ISSN 0040-5795, Theoretical Foundations of Chemical Engineering, 2009, Vol. 43, No. 3, pp. 227–237. © Pleiades Publishing, Ltd.

, 2009.
Original Russian Text © S.K. Myasnikov, A.D. Uteshinsky, N.N. Kulov, 2009, published in Teoreticheskie Osnovy Khimicheskoi Tekhnologii, 2009, Vol. 43, No. 3, pp. 243–253.

Hybrid Separation Processes Combining Vacuum Distillation

with Fractional Crystallization, Partial Melting, and Granulation
S. K. Myasnikov, A. D. Uteshinsky, and N. N. Kulov
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 119991 Russia
e-mail: msk@igic.ras.ru
Received December 15, 2008

Abstract—The physicochemical fundamentals of the combined processes of distillative crystallization (also

called distillation crystallization or distillative freezing) and distillative sweating (also called distillation sweat-
ing or distillation melting) are considered. Results of the experimental study of the kinetics of separation of
binary and ternary organic mixtures of various forms (liquids, powders, continuous layers, and granules) are
presented. The high efficiency of the combined processes that make it possible to rapidly decrease the impurity
content by one to two orders of magnitude after a single stage is shown. It is found that these processes can be
used for effective separation of the mixtures of a eutectic composition when conventional crystallization is not
applicable. Dependences of the important kinetic characteristic—an effective diffusion coefficient—on pres-
sure are determined for a number of mixtures. An empirical formula for estimating its values is proposed. It is
found that the kinetic features of the combined processes conducted under nonequilibrium conditions can cause
both a decrease and an increase in the efficiency of separation of the mixtures of different types in comparison
with calculated values for the equilibrium process. A method is developed that makes it possible to combine
distillative crystallization with the granulation of a melt in a semicontinuous or continuous process on a cooled
movable belt. The method ensures the additional purification of solidifying granules from volatile impurities.
Results of calculating the main characteristics of the combined process for purifying naphthalene granules in
the batch and continuous modes are given.

DOI: 10.1134/S0040579509030014

INTRODUCTION In this work, the results of studying the efficiency of

The development of hybrid processes is one of the
main ways of solving the problem of energy and
resources saving in the chemical and allied industries.
In recent years, hybrid processes attract more and more
attention. The number of publications in the field of
hybrid separation and reaction–separation processes
has increased. Interest in hybrid processes on the basis
of crystallization or with its involvement has grown
markedly. Crystallization is successfully integrated
both with reactive processes and with mass transfer
processes: distillation, extraction, membrane separa-
tion, and chromatography [1–9].
An important feature of crystallization is the possi-
bility of forming combined processes on its basis,
which are the most effective solution and the highest
stage of organization of hybrid processes allowing two
or more unit operations to be simultaneously carried
out in a single apparatus. Crystallization can be com-
bined with distillation, extraction, and membrane pro-
cesses. Such processes are implemented in laboratory
conditions, intensively studied, and used in practice
[10–19].
separation of liquid and solid binary mixtures of differ-
ent types in the combined processes of distillative
sweating and distillative crystallization are presented,
and various versions (batch, semicontinuous, and con-
tinuous) of organization of these processes, their sepa-
ration capabilities, kinetic regularities, and specific fea-
tures are discussed.
COMBINATION OF DISTILLATION
WITH CRYSTALLIZATION AND MELTING
Physicochemical principles. Equilibrium in the
vapor–liquid–solid system for binary mixtures allows a
wide variety of possible types of phase diagrams, since
they are formed as a result of superposition (intersec-
tion) of the diagrams of the liquid–vapor and liquid–
solid two-phase equilibria. Each of them can also have
several variants depending on the mutual solubility of
components in the liquid and solid states, the ability to
form intermolecular compounds, etc. As distinct from
the liquid–vapor diagram, the isobaric solid–liquid dia-
gram is barely variable in the pressure range from 0 to
1 atm. Therefore, with decreasing pressure, the boiling
curve approaches the liquidus line on the phase dia-

227
228 MYASNIKOV et al.
T, K
290
280 S+V
V
Tt.e
L+V S+L
270
Tt.e L
S+L
TE
S composition ë0 consists of nearly pure crystals of a
260
0 20 40 60 80 100
C6H6 C, mol % (CH3)3COH
Fig. 1. Phase diagram of the benzene–tert-butanol mixture
in the region of the solid (S)–liquid (L)–vapor (V) three-
phase equilibrium.
grams, and they can intersect near or at the triple point
pressure of one of the components. As a result of inter-
section, the line of the three-phase equilibrium appears,
along which the main stage of the processes of distilla-
tive crystallization and distillative melting occurs.
The most commonly encountered type (I) of organic
mixtures, the components of which are unlimitedly sol-
uble in the liquid state and, at the same time, insoluble
in the solid state (systems with simple eutectics), is the
best for separation. In this case, it is preferable that the
impurity have a higher volatility (Ia), but could also be
less volatile (Ib) in comparison with a major compo-
nent or form an azeotrope with it (Ic). The necessary
condition is that the impurity concentration in the vapor
at the three-phase equilibrium should be higher than
that in the original mixture. It is desirable that the triple
point pressure of a major component is not less than
1 Torr and the temperature of crystallization is not very
low.
Based on theoretical calculations and experimental
data, phase diagrams were constructed at different pres-
sures in the region of the three-phase equilibrium for a
number of binary mixtures of type I: naphthalene–
biphenyl (Ib or Ia depending on the concentration of
components), biphenyl–benzoic acid (Ia and Ib), ben-
zene–cyclohexane (Ic), benzene–tert-butanol (Ic), etc.
The major components with a purity from 99.5 to
99.97 wt % were isolated from these mixtures of differ-
ent initial concentrations C0 that are in the liquid or
solid state by distillative crystallization or distillative
sweating, respectively. In [14], the phase diagram of the
naphthalene–biphenyl system (types Ib and Ia) was pre-
sented, and the principles and kinetic regularities of the
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
purification of granular materials in distillative sweat-
ing were discussed. This study presents the results of
separating a wider range of liquid and solid mixtures of
different types and the possible variants of organization
of the combined processes.
Figure 1 shows the phase diagram of the benzene–
tert-butanol mixture (type Ic), the components of which
are soluble in the liquid state and insoluble in the solid
state. At a pressure of P = 760 Torr, an azeotrope with a
concentration of Caz = 37 wt % tert-butanol forms in
this system. The value of Caz decreases with a reduction
in pressure. At P = 20 Torr, which is lower than the tri-
ple point pressures of both components (Pt.p = 36 and
42 Torr, respectively), two lines of the three-phase equi-
librium at different temperatures Tt.e appear on the
phase diagram. At Tt.e.e, the original mixture of the
major component (benzene on the left and tert-butanol
on the right) and a liquid phase with an increased con-
centration of a minor component. Under a vacuum, this
liquid rapidly evaporates, and the vapor of the compo-
sition ëV is withdrawn into a condenser. The process is
carried out until the liquid phase is almost completely
removed.
It can be seen from the diagram that the equilibrium
composition of the vapor C *V at the three-phase equilib-
rium is determined by the concentration of the liquid
C *L and does not depend on ë0. Owing to this, as the
fraction of the liquid evaporated G increases and the
current concentration of the mixture ë decreases, the
impurity distribution coefficient between the vapor and
the solid–liquid mixture under equilibrium conditions
k = C *V /C increases. This favors the purification of a
major component not only from more volatile impuri-
ties, but also from less volatile impurities (if CV > C0).
An experimental study of the kinetics of the com-
bined processes was conducted using a setup shown in
Fig. 2. The main apparatus is a thermostated vessel 1
with a volume of 0.3 l with a mechanical stirrer 3 and a
hermetically sealed cover 2, which is connected to a
vacuum pump 7 via a cooled trap-condenser 6. The
original liquid or solid mixture 4 is loaded into this
apparatus. In some experiments, vessel 1 was immersed
into a heated ultrasonic bath 5 for the intensification of
the process.
Distillative crystallization. The results of the puri-
fication of liquid tert-butanol from more volatile ben-
zene with C0 = 12 wt % and from less volatile p-xylene
with C0 = 5 wt % by distillative crystallization are
shown in Fig. 3. In both mixtures, the impurity content
was reduced by about two orders of magnitude, but, in
the former case, the efficiency of purification and the
yield are higher, and the final value of G is lower
(Fig. 3, curve 1). Under conditions of adiabatic evapo-
ration of the tert-butanol–p-xylene mixture, the con-
centration of a less volatile impurity even slightly
Vol. 43 No. 3 2009
 HYBRID SEPARATION PROCESSES COMBINING VACUUM DISTILLATION 229

P 2

6
3 5
1

8
4
7
T

Fig. 2. Setup for distillative crystallization (melting) under a vacuum: (1) crystallizer, (2) heated cover, (3) stirrer, (4) mixture being
separated, (5) thermostatically controlled vessel or heated ultrasonic bath, (6) condenser (desublimator), (7) vacuum pump, and
(8) thermostat.

increases in the starting period and C > C0 (Fig. 3,
curve 3) until the liquid is cooled to the temperature of
the onset of crystallization. Therefore, before Tt.e is
reached, it is more advantageous to lower the tempera-
ture in a forced manner with the use of a coolant (Fig. 3,
curve 2) and, under conditions of evaporative cooling,
to work at total reflux. In fact, all three processes occur
in distillative crystallization: distillation, crystalliza-
tion, and sublimation. However, distillation plays an
auxiliary role (initial cooling and removal of the liquid
phase enriched with impurities), and sublimation starts
at the end of the combined process (when the liquid is
barely present). Since both precrystallization distilla-
tion and postcrystallization sublimation decrease the
yield of a crystalline product, it is desirable to reduce
their contribution to a minimum.
After studying the kinetics of separation of some
binary mixtures of different types, experiments were
performed on the separation of the following ternary
mixtures: p-xylene–tert-butanol–benzene, p-xylene–
benzene–chloroform, and tert-butanol–p-xylene–ben-
zene. In all cases, the concentration of the first (major)
component was raised from 90 to 99.9–99.95 wt % at a
product yield of 60–80%. The lowest yield was
obtained in the purification of tert-butanol, since, in this
system, one impurity (5 wt % p-xylene) is less volatile
than the major component.
Distillative sweating. Experiments on distillative
sweating were performed using solids of various forms
(continuous crystalline layers, granules, and powders)
in the purification of naphthalene, biphenyl, caprolac-
tam, and benzoic acid. Two modes were used: constant
temperature and its gradual increase as the liquid phase
is removed. In the former case, the yield of the final
product is higher, and, in the latter case, the rate of the
process is higher and the degree of purification is some-
times higher. Apparently, the combined variant is more
preferable: the process is carried out at constant tem-
perature that is slightly higher than the eutectic temper-
ature, and, finally, the temperature of the apparatus is
increased for a short time nearly to the melting point of
the component being purified for removing the remain-
ing liquid phase.
The results of the purification of naphthalene from
biphenyl and p-dichlorobenzene impurities in different
layers of approximately equal thickness h = 10–12 mm
are compared in Fig. 4. The removal of impurities from
the pores of a continuous polycrystalline layer grown
from the melt on a cooled wall is slowest (Fig. 4,
curves 1 and 2). The purification of a bed of granules
with a size of 4 × 4 mm that are placed in three layers
occurs more rapidly (Fig. 4, curve 3). The impurity is
even more rapidly removed from a bulk bed of crystals
–log (C / C0)
2.5
1
2.0
2
3
1.5
1.0
0.5
0
0 0.2 0.4 G
Fig. 3. Variation of the concentration of (1) benzene and
(2, 3) p-xylene in tert-butanol in distillative crystallization:
(1, 3) evaporative cooling of the mixture; (2) forced pre-
cooling.

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 43 No. 3 2009

230 MYASNIKOV et al.
C/C0
1.0
0.8 1 the same time, it does not evaporate too rapidly and its
0.6
0.4
0.2
4 ing of the biphenyl–naphthalene mixture of the eutectic
3 composition C0 = CE are shown in Fig. 5. The process
5
0 10 20 30 40 50
t, min
Fig. 4. Kinetics of the removal of (1–3) biphenyl and
(4, 5) p-dichlorobenzene impurities from solid beds of
(2) benzoic acid and (1, 3–5) naphthalene of various forms
in distillative sweating: (1, 2) a continuous layer with a
thickness of 9.9 and 11.2 mm, respectively; (3) granules
with a size of 4 × 4 mm placed in three layers; and (4, 5) a
powder bed without and with stirring, respectively.
(Fig. 4, curve 4), especially with its stirring (Fig. 4,
curve 5). At a stirrer speed of 100 rpm, five minutes is
sufficient for an almost complete purification of naph-
thalene.
Separation of the mixtures of the eutectic compo-
sition. Analysis of phase diagrams in the region of the
three-phase equilibrium and the kinetic features of the
distillation and crystallization (melting) stages has
shown that the combined processes can be used to
effectively separate the mixtures of the eutectic compo-
sition (it will be recalled that ordinary fractional crys-
tallization is not applicable in this case). This inference
has been confirmed experimentally. The separation of
the eutectic biphenyl–naphthalene (the eutectic compo-
sition is 40 wt % naphthalene) and biphenyl–benzoic
acid (the eutectic composition is 15 wt % benzoic acid)
mixtures that are originally in the liquid or solid state
by distillative crystallization and distillative sweating
was conducted using the laboratory setup shown in
Fig. 2. Both processes make it possible to isolate a
nearly pure crystalline component at a sufficiently high
yield.
In the case of a solid eutectic mixture, the process
should be started under nonequilibrium conditions
when the mixture is heated to the eutectic temperature
TE, not waiting for complete melting. As soon as the
first portions of a liquid appear and impregnate (wet)
the mass of a porous solid phase due to the effect of
capillary forces, a vacuum pump is switched on, and a
pressure close to the pressure in the point of the four-
phase equilibrium Pf.e is set in the system. As a result of
starting the distillation, the composition of the liquid
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
changes, and a less volatile component will addition-
ally crystallize from it at the temperature TE. Heat sup-
ply and pressure in the system should be maintained at
such a level that the liquid does not accumulate, but, at
additional crystallization has time to occur. As the more
volatile impurity is removed, the temperature can be
2 raised to increase the rate of the process. This is partic-
ularly useful to do at the end of the purification process
when a rise in T up to nearly the melting point of a pure
component T0 facilitates the removal of the remaining
impurity.
Some results of separation in the distillative sweat-
was carried out for 1–1.25 h either at a constant temper-
ature of the apparatus walls of T = 40.4°C (TE = 39.4°C)
or with its gradual rise at constant rate up to the final
temperature Tfin after 20 min holding at 40.4°C. From
Fig. 5a, it is seen that the average rate of the purification
process (removal of the vapor) increases with a rise in
T, and, at Tfin = 68°C (for biphenyl T0 = 68.8°C), it is
nearly three times higher than that at T = 40.4°C. Evap-
oration is accompanied by active additional crystalliza-
tion and recrystallization: through the glass walls of the
apparatus, it is clearly seen as the dendrites of biphenyl
grow from the crystalline mass. The achieved efficiency
of purification that is determined by the relationship
C/C0 = f(G) is presented in Fig. 5b (curve 1). Curve 2
calculated for the distillation of the same mixture under
equilibrium conditions with a separation factor in the
liquid–vapor system of αd = 5.5 was constructed in
Fig. 5b for comparison. A significant increase in the
slope of curve 1 in Fig. 5b with an increase in G up to
0.6 is indicative of a lesser change in the composition
of the vapor and, accordingly, the liquid during the
combined process than that in simple distillation. This
is the consequence of additional crystallization, which
tends to raise the concentration of naphthalene in the
liquid phase, while evaporation decreases it. For exam-
ple, even with a rise in the final temperature up to Tfin =
64°C, the average concentration of naphthalene in the
removed fraction G = 0.6 was 66 wt % (at lower values
of Tfin, it reached more than 80 wt %). In this experi-
ment, the concentration of naphthalene in the mixture
was reduced by a factor of 140 at a biphenyl yield of
65%. A further increase in the value of G for the pur-
pose of obtaining a purer product results in a significant
decrease in the yield (for example, at G = 0.74, purifi-
cation by nearly a factor of 103 is achieved, but at a
yield of only 44%). This tendency is marked by a
decrease in the slope of the curve in Fig. 5b at G > 0.6.
The curve breakpoint appears when the magnitude of G
approaches the value of C0/CV (in the given case,
0.4/0.66 = 0.606).
For comparison, an experiment was performed on
the separation of the same eutectic mixture being in the
liquid original state by distillative crystallization. At
Vol. 43 No. 3 2009
 HYBRID SEPARATION PROCESSES COMBINING VACUUM DISTILLATION 231

G C/C0
0.8 (‡) 1000 (b) 1

0.6 100

0.4 10

0.2 1
40 50 60 70 0 0.2 0.4 0.6 0.8
Tfin, °C G

Fig. 5. Separation of the biphenyl–naphthalene mixture of the eutectic composition C0 = CE = 40 wt % naphthalene: (a) an increase
in the fraction of the liquid evaporated G with a rise in the final temperature of the process with a duration of 1–1.25 h; (b) separation
efficiency as a function of G: (1) experiment and (2) calculation for simple distillation of the same mixture at αd = 5.5.

G = 0.27, the concentration of naphthalene was reduced
by a factor of 1.6, which is close to the results obtained
in distillative sweating. This experiment has shown that
in distillative sweating near the eutectic temperature, an
amount of the liquid forms that is sufficient to impreg-
nate the entire crystalline mass and to prevent evapora-
tion through sublimation at the initial stage.
Separation of azeotropic mixtures. If an azeotrope
that is not broken with decreasing pressure and temper-
ature exists in the system, the composition of the vapor
withdrawn cannot get over the azeotropic point. In this
case, the combined process makes it possible to sepa-
rate a pure component from a mixture of any composi-
tion, except for a range between the eutectic and azeo-
tropic points. Since the composition of the azeotropic
mixture, as distinct from the eutectic mixture, can vary
greatly with a decrease in pressure, it is necessary to
have reliable data on the three-phase equilibrium in
order to determine this “forbidden” range of composi-
tions. For example, the study of the equilibrium in the
benzene–tert-butanol system has shown that with a
decrease in pressure from 760 to 20 Torr, the composi-
tion of the azeotrope varies from 37 to 11–12 wt % tert-
butanol at a eutectic concentration of 45 wt % tert-
butanol. Therefore, the crystals of pure benzene were
obtained only from the original mixture containing up
to 8 wt % tert-butanol, and the crystals of tert-butanol
were produced even from the mixtures with 50 wt %
benzene. In the forbidden range, it is possible to use a
two-stage process: first, to carry out conventional frac-
tional melting (or fractional crystallization) and, after
leaving the forbidden range due to the separation of the
crystals of a major component from the impure mother
liquid, to conduct their afterpurification by the com-
bined process.
Effect of kinetic factors. Since, in practice, the
combined processes occur at fairly high rates of phase
changes and ideal conditions are not satisfied, there are
certain deviations from equilibrium parameters, and
ideal separation factors are usually not attained. The
presence of a considerable fraction of the solid phase in
the mixture being separated, which slows down mass
transfer processes, facilities such deviations. However,
the deviation from the ideal process does not always
exert a negative influence on separation. In some cases,
it is possible to use the kinetic features of the combined
process (i.e., individual features of the interdependent
processes of distillation and crystallization that are part
of it) even for increasing the efficiency of separation.
Analysis of the samples of the condensate (desubli-
mate) taken from a trap has shown that at the beginning
of the combined process, the composition of the vapor
is close to the equilibrium value C *V , determined from
a phase diagram. However, as G increases, the real
quantity ëV begins to deviate from equilibrium values.
The extent of the deviation from the equilibrium is
determined by the magnitude of the efficiency factor
η = ëV/ C *V , which is equal to the ratio of the degrees of
impurity removal in the real ψ = GëV/C0 = 1 – C(1 –
G)/C0 and ideal ψ* = G C *V /C0 processes: η = ψ/ψ*. The
efficiency factor η can be used as a kind of performance
characteristic of the combined process. This quantity
depends on the nature and concentration of the compo-
nents of a mixture and the conditions and rate of the
process. With an increase in the rate and at large values
of k and G, deviations from the equilibrium and,
accordingly, η from unity increase.
In mixtures of type Ia under conditions of rapid
evaporation and at a high rate of change in ëL and ë,
the value of ëV is less than C *V , the useful process of
additional crystallization does not have time to occur,
and the value of η decreases (Fig. 6b). The magnitude

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 43 No. 3 2009

232 MYASNIKOV et al.
η
1.5 (‡)
1.0
2 1
0.5
0 0.2 0.4
Fig. 6. Dependence of the efficiency factor on the fraction evaporated in the (a) naphthalene–biphenyl and (b) biphenyl–naphthalene
systems with C0 = 4–6 wt % in distillative sweating: (1) powder and (2) granules with a size of 4 × 4 mm. The dotted lines represent
Gfin.
of η decreases particularly rapidly at G > Gfin = C0/ C *V ,
when, in the ideal process, all of the impurity would be
already removed (the breakpoint on curve 1 in Fig. 5b
is marked at approximately the same values of G). In
the real process, the remaining liquid with an impurity
is removed from the solid phase with difficulty, espe-
cially in the case of continuous layers and large gran-
ules. The appearance of the sections of the solid phase
that are free from the liquid leads to the sublimation of
a major component and, accordingly, a decrease in the
values of ëV and η.
At the same time, in mixtures of type Ib, conversely,
it is advantageous that the composition of the vapor is
as little different from the concentration of the liquid
evaporated as possible, and the adverse process of par-
tial melting does not have time to take place. In this
case, the use of kinetic factors under conditions of suf-
ficiently rapid evaporation without stirring the liquid
phase helps to raise η even slightly higher than unity
and increase the efficiency of purification. The maxi-
mum value of η achieved in the combined process in
the purification of naphthalene from less volatile biphe-
nyl is 1.25 (Fig. 6a).
Thus, the kinetic features of individual stages,
including those associated with different relaxation
times in the liquid–vapor and liquid–solid systems, can
be used to increase the efficiency of the combined pro-
cesses and to get over the specific points in phase dia-
grams.
Determination of the kinetic parameter—effec-
tive diffusion coefficient. In the technological calcula-
tion of the combined process, it is required to determine
its operating parameters and kinetic characteristics. The
main operating parameters are the operating tempera-
ture and pressure in the apparatus, as well as the con-
centration of vapors withdrawn into a condenser. The
main kinetic characteristic of distillative sweating is the
effective diffusion coefficient Def of a vapor–liquid
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
1.2 (b)
1 0.8
0.4 2
0.6 0 0.2 0.4 0.6
G G
mixture in the pores of the original solid material (in the
form of continuous crystalline layers or bulk powdery
beds, granules, or pellets). In the case of a considerable
influence of the operating parameters on the kinetic
characteristics, in order to calculate the process, it is
necessary to have the relevant functional relationships
that relate them.
Pressure greatly affects not only equilibrium charac-
teristics, first of all, the value of Tt.e, but also kinetic
characteristics: at its decrease, the rate of impurity
removal increases. For the majority of organic com-
pounds that can be purified in the process under consid-
eration, the values of Pt.p and, accordingly, P are in the
range from 1 to 40 Torr. To measure pressure in this
range, a VMP-2M digital device that is specially
designed for a low vacuum and operates at P > 0.1 Torr
was used. The dependences of Tt.e on P for a number of
binary mixtures (benzen–tert-butanol, p-xylene–tert-
butanol, p-dichlorobenzene–naphthalene, and naphtha-
lene–biphenyl) were constructed using this device and
a digital thermometer. Experimental data are compared
with the results of calculating Tt.e from the interpolation
equation
T 0 T E ln ( P t.p /P f.e )
T t.e = -----------------------------------------------------------------------------------
-.
( T E – T 0 ) ln P + T 0 ln P t.p – T E ln P f.e
Measurements have shown that, for the quantity Tt.e, the
maximum deviations are 1–1.5°ë.
Then, from experimental data, we determined the
values of Def at different pressures using the first term
of kinetic dependences of the impurity concentration
on the diffusion Fourier number Fo, which were pro-
posed earlier [12–14]:
k d µ 1 D ef t
2
C 0 ( C V – C )B 1
k d µ 1 Fo = --------------------
2
- = ln ---------------------------------
- ,
R
2 C ( CV – C0 )
Vol. 43 No. 3 2009
 HYBRID SEPARATION PROCESSES COMBINING VACUUM DISTILLATION
where B1 and µ1 are the coefficient of the first term of a
series and the root of the characteristic equation,
respectively; kd is the equilibrium distribution coeffi-
cient of the impurity between the vapor and liquid; R is
the characteristic dimension (radius for a sphere or cyl-
inder); and t is the time from the beginning of the pro-
cess.
The value of Def was found from the slope of the
kinetic straight line constructed by the least-squares
method from experimental data for C and CV in the reg-
ular mode of impurity removal.
The results have shown that for different organic
systems, the values of Def are rather close at the same
relative pressure P/Pt.p and the same form of a solid
phase (Fig. 7). At the same time, they greatly vary in the
transition from one form of the original solid mixture to
another. Minimum values of Def are observed for gran-
ules, they are slightly higher for continuous crystalline
layers, and maximum values of Def are typical of bulk
powdery beds. The cause of such an increase in Def is a
change in the form and size of pores in this series of
solid products and the conditions of heat transfer on
their outer surface. The obtained values of Def are typi-
cal of solids with macropores. For tentative estimation
of the value of Def in the range P > 0.1Pt.p, it is possible
to use an approximate empirical formula Def = APt.p/P,
where the coefficient A is determined by the form of a
solid phase and, at a very high concentration of impu-
rity, by its concentration as well (due to an increase in
the pore size, Def noticeably increases at C0 > 10 wt %).
For example, at an initial impurity concentration of less than
5–10 wt %, for continuous layers, A = (1.5 ± 0.5)–9 m2/s,
and, for bulk beds, it is an order of magnitude higher.
Calculation of a batch process. Processes that
occur under a vacuum and are associated with the pro-
cessing and movement of solid materials are easier to
implement in the batch mode. To carry out the batch
process of distillative sweating on an industrial scale,
apparatuses for vacuum sublimation can be used. On
the basis of the obtained data, a method for precalculat-
ing such a version of the combined process is proposed.
The main technological characteristics of distillative
sweating, such as operating temperature, the rate of
impurity removal, the achieved degree of purification,
the yield of a product, and required energy input, are
calculated. As an example, the calculation of a vacuum
shelf apparatus for purifying 100 kg of granular 98%
naphthalene to a final purity of 99.9 wt % is carried out.
It is shown that, at a temperature of 47°C, the time of
the purification stage is 11 min (the time of pre-exhaus-
tion to the operating pressure is 15 min) at a product
yield of 73%. The total consumption of heat and
mechanical energy is 280 kJ/kg of the pure product,
which is less than the double melting heat of naphtha-
lene. The calculated energy input is two to three times
less than that for the same purification in a two- or
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
233
Def × 109, m2 /s
12
3
2
8
4
1
0 2 4 6 8
Pt.p /P
Fig. 7. Dependence of the effective diffusion coefficient on
pressure in the (1) biphenyl–naphthalene, (2) naphthalene–
biphenyl, and (3) benzoic acid–biphenyl systems.
three-stage scheme combining fractional crystalliza-
tion with partial melting.
COMBINATION OF DISTILLATION,
CRYSTALLIZATION, AND GRANULATION
Organization of a semicontinuous or continuous
process. Batch processes associated with the charge
and discharge of solid products poorly suit present-day
production. A method is proposed that makes it possi-
ble to carry out a semicontinuous (continuous) com-
bined process based on the application of distillative
crystallization directly during the solidification and/or
granulation of the melt on a cooled moving belt. The
schematic diagram of a setup is shown in Fig. 8. The
original substance or mixture in the molten state is sup-
plied to feeder 4 of a rotor or other type, which uni-
formly distributes the drops (or continuous layer) of the
melt over the surface of a moving metal belt of con-
veyer 3 [13]. From the reverse, the belt is cooled using
device 5 by the trickles of a coolant (commonly, water).
Owing to this, partial solidification of the melt from
below occurs, and the moving solidification front
rejects impurities upwards. After the surface is filled,
the belt is stopped, and the cap of vacuum chamber 9
with a height of ≤1 cm is pressed to it from above. Due
to the small volume of the chamber, the required vac-
uum (usually, about 1–10 Torr) is attained very rapidly
using vacuum pump 1. Portions of the melt enriched
with impurities are evaporated and, then, caught in con-
denser (desublimator) 2. When a portion of the melt is
evaporated, the remaining melt is cooled and crystal-
lizes completely. After that, the vacuum line is switched
off, the vacuum in the chamber is released, and it moves
off the surface of the belt, which resumes the motion.
The solid products enter collector 7.
Vol. 43 No. 3 2009
234 MYASNIKOV et al.
Feed 6
9
4
3
5 7
Fig. 8. Semicontinuous setup for purifying organic compounds during their solidification (granulation): (1) vacuum pump, (2) con-
denser–desublimator, (3) conveyer, (4) feeder, (5) cooling system, (6) device for moving a vacuum chamber, (7) product collector,
(8) granules, and (9) vacuum chamber.
Using the same principle, the organization of a con-
tinuous process in which two parallel transporting belts
move towards each other is possible. Instead of one
vacuum chamber, the setup includes several movable
chambers with a smaller length l that can move together
with the belt at a velocity of v. After the initial section
of the belt is filled with the drops of a melt, the first
chamber is lowered on it, and, in the period t = l/v, the
second chamber is lowered on the place that is free as a
result of its motion, etc. When each chamber reaches
the end of the belt (where a collector of granules is
located), it moves away from it, is lowered on the initial
section of the second belt, and moves in the opposite
direction. The productivity of such a setup increases in
comparison with a semicontinuous variant due to the
nonstop motion of the belt and a decrease in the pump-
down time as a result of a reduction in the working vol-
ume of the chambers.
Model experiment and its results. At the first
stage, a vacuum unit with a chamber with a height of
5 mm was manufactured and tested on a laboratory
scale. To model conditions on the belt of a conveyer, the
vacuum chamber was pressed to the smooth surface
(with a size of 150 × 250 mm) of a crystallizer that is
made of stainless steel and cooled from the inside using
a circulation cryothermostat. Individual drops (or a cer-
tain portion) of molten organic compounds were
extruded on the cooled surface through a capillary.
First, the kinetics of solidification of the drops of differ-
ent substances (heptadecane, biphenyl, diphenyl ether,
caprylic acid, caprolactam, and naphthalene) and the
form and size of the obtained granules as a function of
the supercooling of the surface was studied. For all of
these substances, a minimum on the dependence of the
time of solidification on the supercooling ∆T is
observed, the minimum time being 5–10 s at ∆T = 35–
40°C for caprolactam and ∆T = 15–20°C for the other
melts. Viscous caprolactam is susceptible to supercool-
ing and starts to crystallize only at ∆T > 15°C. Having
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
2
1
Residue
8
Product
data on the rate of solidification, it is possible to deter-
mine the necessary temperature of a cooled belt at a
given velocity of its motion.
The height of the obtained granules (or pastilles) h
depends on their diameter d. At d > 5 mm, all granules
take on the form of segmental pastilles with h/d of about
0.2. With a decrease in d, the value of h/d for naphtha-
lene and biphenyl rapidly increases and the form of
granules at d = 3 mm tends to a spherical form, and, for
caprolactam, it is barely variable.
Next, the rate and efficiency of the removal of vola-
tile impurities from the partially solidified pastilles of
tert-butanol under a vacuum were studied. During the
solidification of large pastilles (d is up to 10 mm), mea-
surements of the rate of evaporation as a function of
pressure in the chamber and the temperature of the
crystallizer surface were carried out. The results are
presented in Fig. 9 as the dependence of the fraction of
substance G/t evaporated per unit time on pressure. In
the region of the triple point of tert-butanol (298.5 K
and 42 Torr), 3–5% of the substance is removed for a
minute. The rate of evaporation of the liquid phase from
small granules having a larger specific surface area is
even higher under comparable conditions.
The kinetics of impurity removal in the combined
process was studied using model binary mixtures of
tert-butanol with benzene, cyclohexane, and water. The
majority of the experiments was carried out in the crys-
tallization field of tert-butanol at a temperature of the
three-phase equilibrium close to 273 K (see Fig. 1). The
maximum efficiency of the purification of pastilles is
achieved for benzene and cyclohexane impurities at
C0 = 4–6 wt % (Fig. 10, line 1). The impurity content is
decreased by nearly an order of magnitude for several
minutes when evaporating 12–13% of the entire mix-
ture. Such a purification corresponds to the average val-
ues of the effective (real) distribution coefficient of
impurity between the solid–liquid mixture and the
Vol. 43 No. 3 2009
 HYBRID SEPARATION PROCESSES COMBINING VACUUM DISTILLATION
G/t × 102, 1 /min
8 1.2
1 c
6 2
4 3
0 G
1 10 100 1000
P, Torr
Fig. 9. Rate of the evaporation of tert-butanol G/t as a func-
tion of the residual pressure P at different temperatures of
the heat transfer medium: (1) 299, (2) 297, and (3) 291 K.
vapor kef = 17. With an increase in the concentrations of
the same impurities in the original mixture up to C0 =
9–11 wt % (line 2), it is necessary to evaporate already
about 20% of the mixture in order to reach a similar
separation efficiency. In practice, the impurity content
in a feed melt is usually lower than 5 wt %; therefore,
the rate and efficiency of purification can be even
higher.
A rise in the temperature of the crystallizer surface
up to 288 K (line 3) substantially reduces the efficiency
of purification (in proportion to a decrease in the impu-
rity content in the equilibrium liquid and, accordingly,
in the equilibrium vapor). In purifying tert-butanol
from water with ë0 = 2 wt %, the efficiency is still
lower, even at 273 K (Fig. 10, line 4). Water forms an
azeotrope with alcohol at a concentration of 10–12 wt %
H2O and, at low temperatures, an unstable molecular
compound that forms a eutectic with tert-butanol.
Therefore, it is impossible to reach a fairly high water
content in the removed vapor.
Calculation of the continuous process. On the
basis of obtained data, a method for precalculating the
continuous combined process is proposed. Experiments
have shown that the solidification of granules occurs
quite rapidly; therefore, the limiting stage of the pro-
cess is the evaporation of volatile impurities from the
pores of granules. This stage determines the residence
time of granules on the belt of a conveyer and, conse-
quently, the rate of its motion. A procedure for calculat-
ing the operating parameters and the kinetics of impu-
rity removal from single granules differs little from the
procedure developed at the previous stage for a batch
process. Since the characteristic size of the granules
obtained from the individual drops of a melt is small,
the time of their purification (it is proportional to the
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
235
–log C/C0 ‡
b
1 2 3 4
0.8
0.4
0 0.4 0.8
Fig. 10. Degree of tert-butanol purification from (a) ben-
zene, (b) cyclohexane, and (c) water as a function of the
evaporated fraction of the mixture at different values of C0:
(1) 4.2 wt % benzene or 5.7 wt % cyclohexane, (2) 9.5 wt %
benzene or 11 wt % cyclohexane, (3) 4.2 wt % benzene, and
(4) 2 wt % water; (1, 2, 4) T = 273 and (3) 288 K.
size squared) decreases to 1–5 min. The millimeter
height of granules makes it possible to abruptly
decrease the height of vacuum chambers and, accord-
ingly, the calculated time of their evacuation to the
operating pressure.
Comparative (with a batch process) calculation of a
hybrid setup with two belts for the continuous granula-
tion and purification of 98% naphthalene up to a purity
of 99.9 wt % is conducted. It is shown that such a setup
is capable of yielding 75 kg/h of the purified pastilles
with a size of 5 × 1 mm. The total consumption of heat
and mechanical energy is 410 kJ/kg of the pure product.
At first sight, it is substantially higher than that in a
batch process (280 kJ/kg). However, then, the issue was
the purification of the already produced granules. Cal-
culation shows that the individual stage of their produc-
tion requires 220 kJ/kg, and the serial combination of
two stages yields 500 kJ/kg in the total. The advantage
of the hybrid process in 90 kJ/kg is attained due to sav-
ing energy consumption on the solidification of drops
(the crystallization heat is removed as a result of their
partial evaporation) and decreasing the power of a vac-
uum pump. Another advantage of the continuous pro-
cess is the elimination of handling stages, which are
unavoidable in the batch process.
CONCLUSIONS
The statics and kinetics of the hybrid processes
combining vacuum distillation with fractional crystalli-
zation, partial melting, and granulation are studied.
Various variants of organization of these processes in
separating liquid organic mixtures and purifying solid
materials of different types from volatile impurities are
considered. In separating a number of binary and ter-
Vol. 43 No. 3 2009
236 MYASNIKOV et al.
nary mixtures, the values of the effective separation
factor αef = 10–20 are achieved. This made it possible
to separate a major component with a purity of 99.5–
99.97% at a product yield of 60–80% from these mix-
tures (including ones with specific points on phase dia-
grams) containing up to 40 wt % impurities.
The combined processes considered can be used in
small-tonnage productions for purifying a whole series
of substances (for example, anthraquinone—Pt.p =
100 Torr, tert-butanol—42 Torr, benzene—36 Torr,
acetic acid—10 Torr, naphthalene—8 Torr, p-xylene—
4 Torr, etc.) from impurities with close (higher or even
lower) volatility.
ACKNOWLEDGMENTS
This study was supported by the Russian Founda-
tion for Basic Research, project no. 06-03-32963.
NOTATION
A—coefficient, m2/s;
B1, µ1—coefficient and root of the characteristic
equation, respectively;
C0, C—initial and current concentration of the
impurity, respectively, wt %;
Caz, CE—impurity concentration in the azeotropic
and eutectic point, respectively, wt %;
CL, C *L —real and equilibrium concentration of the
impurity in the liquid, respectively, wt %;
CV, C V* —real and equilibrium concentration of the
impurity in the vapor, respectively, wt %;
Def—effective diffusion coefficient of the vapor–liq-
uid mixture in the pores, m2/s;
d—diameter of the granules, mm;
G, Gfin—current and final removed (evaporated)
fraction of the mixture, respectively;
h—thickness of the bed or height of the granules,
mm;
k0, k—initial and current distribution coefficient of
the impurity between the vapor and solid–liquid mix-
ture under equilibrium conditions, respectively;
kd—equilibrium distribution coefficient of the impu-
rity between the vapor and liquid;
l—length of the movable vacuum chamber, m;
P, Pt.p, Pf.e—pressure in the apparatus in the triple
point of a major component and in the point of the four-
phase equilibrium, respectively, Torr;
R—characteristic dimension (radius of a sphere or
cylinder), m;
t—time from the beginning of the process, s;
T, Tfin—current and final temperature of the walls of
the apparatus, respectively, °C;
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
T0, TE—melting point of a major component and
eutectic temperature, respectively, °C;
Tt.e—temperature of the three-phase equilibrium,
°C;
∆T—supercooling, °C;
v—velocity of the belt of the conveyer, m/s;
αd—separation factor in the liquid–vapor system (in
distillation);
αef—effective separation factor in the vapor–solid–
liquid mixture system;
η = ëV/ C *V —efficiency factor (extent of deviation
from the equilibrium);
ψ, ψ*—degree of impurity removal in the real and
equilibrium process, respectively.
REFERENCES
1. Berry, D.A. and Ng, K.M., Synthesis of Reactive Crys-
tallization Processes, AIChE J., 1997, vol. 43, p. 1737.
2. David, A., Berry, D.A., and Ng, K.M., Synthesis of Crys-
tallization-Distillation Separation Process, AIChE J.,
1997, vol. 43, p. 1751.
3. Eck, B., Heimann, F., and Schoenmakers, H., Hybrid
Processes Combining Distillation and Crystallisation,
EFCE Working Party on Distillation, Absorption and
Extraction, Helsinki, 2003.
4. Ye, Q., Qiu, Z.R., and Zhong, Q., Study on Distillation-
Falling Film Crystallization Hybrid Separation Process,
Natural Gas Chem. Ind., 2006, vol. 31, no. 3, p. 38.
5. Putrawan, I.D.G.A. and Soerawidjaja, T.H., Separation
of Dimethylnaphthalene Isomers by Extractive Crystal-
lization, Sep. Purif. Technol., 2004, vol. 39, nos. 1–2,
p. 79.
6. Curcio, E., Criscuoli, A., and Drioli, E., Membrane
Crystallizers, Ind. Eng. Chem. Res., 2001, vol. 40,
p. 2679.
7. Gryta, M., Concentration of NaCl Solution by Mem-
brane Distillation Integrated with Crystallization, Sep.
Sci. Technol., 2002, vol. 37, p. 3535.
8. Lorenz, H., Sheehan, P., and Seidel-Morgenstern, A.,
Coupling of Simulated Moving Bed Chromatography
and Fractional Crystallization for Efficient Enantiosepa-
ration, J. Chromatogr. A, 2001, vol. 908, p. 201.
9. Fung, K.Y., Ng, K.M., and Wibowo, C., Synthesis of
Chromatography-Crystallization Hybrid Separation Pro-
cesses, Ind. Eng. Chem. Res., 2005, vol. 44, p. 910.
10. Cheng, C.-Y. and Cheng, S.-W., Distillative Freezing
Process for Separating Volatile Mixtures and Appara-
tuses for Use Therein, US Patent 4218893, 1980.
11. Cheng, C.-Y. and Cheng, S.-W., Wet and Dry Distillative
Freezing Process for Separating Mixtures and Appara-
tuses for Use Therein, US Patent 4578093, 1986.
12. Myasnikov, S.K., Uteshinsky, A.D., and Kulov, N.N.,
Distillation Sweating Under Vacuum − A Novel Com-
bined Separation Process, Recents Prog. Genie Pro-
cedes, 1999, vol. 13, no. 68, p. 1.
13. Gierke, S., Ulrich, J., Bulau, H.C., Chianese, A., Bruin-
sma, O.S.L., Van der Gun, M., Verdoes, D., Kulov, N.N.,
Myasnikov, S.K., and Uteshinsky, A.D., The Granupure
Vol. 43 No. 3 2009
 HYBRID SEPARATION PROCESSES COMBINING VACUUM DISTILLATION
process. New Technology for Energy Efficient Separa-
tion of Melts by Combination of Granulation and Wash
Column Purification. Final Publishable Report. The
European Commission Joule III Programme, 1999.
14. Myasnikov, S.K., Uteshinsky, A.D., and Kulov, N.N.,
Removing Volatile Impurities from Granules by Distilla-
tion Sweating, Teor. Osn. Khim. Tekhnol., 2001, vol. 35,
no. 5, p. 457 [Theor. Found. Chem. Eng. (Engl. Transl.),
vol. 35, no. 5, p. 433].
15. Shiau, L.-D., Wen, C.-C., and Lin, B.-S., Separation and
Purification of P-Xylene from the Mixture of M-Xylene
and P-Xylene by Distillative Freezing, Ind. Eng. Chem.
Res., 2005, vol. 44, p. 2258.
16. Shiau, L.-D., Wen, C.-C., and Lin, B.-S., Application of
Distillative Freezing in the Separation of o-Xylene and
p-Xylene, AIChE J., 2006, vol. 52, no. 5, p. 1962.
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
237
17. Shiau, L.-D., Liu, K.-F., Jang, S.-M., and Wu, S.-C., Sep-
aration of Diethylbenzene Isomers by Distillative Freez-
ing, J. Chin. Inst. Chem. Eng.s, 2008, vol. 39, no. 1,
p. 59.
18. Myasnikov, S.K., Uteshinsky, A.D., and Kulov, N.N.,
Hybrid of Pervaporation and Condensation–Distillation
Crystallization: A New Combined Separation Technology,
Teor. Osn. Khim. Tekhnol., 2003, vol. 37, no. 6, p. 563 [Theor.
Found. Chem. Eng. (Engl. Transl.), vol. 37, no. 6, p. 527].
19. Lipatov, D.A., Myasnikov, S.K., and Kulov, N.N., Sepa-
ration of Paraffins by Membrane Extraction Combined
with Crystallization, Teor. Osn. Khim. Tekhnol., 2005,
vol. 39, no. 2, p. 120 [Theor. Found. Chem. Eng. (Engl.
Transl.), vol. 39, no. 2, p. 110].
Vol. 43 No. 3 2009