high-pressure technlogies as promising ......high-pressure technlogies as promising green methods...

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HIGH-PRESSURE TECHNLOGIES AS PROMISING GREEN METHODS FOR EXTRACTION OF COCOA SHELL Tanja Gagić 1 , Stela Jokić 2 , Željko Knez 1,3 and Mojca Škerget 1 1 Faculty of Chemistry and Chemical Engineering, University of Maribor, Smetanova 17, Maribor 2000, Slovenia; [email protected] (T.G.); [email protected] (Ž.K); [email protected] (M.Š.) 2 Faculty of Food Technology Osijek, Josip Juraj Strossmayer University of Osijek, Franje Kuhača 20, Osijek 31000, Croatia; [email protected] (S.J.); 3 Faculty of Medicine, University of Maribor, Taborska ulica 8, Maribor 2000, Slovenia Cocoa shell represents a waste from the industrial production of cocoa and chocolate. However, it attracts a lot of attention because it is rich in valuable compounds. Re-use of cocoa shell won’t increase only profitability and avoid environmental pollution, it could also found application in cosmetic, pharmaceutical and food industry due to its antioxidant, antimicrobial, anti-ageing, anti-radical and anticarcinogenic properties. Different methods were used for extraction of cocoa shell, but the data related to the use of green separation techniques are limited in the literature. Therefore, the aim of this work was to use both green-based and conventional extraction methods in order to compare results.Supercritical CO 2 extraction was performed at pressures of 200 and 300 bar and at temperatures 40, 60 and 80 ˚C. Subcritical water extraction was carried out in a batch reactor at temperatures of 170 ˚C and 220 ˚C. Soxhlet extraction with hexane and extraction with 50 % acetone were also performed. Total phenol content, total proanthocyanidin content and antioxidant activity of extracts were determined. Besides phenolic compounds, some extracts contained high amounts of theobromine, followed by caffeine and theophylline. Furthermore, subcritical water extracts were rich in sugars and their derivatives. Fatty acids were also obtained using supercritical CO 2 and Soxhlet extraction of cocoa shell and were analysed by gas chromatography. INTRODUCTION EXPERIMENTAL METHODS CONCLUSION AND FUTURE APPLICATIONS Green-based method such as supercritical CO 2 and subcritical water extraction showed more efficient results than conventional methods. Supercritical CO 2 and subcritical water extractions need shorter extraction time and their extracts are free of hazardous solvents. Furthermore, subcritical water and CO 2 are environmentally friendly, low-cost and safe extraction solvents, which could be promising alternative for recovery of bioactive compounds. Precisely, supercritical CO 2 extraction showed high efficiency for fat recovery, whereas subcritical water technology found application for extraction of sugars, methylxanthines and phenolic compounds. Furthermore, the chemical composition of cocoa shell implies that it could be used in food, cosmetic and pharmaceutical industries. RESULTS 1,85 1,99 2,6 2,75 3,05 2,77 2,86 0 0,5 1 1,5 2 2,5 3 3,5 yield of extract, % The yield of extracts obtained by supercritical CO 2 extraction at different conditions and Soxhlet extraction with hexane. 0 20 40 60 80 100 120 140 160 total phenol content, mg/(g of extract) Total phenol content in extracts obtained by subcritical water extraction and extraction with 50 % acetone. 170˚C 30 min 220˚C 30 min 200 bar 300 bar 0 1 2 3 4 5 6 7 total proanthocyanidin content, mg/(g of extract) Total proanthocyanidin content in extracts obtained by subcritical water extraction and extraction with 50 % acetone. 170˚C 30 min 220˚C 30 min 200 bar 300 bar Compounds extracted from cocoa shell 0 10 20 30 40 50 60 70 yield of extracts, % The yield of cocoa shell extracts obtained by subcritical water extraction and extraction with 50 % acetone. 170˚C 30 min 220˚C 30 min 200 bar 300 bar 0 20 40 60 80 100 Antioxidant activity, % The antioxidant activity of extracts obtained by subcritical water extraction and extraction with 50 % acetone. 170˚C 30 min 220˚C 30 min 200 bar 300 bar

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Page 1: HIGH-PRESSURE TECHNLOGIES AS PROMISING ......HIGH-PRESSURE TECHNLOGIES AS PROMISING GREEN METHODS FOR EXTRACTION OF COCOA SHELL Tanja Gagić 1, Stela Jokić2, ŽeljkoKnez 1,3 and Mojca

HIGH-PRESSURE TECHNLOGIES AS PROMISING GREEN METHODS FOR

EXTRACTION OF COCOA SHELLTanja Gagić 1, Stela Jokić 2, Željko Knez 1,3 and Mojca Škerget 1

1 Faculty of Chemistry and Chemical Engineering, University of Maribor, Smetanova 17, Maribor 2000, Slovenia; [email protected] (T.G.); [email protected] (Ž.K);

[email protected] (M.Š.)2 Faculty of Food Technology Osijek, Josip Juraj Strossmayer University of Osijek, Franje Kuhača 20, Osijek 31000, Croatia; [email protected] (S.J.);

3 Faculty of Medicine, University of Maribor, Taborska ulica 8, Maribor 2000, Slovenia

Cocoa shell represents a waste from the industrial production of cocoa and chocolate. However, it attracts a lot of attention because it is rich in valuable compounds. Re-use of cocoa shell won’t

increase only profitability and avoid environmental pollution, it could also found application in cosmetic, pharmaceutical and food industry due to its antioxidant, antimicrobial, anti-ageing, anti-radical

and anticarcinogenic properties. Different methods were used for extraction of cocoa shell, but the data related to the use of green separation techniques are limited in the literature. Therefore, the

aim of this work was to use both green-based and conventional extraction methods in order to compare results. Supercritical CO2 extraction was performed at pressures of 200 and 300 bar and at

temperatures 40, 60 and 80 ˚C. Subcritical water extraction was carried out in a batch reactor at temperatures of 170 ˚C and 220 ˚C. Soxhlet extraction with hexane and extraction with 50 %

acetone were also performed. Total phenol content, total proanthocyanidin content and antioxidant activity of extracts were determined. Besides phenolic compounds, some extracts contained high

amounts of theobromine, followed by caffeine and theophylline. Furthermore, subcritical water extracts were rich in sugars and their derivatives. Fatty acids were also obtained using supercritical

CO2 and Soxhlet extraction of cocoa shell and were analysed by gas chromatography.

INTRODUCTION EXPERIMENTAL METHODS

CONCLUSION AND FUTURE APPLICATIONSGreen-based method such as supercritical CO2 and subcritical water extraction showed more efficient

results than conventional methods. Supercritical CO2 and subcritical water extractions need shorter

extraction time and their extracts are free of hazardous solvents. Furthermore, subcritical water and

CO2 are environmentally friendly, low-cost and safe extraction solvents, which could be promising

alternative for recovery of bioactive compounds. Precisely, supercritical CO2 extraction showed high

efficiency for fat recovery, whereas subcritical water technology found application for extraction of

sugars, methylxanthines and phenolic compounds. Furthermore, the chemical composition of cocoa

shell implies that it could be used in food, cosmetic and pharmaceutical industries.

RESULTS

1,85

1,99

2,6

2,75

3,05

2,772,86

0

0,5

1

1,5

2

2,5

3

3,5

yie

ld o

f extr

act,

%

The yield of extracts obtained by supercritical CO2 extraction at different

conditions and Soxhlet extraction with hexane.

0

20

40

60

80

100

120

140

160

tota

l p

hen

ol co

nte

nt,

mg/(

g o

f extr

act)

Total phenol content in extracts obtained by subcritical water

extraction and extraction with 50 % acetone.

170˚C 30 min 220˚C 30 min

200 bar 300 bar

0

1

2

3

4

5

6

7

tota

l p

roan

tho

cyan

idin

co

nte

nt,

mg/(

g o

f extr

act)

Total proanthocyanidin content in extracts obtained by subcritical

water extraction and extraction with 50 % acetone.

170˚C 30 min 220˚C 30 min

200 bar 300 bar

Compounds extracted from cocoa shell

0

10

20

30

40

50

60

70

yie

ld o

f extr

acts

, %

The yield of cocoa shell extracts obtained by subcritical water

extraction and extraction with 50 % acetone.

170˚C 30 min 220˚C 30 min

200 bar 300 bar

0

20

40

60

80

100

An

tio

xid

an

t acti

vit

y, %

The antioxidant activity of extracts obtained by subcritical water

extraction and extraction with 50 % acetone.

170˚C 30 min 220˚C 30 min

200 bar 300 bar