R&D NOTE

Citrus Essential Oil Deterpenation by Liquid-

Liquid Extraction
Alberto Arce*, Alicia Marchiaro1, José M. Martínez-Ageitos and Ana Soto
Department of Chemical Engineering, University of Santiago de Compostela, E-15782 Santiago, Spain

The object of the present work is to evaluate the possibility of carrying out the deterpenation of the citrus essential oil by using a mixture of
ethanol and water as a solvent for liquid-liquid extraction. Liquid-liquid equilibrium has been determined for limonene + linalool + ethanol +
water quaternary system at 298.15 K. Partitioning and selectivity of extraction were analyzed. Experimental data were correlated using the
UNIQUAC and NRTL equations and the energetic parameters of these models at this temperature are determined.

L’objet du présent travail est d’évaluer la possibilité de réaliser la déterpénation de l’huile essentielle du citron en utilisant un mélange d’éthanol
et d’eau comme solvant en extraction liquide-liquide. On a déterminé l’équilibre liquide-liquide pour le système quaternaire Limonène + Linalool
+ Éthanol + Eau à 298,15 K. On a analysé le partitionnement et la sélectivité de l’extraction. Les données expérimentales ont été corrélées à
l’aide d’équations UNIQUAC et NRTL, et les paramètres énergétiques de ces modèles à cette température sont déterminés.

Keywords: LLE, limonene, linalool, ethanol, deterpenation, essential oil

E
ssential oils are vegetable products, which are basically a using the UNIQUAC and NRTL equations and the energetic
mixture of terpenic hydrocarbons and oxygenated deriva- parameters of these models at this temperature were
tives such as aldehydes, alcohols and esters. Citrus determined.
essential oil is used as a flavouring agent in pharmaceuticals as
well as a fragrant ingredient in soaps, detergents, creams, lotions
and perfumes. From its components, oxygenated compounds are EXPERIMENTAL SECTION
mainly responsible for the aroma and flavour, and their content
has become a definitive parameter in establishing the price of Materials
the oil and representing a reference of quality. All chemicals used were chromatography-grade products,
In a previous work (Arce et al., 2004), we have showed the supplied by Fluka with nominal purities of 98 mass % for
possibility of carrying out the citrus essential oil deterpenation limonene (4-isopropenyl-1-methylcyclohexene) and 97 mass %
using a mixture of ethanol and water as a solvent for liquid- for linalool (3,7 dimethyl 1,6-octenedien-3-ol), and by Merk
liquid extraction. In that work, the citrus oil was considered as with nominal purity of 99.8 mass % for ethanol. Water was
a binary mixture of limonene and linalool, and we studied liquid purified using Milli-Q plus system. These purities were verified
liquid equilibrium (LLE) for ternary systems involved in the by gas chromatography and the chemicals were used without
process. However, only the study of quaternary LLE would allow further purification. Their densities and refractive indices were
the knowledge of the influence of limonene/linalool proportion measured at 298.15 K and atmospheric pressure, and are
in essential oil, the percentage of water in the solvent, and compared with published values (Riddick et al., 1986, Comelli
essential oil/solvent ratio, on the partitioning and selectivity of et al., 2002) in Table 1. Densities were measured with an Anton
extraction. Paar DMA 60/602 densimeter precise to within ± 10-5 g·mL.
With this in mind, liquid-liquid equilibrium has been
determined for Limonene + Linalool + Ethanol + Water
* Author to whom correspondence may be addressed.
quaternary system at 298.15 K. Partitioning and selectivity of the E-mail address: [email protected]
extraction were analyzed. Experimental data were correlated 1. Present address: Facultad de Ciencias Natruales, Universidad
Nacional de la Patagonia, Argentia
366 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 83, APRIL 2005
 Table 1. Densities (ρ) and refractive indices (nD) of the pure components at 298.15 K and atmospheric pressure.

Component ρ (g·mL–1) nD
Experimental Literature Experimental Literature *
Limonene 0.83717 0.8383(1) 1.47027(1) 1.4701
Linalool 0.85774 0.85760(2) 1.45970 Not found
Ethanol 0.78522 0.78493(1) 1.35920(1) 1.35941
Water 0.99704 0.99704(1) 1.33250(1) 1.33250
(1) Riddick et al., 1986
(2) Comelli et al., 2002

Table 2. Experimental tie lines of the limonene (1) + linalool (2) + ethanol (3) + water (4) System 298.15 K. Compositions are given as mol
fractions.

Water rich phase Limonene rich phase

x1 x2 x3 x4 x1 x2 x3 x4
0.0000 0.0006 0.0305 0.9689 0.1588 0.6147 0.0819 0.1446
0.0000 0.0006 0.0387 0.9607 0.1506 0.5794 0.1065 0.1635
0.0000 0.0006 0.0718 0.9276 0.1248 0.4821 0.2025 0.1906
0.0000 0.0007 0.0837 0.9156 0.1120 0.4316 0.2468 0.2096
0.0000 0.0008 0.1119 0.8873 0.0944 0.3624 0.3127 0.2305
0.0000 0.0013 0.1357 0.8630 0.0724 0.2771 0.3774 0.2731
0.0000 0.0030 0.1785 0.8185 0.0487 0.1986 0.4113 0.3414
0.0011 0.0095 0.2395 0.7499 0.0371 0.1365 0.3981 0.4283
0.0024 0.0174 0.2635 0.7167 0.0264 0.1152 0.3869 0.4715

0.0000 0.0001 0.0813 0.9186 0.7865 0.1662 0.0313 0.0160

0.0001 0.0003 0.1282 0.8714 0.7101 0.1589 0.1023 0.0287
0.0001 0.0003 0.1512 0.8484 0.6955 0.1587 0.1159 0.0299
0.0003 0.0011 0.1983 0.8003 0.6366 0.1359 0.1801 0.0474
0.0056 0.0111 0.3561 0.6272 0.5064 0.1137 0.2776 0.1023
0.0342 0.0302 0.4738 0.4618 0.4377 0.0928 0.3438 0.1257
0.0878 0.0422 0.5242 0.3458 0.3821 0.0750 0.4003 0.1426
0.1236 0.0500 0.5098 0.3166 0.2846 0.0743 0.4466 0.1945

0.0000 0.0003 0.0283 0.9714 0.5933 0.3318 0.0322 0.0427

0.0000 0.0004 0.0843 0.9153 0.5103 0.2944 0.1277 0.0677
0.0000 0.0004 0.1076 0.8920 0.4752 0.2754 0.1696 0.0798
0.0000 0.0006 0.1349 0.8645 0.4214 0.2481 0.2272 0.1033
0.0007 0.0012 0.1674 0.8307 0.3919 0.2164 0.2730 0.1187
0.0000 0.0021 0.2013 0.7966 0.3408 0.1955 0.3201 0.1436
0.0014 0.0047 0.2522 0.7417 0.3052 0.1693 0.3520 0.1735
0.0044 0.0103 0.3458 0.6395 0.2392 0.1302 0.4038 0.2268
0.0082 0.0172 0.3801 0.5945 0.2044 0.1172 0.4202 0.2582
0.0186 0.0288 0.4122 0.5404 0.1750 0.0993 0.4349 0.2908
0.0409 0.0418 0.4390 0.4783 0.1417 0.0821 0.4482 0.3280

0.0000 0.0006 0.0229 0.9765 0.3664 0.4854 0.0582 0.0900

0.0000 0.0006 0.0533 0.9461 0.2852 0.4823 0.1240 0.1085
0.0000 0.0007 0.0787 0.9206 0.2556 0.4112 0.1875 0.1457
0.0000 0.0008 0.1008 0.8984 0.2392 0.3562 0.2425 0.1621
0.0000 0.0009 0.1161 0.8832 0.2166 0.3155 0.2934 0.1745
0.0000 0.0017 0.1650 0.8333 0.1592 0.2373 0.3649 0.2386
0.0012 0.0064 0.2374 0.7550 0.1008 0.1461 0.4195 0.3336
0.0124 0.0301 0.3356 0.6219 0.0486 0.0758 0.4021 0.4735

Refractive indices were measured with an Atago RX-5000 where x is the mole fraction of the component in the binary
refractometer with a precision of ± 4×10-5. mixture. The values of m used were 0, 0.2, 0.4, 0.6, 0.8 and 1.
Each of these pseudoternary systems corresponds to a distinct
Apparatus and Procedure plane in the tetrahedral composition diagram. For further details
In order to cover the full range of compositions of the quaternary of this approach, see Arce et al. (1998a,b). Solubility curves for
system, we have prepared pseudoternary systems of water, pseudoternary systems at 298.15 K were determined by the
ethanol and a pre-prepared binary mixture [m Linalool + (1-m) cloud point method (Othmer et al., 1940). These curves were
Limonene] in which: used to calibrate the gas chromatograph by an internal standard
xLinalool method. The chromatograph used was a Hewlett-Packard 5890
m= (1) Series II apparatus equipped with a thermal conductivity
xLinalool + xLimonene
detector and a HP-FFAP: 25 m×0.2 mm×0.3×µm capillary

VOLUME 83, APRIL 2005 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 367
 Table 3. Binary interaction parameters and residual functions (eq. 3) for NRTL(α = 0.2) and UNIQUAC models fitted to LLE data for the limonene
(1) + linalool (2) + ethanol (3) + water (4) system at 298.15 K.

NRTL UNIQUAC
pair ∆gij (J·mol-1) ∆gij (J·mol-1) F ∆uij (J·mol-1) uji (J·mol-1)
∆u F
1-2 –4832.5 2627.6 2817.6 –1989.5
1-3 836.80 2075.3 4311.6 –811.61
1-4 5196.5 4782.3 9379.7 537.43
2-3 –3376.5 1288.7 2459.1 –2010.0
2-4 276.14 6518.7 3518.3 794.33
3-4 –1196.6 2502.0 1.44 13878 –2772.1 1.31
Structural parameters for the UNIQUAC equation
Limonene Linalool Ethanol Water
r 6.2783 7.0356 2.1055 0.92
q 5.2080 6.0600 1.972 1.40

RESULTS AND DISCUSSION

Experimental data
The experimental tie-line data for limonene + linalool +
ethanol + water at 298.15 K are listed in Table 2. Solubility
curves for the ternary systems corresponding to the faces of the
tetrahedral composition diagram were taken from earlier work
(Arce et al., 2004). Figure 1 shows experimental equilibrium
data and a view of binodal surface obtained.

Correlation
Experimental quaternary LLE data and the sets of ternary
Figure 1. Experimental equilibrium data and a view of binodal surface constituent systems (Arce et al., 2004) were correlated using the
for Limonene + Linalool + Ethanol + Water system at 298.15 K. () m = 0; widely employed NRTL (Renon and Prausnitz, 1968) and
() m = 0.2; () m = 0.4; () m = 0.6; () m = 0.8; () m = 1. UNIQUAC (Abrams and Prausnitz, 1975) equations. The value of
the NRTL nonrandomness parameter was set successively to 0.1,
0.2 and 0.3, and the results given in Table 3 are the best of these
three sets. The UNIQUAC structural parameters r and q were
taken from literature (Bondi, 1968; Daubert and Danner, 1989;
Prausnitz et al., 1980).
The computer program used to fit these equations minimizes
the objective function

∑ ∑ ∑ (xijk − xˆijk )
2
F .O. = (2)
k i j

where xijk is the experimental mole fraction component i in

Figure 2. Experimental tie lines for Limonene + Linalool + Ethanol + phase j on tie line k, Xˆ ijk is the value calculated, using the
Water system at 298.15 K (s), and those obtained optimizing a parameters being optimized, for the corresponding end of a tie-
UNIQUAC model (). a) Tetrahedral representation, b) Orthogonal line.
projection. Table 3 lists the binary interaction parameters obtained for the
quaternary system, and for both UNIQUAC and NRTL equations.
column. Helium was used as mobile phase. The injection The quality of the correlation is measured by the residual
volume was 0.5 µl, and the split ratio 1:100. Separation was function F
carried out at 403.15 K under isothermal conditions. The greatest 0.5

(xijk − xˆijk )
2
errors in the determination of mole fraction compositions using
 
the calibration curves were ±0.004. F = 100  ∑∑∑ 8M  (3)
The tie-line data were determined by analysis of the two  k i j 
layers of heterogeneous mixtures. In each case, a mixture with a
bulk composition in the immiscibility region was placed inside where M is the number of experimental tie-lines.
an equilibrium cell, where it was stirred for 1 h in order to Figure 2 compares experimental tie-line values for the
ensure intimate contact between the phases and was then left limonene + linalool + ethanol + water system with those
standing for 4 h to achieve thermodynamic equilibrium. The calculated using the UNIQUAC equation at the considered
whole procedure was carried out at constant temperature in a temperature a view of tetrahedral and an orthogonal projection
thermostatic bath. When thermodynamic equilibrium had been is shown.
attained, samples of both liquid phases were collected and
analyzed by gas chromatography.

368 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 83, APRIL 2005
Figure 3. Distribution coefficient vs. linalool concentration in organic Figure 6. Selectivity vs. linalool concentration in organic phase to
phase to Limonene + Linalool + [m’ Ethanol + (1-m’) Water], with m = 0.6, Limonene + Linalool + [m’ Ethanol + (1-m’) Water], with m’ = 0.85,
where the essential oil/solvent ratio is () 3; () 9; () 15; (•) 33. where the essential oil/ solvent ratio is () 2; () 3; () 4; (•) 6.

Figures 3 and 4 present the distribution coefficient

I
wLinalool
K= (5)
II
wLinalool

being WILinalool is mass fraction of linalool in aqueous phase

and WIILinalool is mass fraction of linalool in organic phase.
Representation is done to different essential oil/solvent ratios
and for ethanol solution concentrations (m´) of 0.6 and 0.85 in
Figures 5 and 6, respectively. The same analysis was done in
Figures 5 and 6 for selectivity

K Linalool
α= (6)
K Limonene
Figure 4. Distribution coefficient vs. linalool concentration in organic
phase to Limonene + Linalool + [m’ Ethanol + (1-m’) Water], with m’ =
0.85, where the essential oil/ solvent ratio is () 2; () 3; () 4; (•) 6.
CONCLUSIONS
The liquid-liquid equilibrium for the limonene + linalool +
ethanol + water quaternary system has been measured at
298.15 K. Correlation of the experimental quaternary LLE data
and the sets of ternary constituent systems (Arce et al., 2004)
was satisfactorily done by the UNIQUAC and the NRTL equations.
The corresponding optimized binary interaction parameters are
reported in Table 3.
From Figures 3 and 4 we can see that this quaternary system
presents solutropy, as at low ethanol concentrations distribution
coefficients are less than 1, and at higher concentrations are
greater than 1. Also from these figures, it can be seen that for a
given essential oil (a fixed limonene/linalool ratio) and using a
given essential oil/solvent ratio, the distribution coefficients
increase with the ethanol proportion (m´) in solvent. Moreover,
Figure 5. Selectivity vs. linalool concentration in organic phase to
Limonene + Linalool + [m’ Ethanol + (1-m’) Water], with m’ = 0.6, distribution coefficients are higher in essential oils with low
where the essential oil/ solvent ratio is () 3; () 9; ()15; (•) 33. linalool content. This effect is increased when lowering the
essential oil/solvent ratio.
Solvent Evaluation From Figures 5 and 6 we can see that selectivity is greater
than 1 in all cases, but the highest values are obtained for
The experimental data obtained were reorganized using the essential oils with low linalool content and using high ethanol
UNIQUAC correlation to define new pseudoternary systems, proportion (m´) in solvent. Thus, to carry out the citrus essential
limonene + linalool + [m’ Ethanol + (1-m’) Water], in oil deterpenation using a mixture of ethanol and water as the
which: solvent for liquid-liquid extraction, high ethanol proportion in
wEthanol solvent and low essential oil/solvent ratio should be used.
m′ = (4)
wEthanol + wWater
ACKNOWLEDGEMENTS
where w is the mass fraction of the component in the binary The authors are grateful to the Ministerio de Ciencia y Tecnología
mixture. (Spain) for financial support under project PPQ2003-01236.

VOLUME 83, APRIL 2005 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 369
A.M. is grateful to the European Union for financial support Prausnitz, J. M., T.F. Anderson, E.A. Grens, C.A. Eckert, R.
(Project ALFA-PROQUIFAR). Hsieh and J.P. O’Connell, “Computer Calculations for
Multicomponent VLE and LLE”, Prentice Hall, Englewood
Cliffs, NJ (1980).
NOMENCLATURE Renon, H. and J.M. Prausnitz, “Local Compositions in
F average error in composition (Eq. 3) Thermodynamic Excess Functions for Liquid Mixtures”
K distribution coefficient AIChE J. 14, 135–144 (1968).
M number of tie-lines Riddick, J.A., W.B. Bunger and T.K. Sakano, “Organic Solvents.
x experimental mole fraction Physical Properties and Methods of Purification”, 4th ed.,
x̂ calculated mole fraction John Wiley & Sons, New York, NY(1986).
w mass fraction

Subscripts Manuscript received March 24, 2004; revised manuscript received

i component identifier August 27, 2004; accepted for publication December 3, 2004.
j phase identifier
k tie line identifier

Greek Symbols
α NRTL non-randomness parameter or selectivity
∆g
∆g optimizable binary NRTL parameters
∆u optimizable binary UNIQUAC parameters

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370 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 83, APRIL 2005