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Process-intensified waste valorization and environmentally friendly d-limonene extraction

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Abstract

Supercritical fluid extraction (SFE) is an innovative, clean, sustainable, and efficient technology to obtain essential oils and bioactive substances from plants and herbs. This work focused on the SFE of lemon essential oil using dehydrated and ground waste peels from a Protected Geographical Indication Italian cultivar. After the characterization of peels, both traditional hydro-distillation and SFE were applied to extract lemon essential oil. The most abundant compound in extract was d-limonene, equal to 82% in fruits harvested in November, 88% in December, and 80% in January. The effect of operating conditions on total extract and d-limonene yield was analyzed in a series of experiments at 35–50 °C and 12.5–20 MPa. The optimum conditions for limonene extraction were 15 MPa and 40 °C. The effect of ripening stage, particle size, and CO2 flow rate was also investigated and discussed. Moreover, theoretical and experimental pressure drop and bed void fraction during SFE were analyzed, showing a packing phenomenon. Sovová’s approximate model was applied to analyze the experimental results and it successfully fitted the extraction kinetics of essential oil. SFE can successfully be integrated in an intensified green process of citrus peel valorization to produce high-value and quality essential oil, with no use of chemical solvents, downstream treatments, and long-time extractions for a greener environment.

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Abbreviations

a 0 :

Specific surface area \(\left( { = \frac{6\;(1 - \varepsilon )}{d}} \right)\) (m2/m3)

a s :

Specific area between the regions of intact and broken cells (m2/m3)

d :

Particle size (m)

e :

Extraction yield, massextract/massinsoluble solid (kg/kg)

k f :

Supercritical-phase mass transfer coefficient (m/s)

k s :

Solid-phase mass transfer coefficient (s−1)

K :

Partition coefficient

L :

Bed height (m)

m :

Mass of particles in the extraction column (kg)

N m :

Charge of insoluble solid \(\left( { = \left( {1 - \frac{{x_{0} }}{{1 + x_{0} }}} \right) \times m} \right)\) (kg)

Q :

CO2 flow rate (kg/s)

q :

Solvent ratio, massCO2/massmatrix (kg/kg)

q c :

Value of q at the crossing point with the estimate for the second part of extraction curve

\(\dot{q}\) :

Specific flow rate of solvent [mass of CO2/(mass of peels × time)]

r :

Grinding efficiency in the particles (fraction of broken cells)

S :

Cross section of the extraction column (m2)

u :

Superficial velocity of the supercritical CO2 (m/s)

x 0 :

Concentration in the untreated solid, mass of solute/mass of dry peels (kg/kg)

Y :

Percent extraction yield, mass of extract/mass of dry peels × 100 (%)

y 0 :

Initial fluid-phase concentration, mass of solute/mass of solvent (kg/kg)

z :

Axial coordinate

\(\Delta P\) :

Pressure drop in extraction column

γ :

Solvent-to-matrix ratio in the bed, mass of solvent/mass of insoluble solid, \(( = \rho_{\text{f}} \varepsilon /[\rho_{\text{s}} \;(1 - \varepsilon )])\) (kg/kg)

ε :

Bed void fraction

ρ a :

Apparent (bulk) density of particles (kg/m3)

ρ f :

Density of solvent (kg/m3)

ρ s :

Density of solid phase (kg/m3)

μ :

Viscosity of supercritical CO2 (kg/m/s)

References

  • Akgün M, Akgün NA, Dinçer S (2000) Extraction and modeling of lavender flower essential oil using supercritical carbon dioxide. Ind Eng Chem Res 39:473–477

    Google Scholar 

  • Aleksovski SA, Sovová H (2007) Supercritical CO2 extraction of Salvia officinalis L. J Supercrit Fluids 40:239–245

    Google Scholar 

  • Asekun OT, Grierson DS, Afolayan AJ (2007) Effects of drying methods on the quality and quantity of the essential oil of Mentha longifolia L. subsp. Capensis. Food Chem 101:995–998

    Google Scholar 

  • Atti-Santos AC, Rossato M, Serafini LA, Cassel E, Moyna P (2005) Extraction of essential oils from lime (Citrus latifolia Tanaka) by hydrodistillation and supercritical carbon dioxide. Braz Arch Biol Technol 48:155–160

    Google Scholar 

  • Bensebia O, Barth D, Bensebia B, Dahmani A (2009) Supercritical CO2 extraction of rosemary: effect of extraction parameters and modelling. J Supercrit Fluids 49:161–166

    Google Scholar 

  • Berna A, Tárrega A, Blasco M, Subirats S (2000) Supercritical CO2 extraction of essential oil from orange peel; effect of the height of the bed. J Supercrit Fluids 18:227–237

    Google Scholar 

  • Carvalho RN Jr, Moura LS, Rosa PTV, Meireles MAA (2005) Supercritical fluid extraction from rosemary (Rosmarinus officinalis): kinetic data, extract’s global yield, composition, and antioxidant activity. J Supercrit Fluids 35:197–204

    Google Scholar 

  • Celiktas OY, Bedir E, Sukan FV (2007) In vitro antioxidant activities of Rosmarinus officinalis extracts treated with supercritical carbon dioxide. Food Chem 101:1457–1464

    Google Scholar 

  • Chemat F, Vian MA, Cravotto G (2012) Green extraction of natural products: concept and principles. Int J Mol Sci 13:8615–8627

    Google Scholar 

  • Ciriminna R, Fidalgo A, Delisi R, Carnaroglio D, Grillo G, Cravotto G, Alfredo T, Ilharco LM, Pagliaro M (2017) High-quality essential oils extracted by an eco-friendly process from different citrus fruits and fruit regions. ACS Sustain Chem Eng 5(6):5578–5587

    Google Scholar 

  • da Francisco JC, Sivik B (2002) Solubility of three monoterpenes, their mixtures and eucalyptus leaf oils in dense carbon dioxide. J Supercrit Fluids 23: 11–19

    Google Scholar 

  • del Valle JM, Uquiche EL (2002) Particle size effects on supercritical CO2 extraction of oil-containing seeds. J Am Oil Chem Soc 79:1261–1266

    Google Scholar 

  • del Valle JM, Calderón D, Núñez GA (2019) Pressure drop may negatively impact supercritical CO2 extraction of citrus peel essential oils in an industrial-size extraction vessel. J Supercrit Fluids 144:108–121

    Google Scholar 

  • Diaz MS, Brignole EA (2009) Modeling and optimization of supercritical fluid processes. J Supercrit Fluids 47:611–618

    Google Scholar 

  • Disciplinare “Limone di Rocca Imperiale” IGP. http://www.politicheagricole.it/flex/cm/pages/ServeBLOB.php/L/IT/IDPagina/2052.

  • Edris AE (2007) Pharmaceutical and therapeutic potentials of essential oils and their individual volatile constituents: a review. Phyther Res 21(4):308–323

    Google Scholar 

  • Ferreira SRS, Meireles MAA (2002) Modeling the supercritical fluid extraction of black pepper (Piper nigrum L.) essential oil. J Food Eng 54:263–269

    Google Scholar 

  • Filho CA, Silva CM, Quadri MB, Macedo EA (2003) Tracer diffusion coefficients of citral and D-limonene in supercritical carbon dioxide. Fluid Phase Equilib 204:65–73

    Google Scholar 

  • Fornari T, Ruiz-Rodriguez A, Vicente G, Vázquez E, García-Risco MR, Reglero G (2012a) Kinetic study of the supercritical CO2 extraction of different plants from Lamiaceae family. J Supercrit Fluids 64:1–8

    Google Scholar 

  • Fornari T, Vicente G, Vázquez E, García-Risco MR, Reglero G (2012b) Isolation of essential oil from different plants and herbs by supercritical fluid extraction. J Chromatogr A 1250:34–48

    Google Scholar 

  • Gaspar F, Lu T, Santos R, Al-Duri B (2003) Modelling the extraction of essential oils with compressed carbon dioxide. J Supercrit Fluids 25:247–260

    Google Scholar 

  • González-Molina E, Domínguez-Perles R, Moreno DA, García-Viguera C (2010) Natural bioactive compounds of Citrus limon for food and health. J Pharm Biomed Anal 51:327–345

    Google Scholar 

  • Goto M, Roy BC, Hirose T (1996) Shrinking-core leaching model for supercritical-fluid extraction. J Supercrit Fluids 9:128–133

    Google Scholar 

  • Han X, Cheng L, Zhang R, Bi J (2009) Extraction of safflower seed oil by supercritical CO2. J Food Eng 92:370–376

    Google Scholar 

  • Hussain AI, Anwar F, Sherazi STH, Przybylski R (2008) Chemical composition, antioxidant and antimicrobial activities of basil (Ocimum basilicum) essential oils depends on seasonal variations. Food Chem 108:986–995

    Google Scholar 

  • Ibrahim MA, Kainulainen P, Aflatuni A, Tiilikkala K, Holopainen JK (2001) Insecticidal, repellent, antimicrobial activity and phytotoxicity of essential oils: with special reference to limonene and its suitability for control of insect pests. Agric Food Sci Finl 10:243–259

    Google Scholar 

  • John I, Muthukumar K, Arunagiri A (2017) A review on the potential of citrus waste for D-Limonene, pectin, and bioethanol production. Int J Green Energy 14:599–612

    Google Scholar 

  • Kondo M, Akgun N, Goto M, Kodama A, Hirose T (2002) Semi-batch operation and countercurrent extraction by supercritical CO2 for the fractionation of lemon oil. J Supercrit Fluids 23:21–27

    Google Scholar 

  • Kumar SPJ, Prasad SR, Banerjee R, Agarwal DK, Kulkarni KS, Ramesh KV (2017) Green solvents and technologies for oil extraction from oilseeds. Chem Cent J 11:1–7

    Google Scholar 

  • Loizzo MR, Tundis R, Bonesi M, Di Sanzo G, Verardi A, Lopresto CG, Pugliese A, Menichini F, Balducchi R, Calabrò V (2016) Chemical Profile and Antioxidant Properties of Extracts and Essential Oils from Citrus × limon (L.) Burm. cv. Femminello Comune. Chem Biodivers 13:571–581

    Google Scholar 

  • Lopresto CG, Petrillo F, Casazza AA, Aliakbarian B, Perego P, Calabrò V (2014) A non-conventional method to extract D-limonene from waste lemon peels and comparison with traditional Soxhlet extraction. Sep Purif Technol 137:13–20

    Google Scholar 

  • Mamma D, Christakopoulos P (2014) Biotransformation of citrus by-products into value added products. Waste Biomass Valoriz 5(4):529–549

    Google Scholar 

  • Miller JA, Thompson PA, Hakim IA, Lopez AM, Thomson CA, Chew W, Hsu C-H, Chow H-HS (2012) Safety and feasibility of topical application of limonene as massage oil to the breast. J Cancer Ther 3:1–12

    Google Scholar 

  • Murali R, Saravanan R (2012) Antidiabetic effect of d-limonene, a monoterpene in streptozotocin-induced diabetic rats. Biomed Prev Nutr 2:269–275

    Google Scholar 

  • Murali R, Karthikeyan A, Saravanan R (2013) Protective effects of d-Limonene on lipid peroxidation and antioxidant enzymes in streptozotocin-induced diabetic rats. Basic Clin Pharmacol Toxicol 112:175–181

    Google Scholar 

  • Negro V, Mancini G, Ruggeri B, Fino D (2016) Citrus waste as feedstock for bio-based products recovery: review on limonene case study and energy valorization. Bioresour Technol 214:806–815

    Google Scholar 

  • Oliveira ELG, Silvestre AJD, Silva CM (2011) Review of kinetic models for supercritical fluid extraction. Chem Eng Res Des 89:1104–1117

    Google Scholar 

  • Oulebsir-Mohandkaci H, Baba Aissa A, Badaoui S et al (2018) Comparative study of the toxicity of phenolic compounds of coriander (Coriandrum sativum) and false fennel (Aneth graveolens) on Galleria mellonella (Lepidoptera, Pyralidae). Euro-Mediterr J Environ Integr. https://doi.org/10.1007/s41207-018-0071-z

    Article  Google Scholar 

  • Papamichail I, Louli V, Magoulas K (2000) Supercritical fluid extraction of celery seed oil. J Supercrit Fluids 18:213–226

    Google Scholar 

  • Pereira CG, Meireles MAA (2010) Supercritical fluid extraction of bioactive compounds: fundamentals. applications and economic perspectives. Food Bioprocess Technol 3:340–372

    Google Scholar 

  • Pereira CG, Gualtieri IP, Maia NB, Meireles MAA (2008) Supercritical extraction to obtain vetiver (Vetiveria zizanioides L. Nash) extracts from roots cultivated hydroponically. J Agric Sci Technol 2:44–50

    Google Scholar 

  • Poiana M, Sicari V, Mincione B (1998a) A comparison between the chemical composition of the oil, solvent extract and supercritical carbon dioxide extract of Citrus medica cv. Diamante. J Essent Oil Res 10:145–152

    Google Scholar 

  • Poiana M, Sicari V, Mincione B (1998b) Supercritical carbon dioxide (SC-CO2) extraction of grapefruit flavedo. Flavour Fragance J 13:125–130

    Google Scholar 

  • Poiana M, Fresa R, Mincione B (1999) Supercritical carbon dioxide extraction of bergamot peels. Extraction kinetics of oil and its components. Flavour Fragr J 14:358–366

    Google Scholar 

  • Pourmortazavi SM, Hajimirsadeghi SS (2007) Supercritical fluid extraction in plant essential and volatile oil analysis. J Chromatogr A 1163:2–24

    Google Scholar 

  • Putnik P, Bursać Kovačević D, Režek Jambrak A, Barba FJ, Cravotto G, Binello A, Lorenzo JM, Shpigelman A (2017) Innovative “green” and novel strategies for the extraction of bioactive added value compounds from citrus wastes—a review. Molecules. https://doi.org/10.3390/molecules22050680

    Article  Google Scholar 

  • Raeissi SC, Peters J (2005) Experimental determination of high-pressure phase equilibria of the ternary system carbon dioxide+limonene+linalool. J Supercrit Fluids 35:10–17

    Google Scholar 

  • Reis-Vasco EMC, Coelho JAP, Palavra AMF (1999) Comparison of pennyroyal oils obtained by supercritical CO2 extraction and hydrodistillation. Flavour Fragance J 14:156–160

    Google Scholar 

  • Reverchon E (1996) Mathematical modeling of supercritical extraction of sage oil. AIChE J 42(6):1765–1771

    Google Scholar 

  • Reverchon E, De Marco I (2006) Supercritical fluid extraction and fractionation of natural matter. J Supercrit Fluids 38:146–166

    Google Scholar 

  • Reverchon E, Marrone C (1997) Supercritical extraction of clove bud essential oil: isolation and mathematical modeling. Chem Eng Sci 52(20):3421–3428

    Google Scholar 

  • Reverchon E, Sesti Osséo L (1994) Supercritical CO2 extraction of basil oil: Characterization of products and process modeling. J Supercrit Fluids 7:185–190

    Google Scholar 

  • Reverchon E, Daghero J, Marrone C, Mattea M, Poletto M (1999) Supercritical fractional extraction of fennel seed oil and essential oil: experiments and mathematical modeling. Ind Eng Chem Res 38(8):3069–3075

    Google Scholar 

  • Rodrigues VM, Rosa PTV, Marques MOM, Petenate AJ, Meireles MAA (2003) Supercritical extraction of essential oil from aniseed (Pimpinella anisum L) using CO2: solubility, kinetics, and composition data. J Agric Food Chem 51:1518–1523

    Google Scholar 

  • Roy BC, Goto M, Hirose T (1996) Extraction of ginger oil with supercritical carbon dioxide: experiments and modeling. Ind Eng Chem Res 35:607–612

    Google Scholar 

  • Roy BC, Hoshino M, Ueno H, Sasaki M, Goto M (2007) Supercritical carbon dioxide extraction of the volatiles from the peel of Japanese Citrus fruits. J Essent Oil Res 19:78–84

    Google Scholar 

  • Salgın U, Döker O, Çalımlı A (2006) Extraction of sunflower oil with supercritical CO2: experiments and modeling. J Supercrit Fluids 38:326–331

    Google Scholar 

  • Shah BB, Mehta AA (2018) In vitro evaluation of antioxidant activity of d–limonene, Asian. J Pharm Pharmacol 4:883–887

    Google Scholar 

  • Sovová H (1994) Rate of the vegetable oil extraction with supercritical CO2 - I. Modelling of extraction curves. Chem Eng Sci 49:409–414

    Google Scholar 

  • Sovová H (2005) Mathematical model for supercritical fluid extraction of natural products and extraction curve evaluation. J Supercrit Fluids 33:35–52

    Google Scholar 

  • Sovová H, Komers R, Kučera J, Jež J (1994) Supercritical carbon dioxide extraction of caraway essential oil. Chem Eng Res Des 49:2499–2505

    Google Scholar 

  • Sovová H, Stateva RP, Galushko AA (2001) Essential oils from seeds : solubility of limonene in supercritical CO2 and how it is affected by fatty oil. J Supercrit Fluids 20:113–129

    Google Scholar 

  • Sugiyama K, Saito M (1988) Simple microscale supercritical fluid extraction system and its application to gas chromatography-mass spectrometry of lemon peel oil. J Chromatogr 442:121–131

    Google Scholar 

  • Sun J (2007) D-Limonene: Safety and Clinical Applications. Altern Med Rev 12:259–264

    Google Scholar 

  • Thoppil RJ, Bishayee A (2011) Terpenoids as potential chemopreventive and therapeutic agents in liver cancer. World J Hepatol 3:228–249

    Google Scholar 

  • Virot V, Tomao V, Ginies C, Visinoni F, Chemat F (2008) Green procedure with a green solvent for fats and oils determination. Microwave integrated soxhlet using limonene followed by microwave Clevenger distillation. J Chromatogr A 1196:147–152

    Google Scholar 

  • Yu X, Lin H, Wang Y, Lv W, Zhang S, Qian Y, Deng X, Feng N, Yu H, Qian B (2018) D-limonene exhibits antitumor activity by inducing autophagy and apoptosis in lung cancer. Onco Targets Ther 11:1833–1847

    Google Scholar 

  • Zizovic I, Stamenić M, Orlović A, Skala D (2005) Supercritical carbon dioxide essential oil extraction of Lamiaceae family species: mathematical modelling on the micro-scale and process optimization. Chem Eng Sci 60:6747–6756

    Google Scholar 

  • Zizovic I, Stamenić M, Orlović A, Skala D (2007) Supercritical carbon dioxide extraction of essential oils from plants with secretory ducts: mathematical modelling on the micro-scale. J Supercrit Fluids 39:338–346

    Google Scholar 

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Acknowledgements

We thank Mr. Gaetano Di Leo for providing the fruit samples and the Research Project SILA, MIUR (PONa3_00341-CUP H21D11000020007) for the financial support.

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Authors and Affiliations

  1. Department of Informatics, Modeling, Electronics and System Engineering, University of Calabria, Rende, CS, Italy

    Catia Giovanna Lopresto, Alessandra Meluso, Sudip Chakraborty & Vincenza Calabrò

  2. Laboratory of Biotechnologies, ENEA Trisaia, Rotondella, MT, Italy

    Giuseppe Di Sanzo

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  1. Catia Giovanna Lopresto
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  2. Alessandra Meluso
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  3. Giuseppe Di Sanzo
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  4. Sudip Chakraborty
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  5. Vincenza Calabrò
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Correspondence to Catia Giovanna Lopresto.

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Lopresto, C.G., Meluso, A., Di Sanzo, G. et al. Process-intensified waste valorization and environmentally friendly d-limonene extraction. Euro-Mediterr J Environ Integr 4, 31 (2019). https://doi.org/10.1007/s41207-019-0122-0

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