Valuable Component Recovery from

Sunflower Oil Production Waste

Müberra Nur Kılıçarslan1, Mehmet Emin Argun2

Abstract
The evaluation of wastes from edible oil production industry has increasing importance because of
resources deficiency and growing population day by day. It was aimed to investigate the recovery potential
of oil and valuable components such as total flavonoid content (TFC) and antioxidant activities with
conventional and green extraction methods from edible sunflower oil production wastes. Firstly, Soxhlet
extraction was applied on the waste samples from filtration of the oil and then supercritical CO2 (SC- CO2)
extraction was performed to compare extraction yield. The statistical evaluation of the SC- CO2 extraction
experiments was conducted with the Minitab Software program. It was concluded that 33% extraction yield
was obtained with the mixture of perlite and waste sample, while the highest recovery was observed as 23%
for the perlite-free sample. The interaction of independent variables (temperature and pressure) on the
recovery yields were determined as significant (p=0.002). Pressure was detected more effective on the
valuable substance contents of the extracts than temperature. The most efficient conditions were 40 oC and
20 MPa for oil recovery, while 50-60 oC and 20 MPa for valuable substance recovery.
Keywords: Sunflower oil, Waste, Supercritical CO2 extraction, Value added content, Upcycling

1. INTRODUCTION
The importance of food production waste has increased to rising of food supply. Sunflower oil is the most
consumed oil product in the World [1]. By-products of sunflower oil contain valuable components that can be
used in the food industry [2]. Bio-oil production from sunflower seed husks by hydrothermal pre-treated
pyrolysis has been reported as a recovery method [3]. Another study focused on the antioxidant activities of
polysaccharides from the pulp of sunflower oil production [4]. Jagruti et al. investigated the use of sunflower
acid oil, which is a waste from vegetable oil refinery, as glucose-containing feedstock for sophorolipid
production [5]. In recent years, SC-CO2 has been used as an innovative and environmentally friendly extraction
method to produce high quality product yield [4]. Athar Daraee et al (2019) studied the SC-CO2 extraction of
chlorogenic acid from sunflower (Helianthus annuus) seed kernels [6].
In all these studies, it is aimed to contribute to the food industry. However, as far as we know, the residual oil
and valuable component potential in different fillers used in sunflower oil production stages has not been
studied. At the same time, while many studies focus on a single waste material, our study aimed to evaluate

1
Corresponding author: Konya Technical University Environmental Engineering Department, 42250, Selçuklu/Konya
mnkilicarslan@ktun.edu.tr
2
Konya Technical University Environmental Engineering Department, 42250, Selçuklu/Konya meargun@ktun.edu.tr
EurAsia Waste Management Symposium, 24-26 October 2022, İstanbul/Türkiye
several production wastes. Therefore, the recovery potential of oil and valuable components from sunflower oil
production waste was investigated with SC-CO2 extraction.

2. MATERIALS AND METHODS

2.1. Materials
Samples were obtained from Guzeloglu food - Zevk sunflower oil factory (Konya, Turkey). Three types of
waste are generated from the production of sunflower oil after different processes such as sunflower pulp which
is de-oiled with hexane, waxy perlite (WP) soil and oily bentonite (OB) soil.

2.2. Experimental Design

The effect independent variables of pressure and temperature on the SC-CO2 extraction was studied according
to the experimental design (central composite design) created by using Design Expert statistical program for
the WP sample (Table 1). The results were statistically evaluated by ANOVA test. Also, the effect of mixing
expanded granular perlite with the wastes on SC-CO2 extraction was investigated.
Table 1. Ranges of independent variables in the experiments

Independent Variables Min value -1 Midpoint +1 Max value

Temperature (°C) 36 40 50 60 64,1
Pressure (MPa) 7,93 10 15 20 22,1

2.3. SC-CO2 Extraction

SC-CO2 extraction was conducted with the SUPEREX F-500 device (Biosan, Superex comp., Türkiye). The
extractor has 500 mL column, pressure and temperature can be increased up to 34.5 MPa and 70 °C,
respectively.
For extraction experiments, 10 g sample was placed into device and falcon tube, in which the extract will
accumulate, was placed in separator chamber. The CO2 pump was started after temperature reached the desired
value. The extraction process was carried out for 2 hours, the first 30 minutes being static and 90 minutes of
dynamic flow mode. The extracts obtained from WP and OB were abbreviated as WPE and OBE, respectively.

2.4. Analysis Methods

Oil-grease analysis was done with Soxhlet gravimetric method [7] to determine extraction yield of the SC-CO2
extraction. Extraction efficiency was calculated by dividing the amount of extract obtained by SC-CO2
extraction by the oil-grease content determined by the Soxhlet method.
The changes in the components of the extracts were monitored by total flavonoid contents (TFC) and
antioxidant activity assays (ABTS and DPPH). TFC of the samples were analyzed according to Zhishen et al
[8]. Trolox equivalent antioxidant capacity were spectrophotometrically measured in respect of DPPH and
ABTS radical scavenging activities (Hach-Lange, Dr 5000). DPPH radical scavenging capacity of the samples
and extracts were determined using 0.1 mM DPPH (2,2-diphenyl-1-picryhydrazyl radical) according to the Yu
et al. (2002) [9]. Radical cation scavenging capacity was determined with ABTS solution [10].

3. RESULTS AND DISCUSSION

3.1. Oil Recovery from the Waste Materials

Volumetric (v/v) and gravimetric (w/w) oil recovery (OR) efficiencies for SC-CO2 extraction of the WP ranged
from 0.3% to 9% and from 0.3% to 8%, respectively (Figure 1). It was observed that amount of the extracts
increased with the increase of pressure and decrease of temperature, and it was maximizing above 20 MPa.
Similar to our results, it was reported that increased pressure (28-34 MPa) of SC-CO2 and milling time of chia
seeds increased oil yield, but higher temperature (60-80 °C) could decrease the yield [11].
Higher extraction yields were obtained for SC-CO2 extraction of the OB waste samples than WP. The yields
for OB wastes ranged from 7% to 26% (v/v) and from 4% to 23% (w/w), respectively. Extraction of expanded
granular perlite (10 g) and OB waste sample (20 g) mixture with SC-CO2 at 40 °C and 20 MPa was also
investigated to increase the amount of extract. Oil recovery efficiency increased from 23% to 33% (w/w) by
using the expanded perlite. It was concluded that interaction between SC-CO2 and waste sample was increased
by expanded perlite because of its high surface area.
 Valuable Component Recovery from Sunflower Oil Production Waste
Müberra Nur Kılıçarslan, Mehmet Emin Argun
Although higher extract amount can be obtained by using conventional chemicals such as hexane [12], it should
be stated that SC-CO2 extraction provides more stable, healthy extracts and lower toxic residue.
Design-Expert® Software
Factor Coding: Actual OR (%,Design-Expert®
v/v)
Factor
Software
Coding: Actual
60
OR (%, w/w)
OR (%, v/v) 60 OR (%, w/w)
9.0 7.9

0.3 0.3
2
X1 = A: Pressure X1 = A: Pressure
X2 = B: Temperature X2 = B: Temperature
55 55

B: Temperature (oC)
B: Temperature (oC)

2 4

50 50
6

45 45

2
8

40 40
(a) 10 12 14 16 18 20 (b) 10 12 14 16 18 20

A: Pressure (MPa) A: Pressure (MPa)

Figure 1. Binary effects of temperature and pressure on the oil recovery (OR) efficiency calculated by
using (a) extract volume of WP and (b) extract mass of WP

3.2. The Change of Valuable Components

TFC which was the main phenolics in the extract increased at the high pressure and temperature for WP extracts,
while similar results were also obtained at lowest conditions (Figure 2). Similarly, maximum TFC concentration
for OBE was obtained as 7415 mg QE /L at the condition of 60 °C and 20 MPa (Table 2). It can be said that
the increase in polarity of CO2 at high pressure increases the solubility of polar phenolic compounds such as
flavonoids in CO2.
Antioxidant scavenging assays in respect of DPPH and ABTS radicals for WPE increased significantly by SC-
CO2 extraction compared to conventional extraction method (Soxhlet). The highest antioxidant activity of WPE
was achieved at 40 °C and 20 MPa for DPPH assay and 60 °C and 20 MPa for ABTS assay. Pressure was
determined as the most effective experimental variable like for TFC results. The highest recovery of valuable
compounds for OBE was obtained at the operating conditions higher than 50 °C and 20 MPa (Table 2). In
addition, the extract of the perlite-OB mixture had lower antioxidant capacity than OBE, while it had average
TFC value.
Table 2. The effect of experimental conditions of the SC-CO2 extraction on the oily bentonite (OB) extracts

Temperature Pressure TFC DPPH ABTS

Sample
(°C) (MPa) (mg QE/L) (µM TE) (µM TE)

50 22,1 4473 - 1084

Oily Bentonite Extract 40 20 3269 - 825
(OBE) 60 20 7415 516 423
50 15 4492 375 538
Mixture of perlite and
40 20 3639 - 278
oily bentonite (OB)

Antioxidant activity of the WPE was between 90 and 1878 µM TE in respect of ABTS assay, while it was
found between 57 - 220 µM TE for DPPH assay. Less antioxidant activity was found for OBE compared to the
WPE sample. It was reported that antioxidant activity in the extracts of sunflower by-product obtained by using
microwave-assisted extraction was in the range of 180 to 266 µM TE [12]. Although we obtained similar results
with the literature, the antioxidant activity showed a wide range of variation. This may be a result of variation
of the extracted compounds, which may be responsible for the antioxidant activity, under different experimental
conditions.
 EurAsia Waste Management Symposium, 24-26 October 2022, İstanbul/Türkiye
Design-Expert® Software
Factor Coding: Actual
60
TFC (mg QE/L)
TFC (mg QE/L)
1756.7

3.3 1500
1000
X1 = A: Pressure
X2 = B: Temperature
55

B: Temperature (oC)

50

1000
45 1500

500

40
10 12 14 16 18 20
(a)

A: Pressure (MPa)
Design-Expert® Software
Factor Coding: Actual
60
DPPH (uM TE)Actual
Design-Expert® Software
Factor Coding:
60
ABTS (uM TE)
DPPH (uM TE) ABTS (uM TE)
827.498 1438.62

28.6757 89.3515

X1 = A: Pressure X1 = A: Pressure
X2 = B: Temperature
55
100 X2 = B: Temperature
55 1200
B: Temperature (oC)
B: Temperature (oC)

50
200 300 400 50
800 1000

500
600

45 45

40 40

(b) 10 12 14 16 18 20 (c) 10 12 14 16 18 20

A: Pressure (MPa) A: Pressure (MPa)

Figure 2. Binary effects of the experimental variables on the valuable components; (a) TFC value, (b)
DPPH assay and (c) ABTS assay

3.3. Statistical Analysis

OR efficiencies in respect of the volumetric and mass recovery of WPE statistically resulted significant in
quadratic model (p value: 0.0015 and p value: 0.0010). The most significant variable on OR value was pressure
(volumetric; p value: 0.0003 – mass; p value: 0.0002) while two independent variables were also had great
significance (Table 3). Similar results have reported in literature regarding the significance of experimental
variables for extraction of sunflower seed kernels by SC-CO2 extraction method [6].
The effect of experimental variables on the TFC and ABTS values was not statistically significant (p value:
0.099 and p value: 0.076, respectively). However, it was observed that experimental variables have significant
effect on the DPPH antioxidant activity values of the extracts (p value: 0.035). Pressure was more effective on
the recovery of valuable compounds than temperature (Table 3).
 Valuable Component Recovery from Sunflower Oil Production Waste
Müberra Nur Kılıçarslan, Mehmet Emin Argun
Table 3. ANOVA results for oil recovery (OR) efficiency and extract quality parameters of the studied waste samples

OR OR DPPH• ABTS•+ TFC

ANOVA terms (%, v/v) (%, w/w) µM TE µM TE mg QE/L
F p F p F p F p F p
Source Quadratic Quadratic Linear Linear 2FI
Model 41.9 0.0015 51.2 0.001 5.61 0.035 3.81 0.076 3.29 0.099
Temperature 28.5 0.0059 33.9 0.004 0.45 0.522 1.28 0.295 0.019 0.895
Pressure 147 0.0003 185 0.0002 10.76 0.014 6.34 0.040 0.33 0.587
Lack of Fit - - 136 0.06 245 0.049 26.41 0.148 966 0.024
Std. Dev. 0.61 0.50 180.4 371.5 490.5
Mean 3.70 3.20 308.5 884.6 1199.6
C.V. % 16.4 15.6 58.5 42.0 40.9
R-Squared 0.98 0.99 0.62 0.52 0.62
Adeq Precision 16.0 18.2 5.98 4.71 5.52

4. CONCLUSION
It has been observed that SC-CO2 extraction was more effective on the oily bentonite (OB) wastes to recover
oil and valuable components than waxy perlite (WP) waste. The ANOVA tests of the developed models resulted
in high coefficient of determination for oil recovery values for extract volume (R2 = 98%) and mass (R2 = 99%).
It was detected that pressure variable was the most important variable affecting the significance for all analyses.
No significant relationship was found between TFC value and independent variables of SC-CO2 extraction. Oil
recovery (33%) significantly increased with the addition of perlite to the waste sample before SC-CO2
extraction. Due to the high TFC and antioxidant content in the extracts, it may be possible to use these products
in different sectors (cosmetics, pharmaceuticals, food, etc.).

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EurAsia Waste Management Symposium, 24-26 October 2022, İstanbul/Türkiye

BIOGRAPHY
Müberra Nur KILIÇARSLAN works as a research assistant at Konya Technical University
Environmental Engineering Department.
Kılıçarslan received her BSc and MSc in Environmental Engineering in 2016 and 2019 from Selcuk
University, Konya, Turkey. She is still PhD student on Waste Recovery and Biofuels at Konya
Technical University Environmental Engineering Department.
Kılıçarslan is a member of Konya Technical University Zero Waste Commission.
She may be contacted at mnkilicarslan@ktun.edu.tr.