IrenTechnology

Journal of Chemical Tsibranska,and

Bartosz Tylkowski
Metallurgy, 51, 5, 2016, 489-499

Solid-liquid extraction of bioactive compounds:

effect of polydispersity and particle size evolution
Iren Tsibranska1, Bartosz Tylkowski2

1
Institute of Chemical Engineering Received 06 January 2016
Bulgarian Academy of Sciences Accepted 02 April 2016
1113 Sofia, Bulgaria
E-mail: tsibranska@ice.bas.bg
2
Universitat Rovira i Virgili
Departament de Enginyeria Química
Av. Països Catalans, 26 - 43007 Tarragona
Spain

ABSTRACT

Extraction of bioactive compounds from natural products is of growing research interest. The present study
focuses on the role of polydispersity in analyzing the kinetic curves of solid-liquid extraction and determining the ef-
fective diffusion coefficients in the solid. A numerical solution of the polydisperse particles diffusion model is applied.
Partial dissolution of the solid matrix is included taking into consideration the time evolution of the particle size. The
asymmetry of the particle size distribution and the necessity to apply the polydisperse model or the mean average
size as a modeling approach is thoroughly discussed. Examples referring to two experimental systems (Propolis and
Sideritis ssp. L) are given. Conventional batch extraction of polyphenols by an ethanolic solvent is considered there.
Keywords: solid-liquid extraction, polyphenols, particle size distribution, mathematical modeling.

INTRODUCTION the extract. Typically bioactive compounds accumulate

A number of investigations are lately focusing on the
physico-chemical and therapeutic properties of bioactive
substances present in natural resources through develop-
ment of techniques for their extraction and means for
quality control. Solid-liquid extraction under controlled
process conditions is important for the reproducibility
of the end products and preservation of their bioactiv-
ity. Standard low pressure extraction, CO2 supercritical,
ultrasound or microwave assisted extraction have been
studied in order to find the optimal extraction condi-
tions and to compare the yield obtained and extract
composition. An important part of such investigations
concerns the extraction kinetics and the respective rate
parameters because of their predictive capabilities in the
process evaluation.
The process of extraction is quite difficult for de-
scription and modeling due to the diversity and specific-
ity of the starting structure of the solid and its change
throughout the process, the extraction of ballast com-
pounds and the reproducibility of the initial content of
at higher concentrations in specific parts of the plant
(leaves, stems, roots, flowers, seeds) or are located in
the surface or interior layers. The raw materials after
grinding contain particles of various sizes irregularly-
shaped, often with an effective amount of two spatial
coordinates, as well as particles of a critical size in the
three-dimensional space. The solid phase polydispersity
and the presence of anisotropy have to be also taken
into account in treating many raw materials. The repro-
ducibility of the extract solutions obtained which may
contain greater or fewer amounts of active substances
(by weight ratio) among other ballast ones extracted are
other issues of interest. In fact the accurate description of
the extraction mechanism requires the treatment of the
possible interactions between the solvent and the solid
matrix (soaking the solvent and swelling of the material),
the target component content (possible degradation) at
any stage of the process well as the effect of various
factors on the extraction effectiveness. An important
criterion from practical point of view is the ability of the
model to predict correctly the approach to equilibrium, as
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 Journal of Chemical Technology and Metallurgy, 51, 5, 2016
the latter determines the contact time for the extraction
process. With regard to the correct description of the
kinetics of extraction from plant materials, models of
different complexity are used, mostly based on the Fick’s
law, the chemical rate law and empirical models, which
have proved to be applicable to most extraction curves. A
comprehensive review of these mathematical approaches
for modeling batch extraction processes is given in [1].
The unsteady state models, providing estimation of the
effective (constant or variable) intraparticle diffusion
coefficient (De) are of special interest [2], because solid
phase diffusion is usually the controlling mass transfer
step. The determination of the rate of mass transfer, De,
is of importance for the equipment design. The analytical
solution of the diffusion equation in case of negligible
external mass transfer resistance
kf R
( Bi
= > 100 )
De
is often used to determine the effective diffusivity:
C − Ce 4 ⋅ R ∞ 1 − (−1) n  n 2π 2 
=
C0 − Ce
∑
π n =1 n ⋅ π
exp  − 2 De t  (1)
 R  design and control.
where C0 and Ce refer to the initial and equilibrium
concentration of the solid phase, respectively.
Truncated to the first term Eq.(1) is easily applied
to experimental data, including polyphenols extraction
from white distilled grape pomace [3], S. aromaticum
and C. cassia [4]:
d ln((C − Ce ) /(C0 − Ce )) π2
= − 2 De (2)
dt R Empirical models
When conventional extraction from plant materials
is considered, the observed values of De are in the range
of 10-11 m2/s down to 10-14 m2/s [1]. Particles of a size
less than 1mm are usually applied [1] in order to enhance
the mass transfer in the diffusion step and to reduce the
extraction time. The initial plant material, consisting
of stems, leaves flowers, is either sorted in individual
groups and sieved (when the valuable substances are
differently distributed in the respective parts of the
plant) or grinded and subjected to extraction as a whole
(when the bioactive compounds are found everywhere
in the plant in comparative quantities). The latter gives
particles of a size of the micron order, yet various in
shape (cylindrical, plate) and characteristic length. Some
490
authors apply a two-shape extraction model to describe
adequately the experimental data [5].
Different interpretations of the mass transfer pro-
cedure, affecting the initial course of the kinetic curves
are proposed in a number of simplified models related to
the external mass transfer in the liquid film around the
particles, the washing, the swelling of the solid particles,
etc. The description of the initial section of the extraction
curve can be also improved by decrease of the particles
size, though the effect of this parameter should be also
accounted of in respect to the rate limiting mechanism.
Moreover, polydisperse systems will affect essentially
the course of the kinetic curve because of the asymmetry
of the particle size distribution (PSD). In principle the
particle size is the parameter of primary significance
among those affecting the conventional extraction kinet-
ics. In view of its importance the modeling of complex
polydisperse systems and the parameter identification
of the kinetic coefficients is of certain interest. In this
case models of better theoretical grounds are preferably
used as they are expected to possess greater predictive
capabilities and applicability to process optimization,
The present study focuses on the role of polydisper-
sity in analyzing the kinetic curves of solid-liquid extrac-
tion and determining the effective diffusion coefficients
in the solid. Two experimental systems are considered,
including constant PSD or particle size evolution (due
to partial dissolution of the solid matrix). In both cases
conventional batch extraction of polyphenols with etha-
nolic solvent is applied (Propolis and Sideritis ssp. L).
Because of a similarity between extraction and
sorption kinetics, a number of simplified models, known
from modeling the sorption kinetics, have been used,
including examples referring to polyphenols extraction
from plant materials. A comparison of different simpli-
fied kinetic models, mostly used for extraction of bioac-
tive compounds from plant material, is given in [6-9]
including examples of total polyphenols extraction from
grape marc and yerba mate. The results are in favor of
the pseudo-first order kinetics:
C∞
C
=l C∞ −
exp ( kt + a )
or in logarithmic form:
 Iren Tsibranska, Bartosz Tylkowski
 C∞ 
ln   vs t (3)
 C∞ − Cl 
and the standard function technique [10]:
Cl =
A − Bexp(−kt) (4)
where Cl refers to the current concentration in the liquid
phase, C∞ is C∞ the equilibrium concentration, while k
(s-1) is the rate constant. A similar expression, resulting
from the Fick´ s law solution for great time and infinite
flat geometry is used in modeling yerba mate aqueous
extraction kinetics [11].
The second-order kinetic model:
dCl
= k(C∞ − Cl ) 2
dt
is transformed to after integration and subsequent lin-
earization to:
t 1 t C= C∞w t + Cd 1 − exp(−kt)
= + ∞( ) (11)
Cl kC∞2 C∞ Tw + t
(5)
This model has been found successfull in case of
polyphenols extraction from peel and seeds of pome-
granate marc [9], as well as in their ultrasound-assisted
extraction [12]. Another three empirical models are
equally suited for modelling the extraction of total
polyphenols from soybeans [13]:
- The hyperbolic model, known as Peleg’s model:
t
C= ; (6)
K1 + K 2 t
- The Weibull type model, known also as Page model,
C exp(−kt n )
= (7)
- The logarithmic model: C = a log t + b (8)
C is evaluated as mg galic acid equivalent per g dry beans
in Eqs.(6) to (8). The describtion of the solid–liquid ex-
traction kinetics of total polyphenols from grape seeds
[14], as well as the β-carotene batch extraction from rose
hip (Rosa canina) by the Peleg equation is characterized
by a high correlation coefficient [15].
The extracted amount under diffusion controlled
conditions can be generally described by a power law
expression [7, 11]:
C = Bt n (9)
where C is dimensionless quantity, while and the expo-
nent n=0.5 for Fick’s diffusion in case of flat geometry.
Additional intercept term is usually inserted to model the
fast initial release from the particles and to take account
of the washing, or external mass transfer. This form of
the equation can be obtained also as a partial case of the
parabolic diffusion model [7] in the form:
C A 0 + Bt1/ 2
= (10)
The search of a better description of the extraction
kinetics, which is never as simple as the referring to
one-dimensional diffusion mechanism, has lead to com-
bined empirical equations, where two additive terms are
ascribed to different mass transfer mechanisms. Exam-
ples of such equations modeling the extraction kinetics
of polyphenols from plant materials are given below:
- Washing/swelling followed by intraparticle dif-
fusion [11]:
Here the concentration C (g/l) stands for the sum of
Cw and Cd referring to the concentrations achieved by
washing/swelling and diffusion, correspondingly. This
equation gives satisfactory description of the bioactive
components extraction from yerba mate [11].
- Two-rates exponential equation [7, 16]:
C =a (1 − exp(−bt)) + c(1 − exp(−dt)) (12)
which provides the evaluation of the solute concentra-
tion C (mg GAE/g) when the extraction proceeds with
two different rates.
Effect of polydispersity and particle size evolution
All empirical models pointed above are more or
less able to correlate the experimental results, but the
physical meaning of the parameters involved is not al-
ways clear. Two-stage models like the ones developed
by Sovova [17] for supercritical fluid extraction fitted to
the experimental data, may lead to somewhat unrealistic
overestimation of a given part of the plant material con-
nected with a given release mechanism. The two-stage
character of the kinetic curve accepted in a number of
cases can be described by taking into account the actual
polydispersity. Such a model is developed in [18] and
applied to extraction of oil from white lupin seeds. The
modification includes more or less adjusting parameters.
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 Journal of Chemical Technology and Metallurgy, 51, 5, 2016
For example, an additional dust fraction is formally
considered aiming better approximation. The mechanism
corresponding to the initial fast release observed in the
kinetic curve is not fully understood, but polydispersity
is regarded as a possible reason for that [19], even not
the only one [20].
The formal introduction of a time dependent diffu-
sion coefficient can lead to a better description of the
kinetic curve in absence of additional supporting infor-
mation. Thus the applicability of the simple diffusion
models, where the effective diffusion coefficient De is
the only adaptation parameter, can be increased. The
initial value of De as well as the type and mathematical
formulation of the introduced function can be regarded
as adjustable parameters, unless additional physical
evidence is available. An example of a decreasing De(t)
relation, which can be satisfactorily modeled through
the concentration dependence De (C ) is observed during
extraction from mangrove barks [21,22]. Through analy-
sis of the kinetic curve, an increasing two-parametric
De (C ) function is found to provide a better match of
the experiment results. However, a pronounced concen-
tration dependence of the diffusivity is not expected for
highly diluted plant extracts, which is often the case.
An example of diffusivity De(t) increasing with time
is found when additional degradation of the solid occurs
[20] (ex. release through polymeric microcapsules). It is
expressed in the form of a D(Mw) polynomial relation
(Mw being the molecular weight of the solid polymer).
Solid-liquid extraction with particles of broad (and
typically asymmetric [19, 23] size distribution should
be analyzed using polydisperse models [18, 24] to avoid
unrealistic values of the inner mass transfer coefficient
[25]. Such results may be obtained because of a faster
R2
extraction (or lower diffusion time , respectively)
De
on behalf of the smallest particles and hence a delayed,
slower approach to equilibrium for the larger particles
in the tail of the distribution, whose characteristic dif-
fusion time is much longer. Moreover, the inner mass
transfer is differently influenced by the different parts of
the particle size distribution, PSD. As the characteristic
diffusion time increases proportionally to the square of
the particle size, small particles have a stronger effect on
the steep initial part of the kinetic curve. The influence
of the right part of the PSD becomes important at larger
extraction times, which in turn is essential for the ap-
492
proach to equilibrium and the correct determination of the
contact time required. In cases of pronounced asymmetry
the description of the kinetic data by an effective diffusion
coefficient based on a representative mean diameter may
turn to be unsatisfactory [19, 25, 26], i.e. it may lead to
the identification of different or unprobable value of the
diffusion coefficient.
Polydispersity may prevail in scaling-up [25], and
hence the mathematical description which takes it into
account seems reasonable. The correct analysis of the
calculations requires the effect of polydispersity to be
greater than the experimental error, i.e. the deviation
between the two calculated curves – that of a constant
(mean average) size and the other one of PSD, to be
greater than the scattering of the experimental points
determined by the reproducibility of the raw material
and the analytical method. Furthermore, the calculated
curve has to describe the kinetic data in the entire range
of time, including the approach to equilibrium, which
for practical purposes is defined as that required for 90
% extraction of the raw material.
Model description
A model considering the effects of polydispersity
and particle size evolution is given in Table 1. The as-
sumptions of the model are as follows:
- One-dimensional unsteady state Fick’s diffusion
within the particle with constant coefficient of internal
diffusion De (m2/s) (eq.15.1); a regular form is sug-
gested for each class of particles; it is denoted by the
corresponding value of the form factor a (= 0 plate, 1
for cylinder and 2 for sphere).
- The regular geometry supposes symmetry, as
shown by boundary condition (15.2);
- The surface of all particles is surrounded at any
time by fluid of concentration Cl (mg/ml), i.e. perfect
mixing conditions exist in the extraction vessel, so that
Cl is only time dependent. The flux through the fluid film
around each class of particles is different because of the
different size, the external mass transfer coefficient and
the surface concentration C R (see boundary condition
15.3a). The latter assumes implicitly a solid/liquid distri-
bution coefficient equal to 1, which is reasonable for low
concentrations of the solutes observed in plant extracts.
When intensive stirring is applied and the external mass
transfer resistance is reduced to be neglected, the result-
ing Eq.(15.3b) is used;
 Iren Tsibranska, Bartosz Tylkowski

Table 1. Model equations.

Each class of ∂C 1 ∂ a ∂C Eq.

particles in the PSD = De a (r ⋅ ),
∂t r ∂r ∂ r (15.1)

Boundary conditions Center, r=0 Surface, r=Rj (15.2)

∂C ∂C (15.3a)
=0 D = k f (t )(C R − C l )
∂r ∂r R

C R = Cl (15.3b)
Or

1 d (Vs C )
Mass balance in the (15.4a)
extraction vessel dCl 1 dR
=− = − ρ s 4πR 2 N
dt Vl dt Vl dt
Where N, number of particles, Rj(t)
dCl V d C (15.4b)
Or =− s (Rj=const)
dt Vl dt
Average solid (15.5)
concentration
∞
(a + 1) R j a 
C = ∫ a +1 ϕ ( R j )  ∫ r ⋅ C (r ) ⋅ dr dR j
0
R  0 
ϕ ( R j ) - distribution function
Particle radius dR ∂C (15.6)
change R(t) ρs
dt
(
= −k f (t ) C R
)
− Cl = D
∂R R
External mass Sh=(4+1.2Pe2/3)1/2 (15.7)
transfer coefficient ρ 2R ⋅ v ν k 2R [36]
Pe=Re.Sc; Re= l ; Sc = l ; Sh = f
µl D AB D AB

- The volume averaged solid phase concentration is K

4
calculated in accordance with Eq. (5), where C (mg/mL) Vs ∑ϕ ( R ) πR 3j
j
3
= K1 (14)
is the local concentration inside the particle; Vs 0 4
- This flux is related to the particle size evolution
∑1 ϕ ( R j 0 ) 3πR j 0
3

(Eq.15.6), if we observe a partial dissolution of the solid

(as in the case of Propolis [23]). In both cases when
polydispersity is present, the value of the external mass
transfer coefficient has to be recalculated for every
particle size according to correlations known (Eq.7).
- The solid volume Vs (see eq.4) is determined at
any time on the ground of the particle size change, the
initial value being:
We assume a constant volumetric part of the par-
ticles in the PSD ϕ ( R j ) = ϕ ( R j 0 ) = const , which means
a similar particles size evolution with no change in the
distribution form. This is a rough simplification of the
real picture. The observations on Propolis show that the
particle sizes distribution curve is shifted to the left and
straitened during extraction [23], see Fig. 1.

Ms Results and discussion

Vs 0 = (13)
ρs
● PSD characterization
where Ms and ρs are the solid mass and density, corre- The analysis of the particles by size is carried out by
spondingly. Vs is related to its initial value Vs0 through: the Image-Pro plus 5® software. Size evolution of the

493
 Journal of Chemical Technology and Metallurgy, 51, 5, 2016
Fig. 1. Propolis particle size distribution measured at different extraction times.
particles during extraction is continuously followed by
microscope Axiovert 4OC for transmitted-light bright-
field and phase contrast with condenser 0.4 and object
traverser M. The optical micrographs of the particles are
taken by digital camera DeltaPix Invenio 3S connected
to the microscope [23]. Two examples of PSD from
milled raw material are considered:
A) Extraction of polyphenols from Sideritis ssp.
L, details of the experimental procedure being given in
[19]; the particle size of the milled plant ranges from
10µm to 200µm, while the mean number-based particle
size is 40.8 µm.
B) Extraction of polyphenols from Propolis; the
initial PSD shows that 90% of the particles size are in
the range of (15-52) ±2 μm with a mean number-based
diameter of 32 μm [23, 27]. Partial dissolution of the par-
ticles occurs during extraction so that the initial of 36μm
changes to a final volume averaged size of 15μm [23].
The PSD observed are shifted to the left and straitened
during the extraction, see Fig. 1. The partial dissolution
of the solid matrix, as well as the destruction of mechani-
cally unstable bigger agglomerates of particles in contact
with the solvent contributes most probably to it.
To quantify these observations the experimental
PSD data is modeled by the cumulative Rosin–Rammler
distribution function:
494
V   d  b 
= 1 − exp−   
Vtot  a  (16)
 
where V denotes the total volume contained by micropar-
ticles of diameter less than d, Vtot is the total volume of
the population, while a and b are parameters referring
to the main mean diameter and the spread of the mic-
roparticles sizes.
In accord with the analysis reported in ref. [20], the
polydispersity affects the kinetics and has to be account-
ed for by the model in order to provide an adequate fit of
the experimental data for distributions of b ≤ 3 (eq,16).
The following values for the Rosin-Rammler pa-
rameters a and b are obtained (see Fig. 2a and Fig. 2b)
on the ground of the experimental data:
a=142 µm and b=3.03 (R2=0.925) for the PSD of case A);
a=46.7 µm and b=4.43 (R2=0.961) for the PSD of case B);
In case A) the regression coefficient is lower, which
can be explained by the cylindrical shape of the parti-
cles (of predominantly fibrous structure) as well as the
distribution curve tendency to binomial one because of
fragmentation of other parts of the plant material (see
[19]). In such cases the Rosin–Rammler function cannot
perform well [28]. The pronounced spread of the PSD
is expected to influence the kinetics as suggested also
 Iren Tsibranska, Bartosz Tylkowski
Fig. 2. Cumulative Size Distribution of particles and Rosin-Rammler curve fit referring to: A) Sideritis; B) Propolis.
by the value of b (=3.03), eq. (16).
In case B) where the particles shape is close to the
spherical one and the PSD is more symmetrical a better
correspondence between calculated and experimental
data is observed, the value of b being 4.4. During extrac-
tion this parameter tends to increase, i.e. polydispersity
decreases, as the experimental PSD is straitened and
shifted to the left (Fig.1). According to the results
reported in ref. [20] the deviation between the model
accounting for PSD and the mean diameter-based model
becomes negligible in this case, i.e. the latter provides
a satisfactory description of the experimental kinetics.
Effect of polydispersity
A. No time evolution of the PSD (Rj=const):
Example with polyphenols extraction from Sideritis ssp. L).
The effective diffusion coefficient is searched by
fitting the experimental kinetic curves of the liquid
phase concentration with the solution of Eqs. (15): 1,
2, 3a, 4b, and 5 in Table 1. A value of 1.5 10-12 m2/min
is obtained (see the calculated and experimental kinetic
shown in Fig. 3).
When simplified models like that described by Eq.
(2) are used to determine the effective solid phase dif-
fusion coefficient, the calculation is based on the mean
averaged size of the dried and powdered plant material
(40.8 µm). The value De = 0.56 10-12 m2/min is obtained
from the slope of the plot (C − Ce ) /(C0 − Ce ) vs time
shown in Fig. 4. It is lower than that obtained by the
numerical solution accounting for polydispersity, and
reflects the influence of the right part of the kinetic curve
where diffusion is slower due to the presence of bigger
particles. A better correlation (R2=0.989) and diffusivity
values closer to that obtained by the model accounting
for PSD (1.12 10-12 vs 1.52 10-12) is obtained in case
of considering only the first 60 min of the extraction,
where the effect of the initial part of the kinetic curve
is stronger. A diffusion coefficient decreasing with time
is to be expected if it is attributed to the asymmetric
(extended to the right) experimental PSD.
The correspondence between the calculated (accord-
ing to Eq. 1) and the experimental solid phase extraction
curve is shown in Fig. 5. The observed deviation is due
to the fact that the simplified model fails to describe the
very different parts of the kinetic curve. The experimen-
tal data is based on the maximum extractable quantity
of total polyphenols (17.5 mg/(g solid) [19]), while the
final concentration in the solid (Cequil) is calculated
according to the mass balance for a solid/liquid ratio of
1:15. The same figure shows the kinetic curve calculated
(R² = 0.932) by the power model (Eq.9). The intercept
is set equal to the experimentally observed value of 17.5
mg/g solid. The obtained value of n = 0.433 corresponds
Fig. 3. Liquid phase kinetic curve for Sideritis calculated by
the model accounting for PSD [19] (solid/liquid ratio 1:15;
C t =0
=17.5 mg/g solid [17]; Ce (Cl final) = 116.7 mg/ml).
495
 Journal of Chemical Technology and Metallurgy, 51, 5, 2016

Fig. 4. Plot of experimental data for Sideritis [19] in ac- Fig. 6. Propolis: Extracted polyphenols vs liquid/solid ratio.
cordance with Eq.(2).

Fig. 5. Experimental and calculated solid phase kinetic data Fig. 7. Propolis: Experimental and calculated particle size
for Sideritis in accordance with Eq. 1 and the power model. evolution.

to the theoretical one expected for Fick’s type diffusion follows its evolution in correspondence with Eq. (15.6)
in spherical geometry. In general, the power law model where the solid density ρs is equal to1180 kg/m3 [23].
applied to extraction from vegetal material reports a The initial solid phase concentration is set equal to the
wide range of values for the diffusion exponent less maximum extractable quantity of polyphenols. The latter
than 1 (n < 1) [8, 15]. is defined on the ground of the plateau in Fig. 6 where
B. Particle size evolution (Rj=f(t)): Example with experimental data for extracted polyphenols
polyphenols extraction from Propolis
Vl ⋅ C l
The particle size evolution observed in ethanolic (M = ) is plotted versus the liquid/solid ratio
extraction from Propolis [23] is another effect related Ms
to polydispersity Mass transfer of Propolis constitu- (LSR).
ents [23, 29] is not thoroughly studied despite the great The dependence in Fig. 6 is treated as a nonlinear
interest to its bioactivity and the appropriate extraction function of the type:
technique [30-34] as well as the solvent effect [35] - 1
⋅ SLR
ethanol, water, nonethanolic mixture [36]. The results M= A
B
reported in ref. [23] confirm that partial dissolution of 1 + SLR
A
the solid matrix proceeds in parallel with the solid-liquid which is linearized in coordinates 1/M vs 1/LSR
extraction.
1 1
The mathematical description of the process is given ( =A + B ).
M SLR
by Eqs.(15): 1, 2, 3a, 4a, 6, 7 in Table 1. The solution
starts with the mean particle size of the initial PSD and The value of 1/B corresponds to the plateau of the

496
 Iren Tsibranska, Bartosz Tylkowski
Fig. 8. Experimental and calculated kinetic curves referring
to polyphenols extraction from Propolis.
initial curve in Fig.6, i.e. the maximum extractable mass
of polyphenols per gram solid. This value is estimated
equal to 680 mg/g (R2 = 0.89) and is also checked by
the experimental observation that extracted polyphenols
constitute 67.6 % of the solid substances dissolved [23].
The comparison between the experimental data
and that calculated by the model particle size evolution
(Eq.15 in Table 1) and extraction kinetic curves is illus-
trated in Figs. 7 and 8 for liquid/solid ratio of 19.8. The
whole soluble part of the solid is practically dissolved
in view of the previous experimental observations at a
liquid-solid ratio of 20 (ml g-1). The experimental kinetic
curves in Figs. 7 and 8 are successfully fitted by the
model solved for an effective intra-particle diffusion
coefficient of 1⋅10-13 m2 s-1. The initial value of the
external mass transfer coefficient in these calculations
is 1.4⋅10-6 m s-1 (Bi = 440) which is in agreement with
previous experimental observation [23] of the effective
mass transfer coefficient being of the order of 10–6 m s-1.
This coefficient is recalculated following the change of
the particle size according to Eq. (15.7).
CONCLUSIONS
The present study reports the mathematical de-
scription of solid-liquid extraction curves taking into
account the presence of polydisperse particles. The
results obtained are illustrated by two experimental batch
extraction systems where extraction of polyphenols by
an ethanolic solvent is carried out (Sideritis ssp. L and
Propolis). Broad and asymmetric dispersion of particles
of a different shape (cylinders, plates) is observed in
the first case as a result from milling the whole aerial
part of the plant. The course of the kinetic curve is sat-
isfactorily described as one-step diffusion controlled
mass transfer with a constant diffusion coefficient by a
model accounting for the polydispersity. In the second
case of predominantly spherical particles of less PSD
asymmetry the kinetics of extraction and particle size
evolution are successfully modeled on the ground of the
mean average size of PSD. The latter is regarded as time
varying because partial dissolution of the solid matrix
proceeds. The application of the simplified empirical
models in case of polydispersity and/or time evolution
of the solid particles may lead to unrealistic values of
the intra-particle mass transfer coefficient as evidenced
by the two systems studied. Models of better theoretical
grounds have greater potential in such cases in view of
the physical meaning, the predictive capabilities and
applicability to process optimization.
References
1. Ch.-H. Chan, R. Yusoff, G.-Ch. Ngoh, Modeling and
kinetics study of conventional and assisted batch
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