydrated ethanol, water–ethanol mixtures, azeotropes, distillation,
hybrid process.
DOI: 10.1134/S0040579510040342

Bioethanol is considered to be the most promising icy could ensure a fivefold increase in the proportion
fuel of the future since it is obtained from renewable of biofuel used in the world transport, specifically from
sources, namely, biomass and is environmentally 1% today to 6% in 2020. The world bioethanol output
friendly. Ethanol raises the octane number of gasoline, in 2007 was 49.6 billion liters. The total annual average
is an antiknock agent, and can replace existing gaso bioethanol output growth rate in the world in 2002–
line additives. In the United States, the fuel containing 2007 was 19%. The world leaders in bioethanol pro
10 wt % ethanol is becoming increasingly popular duction are the United States and Brazil (Table 2).
because of the recent limitations imposed on the con Their contribution to the world bioethanol output is
centration of ethers in the fuel, including methyl tert 87.9%. EU countries, China, Canada, Thailand,
butyl ether, a detrimental oxygenate. Fuel composi India, and Australia are stepping up their ethanol out
tions containing at least 10 wt % ethanol need no anti
freeze in the cold season. The introduction of ethanol
not only saves gasoline (fuel derived from nonrenew Table 1. Ethanol production in the world [3, 7]
able natural sources) by replacing it, but also markedly
raises the extent of combustion of the fuel, thereby Annual ethanol output, mil. l/yr
reducing the carbon monoxide level in the exhaust. Country
2003 2004 2005 2006
Ethanol enhances the efficiency of the engine and is
an excellent enginecleaning agent [1, 2]. United States 10900 13950 16139 18376
The data listed in Table 1 characterize ethanol pro Brazil 14428 15338 15999 16998
duction in some countries. Note that 73% of the world China 3400 3650 3800 3 849
ethanol output is fuel ethanol. The fuel ethanol is
mainly bioethanol obtained via enzymatic processes India 190 2000 1669 1900
[3, 4]. National bioethanol programs in various coun France 817 830 908 950
tries take into consideration not only their own Germany 280 270 431 765
demand for fuel ethanol, but also social and environ Russia 745 766 749 647
mental aspects, such as mitigation of climatic conse
quences and energetic security enhancement [5, 6]. Canada 204 245 231 579
Because of the high price of petroleum and the poor Spain 304 420 352 462
choice of alternative motor fuels, Brazil, some EU South Africa 404 409 390 386
countries, India, and China actively develop their liq Thailand 250 280 299 352
uid bioethanol production.
Note that, in many countries, the government pro England 410 400 348 280
vides strong support for biofuel programs in order to Ukraine 284 290 246 269
make this branch of industry competitive. This support Columbia – – 270 269
includes tax credits and regulations making use of bio Poland – – 220 250
fuel obligatory. EU and US manufacturers receive
additional support as high ethanol import tariffs. Saudi Arabia 350 340 121 200
According to some estimates, a protective biofuel pol Italy 240 210 151 162

545
546 FROLKOVA, RAEVA
Table 2. Bioethanol production in 2007
Annual average Contribution
Amount,
Country output growth to the world
bil. l
rate*, % output, %
United States 24.6 25 49.6
Brazil 19 8.6 38.3
EU*** 2.2 35.1 4.4
China 1.8 124.2** 3.7
Notes: * In 2002–2007.
** In 2003–2007.
*** Thirtytwo manufacturers.
put. New bioethanol facilities have been put into oper
ation in Columbia, Central America, Turkey, Paki
stan, Peru, Argentine, and Paraguay [8].
Evidently, the steady growth of the world consump
tion of bioethanol has stimulated research aimed at
improving and optimizing all bioethanol production
stages. This survey of the scientific and technical liter
ature is limited to the dehydration of ethanol resulting
from enzymatic processes. At present, absolute etha
nol containing 99.5 wt % alcohol or more is in greatest
demand in fuel applications. The presence of water in
the fuel is undesired because of the formation of sepa
rating mixtures with hydrocarbons.
The separation strategy for systems of various com
positions into products with preset quality is dictated
by the existence of azeotropy in the ethanol–water
system. This strategy involves methods of separation of
azeotropic mixtures (azeotropic, heteroazeotropic,
extractive, and salteffect distillation techniques; dis
tillation combined with phase separation; pressure
swing distillation; etc.), which are aimed at circum
venting thermodynamic limitations and are based on
the principle of concentration field redistribution
between distillation regions [9, 10]. In the foreign lit
erature, these techniques are considered as separate
engineering solutions.
The purpose of this survey of data published in the
latest decade is to compare approaches to the dehydra
tion of fermentative and synthetic ethanol and to find
the conditions under which each particular dehydra
tion technique is preferable. Significant points here
are the process capacity and the stock composition.
For example, extraction, pervaporation, and molecu
lar sieve adsorption are not usually employed in large
scale ethanol dehydration. At the same time, these
techniques are successfully used in the continuous
separation of small amounts of water–ethanol mix
tures. Below, these techniques will be considered in
greater detail.
PERVAPORATION
The separation efficiency in pervaporation is manly
determined by the properties of the membranes and
JOURNAL OF CTHEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44
process conditions. Here, the physicochemical prop
erties of the components being separated and those of
the mixture are of much lower significance than in the
case of distillation. This allows azeotropic mixtures to
be separated. In pervaporation, the mixture to be sep
arated does not need to be brought to boiling and it is,
therefore, possible to utilize lowgrade heat. As dis
tinct from distillation, which needs multiple evapora
tions of the entire mixture, pervaporation consumes
energy only for permeate evaporation. Pervaporation
generally does not require any extra reagents. Azeotro
pic and extractive distillation, extraction, and other
methods employing extra chemicals (separation or
extracting agents) need subsequent recovery of these
chemicals, which complicates the separation technol
ogy.
The operational advantages of membrane units are
obvious. Their modular design allows their capacity to
be varied by simply adding or cutting off membrane
modules and makes easier their maintenance. The
specific surface area of a membrane (phase contact
area) in a membrane unit is several times larger than
the same parameter in any tray or packed distillation
column. Accordingly, membrane modules are much
smaller [11, 12].
All of the above facts are undoubtedly of great sig
nificance. However, the optimality of a given technol
ogy is governed by its cost. We compared the operating
expenses of ethanol dehydration to 99.8 wt % by per
meation, pervaporation, distillation, and adsorption
for a fixed production rate of 30 t/day, which were
found to be $15.75, $12.6–16.6, $31.95–45.65, and
$36.6 per ton, respectively [13].
In addition, we think that there is a plant equip
ment standardization problem. A distillation tray of a
particular type can be used in the separation of various
mixtures. The decisive criteria in the selection of a tray
are its efficiency and some performance parameters.
For example, perforated trays should not be used for
polymerizable substances, because temperature dis
turbances can cause their failure.
By contrast, the performance of a membrane in
separation of various mixtures depends on its chemical
nature. In pervaporation, it depends on the water con
tent of the initial ethanol–water mixture whether
hydrophilic membranes should be used to separate
water or hydrophobic membranes should be employed
to separate ethanol [8, 14]. It is theoretically possible
to organize consecutive separation of solutions con
taining different ethanol concentrations on mem
branes of different natures. However, the separation
capacity of moist membranes is insufficient for com
mercialscale basic organic synthesis. Raising the
number of membranes modules shortens the pervapo
ration time and thus reduces energy consumption, but
it increases the depreciation cost of the membranes.
This is a restrictive factor in the replacement of distil
lation with pervaporation in largescale separation
technologies. In order to promote the commercializa
No. 4 2010
 BIOETHANOL DEHYDRATION: STATE OF THE ART
Table 3. Comparison of methods of ethanol dehydration from 94 to 99.9 vol % [12]
Expense item
permeation pervaporation
Steam – 6.4
Electricity 20.0 8.8
Cooling water 2.0 2.0
Replacement of membranes 9.5 15.3
Entrainer – –
Replacement of molecular sieves – –
Total cost 31.5 32.5
Note: Costs are in DM/t as of the year 1991.
tion of the pervaporation separation of water–ethanol
mixtures, it is necessary to continue search for mem
branes and membrane materials meeting the specific
requirements of this separation problem and to study
the main factors in their separation efficiency, such as
the feed composition, process temperature, and per
meate pressure [15, 16].
In 2000, Sulzer Chemtech Membrantechnik AG
(Germany) installed ethanol dehydration membrane
modules with 500–150000 l/day capacity at 24 plants
[12]. Table 3 presents a comparison between the costs
of ethanol dehydration from 94 to 99.9 vol % by differ
ent methods. Evidently, the membrane separation
methods are highly competitive. However, these data
leave aside the costs of ethanol solution preconcentra
tion to a nearazeotropic composition.
ADSORPTION
Two water adsorption techniques are used in the
separation of water–ethanol mixtures—liquidphase
and vaporphase adsorption. Adsorbents employed in the
liquidphase process are type A zeolites, cellulosebased
materials, etc. Vaporphase water adsorption widely
relies on inorganic adsorbents, such s zeolite molecular
sieves (3A and 4A), lithium chloride, and silica gel. Sub
stances of biological origin are considered only as poten
tial adsorbents for this application [17].
Molecular sieves with a small pore size adsorb
water molecules well, so they are most efficient in
water removal from solutions with low water content.
There is an ethanol dehydration method in which the
water–ethanol solution is concentrated by distillation,
the product is then dehydrated using molecular sieves,
and the adsorbent is regenerated by desorption [18]. A
drawback of this method is the large amount of liquid
forming at the molecular sieve regeneration stage.
Carrying out this process in the vapor phase excludes
the wetting of the molecular sieves in adsorption and
their drying in desorption, thus reducing heat and
energy consumption [18].
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44
547
Cost
heteroazeotropic distillation with adsorption on molecular
cyclohexane sieves
60.0 40.0
4.0 2.6
7.5 5.0
– –
4.8 –
– 25.0
76.3 72.6
Ethanol dehydration over synthetic molecular
sieves offers some technological advantages, such as a
simple process design, a long service life of up to 5
years, ease of regeneration, and high economic effi
ciency. The latter is due to the high adsorption capac
ity and the considerable water diffusion rate. However,
as compared to pervaporation, water adsorption is
now attracting much less attention. Researchers’ cur
rent efforts are being focused on experimental deter
mination of the capacity of various zeolites for sepa
rating ethanol–water mixtures and on simulation of
adsorption in particular systems [19, 20].
Carbon is another efficient water adsorbent. It can
dehydrate water–ethanol vapor mixtures containing
1.6–50.9% water. Carrying out the process in an adia
batic carbon adsorber demonstrated that the adsor
bent is stable over 85 adsorption–desorption cycles
using hot air or nitrogen (80–120°C). However, as in
the case of pervaporation, integration of different
methods is appropriate here: dilute ethanol should be
concentrated to a nearazeotropic composition by dis
tillation, and the product should be further dehydrated
by adsorption [21].
The presentday commercialscale process named
Pressure Swing Adsorption (PSA) is conducted in an
adsorber–desorber complex. Adsorption is carried out
on zeolites at an elevated pressure of 379.2 kPa and a
temperature of 440 K. The feed, which contains
92 wt % ethanol, is introduced into the top section of
the column at a rate of 10410 kg/h. The ethanol con
centration in the product stream is above 99.5 wt %.
The regeneration of the adsorbent includes the follow
ing steps: reducing the pressure to 13.8 kPa, which
causes partial water desorption; water desorption at
3.8 kPa; removal of residual water with part of the
vaporous product stream (99.5 wt % ethanol); and
raising the pressure to 379.2 kPa.
The duration of a cycle is 345 s. Unlike conven
tional adsorption, the PSA processes does not use hot
nitrogen or air in regeneration [22].
No. 4 2010
548 FROLKOVA, RAEVA
EXTRACTION
The solvents used in the liquid–liquid extraction of
ethanol from dilute aqueous fermentation solutions
must meet not only standard requirements, including
low solubility in the aqueous phase, short separation
time, chemical inertness, and environmental friendli
ness, but also a number of specific requirements. For
example, if the aqueous phase is returned to the fer
menter, the extracting agent should be both nontoxic
and innutritious to microorganisms [23].
It is pertinent to use extraction for aqueous solu
tions containing 2–5 wt % ethanol. The dilute solu
tion is sometimes concentrated to an ethanol content
of 10–30 wt %. Extraction with paraffin oil is con
ducted at 105°C, and the extract is then cooled to
30°C. The resulting ethanolic phase contains 4–
5 wt % light hydrocarbons and can be added directly to
a fuel [22]. Obviously, this technology does not include
ethanol dehydration.
A new process was suggested for ethanol isolation
from fermentation broths. In this process, the extract
ing agent is completely soluble above the upper critical
solution temperature (UCST) and is partially soluble
at lower temperatures (in the twophase region at 60–
100°C). The hot solvent, which is hexadecane, is
brought into contact with the water–ethanol mixture
at 115°C (15° above UCST) to extract ethanol. The
ethanol–solvent mixture is then cooled to 30°C in a
separator, and the solvent is returned to the extractor.
According to experimental data, this separation pro
cess affords ethanol containing <1% water [24].
Separation of water–ethanol mixtures with super
critical CO2 has not been commercialized in the basic
organic synthesis industry. However, this extractant is
used in the pharmaceutical industry. Supercritical CO2
has a comparatively low critical point (7.38 MPa,
304.25 K) and is inexpensive. Furthermore, it is envi
ronmentally friendly [25]. Carbon dioxide is easy to
recover: it is readily separable from ethanol in a distil
lation column under elevated pressure. Since the
CO2–ethanol–water mixture is zeotropic at 333.2 K
and 10 MPa, it can be separated by conventional dis
tillation as well [26, 27]. Budich and Brunner [28]
compared the amounts of energy required for obtain
ing anhydrous ethanol (kJ/l) by various methods: pres
sure swing, 4730; heteroazeotropic distillation with
pentane, 8100; extraction with supercritical CO2,
2500.
The potential of supercritical carbon dioxide for
separation of aqueous ethanol solutions is now being
investigated. In particular, the following factors in
batch extraction are discussed: reflux ratio, ethanol
concentration in the initial solution, and extraction
conditions and time. There have been studies on the
separation of dilute fermentation solutions of ethanol
(0.1–1.7 wt %) with supercritical carbon dioxide. It
was demonstrated that raising the pressure, tempera
JOURNAL OF CTHEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44
ture, and ethanol concentration in the initial solution
is favorable for extraction [22, 28, 29].
Since the aqueous solutions resulting from fermen
tation are dilute (4–15% ethanol, according to differ
ent sources), they can be directly separated by extrac
tion, pervaporation, or pervaporation or preconcen
trated to a nearazeotropic composition by distillation
[21, 25, 29].
As was noted above, the presentday approach to
separation of azeotropic mixtures is based on concen
tration field redistribution between separation regions.
The basic elements of this azeotropic separation tech
nology include separation complexes (sets of appara
tuses coupled by feedforwards and feedbacks) each
executing its particular function. In recent years, there
have been extensive theoretical studies of the opera
tion of these complexes [9, 10]. We will dwell on con
tinuous dehydration processes for the azeotropic eth
anol–water system that are based on the principle of
concentration field redistribution between separation
regions and have been commercialized in the basic
organic synthesis industry.
PRESSURESWING DISTILLATION
If the composition of the binary azeotrope changes
as the external conditions (temperature, pressure) are
varied, it is possible to separate the mixture in a com
plex of distillation columns operating at different pres
sures. Ethanol dehydration by this method was sug
gested by L’vov [30] as early as 1960. At present, this
method is used in the dehydration of ethanol resulting
from fermentation [31]. An efficient way of isolating
ethanol from the fermentation solution is by pervapo
ration, which affords an ethanol concentration of up
to 40 mol %, followed by distillation under varying
pressure (pressureswing distillation). In this tech
nique, utilizing the heat of the streams coupling the
columns can reduce the operating expenses for etha
nol production by 44% [32].
Figure 1 shows the typical distillation flowsheet for
the ethanol (1)–water (2) mixture with the composi
tion XF. The appropriateness of this flowsheet is gov
erned by the value of the azeotropic shift Δx = x' – x''
(change in the azeotrope composition) caused by a
change in pressure from P1 to P2. The maximum Δx
value in the technologically acceptable pressure range
minimizes the recycle rate and reduces the energy
required for separation [33].
EXTRACTIVE DISTILLATION
In the case of extractive distillation, the principle of
concentration field redistribution between continuous
distillation regions means directed transformation of
the phase diagram of the initial system in the presence
of an appropriate separating agent selectively changing
the relative volatility of the components. With an
appropriate highboiling separating agent, this separa
No. 4 2010
 BIOETHANOL DEHYDRATION: STATE OF THE ART
tion method is the least energyintensive because the
separation agent almost does not evaporate. The
binary azeotropic mixture ethanol–water with the ini
tial composition xF is separated using the standard uni
form complex consisting of two columns (Fig. 2),
namely, an extractive distillation column (I) and a
simple distillation column recovering the separation
agent (II) [34]. Here, the separation agent can be a
compound forming homogeneous mixtures with the
azeotrope components, such as ethylene glycol, glyc
erol, 1,3diaminopentane, diethylenetriamine, and
hexachlorobutadiene.
General requirements and conventional selection
methods for separation agents were described by
Kogan [35]. The presentday approaches to agent
selection and to prediction of separation results need a
deeper insight into the nonlocal properties of the dia
grams of extractive systems, including the mutual
arrangement of particular manifolds in the concentra
tion simplex: univolatility lines, pseudoideal mani
folds, Bancroft isotherm–isobar lines, and isotherm–
isobar lines of the inversion of partial molar heats of
evaporation [36].
A comparatively new method that has not been
widely commercialized in the industrial separation of
water–ethanol mixtures is extractive distillation in a
single column using ethylene glycol as the separation
agent [37–40]. This technology is promising for batch
distillation of small amounts of mixtures in the phar
maceutical and fine chemical industries. Brito et al.
[37] considered ethanol dehydration in the presence of
ethylene glycol in one column having 20 trays (count
ing from the column bottom). The initial solution
(85 mol % ethanol) is fed to the 12th tray, and almost
pure water (99.27 mol %) is drawn from the 6th tray.
The distillate contains 99.71 mol % ethanol and some
impurities. The bottom product is pure ethylene glycol
(99.98 mol %), which is returned to the column top.
The column can be fitted with a second reboiler [38].
The classical extractive distillation design ensures the
same product quality and ethylene glycol purity, but it
involves two columns (Fig. 2). The first is the ethanol
separation column. It has 20 trays, with the feed intro
duced at the 12th tray and ethylene glycol entered at
the top. The second is the water separation column,
which again has 20 trays, with the feed entered at the
6th tray. This separation design is more energy and
capitalintensive.
Bioethanol dehydration technologies employ not
only conventional separation agents, but also dissolved
salts, mixtures of liquid separation agents and salts,
ionic liquids, and highly branched polymers [17, 41].
Researchers are expressing increasing interest in
ionic liquids. By way of example, we will present the
total numbers of recent publications dealing with ionic
liquids in two wellknown journals: The Journal of
Chemical Engineering Data, over 120 articles from
2000 till now; Fluid Phase Equilibria, over 110 articles
from 2004 till now. In separation technologies, ionic
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44
549
y1 (a) (b)
P1 ,
x
P2
I II
xF
,
x'
0 , X1
xF x' x'' x 2 1
Fig. 1. Pressureswing distillation of the azeotropic mix
ture ethanol (1)–water (2): (a) liquid–vapor equilibrium
diagram; (b) distillation flowsheet involving (I) a column
operating at the pressure P1 and (II) a column operating at
the pressure P2.
liquids can replace many toxic and hazardous volatile
compounds that are used today as separation agents.
As distinct from most conventional solvents, which are
molecular compounds, ionic liquids are salts with a
low melting point. They are liquid in a wide tempera
ture range and are inert toward air and water. In addi
tion, the have a low vapor pressure and do not contam
inate the environment. Most studies have so far been
focused on the effects of ionic liquids on the phase
equilibrium in water–ethanol mixtures of various
compositions [42–49] and on the applicability of
model equations to phase equilibria in systems involv
ing ionic liquids [50].
A variant (limiting case) of extractive distillation is
salteffect distillation. The separation agent in this
technique is a salt solution that is mainly miscible with
one of the mixture components, reducing its relative
volatility. The dissociation of the salt is accompanied
by the solvation of the ions of the less volatile compo
nent (water). Salteffect distillation is a suitable
method for mixtures n which comparatively small
amounts of a salt can markedly raise the relative vola
tility of a component.
1 2
xF
I II
2–3
3
Fig. 2. Extractive distillation of the ethanol (1)–water (2)
mixture with a highboiling separation agent (3) in two dis
tillation columns (I, II).
No. 4 2010
550 FROLKOVA, RAEVA

y solutions [51–55]. Figure 3 shows a phase diagram

1.0 illustrating the effect of a salt on the vapor–liquid
1 equilibrium in the ethanol–water system. One of the
2 unsolved problems of phase equilibrium simulation
and salteffect distillation design, including in ethanol
0.5
dehydration, is that of taking into account the effects
of the salt on the enthalpy of liquid flows in the column
and on the isobaric heat capacities [51, 55].
There has been a historical survey of the commer
0 cialization of this method in industry (HIAG process).
0.5 x1 In 1930–1950, about 100 plants using this technology
was built in Europe, and their total capacity was up to
Fig. 3. Qualitative vapor–liquid equilibrium diagram of 43000 t/yr. The last plant of this type was put into
the ethanol (1)–water (2) system at atmospheric pressure operation in 1965 in Brazil. This ethanol dehydration
in the absence of a salt (dashed line) and in the presence of
a salt (solid line). technology employs a mixture of sodium and potas
sium acetates, which are introduced into the hot reflux
of the distillation column.
Ethanol Dilute ethanol solutions (<10 wt % ethanol) to be
KAc dehydrated should generally be preconcentrated [51].
However, there has been only a single work [55] in
Vapor which two salteffect distillation processes (using
Feed Air
1 potassium acetate) are suggested and completely cal
1 r r 3 culated for dilute and concentrated aqueous solutions
2 2 2 (Figs. 4, 5, respectively). In the former case, dilute
ethanol is fed into extractive distillation column 1. The
salt recovery stage consists of evaporation followed by
Vapor Air KAc drying with hot air in unit 3. The later design includes
Condensate preconcentrating distillation column 1, extractive dis
tillation column 2, and drying unit 3. For these
Fig. 4. Salteffect distillation of dilute aqueous ethanol designs, it is possible to compare the operation param
solutions [55]: (1) extractive distillation column, (2) evap eters of the extractive distillation column (Table 4) and
oration unit, and (3) drying unit. energy consumptions at particular stages pf the pro
cess (Table 5). The total energy consumption is higher
for the dehydration of dilute ethanol.
There are energy consumption data (MJ/(kg etha
Ethanol
nol)) for ethanol dehydration by extractive or azeotro
pic distillation with the following separation agents
KAc [55]: ethylene glycol,
Feed 34.06; diethyl ether, 13.59; benzene, 12.15; pen
1 Air tane, 10.87. The above process involving ethanol pre
2
3 concentration is characterized by the lowest energy
consumption of 9.27 MJ/kg. This technology is being
improved by seeking new separation agents, optimiz
ing heat flows, introducing an extra distillation col
Air KAc umn for concentrating the solution (with a heat pump
Water and optimal side recycle), and using an evaporator for
concentrating and drying the salt [53, 54].
Fig. 5. Salteffect distillation of concentrated aqueous eth
anol solutions [55]: (1) distillation column, (2) extractive The separation efficiency can also be enhanced by
distillation column, and (3) drying unit. combining separation agents. Unlike salteffect distil
lation, this technology does not need salt recovery
(Figs. 4, 5). It is possible to carry out extractive–salt
Various salts, including sodium nitrate, lithium distillation [56, 57]. Table 6 lists column operation
chloride, sodium chloride, potassium chloride, cal parameters for extractive distillation with ethylene gly
cium chloride, potassium iodide, and potassium ace col and calcium chloride (CaCl2 concentration of
tate, were suggested for separation of aqueous ethanol 0.075 g/(ml ethylene glycol)).

JOURNAL OF CTHEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44 No. 4 2010

 BIOETHANOL DEHYDRATION: STATE OF THE ART 551

AZEOTROPIC DISTILLATION Table 4. Comparison between salteffect distillation columns

using potassium acetate [55]
In azeotropic distillation, a substance forming
homogeneous azeotropes with the components of the Parameter values
initial mixture is introduced into the column. The sep Distillation column
aration of the new azeotropic mixture requires a spe parameters dilute ethanol concentrated
cialpurpose technique to be used. It is commonly as the feed ethanol as the feed
thought that azeotropic distillation in most cases is less Feed flow rate, mol/s 555.5 22.22
economic in terms of energy because the azeotrope
forming agent undergoes multiple evaporations. Homo Feed composition, mol % 2.4 60
ethanol
azeotropic distillation is considered to be appropriate
when the mixture of the azeotropeforming agent with Feed temperature, K 303.15 353.45
one of the components is usable without being separated. Number of trays 37 35
For the dehydration of ethanol–water mixtures, he only Feed tray number 18 5
separation agent of this kind is ethylenediamine. It forms Minimum/working reflux 2.1/2.5 1.0/1.2
a homogeneous, maximumboiling azeotrope with water ratio
and is unstable without water [34].
Salt flow rate, mol/s 3.74 1.80
Reboiler power, W 4.85 × 106 3.07 × 105
HETEROAZEOTROPIC DISTILLATION
Note: Distillate composition: 98.9 mol % ethanol; distillate flow rate:
Heteroazeotropic distillation is the azeotropic dis 13.5 mol/s.
tillation technique in which the liquid is separated
deliberately into two phases by introducing a het
eroazeotropeforming agent into the system. A classi Table 5. Energy consumption in salteffect distillation pro
cal example of heteroazeotropic distillation is ethanol cesses [55]
dehydration with benzene [30]. In this process, ben
zene (3), which has limited solubility in water, is added Energy consumption at particular
to the azeotropic ethanol (1)–water (2) mixture process stages, W
(Fig. 6a). In the steadystate operation of the separa Apparatus
dilute ethanol concentrated
tion complex, the role of the heteroazeotropeforming as the feed ethanol as the feed
agent is played by the organic (benzene) layer. Other
separation agents are possible here, including dichlo Extractive distillation 4.85 × 106 3.07 × 105
roethane, isobutyl alcohol, butyl acetate, propyl ace column
tate, diethyl ether, diisopropyl ether, cyclohexane, Preconcentration column – 4.84 × 106
2,2,4trimethylpentane, toluene, npentane, cyclo Evaporation unit 2.16 × 107 –
pentane, methylcyclopentane, nhexane, 2methyl
pentane, hex1ene, 2,2dimethylpentane, and 2,2,3 Drying unit 4.53 × 106 5.55 × 106
trimethylbutane [22, 35, 58, 59]. Total energy consumption 3.1 × 107 10.7 × 106
Since the fermentation of vegetable feedstocks,
biowaste, polysaccharides, sugar, treacle, and other
biomaterials yields dilute aqueous ethanol solutions, it stream is used to heat the bottom section of the initial
is appropriate to carry out conventional distillation to mixture distillation column. The ethanolpure frac
obtain a nearazeotropic composition prior to het tion from desorber II provides the feed for the distilla
eroazeotropic distillation (Fig. 6b). tion column. The distillate from this column, which
has a nearazeotropic composition, is returned to the
ADSORPTION–DISTILLATION COMPLEXES
Ethanol can be dehydrated by combining distilla (a) (b) 3
tion and adsorption. The original scheme of the pres
sure swing adsorption process is presented in Fig. 7. 3
The initial mixture is fed into the vaporizer and is then
directed to a standard adsorption section consisting of xF
adsorber I and desorber II. Adsorption column I is xF
operated at a higher pressure than desorption column
II. The desorption agent is dehydrated ethanol (part of
the product stream). After a certain time, the pressure 1 2 2 1 2
in the columns is changed so that the adsorber
becomes the desorber and vice versa. Fig. 6. Dehydration of ethanol (1)–water (2) mixtures by
heteroazeotropic distillation: (a) structure of the separa
The adsorption product, which is dehydrated etha tion complex; (b) design involving a preconcentration
nol, leaves adsorber I as a vapor. The heat of this stage [22].

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44 No. 4 2010

552 FROLKOVA, RAEVA

Table 6. Column operation parameters for extractive–salt dis permeation. In both processes, the initial mixture (liq
tillation with ethylene glycol and calcium chloride [57] uid in pervaporation and vapor in permeation) is sep
arated by means of partial evaporation through a selec
Parameter values for the columns
tive nonporous membrane and the permeate is in the
Operation parameter Extractive distil Extracting agent vapor state. The retentate is a liquid in pervaporation
lation column recovery column and a vapor in permeation.
A large number of hybrid ethanol dehydration
Feed flow rate, kmol/h 100 44 schemes with different orders of mass transfer pro
Extracting agent flow 30 – cesses for various feedstock compositions (distillation +
rate, kmol/h pervaporation, pervaporation + distillation, distilla
Distillate flow rate, 88.864 13.70 tion + pervaporation + distillation) have already been
kmol/h commercialized [58, 61]. The conceptual scheme of
Feed temperature, K 351.33 394.13 the hybrid separation process is presented in Fig. 8.
Extracting agent tem 353.15 – This scheme includes distillation column 1 for con
perature, K centrating the ethanol–water mixture and pervapora
tion unit 2 for obtaining pure ethanol [62, 63]. The
Reflux ratio 0.35 0.25 dilute aqueous ethanol solutions resulting from fer
Number of theoretical 18 11 mentation are usually subjected to preconcentration.
trays Several pervaporation modules are employed in some
Feed tray number 12 6 cases (Table 7), and this allows very dilute ethanol
Pressure, atm 1 0.2 solutions to be dehydrated [58]. Here, the bottoms of
Energy consumption, 1204 221
the distillation column are almost pure water.
kJ/(kg ethanol) Another possible ethanol dehydration scheme
includes two distillation columns (1, 2) and one per
vaporation module (3) (Fig. 9). This variant is
vaporizer. The bottom product contains only traces of intended for waterrich feedstocks. The diagrams of
ethanol. distillation and evaporation through the membrane
illustrate the principle of concentration field redistri
bution between separation regions. The performance
PERVAPORATION–DISTILLATION of all of the above hybrid schemes can be optimized by
COMPLEXES increasing the surface area of the membrane, by
improving its geometry, by reducing the reflux ratio of
An analysis of the literature demonstrated that the the distillation column, and by optimizing the recycle
development and commercialization of hybrid pro stream (changing from partial to total recycle) [62, 64,
cesses combining distillation and membrane separa 65].
tion is among the priority areas today. Water–ethanol The development of the physicochemical founda
mixtures are usually separated by pervaporation or tions of mass transfer processes has improved conven

Retentate
Vapour
superheater Condencer Condencer Distillate
Distillate
(~95%)
2 6

Evaporizer Col. Col. 3

I II Ethanol
(~70%) Rectifying
column 5 Dehydrated
Feed
ethanol
Feed (~92%)
Dehydrated ethanol (vapour) Permeate
1
Dehydrated
ethanol 4
(~99.6%)
Heat
exchanger Condencer Bottom product
(water) Water

Fig. 8. Distillation–membrane complex for separation of

Fig. 7. Ethanol dehydration via pressure swing adsorption ethanol (1)–water (2) mixtures: (1) distillation column,
and distillation [60]: (I) adsorber and (II) desorber. (2) membrane unit, and (3–6) heat exchangers.

JOURNAL OF CTHEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44 No. 4 2010

 BIOETHANOL DEHYDRATION: STATE OF THE ART 553

Table 7. Outcomes of separation processes combining distillation and pervaporation

Ethanol concentration
Separation data
Feed composition Reference
for distillation composition of the perme
distillate composition number of modules ethanol quality
ate from the last module
43 wt % 82 wt % 1 99.9 wt % Not indicated [62], [63]
4 mol % 60 mol % 2 99.5 wt % 40–50 mol % [58]
8–12 vol % 94 vol % 3 >99.9 vol % 12–20 vol % [11]

tional separation technologies and has given birth to
radically new ones. For example, water–ethanol mix
tures have been separated by the action of pulsed cav
itation and the use of electric fields and ionexchange
sorption for this purpose is discussed.
Electrohydrodynamic distillation columns have
recently been suggested for recovery of comparatively
small amounts of solvents (up to 5000 t per year) in the
electronic industry. Mass transfer in these apparatuses
is intensified and controlled by means of an electric
field in the liquid spraying regime. The water content
of recovered ethanol should not exceed 12 vol %. An
electrohydrodynamic distillation apparatus with a
1mlong contact zone ensures, in a wide range of
reflux ratios, an ethanol concentration of >92 vol % in
the recovered solvent and a residual ethanol concen
tration of below 1 vol % in the bottoms [66].
The introduction of a molecular sieve into the sep
aration system produces an effect on the liquid–vapor
equilibrium in the ethanol–water system: pure ethanol
was obtained from a 40% ethanol solution [67]. It is
likely that distillation and adsorption can be combined
in one apparatus. A separation technology combining
adsorption o molecular sieves, pervaporation, and dis
tillation has been suggested for ethanol–water mix
tures [1].
Another tendency in presentday bioethanol pro
duction technologies is toward combining a chemical
reaction and a separating mass transfer process in one
apparatus. Fermentation has been combined with dis
tillation [68] and with membrane separation [69–72].
It is claimed that fermentation followed by vacuum
membrane distillation is economically attractive. A
hydrophobic and a hydrophilic membrane are used,
respectively, to remove ethanol and water from the
reaction system, and the water is returned to the fer
menter [17].
The comparative analyses of various ethanol dehy
dration methods have mostly been qualitative and have
been limited to ascertaining that distillation is an
energyintensive process and to emphasizing the
advantages of the method developed by a particular
demand for separation, operational stability, and high
productivity (the last statement seems questionable to
us). The main flaw of this technology is the high cost
of the equipment. Extractive distillation with ethylene
glycol is notable for its high productivity and control
reliability. Its obvious disadvantage is high operating
expenses. This is also true for heteroazeotropic distil
lation with cyclohexane. The advantage offered by
vapor permeation is low energy consumption, and its
drawbacks are the high cost of the equipment and the
risk of innovation—this process has not been widely
commercialized as yet.
Unfortunately, we did not find economic assess
ments that would allow a correct comparison of etha
nol dehydration methods as was done for isopropanol
dehydration [74]. Even energy demands cannot be
compared in most cases.
The choice of bioethanol dehydration method
depends primarily on the capacity of the fermentation
unit. For small amounts of bioethanol, it is appropri
ate to use batch extractive distillation, pervaporation,
or adsorption. Kaminski et al. [1] compared the eco
nomic efficiencies of distillation and pervaporation in
ethanol dehydration to a concentration of 99.5 wt %.
For a production rate of 100 l/day, azeotropic distilla
tion with cyclohexane and adsorption are more costly
than pervaporation by a factor of 2 and 1.5, respec
tively. For production rates higher than 100 l/h, the
(a) (b)
x1 = 0.85
y1
Concentrate
3
F0
I
x1 = 0.04 1 Permeate 2
II
Water Ethanol
0 x Az x1 x1 = 0.095

author. The most significant advantages and draw

backs of particular ethanol dehydration technologies Fig. 9. (a) Diagrams of (I) distillation and (II) evaporation
through the membrane. (b) Separation complex for etha
were discussed by Moura and Medeiros [73]. Adsorp nol (1)–water (2) mixtures resulting from fermentation:
tion on molecular sieves is attractive for its low energy (1, 2) distillation columns and (3) membrane module.

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44 No. 4 2010

554 FROLKOVA, RAEVA
cost of pervaporation depends linearly on the produc
tion rate. Pervaporation is economically efficient at water
concentrations below 10 wt %. The residual water con
centration in ethanol in this case is 1–100 ppm. Distilla
tion is preferable at production rates of above 5000 l/h.
Thus, the presentday approach to ethanol dehy
dration reliw on combining different mass transfer
processes. Dilute solutes containing 1–12 wt % etha
nol should be preconcentrated by distillation to a
nearazeotropic composition. This should be followed
by using inhomogeneous separation techniques
involving salteffect distillation, heteroazeotropic dis
tillation, and distillation–pervaporation and adsorp
tion–distillation complexes [22, 55, 58].
REFERENCES
1. Kaminski, W., Marszalek, J., and Ciolkowska, A.,
Renewable Energy Source—Dehydrated Ethanol,
Chem. Eng. J., 2008, vol. 135, no. 1, pp. 95–102.
2. Tsarev, A.V., Balabin, R.M., Karpov, S.A., and Syun
yaev, R.Z., Optimization of the Performance and Envi
ronmental Properties of Ethanol–Gasoline Fuels
Using Microwave Treatment, Alternat. Energet. Ekol.,
2007, vol. 52, no. 8, pp. 69–74.
3. Sanches, O.J. and Cardona, C.A., Trends in Biotech
nological Production of Fuel Ethanol from Different
Feedstocks, Bioresour. Technol., 2008, vol. 99, no. 13,
pp. 5270–5295.
4. Cardona, C.A. and Sanches, O.J., Fuel Ethanol Pro
duction: Process Design Trends and Integration
Opportunities, Bioresour. Technol., 2007, vol. 98, no. 2,
pp. 2415–2457.
5. Wasewar, K.L. and Pangarkar, V.G., Intensification of
Recovery of Ethanol from Fermentation Broth Using
Pervaporation: Economical Evaluation, Chem. Bio
chem. Eng. Q., 2006, vol. 20, no. 2, pp. 135–145.
6. Blackburn, W.J. and Teague, J.M., Coordinating Cali
fornia’s Efforts to Promote Waste to Alcohol Produc
tion, Appl. Biochem. Biotechnol., 1998, vol. 7072, pp.
821–841.
7. Karpov, S.A., Current Aspects of Fuel Ethanol Produc
tion in Russia and Abroad, Chem. Technol. Fuels Oils,
2008, vol. 44, no. 1, pp. 1–4.
8. www.abercade.ru/research/analysis/425.html, www.e
vid.ru/indexm192p63article17596.htm
9. Serafimov, L.A. and Frolkova, A.K., Fundamental
Principle of ConcentrationField Redistribution
between Separation Regions as a Basis for the Design of
Technological Systems, Teor. Osn. Khim. Tekhnol.,
1997, vol. 31, no. 2, pp. 193–201 [Theor. Found. Chem.
Eng. (Engl. Transl.), vol. 31, no. 2, pp. 159–166].
10. Frolkova, A.K., Theoretical Foundations of Multicom
ponent Multiphase Separation Using Functional Com
plexes, Doctoral (Eng.) Dissertation, Moscow: Moscow
Inst. of Fine Chemical Technology, 2000.
11. Polyakov, A.M., Some Aspects of the Pervaporation
Separation of Liquid Mixtures, Krit. Tekhnol. Membr.,
2004, vol. 24, no. 4, pp. 29–44.
JOURNAL OF CTHEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44
12. Kujawski, W., Application of Pervaporation and Vapor
Permeation in Environmental Protection, Pol. J. Envi
ron. Stud., 2000, vol. 9, no. 1, pp. 13–26.
13. Wee, S.L., Tye, C.T., and Bhatia, S., Membrane Sepa
ration Process—Pervaporation through Zeolite Mem
brane, Sep. Purif. Technol., 2008, vol. 63, no. 3,
pp. 500–516.
14. Namboodiri, V.V. and Vane, L.M., High Permeability
Membranes for the Dehydration of Low Water Content
Ethanol by Pervaporation, J. Membr. Sci., 2007,
vol. 306, nos. 1–2, pp. 209–215.
15. Banat, F., Abu, AlRabF., and BaniMelhem, K.,
Desalination by Vacuum Membrane Distillation: Sen
sitivity Analysis, Sep. Purif. Technol., 2003, vol. 33, no.
1, pp. 75–87.
16. Furukawa, S., Goda, K., Zhang, Yi., and Nitta, T.,
Molecular Simulation Study on Adsorption and Diffu
sion Behavior of Ethanol/Water Molecules in NaA
Zeolite Crystal, J. Chem. Eng. Jpn., 2004, vol. 37, no. 1,
pp. 67–74.
17. Huang, H.J., Ramaswamy, S., Tschirner, W., and
Ramarao, B.V., A Review of Separation Technologies
in Current and Future Biorefineries, Sep. Purif. Tech
nol., 2008, vol. 62, no. 1, pp. 1–21.
18. Makarov, V.V. Petrykin, A.A., Skvortsov, E.A., et al., RF
Patent 2?265?473, Byull. Izobret., 2005, no. 34.
19. Lu, L., Shao, Q., and Huang, LuX., Simulation of
Adsorption and Separation of Ethanol–Water Mixtures
with Zeolite and Carbon Nanotube, Fluid Phase
Equilib., 2007, vol. 261, nos. 1–2, pp. 191–198.
20. Ladisch, M.R., Voloch, M., Hong, J., et al., Cornmeal
Adsorber for Dehydrating Ethanol Vapors, Ind. Eng.
Chem. Proc. Des. Dev., 1983, vol. 23, pp. 437–445.
21. Simo, M., Brown, C.J., and Hlavacek, V., Simulation
of Pressure Swing Adsorption in Fuel Ethanol Produc
tion Process, Comput. Chem. Eng., 2008, vol. 32, no. 7,
pp. 1635–1649.
22. Pucci, A., Phase Equilibria of Alkanol/Alkane Mix
tures in New Oil and Gas Process Development, Pure
Appl. Chem., 1989, vol. 61, no. 8, pp. 1363–1372.
23. Offemanm, R.D., Stephenson, S.K., Franqui, P., and
Cline, J.L., Extraction of Ethanol with Higher Alcohol
Solvents and Their Toxicity to Yeast, Sep. Purif. Tech
nol., 2008, vol. 63, no. 2, pp. 444–451.
24. www.ethanolindia.net/molecular_sieves.html,vasatwiki. icri
sat. org/index.php/Grain_alcohol#Purification
25. Rodrigues, M.A., Almeida, J., Li, J., Matos, H.A., and
De Azevendo, E.G., Efficiency of Water Removal from
Water/Ethanol Mixtures Using Supercritical Carbon
Dioxide, Braz. J. Chem. Eng., 2006, vol. 23, no. 2,
pp. 205–212.
26. Knez, Z., Skerget, M., Ilic, L., and Liitge, C., Vapor–
Liquid Equilibrium of CO2–Organic Binary Solvent
Systems (Ethanol, Tetrahydrofuran, orthoXylene,
metaXylene, paraXylene), J. Supercrit. Fluids, 2008,
vol. 43, no. 3, pp. 383–389.
27. Giivenc, A., Mehmetoglu, U., and Calimi, A., Super
critical Extraction of Ethanol, Turk. J. Chem., 1999,
vol. 33, pp. 285–291.
28. Budich, M. and Brunner, G., Supercritical Fluid
Extraction of Ethanol from Aqueous Solutions, J.
Supercrit. Fluids, 2003, vol. 25, no. 1, pp. 45–55.
No. 4 2010
 BIOETHANOL DEHYDRATION: STATE OF THE ART
29. Schacht, C., Zetzl, C., and Brunner, G., From Plant
Materials to Ethanol by Means of Supercritical Fluid
Technology, J. Supercrit. Fluids, 2008, vol. 46, no. 3,
pp. 299–321.
30. L’vov, S.V., Nekotorye voprosy rektifikatsii binarnykh i
mnogokomponentnykh smesei (Topics in the Distillation
of Binary and Multicomponent Mixtures), Moscow:
Akad. Nauk SSSR, 1960.
31. Najmul Arifeen, Ruohang Wang Ioannis, Kookos, K.,
et al., Process Design and Optimization of Novel
WheatBased Continuous Bioethanol Production Sys
tem, Biotechnol. Prog., 2007, vol. 23, no. 6, pp. 1394–
1403.
32. www.chemsite.ru/abstract_25040.htm
33. Serafimov, L.A., Separation of Azeotropic Mixtures, in
Azeotropiya i poliazetropiya (Azeotropy and Polyzeot
ropy), Sventoslavskii, V.V,, Ed., Moscow: Khimiya,
1968, ch. XXI, pp. 1394–1403.
34. Timofeev, V.S. and Serafimov, L.A., Printsipy tekh
nologii osnovnogo organicheskogo i neftekhimicheskogo
sinteza (Principles of Basic Organic and Petrochemical
Synthesis Technology), Moscow: Vysshaya Shkola,
2003.
35. Kogan, V.B., Azeotropnaya i ekstraktivnaya rekti
fikatsiya (Azeotropic and Extractive Distillation), Len
ingrad: Khimiya, 1971.
36. Serafimov, L.A., Frolkova, A.K., and Bushina, D.I.,
Extractive Distillation of Binary Azeotropic Mixtures,
Teor. Osn. Khim. Tekhnol., 2008, vol. 42, no. 5, pp. 521–
530 [Theor. Found. Chem. Eng. (Engl. Transl.), vol. 42,
no. 5, pp. 507–516].
37. Brito, R.R., Maciel, M.R.W., and Meirelles, A.A., New
Extractive Distillation Configuration for Separating
Binary Azeotropic Mixtures, The First European Con
gress on Chemical Engineering, Florence, Italy, 1997,
vol. 2, pp. 1333–1336.
38. Hua Chao, Li Xingang, Xu Shimin, and Bai Peng,
Design and Operation of Batch Extractive Distillation
with Two Reboilers, Chin. J. Chem. Eng., 2007, vol. 15,
no. 2, pp. 286–290.
39. Kotai, B., Lang, P., and Modla, G., Batch Extractive
Distillation As Hybrid Process: Separation of Mini
mum Boiling Azeotropes, Chem. Eng. Sci., 2007, vol. 2.
40. Anokhina, E., Grigorieva, A., and Timoshenko, A.,
Ethanol Dehydration in the Complex Column with
Refining Side Section, Proc. 35th Int. Conf. of Slovak
Society of Chemical Engineering, Tatranske Matliare,
Slovakia, 2008, p. 171.
41. Seiler, M., Kohler, D., and Arlt, W., Hyperbranched
Polymers: New Selective Solvents for Extractive Distil
lation and Solvent Extraction, Sep. Purif. Technol.,
2003, vol. 30, no. 2, pp. 179–197.
42. Zhao Jin, Dong CongCong, Li ChunXi, et al., Iso
baric Vapor–Liquid Equilibria for Ethanol–Water Sys
tem Containing Different Ionic Liquids at Atmospheric
Pressure, Fluid Phase Equilib., 2006, vol. 242, no. 2,
pp. 147–153.
43. Jiang XiaoChuan, Wang JunFeng, Li ChunXi, et al.,
Vapor Pressure Measurement for Binary and Ternary
Systems Containing Methanol, Ethanol and Ionic Liq
uid 1Ethyl3Ethylimidazolium Diethylphosphate, J.
Chem. Thermodyn., 2007, vol. 39, no. 6, pp. 841–846.
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44
555
44. Calvar, N., Gonzalez, B., Gomez, E., and Dominguez, A.,
Study of the Behaviour of the Azeotropic Mixture Etha
nol–Water with ImidazoliumBased Ionic Liquids, Fluid
Phase Equilib., 2007, vol. 259, no. 1, pp. 51–56.
45. Wang JunFeng, Li ChunXi, Wang ZiHao, et al.,
Vapor Pressure Measurement for Water, Methanol,
Ethanol, and Their Binary Mixtures in the Presence of
an Ionic Liquid 1Ethyl3Methylimidazolium Dime
thylphosphate, Fluid Phase Equilib., 2007, vol. 255,
no. 2, pp. 186–192.
46. Jin Zhao, XiaoChuan Jiang, ChunXi Li, and ZiHao
Wang, Vapor Pressure Measurement for Binary and
Ternary Systems Containing a Phosphoric Ionic Liq
uid, Fluid Phase Equilib., 2006, vol. 247, nos. 1–2,
pp. 190–198.
47. Ge Yun, Zhang Lianzhong, Yuan Xingcai, et al., Selec
tion of Ionic Liquids as Entrainers for Separation of
(Water + Ethanol), J. Chem. Thermodyn., 2008, vol. 40,
no. 8, pp. 1248–1252.
48. JunFeng Wang, ChunXi Li, and ZiHao Wang, Mea
surement and Prediction of Vapor Pressure of Binary
and Ternary Systems Containing 1Ethyl3Methylim
idazolium Ethyl Sulfate, J. Chem. Eng. Data, 2007,
vol. 52, no. 4, pp. 1307–1312.
49. Calvar, N., Gonzalez, B., Gomez, E., and Dominguez,
A., VaporLiquid Equilibria for Ternary System Etha
nol + Water + 1Ethyl3Methylimidazolium Ethyl
Sulfate and Corresponding Binary Systems Containing
the Ionic Liquids at 101.3 kPa, J. Chem. Eng. Data,
2008, vol. 53, no. 3, pp. 820–825.
50. Simoni, L.D., Lin, Y., Brennecke, J.F., and Stadtherr,
M.A., Modeling Liquid–Liquid Equilibrium of Ionic
Liquid Systems with NRTL, ElectrolyteNRTL, and
UNIQUAC, Ind. Eng. Chem. Res., 2008, vol. 47, no. 1,
pp. 256–272.
51. Torres, J.L., Grenhlein, H.E., and Lynd, L.R., Com
puter Simulation of the Dartmouth Process for Separa
tion of Dilute Ethanol/Water Mixtures, Appl. Biochem.
Biotechnol., 1989, vol. 20/21, pp. 621–633.
52. Pinto, R.T.P., WolfMaciel, M.R., and Lintome, L.,
Saline Extractive Distillation Process for Ethanol Puri
fication, Comput. Chem. Eng., 2000, vol. 24, no. 2,
pp. 1689–1694.
53. Ligero, E.L. and Ravagnani, T.M.K., Simulation of
Salt Extractive Distillation with Spray Dryer Salt
Recovery for Anhydrous Ethanol Production, J. Chem.
Eng. Jpn., 2002, vol. 35, no. 6, pp. 557–563.
54. LlanoRestrepo, M. and AguilarArias, J., Modeling
and Simulation of Saline Extractive Distillation Col
umns for the Production of Absolute Ethanol, Comput.
Chem. Eng., 2003, vol. 27, no. 4, pp. 527–549.
55. Ligero, E.L. and Ravagnani, T.M.K., Dehydration of
Ethanol with Salt Extractive Distillation—A Compar
ative Analysis between Processes with Salt Recovery,
Chem. Eng. Process., 2003, vol. 42, no. 7, pp. 543–552.
56. Zhigang Lei, Hongyou Wang, Rongqi Zhou, and
Zhanting Duan, Influence of Salt Added to Solvent on
Extractive Distillation, Chem. Eng. J., 2002, vol. 87,
no. 2, pp. 149–156.
57. Gil, I.D., Uyazan, A.M., Aguilar, J.L., et al., Separa
tion of Ethanol and Water by Extractive Distillation
with Salt and Solvent As Entrainer: Process Simula
No. 4 2010
556 FROLKOVA, RAEVA
tion, Braz. J. Chem. Eng., 2008, vol. 25, no. 1, pp. 207–
215.
58. Hilmen, E.K., Separation of Azeotropic Mixtures:
Tools for Analysis and Studies on Batch Distillation
Operation, Thesis Submitted for the Degree of Dr. Eng.,
Norwegian University of Science and Technology,
Department of Chemical Engineering, 2001.
59. Vasconcelos, C.J.G. and WolfMaciel, M.R., Dynamic
and Control of High Purity Heterogeneous Azeotropic
Distillation Process, Comput. Aided Chem. Eng., 2000,
vol. 8, pp. 217–222.
60. Zielinski, L., Bioethanol Dehydration in Pressure
Swing Adsorption Proces, www.msuil.ru/unesco.
forum.doc1/17doc
61. Koczka, K., Mizsey, P., and Fonyo, Z., Rigorous Mod
elling and Optimization of Hybrid Separation Pro
cesses Based on Pervaporation, Central Eur. J. Chem.,
2007, vol. 5, no. 4, pp. 1124–1147.
62. Kafarov, V.V., Gordeev, L.S., and Glebov, M.B., Sepa
ration of Azeotropic Mixtures in MembraneRectifica
tion Processes, Teor. Osn. Khim. Tekhnol., 1996, vol. 30,
no. 2, pp. 180–187 [Theor. Found. Chem. Eng. (Engl.
Transl.), vol. 30, no. 2, pp. 160–167].
63. Olujic, Z., Perez, P., De Bruijn, F.T., et al., Augmenting
Distillation by Membranes: Developments and Pros
pects, Chem. Biochem. Eng. Q, 2006, vol. 20, no. 3,
pp. 301–318.
64. Szitkai, Z., Lelkes, Z., Rev, E., and Fonyo, Z., Optimi
zation of Hybrid Ethanol Dehydration Systems, Chem.
Eng. Process., 2002, vol. 41, no. 7, pp. 631–646.
65. Del Pozo Gomez, M.T., Klein, A., Repke, J.U., and
Wozny, G., A New EnergyIntegrated Pervaporation
Distillation Approach, Desalination, 2008, vol. 224,
nos. 1–3, pp. 28–33.
66. Bologa, M.K. and Maksimuk, E.P., Recovery of Pro
cess Liquids in an Electric Field, Int. Conf. Fizikar
2005, Baku, 2005, no. 114, p. 430.
JOURNAL OF CTHEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44
View publication stats
67. Banat Fawzi, A., Abu AlRub Fahmi, A., and Simandl
Jana, Analysis of Vapor–Liquid Equilibrium of Etha
nol–Water System via Headspace Gas Chromatogra
phy: Effect of Molecular Sieves, Sep. Purif. Technol.,
2000, vol. 18, no. 2, pp. 111–118.
68. Ohashi, R., Kamoshita, Y., Kishimoto, M., and
Suzuki, T., Continuous Production and Separation of
Ethanol without Effluence of WasteWater Using a Dis
tiller Integrated SCM–Reactor System, J. Ferment.
Bioeng., 1998, vol. 86, no. 2, pp. 220–225.
69. Kaseno, A., Miyazawa, I., and Kokugan, T., Effect of
Product Removal by a Pervaporation on Ethanol Fer
mentation, J. Ferment. Bioeng., 1998, vol. 86, no. 5,
pp. 488–493.
70. Calibo, R.L., Matsumura, M., and Kataoka, H., Con
tinuous Ethanol Fermentation of Concentrated Sugar
Solutions Coupled with Membrane Distillation Using a
PTFE Module, J. Ferment. Bioeng., 1989, vol. 67, no. 1,
pp. 40–45.
71. Kargupta, K., Datta, S., and Sanyal, S.K., Analysis of
the Performance of a Continuous Membrane Bioreac
tor with Cell Recycling during Ethanol Fermentation,
Biochem. Eng. J., 1998, vol. 1, no. 1, pp. 31–37.
72. Ghosh, K. and Ramachandran, K.B., Analysis of the
Effect of In Situ Product Removal on the Stability and
Performance of a Continuous Bioreactor with Cell
Separator for Ethanol Production, Chem. Biochem.
Eng. Q., 2007, vol. 21, no. 3, pp. 285–296.
73. Moura, A.G. and Medeiros, J.R., Applying Consistent
Technology for Fuel Ethanol Production, Sugar Tech
nol., 2008, vol. 10, no. 1, pp. 20–24.
74. Van Hoof, V., Abeele, L., Buekenhoudt, A., et al., Eco
nomic Comparison between Azeotropic Distillation
and Hybrid Systems Combining Distillation with Per
vaporation for the Dehydration of Isopropanol, Sep.
Purif. Technol., 2004, vol. 37, no. 1, pp. 33–49.
No. 4 2010