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., 2007.
Original Russian Text N.N. Kulov, 2007, published in Teoreticheskie Osnovy Khimicheskoi Tekhnologii, 2007, Vol. 41, No. 1, pp. 113.
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
Fig. 1. At the outset: N.M. Zhavoronkov (center) and I.V. Kurchatov (right).
KULOV
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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.
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To vacuum
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2
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.
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KULOV
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.
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.
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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
4
1
2
103
104
105
ReG
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.
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
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KULOV
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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.
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
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CB 103, rubles/t
(a)
Liquid
1
30 2
20
Gas
FS, Pa0.5
~
~
(b)
0.6
1.4
2.2
3.4
FS
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 ).
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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
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
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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.
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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KULOV
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.
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).
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
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S3/S4
Residual
hydrocarbons
11
Recycle
to RDC
S3
S1
ReactDZ
AA
RectDZ
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.
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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.
REFERENCES
1. Malyusov, V.A., Zhavoronkov, N.M., Malafeev, N.A.,
and Romeikov, R.N., Study of the Efficiency of Regular
Packings in Water Distillation, Khim. Promst., 1962,
no. 7, p. 53.
2. Zhavoronkov, N.M., Uvarov, O.V., and Sokolskii, V.A.,
Distillation Column for Heavy Oxygen Water Production, Khim. Promst., 1956, no. 7, p. 20.
3. Babkov, S.I. and Zhavoronkov, N.M., Kinetics of Multistage Separation of Binary Mixtures: Rate of Approach
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
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