Desalination 224 (2008) 34–39

Recovery of key components of bilberry aroma using a

commercial pervaporation membrane
Nazely Diban, Ane Urtiaga, Inmaculada Ortiz*
Department of Chemical Engineering, University of Cantabria, Avda. de los Castros, 39005 Santander, Spain
Tel. +34 942 201585; Fax: +34 942 201591; email: ortizi@unican.es

Received 15 January 2007; Accepted 5 April 2007

Abstract
Pervaporation, a membrane technology requiring low energetic demands, is considered to substitute the
conventional distillation unit employed in the beverage industry in order to recover the key aroma compounds, and
that would avoid the damages to the quality of the flavour profile. The analysis of the separation and recovery of
some selected aroma compounds belonging to bilberry juice was made by employing a mathematical model
previously developed for the pervaporation of VOCs. A PV hollow fiber module provided with a PDMS commercial
membrane was considered. For each compound, the characteristic mass transfer parameters are the permeability of
the membrane and the diffusion coefficient in the aqueous phase. Enrichment factors over 100 were achieved for the
aroma compounds with higher permeabilities. The membrane thickness influence over the enrichment factor and flux
of the bilberry impact aroma compound (E-2-Hexen-1-ol) was studied observing higher enrichment factors and lower
fluxes with higher membrane thicknesses until an asymptotic value was reached. The predicted permeate composition
achieved under the simulated conditions did not keep the same proportion of that in the feed composition. A sensorial
analysis should be made to measure the product quality achieved.

Keywords: Pervaporation; Bilberry aroma recovery; PDMS membrane; Modelling

1. Introduction facture of concentrated juices imply high costs

but also damages to the quality of the organo-
Aroma recovery has become a key issue in the
leptical profile of the recovered aroma concen-
beverage industry. The high energetic demands of
trates. Alternative technologies employing low
the distillation unit employed during the manu-
thermal requirements are considered to substitute
the rectification conventional process.
*Corresponding author.

Presented at the 11th Aachen Membrane Colloquium, 28–29 March, 2007, Aachen, Germany.

0011-9164/08/$– See front matter © 2008 Published by Elsevier B.V.

doi:10.1016/j.desal.2007.04.076
 N. Diban et al. / Desalination 224 (2008) 34–39 35

Membrane technologies need low energetic

requirements and facilitate modular configura-
tions that allow the possibility to easily scale-up
the process from pilot to industrial plants. Per-
vaporation has been widely analysed in previous
works [1–3] in order to separate and concentrate
valuable aroma compounds from process streams.
In the review presented by Pereira et al. [4], it
was concluded that the most typical membrane
used to perform the pervaporation of aroma
compounds was made of polydimethylsiloxane Fig. 1. Schematic view of the pervaporation set-up.
(PDMS) material.
The demand for processing bilberries (Vac-
cinium myrtillus L.) has increased in the last years A mathematical pervaporation model that was
[5]. Although these fruits can be eaten fresh, are developed and implemented previously [6] has
more usually processed to obtain products like been used. The characteristic mass balance equa-
jams, fools, juices or pies. Therefore, this wild tion for the aqueous feed circulating through the
fruit has become to be cultivated, mainly in North inside of the hollow fiber in dimensionless form
America. Important bilberry producers among the appears in Eq. (1):
european countries are France, Holland, Ger-
many, Poland and Spain. δCi* δC * 2 δ ⎛ δCi* ⎞
The aim of this study is to adapt a mathe- + (1 − R 2 ) i = ⎜R ⎟ (1)
δt δξ R δR ⎝ δR ⎠
matical model that was previously developed for
the pervaporation of VOCs from wastewaters to
predict the behaviour of the PV separation of This expression is obtained by defining the
aroma compounds from aqueous solutions. A following dimensionless variables and para-
mixture of 7 volatile compounds, characteristic of meters:
the aroma of bilberry juice, has been defined, and Ci
the use of PDMS pervaporation membrane with Ci* = (2)
Ci , z =0,t =0
a hollow fiber configuration has been considered.
The prediction of the flux of each compound and r
the concentration factor obtained in permeate are R= (3)
rt
sought. The influence of the membrane thickness
on both parameters will be discussed. zDi 1
ξ= 2
= (4)
4vrt Pe( z )
2. Mathematical modelling
2 Pm ,i srt
Pervaporation of a synthetic aromatic feed Shw,i = (5)
solution characteristic of bilberry juice was con- lDi
sidered. The system used a PDMS membrane
with a hollow fiber configuration and operated where Ci* is the dimensionless concentration of
with recirculation of the aqueous solution. A compound i in the fluid circulating inside the
schematic view of the set-up is plotted in Fig. 1. pervaporation module, R is the radial coordinate,
36 N. Diban et al. / Desalination 224 (2008) 34–39

ξ the axial coordinate, and the parameter Shw,i is at t = 0 Ci*t = 1 (11)

the Sherwood number of the wall for component
i that expresses the ratio of the mass-transfer ∀t Ci*,int = Ci*, z = L (12)
resistance in the inner fluid to that in the mem-
brane. That means that for Shw 6 4 the membrane
resistance is negligible against the resistance The flux of component i was obtained from
exerted by the liquid phase diffusion, while for the mass balance according to Eq. (13) that is a
Shw = 0 is the membrane resistance which deter- function of time:
mines the mass-transfer phenomena. Di and Pm,i
are the diffusivity in the aqueous phase and the F ρCi , Z = L ⎛ Ci , z = L ⎞
membrane permeability of the compound i, Ji = ⎜⎜ 1 −
2
⎟⎟ [g/m s] (13)
respectively. Individual molecular diffusivities of Ap ⎝ Ci , z =0 ⎠
the organic components into a diluted aqueous
phase were calculated using the Wilke-Chang The water flux was calculated by means of
correlation [7]. Parameters are described in more Eq. (14) that is considered as a constant value due
detail in the Symbol section. to the fact that the water molar fraction xw
The set of boundary conditions for this remains practically constant during the whole
equation is the following: experiment:
Pm , w
at t = 0 ∀ξ ∀R Ci* = 1 (6) Jw = ρ w xw [g/m 2s] (14)
l

∀t at ξ = 0 The enrichment factor βi for the component i,

(7) which is time dependent, was defined according
0 ≤ R ≤1 Ci* = Ci*t to Eq. (15):

∀t at R = 0 Cip
βi = (15)
(8) Cit,t =0
1 δC *
0 ≤ ξ ≤1 =0
i

Pe( L) δR
The mathematical model hereof was implemented
in the simulation software Aspen Custom
δCi* Shw,i * Modeler.
at R = 1 0 ≤ ξ ≤ 1 Pe( L) − = Ci
δR 2
(9)
3. Experimental
The mass transfer model is complemented by
the mass balance to the feed in the tank: The qualitative analysis of the aroma com-
pounds present in this fruit was performed
δCi*t experimentally by CG-MS [9]. The major
V = F ( Ci*,int − Ci*t ) [m 3 / s] (10) chromatographic peaks correspond, in order of
δt appearance, to E-2-Hexen-1-al, 2-butyl-1-octanol,
1-hexanol, E-2-Hexen-1-ol and 1-hexadecanol.
With the initial and boundary conditions: Other minor components present in the sample
 N. Diban et al. / Desalination 224 (2008) 34–39 37

Table 1
Characteristic data of the aroma compounds

Component Mi, (g/ mol) hi (cm3/mol) Di×109 (m2/s) Pm,i×1010 (m2/s) Cit,t = 0 [9] (mg/ kg)
E-2-Hexen-1-ol 100.16 130.7 1.00 2.55 [This study] 0.01
n-Hexanol 102.17 144.5 0.94 9.91 [10] 0.02
E-2-Hexen-1-al 98.14 115.5 1.08 0.81 [11] 0.06
Linalool 154.25 179.4 0.83 0.61 [11] 0.004
Phenyl acetaldehyde 120.15 116.7 1.07 0.08 [11] 0.003
Benzyl alcohol 108.14 103.0 1.15 0.07 [11] 0.08
Z-3-Hexen-1-ol 100.16 116.5 1.07 0.44 [11] 0.06
Ethanol 46.07 59.1 1.28 0.72 [This study] 7,800
Water 18.02 17.6 — 0.01 [This study] 992,200

analysed are Z-3-Hexen-1-ol, linalool, phenyl Table 2

acetaldehyde and benzyl alcohol. Previous studies
agreed that E-2-Hexen-1-ol is one of the charac-
teristic impact components of the flavour [8] of
bilberries.
For this multi-component mixture of aroma
compounds considered upwards, simulation of
the PV performance with the mathematical model
proposed is studied. Permeabilities of the aroma
compounds through the PDMS membrane are
needed to apply the model and their values are
extracted from literature, except for E-2-Hexen-1-
ol which value was obtained experimentally:
Pm,hex = 2.55× 10!10 m2/s at 30EC. The values of
permeability, the aroma diffusivity coefficient
values and the initial feed concentration in the
tank together with other component features are
compiled in Table 1. As no quantitative aroma
analysis was made, the feed concentration of the
aroma com-pounds was selected according to
those found by Hirvy and Honkanen [9].
Four commercial membranes with different
thicknesses (1.48, 1.96, 2.53 and 4.33×10!4 m)
were available to study, although to complete the
profile evolution a wider range of membrane
thicknesses between 1.48×10!5 to 1.48×10!3 m
was studied. The operating conditions were con-
sidered according to the data used in experiences
made in Garcia et al. [9] and they are presented in
Table 2.
Characteristic data of the laboratory membrane module
v̄ (m/s) 1230.4
ξ 2.53×10!4
Module length, L (m) 0.375
ID (m) 5.16×10!4
Membrane area, Ap (m2) 0.0056
Shape factor, s 1.343
The trend of the enrichment factor, βi, the per-
meate concentration, Cip , and the partial flux, Ji,
of E-2-Hexen-1-ol (subscript “Hex”) with the
thickness of the PDMS membrane is plotted in
Fig. 2. A clear increase of the enrichment factor
and permeate concentration with thicker mem-
branes is observed while the partial fluxes
decrease markedly. An asymptotic profile for all
the parameters under study is obtained, meaning
that a maximum level of permeate concentration
and a minimum value of partial flux of the aroma
compound can be reached by increasing the
membrane thickness. Similar trend appears for
the rest of the aroma compounds.
The results of the enrichment factor, permeate
concentration and partial fluxes for the different
aroma compounds at the beginning of the ope-
ration using the membrane module employed
during the laboratory experiments in Garcia et al.
[9] (1.96×10!4 m thickness), are summarised in
Table 3.
38 N. Diban et al. / Desalination 224 (2008) 34–39

Fig. 2. Profile of enrichment factor, βHex; permeate concentration, CpHex; and partial flux, JHex, of E-2-Hexen-1-ol with
membrane thickness.

Table 3 1. Higher membrane thicknesses give as a

Simulation results for the aroma compounds result higher enrichment factors for the aroma
compounds under study until an asymptotic value
Component βi Cip (mg/ kg) Ji (g/m2/h) is reached, though partial fluxes decrease
E-2-Hexen-1-ol 120.6 1.21 3.78×10!5 considerably.
n-Hexanol 236.9 4.74 14.9×10!5 2. The composition achieved in permeate with
E-2-Hexen-1-al 46.3 2.78 8.70×10!5 the PDMS membrane type under study is dif-
Linalool 49.3 0.20 0.62×10!5 ferent than feed composition.
Phenyl acetaldehyde 5.5 0.02 0.05×10!5 Nevertheless:
Benzyl alcohol 4.2 0.33 1.05×10!5 C Sensorial analysis should be made in order to
Z-3-Hexen-1-ol 27.4 1.64 5.15×10!5
check the organoleptical quality of the aroma
Ethanol 13.7 106,934 2.51
Water 0.9 893,057 20.9
concentrate obtained.
C Other membrane types must be tried in order
to achieve higher aroma selectivity.

From comparison of the data in Tables 1 and 5. Symbols

3, it is concluded that the distribution of the
Ap — Effective membrane area, m2
volatile organic compounds in permeate is some-
C — Concentration, m2
how different from the feed composition.
D — Molecular diffusivity, m2/s
Nevertheless, a sensorial analysis should be made
F — Flow rate, m3/s
to measure the product quality achieved.
J — Partial flux, g/m2 s
Water content in the permeate is not reduced
l — Membrane thickness, m
significantly. Other types of pervaporation mem-
L — Module total length, m
branes should be tested to check membranes with
M — Molecular weight, g/mol
lower water fluxes that allow higher aroma
Pe — Peclet number
enrichment.
Pm — Membrane permeability, m2/s

r — Radial coordinate, m
4. Conclusions
R — Dimensionless radial coordinate
The following conclusions have been rt — Total membrane fibre radio, m
obtained: s — Shape factor
 N. Diban et al. / Desalination 224 (2008) 34–39 39

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