ISSN 0040-5795, Theoretical Foundations of Chemical Engineering, 2007, Vol. 41, No. 1, pp. 112. Pleiades Publishing, Ltd.

., 2007.
Original Russian Text N.N. Kulov, 2007, published in Teoreticheskie Osnovy Khimicheskoi Tekhnologii, 2007, Vol. 41, No. 1, pp. 113.

Some Problems of Separation of Mixtures

N. N. Kulov
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii pr. 31,
Moscow, 119991 Russia
e-mail: kulov@igic.ras.ru
Received September 26, 2006

AbstractThe paths of the development of research and the change of priorities in the area of separation of mixtures are tracked by the example of analysis of the works of the laboratory founded by N.M. Zhavoronkov in 1945.
The studies performed encompass a wide range of basic problems of heat and mass transfer in gas absorption, distillation (including vacuum, molecular, etc.), fractional crystallization, and melting. The subjects of the works under
consideration include separation of isotopes of light elements, design of mass-transfer apparatuses with high unit
power, investigation of the mechanism and kinetics of separation processes, studies of separation enhancement
methods, and development of hybrid energy- and resource-saving processes and equipment.
DOI: 10.1134/S0040579507010010

The 40th anniversary of the journal Theoretical

Foundations of Chemical Engineering gives us impetus
to remember our teachers and the path that has been
traveled by chemical engineering over the last half-century in the search for scientific truths and practical solutions. The year 2007 is the centenary of the birth of

Academician N.M. Zhavoronkov, the founder and first

editor in chief of the journal. In this context, it is pertinent to mention one more event, to which this article is
devoted, namely, the 60th anniversary of the scientific
laboratory founded by Zhavoronkov on I.V. Kurchatovs initiative (Fig. 1).

Fig. 1. At the outset: N.M. Zhavoronkov (center) and I.V. Kurchatov (right).

KULOV
3

11
8
10
9
6

2
7

1
4

Fig. 2. Column packed with vertical packs of thin metal

sheets: (1) lower housing, (2) column, (3) column head, (4)
ring, (5) support beam, (6) 1000-mm-high pack, (7)
80-mm-high pack, (8) irrigator, (9) lower grate, (10) upper
grate, and (11) sprayer.

In 1945, at the Karpov Institute of Physical Chemistry, Laboratory no. 3 was founded, which later received
the open name of the Laboratory of Chemistry and
Technology of Stable Isotopes of Light Elements. The
foundation of this laboratory was caused by the necessity of having a highly authoritative center for the main
problems of separation of mixtures.

In the 1940s1950s, the laboratory had four groups,

headed by V.A. Malyusov, S.I. Babkov, O.V. Uvarov,
and M.E. Aerov, but the productive and creative atmosphere was mainly created by its head, Prof. Zhavoronkov, head of the laboratory.
The laboratorys personnel developed methods for
producing heavy water and some other stable isotopes,
mainly, by distillation and chemical exchange. The
unique properties of deuterium, a heavy stable hydrogen
isotope, make it an indispensable product for nuclear
power engineering and nuclear weapons. Therefore, it
was necessary to create industrial production of deuterium, both in the pure form and in the form of heavy water.
In late 1945, the Karpov Institute of Physical Chemistry
was assigned to develop the scientific and technical principles of industrial production of heavy water.
To fulfill this assignment as soon as possible,
Zhavoronkov organized the interdepartmental Scientific and Technical Council for Heavy Water, of which
he was chair and M.G. Slinko was Scientific secretary.
The council included leading specialists of various
institutes and organizations of the country.
The development of many enrichment processes
was planned. Among them were water distillation
under normal and decreased pressures, liquid ammonia
distillation, low-temperature distillation of liquid
hydrogen, two-temperature enrichment in the H2SH2O
system, and multistage electrolysis of aqueous solutions in combination with isotope exchange between
water and hydrogen.
As head of the laboratory, Zhavoronkov directly
supervised investigations of water distillation for enrichment in deuterium. Original packings were designed for
columns with low hydraulic resistance, and the optimal
cascade was calculated.
Figure 2 presents a column designed in the laboratory. The column was 17.5 m in height and 0.48 m in
diameter and was packed with vertical packs of thin
metal sheets on both sides of which a thin liquid film
flowed down and vapor flowed up in countercurrent to
the liquid [1]. The column was intended for heavy
water production by vacuum distillation. Later, columns with such a packing were successfully used in a
number of processes, in particular, in large-scale caprolactam production.
A laboratory-scale column for producing heavy
18
oxygen water H 2 O by water distillation under vacuum
(Fig. 3) was designed and listed by Uvarov and
Sokolskii [2]. The separation coefficient = 1.0032
found in experiments at the normal water boiling point
differs from unity only at the third decimal place. This
means that an enormous number of separation stages is
necessary to reach a given enrichment.
In 1956, in the journal Doklady Akademii Nauk
SSSR (Proceedings of the USSR Academy of cience)
[3], Zhavoronkov and Babkov published a mathematical model of an unsteady state of a separation system,

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SOME PROBLEMS OF SEPARATION OF MIXTURES

24

30

23

31
To vacuum

which allowed one to calculate the startup period of a

separation cascade. The BabkovZhavoronkov equation was rapidly adopted in computational practice. It
was shown that, from raw material with a low concentration of a desired isotope, it is virtually impossible to
obtain a highly enriched product without using a cascade. For example, in separation of oxygen isotopes by
vacuum water distillation in a single column, because
of the small value of the enrichment coefficient = 1
, the time it takes for the 18O concentration to reach
95 at % would exceed the plant depreciation period.
A special building built on the territory of the Karpov Institute of Physical Chemistry had a high-rise part,
in which a larger scale plant consisting of a cascade of
three distillation columns of different diameters was
installed. It is at this plant that a then-unique technology for separating stable oxygen isotopes was
designed.
In industry, the distillation column height equivalent
to a single separation stage is usually 0.30.5 m. However, a packing of trihedral stainless steel wire helices
turned out to be very efficient and ensured a height
equivalent to a theoretical plate of 1 cm. This meant
that, in distillation columns of a cascade with a total
height of 10 m, it became possible to obtain about 1000
theoretical separation stages. It took several years to
build the building and install the plant, but this resulted
in production of heavy oxygen water with an 18O concentration up to 30 at %.
Using the results of these studies, at the Moscow
Electrolysis Works, an industrial plant was constructed,
which successfully worked for more than 20 years, satisfying the demand of the country for the heavy oxygen
isotope.
In the past 1015 years, the demand for the isotope
18O has abruptly increased because of a rapid increase
in the number of positron emission tomography centers
in the United States, Europe, Russia, Japan, and elsewhere. Interestingly, vacuum water distillation in columns with helical prismatic packing, a technology
developed in the 1950s, remains most reliable and efficient.
Investigations of separation of nitrogen isotopes [4]
led to the construction of the Soviet Unions first industrial plant for producing the isotope 15N by chemical
isotope exchange between gaseous ammonia and an
aqueous ammonium nitrate solution at the Novomoskovsk Chemical Integrated Works in 1960.
A large series of works performed in the laboratory
solved a number of fundamental problems in separation
of mixtures by molecular distillation, in which the distance from the evaporation surface to the cold surface
of a condenser is comparable to the molecule free path
length.
Figure 4 shows a multistage apparatus that was
designed in the laboratory and used in experiments on
applying molecular distillation to separating the lithium

21
22

25
26
28

20
29
19

27

32

18

16
14

13

12
11

15
17
9

10
8

4
5
4

6
2

Fig. 3. Laboratory-scale column for producing heavy oxy18

gen water H 2 O: (1) reboiler, (2) electric heater, (3) waterlevel gage glass, (4) clamps, (5) dropper, (6) baffle, (7) thermocouple pocket, (8) ring with grid, (9) manometer tube,
(10) packing, (11) coil contact, (12) coil, (13) vacuum
jacket, (14) shield, (15) spacer rings, (16) column, (17)
traps, (18) mercury manometer, (19) bellows, (20) upper
ring with grid, (21) upper heater, (22) differential manometer, (23) upper thermocouple pocket, (24) condenser, (25)
capillary, (26) filter, (27) upper vessel, (28) trap with Dewar
flask, (29) upper dropper, (30) mercury manometer, (31)
pressure tank, and (32) insulator.

isotopes 6Li and 7Li in 19551956 [5]. Later, such

apparatuses also found application in vitamin production.

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To vacuum pump
Water

Water

25

6
10

4
7

Fig. 4. Multistage apparatus for molecular distillation: (1) apparatus housing, (2) condenser, (3) insert pan, (4) water cooler, (5)
Dowtherm condenser, (6) apparatus cover, (7) device for taking samples and measuring temperature, (8) thermocouple pocket, (9)
shield, and (10) trough.

KG, kg/(m2 h mm H2O)

(b)

KL, m/h
(a)
4

0.40

2
3

0.20
3

0.10
1

0.04
1

20

40 60 80 100
UG, m/s

0.02

4 6

10

20 40
UG, m/s

Fig. 5. Absorption of (a) carbon dioxide and (b) ammonia by water [6] in (1) countercurrent, (2) upward cocurrent, and (3) downward cocurrent flows. KL and KG are the mass-transfer coefficients in the liquid and gas phases, respectively; and UG is the gas
velocity.

In developing technologies for producing heavy

water and products enriched in isotopes of light elements, extensive physicochemical studies were performed to determine the separation coefficients of the
isotopes of hydrogen, nitrogen, carbon, boron, and lithium in equilibrium liquidvapor systems.
Isotopes of light elements attracted the attention of
researchers in the 1940s1950s in the context of the
creation of nuclear and thermonuclear weapons; therefore, industrial methods for concentrating and isolating
such isotopes as 2H(D), 6Li, and 10B were the first to be
implemented.
In the 1960s, peaceful uses of atomic energy and
wide application of the tracer method in various areas
of human activity favored the implementation of industrial methods for separating the isotopes of nitrogen,
oxygen, and carbon. In Zhavoronkovs laboratory, by

the early 1960s, technologies for producing 15N, 18O,

and 13C had been developed and tested on an industrial
scale. Thus, the first period of work of the laboratory,
which lasted from 1945 to 1963, was mainly devoted to
solving practical problems of isotope separation.
In January 1964, the laboratory joined the Kurnakov
Institute of General and Inorganic Chemistry, USSR
Academy of Sciences, and received the name of the
Laboratory of Processes of Separation and Fine Purification of Substances. At that time, of importance was
the creation of columns of high unit power. It was still
at the Karpov Institute of Zhavoronkov and Malyusov
were started to study the upward cocurrent flow in film
columns in which a thin liquid film creeps up the walls
of an irrigated tube against gravity.
Previous studies showed that the gas flow velocity in
columns packed with packs of sheets is two to three

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SOME PROBLEMS OF SEPARATION OF MIXTURES

times higher than that in ordinary packed and tray columns. However, the cocurrent flow of a gas and a liquid
in tubes and channels allows one to reach gas (vapor)
velocities of several tens of meters per second without
disturbing the column operation and, thereby, to significantly increase the apparatus output. Thus, using the
gravity flow of a liquid film, a column with very low
hydraulic resistance can be created, and, using the
cocurrent flow, high flow velocities can be reached.
Cocurrent-flow apparatuses are also suitable for work
under no gravity.

GL
6
4

At the laboratory, efficient apparatuses for absorption and desorption of gases were designed that operated in the downward flow and were characterized by
very high liquid flow rates (up to 600 m3/(m2 h)). These
apparatuses have found industrial application for
wastewater treatment and ammonia desorption at PO
Azot (Grodno) and other enterprises.

7
6
5
4
3

2
9

101

Figure 5 presents comparative data on the film

absorption of carbon dioxide (liquid-phase mass transfer) and ammonia (gas-phase mass transfer) by water in
three flow patterns: countercurrent, upward cocurrent,
and downward cocurrent flows. Figure 5 shows that, in
the cocurrent flows, the mass-transfer coefficients are
almost an order of magnitude larger and, hence, the
apparatus output is also much higher.
Further, the upward cocurrent flow showed little
promise because of a narrow range of working flow
rates: the apparatus began to work at high gas (vapor)
velocities and a subsequent increase in the gas flow rate
led to sharp enhancement of spray entrainment. Highvelocity downward cocurrent-flow apparatuses for
absorption, desorption, and distillation turned out to be
more promising. Figure 6 presents generalized curves
for the hydraulic resistance versus ReG, which encompass all the practically used downward two-phase flow
patterns.

4
1

2
103

104

105
ReG

Fig. 6. GL versus ReG curves at various irrigation densities

[7]: line 1 is calculated by the Blasius formula for smooth
tubes, lines 27 correspond to ReL = 60011000, line 8 is
the boundary between two flow patterns, and line 9 is the
boundary between the regions of weak and strong hydrodynamic interaction of the phases.

The development of experimental equipment

allowed researchers to perform a series of important
studies of the mechanism of convective mass transfer in
liquid films. At the Kurnakov Institute of General and
Inorganic Chemistry, the first computer-equipped automated test bench (Fig. 7) was designed to measure the
pattern of waves on the film surface and simultaneously
determine the instantaneous concentrations of oxygen
being dissolved in different cross sections of the flow.
Figure 8 shows a test bench for measuring the profile of
turbulent velocity pulsations near the free surface of a
liquid film using a laser Doppler anemometer. These
then-unique experiments formed the basis for creating

2
9

4
7

13

12

N2

N2

11

20

10

16

17

18

19

14

15
6

Fig. 7. Determination of the wave pattern and the local concentrations in a liquid film flowing down [8]: (1) inclined chute, (2) liquid
distributor, (3) rotameter, (4) flow regulator, (5) centrifugal pump, (6) desorbercollector, (7) compressed nitrogen cylinder, (8)
packed column for gas humidification, (9) platinum/silver electrodes, (10) oximeter, (11) digitizer, (12) electrochemical sensors for
measuring the instantaneous film thickness, (13) liquid film flowing down, (14) current converter, (15) low-frequency generator,
(16) computer, (17) integrator, (18) printer, (19) printer, (20) electrochemical cell for measuring the instantaneous concentration of
oxygen dissolved in water.
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KULOV
8
7

9
15

10

16

14

17

18

12

13

11

Fig. 8. Measurement of the profile of turbulent velocity pulsations in a liquid film flowing down [9]: (1) LG-38 laser, (2) acoustooptical modulator, (3) mirrors, (4) focusing lenses, (5) liquid film, (6) measuring volume, (7) Era-6M objective lens, (8) diaphragm,
(9) photomultiplier, (10) DISA 55L30 preamplifier, (11) generator, (12) mixer, (13) DISA 55L20 servo system, (14) selective microvoltmeter, (15) frequency meter, (16) marker generator, (17) DISA 55L35 squarer, and (18) N-306 plotter.

h, mm
0.76
4

L, m/s
6
0

0.1

0.2

0.3

0.4

t, s

104

102

I
3

II

103

104 ReL

Fig. 9. Mass-transfer kinetics in the laminarwave and turbulent flows of a liquid film [10]: (I) oxygen desorption from water, (II)
carbon dioxide absorption by water, (1) theoretical calculation for the laminarwave flow, and (2) theoretical calculation for the
turbulent flow. In the inset is the instantaneous liquid film thickness as a function of time t.

theoretical models of convective mass transfer in films

flowing down.
Figure 9 compares the (3, 4) experimental and (1, 2)
theoretical values of the mass-transfer coefficients for
the laminarwave and turbulent flow regions [10]. In
the inset, the instantaneous liquid film thickness h is
represented as a function of time t. The frequency fB of
large waves, which are well distinguishable against the
background of small capillary waves, determines the
mass-transfer rate in the liquid film. Dashed line 1 was

calculated by the formula L = D AL f B for nonstationary mass transfer. In the turbulent region, there is also
unsteady-state mass transfer. The interface is renewed
by pulsations incident on the surface at an acute angle.
Dashed line 2 was calculated by the theoretical expression L =

D AL L ( u' ) /2 [10].
3

All this resulted in the development of scientifically

substantiated methods for calculating the hydraulics
and mass transfer in a new generation of high-effi-

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SOME PROBLEMS OF SEPARATION OF MIXTURES

CB 103, rubles/t

(a)
Liquid

1
30 2

20

Gas
FS, Pa0.5

~
~

(b)

0.6

1.4

2.2

3.4

FS

Fig. 11. Reduced cost in distillation under pressure: (1)

Glitsch valve tray, (2) valve ballast tray, (3) S-shaped valve
tray, and (4) vortex tray.

2
0

40

80

120
160
200
Irrigation density, m3/(m2 h)

Fig. 10. Swirling-flow apparatus: (a) vortex tray and (b) the
working flow rate range (FS = uG G ).

ciency apparatuses for separating mixtures. Not only do

theoretical models underlie these methods, but they
also show the ways to enhance heat and mass transfer.
In the mid-1970s, on the initiative of the Commission for Column Mass-Transfer Equipment, State Committee for Science and Technology, USSR Council of
Ministers, a working group was established from representatives of a number of organizations of the Soviet
Union and the German Democratic Republic (Institute
of Physical Chemistry, Academy of Sciences of the
GDR, Berlin; High Technical School, Merseburg; and
VEB Maschinenfabrik Germania, Karl-Marx-Stadt).
The Kurnakov Institute of General and Inorganic
Chemistry coordinated the work. Five-year efforts
resulted in the design of a mass-transfer apparatus with
swirling flows of a liquid and a gas. The apparatus had

an extremely wide range of flow rates at high efficiency

(Fig. 10).
Figure 11 presents the cost of capital construction
and the current expenses for power, water, maintenance, etc., for a number of designs. Comparison of the
developed design with a modern high-efficiency valve
tray (Glitsch, Unated States) shows that the output of
the vortex tray is three times higher than that of the
Glitsch tray and the cost per ton of product of the vortex
tray is half as high as that of the Glitsch tray.
Still more intense mass transfer can be ensured in a
high-velocity rotor apparatus (Fig. 12). Rotation of a
contact element within the apparatus housing causes a
centripetal force on the order of 3002000 g. The liquid
within the stainless steel wire gauze contact element is
uniformly distributed and intensely interacts with the
gas flow. Apparatuses of such a type can process greater
material flows within a smaller working volume than
ordinary distillation columns and also have high efficiency and low hydraulic resistance [11].
Significant attention was paid to improvement of
distillation calculation methods. The effect of temperature gradients between phases and surface tension gradients was studied, and an improved method for calculating the distillation of binary systems was proposed
[6]. Figure 13 compares experimental data with the
results of calculation by the diffusion model taking into
account the temperature gradients. The diffusion model

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KULOV
k

2.0
3

L
2

1.5

1
2
3
4
5
6
7

1.0
G
0.5

0
2.50

5
L
Fig. 12. Heat- and mass-transfer apparatus with rotating
packing: (1) contact element, (2) housing, (3) liquid feed
tube, (4) gas removal tube, and (5) shaft.

KG 10, kmol/(m2 h)
3.6

I
II

2.8

0.2

0.4

0.6

0.8

Fig. 13. Experimental data on (I) isotope exchange and (II)

distillation and the results of (1) calculations by the diffusion model and (2) calculations taking into account the temperature gradients [6].

well fits the data on isotope exchange without temperature gradients. Taking into account the thermal effects
allowed researches to describe the extreme behavior of
the experimental data for the system considered.
In the early 1980s, a new important area of research
in the laboratory was fractional crystallization from the
melt, namely, the investigation of the principles of
directional solidification of a melt and the development
of a countercurrent flow crystallization method.
Let us consider only one example [12] characterizing the unusual behavior of a system in directional
solidification of a melt. A study of a number of organic

1.25

Jcr 1.25

logJ

Fig. 14. Average effective distribution coefficient k for the

diphenylnaphthalene system at various concentrations versus dimensionless heat flux J according to the data of (13)
Meyer, (4, 5) Chernyaev, and (6, 7) Rasskazov and Myasnikov [12].

systems revealed a special crystallization mode that

leads to inverse values of the effective distribution coefficient (Fig. 14). Within a narrow range of critical values of the dimensionless heat flux J, the effective distribution coefficient k may be both larger and smaller than
unity. In this case, if, in the region of subcritical flow
rates, the distribution coefficient is smaller than unity,
then, in the supercritical region, this coefficient is larger
than unity. There is an inversion of the compositions of
the phases, and the crystal layer growth mechanism
changes.
In 1988, the laboratory received its present name of
the Laboratory of Theoretical Foundations of Chemical
Engineering. The subjects of research, remaining
within the conventional scope of the laboratorys interests (separation of mixtures), continuously change
according to world tendencies.
The current stage of the work of the laboratory is
characterized by the search for physicochemical ways
to enhance separation processes and the development
of new separation methods based on hybrid processes.
The fundamental difference from the previous stage is
that an increase in the velocities of the flows of contacting phases leads to a linear increase in the separation
efficiency, whereas the energy losses increase proportionally to the square of the velocity. Enhancement by
physicochemical methods can increase the separation
efficiency by a factor of 34 at low energy consumption. The difficulty is that, to control a process, it is necessary to know its detailed mechanism.
One can distinguish three main areas of research that
are currently most important in designing separation processes and are being developed in the laboratory:

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SOME PROBLEMS OF SEPARATION OF MIXTURES

Q 102, mol/m2
18

12

10

20

30

40
t, s

0.5

Fig. 15. Carbon dioxide absorption by water: (1) theoretical calculation taking into account the surface convection, (2) calculation
using the unsteady-state diffusion model, (a) experimental data [13], (b) data on absorption [14], and (c) data on desorption of CO2
from water.

development of methods for conceptual calculation

and design of separation systems for accelerating the
implementation of new processes;
investigation of the mechanisms and kinetics of separation processes and methods for their enhancement;
elaboration of new separation methods, including
hybrid energy-saving separation complexes for manufacturing new products and materials with high technological performance.
The least studied area of the scientific principles of
separation of mixtures is the kinetics of mass-transfer
processes far from thermodynamic equilibrium. The
limiting factor is often heat- and mass-transfer processes near and at the interface. Below, two examples of
enhancement of mass transfer in the liquid and gas
(vapor) phases near the interface are considered.
Marangoni diffusionthermal instability in liquid
layers was theoretically and experimentally studied. In
gas absorption, liquid extraction, and distillation, near
the liquidgas (vapor) and liquidliquid interface under
certain conditions, there is self-organization of liquid
microflows and emergence of stable structures. This
phenomenon is caused by local surface tension gradients (the Marangoni effect) induced by temperature or
concentration gradients and density gradients (Rayleigh convection).
In diffusionthermal instability in gas absorption,
surface convection arises because of the release of the
heat of absorption on the free surface, i.e., when the liquid is heated from above. It is usually supposed that
heat- and mass-transfer processes for a positive temperature gradient (heating from above) are stable; however, in the case under consideration, the situation is
radically different.

It was experimentally shown that absorption of carbon dioxide (Fig. 15, curve 1) is much more intense
than its desorption; this can be explained by the emergence of convective flows in the surface liquid layer.
Curve 1 in Fig. 15 was calculated using a theoretical
model for a convective mode of gas dissolution at a
supercritical contact time [13].
Photographs of the interference patterns obtained by
holographic interferometry and t films of the time
development of interfacial instability in carbon dioxide
absorption by water and aqueous solutions of KOH and
monoethanolamine, which were made at the Kurnakov
Institute of General and Inorganic Chemistry, demonstrated a more complex hydrodynamic pattern in the
surface liquid layer than the pattern that would be determined by the Marangoni effect alone. Probably, it is
also necessary to take into account the possibility of the
emergence of density Rayleigh convection, the dependence of the viscosity on temperature, and other physicochemical factors. All these effects were studied by
calculations, which gave insight into the actual mechanism of enhancement under various conditions.
The self-organization in the gas phase was investigated during evaporation [15, 16]. The diffusion of
light molecules evaporating into a heavy inert gas
can also be accompanied by the emergence of convective flows and the enhancement of mass transfer by
physicochemical processes, which lead to an unstable
density distribution along the height of the vaporgas
layer (Rayleigh instability).
Note another important feature of Rayleigh convection in gases. It turned out that, in a multicomponent
mixture, a light component, initiating convection,
involves a heavy component in the motion and accelerates its transfer from the interface into the bulk of the

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Q, mol/m2
0.4

0.3
1
0.2
0.1
0

10

20

30

40

50

60

70

80
t, s

0.5

Fig. 16. Evaporation of formic acid into argon: (1) calculation by equations for unsteady-state molecular diffusion and
(2) calculation by a model for convective diffusion.

gas layer. For example, in evaporation of formic acid

and water into argon (Fig. 16), water, vapor, which is a
light component in comparison with argon, causes
Rayleigh convection and also accelerates the transfer of
heavy molecules of formic acid by involving them in
convective motion.
In conclusion, note that the Marangoni effect in liquids and Rayleigh diffusion in gases are a striking illustration of physicochemical methods for enhancing mass
transfer and can be practically used, especially in absorption with chemical reaction and catalytic distillation.
In the chemical industry, each unit operation is most
often performed in an individual apparatus. However,
in recent decades, processes that do not fit into this
scheme have been created more and more frequently.
Researchers develop hybrid processes consisting of
individual steps coupled by both forward and reverse
flows in which several unit processes are optimally

combined within a single combined system or a single

apparatus. The main principle of such integration is the
combination of advantages of the various processes and
the mutual compensation of their disadvantages. Hybrid
processes occurring simultaneously in the same apparatus are called combined processes. Combined processes
are characterized by a decrease both in energy consumption and in capital cost.
An analysis shows that, in the next 20 years, distillation will remain a key separation process. It is also
expected that separation methods will be developed
using a larger number of hybrid processes involving
distillation (distillation with crystallization, with membrane processes, etc.). Some specialists assume that up
to 20% of classical distillation processes will be
replaced by hybrid processes.
In recent years, especially in production of materials
with high technological performance, it is necessary to
separate mixtures whose components have high molecular weights. This means that they can be separated by
distillation only partially. The final purification should
be performed by fractional crystallization, which is
now gaining in importance.
At the Kurnakov Institute of General and Inorganic
Chemistry, a separation process combining crystallization from melt and vacuum distillation was developed
[17, 18]. As an example, Fig. 17 presents the results of
experiments on naphthalene purification by removing
impurities of diphenyl and p-dichlorobenzene in a combined distillationcrystallization process (Fig. 17a).
Figure 17b illustrates the efficiency of separation of a
diphenylnaphthalene binary mixture of eutectic composition. It is easy to see that the efficiency of the combined
process (curve 1) is significantly higher than that of distillation (curve 2). Investigation of distillation sweating
and crystallization for a large number of systems showed
that this combined process is preferable with regard to

C/C0
()

1.0

C0/C
1000

(b)
1

100
0.4

2
10

3
4
0

20

40
t, min

1
0

0.5
G

1.0

Fig. 17. Efficiency of purification of binary mixtures (C0 and C are the initial and current concentrations of impurities in distillation
sweating, respectively) as a function of time t and the fraction G of the evaporating part of the mixture. (a) The removal of impurities
of (1, 2) diphenyl and (3, 4) p-dichlorobenzene from naphthalene layers 1012 mm in thickness: (1) continuous polycrystalline
layer, (2) 4 4 mm granules arranged in three layers, (3) powder layer without mixing, and (4) powder layer being mixed. (b) The
separation of a diphenylnaphthalene mixture of eutectic composition (40 wt % naphthalene): (1) experimental data and (2) results
of calculation for simple distillation (the relative fugacity coefficient is taken to be 5.5).
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S3/S4

Residual
hydrocarbons

11

Recycle
to RDC

S3

S1

ReactDZ

AA

RectDZ

SOME PROBLEMS OF SEPARATION OF MIXTURES

NA
S2
C1

C2

Water

SDZ

Water
and salts

AA (to recycle)

sec-Butyl acetate
or isopropyl acetate

Fig. 18. Flowsheet of catalytic distillation process: RDC, reactive distillation column (SDZ, stripping distillation zone; ReactDZ,
reactive distillation zone; RectDZ, rectifying distillation zone); C1, C2, distillation columns; S1, S2, S3, settling separators; F,
hydrocarbon mixture; AA, acetic acid; and NA, neutralizing agent.

energy consumption and much more efficient than simple distillation, sublimation, and ordinary fractional
melting.
The laboratory has long carried out studies on catalytic distillation. It is clearly understood that the calculation and design of a separation system should take into
account the operation of the reactor block. The best variants of flowsheets are based on a combination of a reactor and a separation system within a single apparatus.
Catalytic distillation studies supported by the Ministry of Industry and Science of the Russian Federation
have been conducted in recent years at the Kurnakov
Institute of General and Inorganic Chemistry with the
participation of the Lomonosov State Academy of Fine
Chemical Technology and Yaroslavl State Technical
University. The complexity of physical modeling of
catalytic distillation stimulated the development of
methods of conceptual design, which seek modes of
operation suitable for further investigation in more
detail.
Previously, at the Lomonosov State Academy of Fine
Chemical Technology, a method of thermodynamic
topological analysis of the statics of reactive distillation
processes was developed. This method can serve as the
basis for conceptual design. However, methods for calculating catalytic distillation kinetics are very few. In studies performed at the Kurnakov Institute of General and
Inorganic Chemistry, the mass-transfer kinetics was proposed to be described using a model of unsteady-state
catalytic distillation in a packed column with different
lengths of the reaction zone.

In these studies, a new technology for producing

sec-butyl acetate from n-butenes and butanebutene
fractions was developed, experimentally investigated,
and tested on a large-scale pilot plant at Yaroslavl State
Technical University.
Figure 18 presents the optimal flowsheet for secbutyl acetate production by catalytic distillation. This
flowsheet contains a smaller number of apparatuses
than the flowsheet with cocurrent reactors and ensures
more complete conversion (9697%) than in the cocurrent reactor (7980%). Economic calculation showed
that the expected cost of the sec-butyl acetate is half as
high as the cost of n-butyl acetate used now in the paint
and varnish industry and the film and photographic
materials industry. Sec-Butyl acetate samples obtained
in the combined process have successfully passed tests
in mixed solvents for the paint and varnish industry, in
particular, in the widely used solvent R-646.
The demand for improving separation processes does
not decrease with time; conversely, it has increased,
especially in recent decades, when the problems of
energy and resource saving were supplemented with rigorous requirements for environmental safety of chemical
engineering processes. The efficiency of separation of
mixtures in many cases determines the energy consumption and the capital cost of the entire process and also its
environmental safety and competitiveness. Further progress of separation processes requires thorough investigation of the mechanism of transfer phenomena in chemically reactive media and the search for new processes
adequate to increasing requirements of tomorrow.

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12

KULOV

NOTATION
C0, Cinitial and current concentrations of impurities in distillation sweating, respectively, wt %;
CBreduced cost, rubles/kg;
DABmolecular diffusion coefficient, m2/s;
DALmolecular diffusion coefficient in the liquid
phase, m2/s;
FS = UG G F factor, Pa0.5;
fBfrequency of large waves, 1/s;
Gfraction of the evaporating part of the mixture;
ggravitational acceleration, m/s2;
hmean liquid film thickness, m;
J = jH/jTdimensional heat flux, which is equal to
the ratio of the heat flux jH toward the surface of the
crystal layer to the heat flux jT of phase transition;
Jcrcritical value of J;
KGmass-transfer coefficient in the gas phase,
kg/(m2 h mm H2O);
KLmass-transfer coefficient in the liquid phase,
m/h;
keeffective distribution coefficient;
Qamount of gas absorbed in absorption per unit
surface area, mol/m2;
qlinear irrigation density, m2/s;
ttime, s;
UGaverage gas velocity, m/s;
u'pulsation velocity in a liquid film, m/s;
WLirrigation density, m3/(m2 h);
xmole fraction of a highly volatile component in
the liquid phase;
separation coefficient;
Lmass-transfer coefficient in the liquid phase,
m/s;
= ( 1)enrichment coefficient;
GLhydraulic friction factor;
Lkinematic viscosity of a liquid, m2/s;
L, Gliquid and gas densities, respectively,
kg/m3;
surface tension, N/m.
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