Accepted Manuscript

Operational efficiencies of six microwave based extraction methods for orange

peel oil

Seyed Elyas Razzaghi, Akbar Arabhosseini, Mohammad Turk, Thibault Soubrat,

Aurélie Cendres, Mohamad Hosein Kianmehr, Sandrine Perino, Farid Chemat

PII: S0260-8774(18)30307-8

DOI: 10.1016/j.jfoodeng.2018.07.018

Reference: JFOE 9332

To appear in: Journal of Food Engineering

Received Date: 05 September 2017

Accepted Date: 17 July 2018

Please cite this article as: Seyed Elyas Razzaghi, Akbar Arabhosseini, Mohammad Turk, Thibault
Soubrat, Aurélie Cendres, Mohamad Hosein Kianmehr, Sandrine Perino, Farid Chemat,
Operational efficiencies of six microwave based extraction methods for orange peel oil, Journal of
Food Engineering (2018), doi: 10.1016/j.jfoodeng.2018.07.018

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 ACCEPTED MANUSCRIPT

1 Operational efficiencies of six microwave based extraction methods for orange peel oil

2 Seyed Elyas Razzaghi a, Akbar Arabhosseini a*, Mohammad Turk b*, Thibault Soubrat c,

3 Aurélie Cendres d, Mohamad Hosein Kianmehr a, Sandrine Perino b, Farid Chemat b

4 a Department of Agrotechnology, College of Aburaihan, University of Tehran

5 b UMR408 Sécurité et Qualité des Produits d’Origine Végétale, Université d’Avignon et des 7

6 Pays du Vaucluse, F-84000 Avignon, France

7 c UMR408 Sécurité et Qualité des Produits d’Origine Végétale, INRA, F-84000 Avignon, 10

8 France

9 d Atelier du Fruit, 7 rue des Pommerets, 21 600 Longvic-FRANCE 9

10 Corresponding authors :

11 Mohammad TURK

12 UMR408 Sécurité et Qualité des Produits d’Origine Végétale,

13 Université d’Avignon et des Pays du Vaucluse, F-84000 Avignon, France

14 E-mail : mohammad.turk@gmail.com

15

16 Akbar Arabhosseini

17 Department of Agrotechnology, College of Aburaihan,

18 University of Tehran

19 E-mail : ahosseini@ut.ac.ir

20

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21 Abstract

22 Microwave is a very efficient energy carrier for the extraction of essential oils from aromatic

23 plants in unit operations intended for distillation. The aim of this work was to compare six

24 extraction processes: four Microwave Assisted Extraction (MAE) and two conventional

25 processes for the extraction of orange essential oils. The comparison was based on different

26 processing and qualitative criteria such as extraction yield, power efficiency, biochemical and

27 sensorial attributes. Two multiple criteria methods were developed to select the most efficient

28 process.

29 The first method is based on the income over energy cost index. The results show that among

30 the set of extraction processes studied only Microwave Hydrodiffusion and Gravity (MHG)

31 would be operational cost efficient. The second method combines both processing and

32 qualitative criteria. The results show that the extraction processes with combination of

33 microwaves and steam are best ranked followed by those with just microwaves.

34 Keywords: Microwave assisted extraction, Green extraction, circular economy, sustainable

35 process.

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36 1. Introduction

37 Oranges are one of the most cultivated fruits in the world with an estimated production of 72

38 million of tones in 2014 (FAOSTAT, 2014). Almost 50% of orange fruits are used for juice

39 processing. Large quantities of by-products are generated including peels, seeds and pulps.

40 Citrus molasses, terpene oils, citric acid, pectins and essential oil are the main products

41 recovered from orange processing waste. Essential oil extracted from orange peels contains a

42 mixture of volatile compounds like terpenes and oxygenated derivatives such as aldehydes,

43 alcohols and esters. Commonly applied process in the production of essential oils are cold

44 mechanical processes including oil recovery from peels after juice extraction, simultaneous

45 extraction of juice and emulsion from whole fruit, and recovery of oil from peels following

46 removal from the whole fruit by abrasion or shaving (Sandhu et al. 2012).

47 The current environmental trends are to reduce energy, solvent consumption and limit the

48 carbon footprint. These trends incited researchers to focus on introducing novel techniques

49 such as supercritical carbon dioxide extraction (Zizovic et al. 2007), subcritical water

50 extraction (Jiménez-Carmona et al. 1999), ultrasound-assisted extraction (UAE) (Wang &

51 Weller, 2006), ohmic assisted hydro-distillation (OAHD) (Gavahian et al. 2015) and

52 microwave assisted extraction (MAE) (Chemat et al. 2012) as an alternative to conventional

53 processes for essential oil extraction. MAE brings a number of advantages to essential oil

54 extraction thanks to their reduced equipment size, ease-of-use, speed, ability to control a

55 process via mild increments in heating and low solvent consumption, all of which contribute

56 to reducing environmental impact and costs. Studies show that several extraction processes

57 based on microwaves can be suitable for extracting the essential oil (Chemat et al., 2017).

58 Extraction time, yield of essential oil, energy consumption and the quality of essential oil are

59 among the main criteria to select and optimize. The choice of the best process depends not on

60 one criterion but on a compromise between several criteria and it becomes very complicated

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61 as the number of processes and criteria become very high. In fact, there is a lack of

62 methodology for comparing several techniques and criteria at the same time in order to select

63 the best compromise.

64 For example, Périno-Issartier et al., 2013 compared eight extraction techniques for the

65 extraction of Lavandin flowers EO ranging from conventional processes such as

66 hydrodistillation (HD), steam distillation (SD), turbohydrodistillation (THD) through

67 innovative techniques such as ultrasound assisted extraction followed by steam distillation

68 (US-SD) and microwave assisted techniques such as microwave generated hydrodistillation

69 (ISMH), microwave steam diffusion (MSDf), microwave steam distillation (MSD),

70 microwave hydrodiffusion and gravity (MHG). The authors considered extraction yield,

71 essential oil composition and sensorial analysis for the comparison and the choice of the best

72 extraction process (MHG) was based mainly only on the performance criteria and extraction

73 time. But when it comes to the qualitative aspects, it was difficult to derive clear conclusions.

74 The aim of this study was to compare several processes of essential oil extraction and to

75 provide an efficient multi-criteria evaluation approach to choose the best process among

76 existing and emerging processes. In this study, Orange essential oil was taken as an example

77 to illustrate the multi-criteria approach. Several extraction processes were conducted using the

78 same glassware assemblies and compared.

79 2. Materials and methods

80 Orange essential oil was recovered from peels using six extraction processes (Fig. 1). The

81 same apparatuses were used and set with differing configurations to perform the different

82 processes: conventional (steam distillation (SD); and steam hydro-diffusion (SHDf));

83 microwaves (solvent free microwave extraction (SFME); and microwave hydrodiffusion and

84 gravity (MHG)); and microwaves combined with steam (microwave steam distillation (MSD);

85 and microwave steam diffusion (MSDf)).

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86 2.1 Plant material

87 Sweet Orange peels (Citrus sinensis) purchased from Spain were sized between 2 to 4 cm

88 length and 0.3 to 0.7 cm thick. They were kept in the freezer at -20 °C. Before each

89 experiment, a quantity of peels needed for three repetitions of an extraction process was

90 thawed overnight at 4 °C. The moisture content was determined by using a moisture analyzer

91 (OHAUS-MB35). The initial moisture content of the orange peel was 73 ± 0.15 %.

92 2.2 Experimental material

93 2.2.1 Extraction vessel

94 The extraction vessels (with or without adapter cone on its bottom) is a 1.6 L Pyrex type glass

95 (Fig. 1). A top (with or without adapter cone) and a Teflon sealing ring completed the

96 assembly to prevent mass loss during processing. According to the extraction process, the

97 adapter cones were used to connect the reactor to the condenser or to the steam generator.

98 2.2.2 Microwave treatment

99 Microwave treatment was carried out in a Milestone ETHOS X oven (Milestone, Italy)

100 equipped with two 950 Watt magnetrons and an infrared temperature sensor. The system

101 additionally employs a rotating diffuser that evenly distributes the microwaves throughout the

102 cavity. Applied power, cycle time and temperature limit are controlled via ETHOS X compact

103 terminal. The applied power (PN,heating) was set to 400 watts throughout all the microwave

104 experiments.

105 2.2.3 Steam production

106 Steam was generated by a heating mantle (HORST 6145 Lindenfels type HME 2/1) and a

107 1000 mL glassware flask filled with 700 mL of distilled water. The mantle delivered a

108 constant power of 300 watts.

109 2.2.4 Cooling system

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110 The cooling system was a Smart H150-2100 chiller (Lab Tech; USA). The temperature and

111 pressure of cooling water were set to 8 °C and 2.3 bars respectively. The nominal power

112 (PN,condensation) of the chiller was 600 W. A spiral and double jacketed condenser was

113 connected to the chiller that ensures the cooling water at a constant temperature of 8 °C.

114 2.3 Extraction of essential oil

115 Orange peels (m= 400 g) were introduced in the extraction vessel. The bulk density was

116 calculated by measuring the dimensions of the occupying space of each sample inside the

117 vessel. The weight of the sample was then divided by its volume. The bulk porosity was

118 calculated by measuring the bulk volume of the interstices inside the sample by adding some

119 water inside the reactor without changing the primary bulk volume of the orange peel sample.

120 Water was added until all of the interstices inside the sample were filled with water. The

121 volume of water was then divided by the total bulk volume of the sample. The bulk porosity

122 and bulk density of the orange peel samples were 38.8 ± 0.26 % and 390 ± 2 g/L respectively.

123 When the extraction process requires steam and microwave (eg. MSD and MSDf), microwave

124 treatment starts when the first vapors leave the steam generator and reach the vessel. The

125 extraction time was set to 50 minutes for all the extraction processes except for steam

126 distillation and steam hydrodiffusion which were longer (120 minutes). The last two cycle

127 times are higher because the time lag between the start of the extraction cycle and the

128 appearance of the first drops of condensate is much greater in processes requiring steam.

129 During the experiments, an approximate volume between 12-15 mL of distilled water and

130 essential oil mixture were collected in small tubes and the time of the volume recovery was

131 recorded. This procedure is repeated throughout the extraction cycle. Then essential oil was

132 separated from the mixture and the volumes of distilled water and essential oil were measured

133 separately. The ratio of essential oil per distilled water in each tube was also calculated. This

134 ratio shows the amount of oil obtained from a specific amount of water (evaporated and
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135 condensed) used. All essential oil samples were dried with anhydrous sodium sulfate; their

136 density was measured and they were then stored at 4°C in black bottles until their quality

137 assessment.

138 The maximum amount of essential oil (EO total) that can be recovered from orange peels was

139 determined by hydrodistillation (HD) for 120 minutes. A 1000 mL vessel was filled with

140 400 g of orange peels and the same amount of distilled water. The heating and cooling tools

141 were the same as for the other processes. An exact volume of 7 mL of essential oil was

142 recovered from orange peels and was assumed to be the maximal extractable amount of

143 essential oil in all samples (EO total).

144 2.4 Quality assessment

145 2.4.1 Chemical analysis of essential oil compounds by GC-FID and GC-MS

146 GC-FID and GC-MS

147 Essential oils were dissolved in hexane before injection. Volatile compounds were quantified

148 by an GC-FID System (Clarus 500, Perkin Elmer, USA) equipped with a OPTIMA-5MS

149 capillary column (30 m*0,25 mm ID, 0,25 µm film thickness) and coupled with a flame

150 ionization detector (FID).

151 The analyses were carried out using helium as carrier at 1 mL/min in a split ratio of 20:1. The

152 temperature of the injector, ion source and interface were 250, 200 and 250 °C respectively.

153 The oven temperature was programmed starting at 60 °C for 8 min, then with an increasing

154 rate of 4°C/min to 250°C.

155 In parallel, volatile samples were identified by a GC–MS system (CPG/MS/QP2010

156 (Shimadzu, Kyoto, Japan)) equipped with a ZB-5MS capillary column (30 m, 0.25 mm i.d.,

157 0.25 μm film thickness).

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158 Injection was in split ratio mode 20:1. at 250 °C. The vector gas was helium with a constant

159 flux of 1 mL/min . The oven temperature program was exactly the same as that of the GC-FID

160 program. Mass spectra were obtained by electron impact at 70 eV, with scanning from 29 to

161 250 amu at 2 scans/s.

162 Determination of essential oil composition

163 Identification of the oil components was made based on retention indices which were

164 calculated by using retention times of alkanes (C8–C20) that were injected after the oil at the

165 same chromatographic conditions.

166 The compounds were identified by comparison of their relative retention indices with those in

167 the literature (Adam RP). In addition, compounds were identified by their mass spectrum

168 using the mass spectral database NIST 14 (US National Institute of Standards et Technology

169 (NIST), Gaithersburg, MD, USA)].

170 Quantitative data were obtained from the electronic integration of the Flame Ionization

171 Detector (FID) relative peak areas.

172 2.4.2 Sensory analysis of essential oil

173 Organoleptic assessment was conducted by a panel of twelve trained assessors (7 females and

174 5 males) who were staff members at the laboratories of the University of Avignon. Randomly

175 coded samples were individually served to the assessors.

176 The odor freshness, pleasantness, offensiveness and taste were considered as the valuable

177 characteristics as suggested by the ISO standard for essential oils (ISO/TC 54). The assessors

178 also identified the color and clarity of the oil samples.

179 Samples of pure oil, in same quantity inside glass tubes, were used for the olfactory analysis.

180 For the taste analysis, an aqueous solution of 10% sugar and 0.2% essential oil was prepared.

181 For the color and clarity assessment, a test room with a stable light was prepared in order to

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182 avoid the effects fluctuations in light intensity and angle of radiation and samples of pure oil

183 in same quantity were used.

184 The assessors were asked to rank the oil samples to determine the best sample for each

185 sensorial attribute. The samples with the most pleasing and freshest odor, the best tasting as

186 well as the most colorless and clearest sample were to be ranked 6. The samples with the most

187 offensive smell were to be ranked 1.

188 2.5 Statistical analysis

189 Each extraction was repeated at least three times. Statistical analysis was performed with

190 Statgraphics Centurion (Statpoint Technologies, Inc, USA). Mean values were calculated.

191 When needed, means were compared using ANOVA followed by LSD testing at p < 0.05

192 level in order to follow differences between treatments.

193 3. Results and discussions

194 3.1 Essential oil extraction kinetics

195 Different extraction kinetics of an MAE process are presented in Fig. 2A. Two types of

196 extraction were tested according to the water source used for the vaporization of the orange

197 essential oil : those that use only the intrinsic water (SFME and MHG) and those that also use

198 additional steam (MSD and MSDf). The result is a large variation in the volume of mixture

199 recovered at the end of the extraction cycle (Fig. 2 A). For example, SHDf generates the

200 largest volume of distillate mixture (V=655 mL). While SFME and MHG are the smallest

201 volume of mixture producing processes since only the in situ water of the plant material is

202 evaporated (V=149 mL).

203 The kinetics of essential oil (EO) extraction indicate that MHG and SFME have the most

204 rapid extraction cycle and give the highest EO amounts among the assessed processes

205 (Fig. 2 B). These results are in good agreement with the reports of Farhat et al. (2011) for

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206 orange peel essential oil, Chemat et al. (2006) when they compared SFME with SD for the

207 extraction of lavender EO. On the other hand, when steam is injected during MHG and SFME

208 treatment, the quantity of essential oil surprisingly decreased (ex. 6.1 mL for MHG vs. 4.8 mL

209 for MSDf). These results can be explained by the loss of some essential oil compounds due to

210 excessive heating and also due to an increase in EO solubility in water. The results show that

211 MHG and SFME are able to extract more than 80% of the oil initially present in less than 1 h.

212 The variation in the ratio of essential oil to mixture has one of two characteristic behaviors

213 depending on the extraction processes (Fig. 2 C). In the first, based on the phenomenon of

214 hydro-diffusion assisted by gravity (MHG, MSDf, SHDf), the essential oil is extracted early

215 in the cycle, first in small quantities, which then increases to a turning point and then

216 gradually decreases. In the second, SFME, MSD and SD, there is no optimum in the

217 oil/mixture curve but rather a maximum release of the essential oil at the beginning of the

218 extraction followed by a decrease throughout the extraction cycle.

219 In order to explain the turning point, the flow of evaporated mixture can be separated in two

220 categories. Initially, the vapour mixture, which is poor in essential oil, flows down directly

221 due to gravity. Subsequently, the vaopur which is rich in essential oil flows up and remains

222 trapped in the upper part of the extraction vessel. But when this makes contact with the glass

223 wall of the reactor, the vapor condenses, falls by gravity and cools down before being

224 collected. As the extraction cycle continues,, the amount of essential oil present in the matrix

225 decreases faster than the intrinsic water, which leads to an inversion in the curve.

226 3.2 Energy consumption analysis and optimization

227 Two types of power were considered in this study. The first corresponds to the nominal power

228 (PN) that was applied to the various unit operations of the extraction processes (condenser,

229 microwave heating and mantle). The second power corresponds to the power actually used for

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230 the extraction of the essential oil. It can be calculated by estimating the effective energy (qn)

231 that was absorbed from the heating and condensation units in each process according to Eq.1.

232 𝑞𝑛 = 𝑞h𝑒𝑎𝑡𝑖𝑛𝑔 + 𝑞𝑒𝑣𝑎𝑝𝑜𝑟𝑎𝑡𝑖𝑜𝑛 + 𝑞𝑐𝑜𝑛𝑑𝑒𝑛𝑠𝑎𝑡𝑖𝑜𝑛 + 𝑞𝑙𝑜𝑠𝑠 Eq.1

233 Where qheating is the energy needed to increase the sample from its initial temperature to the

234 boiling point (100°C), qevaporation is the energy needed to evaporate the mixture of essential oil

235 and water, qcondensation is the energy needed to condense and decrease the temperature of the

236 mixture to its final value, and qloss corresponds to the energy loss due to heat exchanges with

237 the ambient environment. Since the glassware and apparatuses were the same for all

238 extraction processes and the initial conditions, power and time were also equivalent, it was

239 assumed that the heat energy loss was similar for all of the extraction processes and the term

240 qloss was brought to the left side of Eq. 1. The effective energy (q) actually used to extract the

241 essential oil can be calculated according to Eq.2.

242 𝑞 = 𝑞𝑛 ‒ 𝑞𝑙𝑜𝑠𝑠 = 𝑞h𝑒𝑎𝑡𝑖𝑛𝑔 + 𝑞𝑒𝑣𝑎𝑝𝑜𝑟𝑎𝑡𝑖𝑜𝑛 + 𝑞𝑐𝑜𝑛𝑑𝑒𝑛𝑠𝑎𝑡𝑖𝑜𝑛 Eq.2

243 The energy consumed in heating the sample qheating was calculated according to Eq.3, where

244 M (400 g) and cp (3.2 kJ/kg/K) are the mass and the specific heat of the treated orange peel

245 samples respectively (Munoz, 2012). Theating is the temperature evolution of the plant materials

246 from initial temperature (4°C) to the boiling point of water.

247 𝑞h𝑒𝑎𝑡𝑖𝑛𝑔 = 𝑀.𝑐𝑝.∆𝑇h𝑒𝑎𝑡𝑖𝑛𝑔 Eq.3

248 The energy consumed in evaporating the distillate mixture qevaporation was calculated according

249 to Eq.4, where meo, mw, le,eo (289.2 kJ/kg), le,w (2257 kJ/kg) are the mass of essential oil, the

250 mass of distilled water, the latent heat of evaporation of the essential oil and the latent heat of

251 evaporation of water respectively.

252 𝑞h𝑒𝑎𝑡𝑖𝑛𝑔 = 𝑚𝑒𝑜.𝑙𝑒,𝑒𝑜 + 𝑚𝑤.𝑙𝑒,𝑤 Eq.4

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253 The energy absorbed by the condenser qcondensation is calculated according to Eq.5; where

254 cp,eo (1.383 kJ/kg/K), cp,w (4.187 kJ/kg/K) are the specific heat of the essential oil and water

255 respectively. Tcondensation was the temperature evolution from the boiling point to the final

256 temperature of the condensates. The values of meo, mw are time dependent (Fig. 2 A and B).

257 𝑞𝑐𝑜𝑛𝑑𝑒𝑛𝑠𝑎𝑡𝑖𝑜𝑛 = 𝑚𝑒𝑜.𝑙𝑒,𝑒𝑜 + 𝑚𝑤.𝑙𝑒,𝑤 + (𝑚𝑒𝑜.𝑐𝑝,𝑒𝑜 + 𝑚𝑤.𝑐𝑝,𝑤).∆𝑇𝑐𝑜𝑛𝑑𝑒𝑛𝑠𝑎𝑡𝑖𝑜𝑛 Eq.5

258 The results of the effective energy (q) during an extraction cycle (Eq. 2) are presented in

259 Fig. 3. The slope of the linear part of the energy time curves corresponds to the effective

260 power (P). Finally, the total power efficiency ( power) can be calculated according to Eq. 6;

261 where PN,heating and PN,condensation are nominal power of the heating (microwave, kettle) and

262 cooling (chiller) respectively.

𝑃 𝑃
263 𝑝𝑜𝑤𝑒𝑟 = 𝑃 = 𝑃 + 𝑃 Eq.6
𝑁 𝑁,h𝑒𝑎𝑡𝑖𝑛𝑔 𝑁,𝑐𝑜𝑛𝑑𝑒𝑛𝑠𝑎𝑡𝑖𝑜𝑛

264 The results in Fig.4 show that the combination of microwaves and steam improve energy

265 attributes of the extraction processes since MSDf and MSD have the highest power efficiency.

266 Also, the use of microwaves alone, in particular for MHG and SFME, increases the power

267 efficiency compared to conventional extraction.

268 Another way to compare the efficiency of an extraction processes can also be described by an

269 active efficiency index ( a,p) as determined according to Eq.7. The optimal cycle time can

270 also be determined for each method with this index. The equation is simply a ratio of income

271 over cost. The income is determined by the product of the selling price (EO price) and the

272 recovered quantity (EO extracted) during an extraction cycle of the essential oil. The term

273 EO extracted in Eq.7 is time dependent as shown in Fig. 2B. The reference price for essential oil

274 (EO price) was set at 200€/kg.

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275 The manufacturing cost is divided into three categories, namely the direct costs, the fixed

276 costs and the general costs. The terms Qk and Pk, are respectively the quantity and the price of

277 the direct cost k (ex. raw materials, water, energy etc.). However in this research, in a purely

278 theoretical comparison approach, only the direct costs were considered, specifically the cost

279 of electrical energy (Pe) (0.0012 €/kW.h).The electrical energy (qe) is time dependent and can

280 be presented in Eq. 8.

𝐸𝑂𝑒𝑥𝑡𝑟𝑎𝑐𝑡𝑒𝑑.𝐸𝑂𝑝𝑟𝑖𝑐𝑒 EO𝑒𝑥𝑡𝑟𝑎𝑐𝑡𝑒𝑑.𝐸𝑂𝑝𝑟𝑖𝑐𝑒
281 𝑎,𝑝 = ∑𝑄 ≅ 𝑞𝑒.𝑃𝑒 Eq.7
𝑘.𝑃𝑘

282 𝑞𝑒 = 𝑃𝑁.𝑡 Eq. 8

283 PN (kW) is the nominal power and t (minutes) is the extraction cycle time. The results of the

284 active efficiency index ( a,p) vs. time are presented in Fig.5. There is a time where the curve

285 intersects with a threshold line which represents 1 on the y axis. This value means that there is

286 a balance between costs and income. As long as a,p is greater than ,1 the process is efficient.

287 If the curve is below this line, the extraction cycle should be stopped as the extraction would

288 not be operational cost efficient.

289 Among the sets of extraction processes studied only MHG would be operational cost efficient.

290 The other curves are all below the threshold under the conditions of price per kg of essential

291 oil and energy chosen in this study. In order to remain efficient, the extraction cycle by MHG

292 must be stopped at a maximum of 40 minutes.

293 3.3 Chemical analysis of essential oil

294 The repartition of 22 volatile compounds in orange essential oil obtained from six extraction

295 processes is presented in Table 1. Monoterpenes constitued the largest chemical group with

296 D-limonene being the major constituent. The most important contributors to the aroma of

297 essential oils are beta-myrcene, D-limonene, linalol and valencene, in accordance with reports

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298 on the orange essential oils (Chisholm et al. 2003). The six processes reached a « classical »

299 orange essential oil ranking with the most important contributors to the aroma. In this research

300 the term Pdc (Table 1) was introduced to compare different processes and was calculated

301 according to Eq. 9.

𝑛
302 𝑃𝑑𝑐 = 100 ‒ ∑𝑖 = 1|𝑃𝑑𝑐,𝑖 ‒ 𝑃𝑠,𝑖| Eq.9

303 Pdc,i - Ps,i  is the absolute difference between the concentration percentage of desired

304 components obtained by different extraction processes (Pdc,i ) (Table 1) and the ISO NFT75-

305 203 standard values (Ps,i). It was assumed that a process with higher value of accumulation of

306 deviations is of lower Pdc value. 100 was assumed to be the score of the component that has

307 the sum of deviations of zero.

308 The content of volatiles of orange essential oil content is not a discriminating factor to

309 compare the MAE extraction processes. The various extraction processes all provided

310 essential oil with a chemical composition in agreement with the current ISO standard.

311 3.4 Sensory analysis of essential oil

312 The perception of essential oil differs from one extraction method to another and ANOVA

313 analysis seems to confirm the significance of some sensorial attributes especially for color and

314 pleasantness (Table 2).

315 In order to compare the extraction processes, the results of the organoleptic tests were

316 quantified using the term j (j=1, ..., 6) according to Eq. 10, where Sj is the total score of EO j

317 and St is the total score that a sample could obtain during the organoleptic test by the

318 assessors, that is 36. The calculated values are presented in table 2.

𝑆𝑗
319 𝜉𝑗 = 𝑆 Eq.10
𝑡

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320 The assessors seem to appreciate most EO obtained from distillation as the highest scores for

321 j term were attributed to MSD, SD and SFME processes respectively. The combination of

322 microwaves and distillation reaped the best scores for taste and freshness. The statistical test

323 shows that the score of these two attributes is significant when comparing the different

324 extraction processes. Hydro-diffusion and gravity process are responsible for the highly

325 colored orange essential oil. It is possible that essential oil acts as a solvent that dissolves the

326 colorant compounds during the extraction (Virot et al. 2008). Finally, it seems that the

327 assessors could not agree on the clarity and offensiveness attributes. Indeed, neither the results

328 of the ANOVA nor the ranking test are significant.

329 3.5 Overall process index for the comparison of the extraction methods

330 Different process can be compared by considering their extraction yield, their power

331 efficiency and the quality of the product. The time lapse of the process is also included when

332 discussing the power efficiency. The overall process index ( o,p) was determined according

333 to Eq. 11:

1 1 1
𝑏 𝑏 𝑏
1 2 3
334 𝜂𝑜,𝑝 = (η𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑖𝑣𝑖𝑡𝑦) (𝜂𝑝𝑜𝑤𝑒𝑟) (𝜂𝑞𝑢𝑎𝑙𝑖𝑡𝑦) Eq.11

335 where power,  quality are the power efficiency, and the quality index respectively and they

336 have a value between zero and one as discussed earlier.

337 The extraction yield index ( yield) was determined as:

𝐸𝑂𝑒𝑥𝑡𝑟𝑎𝑐𝑡𝑒𝑑
338 𝑦𝑖𝑒𝑙𝑑 = EO𝑡𝑜𝑡𝑎𝑙 Eq. 12

339 where EO extracted is the amount of oil recovered at the end of the extraction cycle.

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340 The exponents b1,2,3 represent the priority of each criteria and depend on various parameters

341 such as the energy costs and availability, the aim of the unit operation etc. These parameters

342 can be prioritized by giving a number between 1 and 3 or even by trial and error.

343 The quality index  quality was defined as the combination of the chemical and sensorial

344 analysis of essential oils (Eq. 13).

345 𝜂𝑞𝑢𝑎𝑙𝑖𝑡𝑦 = 𝑝𝑑𝑐𝜉 Eq.13

346 Table 3 summarizes all the parameters that were presented earlier as well as the result of the

347 comparison method. The classification of the most appropriate process of extraction differs

348 according to the considered criterion. For example, if only the extraction yield is taken into

349 account, MHG comes in first place. But considering the other criteria, it seems that this

350 process has a lower ranking. The classification of processes is easy to do when only one

351 criterion is considered. But the choice of the most appropriate process becomes complex as

352 soon as several criteria intervene. It is in this sense that the proposed method makes it possible

353 to make a choice in a simple way in relation to all the criteria of this study.

354 We chose in this study to assign the same weight to all exponents (b1 = b2 = b3 = 1) in Eq. 13.

355 The results show that the extraction processes with combination of microwaves and steam are

356 best ranked followed by processes with only microwaves. Thus, the classification of the

357 extraction methods in decreasing order would be MSDf> MSD> MHG> SFME> SHDf> SD.

358 But let us not forget that the optimization of the extraction cycle  a,p (Fig. 5 ), which

359 includes the notions of costs and benefits, shows that MHG would be the most operational

360 cost efficient.

361 3.6 Conclusion

362 In conclusion, six MAE extraction processes are evaluated based on extraction yield, energy,

363 qualitative and economical criteria. Two methods of comparison are proposed to establish a

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364 choice integrating all the considered criteria. The first is an active efficiency index which

365 integrates the notions of yield, energy and above all financial considerations. It was possible

366 to optimize the duration of each extraction process cycle and determine the sole cost-effective

367 process, that is MHG. The overall process index is a more complete assessment as it also

368 includes qualitative criteria. The two methods are complementary and led to chose the most

369 competitive method among the conventional extraction processes.

370 Acknowledgment

371 This work was supported by funds received from BPI (Banque pour l’Investissement) région

372 Bourgogne-Franche Comté, région Provence Alpes Côte d’Azur, France, Europe, FEDER

373 (fonds européen de développement régional), Grand-Dijon, and Grand-Avignon, in the form

374 of Fond Unique Interministériel. The name of the project is Natarome+. The project is co-

375 labeled by Terralia and Vitagora. Authors also thank Ing. Isabelle Lellouche for her help with

376 preparation of the manuscript.

377 Bibliography

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387 Concept and Principles. International Journal of Molecular Sciences, 13, 8615–8627.

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388 Chisholm, M. G., Wilson, M. A., & Gaskey, G. M. (2003). Characterization of aroma

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395 255–261.

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410 of Fruits and Fruit Processing, Second Edition (pp. 489–533). Wiley‐Blackwell.

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411 Virot, M., Tomao, V., Ginies, C., & Chemat, F. (2008). Total Lipid Extraction of Food Using

412 d-Limonene as an Alternative to n-Hexane. Chromatographia, 68, 311–313.

413 Wang, L., & Weller, C. L. (2006). Recent advances in extraction of nutraceuticals from

414 plants. Trends in Food Science & Technology, 17, 300–312.

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416 extraction of essential oils from plants with secretory ducts: Mathematical modeling

417 on the micro-scale. The Journal of Supercritical Fluids, 39, 338–346.

418

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Table 1: Volatile compounds percentage (%) in orange essential oil recovered with different
extraction methods
Method of Extraction*
Component MSDf MSD SFME MHG SD SHDf NF T 75-203
Monoterpenes
α Pinene 0.3 0.3 0.4 0.3 0.3 0.3 0.6
β Pinene 0.5 0.4 0.5 0.5 0.5 0.5 0.1
β Myrcene 1.7 1.7 1.7 1.7 1.7 1.7 2.5
α Phellandrene 0.1 0.0 0.1 0.1 0.1 0.1 -
 3- Carene 0.3 0.3 0.3 0.3 0.4 0.4 -
α Terpinene 0.1 0.1 0.1 0.1 0.1 0.1 -
Limonene 93.9 94.2 94.2 94.1 93.6 94.0 94.5
Sabinene 0.4 0.3 0.3 0.3 0.4 0.4 0.4
α Terpinede 0.1 0.1 0.1 0.1 0.1 0.1 -
Oxygenated Monoterpenes
Linalool 0.6 0.5 0.5 0.5 0.5 0.5 0.4
Citronellal 0.1 0.1 0.0 0.1 0.1 0.1 -
Neral 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Terpin-4-ol 0.1 0.1 0.1 0.0 0.1 0.1 -
Nerol 0.1 0.1 0.1 0.1 0.1 0.1 -
Geranial 0.1 0.1 0.1 0.1 0.1 0.1 0.2
α Terpineol 0.1 0.1 0.1 0.1 0.1 0.1 -
sesquiterpenes
Valencene 0.2 0.2 0.2 0.2 0.2 0.1 0.2
Other terpenoids
Decanal 0.4 0.4 0.3 0.4 0.5 0.4 0.4
1-Octanol 0.1 0.1 0.1 0.1 0.1 0.1 -
gamma-Terpineol 0.3 0.3 0.4 0.4 0.4 0.3 -
p-Cymene 0.1 0.1 0.1 0.1 0.1 0.1 -
Octanal 0.3 0.3 0.2 0.2 0.3 0.3 0.3
Pdc 0.976 0.980 0.978 0.977 0.973 0.977
* The results are presented in percentage (%). Mean value (n=4)
MSDf: microwave steam diffusion; MSD: microwave steam distillation; SFME: solvent free
microwave extraction; MHG: microwave hydro-diffusion and gravity; SD: steam distillation;
SHDf: Steam Hydro-diffusion
NFT 75-203: Iso Reference of Oil of sweet orange (Citrus sinensis (Linnaeus) Obsbeck),
obtained by mechanical treatment
Pdc: a parameter that is introduced to compare different extraction methods (Eq.9)
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419

Table 2: Sensory analysis of orange essential oil obtained from different extraction methods. differences
significant are determined by letters
Attribute Freshness Pleasantness Offensiveness Taste Color Clarity
p-value 0,0859 0 0,5945 0,1011 0 0,9204 
Extraction method
MSDf 2,3 (a) 3,1 (b) 3,5 (a) 2,5 (a) 2,1 (b) 2,5 (a) 0,42
SFME 4,4 (c) 4,8 (c) 4,2 (a) 2,6 (a) 5,2 (e) 2,6 (a) 0,49
MHG 3,8 (abc) 2,9 (b) 3,1 (a) 3,6 (ab) 3 (c) 3,6 (ab) 0,39
MSD 3,9 (bc) 4,5 (c) 3,2 (a) 4,4 (b) 4,4 (d) 4,4 (b) 0,52
SD 3,5 (abc) 4,6 (c) 3,4 (a) 3,7 (ab) 5,3 (e) 3,7 (ab) 0,51
SHDf 2,8 (ab) 1,4 (a) 2,8 (a) 3,4 (ab) 1 (a) 3,4 (ab) 0,24
p-value: statistical significance between means determined by 2 levels ANOVA at α-0.05
(a) Significant differences (Tukey HSD test. P = 0.05). Different letters in a same column suggest a
significant difference
MSDf: microwave steam diffusion; MSD: microwave steam distillation; SFME: solvent free microwave
extraction; MHG: microwave hydro-diffusion and gravity; SD: steam distillation; SHDf: Steam Hydro-
diffusion
 Ratio of total score of an extraction over the maximum score that a sample could obtain during the
organoleptic which is 36
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422

Table 3- Summary of the different parameters considered in the overall process index
calculation
Extraction method
Parameter
MHG MSDf SFME MSD SD SHDf
Pdc 0,98 0,98 0,98 0,98 0,97 0,98
 0,39 0,42 0,49 0,52 0,51 0,24
 quality 0,38 (5) 0,41 (4) 0,48 (3) 0,51 (1) 0,50 (2) 0,23 (6)
 power 0,55 (3) 0,87 (1) 0,37 (5) 0,63 (2) 0,21 (6) 0,52 (4)
 yield 0,92 (1) 0,67 (5) 0,81 (2) 0,71 (4) 0,64 (6) 0,72 (3)
 o,p 0,19 (3) 0,24 (1) 0,15 (4) 0,23 (2) 0,07 (6) 0,09 (5)
* 1.16 (1) 0.56 (5) 1.00 (2) 0.48 (6) 0.60 (4) 0.64 (3)
a,p

*The maximum value  a,p in Fig.5 was considered.

(1): number in bracket shows the ranking of each extraction method regarding each
considered parameter.
423

424

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Fig. 1: Scheme of the experimental microwave and classical extraction methods

Fig. 2: Extraction kinetics of distillate mixture (A), orange essential oil (B) and the ratio of
essential oil over mixture (C) recovered from six extraction methods (white square: MSDf ;
black square: MHG; white triangle: MSD; black triangle: SFME; white diamond: SHDF;
white circle: SD)

Fig. 3: Effective energy (q, J) vs. time used for the extraction of orange essential oil from six
extraction methods (white square: MSDf ; black square: MHG; white triangle: MSD; black
triangle: SFME; white diamond: SHDF; white circle: SD)

Fig. 4: Total power efficiency ratio ( power) of orange essential recovered from six extraction
methods (MSDf: microwave steam diffusion; MSD: microwave steam distillation; SFME:
solvent free microwave extraction; MHG: microwave hydro-diffusion and gravity; SD: steam
distillation; SHDf: Steam Hydro-diffusion)

Fig. 5: Active efficiency ratio ( a,p) of orange essential recovered from six extraction
methods (MSDf: microwave steam diffusion; MSD: microwave steam distillation; SFME:
solvent free microwave extraction; MHG: microwave hydro-diffusion and gravity; SD: steam
distillation; SHDf: Steam Hydro-diffusion). Efficiency zone is the profitable part of the curve.
The vertical dashed line corresponds to the optimum cycle time.
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Highlights

 Orange essential oils were extracted using six extraction processes

 Productivity, power efficiency, chemical and sensory analysis were carried out
 Two multi-criteria methods were proposed to select and optimize the most suitable
method
 Essential oil microwave extraction is an economically viable solution