Green Process Synth 2018; 7: 68–73

Evgeni Simeonov, Zvezdelina Yaneva* and Chavdar Chilev

Kinetics of green solid-liquid extraction of

useful compounds from plant materials: kinetics
coefficients and modeling
DOI 10.1515/gps-2016-0179 possibility to extract maximum valuable compounds in
Received November 9, 2016; accepted February 19, 2017; previously short time is of significant interest for the practice.
published online March 30, 2017 In scientific literature, the processes of solid-liquid
extraction of biologically active substances from various
Abstract: A mathematical model for modeling solid-liquid
natural materials are described and simulated by several
extraction from plants was developed. Two extraction
mathematical models. Some of the extensively applied
systems, System I Nicotiana tabacum L.-water and System
theoretical models: of Crank [13], the film theory and
II Geranium sanguineum L.-water, were investigated. The
unsteady state diffusion model [14], are derived from
effect of agitation rate on the mode of the extraction pro-
Fick’s second law of diffusion [6, 15]. Model equations that
cess was studied, as the limit values in the case of inter-
are based on a second-order rate law are used for the mod-
nal diffusion for System I and System II were determined.
eling of conventional and nonconventional extraction
The kinetics of extraction for both systems at determined
processes [16]. Commonly applied empirical models were
technological parameters (temperature and solid/liquid
proposed also by So and Macdonald, Patricelli, Peleg,
ratio) was experimentally investigated. The values of the
Perez and applied for modeling of rapeseed extraction, oil
partial mass transfer coefficient, k, were determined by
extraction and wild sunflower extraction, respectively [17,
the Regular regime method. A four-parameter empirical
18]. The kinetics equations of Ponomaryov and a model
model for prediction of the effective diffusivity, Deff, was
based on nonstationary diffusion through the plant mate-
also presented. The model adequacy is verified with the
rial were applied for describing the kinetics of total extrac-
experimental data and shows very good coincidence.
tives and inositol hexaphosphate from sesame seeds [19].
Keywords: diffusion coefficient; kinetics; modeling; plant Resinoid extraction from Hypericum perforatum L. aerial
material; solid-liquid extraction. parts was successfully modeled by the parabolic diffu-
sion model, power law model, Weibull’s and Elovich’s
equations [20]. The effect of particle size and solid-liquid

1 Introduction ratio on the kinetics of green solid-liquid extraction of

andrographolide from Andrographispaniculata (AP) were
investigated. The second-order rate law showed a better
Solid-liquid extraction is a process which gives products
agreement with the experimental data. It was established
that are widely used in the pharmaceutical, cosmetics,
that the extraction rate coefficient significantly increased
tobacco, and food industries and also applied for envi-
with a decrease in particle size and an increase in solid-
ronmental purposes. The latter provoked numerous scien-
liquid ratio [21]. So and Macdonald’s model was suitable
tific studies focused on the process kinetics [1–3], yield of
to describe the kinetics of the three stages (fast initial
extraction [2, 4–7], and process design [8, 9].
washing period, fast diffusion, and slow diffusion) of
The mathematical modeling is a powerful tool for
caffeine and total catechins extraction from green tea at
equipment optimization, simulation, design, and control
different pressures [17]. Two mathematical models were
allowing theoretical description of the process and eval-
developed by Winitsorn et al. [22] for solid-liquid extrac-
uation of the mass transfer coefficients [3, 10–12]. The
tion from tamarind seed coat and green tea. When com-
paring results of neglecting and considering external
*Corresponding author: Zvezdelina Yaneva, Chemistry Unit, mass transfer resistance, both models displayed satisfac-
Department of Pharmacology, Animal Physiology and Physiological tory applicability for prediction of the extraction yield.
Chemistry,Trakia University, Students Campus, 6000 Stara Zagora,
In order to set up an experimental installation the dif-
Bulgaria, e-mail: z.yaneva@abv.bg
Evgeni Simeonov and Chavdar Chilev: Department of Chemical
fusion type and the factors that are of main importance
Engineering, University of Chemical Technology and Metallurgy, for the process have to be known. There are three different
8 Kl. Ohridski, 1756 Sofia, Bulgaria approaches for that purpose: analytical solution for the

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 E. Simeonov et al.: Kinetics of green solid-liquid extraction from plant materials      69

three classic shapes of the solid phase, numerical solu- extraction, the samples were taken and filtrated through plaited filter
tions based on simplifications, and experimental data to separate the solid from the liquid phase.

description applying the method of standard or character-

istic functions [9, 23].
2.3 Analytical methods for the extraction analysis
The extraction of valuable components from plant
raw material is almost ever limited by the mass transfer
A weighing method with a precision of 10−3 g was applied for the
inside the pores of the solid phase. Each experimental
quantitative determination of tobacco concrete and extractive com-
kinetic curve (dependence) represents in a hidden way pounds. The extracts were evaporated in a drying oven at t = 70°C.
all the factors influencing the diffusion process veloc-
ity like: polydispersion, anisotropy, solid particles form,
and liquid phase concentration change. These factors are
given quantitatively by the effective diffusion coefficient 3 K
 inetics study, diffusion
(Deff ) [3, 12, 23].
Such a kinetic curve can be represented by an equa-
­coefficients, and modeling
tion of the type:
3.1 Diffusion model
C1 = A − B ⋅ e( − H⋅τ ) , (1)

The extraction from the solid phase can be described with

where A, B, and H are constants determined numerically
a mathematical model of the type:
on the basis of the experimental data that have specific
physical meaning, compared with the analytical solutions ∂ C2  ∂ 2 C t ∂C2 
= Deff  22 + (2)
of the process of solid phase extraction [12]. Quantitatively, ∂τ  ∂x x ∂x 
these factors are reported by the effective diffusion coeffi- 
cient (Deff ). The exact calculation of Deff is important for the
with boundary conditions:
process engineering. The combination of the experimen-
tal and process analytical data is used for the calculation  ∂C   C2 
of Deff using the method of Regular regime [12, 23]. − Deff  2  = k  x = x − C1  (3)
 ∂x  x = x  m 
The aim of this work is to study experimentally the 
effect of agitation rate on the diffusion mode during the
extraction of valuable target components from plant raw  ∂ C2 
materials, as well as to determine the values of the kinet-  ∂x  = 0 (4)
  x =0
ics coefficients (effective diffusivity, Deff and partial mass 
transfer coefficient, k) by the Regular regime method. C2,τ=0 = C0 (5)

where m is the distribution coefficient, m ≈ 1 because of

2 Materials and methods the low concentration range (well-known fact in literature
for the investigated plant material).
The general analytical solution has the form:
2.1 Plant materials
C0 − C2
Experiments were carried out with two important to practice plant =
C0 − Cm
materials. System I Nicotianatabacum L.-water and System II Gera-
Deff τ
1 ∞
4.( υ + 1)
2
nium sanguineum L.-water for obtaining extractive substances. − µn
−∑ 2 ⋅ exp R2
, (6)
1 + β n=1 µn + 4( υ + 1) ⋅ β(1 + β)
2

2.2 Extraction design
The kinetic experiments were performed in a stirred vessel. The
ground raw material with suitable size was placed in the reactor and
poured on with H2O. The reactor was immersed in a water bath and
the temperature was maintained constant, controlled by a thermom-
eter. The mixture was continuously stirred. To ensure limiting inter-
nal diffusion the angular velocity of the mixer was regulated. After

where C0 is the initial concentration in the solid phase;
Cm = C1i by periodical processes; C1i is the initial concentra-
tion in the liquid phase; C2 is the average concentration
in the solid phase; Deff is the effective diffusion coefficient
in the pores of the solid phase; R is the size of the solid
C1eq
particles; τ is the time; β = ; C is the equilibrium
C0 − C1eq 1eq

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70      E. Simeonov et al.: Kinetics of green solid-liquid extraction from plant materials

concentration in the liquid phase; μn is the roots of the Table 1: Boundary values of the parameters for a plate and sphere.
characteristic equation; and ν is the shape factor for the
solid phase.   β  ≈ 0   Bi → ∞ , β ≈ 0
   
Sphere   Plate Sphere   Plate

μ1   µ   µ   π   π/2
tg µ = cot g µ =
1 − Bi Bi
3.2 M
 ethod using Regular regime
B1   6Bi2   2Bi2   6/π2   8/π2
The Regular regime is a method for determination of Deff µ ( µ − Bi + Bi2 )
2 2
µ ( µ + Bi + Bi2 )
2 2

based on the combination between the analytical solu-

tions of Eq. (1) and the experimentally obtained C2 = f ( τ )
F0       0.1   0.264
for the boundary case Bi → ∞ , β → 0 [20]. This method is
based on a comparison between the experimental
obtained data, for a nonconstant mass transfer from the 15
solid into the liquid phase, with the analytical solutions
at the same conditions of mass transfer. It is known that
at the beginning of this regime Deff = const and for Eq. (6)
for plate and sphere shape of the solid phase by τ = 0, 10
C2 = C0 = const, Cli = 0, we can obtain:
C1 (kg·m–3)
–– plate
2
C2 ∞ 8
π
− (2 n−1)2 F0 5
=∑ 2 e 4
, (7)
C0 n=1 π (2n − 1)2


–– sphere 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
_ n (s–1)
D τ
C2 ∞ 6 − π 2 n 2 eff

(8)
=∑ e R2
,
C0 n=1 π2n2 Figure 1: Dependence of tobacco concrete liquid phase concentra-
 tion on the agitation rate at t = 20°C; ζ = 0.04 m3/kg and solvent
water.
where C1 is the concentration in the liquid phase; C1i is the
D
initial concentration in the liquid phase; F0 = eff2⋅τ is the
R
Fourier number. 4 Results and discussion
With the increase of Fo (and respectively τ) the conver-
gence of Eq. (6) becomes fast growing and can practically
4.1 Kinetics study
be limited to the first member. Equation (6) is rearranged
in the form:
4.1.1 Effect of agitation rate on the rate limiting stage of
the extraction process
C0 − C2 1 − µ2 F
= − B1e 1 0 (9)
C0 − Cm 1 + β Series of experiments with both studied systems at

various agitation rates, extraction temperature t = 20°C
and solvent-water, were conducted.
or [20, 21]:
System I Nicotiana tabacum L. leaves-water: Five
experiments at agitation rates n = 1, 1.5, 2, 3; and 4/s, solid/
 1 C −C  D τ
lg  − 0 2  = lg B1 − 0.434 µ12 eff2 (10) liquid ratio ξ = 0.04  m3/kg and extraction time τ = 900  s
 1 + β C0
− Cm
R were conducted. The derived relationship between the

concentration of the tobacco concrete in the liquid phase
For the investigated system, the limit values of the para- and the agitation rate is graphically displayed in Figure 1.
meters at intraparticle diffusion, for a plate and sphere, System II Geranium sanguineum L. roots-water: Figure 2
are presented in Table 1. presents the dependence of the liquid phase concentration

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 E. Simeonov et al.: Kinetics of green solid-liquid extraction from plant materials      71

of the extractable components on the agitation rate. The

7
plot was obtained by the data from five experiments con-
ducted at agitation rates n = 0.5, 1, 1.5, 2, and 4/s, solid/ 6
liquid ratio ξ = 0.03 m3/kg and extraction time τ =  3600 s.
5
The plots on Figures 1 and 2 displayed that at agita-

C1 (kg·m–3)
tion rates n > 1.5–2 s−1, the process was limited by external 4
diffusion, i.e. the liquid concentration of the extract-
3
able components remains constant at these conditions.
Consequently, the external mass transfer resistance was 2
eliminated.
1

0
4.1.2 Kinetics of periodical batch extraction 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
n (s–1)

The kinetics of periodical batch extraction from the plant Figure 2: Dependence of Geranium sanguineum L. liquid phase
raw materials – tobacco (Nicotiana tabacum L.) and red concentration on the agitation rate at t = 20°C; ζ = 0.03 m3/kg and
geranium (Geranium sanguineum L.) in a stirred tank was solvent water.

investigated at the following working conditions:

Table 2: Values of the constants A, B, and H in Eq. (1).
–– for extraction from tobacco leaves – extraction tem-
perature t = 20°C, solvent water, solid/liquid ratio Plant raw material Working conditions A B H × 103
ξ = 0.05 m3/kg and agitation rate n = 3 s−1;
Tobacco leaves t = 20°C; solvent – water; 6.443 6.234 0.549
–– for extraction from red geranium roots – extraction
ξ = 0.05 m3/kg; n = 4 s − 1
temperature t = 20°C, solvent water, solid/liquid ratio Red geranium roots t = 20°C; solvent – water; 3.883 3.705 0.254
ξ = 0.04 m3/kg and agitation rate n = 4 s−1. ξ = 0.04 m3/kg; n = 3 s − 1

The kinetics at constant technological parameters

(solvent, solid/liquid ratio, and temperature) could be
described by an equation of type (1), where A, B, and H
are constants determined numerically on the basis of the
experimental data. The values of these constants are pre-
sented in Table 2.
The experimental kinetic curves are presented in
Figure 3 for System I and in Figure 4 for System II.

4.2 N
 umerical solution and determination of
the diffusion coefficients by the Regular
regime method
The programming environment Matlab 8.0.1 was used for
modeling of the obtained experimental data. For accurate
modeling of an extraction process, the effective diffusiv-
Figure 3: Dependence of concentration on time at t = 20°C;
ity, in the equation describing solid phase mass transfer,
ζ = 0.05 m3/kg and solvent water for System I.
has to be approximated with an appropriate function
dependent on time.
The results in the present study were obtained by A four-parameter model for the effective diffusivity was
applying Eq. (10) and the solid phase form was accounted: suggested:
–– for tobacco leaves – R = 0.75 × 10−3 m; B1 = 8/π2; μ1 = π/2;
Deff = a ⋅ e bτ + c ⋅ e dτ (11)
ρs = 930 kg/m3; ε = 0.7 m3/m3;
–– for red geranium roots – R = 0.5 × 10−3 m; B1 = 6/π2; The parameters there in can be determined by linear
μ1 = π; ρs = 1100 kg/m3; ε = 0.4 m3/m3. regression of the experimental data.

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72      E. Simeonov et al.: Kinetics of green solid-liquid extraction from plant materials

×10–10
3.5
Exp.
3 Model

2.5

Deff (m2·s–1)
1.5

0.5

–0.5
0 1000 2000 3000 4000 5000 6000 7000 8000
τ (s)
Figure 4: Dependence of concentration on time at t = 20°C;
Figure 6: Experimental data and model curve of Deff for System II at
ζ = 0.04 m3/kg and solvent water for System II.
t = 20°C and ξ = 0.04 m3/kg.

×10–9
3.5 Table 3: Values of the constants A, B, H, Bi number, and the partial
Exp. mass transfer coefficient k.
Model
3
System N A B H  × 103 Bi k × 106
2.5
s−1 – – – – m/s
Tobacco-water 3 6.443 6.324 0.549 61.63 1.796
Deff (m2·s–1)

2
Geranium-water 4 3.883 3.705 0.254 72.31 0.192

1.5

1 transfer coefficient k. This coefficient mainly depends on

0.5
0
0 1000 2000 3000 4000
τ (s)
Figure 5: Experimental data and model curve of Deff for System I at
t = 20°C and ξ = 0.05 m3/kg.
The applicability of the model was analyzed based
on the experimental data and model plots presented in
Figures 5 and 6 for System I and System II, respectively.
The results obtained display that the value of Deff
decreases with time to a final value. The authors suppose
that the reduction observed is related to the fact that with
the progress of the process, extraction of the substance
from pores that were previously unavailable or too hard
to be reached, takes place. These are usually micropo-
res, in which the mass transfer is limited and the general
mass transfer as a whole decreases, i.e. the value of Deff
decreases. The intensity of the mass transfer in the bound-
ary layer around the particle depends on the partial mass
the nature of the solvent and the extractable component
and its value is in the range of 10−6–10−4 m/s. Depending
on the values of k and the effective diffusivity (respectively
5000 6000 Biot number) the rate limiting stage – external or intra-
particle diffusion, could be determined. The values of the
partial mass transfer coefficient, k, were derived by the
Regular regime method and presented in Table 3 for both
studied systems.
The values of the constants A, B, and H are obtained
at time τ = 900  s for the system tobacco-water and at
τ = 3600 s for the system geranium-water.
5 Conclusions
The kinetics of extraction of valuable target compounds
from tobacco leaves (Nicotiana tabacum L.) and red gera-
nium roots (Geranium sanguineum L.) with solvent water
at periodic conditions in a batch mode was experimentally
investigated. The effect of agitation rate on the regime of
the extraction process was determined by means of the
calculated Biot number Bi 61.63 for System I and Bi 72.31

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 E. Simeonov et al.: Kinetics of green solid-liquid extraction from plant materials      73

for System II. The experimentally obtained kinetics data [22] Winitsorn A, Douglas PL, Douglas S, Pongampai S, Teppaitoon
were presented by the Regular regime method for both W. Chem. Eng. Commun. 2008, 195, 1457–1464.
[23] Axelrood GA, Lisjanski W. Extraction (Solid-Liquid Systems)
studied systems. The partial mass transfer coefficients:
Chimia, St. Petersburg, USSR, 1974.
k = 1.796 × 10−6 m/s for System I, and k = 0.192 × 10−6 m/s for
System II, were calculated. An empirical four-parameter
model for variable effective diffusivity, Deff, was suggested.
The empirical solutions that were obtained in the recent Bionotes
study display its satisfactory applicability to the experi-
mental kinetics data of extraction of valuable target com- Evgeni Simeonov
pounds from plant raw materials.

Acknowledgments: The authors would like to thank the

Science & Research Programme of the UCTM (Sofia) for
the financial support (project 11 574).
Evgeni Simeonov has been a lecturer and a researcher at the Depart-
ment of Chemical Engineering, University of Chemical Technology
and Metallurgy, Sofia, Bulgaria since 1989. His scientific interests
References are: heat/mass transfer processes, design of heat/mass transfer
equipment, mathematical modeling, nanofiltration. He is an author
of three textbooks, over 60 scientific publications and 200 citations,
[1] Wongkittipong R, Prat L, Damroglerd S, Gourdon C. Separ.
and has participated in international university/research exchanges
Purif. Technol. 2004, 40, 147–154.
at universities in Germany, France, and England.
[2] Bucić-Kojić A, Planinića M, Tomasa M, Bilića M, Velića D. J. Food
Eng. 2007, 81, 236–242.
Zvezdelina Yaneva
[3] Simeonov E, Tsibranska I, Minchev A. Chem. Eng. J. 1999, 73,
255–259.
[4] Pinelo M, Sineiro J, Núñez MJ. J. Food Eng. 2006, 77, 57–63.
[5] Seikova I, Simeonov E, Ivanova E. J. Food Eng. 2004, 61, 165–171.
[6] Cacace JE, Mazza G. J. Food Eng. 2003, 59, 379–389.
[7] Mantell C, Rodríguez M, Martínez de la Ossa E. Chem. Eng. Sci.
2002, 57, 3831–3838.
[8] Simeonov E, Nedialcova J. J. UCTM 2006, 41, 445–448.
[9] Simeonov E, Seikova I, Pentchev I, Mintchev A. Ind. Eng. Chem.
Zvezdelina Yaneva works at Chemistry Unit, Department of Phar-
Res. 2004, 43, 4903–4907.
macology, Animal Physiology and Physiological Chemistry, Faculty
[10] Hou K, Zheng Q, Li Y, Shen J, Hu S. Comput. Chem. Eng. 2000,
of Veterinary Medicine, Trakia University, Stara Zagora, Bulgaria.
24, 1343–1348.
Her current research interests are focused on sorption phenomena,
[11] Meireles A. Extracting Bioactive Compounds For Food Products:
organic synthesis and UV/VIS, HPLC analyses of biologically active
Theory and Applications, CRC Press, Taylor & Francis Group:
organic substances, FTIR analyses, mathematical modeling of mass
Boca Raton, FL, 2009.
transfer processes, and wastewater treatment. She has over 50
[12] Chilev Ch, Koleva V, Simeonov E. Ind. Eng. Chem. Res. 2014, 53,
publications and 130 citations to her credit.
6288–6296.
[13] Petrovic SS, Ivanovic J, Milovanovic S, Zizovic I. J. Serb. Chem.
Chavdar Chilev
Soc. 2012, 77, 799–813.
[14] Velickovic DT, Milenovic DM, Ristic MS,Veljkovic VB. Ultrason.
Sonochem. 2006, 13, 150–156.
[15] Martinez-Vera C, Ruiz-Martinez RS, Vizcarra-Mendoza MG,
Álvarez-Calderón J. J. Food Eng. 2010, 101, 16–22.
[16] Pan Z, Qu W, MaH, Atungulu GG, Mchugh TH. Ultrason. Sono-
chem. 2012, 19, 365–372.
[17] Xi J, Yan L, He L. Sep. Purif. Technol. 2014, 133, 155–159.
[18] Fernandez MB, Perez E, Crapiste GH, Nolasco SM. J. Food Eng. Chavdar Chilev works at the Department of Chemical Engineering,
2012, 111, 682–689. University of Chemical Technology and Metallurgy, Sofia, Bulgaria.
[19] Zdravković A, Nikolić V, Ilić-Stojanović S, Stanojević L, Savić I. His research interests are in the field of biomass valorization
Adv. Technol. 2012, 1, 48–57. process, nanotechnology, high pressure adsorption, separation
[20] Kitanovic S, Milenovic D, Veljkovic VB. Biochem. Eng. J. 2008, technology, distillation, solid-liquid/liquid-liquid extraction, sepa-
41, 1–11. ration, and purification of gas mixtures. He is skilled in a number of
[21] Abubakar UI, Chua LS, Aziz R. Green Process. Synth. 2015, 4, spectrophotometry and chromatography analytical methods (AAS,
399–410. ICP-AAS, GTA, VGA, UV/VIS).

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