Comparison Between 2 Methods of Solid–Liquid

Extraction for the Production of Cinchona

calisaya Elixir: An Experimental Kinetics
and Numerical Modeling Approach
Daniele Naviglio, Andrea Formato, and Monica Gallo

Abstract: The purpose of this study is to compare the extraction process for the production of China elixir starting from
the same vegetable mixture, as performed by conventional maceration or a cyclically pressurized extraction process (rapid
solid–liquid dynamic extraction) using the Naviglio Extractor. Dry residue was used as a marker for the kinetics of the
extraction process because it was proportional to the amount of active principles extracted and, therefore, to their total
E: Food Engineering &
Physical Properties

concentration in the solution. UV spectra of the hydroalcoholic extracts allowed for the identification of the predominant
chemical species in the extracts, while the organoleptic tests carried out on the final product provided an indication of
the acceptance of the beverage and highlighted features that were not detectable by instrumental analytical techniques.
In addition, a numerical simulation of the process has been performed, obtaining useful information about the timing of
the process (time history) as well as its mathematical description.

Keywords: Cinchona calisaya, elixir, Naviglio extractor, numerical simulation, RSLDE

Practical Application: Compared to a conventional method, the rapid solid–liquid dynamic extractor allowed for
extraction at room temperature using a cyclic pressurization of the extracting liquid above a solid matrix to facilitate
extraction. In this way, it was possible to avoid a thermal stress load of thermolabile substances while simultaneously
reducing the extraction time. In addition, the numerical simulation of the process made it possible to obtain useful
information about the kinetics of the same process and its mathematical description. The results obtained, as well as laying
a scientific foundation for rapid solid–liquid extraction, provide clarification of the model; therefore, applications of the
model can be extended to various types of vegetable matrices.

Introduction
Elixirs and bitters are currently produced by strictly following
traditional recipes, whose origins have been lost over time. In most
cases, these recipes are secret, or the preparation or extraction pro-
cess has a magical component (Tonutti and Liddle 2010). Room
temperature maceration in ethanol is a very ancient technique to
extract active principles from medicinal plants; it is still used today
because it is simple to perform and uses inexpensive materials:
it requires only a closable container (macerator) constituted of a
material (glass or stainless steel) that is inert with respect to the
extractant. The extractive process of maceration is mainly based
on the diffusion of solute molecules from the surface of a solid
matrix (vegetables) surrounded by an adequate volume of extract-
ing liquid. Two ways to improve the process kinetics exist: (1)
increase the temperature as a means to increase the diffusivity of
compounds in the solvent liquid and (2) agitate the mixture so
a mass convection phenomenon becomes more important than
MS 20140407 Submitted 3/11/2014, Accepted 6/16/2014. Author Naviglio is
with Dept. of Chemical Sciences, Univ. of Naples Federico II, via Cintia 21, 80126
Naples, Italy. Author Formato is with Dept. of Agricultural Science, Univ. of Naples
Federico II, via Università, 100; 80055 Portici (Naples), Italy. Author Gallo is with
Dept. of Molecular Medicine and Medical Biotechnology, Univ. of Naples Federico
II, via Pansini, 5, 80131 Naples, Italy. Direct inquiries to author Daniele Naviglio
(E-mail: naviglio@unina.it).
diffusion to transfer molecules from the solid phase to the sol-
vent liquid. This technique allows the internal mass transfer to
become the limiting process. Such an effective diffusion process
depends on many parameters, for example, the total surface of a
solid (granulometry) or the degree of dryness of the vegetables,
also goes to completion very slowly (Naviglio 2003). Maceration
and extraction depend mainly on the diffusion of compounds from
the solid matrix into the extracting liquid and on an unpredictable
transformation that can occur in a microsystem generated at the
surface and in the natural cavities of the vegetable matrix (Cissé
and others 2012). However, the rapid solid–liquid dynamic extrac-
tor (RSLDE) performs a dynamic extraction at room temperature,
using the pressurization of the extracting liquid on the solid ma-
trix to facilitate extraction. The importance of low-temperature
extraction is that the thermal stress of thermolabile substances is
avoided. It is therefore possible to reproduce the composition of
the substances in medicinal plants without changing the load of
the active ingredients, which are usually the compounds more
“sensitive” to extract, as they are affected by temperature effects.
The Cinchona or China calisaya is a tree-like plant of the genus
Cinchona and is widespread in the Andes and known originally for
its use in pharmacopoeia because of the alkaloids present in the
bark. C. calisaya bark is known as Peruvian bark and was used until
the early decades of the twentieth century for the extraction of
quinine, a substance used for the prevention of malaria. With the

C 2014 Institute of Food Technologists

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E1704 Journal of Food Science r Vol. 79, Nr. 9, 2014 doi: 10.1111/1750-3841.12563
Further reproduction without permission is prohibited
Production of Cinchona calisaya elixir . . .

gradual disappearance of the disease from Europe, the China elixir
lost its medicinal status and became, in modern times, a simple
bitter digestive aid. This elixir is typically prepared with a mixture
of alcoholic extracts of C. calisaya bark sweetened with an aqueous
sugar solution (syrup) and flavorings (bitter orange and others). In
the literature, there are no articles of scientific importance about
the elixir’s production process, and this is certainly due to the com-
plexity of the solid matrix, the long extraction time and because
the maceration extraction process is difficult to control, making
precise repetition problematic. In this paper, 2 extractive methods
for the production of China elixir were compared: maceration and
cyclically pressurized solid–liquid extraction. Dry residue present
after evaporation was taken as an indicator of the efficiency of the
extractive process because it was directly linked to the amount of
active principles extracted. In general, higher values of the dry
eration of solid–liquid extraction by means of a programmable
pressurization cycle of the liquid in contact with the solid be-
tween atmospheric pressure and 8–9 bar (Naviglio 2003; Naviglio
and others 2009). The Naviglio Extractor R
mod. 500 cc was used
in these experiments; it has 2 extraction chambers, each consisting
of a stainless-steel cylinder with a piston. On the bottom of the
chambers, the liquid phase is introduced through 2 porous plugs,
while the solid phase is blocked. The 2 extractive chambers are
connected with a pipe that includes a solenoid valve. The solenoid
valve is closed during the extraction process and opens at the end
of the cycle to let out the liquid from the system. The maximum
value of the pressure programmed is maintained constant for a
preset time (static phase). Then, the pressurized air is rapidly evac-
uated, disrupting the equilibrium of the pistons, which causes a
negative pressure gradient between the inside and outside of the

E: Food Engineering &

residue after evaporation will generate higher concentrations of solid matrix (dynamic phase). At this stage, the compounds that are

the active principles present in the extract. An organoleptic test
of final products was used to calibrate the timing of the extraction
process.
Materials and Methods
Samples and chemical analysis
A comparison was made between china elixir obtained by a
traditional maceration process in alcohol (T) and that obtained
with an extraction process in alcohol by applying cyclical pres-
surization to the extracting liquid (I) using a dynamic extractor.
The RSLDE (Naviglio Extractor R
; Atlas Filtri Engineering srl,
Padua, Italy; Figure 1) is an apparatus that allows for the accel-
Physical Properties
not bonded chemically to the solid matrix are physically extracted
and transferred into the solvent. The pressure changes cyclically
and rapidly between 0 (atmospheric pressure) and 9 bar (Naviglio
2003).
Experimental tests
Solid matrix samples were chopped spheroidally and placed in
the extraction chamber in a food-grade polyethylene bag with a
porosity of 1 mm. The chamber was filled with a hydroalcoholic
solution (40% v/v). After the extraction chamber was loaded, the
pressure was increased to approximately 9 bar. The operating pa-
rameters for the extraction procedure were then set. The operating
parameters consisted of the number of total cycles (150), the total
duration of the extraction process (10 h), the number of shots in
the swing phase (12), the duration of the static phase (2 min),
and the duration of the dynamic phase (2 min). At the end of
the process, measurements were carried out to compare the results
obtained with the RSLDE process and the traditional method (T;
classic maceration). The sample composition of the vanilla China
mixture was as follows: China 85 g, Bitter Orange 8 g, vanilla pod
7 g. The total weight was 100 g.
To carry out traditional maceration (T), 5 100-g aliquots of the
china vanilla mixture were placed into 5 closable glass containers
to which 550 mL of 40% ethyl alcohol (v/v) were added and
macerated without stirring for 3, 7, 14, 21, and 28 d. To carry
out the cyclically pressurized extraction process (I), portions of
the china vanilla mixture were subjected to a cyclically pressurized
extraction process by Naviglio Extractor mod. 500 cc.
The following equipment was also used: a stove (EU-77 L,
obtained from Thermo Electron Corp., Waltham, Mass., U.S.A.),
an analytical balance (Mettler Toledo, Switzerland), a UV-VIS
spectrophotometer, mod. UV 1601 (Shimadzu, Tokyo, Japan),
and quartz cuvettes with an optical path of 1.00 cm.
The measurement of the absorption spectrum of the alcoholic
extracts was performed over a wavelength range of 200 to 600
nm. The alcoholic extract was opportunely diluted before mea-
surement.

Procedure for determining particle dimensions

The length, width, and thickness of China root particles were
measured with a digital calliper. The sphericity and geometric
mean diameter of the solid matrix of the China root particles were
determined (Jain and Bal 1997) from these values, which were then
used in the numerical simulations. China root solid matrix (100 g)
samples were weighed on scales with 0.01-g accuracy (Gibertini
Figure 1–The laboratory model (500 cc) of rapid solid–liquid dynamic Europe 1700).
extractor (RSLDE).

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 Production of Cinchona calisaya elixir . . .

Procedure for determining the initial volume Sensory analysis

In order to evaluate volume without changing the moisture
content, the solid matrix of China root particle samples was sealed
under vacuum within a plastic material (food-grade polyethylene)
that perfectly adhered to the solid matrix, then the initial total
volume (Vpt ) was measured by immersion in 200 mL of water in
a 500-mL graduated cylinder.
The predetermined volume of the mass accessory (Va ) was de-
ducted from the total initial volume (Vpt ), resulting in the sample
volume (Vp ): Vp = (Vpt − Va ).
Procedure to determine the dry residue (M) of the alcohol
extract at 105 °C
Exactly 10 mL of prefiltered alcoholic extract were carefully
E: Food Engineering &
The sensory analysis of the China elixir obtained was performed
in collaboration with the sensory laboratory Polcaro Phytoprepa-
rations (Roccarainola, Naples, Italy). Eighteen people who con-
sumed China elixir regularly were selected for the test: 9 men and
9 women between the ages of 24 and 62 y. During the assessment
phase, three 5 cc China elixir product samples were presented to
each tester. The samples, which had been previously encoded with
3-digit numerical codes, were served anonymously and randomly.
A 2nd sensory analysis was carried out according to a hedonic
method in order to verify whether the product that had been pro-
cessed with RSLDE (I) was more pleasant than the one that had
been processed traditionally (T). Six China elixir product sam-
ples were considered using a MasterCard table. Each sample had
its own identification number, and results were analyzed using a

statistical analysis program. Tasters were asked to try the samples

Physical Properties

transferred into a calibrated porcelain dish and evaporated to dry-

ness in an oven at 50 °C. When the volume of the liquid had and judge the pleasantness of the product on 1-to-9 scale. Both
become negligible, the temperature was raised to 105 °C. Then, tests used samples from boxes that had been processed on the same
the capsule was transferred to a desiccator, incubated until ambi- day from the same batch of raw materials (Meilgaard and others
ent temperature was reached, and then weighed on an analytical 1999).
balance. This operation was repeated until a constant weight was
reached. Finally, the dry weight was calculated as the difference Analytical approach
between the sample and the tare. Each determination was repeated The process should follow Fick’s 2nd law of diffusion during
3 times, and the average result was reported. a diffusion process carried out at a constant temperature. Fick’s
The amount of extracted Me was calculated from the following 3-dimensional equation for an axisymmetric diffusion is as follows:
relationship: Mt = Ms + Me , where
 2 
∂M ∂ M ∂2 M ∂2 M
M (t) = mass extracted at time t =D + + (1)
∂t ∂ x2 ∂ y2 ∂z2
Me = mass extracted final
Mi = initial mass extracted (initial phase after 0.001 s) where M is the instantaneous concentration of the solute extract
and Ms = dry mass. from the solid matrix at a specified time t and D is the diffusion
coefficient. The solution of the equation above for an object with
The quantity M changes during the extraction process and a spherical shape with radius r was presented by Crank (1975) as:
therefore changes the ratios of M/Mt and M/Ms . After deter-   ∞    
mining the initial weight and volume, the extraction processes, M − Mi 6 1 2 2 t
MR = = 1− exp −Di π 2 (2)
designated as (I) or (T), was carried out. The weight and volume Me − Mi π 2 i −1 i 2 r
determinations described above, were repeated at various times
(t = 0, 2, 4, 12, 24 h) for samples subjected to the alternative
extraction process (I), while the determinations for the samples M − Mi
extracted by the traditional process (T) were made at t = 0, 84, MR = (3)
168, 336, 504, 672 h. The samples processed using the traditional Me − Mi
method (T) were transferred to beakers to macerate in 500 mL of M is the extract quantity at a specified time t.
alcohol at room temperature, thus simulating the industrial pro-
cess, while maintaining a 1:5 (100 g of a solid matrix of China     
6 2 t
root in 500 mL of hydroalcoholic solution) solid/liquid ratio. The MR = 1 − exp −Dπ
π2 r2
samples processed using method (I) underwent the programmed    
cycles of pressure described above, while maintaining the same 1 2 t
+ exp −4Dπ 2 (4)
solid–liquid alcohol ratios as process (T). All experiments were 4 r
repeated 3 times, and the maximum difference between results
never surpassed 5%; averages were therefore used for models and where MR is the concentration ratio and Mi and Me are respec-
analyses. Furthermore, additional analyses and tests were also car- tively the initial and equilibrium concentrations of the object dur-
ried out: a sensory analysis with a panel test so as to determine ing extraction. In most cases, only a particular number of terms
differences in the perceptions and pleasantness of the products pro- in Eq. (2) is used to estimate the MR values. The majority of
cessed using the 2 (I) and (T) methods; analytical and numerical researchers in fact only uses the 1st 2 terms of the equation.
analyses of the 2 processes to better understand the phenomenon In this research, the experimental MR values (t0 , t1 , t2 , t3 , t4 )
of alcohol diffusion into solid matrix in the conditions considered were calculated at specific time intervals and used as inputs to
optimal; and a comparison between the results of experimental the curve fitting tool box of MATLABR 2011a software, and the
tests with those obtained using the analytical and numerical ap- diffusion coefficient of the solid matrix D was estimated at t0 , t1 , t2 ,
proaches described in current literature, which had been applied t3 , t4 ; (D is the diffusion coefficient relative to a sphere). As the shape
to other types of food with great success (Naviglio and others of a typical China root solid matrix is closer to an ellipsoid than
2013). a sphere, the coefficient of diffusion has to be adjusted in Eq. (1).

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Production of Cinchona calisaya elixir . . .
Gaston and others (2004) presented the following equation to Table 1–Experimental data obtained by the extraction process of
estimate the diffusion coefficient of an ellipsoid (De ): China elixir for maceration and traditional values of the satu-
De = f e2 ×D (5)
where fe is the sphericity factor of an ellipsoid (Gaston and others 0
2002). Then, the coefficient of diffusion D in Eq. (2) should be 84
replaced by the calculated De .
Finite element approach for extraction using the cyclically S
pressurized extracting process
In order to better understand the extraction process (I)—
which used macerating in a cyclically pressurized hydroalcoholic
solution—a numerical simulation was obtained using the ANSYS
(Rel.14.5 2012) software (ANSYS Inc., Canonsburg, PA, USA),
which enabled to evaluate the exchange between the china root
solid matrix and the alcohol during process (I). With the finite
element model (FEM), the time-dependent concentration distri-
bution was determined numerically at set intervals. The model
is considered homogeneous and isotropic. In a finite element ap-
proach, an estimated value for D is supplied in Eq. (1), and the M
values are determined numerically for specified locations at given
intervals. A similar approach has been used for other numerical
applications (Carillo and others 2011; Formato and others 2011,
Figure 2–Finite element grid for a single China particle.
Figure 3–Kinetics of extraction by the maceration process (T).
ration (S) and the rate constant (k) obtained by interpolation of
the function C (t) = S ∗ e-kt , t(T) = (0; 84; 168; 336; 504; 672) h.
Time (h) China elixir (C g/10 ml)
0
0.167
168 0.190
336 0.234
504 0.188
672 0.206
0.217 ± 0.016
K 20.4 ± 13.4
2013; Naviglio and others 2013).With this approach, the following
E: Food Engineering &
assumptions as regards individual solid matrix were made:
Physical Properties
(1) The diffusion coefficient is independent of the concentration.
(2) The solid matrices are isothermal—the heat transfer during
extraction is neglected.
(3) The solid matrices are homogeneous and isotropic.
(4) The surface of the solid matrix maintains a saturation con-
centration (boundary condition) throughout the extraction
process.
(5) The initial solute content of the solid matrix is constant
and distributed uniformly within the solid matrix (initial
condition).
The geometry of a China particle was considered spheroidal,
and one quarter of a spheroidal shape was utilized for a time-
dependent axisymmetric 2-dimensional analysis (Figure 2).
The mesh consisted of approximately 1974 isoparametric ele-
ments with 6143 nodes and 1 freedom degree per node (the con-
centration). The diffusion coefficient, estimated by fitting Eq. (2)
to experimental data, was the input, and the software calculated
the concentration content for each node at 1-s intervals. The over-
all concentration content for the solid matrix was also calculated
at every range time by averaging the concentrations at the nodes.
This procedure was performed for the (I) extraction process.
Because pressure gradients in this type of system are usually low
and do not cause significant compressibility effects, the solute and
solvent were considered incompressible. The density and dynamic
viscosity for the solvent were ρ = 806 kg/m3 and μδ = 1 × 10−3
Pa s, respectively.
The substance diffusion (mass diffusion) process has been mod-
eled by Fick’s 2nd law. The application of the variational princi-
ple and finite element approximation of the above equation pro-
duced an ordinary matrix equation, which was solved in time
and space using an iterative solver (a preconditioned conjugate
gradient solver in space and a 1st order Crank Nicolson scheme
in time). A difference in the saturation levels between substances
was adopted as the initial condition. That difference is responsi-
ble for the discontinuity in the concentration across the material
interface. To model such a discontinuity, a normalized concen-
tration approach has been used. After the finite element problem
was solved for the nodal concentration vector, the diffusion gra-
dient, and the diffusion flux, these values were evaluated at the
integration points.
Peleg model
In an attempt to simplify the mode of solute absorption of
alcohol by the solid matrix, a 2 parameter, nonexponential
Vol. 79, Nr. 9, 2014 r Journal of Food Science E1707
 Production of Cinchona calisaya elixir . . .

empirical equation was proposed Table 2–Experimental data obtained by extraction of mixtures
(now known as the Peleg equation) of plants with pressurized cyclically maceration (RSLDE) and
relative values of saturation (S) and the rate constant (k) obtained
(Peleg 1988). This is one of the most popular empirical by interpolation of the function C (t) = S ∗ e-kt , t(I) = (0; 2; 4;
models to estimate the overall concentration content M as a 12; 24) h.
function of time t during an extraction process. The Peleg model
Time (h) China elixir (C g/10 ml)
is defined as:
0 0
t
M = Mi + (6) 2 0.099
k1 + k2 t 4 0.139
12 0.171
24 0.150
As t − >∞ Me = Mi + 1/K2 S 0.171 ± 0.013
k 0.986 ± 0.34
where M represents the overall concentration content at time t
during the extraction process and Mi is initial concentration con-
tent; k1 and k2 are respectively the Peleg rate constant (h%−1 ) and Table 1. The process is rather slow, and the system reaches its
E: Food Engineering &

the Peleg capacity constant (%−1 ; Abu-Ghannam and McKenna equilibrium after an extraction step that takes many days. The
Physical Properties

1997). These 2 constants must be determined for a certain prod-
uct with a particular extraction process. The Peleg model was used
to estimate the total concentration content of the solid matrixes
during the extraction process. The data for total concentration
contents at specified time intervals was used as an input to the
curve fitting tool box of the MATLAB commercial, thus deter-
mining the 2 constants of the Peleg model.
Comparison and evaluation of the models considered
The fit for the FEM, the analytical solution and the Peleg model
were assessed by calculating the determination coefficient (R2 ) and
root mean square error (RMSE) using the following equations:
 2
Me M p
R =  2 2
2
(7)
Me Mp

 2
M p − Me
RMSE =
n the compounds in ethyl alcohol and the different distributions of
where Me and Mp are respectively the experimental and predicted
moisture ratio. A model with a high R2 (close to 1) and a low
RMSE (close to 0) value is considered to be a well-fitted model.
Results and Discussion
Kinetics of extraction of maceration (T)
Figure 3 shows the kinetics of extraction of macerated China extraction process (I)
elixir mixtures, and the experimental results are reported in
Figure 4–Kinetics of extraction obtained by the cyclically pressurized pro- In this case, diffusion and osmosis are negligible compared with
cess (RSLDE).
equilibrium, represented by the part of the curve with zero slope,
occurs after approximately 240 h of extraction, that is, after 10 d.
The function which interpolates the experimental points best is
C(t) = S∗ e−(k/t) , where C(t) is the concentration of the extracts at
time t, S is the saturation value, that is, the maximum concentra-
tion value that remains constant to t = infinity (the equilibrium
concentration), and k is the kinetic constant, which represents the
speed with which the system reaches its equilibrium, expressed in
time units (hours).
The functions that interpolate the experimental data indicate
that the system, at room temperature, is saturated after 240 h;
consequently, the initial extraction stage lasts for quite a long time.
Previous works (Naviglio and others 2001; Nota and others 2001)
have highlighted that, during the maceration of lemon skins in
ethyl alcohol, a portion of the essential oils—including limonene,
beta-pinene, and gamma-terpinene—are extracted with faster ki-
netics than other minor components (such as sabinene, alpha-
pinene, and geranial) that are important for the final taste of the
beverage. This result is due to both the various solubilities of
(8)
the compounds within the essential oil of the lemon. Micali and
others (1996) have shown how 20 d of maceration (see official
Pharmacopoeia) are insufficient for the complete extraction of
the hypericin active principle from hypericum leaves (Hypericum
perforatum).
Kinetics of extraction by the cyclically pressurized
Figure 4 shows the kinetics obtained for the RSLDE, and the
experimental data are listed in Table 2. As observed, the experi-
mental data are interpolated by the same type of function (C(t) =
S∗e−(k/t) ), where C(t) is the value of the concentration at the time
the dry residue occurs (t), S represents the value of the maximum
concentration that the system achieves and remains constant until
t = infinity (the saturation or equilibrium concentration) and k
is the kinetic constant, which indicates the speed with which the
system reaches equilibrium, or the saturation concentration.
Therefore, the rapid solid–liquid extraction kinetics trend is
equal to that for maceration and is essentially characterized by a
change in the kinetic constant k. In this case, the initial extrac-
tion phase is rather quick, and the system reaches equilibrium in
approximately 12 h, meaning that RSLDE extraction is at least
20 times faster. In fact, the constant k rate value for maceration is
approximately 20 h, while for extraction rapid solid–liquid dynam-
ics, the rate constant is approximately 1 h (Figure 4 and Table 2).

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Production of Cinchona calisaya elixir . . .
Table 3–Some physical characteristics of the experimental China roots particles. (Data are expressed as mean ± SD. GMD [geo-
metric mean diameter]).
Hours L1 Length (mm) L2 Width (mm) L3 Thickness (mm)
t0 =0 11.0 ± 1.9 9.1 ± 1.5 8.1 ± 1.2
t1 =2 11.0 ± 1.8 9.0 ± 1.3 8.0 ± 1.1
t2 =4 10.7 ± 1.7 8.8 ± 1.2 7.7 ± 1.0
t3 =12 10.1 ± 1.7 8.7 ± 1.2 7.5 ± 1.0
t4 =24 10.0 ± 1.7 8.0 ± 1.2 7.0 ± 1.0
the effect of Naviglio’s Principle (Naviglio 2003). The RSLDE
showed a total recovery time of approximately 12 h. The limit the
value of the dry residue approaches with the RSLDE is slightly less
than 10% (w/w) for all cases, compared to the value obtained for
the same extract using the maceration process. The explanation
for this difference is that during the long contact time between
the extracting liquid and the solid matrix, the latter produces col-
loidal particles that disperse in the system, which increases the
value of the dry residue. These substances are generally unwanted
because they result from the disintegration of the solids that consti-
tute the solid matrices (cellulose, cellular components, polymeric
substances, and so on).
Furthermore, it has to be taken into account that during the
cyclically pressurized extraction process, a rapid initial alcohol up-
take occurs, which is probably due to the filling of the capillaries
on the surface of the seed coats and hilum (Hsu and others 1983).
As the alcohol absorption process continues, the rate begins to
drop due to the increased extraction of soluble material from the
solid matrix and the filling of capillaries and intermicellar spaces
with water (Plhak and others 1989). The main element that con-
trols the rate of solute absorption in alcohol during the extraction
process is seed coat. In this study, we found out that the cyclically
pressurized extracting process (I) significantly increased the extrac-
tion rate of China and that equilibrium conditions were attained
much quicker than with the macerating process (T). The cyclically
pressurized extracting process has the advantage of improving seed
coat plasticity and eliminating the presence of those hard-shelled
cells that fail to imbibe alcohol by alternating the pressure during
the process. The quick pressure changes (0 to 10 bar) produce
impulsive forces that enable the opening of new channels within
the solid matrix through which the alcohol flows, increasing its
total solute concentration. This phenomenon does not occur if
the pressure value remains constant during the process, as new
channels within the solid matrix do not form.
Recovery of ethyl alcohol at the end of the extraction
process
Figure 4 shows extracts of China Elixir obtained at 2, 4, and
12 h using the RSLDE, while the last batch to the right is the
maceration extract from the same mixture of plants after 1 day
with the solid/liquid ratio maintained. The extract obtained by
the RSLDE after 12 h has the same staining intensity as the extract
obtained using the traditional extraction method.
The comparison of two procedures reflects the results of the
determination of the dry residue as well as the value of the kinetic
constant process. Furthermore, a significant loss of ethyl alcohol
occurs during the maceration extraction process; in fact, only
80% is recovered, and the remaining 20% is lost in the solid ma-
trix, which represents an economical loss in the bitter production
process. Sensory analysis
In extracts obtained by the RSLDE, the ethyl alcohol loss is
negligible and this is another advantage of the innovative technique proved that a group of regular China liquor consumers (18 people:
GMD = D (mm) Sfericity φ Sphericity factor—fe
8.6 0.984 0.989
8.5 0.983 0.970
8.2 0.982 0.931
8.1 0.981 0.912
7.5 0.979 0.901
of solid–liquid extraction. Because the contact time between the
solid and liquid phases is minimized, the release of unwanted
substances in the extract is minimized.
The long contact period of the ethyl alcohol with herbs dur-
ing the maceration stage facilitates solid matrix disintegration and
E: Food Engineering &
the release of undesired substances, which, as previously men-
Physical Properties
tioned, increases the content of dry matter, while simultane-
ously, a substantial part of the liquid is retained by the solid
matrix, which is not recoverable at the end of the extraction
process.
In addition, during the long extraction time, extracted com-
ponents transform, and the system moves into an “aging” phase,
which is not always advantageous. Such a phenomenon causes a
slight increase in dry residue that is always detected during macera-
tion compared to rapid extraction. During maceration, the extract
is enriched for colloidal substances that are derived in part from
the solid matrix and in part from polymerization reactions that
occur between extracted compounds.
Nonspecific RSLDE
An important aspect of solid–liquid extraction is the selectivity
of the extraction in relation to the extracting solvent. Traditional
extraction techniques like, for example, maceration, percolation,
and Soxhlet, are essentially based on the phenomena of diffusion
and osmosis and enable to extract substances that are solubilized
in the extracting liquid; therefore, the basis of such extraction
processes is that the compounds drawn out of the solid matrix
are soluble in the solvent, which precisely dissolves and solubilizes
them (Zimmerman and Weindorf 2010).
In the RSLDE, rather than dissolution, the driving effect of
the extraction is the pressure difference (p) existing between the
inside and outside of the solid matrix, when the system pressure is
p = 0. In this case, the substances, which are not bound chemically
to the solid matrix, are removed due to the pressure difference
(which causes movement of the liquid). Consequently, molecules
not soluble in the extracting liquid are conveyed outside into the
heterogeneous phase.
Some applications that can be found in the literature, such as
the extraction of lycopene from tomato skins with water (Nav-
iglio and others 2008) and the extraction of bergamot oil with
water (Jaeger and others 2011), show that it is possible to extract
lipophilic substances, which are nonpolar and therefore immis-
cible, in a polar solvent such as water. Finally, the RSLDE has
been used advantageously for the extraction of active principles
from Malva Silvestris (Cutillo and others 2006), the extraction of
soil contaminant substances (Formato and others 2013) and the
extraction of the principal components of hops to be added to
beer (Formato and others 2013).
From a sensory perspective, the consumer test we performed
Vol. 79, Nr. 9, 2014 r Journal of Food Science E1709
 Production of Cinchona calisaya elixir . . .

9 men and 9 women), to whom we submitted blinded product
samples using a triangular test method, could not identify which
samples were prepared using RSLDE. The number of correct
answers for these tasters, (that is, the number of individuals who
identified which one of the 3 samples was different) must be P10
for the results to reach a 95% confidence level (that is, an error
factor a equal to 0.05).
E: Food Engineering &
Physical Properties
The tasters provided only 3 correct answers and, therefore, we
can conclude that 2 systems result in similar texture characteristics.
However, the data obtained through preference tests suggest that,
although there were fewer samples prepared with RSLDE, they
were preferred to those obtained with the traditional method (5.13
compared with 7). These preliminary results confirmed that the 2
extraction systems produced analogous results and could thus be
considered equivalent.

Figure 5–Typical distribution of solute concentration (diffusion) in the solid matrix during the extraction process, as determined by finite element
analysis (A) 0 h; (B) 2 h; (C) 4 h; (D) 12 h (E) 24 h. The bar below each shape represents the level of concentration M within a China particle region at a
given time.

E1710 Journal of Food Science r Vol. 79, Nr. 9, 2014

Production of Cinchona calisaya elixir . . .

Table 4–Values of the measured concentration with the experi- In fact, Cissè and others (2012) calculated the coefficient of
mental model, the FEM model and the model of Peleg at differ- diffusion for the extraction of anthocyanins from Hibiscus sabdariffa
ent times considered. −11 −10
within a range of 3.9 × 10 to 1.35 × 10
2
m /s between
Time (h) Mexp MFEM MPeleg 25 ˚C and 90 ˚C. Furthermore, Linares and others (2010) estimated
t0 =0 0 0 0 this coefficient for yerba mate aqueous extraction kinetics; the
t1 =2 0.099 0.099 0.089 values ranged from 6.092 × 10−11 to 9.469 × 10−11 .
t2 =4 0.139 0.138 0.139 The higher De calculated for the solid matrix of China roots
t3 =12 0.171 0.169 0.161 indicates that the solute diffuses into the solid matrix at a higher
t4 =24 0.150 0.149 0.147
rate than the considered cases.

Table 5–Estimated coefficients of determination (R2 ) and root Numerical analysis

mean square errors (RMSE) for the considered models. The diffusion coefficient was substituted into Eq. (1), and
Model R2 RMSE the resulting equation was solved by a finite element approach
in order to estimate the concentration distribution within the
Finite element 0.989 0.0158
Peleg 0.924 0.1085
solid matrix at various time intervals. The FEM provided a good

E: Food Engineering &

prediction of the M values at the end of the extraction process,

Physical Properties
while during the initial and intermediate stages, the model slightly
overestimated the M values. The finite element predictions for
In the organoleptic test, tasters sampled the 2 types of bitter the concentration content are included in Figure 5 (A–E) at 0, 2,
following the 2 procedures described in Materials and Methods 4, 12, 24 h after the beginning of the extraction process. Figure 5
and indicated their preferences. The results of the test showed shows a gradual transfer of the solute extract from the centre of
that the bitters prepared according to the traditional procedure a solid matrix to the surface. Theoretically, the FEM, as shown in
and by the innovative procedure were equivalent in taste. The Figure 5, indicates that the concentration content throughout the
spectrophotometric analysis of the extracts diluted 1:1000 showed solid matrix is still not quite uniform at the end of the extraction
an absorption level of between 230 and 280 nm for both extraction process. This indicates that the average concentration content
methods (spectra not reported). reached its saturation level (0.17121) after 25 h. Figure 5 indicates
that the solute extract gradient within a solid matrix is large at
Comparison between the analytical and numerical models the beginning of the extraction process and that the gradient
The results achieved via numerical analysis for process (I) are decreases during the progression of the extraction process. After
discussed below. For China particles, the geometric parameter 24 h, the concentration content is practically uniform and it
characteristics are as follows: reaches a definitive value at all nodes. The fault of the FEM,
L1 length along the x-axis of the particle (mm)—largest principal when compared to the analytical model, is that the former is
dimension, mm; based on a coefficient of diffusion developed using other sources,
L2 length along the y-axis of the particle (mm)—2nd largest prin- that is, analytical modeling or experimental values.
cipal dimension, mm; and
L3 length along the z-axis of the particle (mm)—smallest principal Peleg model
dimension, mm. Two constants have been determined for process (I): K2 = 17.54
and K1 = 15.48, giving the expression:
The sphericity of the considered particles was measured fol-
lowing the Jain and Bal method (1997) to determine an index of t
M = 0.093 + (9)
the roundness of the particle. For nonspherical particles, spheric- 15.48 + 17.54 · t
ity is calculated as the ratio of the surface area of the equivalent
sphere to the surface area of the grain (McCabe and Smith 1984). As shown in Table 4, the Peleg model underestimated the M
The measured physical characteristics of the solid matrix of China values at the initial and final stages of the extraction process.
roots before and after the extraction process (I) are presented in Table 4 contains reported values for the measured concentra-
Table 3. These dimensions indicate that the solid matrix’s geom- tion with the experimental model, the FEM model and the Pe-
2
etry is nearly spheroidal in shape and retains this shape even after leg model at various times. Comparing R values for the above
the extraction process. However, due to a relative decrease in the models, the FEM is more appropriate than the Peleg model for
thickness and width of the solid matrix, the sphericity of the solid predicting the extraction process by the solid matrix because the
matrix decreased from 0.984 to 0.979. R2 value for the Peleg model is lower than the R2 value for the
This decrease in dimensions was due to the migration of the FEM model. Furthermore, the RMSE value for the FEM is very
solute content in the solid matrix within the China root cells, close to 0 and lower than the value obtained with the Peleg model.
causing a general deflation of the solid matrix. Ahromrit and others The finite element approach is well-suited for modeling this ex-
(2006) provide a detailed analysis of dimension changes during the traction process even if it slightly overestimated the M values for
extraction process. the solid matrix at the initial stages. The FEM is superior due to
The sphericity factor (fe ) for an average solid matrix particle was its capacity of predicting the concentration changes at specified
calculated and ranged between 0.901 and 0.989. Using Eq. (4) nodes within China particles rather than just calculating an overall
and (5), the coefficient of diffusion De was calculated to be equal concentration for a single particle.
to 1.187e-006 m2 /s, within a range of 6.588e-007 m2 /s, much
higher than that obtained with traditional maceration methods and Comparison of coefficients
compared to the values for other types of extracts for traditional The R2 and RMSE values calculated for the FEM, the analytical
maceration. solution, and the Peleg model are shown in Table 5. Comparing

Vol. 79, Nr. 9, 2014 r Journal of Food Science E1711

 Production of Cinchona calisaya elixir . . .
the R2 values of the above models, the FEM is more appropriate
than the Peleg model for predicting the extraction process using a
solid matrix because the R2 value for the Peleg model is lower than
the R2 value for the FEM model. Furthermore, the RMSE value
for the FEM is very close to 0 and lower than the value obtained
with the Peleg model. Therefore, the finite element approach
is well-suited for modeling this extraction process. The FEM,
however, slightly overestimated the M values of the solid matrix
in the initial phases. The FEM is superior due to its capacity of
predicting the concentration changes at specified nodes within
China particles rather than just calculating the total concentration
for a single particle.
Conclusions
In this work, a comparison between the maceration process (T)
E: Food Engineering &
and the solid–liquid extraction rapid process (I) for bitter pro-
Physical Properties
duction has been performed. The kinetics curves obtained were
interpolated in order to obtain a mathematical model for the 2
extraction processes. The model was applied to different cases
from the literature and has been shown to be valid for predict-
ing kinetic trends for extraction by maceration as applied to rapid
solid–liquid extraction. The experimental data obtained from the 2
extraction techniques have been interpolated using the optimum
function. The extraction phenomena have been interpolated in
both cases by the equation C(t) = S∗ e−k/t , where C(t) is the con-
centration of the extracts at time t, S represents the saturation
of the solution with respect to the extracted substance, k is the
rate constant and t is time. The difference in extraction kinet-
ics showed a ratio of approximately 20 between the maceration
and the RSLDE. This model has been applied to cases studied in
the literature and has led to some good preliminary results, using
the extraction kinetics of the Naviglio Extractor as a prediction
of the maceration kinetics. Because, in general, the extraction ki-
netics indicate that the RSLDE is faster and because all the other
recovery and efficiency parameters are unchanged, the substitution
of this new technology of solid–liquid extraction for the now ob-
solete and outdated maceration technique is a natural consequence
due to these favorable results. By means of numerical simulation,
once the model was developed, it was possible to estimate the
concentration at each node of the particle and during every mo-
ment of the extraction process (I). It was possible to perform a
comparison with the Peleg model, and we have shown that the
FEM is better able to describe the entire extraction process.
The model obtained for the bitter can be applied to other cases
of extraction using mixtures of herbs in ethyl alcohol. While it is
necessary to study various systems in relation to the characteristics
of the solid matrix as a whole, freshness, the part of the plant sub-
jected to the extraction and temperature control of the extraction
system are strongly dependent on this parameter because of diffu-
sion and osmosis. Finally in this work, it was intended to determine
the scientific and quantitative basis for the rapid extraction solid–
liquid process. The results we obtained for the extraction process
of bitter liqueur and the mathematical model definitely encourage
us to improve upon the model and to extend its applications to
various types of vegetable matrices.
E1712 Journal of Food Science r Vol. 79, Nr. 9, 2014
Author Contributions
Daniele Naviglio designed the study, collected all test data, in-
terpreted the results and drafted the manuscript. Andrea Formato
performed the numerical simulation of the process to obtain use-
ful information about the timing of the process (time history) and
its mathematical description. Monica Gallo interpreted the results
and drafted and improved the manuscript.
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