CRITICAL REVIEW OF SUPERCRITICAL FLUID EXTRACTION OF .

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Macedonian Journal of Chemistry and Chemical Engineering, Vol. 30, No. 2, pp. 197–220 (2011)ISSN 1857-5552MJCCA9 – 582UDC:542.613.4:635.7Received: June 28, 2010Accepted: December 23, 2010ReviewCRITICAL REVIEW OF SUPERCRITICAL FLUID EXTRACTIONOF SELECTED SPICE PLANT MATERIALSMilan N. Sovilj1, Branislava G. Nikolovski1, Momčilo Đ. Spasojević2Faculty of Technology, University of Novi Sad, 21000 Novi Sad, SerbiaFaculty of Technical Sciences, University of Novi Sad, 21000 Novi Sad, Serbiamiso@uns.ac.rs // barjakb@uns.ac.rs // momcilos@uns.ac.rs12Supercritical fluid extraction (SFE) is one of the relatively new efficient separation method forthe extraction of essential oils from different plant materials. The new products, extracts, can be used asa good base for the production of pharmaceutical drugs and additives in the perfume, cosmetic, and foodindustries. The aim of this work was to analyze the supercritical carbon dioxide extraction (SC-CO2) of oilsfrom the selected spice plant materials. In this paper the process parameters such as pressure, temperature,solvent flow rate, size of grinding materials, and ratio of the co-solvent were presented for the selected spiceplant materials: black pepper, caraway, celery, cinnamon, clove, coriander, daphne, fennel, ginger, hyssop,juniper, lavender, oregano, pennyroyal, red pepper, safflower, sage, turmeric, and vanilla. The values ofoperating conditions were: pressure from 7.5 to 68 MPa, temperature from 293 to 363 K, solvent flow ratefrom 0.003 to 30.0 kg/h, and diameter of grinding material from 0.17 to 3.90 mm. The global yield andquality of the extracts all of the plant material investigated, as well as the possibility of their application inthe food, cosmetics and pharmaceutical industries were analyzed. The composition of the extracts was werycomplex, and in every case the extract was composed of more than 200 components. All the compoundsfrom the CO2 extracts were classified in the following groups: monoterpene, sesquiterpene, oxygenatedmonoterpene, and oxygenated sesquiterpene and other hydrocarbon groups. In some of the systems investigated the different mathematical models (Sovová, Hong), which have taken from the literature, were usedto correlate the experimental data.Keywords: supercritical fluid extraction; spice plant materials; process parameters; global extraction yieldКРИТИЧКИ ПРЕГЛЕД НА СУПЕРКРИТИЧНА ФЛУИДНА ЕКСТРАКЦИЈАНА ИЗБРАНИ ЗАЧИНСКИ РАСТИТЕЛНИ МАТЕРИЈАЛИСуперкритичната флуидна екстракција (SFE) е релативно нова и ефикасна сепарациона методаза екстракција на етерични масла од зачински растителни материјали. Новите продукти, екстракти,можат да се користат како добра основа за производство на фармацевтски препарати и адитиви воиндустриите за парфеми, козметика и храна. Целта на овој труд е да се анализира а со јаглероден диоксид (SC-CO2) од масла од избрани зачински растителни материјали.Во овој труд се изнесени работните параметри како што се притисок, температура, брзина напроток на растворувач, големина на мелен материјал и однос на корастворувач за следните зачинскирастителни материјали: црн пипер, ким, целер, цимет, каранфилче, коријандер, лавор, морач, ѓумбир,изоп, смрека, лаванда, оригано, ситнолисно нане, црвен пипер, шафран, жалфија, куркума и ванила.Вредностите на работните параметри беа: притисок од 7,5 до 68 MPa, температура од 293 до 363 K,брзина на проток на растворувачот од 0,003 до 30,0 kg/h и дијаметар на мелениот материјал од 0,17до 3,90 mm. Општо земено, беше следен приносот и квалитетот на екстрактот од целиот испитуван

198M. N. Sovilj, B. G. Nikolovski, M. Đ. Spasojevićматеријал, како и можноста за негова примена во индустријата за храна, козметика и фармација.Составот на екстрактите е многу комплексен и секој од нив содржи повеќе од 200 компоненти.Сите супстанции од екстрактите на CO2 беа класифицирани во следните групи: монотерпени,сесквитерпени, кислородни сесквитепрени и други јаглеводородни соединенија. Различнитематематички модели (Sovová, Hong) земени од литературата беа искористени за корелирање наексперименталните податоци за некои од испитуваните системи.Клучни зборови: суперкритична флуидна екстракција; зачински растителни материјали;работни параметри; вкупен принос од екстракција1. INTRODUCTIONExtracts of aromatic herbs, spices, andmedicinal plants are used in food and pharmaceutical processing to impart flavor or otherfunctional properties, as well as ingredients inthe pharmaceutical products. It is important toaccount naturally occurring antioxidants, notonly to prevent food degradation, but also to formulate functional mixtures for use by the pharmaceutical and cosmetic industries. Use of supercritical fluid extraction (SFE) under differentconditions can allow selecting the extraction ofdifferent constituents.Traditionally, volatile essential oils fromplant materials are obtained by hydrodistillation(steam, water, or combined steam and water),and this process can be charged by issues likehydrolytical reactions, chemical alteration andthermal degradation of products. One of the maindisadvantages of the hydrodistillation method isthat essential oils suffer chemical alteration andthe heat-sensitive compounds can easily be destroyed. The extract obtained by organic solvents(e.g., hexane, dichloromethane, dichloroethane,etc.) extraction is called oleoresin and containsall the ingredients that are soluble in the organicsolvent, including the volatile oils and the resins. Unfortunately, organic solvent extraction ofplant materials, such as spices may lead to oxidation of aroma and coloring compounds, especially in the presence of air. However, the use oforganic solvents causes also a high energy costsand safety hazards. The SFE has found applications in the extraction of flavors and fragrancesfrom their natural sources and as a result manystudies have been published using this environmentally friendly extraction method. SFE as analternative process to conventional solvent extraction and steam distillation for essential oilshas great potential use especially in food, cosmetic and pharmaceutical industries. Processingmedia such as carbon dioxide, water, and ethanolunder pressure, offer a safe and effective way ofextracting, refining, and concentrating extractsfor the market. Fluid-phase extraction with a solvent in a near critical state (sub- or supercritical fluid), is an energy efficient, environmentallyfriendly alternative to the traditional methods forisolation of natural products for nutraceuticaland pharmaceutical ingredients. Among severalpossible fluids, carbon dioxide (CO2) is the mostexploited one, since it is gentle-natured solvent,since its critical point (304 K, 7.4 Mpa) allowslow temperature extraction conditions, consequently avoiding thermal degradation of a product; additionally CO2 is inexpensive, and readilyavailable [1]. Carbon dioxide and the extract areeasily separated by the pressure reduction behind the extractor, and contrary to the conventional solvent extraction product, the extract isfree of any undesirable solvent without time andenergy consuming additional separation processes. The low viscosity and high diffusivity ofthe supercritical fluid enhance the penetratingpower based in the high mass transfer rate of thesolutes into the fluid, allowing an efficient extraction of the compounds from the raw material.Moreover, low viscosity contributes to the lowerfluid transportation costs. The extracts from SFEare free of solvent residues, and the process canbe conducted at low temperature, which is veryMaced. J. Chem. Chem. Eng. 30 (2), 197–220 (2011)

Critical review of supercritical fluid extraction of selected spice plant materialsimportant to thermo-liable materials becausethe high temperature could devalue the productsfrom it.However, like any other CO2 in supercritical conditions as a solvent can not be effectivelyutilized for all tasks, and is a poor solvent forpolar compounds. For certain applications, theaddition of a minimal amount of a polar co-solvent/entrainer suffices to improve the extractionof targeted components from a natural productmatrix, such as water, ethanol, methanol, aceticacid, and ethylene glycol.Spices may be defined as a class of strongly flavored or aromatic substances obtained fromplants, commonly used as condiments and utilized for their flavor and preservative qualities.Both individual spice extracts and their formulations are used not only to camouflage undesirable odors in food, but also to add flavor tostimulate appetite and to imbibe preservative andtherapeutic values in food, soft drinks, beverages, confectioneries, and health tonics [2]. Thereis hardly any spice which does not have at leastsome medicinal effect and therapeutic benefitsbased upon the number of bioactive componentspresent, pertaining to particular biological actions. Most commonly used spices are all proven to be medicinal, for example, black pepper,thyme, juniper, cayenne, cinnamon, garlic, ginger, licorice, onion, chives, etc. [2].There are at least two kinds of spice extracts: the one responsible for aroma or flavor,called an essential oil or simply essence; and theother, a higher boiling fraction responsible fortaste or pungency of the spice, called oleoresin[2]. Essential oils represent a small fraction of aplant’s composition but confer the characteristicsfor wich aromatic plants are used in the pharmceutical, food and fragrance industries. Essentialoils have complex composition, containing froma few dozen to several hundred compounds, especially hydrocarbons (terpenes and sesquiterpenes), and oxygenated compounds (alcohols,aldehydes, ketones, acids, phenols, oxides, lactones, acetals, ethers and esters). Both hydrocarbons and oxygenated components are responsible for the characteristic odours and flavours.Maced. J. Chem. Chem. Eng. 30 (2), 197–220 (2011)199The purpose of this work is to enlightenthe state of the art in the field of supercriticalfluid extraction of spice plant materials. Maincharacteristics and usage of the most prominentspices are listed, supercritical fluid extractionprocess characteristics are emphasized, and theliterature review of the SFE of spices are given.2. REVIEW OF EXPERIMENTAL DATAAND ANALYSISThe extraction yield (Y) in supercriticalcarbon dioxide extraction (SC-CO2) was calculated by equation:mextY mmatx 100, %(1)where: mext – mass of extract, mmat – mass of rawmaterial.This review provides a detailed and updated discussion of applications of SC-CO2 extraction in the isolation of essential oils and oleoresins from selected spices. SC-CO2 extractionhas been compared with conventional extractionmethods in terms of selectivity, and possibilityof manipulating the composition of the extract.State of the art in a rapidly developing field ofsupercritical fluid extraction of spices is summarized in the following text.Black pepper (Piper nigrum L.) is perennial woody vine from the Piperaceae familly. Thecontent of essential oil from pepper is 2 to 4.5 %(w/w) and it has been found to consist mainly ofmonoterpenes and sesquiterpenes. Several authors investigated the supercritical extraction ofblack pepper [3–5]. Ferreira et al. [3] studied afixed bed extraction of black pepper essential oilusing supercritical CO2 as a solvent. Experimentswere carried out at temperatures of 303, 313, and323 K, and pressures of 15, 20, and 30 MPa. Theprocess parameters, as well as a content of oil inthe feed and extraction yield for all the spice materials analyzed in this paper is shown in Table 1.

200M. N. Sovilj, B. G. Nikolovski, M. Đ. SpasojevićTable1Amount of oil in the feed and process parameters in supercritical carbon dioxide extractionof the selected oil seeds(P – pressure; T – temperature; M, V – solvent flow rate; dav – average diameter of grinding materials; v – superficial velocity of solvent; W – moisture content).Spice materialAmount ofoil in thefeed,% (w/w)Globalextractionyield,% (w/w)Ref.P 15–30 MPa; T 303–323 K2.05[3]1.5P 9–15 MPa; T 313–323 K;M 1.0–3.0 kg/h; dav 0.175 mm13.2[4]6.2P 16–26 MPa; T 308–323 K; V 0.2–0.4 m3/h;dav 20–50 meshes6.2[5].P 7.5–30 MPa; T 305–348 K; M 4.0 kg/h7.5[7][8]1.45–3.46Black pepper(Piper nigrum L.)Caraway(Carum carvi L.)3.0–7.0Process parameters–P 20.8 MPa; T 297–333 K––P 9 MPa; T 323 K–[9 ]–P 10–20 MPa; T 318–327 K–[10]P 14–35 MPa; T 313 K; M 1.5 kg/h6.0[11]–P 22–25 MPa; T 308–313 K; M 1.5 kg/h1.65[12]Cinnamon(Cinnamomum verum,synonymC. zeylanicum)3.0P 9–12 MPa; T 313–323 K; M 6.0 kg/h;dav 0.3–0.8 mm; W 10.0 % (w/w)0.78[13]Clove bud(Syzygium aromati cum)15.5Celery(Apium graveolens L.)Coriander(Coriandrum sativumL.)family UmbelliferaeDaphne(Laurus nobilis L.)Fenel(Foeniculum vulgareMill.)3.0–P 35 MPa; T 313 K; M 30 kg/h–[14]–P 22.5 MPa; T 323 K; dav 0.3 mm;V 9.0 · 10–3 m3/h–[15]P 8–20 MPa; T 313–323 K;M 0.6–1.2 kg/h; dav 0.33–0.35 mm19.0–P 10–30 MPa; T 303–323 K23.95[17]–P 11–19 MPa; T 325–416 K–[18]0.61[19]0.65P 15 MPa; T 323 K; V 3.0 · 10 m /h–33[16]–P 20–30 MPa; 308 K–[20]–P 9–15 MPa; T 313–323 K, dav 0.4–0.8 mm;M 0.79–1.56 kg/h–[21]–P 11.6–28 MPa; T 311–331 K14–28P 14–68 MPa; T 348 K; dav 0.17 mmP 9–25 MPa; T 313 K–[22]27.5[23]–[24]–[25]5.5[26]–P 8.2–8.4 MPa; T 304–308 K; V 2 · 10 m /h–P 8.0–15.0 MPa; T 313–330 K; M 0.2 kg/h–P 9–20 MPa; T 313–323 K;M 0.5–1.5 kg/h; dav 0.37 mm–[27]–P 20.65–36.14 MPa; T 318–328 K–[28]–33Maced. J. Chem. Chem. Eng. 30 (2), 197–220 (2011)

201Critical review of supercritical fluid extraction of selected spice plant materialsHyssop(Hyssopus officinalis)–P 10 MPa; T 313 K2.29[29]–P 10.13–35.46 MPa; T 308–348 K2.1[30]–P 9–10 MPa; T 313–323 K;M 0.0212–0.022 kg/min; dav 0.3–0.8 mm.–[31]Ginger(Zingiber officinaleRoscoe)–P 20–25 MPa; T 298–308 K;M 0.2034–0.2167 kg/h; W 17.0 % (w/w)2.65[32]3.0P 15–25 MPa; T 293–313 K;M 0.2016 kg/h; W 14.0 % (w/w)–[33]Juniper(Juniperus communisL.,family Cupressaceae)0.2–3.42P 8–20 MPa; T 313 K;M 0.2 kg/h; dav 0.25–0.40 mm0.65–4.0–P 20–30 MPa; T 323 K–Bruno–P 9–20 MPa; T 313 K; M 0,4 kg/h–Skala[34–38]–P 8–12 MPa; T 308–333 K4.9[41]Lavender flowers (La vandula angustifolia)–P 8–12 MPa; T 308–333 K–[42]–P 8–14 MPa; T 308–323 K;M 0.06552–0.1310 kg/h–[43]Oregano(Origanum majoranaL.)–P 45 MPa; T 323 K; M 7.0 kg/h3.8[44]–P 10–20 MPa; T 298–318 K–[45]–P 10–40 MPa; T 313–333 K–[46]–P 10.13–30.39 MPa; T 328–363 K–[47]-P 9–10 MPa; T 313–323 K;M 1.6 kg/h; W 9.0% (w/w)–[48]–Red pepper(Capsicum annuum L.) –P 10–40 MPa; T 308–328 K11.5[49]P 32–54 MPa; T 313 K; v 2.052–4.5 m/h;dav 0.273–3.90 mm; W 4.0 % (w/w)56.0[50]Safflower(Carthamus tinctoriusL.)29.0P 22–28 MPa; T 308–333 K;M 0.98–3.74 kg/h; dav 0.35–0.85 mm28.0[51]–P 9–30 MPa; T 308 K; M 3.74 kg/h–[52]Sage(Salvia officinalis L.)2.7P 9–12.8 MPa; T 298–323 K; M 0.003–0.021kg/h4.8[53]–P 10–30 MPa; T 323 K–[54]Turmeric(Curcuma longa L.)3.0–6.0P 30 MPa; T 303 K; M 0.147–0.169 kg/h;W 66.7 % (w/w)8.0[55]–P 20–40 MPa; T 313–333 K–[56]–P 10–13 MPa; T 306–309 K; M 2–62 g CO2/g–[57]–P 15–24 MPa; T 308–328 K; dav 0.30–0.80 mm–[58]Pennyroyal(Mentha piperita L.)VanillaSolubility of oil increased with increaseof the pressure, because of the solvent densityincrease. It was possible to identify the constant extraction rate period in the extractioncurves as well as the failing and diffusion rateperiod. When the yield of the SC-CO2 extraction was compared with that of steam distillation it can be concluded that SFE was an ef-Maced. J. Chem. Chem. Eng. 30 (2), 197–220 (2011)ficient process for black pepper oil extraction.Perakis et al. [4] showed the results of the SCCO2 extraction of ground black pepper. Theyexamined effect of process parameters, namelypressure (9, 10, 15 MPa), temperature (313,323 K) on extraction rate. The authors [4] concluded also that oil consists mainly of monoterpenes and sesquiterpenes. Effect of temperature

202M. N. Sovilj, B. G. Nikolovski, M. Đ. Spasojevićon the extraction yield of black pepper versusthe specific amount of solvent (Q) at 10 MPaand a solvent flow rate of 2 kg CO2/h shown inthe Figure 1.Fig. 1. Effect of temperature on the extraction yieldof black pepper versus the specific amount of solvent(Q) at 10 MPa, and a solvent flow rate of 2 kg CO2/h.[Source: Perakis et al., J. Food Eng., 71, 386–393(2005)].As shown in Figure 1 the temperature increase from 313 to 323 K at 10 MPa, resultedin the decrease of solvent’s density, whose effect seems to have dominated over the increaseof the solute vapor pressure. Furthermore, thefinal extraction yield was enhanced by 45 %,as temperature decreased. Ferreira et al. [3]studied a fixed bed extraction of black pepperessential oil using SCF and CO2 as a solvent.Experiments were obtained at temperatures of303, 313, and 323 K, pressures of 15, 20, and30 MPa, and solvent flow rate of 1.1, 2.0, 3.0kg/h. The process parameters have different effect on the extraction rate. The extraction rateincreases with increasing pressure because ofthe increase of solvent’s density. Thus, at thehigher pressure (15 MPa) the pepper oil wasextracted faster than at lower pressure (10MPa), but the total amount of extract was almost the same. The minimal extraction yieldwas obseved at 9 MPa due to the fact that somecomponents, which were extracted at 15 MPa,were not soluble in CO2 at 9 MPa. The increaseof the temperature from 313 to 323 K causedthe decrease of the extraction rate, due to thedecrease of solvents density. The increase of thesolvent flow rate resulted in the increase of theextraction rate. This effect was more implicited,when the flow rate was increased up to 3 kg/h. Liet al. [5] investigated SC-CO2 extraction of blackpepper at 16–26 MPa, temperature of 308–323 K,solvent flow rate from 0.2–0.4 m3/h, and diameterof ground material of 20–50 meshes. They concluded that the extraction rate was higher at higher pressure, because of the fact that at constanttemperature, the density of the solvent increaseswith pressure increase and the vapor pressure ofthe solute decrease with pressure increase. Theextraction rate increases with an increase in temperature at 25 MPa and decreases with an increasein temperature at 10 MPa. This behavior could beexplained by appearing so call “cross-over” pressure between this two values of pressure, whichmeans that than exists two competing effects ofreduction in solvent density and the increase insolute vapor pressure with increase in temperature. The fact is that at lower pressure, the changeof the solvent density is more efficient than that ofsolute vapor pressure, as extraction rate increaseswith decrease in temperature. However, at higherpressure (25 MPa) the extraction rate is dependenton the solute vapor pressure and it increase withan increase in temperature. The optimal processcondition of the supercritical fluid extraction forpepper oil was at 22–26 MPa, 318 K, and 0.3–0.4m3/h. The extraction rate increased with increasing particle size due to intraparticle diffusionresistance was smaller for smaller particle sizebecause of shorter diffusion path. Essential oil obtained by SC-CO2 extraction had higher levels ofsesquiterpenes and monoterpenes. The maximumvalues of extraction yield (global extraction yield)for most of the systems investigated is shown inthe Table 1.Caraway (Carum carvi L.) is a member ofthe family of Umbelliferae, which contain considerable amounts of monoterpenes. Caraway iscultivated in the Netherlands, Eastern Europe andGermany, furthermore North Africa. Carawayfruits may contain 3–7% (w/w) essential oil. Thearoma of the oil is mostly dominated by carvone,and limonene [6]. It is known for its extremely efMaced. J. Chem. Chem. Eng. 30 (2), 197–220 (2011)

Critical review of supercritical fluid extraction of selected spice

oresins from selected spices. SC-CO 2 extraction has been compared with conventional extraction methods in terms of selectivity, and possibility of manipulating the composition of the extract. State of the art in a rapidly developing field of supercritical fluid extraction of spices is summa-rized in the following text.

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