Fluid Phme Equilibria, 59 (1990) 135-145

135

Elsevier Science Publishers B.V., Amsterdam

PHASE EQUILIBRIA OF ESSENTIAL OIL COMPONENTS AND SUPERCRITICAL CARBON DIOXIDE

VINCENZO BRANDANI, GIOVANNI and VITTORIA MUCCIANTE DEL RE, GABRIELE DI GIACOMO
Universitri de L Aquila,

Dipartimento di Chimica, Ingegneria Chimica e Materiali, Z-67040 Monteluco di Roio, L Aquila (Itab)

(Received June 18, 1989; accepted in final form March 8; 1990)

ABSTRACT Brandani, V., Del Re, G., Di Giacomo, G. and Mucciante, V., 1990. Phase equilibria of essential oil components and supercritical carbon dioxide. Fluid Phase Equilibria, 59:
135-145.

The solubility of pure essential oil components and their binary mixtures in supercritical carbon dioxide was correlated using an equation of state with density-dependent mixing rules. This equation was then used to predict the phase diagram of the two binary carbon dioxide-limonene and carbon dioxide-citral systems at temperatures from 308.2 to 323.2 K and over the whole range of pressure and composition. In addition, the phase behaviour of the ternary carbon dioxide-limonene-citral system was calculated at pressures from 9.0 to 10.9 MPa at 323.2 K and over the whole range of composition.

INTRODUCTION

Using a simple single pass flow apparatus we measured the solubilities of limonene, citral and their mixtures in supercritical carbon dioxide

Fig. 1. Molecular structure of limonene, a, and citral, b. 0378-3812/90/$03.50 0 1990 - Elsevier Science Publishers B.V.

136

(Di Giacomo et al., 1989). The molecular structures of limonene and citral are shown in Fig. 1. The experimental results prove the technical feasibility of supercritical deterpenation of lemon oil with carbon dioxide. However, for optimal design and operation of such a process it is necessary to know the phase behaviour of the system over the whole range of operating conditions. We illustrate here how vapour phase solubility data can be used to predict equilibrium liquid phase composition for both binary and ternary systems.
EQUATION OF STATE

All the experimental data were correlated using an EOS, which, following Liidecke and Prausnitz (1985), was obtained using the equation of Mansoori et al. (1971) for the repulsive term and that of Soave (1972) for the attractive term. Using the Mansoori et al. (1971) form for the reference system, the reduced molar residual Helmholtz energy is:

where D, E and F are defined as: m m m F= c ~,a,3 E= cwia;; D =

c yq;

i=l

i=l

(2)

i=l

Here w is either x or y, a, is the hard-sphere diameter of molecule i and m is the number of components. The reduced density is defined as: 5 = bp/4 with
b=

(3)

c c
i=l j=l

m m
wiwjbij

where
b,, = (b;i3

+ b;p)3/8
term is: RT

The Soave perturbation

A

Pert =

gPe t = _

NRT

f! . In (1 + bp)
b parameter

(6)
which reflects attractive inter-

where a is an equation-of-state molecular forces.

137

For pure components

R2T2
a=P,-

a 0 +aT2 lr
1+r2

(7)

RT b = b. - +
c

The pure component parameters ao, a, and b, are determined by fitting the PUT data from 308.2 to 328.2 K and from 0.1 to 15.0 MPa for carbon dioxide (Casci et al., 1972) and the vapour pressures of pure limonene from 287.2 to 448.2 K (Perry and Chilton, 1973). For the citral we used the AMP equation (Abrams et al., 1974; Ma&nick et al., 1977) to extrapolate the available experimental vapour pressure data from 334.9 to 501.2 K (Perry and Chilton, 1973) to the temperatures of interest. This equation, in addition to two adjustable parameters (E, and s), requires the van der Waals volume determined from Bondi s group-contribution correlation (Bondi, 1968). Their values are E,/R = 9920.92 K, s = 9.978 and Vw = 103.57 cm3 mol- , respectively. Average absolute errors, S, were calculated using

where W represents in turn vapour pressures of limonene and citral and total pressure of carbon dioxide. The values of S - 100 obtained by fitting the above-mentioned experimental data are 0.85 for carbon dioxide, 1.21 for limonene and 1.77 for citral. Critical properties of limonene and citral have been calculated with the Lydersen group-contribution method (Reid et al., 1977). Their values are reported in Table 1, while all pure component parameters of the EOS are reported in Table 2. For mixtures, we chose for the attractive parameter a the density-dependent mixing rules proposed by Panagiotopoulos and Reid (1986)
a = t
i=lj=l

wiwj(aiaj)1 2

(1 -kij)

+ g

f
i=lj=l

wiw,(wix,j

wjhji) 00)

TABLE 1 Molecular weight and critical constants of limonene and citral Component Limonene Citral Mw 136.23 152.24 T, W 661.0 694.6 p, (MPa) 2.76 2.29

138 TABLE 2 Pure component parameters of the EOS Component Limonene Citral Carbon dioxide
=0 01 bo

0.399 0.801 0.687

0.173 0.039 0.226

0.0554 0.0937 0.1022

where k,,, Aij and Aji are adjustable parameters.

sionless while Xij and hji are non-dimensionalized

Parameter kij is dimenby:

xii=Xijbii/ai iii =Xjibjj/aZ

01) (12)

where bii, aii, bjj and ajj are calculated at the critical temperature. The three binary interaction parameters for the carbon dioxide-limonene and carbon dioxide-citral systems were calculated from the solubility data reported by Di Giacomo et al. (1989) by minimizing the following objective function:

Q= i
i=l

hp-Ycdf

03)

and y,, are, respectively, the experimental and the calculated whereyexp values of the mole fraction of carbon dioxide in the vapour phase and n is the number of experimental values measured (n = 26 for limonene-carbon dioxide and n = 29 for citral-carbon dioxide). The fugacity coefficients Qi derived from the proposed EOS are:
m

In Qi = 2 + (aAr/&~~),,~,+,, where

~~lwl(a~/aw,)~,,,*+z-l-ln

Cz)

(14)

2 ~ wl(aiaj)1 2(1
j=l

- kij)

139

f j=l

WiWj i k=l

(WjXjk

+ wkxkj)

+b 2wi f Wjhji + 2 f Wj(wiXij+ W,Xji)

j=l j=l

. ln(l+ b

b) +

2a

C wjbij
j=l

bZ

[bp/(l+

bp) -ln(l

+bdl

+ois

+ 2 2 Wjbij( P/4). [ - ( E3/F2 + j=l

1)/(1 - t) + (3DE/F-

E3/F2)

/(l -

0+ (2E3/F2)/(l - 03]

(16)

and z is the compressibility factor. To find the numerical value of the binary parameters for the limonenecitral system we used the experimental data (Di Giacomo et al., 1989) of the ternary carbon dioxide-limonene-citral system. The following objective function:

07)
was minimized only for k,,. Here, u,, and ycal are experimental and calculated values of the mole fraction of carbon dioxide in the vapour phase, YeXP and Y4 are experimental and calculated values of the mole fraction of limonene in the vapour phase on a carbon dioxide-free basis in the ternary system carbon dioxide-limonene-citral and n is the number of experimental value? measured.
TABLE 3 Binary interaction parameters System Carbon dioxide(l)-limonene(2) Carbon dioxide(l)-citral(3) Limonene(2)-citral(3) 0.047 0.085 0.154 -0.011 - 0.097 - 0.0069 - 0.0102

7.5 6.0 6.0 4.5 3.0 1.5 0.0 0.0 r

I = 315.0
K

t
0.992 0.996

0.2

0.4

0.6

0.8 I 8.8 6. 4.

A * a L .

0 A

de ftfwado Stahl.

313.2

K K

2. 0

Gerard

313.2

0.0

a.2

0.4

0.6

0.8

0.992

0.996

10 . T = 323.2 8.
K

10 - . 8. , 6. , 4. 2. 0 0.950

0.0

0.2

0.4

0.6

0.8 CO2

0.975

mole fraction

Fig. 2. Phase behaviour of the carbon dioxide(l)-limonene(2) binary system at temperatures of 308.2, 315.0 and 323.2 K.

The two interaction parameters x2, and x,, for the limonene-citral system were set equal to zero, since limonene and citral have similar molecular structures and only few experimental data are available. All the binary interaction parameters are reported in Table 3.

141

7.6 . T = 308.2 6.0 _ 4.6 .

K

7.5 6.0 4.5 3.0 1.5 0.0

(D E . f ii B L Q

0.0

0.2

0.4

0.6

0.8

8 6 4 2 0

8
7 - 315.0
K

6 4 2
0

10
7 = 323.2 K

10

8 6

8 6

0.0

0.2

0.4

0.6

0.8
CO2

0.98

0.99

mole fraction

Fig. 3. Phase behaviour of the carbon dioxide(l)-citral(3) 308.2, 315.0 and 323.2 K.

binary system at temperatures of

Figures 2 and 3 show the calculated phase diagrams for the carbon dioxide-limonene and carbon dioxide-citral systems at three different temperatures, together with the measured values of solubility. In Fig. 2 (middle),

142

A 0

------

-.-.-.

10.0 10.6

nP*
nP* ._

Kalrs

l taL(9.S

10.9

IlPm
Ill*)

00

0.2

0.4

0.6

0.8

Xl i monene Fig. 4. Y-X diagram, solvent-free system at 323.2 K. basis, for the carbon dioxide(l)-limonene(2)-citral(3)

0.8 0.6 0.4 0.0025 f

e
%

0.2

. . . . . .
0.0

0.0000 I 0.0 0.2 0.4 0.6 0.8

0.9960 0.9975

0.05

0.00
Il.0

0.2

0.4

0.6

0.8

mole fraction CO2

IA
0.90

0.95

Fig. 5. Phase behaviour of the carbon dioxide(l)-limonene(2)-citral(3) ternary system at 323.2 K and pressures of 9.0 and 10.9 MPa. Dotted curves were obtained with k,, = x2, = K,, = 0.

143

corresponding to 315.0 K for the carbon dioxide-limonene system, the solubility measured by Stahl and Gerard (1985) and by de Azevedo et al. (1988) is also shown for purposes of comparison. Figure 4 shows the calculated diagram Y-X for the ternary system carbon dioxide-limonenecitral at 323.2 K and at pressures ranging from 9.0 to 10.9 MPa. Y and X represent the mole fraction, on a carbon dioxide-free basis, of limonene in the vapour phase and in the liquid phase, respectively. Figure 5 shows the calculated phase diagrams for the ternary system carbon dioxide(l)limonene(2)-citral(3) at 323.2 K and 9.0 MPa and at 323.2 K and lo.? MPa; in both these diagrams the predicted curves obtained with k,, = A,, = A,, = 0 are also reported.
CONCLUSIONS

Phase behaviour of binary and ternary systems of lemon oil components and carbon dioxide has been calculated using experimental solubility data in the vapour phase, along with an equation of state with density-dependent mixing rules. The results show that accurate calculation of phase behaviour for the carbon dioxide(l)-limonene(2)-citral(3) system can only be obtained if binary interactions between the two solutes are taken into account.
ACKNOWLEDGEMENTS This

work was supported by the Italian Minister0 della Pubblica Istruz-

ione.
LIST OF SYMBOLS

A ii

D, E, F

Eo
kij

MW N n
P R s

Helmholtz free. energy equation of state parameter equation of state parameter constants defined by eqns. (2) parameter of AMP equation binary adjustable parameter number of components molecular weight total number of moles number of experimental data points pressure objective function gas constant average absolute error

144

T
V W

X
X

Y Y
Z

parameter of AMP equation absolute temperature volume mole fraction liquid-phase mole fraction, solvent-free basis liquid-phase mole fraction vapour-phase mole fraction, solvent-free basis vapour-phase mole fraction compressibility factor

Greek symbols
Aij

t
P

rJ @

binary adjustable parameter reduced density molar density hard-sphere diameter fugacity coefficient

Superscripts pert r ref perturbation part of equation of state residual part of equation of state reference part of equation of state dimensionless quantity

Subscripts
C Cd

eXP

i j ;J 1 2 3

critical calculated quantity experimental quantity component i component j reduced van der Waals component 1 component 2 component 3

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145 Bondi, A., 1968. Physical Properties of Molecular Crystals, Liquids and Glasses. Wiley, New York. Anidride Casci, C., Mac&i, E. and Angelino, G., 1972. Proprieta Termodinamiche dell Carbonica. Tamburini, Milan. de Azevedo, E.G., Matos, H.A., da Ponte, M.N. and Simoes, P.C., 1988. Phase equilibria of systems containing limonene, cineole and supercritical carbon dioxide. Proc. Int. Symp. on Supercritical Fluids, Nice, October 17-19. Societd Fran9aise de Chimie, 1: 135-142. Di Giacomo, G., Brandani, V., Del Re, G. and Mucciante, V., 1989. Solubility of essential oil components in compressed supercritical carbon dioxide. Fhtid Phase Equilibria, 52: 405-411. Kalra, H., Chung, S.Y.-K. and Chen, C.-J., 1987. Phase equilibrium data for supercritical extraction of lemon flavors and palm oils with carbon dioxide. Fluid Phase Equilibria, 36: 263-278. Ltidecke, D. and Prausnitz, J.M., 1985. Phase equilibria of strongly nonideal mixtures from an equation of state with density dependent mixing rules. Fluid Phase Equilibria, 22:1-19. Ma&nick, A.B., Winmck, J. and Prausnitz, J.M., 1977. Vapor pressures of liquids as a function of temperature. Two-parameter equation based on kinetic theory of fluids. Ind. Eng. Chem. Fundam., 16: 392. Mansoori, G.A., Camahan, N.F., Starling, K.E. and Leland, T.W., 1971. Equilibrium thermodynamic properties of the mixtures of hard spheres. J. Chem. Phys., 54: 1523-1525. Panagiotopoulos, A.Z. and Reid, R.C., 1986. Muhiphase high pressure equilibria in ternary aqueous systems. Fluid Phase Equilibria, 29: 525-534. Perry, H.R. and Chilton, C.H., 1973. Chemical Engineers Handbook, 5th edn. McGraw-Hill, New York. Reid, R.C., Prausnitz, J.M. and Sherwood, T.K., 1977. The Properties of Gases and Liquids, 2nd edn. McGraw-Hill, New York. So&e, G., 1972. Equilibrium constants from a modified Redlich-Kwong equation of state. Chem. Eng. Sci., 27: 1197-1203. Stahl, E. and Gerard, D., 1985. Solubihty behavior and fractionation of essential oils in dense carbon dioxide. Perf. Flavor., 10: 29-37.