Chemical Engineering Research and Design 1 6 0 ( 2 0 2 0 ) 39–51

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Chemical Engineering Research and Design

journal homepage: www.elsevier.com/locate/cherd

Optimization of supercritical carbon dioxide

extraction of sweet paprika (Capsicum annuum L.)
using response surface methodology

Dorota Kostrzewa ∗ , Agnieszka Dobrzyńska-Inger, August Turczyn

˛
Łukasiewicz Research Network – New Chemical Syntheses Institute, Al. Tysiaclecia Państwa Polskiego 13A, 24-110
Puławy, Poland

a r t i c l e i n f o a b s t r a c t

Article history: In this work, the design of experiments (DOE) and response surface methodology (RSM)
Received 11 December 2019 were applied to investigate the effect of process parameters including pressure (25–45 MPa),
Received in revised form 1 May 2020 temperature (313.15–333.15 K) and time (10–60 min) on supercritical carbon dioxide extrac-
Accepted 4 May 2020 tion of sweet paprika. Based on the achieved results, statistically significant mathematical
Available online 16 May 2020 models were developed to describe the effect of independent variables on the yield and
quality of the extract. The developed models were used for the optimization of the extrac-
Keywords: tion process. Using the desirability function, the sets of parameters were determined for
Sweet paprika which optimization assumptions were met: maximization of the extraction yield and the
Carotenoids content of carotenoids in the extract. Moreover, the yield and chemical composition of the
Supercritical fluid extraction extract obtained using supercritical carbon dioxide were compared to the results of paprika
Box–Behnken design extraction using the organic solvent.
Optimization © 2020 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction also for their significant role in human health (Arimboor

Paprika (Capsicum L.) is the plant belonging to the Solanaceae
family. Its fruits are used globally as fresh vegetables and
spices adding the color and taste to food (Arimboor et al., 2015).
Paprika is a valuable source of natural carotenoids, vitamins
E and C, pro-vitamin A, B-vitamins, phenols, fats, micro and
macro elements (Alvarez-Parrilla et al., 2011; Arimboor et al.,
2015). Furthermore, it contains a significant amount of car-
bohydrates, folic acid, nicotinic acid, organic acids, vegetable
protein, mineral salts (iron, phosphorus, calcium, magnesium,
potassium), and routine. The content of the main carotenoids
in red paprika ranges from 0.1 to 1.3 g/100 g of dry mass
(Cervantes-Paz et al., 2014; Márkus et al., 1999). Due to its
rich composition, products obtained from paprika are widely
applied in food, cosmetic and pharmaceutical industries.
Carotenoids present in paprika extracts are very impor-
tant compounds not only for their coloring properties but
et al., 2015; Stahl and Sies, 2005). Studies showed that the
increased consumption of carotenoids leads to decreasing
the risk of cardiovascular disease, cancer and chronic dis-
eases, and it has a beneficial effect on eyesight (Arimboor
et al., 2015; Maoka et al., 2001; Márkus et al., 1999; Matsufuji
et al., 1998). The protective effect of carotenoids is related
to their antioxidant properties and scavenging of free rad-
icals which damage lipids, protein and DNA (Aizawa and
Inakuma, 2009; Matsufuji et al., 1998; Stahl and Sies, 2005).
Carotenoids identified in paprika such as capsanthin and
capsorubin show a significant effect of neutralization of
the singlet oxygen as well an inhibiting effect on lipid
peroxidation (Maoka, 2009). Moreover, it was shown that
capsanthin is an effective scavenger of free radicals and it
has an effect on the cholesterol level in plasma increas-
ing the level of good cholesterol HDL (Aizawa and Inakuma,
2009).

∗
Corresponding author.
E-mail address: dorota.kostrzewa@ins.pulawy.pl (D. Kostrzewa).
https://doi.org/10.1016/j.cherd.2020.05.005
0263-8762/© 2020 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
40 Chemical Engineering Research and Design 1 6 0 ( 2 0 2 0 ) 39–51
The most frequently applied technique for obtaining
the paprika extract is extraction with organic solvents,
e.g., n-hexane, acetone, ethyl alcohol (Dong et al., 2014;
Fernández-Ronco et al., 2013). For paprika extraction, non-
conventional extraction methods were also used, which
combine microwave and ultrasound treatment with the tradi-
tional extraction using organic solvents. Microwave-assisted
extraction was applied for obtaining volatile compounds
from paprika using n-hexane (Gogus et al., 2015). Whereas,
ultrasound-assisted extraction was used to extract capsai-
cinoids from hot paprika Capsicum annuum and Capsicum
chinense using methyl alcohol (Barbero et al., 2008; Boonkird
et al., 2008) and to extract carotenoids using n-hexane and
ethyl alcohol (Fernández-Ronco et al., 2013).
The disadvantage of extraction using organic solvents is
the lack of selectivity with regard to extracted components
and problems related to the separation of solvent from the
extract. Separation of solvent is an energy-intensive and dan-
gerous process. Moreover, during the evaporation of solvents,
the degradation of carotenoids contained in the extract is
likely to occur (Jarén-Galán et al., 1999). Additionally, solvents
cannot be completely removed from post-extraction residues
which can lead to losses of solvent and limitations regarding
the use of post-extraction residues for feeds or spice mixtures.
However, the biggest issue is the presence of volatile organic
impurities in the final product. With the increased restric-
tions in the use of organic solvents and the growing demand
for natural products and the latest achievements in green
technologies, there is a growing interest in supercritical fluid
extraction (SFE) to obtain high-quality bioactive compounds
(Hatami et al., 2019a, 2019b). Carbon dioxide is the most fre-
quently applied solvent for SFE because of being non-toxic,
chemically inert, non-explosive, inexpensive, and having low
critical parameters (pc = 7.38 MPa, Tc = 304.25 K) and being eas-
ily removable from the final product.
For studying the effect of process parameters on SFE, con-
ventional methods can be used which involve the replacement
of one parameter with the unchanged values of other parame-
ters (one variable at a time, OVAT) (Bezerra et al., 2008). However,
these methods do not guarantee the determination of the
optimal process conditions (Wernimont, 1995). Monitoring of
changes of one parameter with other stable parameters does
not allow to obtain the real effect of parameters on the stud-
ied process, and it is time-consuming. Therefore, over the
last decades, a growing application of the statistical design of
experiments is observed in numerous fields as an extremely
useful method for the optimization of technological processes.
This approach requires a relatively small number of experi-
ences, which reduces the use of materials and time necessary
for carrying out experiments.
Design of experiments (DOE) methods combined with
response surface methodology (RSM) turned out to be an effec-
tive statistical tool for study not only the individual effect
of parameters on the process but also the effect of their
interactions (Sajilata et al., 2008). This allows determining
the relationships between process parameters and response
variables and effective process optimization. The RSM was
successfully applied in a number of research processes related
to food technologies and the extraction of biologically active
compounds (Dobrzyńska-Inger et al., 2016; Huang et al., 2008;
Wang et al., 2008). The most commonly used experimental
designs for optimization of SFE are the Taguchi method, cen-
tral composite design and Box–Behnken design (BBD) (Sharif
et al., 2014). The BBD has a clear advantage over other designs
with regard to its effectiveness, i.e., the ratio between a num-
ber of coefficients in the model and a number of experiments
being carried out. This design is efficient and effective for test-
ing of numerous variables.
There are literature reports concerning the effect of param-
eters on paprika extraction, but they refer mainly to extracts
obtained from pungency paprika (Daood et al., 2002; de Aguiar
et al., 2013; Duarte et al., 2004; Gnayfeed et al., 2001; Perva-
Uzunalić et al., 2004). These extracts contain capsaicinoids,
the additional components, which can have an effect on
behavior and separation of other components obtained from
paprika using supercritical carbon dioxide. Moreover, studies
presented in the literature are frequently carried out on a small
scale (50 cm3 extraction vessel) or/and in an open system with-
out closing of carbon dioxide circulation (Daood et al., 2002;
del Valle et al., 2003; Gnayfeed et al., 2001; Illés et al., 1999;
Perva-Uzunalić et al., 2004; Uquiche et al., 2004). Because of
this, some phenomena, such as water co-extraction, entrain-
ment or aggregation of particles, may not have been noticed.
These phenomena may be less relevant at the lab-scale, but
they can become a significant issue at the production scale
and have a significant impact on the final results.
As far as we know, there are no reports regarding the opti-
mization of sweet paprika extraction with supercritical carbon
dioxide using the RSM. The RSM was only used for studies
related to the extraction of capsaicinoids from hot paprika
Capsicum frutescens L. (Duarte et al., 2004; Gouveia et al., 2006)
and extraction of oil from red paprika seeds using supercritical
carbon dioxide with modifier and using supercritical butane
(Gu et al., 2017; Li et al., 2011).
The objective of this work was to determine the effect
process parameters (pressure, temperature, and time) on
carotenoids extraction from sweet paprika using supercritical
carbon dioxide. The studies were carried out using RSM with
BBD. This approach is an effective statistical method to define
the effects of independent variables and their interactions on
the process response and to optimize the process parameters.
The results of paprika extraction using supercritical carbon
dioxide were compared with the results obtained using the
organic solvents.
2. Materials and methods
2.1. Materials
Commercial ground red paprika Capsicum annuum L. pur-
chased from P.H. Royal Sp. z o.o. company (Warszawa, Poland)
was used in this study. The color value of paprika was 160
ASTA (American Spice Trade Association color value). Moisture
content determined using analyzer Radwag MAC 50/1 was
10.55 ± 0.28%. The sieve analysis carried out using the labo-
ratory set Multiserw – Morek LPzE-2e showed that the particle
size of raw material was <0.5 mm. Carbon dioxide (purity
99.9%) was purchased from Grupa Azoty Zakłady Azotowe
“Puławy” S.A. (Puławy, Poland) and used as the solvent. Organic
solvents were of analytical quality and were purchased from
Avantor Performance Materials Poland S.A. (Gliwice, Poland).
2.2. Extraction of paprika by Soxhlet extraction (SOE)
30 g of ground paprika and 300 ml of solvent were placed
in a Soxhlet extractor. The sample extracted until the com-
plete discoloration of the sample was achieved (Tepić et al.,
2009) (extraction time 4 h, drop flow of 140 drops/min). After
 Chemical Engineering Research and Design 1 6 0 ( 2 0 2 0 ) 39–51
Fig. 1 – Process flow diagram of SFE system used in this
study: 1 – extraction vessel, 2 – extraction valve, 3 –
separator, 4 – cooling exchanger, 5 – condenser/CO2 tank, 6
– cooling exchanger, 7 – high-pressure pomp, 8 – heat
exchanger, 9 – CO2 cylinder.
extraction, the solvent was removed with evaporation at
reduced pressure using Rotavapor R-210 (Labortechnik AG
Büchi, Switzerland) at 313.15 K. The weight of the obtained
extract was measured gravimetrically, and then the extract
was stored at 277.15 K until the analysis was carried out. The
extraction yield (YSOE ) was calculated as a ratio the weight
of the obtained extract and the weight of raw material used
in this extraction, in percentages. The extraction was per-
formed with n-hexane, acetone, and ethyl alcohol. Extraction
was repeated three times for each solvent and finally, their
mean values were reported.
2.3. Supercritical fluid extractions with carbon dioxide
(SFE-CO2 )
The SITEC unit (SITEC-Sieber Engineering AG, Switzerland)
was used for the extraction of paprika using supercritical car-
bon dioxide (Fig. 1). For every run, 200 g of ground paprika was
placed in the extraction vessel (a volume of 1145 ml). After
closing, the extraction vessel was purged with gaseous carbon
dioxide and then the pressure was increased to the condenser
pressure. The circulation of heating and cooling media was
started. Afterward, the pressure in the system was increased
using a high-pressure pump and carbon dioxide circulated
omitting the extractor (CO2 flow through the by-pass). After
the required parameters were achieved (static time of 10 min),
carbon dioxide started to flow through the extractor. The tem-
perature and pressure were set in the range of 313.15–333.15 K
and 20–50 MPa, and dynamic extraction time (CO2 flowing in
the extractor) in the range of 10–60 min. The CO2 flow rate
of carbon dioxide was kept constant of 15 kg/h. The CO2 flow
rate is measured by a Coriolis mass flow meter (MASS 2100,
SITRANS FC MASSFLO, Siemens, Denmark) located at the end
of the extraction line. The specific extraction parameters range
were selected based on the preliminary studies (Kostrzewa
et al., 2019; Rój et al., 2013). It has shown that pressure above
20 MPa has a positive effect on the extraction of carotenoids.
The use of high temperatures is limited due to the thermola-
bility of carotenoids (Arimboor et al., 2015; Fernández-Ronco
et al., 2010). It is well known that high temperatures can cause
degradation and isomerization of carotenoids.
After extraction, the system was switched back to the by-
pass to wash out extracts deposits left in the plant (20 min).
41
Then, the pressure was reduced to the pressure of carbon diox-
ide condensation and the pump was switched off. In the next
step, the pressure in the extractor was lowered to the atmo-
spheric value. The extractor was opened and post-extraction
residue was removed. The obtained extracts were centrifuged
in the rotating centrifuge Rotina 420R (Hettich Zentrifugen,
Germany) to separate water from the extract. Afterward, the
weight of water and extract was measured gravimetrically.
2.4. Experimental design
The studies of sweet paprika extraction using supercritical
carbon dioxide were carried out using BBD for three indepen-
dent variables namely: pressure, temperature and extraction
time with three repetitions of the central point. Experimental
points in the experimental plan were presented as normalized
process variables Xi . Normalization was carried out pursuant
to Eq. (1):
xi − xi,0
Xi = (1)
xi
where Xi is the coded value of the independent variable; xi
is the real value of the variable i; xi,0 is the real value of the
process variable at the central point; xi is the step change of
variable Xi . Value xi was specified according to Eq. (2).
xi,max − xi,min
xi = (2)
2
where xi,max is the maximal real value of process variable;
xi,min is the minimal value of process variable. The assumed
levels of independent variables were presented in Table 1.
The total number of experiments (N) was calculated using
Eq. (3).
N = 2k(k − 1) + cp (3)
where k is number of independent variable; cp is number of
repetitions of the central point.
For three independent variables and three repetitions of the
central point, the total number of experiments was 15 in our
plan. The effect of independent variables on response vari-
ables was approximated with the second-order polynomial
regression model expressed by Eq. (4).
y = ˇ0 + ˇ1 X1 + ˇ2 X2 + ˇ3 X3 + ˇ12 X1 X2 + ˇ13 X1 X3 + ˇ23 X2 X3
+ ˇ11 X12 + ˇ22 X22 + ˇ33 X32 (4)
where y is response variable; X1 , X2 and X3 are the levels of the
independent variables; ˇ is coefficient of equation expressing:
equation constant (ˇ0 ), major effects of parameters (ˇ1 , ˇ2 , ˇ3 ),
their interactions (ˇ12 , ˇ23 , ˇ13 ), quadratic coefficients (ˇ11 , ˇ22 ,
ˇ33 ).
The regression analysis and optimization were carried
out using the software Design Expert (Version 9.0.6.2, Stat-
Ease Inc., MN, USA). For statistical evaluation of the obtained
results, analysis of variance (ANOVA) was applied. The F test
was carried out to evaluate the significance of the estimated
coefficients in the model. The test of statistical significance
was based on error criteria with confidence level 95%. The
coefficient of determination R2 , adjusted coefficient of deter-
mination R2 , predicted coefficient R2 , lack of fit (LOF) were used
to evaluate the accuracy of adjusting the experimental data to
the model.
42 Chemical Engineering Research and Design 1 6 0 ( 2 0 2 0 ) 39–51
Table 1 – Coded and uncoded values of the independent variables applied in the experimental design.
Independent variables Symbols
Uncoded
Pressure, MPa p X1
Temperature, K T X2
Time, min t X3
2.5. Determination of total carotenoid content and
color value
The total content of carotenoids in paprika extract and the
color value of extract were determined using the spectropho-
tometric method. This methodology was described in the
previous paper (Kostrzewa et al., 2019; Rój et al., 2013). For the
color value of post-extraction residue determining, each post-
extraction residues (0.1000 g) were extracted with 100 cm3 of
acetone and shaken at 300 rpm for 2 min in Shaker ORBIT 1000
(Labnet International Inc., USA). The solution prepared this
way was left at room temperature (without access to light) for
approx. 16 h. After this time, flask with the sample was shaken
again for 2 min and the solution was filtered through a 0.45 ␮m
filter. Measurement of absorbance was carried out with refer-
ence to acetone at 460 nm using the spectrophotometer JASCO
V-650 UV-Vis. Each measurement was repeated three times.
The color value was calculated according to Eq. (5).
16.4A460 f
ASTA = (5)
mp
where ASTA is the American Spice Trade Association color
value; A460 is absorbance of the solution at 460 nm; f is the
coefficient of correction of optical path length; mp is sample
weight (g); 16.4 is the calculator factor.
2.6. Determination of red and yellow carotenoids
concentration
The concentration of red and yellow fractions of carotenoids
was determined according to the methodology described by
Fernández-Ronco et al. (2010). Each extract (approx. 0.1000 g)
was weighed and dissolved in acetone (50 cm3 ). The solu-
tion was shaken in Shaker ORBIT 1000 (Labnet International
Inc., USA) at 300 rpm for 2 min and left at room temperature
for 2 min. A volume of 10 cm3 of extract solution was trans-
ferred to a 100 cm3 volumetric flask, dilute to volume with
acetone and it was mixed. The absorbance of the solution was
measured at 508 nm and 472 nm using the spectrophotometer
JASCO model V-650 UV-Vis. Each measurement was repeated
three times. The concentration of red and yellow fractions of
carotenoids in the extract was calculated according to Eqs. (6)
and (7).
2144A508 − 403.3A472
Cr = (6)
270.9
1724.3A472 − 2450.1A508
Cy = (7)
270.9
Levels
Coded Uncoded Coded
25 −1 (low)
35 0 (center)
45 1 (high)
313.15 −1
323.15 0
333.15 1
10 −1
35 0
60 1
where Cr is the concentration of red carotenoids fraction in
extract (␮g/ml); Cy is the concentration of yellow carotenoids
fraction in extract (␮g/ml); A508 is absorbance of the solution
at 508 nm; A472 is absorbance of the solution at 472 nm.
3. Results and discussion
3.1. Extraction of paprika using the organic solvents
The Soxhlet extraction was applied to determine the amount
of extractable compounds in raw material and to check the
effect of the type of solvent on the yield of paprika extraction
and the quality of the obtained extract. For paprika extrac-
tion was selected n-hexane because the Hildebrand solubility
parameter of n-hexane is similar to the solubility parameter of
carbon dioxide. This allows a comparison of these two types
of extraction (McHugh and Krukonis, 1994). Moreover, acetone
and ethyl alcohol were used which have different polarities
than n-hexane and supercritical carbon dioxide. Results of
paprika extraction using the above-mentioned solvents were
presented in Table 2.
The highest yield (YSOE ) was achieved in the case of
extraction using ethyl alcohol. However, the total content of
carotenoids in the extract (Ck ) was then not high. The yield
of Soxhlet extraction using acetone was 15.10% and it fell into
the medium range between the yield obtained using n-hexane
and ethyl alcohol. The highest color value of extract (Be ) and
the highest total content of carotenoids in the extract (Ck ) were
achieved using n-hexane.
Studies confirmed that the polarity of the solvent plays an
important role in the extraction process. The yield of paprika
extraction grew with the increase of solvent polarity, whereas
the concentration of carotenoids decreased. It indicates that
paprika subjected to extraction contained many intermedi-
ate to high polarity components. These components were
extracted using polar solvents. The obtained results are in
agreement with the results obtained by Jarén-Galán et al.
(1999). Authors showed that the yield of paprika extraction
using acetone (15.60%) was higher than the yield obtained for
n-hexane (9.40%), however, the total content of carotenoids
was lower.
3.2. The yield of the supercritical extraction process
During paprika extraction using supercritical carbon dioxide,
the effect of water co-extraction with paprika extract was
observed. The water co-extraction phenomenon has not been
frequently described in the literature, and it has not been
described and discussed so far for paprika extraction. This is
 Chemical Engineering Research and Design 1 6 0 ( 2 0 2 0 ) 39–51
Table 2 – Results of Soxhlet extraction using organic solvents.
Solvent Polarity index Tw (K)
n-Hexane 0.0 342.15
Acetone 5.1 329.45
Ethyl alcohol 5.2 351.45
due to the fact that tests on lab-scale are carried out using very
small amounts of raw material, and therefore the amount of
obtained extract and water is small. The lower the mass of
extract, the more difficult this effect is to see (Prado et al.,
2011). However, the phenomena apparently absent or insignif-
icant at the lab-scale may become very significant in the case
of scale-up. In present studies, the weight of raw material
used for extraction (200 g) was even tens of times higher than
the weight of raw material used in studies presented in the
literature, and therefore these phenomena could be noticed.
The complete matrix of experimental plan and yield results
obtained during the carrying out of the BBD were presented in
Table 3. Due to the effect of water co-extraction, the following
response variables were taken into account: Yc – total extrac-
tion yield expressed as the ratio of total extract weight (paprika
extract + water) to the weight of raw material, Ye – extract yield
expressed as the ratio of weight of paprika extract after separa-
tion of water to the weight of raw material, Yw – yield of water
extraction expressed as the ratio of weight of water separated
from extract to the weight of raw material.
In the regarded experimental area of independent vari-
ables, total extraction yield (Yc ) ranged from 7.24% to 11.66%,
whereas extract yield ranged from 6.46% to 8.89%. The yield
of water extraction was the lowest and it ranged from 0.05%
to 2.76%. The highest yield values were achieved for paprika
extraction carried out under the pressure of 35 MPa and the
temperature of 333.15 K for 60 min. Supercritical extraction
efficiency was then 92% in reference to Soxhlet extraction
using n-hexane.
Maximum extract yield (Ye ) in present work was lower than
yield achieved by Daood et al. (11.4–11.5%) and Tepić et al.
(10.6%) and higher than yield achieved by Gnayfeed et al. (7.9%)
and Illés et al. (7.2%) (Daood et al., 2002; Gnayfeed et al., 2001;
Illés et al., 1999; Tepić et al., 2009). The cause of higher yield
achieved by Daood et al. and Tepić et al. was greater content of
lipid compounds in the raw material, it was 12.4% and 12.8%
respectively (Daood et al., 2002; Tepić et al., 2009). However,
total extraction yield (Yc ) in the present study was the highest
probably due to the effect of water co-extracted which has an
impact on the final yield of extraction.
Based on the experimental data presented in Table 3, the
statistical analysis of the second-order polynomial equation
for response variables Yc , Ye and Yw were carried out and
regression coefficients were determined. Results of statistical
analysis for full quadratic models were presented in Table 4.
The obtained regression models in the form of the second-
order polynomial equation were statistically significant which
is evidenced with the p-value (p < 0.05). The determination
coefficient R2 for each model was higher than 0.9 which
indicates a high correlation between input and output data.
Moreover, the p-value specified for lack of fit was statisti-
cally insignificant (p > 0.05). Due to the fact that some factors
of the full quadratic models were statistically insignificant
(p > 0.10), the model reduction was effected taking into account
the effect of all the statistically significant factors. The objec-
tive of this was to develop the mathematical model which
with its not-extended structure gives the regression equation
43
YSOE (%) Be (ASTA) Ck (%)
9.70 ± 0.04 1612.00 ± 8.06 4.73 ± 0.03
15.10 ± 0.08 1139.00 ± 5.70 3.34 ± 0.03
42.70 ± 0.21 297.60 ± 1.49 0.87 ± 0.01
describing dependencies between variables, i.e., best fitting
to empirical data and characteristics of high prediction value
of response variable. The step-by-step method was applied
to the reduction of the quadratic models. The reduction of
statistically insignificant factors leads to the improvement of
predicted R2 for response Yc and Yw (0.96 for Yc and 0.88 for
Yw ). The reduced regression models are highly statistically sig-
nificant (p < 0.0001), and lack of fit is statistically insignificant
(p > 0.05). This means that the developed regression models
can be used to predict total extraction yield and yield of water
extraction for the assumed range of independent factors vari-
ability.
It can be concluded from the statistical analysis of regres-
sion coefficients that total extraction yield (Yc ) depends
linearly on extraction temperature (X2 ), time (X3 ), and interac-
tion between temperature and time (X2 X3 ) as well as between
pressure and time (X1 X3 ). Moreover, significant terms of the
model include quadratic terms of pressure (X12 ) and temper-
ature (X22 ). Whereas for the yield of water extraction (Yw ),
significant terms of the model are linear terms of pressure (X1 ),
temperature (X2 ) and extraction time (X3 ) and quadratic terms
of pressure (X12 ) and temperature (X22 ). Interactions of the stud-
ied independent variables and quadratic term of time (X32 ) were
regarded as statistically insignificant. The final reduced math-
ematical models for response variables Yc and Yw in coded
form are given below.
Yc = 8.67 + 0.91X2 + 1.35X3 − 0.21X1 X3 + 0.35X2 X3
+ 0.42X12 + 0.46X22 (8)
Yw = 0.88 − 0.18X1 + 0.66X2 + 0.70X3 + 0.50X12 + 0.367X22 (9)
Model significant terms for the extract yield (Ye ) involve
linear effects of pressure (X1 ), temperature (X2 ) and extrac-
tion time (X3 ), interactions of these variables (X1 X2 , X1 X3 ,
X2 X3 ) and quadratic term of time (X32 ). For the quadratic
model demonstrating the effect of the independent variable
on response variable Ye , no reduction of the model was carried
out because the attempt to reduce factor for which the value
p > 0.05 caused deterioration of model parameters including
coefficient of determination R2 and predicted R2 . Although the
quadratic term of temperature (X22 ) was statistically insignif-
icant, it improved the accuracy of the predicted response to
a large extent. The final mathematical model for response
variables Ye in coded form is given below.
Ye = 7.86 + 0.29X1 + 0.25X2 + 0.65X3 + 0.12X1 X2 − 0.17X1 X3
+ 0.21X2 X3 − 0.097X12 + 0.087X22 − 0.12X32 (10)
The best way to visualize the effect of independent vari-
ables on the response variables is the development of response
surfaces diagrams for two variables, whereas the third one is
to be maintained on a fixed level. The effect of process param-
44 Chemical Engineering Research and Design 1 6 0 ( 2 0 2 0 ) 39–51

Table 3 – The BBD matrix and total extraction yield (Yc ), extract yield (Ye ) and yield of water extraction (Yw ).
Run order Independent variables Dependent variables

Pressure Temperature Time Ye (%) Yw (%) Yc (%)

X1 p, MPa X2 T, K X3 t, min

1 0 35 1 333.15 1 60 8.89 2.76 11.66

2 0 35 0 323.15 0 35 7.83 1.11 8.94
3 0 35 0 323.15 0 35 7.92 0.66 8.58
4 −1 25 1 333.15 0 35 7.76 2.62 10.38
5 1 45 0 323.15 1 60 8.50 1.87 10.37
6 −1 25 −1 313.15 0 35 7.47 1.03 8.50
7 0 35 −1 313.15 −1 10 7.19 0.05 7.24
8 0 35 −1 313.15 1 60 7.99 1.09 9.08
9 −1 25 0 323.15 1 60 8.15 2.45 10.60
10 1 45 1 333.15 0 35 8.48 2.05 10.53
11 1 45 0 323.15 −1 10 7.47 0.47 7.94
12 −1 25 0 323.15 −1 10 6.46 0.86 7.32
13 0 35 1 333.15 −1 10 7.24 1.19 8.43
14 0 35 0 323.15 0 35 7.84 0.75 8.59
15 1 45 −1 313.15 0 35 7.70 1.17 8.87

Table 4 – Regression coefficients of full quadratic models with their statistical significance and model parameters for
response variables Yc , Ye and Yw .
Source Ye (%) Yw (%) Yc (%)

ˇ p-Value ˇ p-Value ˇ p-Value

Model <0.0001 0.0009 <0.0001

Lack of fit 0.1943 0.7683 0.7315
ˇ 7.860 0.840 8.700
X1 0.290 0.0002 −0.180 0.0481 0.110 0.1165
X2 0.250 0.0004 0.660 0.0002 0.910 <0.0001
X3 0.650 <0.0001 0.700 0.0001 1.350 <0.0001
X1 X2 0.120 0.0372 −0.180 0.1240 −0.055 0.5454
X1 X3 −0.170 0.0117 −0.047 0.6397 −0.210 0.0542
X2 X3 0.210 0.0040 0.130 0.2163 0.350 0.0094
X12 −0.097 0.0796 0.510 0.0037 0.410 0.0056
X22 0.086 0.1086 0.370 0.0139 0.460 0.0036
X32 −0.120 0.0386 0.064 0.5455 −0.057 0.5494
R2 0.9928 0.9807 0.9939
Adjusted R2 0.9799 0.9458 0.9828
Predicted R2 0.8983 0.8561 0.9511

p < 0.0001 very highly significant, p < 0.01 very significant, p < 0.05 significant, p > 0.10 not significant.

eters on extract yield (Ye ) and water extraction yield (Yw ) were
presented in Fig. 2.
The extract yield (Ye ), an important variable having the
impact on process economics, increased with increasing pres-
sure at a given temperature. It can be explained by the
increased density of the solvent (Hatami et al., 2012). At a con-
stant temperature, the density of supercritical carbon dioxide
increases with increasing pressure, and this induces higher
solvating capacity in supercritical carbon dioxide (Jash et al.,
2020). Consequently, more dissolution of extract takes place
at a higher pressure. Moreover, with the increase of den-
sity, the distance between molecules decrease and interaction
between extract components and carbon dioxide increase
which also lead to greater extract components solubility in
carbon dioxide (Salea et al., 2014). The obtained results con-
firmed the significant effect of pressure on paprika extract
yield reported in the literature (Ambrogi et al., 2002; Daood
et al., 2002; Gnayfeed et al., 2001; Jarén-Galán et al., 1999;
Uquiche et al., 2004). At temperature 333.15 K, the significantly
higher increase in extract yield was observed with the increase
in pressure that at 313.15 K.
The response Ye also increased with the increase of tem-
perature despite the reduction of carbon dioxide density and
the dominant factor is the increase of solute vapor pressure
(Couto et al., 2009). With increasing temperature, the density
of the solvent decreases, which can cause a decrease in solu-
bility, whereas the solute vapor pressure increases, which can
cause an increase in solubility (Hatami et al., 2014; Kostrzewa
et al., 2019). Furthermore, the high temperature could increase
the mass transfer. From Fig. 2, it can be seen that for experi-
ments carried out under the pressure of 45 MPa, higher values
of response Ye were recorded with the increase of tempera-
ture than for experiments under 25 MPa. The highest increase
of response Ye is observed in the high-pressure region at tem-
peratures ranging from 323.15 to 333.15 K. A similar trend was
also reported in the literature on supercritical fluid extraction
of pequi (Johner et al., 2018).
As can be seen (Fig. 2), extraction time is a highly sig-
nificant factor having the effect on response Ye . It can be
caused by the time required for the solvent to penetrate into
the sample, dissolve the extract and diffuse out from the
material. The positive effect of the contact time on response
Ye is especially visible in the case of extractions carried out
 Chemical Engineering Research and Design 1 6 0 ( 2 0 2 0 ) 39–51
Fig. 2 – Response surface plots for extract yield (Ye ) and yield of water extraction (Yw ) in the function of extraction
parameters.
under lower pressure. For these experiments, extraction time
with higher values of yield was significantly longer than for
experiments carried out under higher pressure. However, a
significant increase in time and pressure led only to a slight
increase in extract yield.
The time and temperature are very significant (p < 0.01)
extraction parameters that also have an effect on the yield of
water extraction (Yw ). As can be observed (Fig. 2), the amount
of water extracted from paprika increases with the increase
of temperature and extraction time at a given pressure. It is
related to the solubility of water in supercritical carbon dioxide
which depends strongly on temperature (Sabirzyanov et al.,
2002). In turn, the pressure is a factor negatively correlated
with the response variable Yw and smaller statistically signif-
icance (p < 0.05).
3.3. Extraction of carotenoids from paprika
Extracts obtained during SFE-CO2 of paprika were subjected to
analysis in order to specify the effect of independent variables
on the quality of the extract. Table 5 presents results of the
spectrophotometric analysis: the color value of extract (Be ), the
total content of carotenoids in extract (Ck ), the concentration
of red (Cr ) and yellow (Cy ) carotenoid as well as results of the
color value of post-extraction residues (Bp ).
The total content of carotenoids in extract ranged from
0.81% to 4.65%. Result analysis showed that the highest con-
tent of carotenoids was achieved for extract obtained under
conditions of 45 MPa, 323.15 K and 60 min (Run 5). The recov-
ery of carotenoid was then approx. 86%. For the discussed
experiment, the highest concentration of red and yellow
carotenoids was achieved. The red fraction constituted 60.81%
of carotenoids in this extract and was slightly higher than in
paprika extract obtained using n-hexane Soxhlet extraction
(59.77%). Extract with the lowest concentration of carotenoids
was obtained under conditions of 25 MPa, 323.15 K and 10 min.
Then the lowest recovery of carotenoid was noticed (11.37%),
45
but the mass participation of yellow carotenoids was high
(69.21%). A similar effect of the increased content of red
carotenoids with the pressure increase was achieved by Tepić
et al. (2009). Concentrations of red and yellow carotenoids in
extracts and their participation changed depending on the
extraction parameters applied (Tepić et al., 2009).
Extracts studied in this work were characteristic of signif-
icantly higher carotenoid content compared to many paprika
extracts described in the literature (Daood et al., 2002;
Gnayfeed et al., 2001; Illés et al., 1999). For example, Tepić et al.
achieved over three times lower concentration of carotenoids
in the extract obtained from paprika using supercritical carbon
dioxide (20–40 MPa) (Tepić et al., 2009).
Based on results presented in Table 5, the statistical anal-
ysis of the second-order polynomial equation for response
variables Be , Ck , Cr , Cy and Bp were carried out and regres-
sion coefficients were determined. The results of the statistical
analysis for full quadratic models were presented in Table 6.
The p-value for each model was less than 0.05. This means that
the quadratic models are statistically significant. However, the
analysis showed that some factors of the full quadratic model
for variables Be , Ck , Cr , Cy , and Bp were statistically insignifi-
cant (p > 0.10). Therefore, the step-by-step reduction of these
factors was carried out in the subsequent stage. The results of
the statistical analysis for reduced mathematical models were
presented in Table 7.
The reduced quadratic models for all response variables
(Table 7) are highly statistically significant (p < 0.001). For the
analyzed models, high values of determination coefficient R2
and adjusted R2 were achieved that inform about the high
correlation between input and output data. The reduction of
statistically insignificant factors led to the improvement of
predicted R2 for the variables Be , Ck , Cr , Cy , and Bp to 0.9666,
0.9664, 0.9292, 0.8990 and 0.9580, respectively. The predicted
R2 for each model was in good agreement with the adjusted R2 .
Moreover, the p-value of the lack of fit was statistically insignif-
icant (p > 0.05). This confirmed that the reduced quadratic
46 Chemical Engineering Research and Design 1 6 0 ( 2 0 2 0 ) 39–51

Table 5 – Results of spectrophotometric analysis of paprika extracts and color value of post-extraction residues.
Run order Be (ASTA) Ck (%) Cr (mg/g) Cy (mg/g) Bp (ASTA)

1 1469.22 4.31 23.10 15.55 33.00

2 1049.18 3.08 14.25 13.21 82.00
3 991.45 2.91 13.19 12.47 88.00
4 717.00 2.10 7.84 10.88 105.00
5 1584.00 4.65 25.26 16.28 19.00
6 637.85 1.87 7.18 8.86 121.00
7 512.07 1.50 6.03 7.24 126.00
8 1294.09 3.80 19.68 14.27 54.00
9 977.00 2.87 12.75 12.60 101.00
10 1527.27 4.48 24.42 15.88 34.00
11 862.72 2.53 11.53 10.94 99.00
12 277.70 0.81 2.19 4.93 144.00
13 749.93 2.20 8.46 11.08 102.00
14 988.51 2.90 13.37 12.41 79.00
15 1308.34 3.84 19.71 14.69 60.00

Table 6 – Regression coefficients of full quadratic models with their statistical significance and model parameters for
response variables Be , Ck , Cr , Cy and Bp .
Source Be (ASTA) Ck (%) Cr (mg/g) Cy (mg/g) Bp (ASTA)

ˇ p-Value ˇ p-Value ˇ p-Value ˇ p-Value ˇ p-Value

Model <0.0001 <0.0001 0.0004 0.0002 <0.0001

Lack of fit 0.2215 0.2236 0.1024 0.4210 0.6295
ˇ 1009.7 2.92 13.60 12.70 83.00
X1 334.10 <0.0001 0.98 <0.0001 6.37 <0.0001 2.56 <0.0001 −32.38 <0.0001
X2 88.88 0.0061 0.26 0.0062 1.40 0.0332 1.04 0.0022 −10.88 0.0007
X3 365.24 <0.0001 1.07 <0.0001 6.57 <0.0001 3.06 <0.0001 −33.00 <0.0001
X1 X2 34.95 0.2611 0.10 0.2625 1.01 0.1969 −0.21 0.4528 −2.50 0.2837
X1 X3 5.49 0.8499 0.02 0.8607 0.79 0.2967 −0.58 0.0712 −9.25 0.0068
X2 X3 −15.68 0.5944 −0.05 0.5839 0.25 0.7309 −0.64 0.0538 0.75 0.7335
X12 −21.54 0.4871 −0.06 0.4819 −0.10 0.8928 −0.48 0.1282 4.5 0.0925
X22 59.44 0.0933 0.17 0.0955 1.29 0.1295 0.36 0.2284 −7.50 0.0180
X32 −62.82 0.0804 −0.18 0.0812 −0.57 0.4572 −1.03 0.0118 3.25 0.1941
R2 0.9927 0.9926 0.9870 0.9911 0.9954
Adjusted R2 0.9795 0.9794 0.9635 0.9751 0.9871
Predicted R2 0.8982 0.8980 0.8037 0.8950 0.9570

p < 0.0001 very highly significant, p < 0.01 very significant, p < 0.05 significant, p > 0.10 not significant.

Table 7 – Regression coefficients of reduced mathematical models with their statistical significance and model
parameters for response variables Be , Ck , Cr , Cy and Bp .
Source Be (ASTA) Ck (%) Cr (mg/g) Cy (mg/g) Bp (ASTA)

ˇ p-Value ˇ p-Value ˇ p-Value ˇ p-Value ˇ p-Value

Model <0.0001 <0.0001 <0.0001 <0.0001 <0.0001

Lack of fit 0.3140 0.3160 0.1151 0.2434 0.5234
ˇ 996.46 2.92 13.93 12.63 87.43
X1 334.09 <0.0001 0.98 <0.0001 6.37 <0.0001 2.56 <0.0001 −32.38 <0.0001
X2 88.88 0.0008 0.26 0.0008 1.40 0.0210 1.04 0.0034 −10.88 0.0002
X3 365.24 <0.0001 1.07 <0.0001 6.57 <0.0001 3.06 <0.0001 −33.00 <0.0001
X1 X3 −9.25 0.0046
X22 61.09 0.0446 0.18 0.0462 −8.05 0.0118
X32 −61.17 0.0443 −0.18 0.0453 −1.01 0.0290
R2 0.9890 0.9889 0.9663 0.9594 0.9883
Adjusted R2 0.9828 0.9827 0.9571 0.9432 0.9818
Predicted R2 0.9666 0.9664 0.9292 0.8990 0.9580

p < 0.0001 very highly significant, p < 0.01 very significant, p < 0.05 significant.

models can be used to predict values for the studied range
of variability of independent variables.
The statistical analysis of regression coefficients shows
that the color value of paprika extract (Be ) and the total con-
tent of carotenoids in extracts (Ck ) depend on the pressure (X1 ),
temperature (X2 ) and extraction time (X3 ). Moreover, statisti-
cally significant were quadratic terms of temperature (X22 ) and
time (X32 ), whereas interactions of the independent variables
(X1 X2 , X1 X3 , X2 X3 ) and quadratic term of pressure (X12 ) were
regarded as statistically insignificant (p > 0.10). For the con-
centration of red carotenoids fraction in the extract (Cr ), only
linear effects of pressure (X1 ), temperature (X2 ) and extraction
 Chemical Engineering Research and Design 1 6 0 ( 2 0 2 0 ) 39–51
time (X3 ) were regarded as statistically significant. Whereas for
the concentration of yellow carotenoids fraction in the extract
(Cy ), linear effects of the studied independent variables (X1 ,
X2 , X3 ) and quadratic term of time (X32 ) were regarded as sta-
tistically significant. The color value of post-extraction residue
(Bp ) decreased with the increase of pressure, temperature and
extraction time. However, interactions between pressure and
time (X1 X3 ), and quadratic term of temperature (X22 ) were also
statistically significant. The final reduced mathematical mod-
els for response variables Be , Ck , Cr , Cy , and Bp in coded form
are given below.
Be = 996.46 + 334.09X1 + 88.88X2 + 365.24X3
+ 61.09X22 − 61.17X32 (11)
Ck = 2.92 + 0.98X1 + 0.26X2 + 1.07X3 + 0.18X22 − 0.18X32 (12)
Cr = 13.93 + 6.37X1 + 1.40X2 + 6.57X3 (13)
Cy = 12.63 + 2.56X1 + 1.04X2 + 3.06X3 − 1.01X32 (14)
Bp = 87.43 − 32.38X1 − 10.88X2 − 33.00X3
− 9.25X1 X3 − 8.05X22 (15)
The effect of independent variables on the response vari-
able Be , Ck , Cr and Cy were presented as response surface
diagrams (Fig. 3). As can be seen in Fig. 3, the pressure and tem-
perature are important parameters that influence the color
value of extract and total content of carotenoids in the extract.
As a result of increasing the extraction pressure from 25 MPa to
45 MPa at 323.15 K, a double increase of variable Be and Ck using
43.8 kg CO2 /kg raw material. Under the pressure of 45 MPa, the
temperature increase from 313.15 K to 333.15 K led to a 20%
increase of variables Be and Ck for the same consumption of
carbon dioxide.
The obtained increase value of response variables Be and
Ck with the increase of pressure at a constant temperature, as
for extract yield, resulting from the increase of solvent den-
sity which led to increasing of carotenoids solubility in carbon
dioxide (Ambrogi et al., 2002; Daood et al., 2002; Gnayfeed et al.,
2001; Jarén-Galán et al., 1999; Uquiche et al., 2004). A posi-
tive effect of temperature could be the effect of the increase
of solute vapor pressure, the rate of heat transfer between
molecules of carbon dioxide and mass transfer coefficients.
The significance of quadratic term of temperature for the total
content of carotenoids in extracts can be explained by inter-
actions between the solute–solute and solute–matrix which
affect the solubility of the solute in the supercritical carbon
dioxide. A positive effect of pressure and temperature on the
solubility of carotenoids was reported by other authors (Jarén-
Galán et al., 1999). For example, de la Fuente et al. observed
the increase of astaxanthin solubility in supercritical carbon
dioxide with the increase of temperature (313.15–333.15 K) and
extraction pressure (10–38 MPa) (de la Fuente et al., 2006).
The increase of extract color value and the total content
of carotenoids in the extract as a result of increasing the
extraction pressure depended also on the extraction time. It
is another factor affecting positively the response variables Be
and Ck . However, as extraction time was increased (35–60 min),
47
a decrease in the amount of the extracted carotenoids was
observed. This may be caused by the fact that the extraction
of carotenoids in the later stage of the process is limited by
diffusion processes.
As can be observed in Fig. 3, the concentration of yel-
low and red carotenoids in extracts was increasing with the
increase of pressure and temperature. At constant tempera-
ture, the supercritical carbon dioxide density increases with
increasing pressure and, accordingly, increases the solubil-
ity of the carotenoids. At constant pressure, the increase of
temperature reduces the density of solvent, thus reducing its
solvating power, but it increases the vapor pressure of solutes,
consequently increasing carotenoid solubility. However, the
effect of temperature, especially for the concentration of red
carotenoids, is smaller. It is due to red carotenoids are less sol-
uble in supercritical carbon dioxide than yellow carotenoid,
because of their higher molecular weight and higher polarity
(Tepić et al., 2009). Also, the effect of water co-extraction, the
solubility of which increases with increasing temperature, can
hinder the extraction of high-molecular red carotenoids, and
consequently, lower the recoveries and concentration of red
carotenoids.
Extraction time also shows a positive effect on concentra-
tions of these two carotenoid fractions. The concentration of
red carotenoids increases linearly with extraction time. How-
ever, the increase of yellow carotenoid with the increase of
extraction time is smaller, which was expressed by a nega-
tive correlation concentration of this fraction and quadratic
term of time (X32 ). The present study shows that carotenoids
extracted under lower pressure contained more fractions of
yellow carotenoids and under higher pressure more fractions
of red carotenoids. It is related to the solubility of carotenoids
in supercritical carbon dioxide (Tepić et al., 2009).
3.4. Process optimization
The major objective of optimization was to find parame-
ters allowing the effective SFE-CO2 of sweet paprika. In the
first stage, optimization for each response variable was car-
ried out maximizing or minimizing its value individually. The
total extraction yield (Yc ), maximization of which increases
not only extract yield but also the yield of water extrac-
tion (by-product), was eliminated from optimization. During
optimization, independent variables X1 , X2 and X3 (pressure,
temperature, extraction time) varied in a full scope of vari-
ability (from −1 to 1). The obtained ranges of independent
variables of the found sets of solutions for each response indi-
vidually were presented in Table 8.
Due to the mismatch between the required optimal sets
of process parameters for studied responses, there is a need
to determine a combine optimum parameter solution for all
responses. Then, the multi-criteria optimization of the extrac-
tion process using the desirability function was carried out
(Derringer and Suich, 1980). During optimization, extract yield
(Ye ), extract color value (Be ), the total content of carotenoids
in extract (Ck ), concentration of red carotenoids (Cr ) and con-
centration of yellow carotenoids (Cy ) were all maximized while
the yield of water extraction (Yw ) and the color post-extraction
residue was minimized (Bp ). The weight factor of 1 and the
importance of 3 were chosen for each response in this analysis
because all the responses are equally important. Based on the
multi-criteria optimization method, the desirability function
was specified finding the set of solutions that meet optimiza-
tion criteria. The optimal paprika extraction parameters were
48 Chemical Engineering Research and Design 1 6 0 ( 2 0 2 0 ) 39–51

Fig. 3 – Response surface plots for the total content of carotenoids in extract (Ck ), the concentration of red (Cr ) and yellow (Cy )
carotenoid in extract and color value of extract (Be ) in the function of extraction parameters.

ranging from: p = 43–45 MPa, T = 319–323 K, t = 54–60 min (the
overall desirability D > 0.83). Under the optimal conditions, the
predicted values of response Ye , Yw , Be , Ck , Cr , Cy , and Bp
were in range 8.18–8.32, 1.63–1.69, 1562.51–1583.66, 4.58–4.65,
25.09–25.90, 16.58–16.84 and 19.06–24.34, respectively.
3.5. Validation of the model
In order to validate the developed mathematical models
paprika extraction was carried out three times under opti-
mal conditions to achieve a high concentration of carotenoids
 Chemical Engineering Research and Design 1 6 0 ( 2 0 2 0 ) 39–51 49

Table 8 – Optimal extraction parameters for each response individually.

Response variable Goal Wa Zb The optimal range of the independent variable D

p (MPa) T (K) t (min)

Ye (%) Maximize 1 3 33.83–44.93 330.69–332.99 51.01–60.00 1.0

Yw (%) Minimize 1 3 32.77–37.44 313.15–318.24 10.00–11.45 1.0
Be (ASTA) Maximize 1 3 40.08–45.00 313.03–332.96 44.66–60.00 1.0
Ck (%) Maximize 1 3 39.87–45.00 313.09–332.73 44.75–60.00 1.0
Cr (mg/g) Maximize 1 3 40.49–45.00 313.15–332.99 51.92–60.00 1.0
Cy (mg/g) Maximize 1 3 37.32–45.00 313.96–332.98 37.96–60.00 1.0
Bp (ASTA) Minimize 1 3 39.44–45.00 313.96–333.15 45.31–60.00 1.0

a
Weight: 1 – linear chance of values in the range from 0 to 1.
b
Z – Importance: 5 – high, 3 – medium, 1 – low, D – desirability.

Table 9 – Results of the validation of mathematical models (extraction parameters: 45 MPa, 323.15 K, 56 min).
Response variable Experimental valuea Predicted value Confidence interval

−95% 95%

Ye (%) 8.48 8.37 8.20 8.53

Yw (%) 1.84 1.80 1.49 2.10
Be (ASTA) 1527.80 1594.20 1525.60 1662.79
Ck (%) 4.48 4.68 4.45 4.85
Cr (mg/g) 25.20 25.82 24.10 27.54
Cy (mg/g) 16.35 17.05 16.13 17.97
Bp (ASTA) 18.70 19.56 11.40 27.73

a
The average value of three experiments.

in extract (p = 45 MPa, T = 323.15 K, t = 56 min). The achieved and reliability of BBD coupled with the desirability function
results and values predicted by the developed regression mod- methodology.
els and 95% confidence interval were presented in Table 9. As
can be noticed for the studied response variables, the obtained
Conflict of interest
results are compliant with the predicted values and they fall
within limits determined by appropriate confidence intervals.
The authors declare no competing financial interest.
This evidences the accuracy of the mathematical descrip-
tion of sweet paprika extraction using the supercritical carbon
dioxide. References

4. Conclusions
This paper presents studies of supercritical carbon diox-
ide extraction of sweet paprika that were conducted using
response surface methodology (RSM) with Box–Behnken
design (BBD). The results showed that operating parameters
(pressure, temperature and extraction time) had a signifi-
cant effect on the extraction yield, carotenoid content in
extract (the total content, the concentration of yellow and
red carotenoid), and color value of extract, as well as the
color value of post-extraction residues. In this work, the water
co-extraction phenomenon also discussed and found that
the amount of water extracted from paprika increases with
the increase of temperature and extraction time at a given
pressure. For the studied response variables, highly statis-
tically significant mathematical models were obtained with
high determination coefficient R2 , adjusted R2 and predicted
R2 . The optimal extraction parameters meeting the assumed
optimization criteria were specified: pressure ranging from
43–45 MPa, temperature 319–323 K and time 54–60 min. In
these conditions, a high yield of extraction was obtained, as
well as a high content of carotenoids in the extract. Validation
of the mathematical models showed that experimental results
were compliant with the predicted values and fell within the
limits determined by accurate confidence intervals. This con-
firmed the accuracy of the assumed mathematical models
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