Journal of Food Engineering 76 (2006) 387–395

www.elsevier.com/locate/jfoodeng

Concentration of aqua solutions of organic components

by reverse osmosis. I: Influence of trans-membrane pressure
and membrane type on concentration of different ester
and aldehyde solutions by reverse osmosis
A. Pozderović *, T. Moslavac, A. Pichler
Faculty of Food Technology, Josip Juraj Strossmayer University of Osijek, Department of Food Technology, F. Kuhaca 18,
P.O. Box 709, HR-31001 Osijek, Croatia

Accepted 19 May 2005

Available online 22 July 2005

Abstract

Volatile aroma components of fruit juices are lost with vapour during concentration by evaporation. However, these components
are mostly retained in fruit juice by membrane processes concentration. Application of reverse osmosis for concentration of ester
and aldehyde solutions, being components of apple juice aroma, was investigated. Influence of process pressure, percentages of dif-
ferent esters and aldehydes (0.01% v/v, 0.05% v/v and 0.1% v/v), influence of molecule structure, molecular mass and membrane
type on concentration of model solutions of esters and aldehydes by reverse osmosis were studied. Effects of activity and activity
coefficient of esters and aldehydes on concentration were investigated too. Research was carried out with model solutions of esters
(ethyl acetate, butyl acetate, hexyl acetate, amyl acetate, iso-amyl acetate, iso-amyl propionate, ethyl butyrate, ethyl 2-methyl buty-
rate) and aldehydes (hexanal, trans-2-hexenal). Reverse osmosis concentration was carried out on laboratory equipment with plates
and frames using two types of composite membranes (aromatic polyamide membrane HR 95 PP of 95% NaCl rejection and HR 98
PP of 97.5% NaCl rejection). Aroma components (esters and aldehydes) of the retentate and permeate were determined by gas chro-
matography with a mass detector (GC/MS) and a ‘‘head space’’ technique. Results of this research showed that ester and aldehyde
water solutions of different molecular mass and structure could be concentrated successfully by reverse osmosis. These results also
give a better insight into mechanisms of aroma compounds retention (esters, aldehydes) in the retentate, during concentration of
water solutions by reverse osmosis. On the membrane HR 98 PP was greater retention of esters: ethyl acetate, butyl acetate, ethyl
butyrate and ethyl 2-methyl butyrate than the membrane HR 95 PP. On the membrane HR 95 PP was greater retention of esters:
hexyl acetate, amyl acetate, iso-amyl acetate, iso-amyl propionate and aldehydes: hexanal and trans-2-hexenal than the membrane
HR 98 PP. Concentration factor was higher in the retentate and OCP (organic components passage) was lower in the permeate when
ester and aldehyde portions in the feed solution and molecular mass were greater. Ester concentration of n-structural form showed a
greater concentration factor in the retentate and lower OCP (organic components passage) in the permeate. The greater retention in
the retentates was realised by aldehyde concentration with a double bond in the molecule. Membrane selectivity and retention of
esters and aldehydes was greater in the retentate than in the permeate with application of higher process pressure.
Ó 2005 Elsevier Ltd. All rights reserved.

Keywords: Concentration; Aroma; Membrane processes; Reverse osmosis; Esters; Aldehydes; Gas chromatography (GC/MS)

1. Introduction

*
Corresponding author. Tel.: +385 31 224313; fax: +385 31 115207. Many authors reported that the profile aroma changed
E-mail address: andrija.pozderovic@ptfos.hr (A. Pozderović). with fruit juice concentration by evaporation (Konja,

0260-8774/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2005.05.038
388 A. Pozderović et al. / Journal of Food Engineering 76 (2006) 387–395
Nomenclature
Vo feed volume (L)
Vr retentate volume (L)
Ap peak area in permeate
Af peak area of feed solution
CFi concentration factor of component in reten-
tate (%)
Ar peak area in retentate
OCP organic components passage (%)
Õ osmotic pressure (Pa)
M molar concentration (mol m3)
Pozderović, & Lovrić, 1988). There is a 90% loss of vola-
tile aroma compounds by evaporation. That deficiency is
partially compensated by aroma recovery unit with a rec-
tification column (Karlsson, 1995; Sancho & Rao, 1993;
Zhang, 1995). Application of other processing solutions
for aroma recovery with fruit juice concentration by evap-
oration was examined in various studies like extraction
technique (Gomez & Martinez, 1992; Simon, Cully, &
Vollbrecht, 1992), adsorption recovery (Cesare, Polesello,
& Nani, 1988; Polesello, Cesare, & Narić, 1989) and per-
vaporation (Borjesson, Karlsson, & Tragardh, 1996; Ols-
son & Tragardh, 1999). New technology was developed in
Australia that gave better results in aroma concentration,
based on column application with a rotary cone (Spinning
Cone Column (SCC)) (Schofild, 1994; Schofield & Riley,
1998). High aroma concentration of small volume was
realized in this process. The promising alternative is fruit
juice concentration by reverse osmosis (RO) and nanofil-
tration (NF) (Alvarez, Alvarez, & Riera, 1997; Braddock,
Sadler, & Chen, 1991; Hayakawa, Igami, & Nakajima,
2000; Medina & Garcia, 1998; Singh & Eipeson, 2000).
Greater retention of volatile aroma compounds, better
compound separation and lower processing temperatures
were realized by membrane process than by evaporation
concentration (Alvarez, Riera, Alvarez, & Coca, 1998;
Alvarez, Riera, Alvarez, & Coca, 2001; Ferrarini, Versari,
& Galassi, 2001; Garcia, Gozalvez, & Lora, 2002).
There are two principal models for the transport pro-
cess: the solution–diffusion model and the capillary pore
model, both of which describe the reverse osmosis pro-
cess. However, the solution–diffusion model is more
widely accepted. The water flux (Fw), and the salt flux
(Fs), is linked to the pressure and concentration gradi-
ents across the membrane (Jiao, Cassano, & Drioli,
2004). From the solution–diffusion model, these terms
are described by the equations: Fw = A (Dp  Dp) where
A is the water permeability constant of the membrane,
Dp is the pressure differential across the membrane,
and Dp is the osmotic pressure difference between the
retentate and permeate sides of the membrane. The os-
motic pressure is directly dependent on the salt concen-
R universal gas constant (Pa m3 mol1 K1)
T absolute temperature (K)
c activity coefficient
a activity
cC combinatorial contribution
cR residual contribution
r i , qi volume and surface area parameters (molecu-
lar parameters)
R k, Q k group volume and surface area parameters
tration of the process stream (White, Ditgens, &
Laufenberg, 2002). The equations describing the salt
flux: Fs = B (C1  C2) where B is the salt permeability
constant, and C1  C2 is the salt concentration differ-
ence across the membrane. Thus, the water flux is pro-
portional to applied pressure but the salt flux is
independent of the applied pressure (Bogliolio et al.,
1996). The salt transport is primarily dependent upon
the concentration of dissolved solids on each side of
the membrane.
Aroma compounds retention, higher in the retentate,
was realized using the composite HR membranes for
fruit juice concentration by reverse osmosis (Shen &
Wiley, 1983; Chou, Wiley, & Schlimme, 1991; Dasgupta
& Jayarama, 1996). Konja et al. reported that retention
of aroma compounds in the retentate was 88% in fruit
juice concentration by reverse osmosis using the mem-
brane HR 98 PP (Konja & Clauss, 1991). Many authors
indicated successfully separation and retention of organ-
ic components from water solutions during RO concen-
tration using different composite membranes (Huang,
Guo, Ohia, & Fang, 1998). Pozderović et al. reported
the possibility of reverse osmosis and composite mem-
brane HR 98 PP application for apple juice aroma con-
centration from evaporator condensate (Pozderović &
Moslavac, 1999). Investigation of model solution con-
centration of individual esters and aldehydes by reverse
osmosis using two different composite membranes was
carried out in this paper as a continuation of the above
mentioned investigation. The aim of the research was
study of retention and recovery phenomenon and mech-
anisms of ester and aldehyde model solutions on mem-
branes during the reverse osmosis processes.
2. Materials and methods
2.1. Preparations of ester and aldehyde solutions
Different esters and aldehydes (purity level p.a.) by
Sigma, Aldrich and Fluka were used for preparation
 A. Pozderović et al. / Journal of Food Engineering 76 (2006) 387–395
of model solutions. Model solutions of esters: ethyl ace-
tate, butyl acetate, hexyl acetate, amyl acetate, iso-amyl
acetate, iso-amyl propionate, ethyl butyrate, ethyl 2-
methyl butyrate and aldehydes: hexanal, trans-2-hexenal
were prepared. All investigations of reverse osmosis con-
centration were realized using water solutions of esters
and aldehydes with the concentration of 0.01% v/v,
0.05% v/v and 0.1% v/v. The concentration of esters in
the model solutions was 0.01% v/v, 0.05% v/v, 0.1%
v/v and of aldehydes was 0.01% v/v, 0.05 %v/v. The bin-
ary solutions consisted of the esters or aldehydes and
water. For the model solution deionised water was
mixed with one organic component (binary solution).
Solutions were prepared by using distilled water,
cooled at 18 °C, followed by reverse osmosis concentra-
tion. Five litres of feed solutions were prepared for the
experiment for all ester and aldehyde solutions of differ-
ent concentrations.
2.2. RO equipment
All investigations of model solution concentration of
every single ester and aldehyde were realized by RO lab-
oratory equipment ‘‘Lab Unit M20’’ with plates and
frames supplied by DDS (Dow Denmark Separation
Systems De Danske Sukkerfabrikker, Copenhagen,
Denmark). High-pressure piston pump Rannie 16.50
was used for solution supplying in the experiment. Con-
centration of ester and aldehyde water solution was real-
ized with composite membranes HR 95 PP and HR 98
PP (high resistance polyamide supported on polysul-
phone HR membrane) of the same firm, as was the
equipment for reverse osmosis (Table 1).
Twelve membranes, total surface of 0.347 m2 were in-
serted in a plate module of reverse osmosis plant. Six
membranes type HR 95 PP and six membranes Hr 98
PP were inserted in the module. All experiments were
carried out parallel, by both membranes at the same
working conditions.
2.3. Concentration procedure
The concentration of each solution was carried out
with retentates recirculation up to the final volume
reduction (VR = 3.33). During concentration, the reten-
tates was cooled with refrigerating water in a heat chan-
ger of the instrument module. Experiments were realized
Table 1
Characteristics of the composite HR 95 PP and HR 98 PP membranes
elements
Types of Permeability Water pH Temperature Pressure
composite % NaCl flux (°C) (bar)
membranes (L/m2h)
HR 95 PP <5 115–155 2–11 0–60 0–60
HR 98 PP <2.5 105–145 2–11 0–60 0–60
389
with 0.1% v/v of ester model solution (ethyl acetate, bu-
tyl acetate, ethyl butyrate) at four operating pressures of
10, 20, 30, 40 bar by 0.05% v/v portion at 30 bar pres-
sure and by 0.01% v/v portion at 30 and 40 bar pres-
sures. The concentration of ester solutions (hexyl
acetate, ethyl 2-methyl butyrate, amyl acetate, iso-amyl
acetate, iso-amyl propionate) was realized by 0.01%
v/v portion at 40 bar pressure. Aldehyde solutions con-
centration by 0.01% v/v and 0.05% v/v portions were
carried out at 40 bar pressure. Permeate samples were
taken for every type of membrane during concentration,
up to the final VR of 3.33. The permeate was taken in
defined time intervals: at the pressure of 10 bar every
10 min, 20 bar every 5 min, 30 bar every 3 min, 40 bar
every 2 min. Total permeate of every membrane type
was obtained by mixing all permeates collected during
the concentration. Retentate samples were taken during
the process: an initial solution (after recirculation of
2 min), an average sample (at VR = 1.6) and a final sam-
ple at the end of the concentration process.
2.4. Aroma analysis
The concentration of every single ester and aldehyde
in the feed water solutions, in permeate and retentate
was determined by gas chromatography with mass
spectrometry (GC/MS) by a ‘‘head space’’ method. An
analysis was carried out with gas chromatography
Hewlett-Packard 5890 Series II with a mass detector
Hewlett Packard 5971 A and a ‘‘head space’’ injector
HP 19395A. The ionisation of the samples was achieved
at 70 eV under the SCAN mode. The mass range studied
was from 10 to 250 m/z. The capillary column used in
this experiment was HP-20M (Carbowax 20M), (length
50 m, capillary column diameter 0.2 mm film thickness
in the column stationary phase 0.2 lm). Helium (He)
5.0 (purity 99.999%; Messer, Austria) was used as a car-
rier gas. Work conditions at GC–MS were the following:
the carrier gas flow rate was 50 mL/min split vent, purge
vent 1 mL/min, head column pressure 1.379 bar, injec-
tor temperature at 250 °C and detector was at 280 °C.
The oven temperature at 50 or 70 °C (1 min) to 120 °C
(10 °C/min), at 120 °C (1 min). Work conditions of a
‘‘head space’’ injector were: bath temperature at 70 °C,
valve loop temperature 75 °C, gas pressurization time
2 min, injected time 2 min, volume of head space sample
2 mL. GC–MS ester and aldehyde analysis was con-
ducted for all experiments, after the permeate and reten-
tate samples had been collected during and after
concentration. Aroma compounds (esters and alde-
hydes) were registered as chromatograph peaks that
come out in specific times of retention from the capillary
column of the gas chromatograph.
Peak area, received at chromatogram, was propor-
tional to the amount of aroma components (esters and
aldehydes) in the analysed sample. Database of mass
390 A. Pozderović et al. / Journal of Food Engineering 76 (2006) 387–395

spectars (WILEY 275.L) (library spectrum) of the Volume and area parameters are determined by
highest number of aroma components (chemical compo- equations
sitions) was used for identification of esters and alde- X
nGr X
nGr
hydes from the sample based on its received mass ri ¼ mki Rk ; qi ¼ mki Qk ð7Þ
spectar. k¼1 k¼1

ri and qi are the molecular parameters (volume and sur-

2.5. Data calculations face area parameters for each molecular species) depend
on the structure of pure components, size and molecular
Chromatogram data obtained by gas chromatogra- area. Values of these parameters were taken from corre-
phy presented peak areas (impulses) of individual esters sponding tables. Rk and Qk are the group volume and
and aldehydes as aroma components. To study the pro- surface area parameters.
cesses of concentration and organic components passage Residual contribution to activity coefficient was cal-
(OCP) of individual esters and aldehydes, the following culated from the equation:
parameters were calculated using the equation:
X
nGr
ðiÞ ðiÞ
Vo ln cRi ¼ mki ðln Ck  ln Ck Þ ð8Þ
VR ¼ ð1Þ
Vr k¼1
ðiÞ
VR is the volume reduction; Vo is the feed volume (L) Here vk is the number of k groups present in species i
ðiÞ
and Vr the retentate volume (L) and Ck is the residual contribution to the activity coef-
Ap ficient of group k in a pure fluid of species i molecules.
OCP ¼  100 ð2Þ Parameter results at the temperature of 20 °C were
Af
calculated by computer analysis using the program
OCP is the organic components passage (%); Ap is the Mathematica 4.2 (Wolfram Research, USA) for UNI-
peak area in permeate and Af the peak area of feed FAC model.
solution. Osmotic pressure is a critically important property in
Ar reverse osmosis that presents the pressure necessary to
CFi ¼  100 ð3Þ reverse osmosis process and return to the initial condi-
Af
tion. The physical significance of osmotic pressure in re-
CFi is the concentration factor of component in reten- verse osmosis is that it represents the minimum pressure
tate (%); Ar the peak area in retentate and Af is the peak that must be applied to a feed solution in order to obtain
area of feed solution. any permeation of flux (Bouchard & Lebrun, 1999).
Microsoft Excel 2000 (Microsoft Corp.), the com- Osmotic pressure was traditionally calculated using
puter program, was used for data calculations. the VanÕt Hoff relationship for dilute solutions (Thorne,
Thermodynamic parameters: activity (a) and activity 1992) using
coefficient (c) were calculated for two-component sys-
tems that represent water model solutions of individual P¼M RT ð9Þ
esters and aldehydes. Mathematical method for UNI- The VanÕt Hoff model assumes that osmotic pressure
FAC model (Universal functional activity coefficient) increases linearly with molar concentration of the solute.
was used for calculating the values of these parameters. The solution osmotic pressure is the function of solution
These could be for example CH3, CH2, CH, CHO, CO, concentration and temperature (Heldman & Hartel,
OH, CH3COO, COOH, NH. 1997).
The equation for activity coefficient calculation is:
log ci ¼ log cCi þ log cR
i ð4Þ
indexes C and R present combinatorial and residual 3. Results and discussion
contribution. Combinatorial contribution relates to the
difference in size and shape of molecules and residual Research data of the process pressure influence on
contribution relates to energetic interactions. different esters portion in the permeate and retentates,
Combinatorial contribution is expressed by: in the concentration by reverse osmosis with the mem-
branes HR 95 PP and HR 98 PP and with the feed solu-
X
nKo
/i z X
nKo
hi / XnKo tion 0.1% v/v are shown in Figs. 1–3. The ethyl acetate
log cCi ¼ xi ln þ qi ln þ li  i x j lj and ethyl butyrate organic components passage (OCP)
i¼1
xi 2 i¼1 /i xi j¼1
in the permeate was reduced by concentration solutions
ð5Þ of every single ester with the pressure increase using the
with membrane HR 95 PP (Fig. 1). The butyl acetate organic
components passage (OCP) in the permeate increased
li ¼ z=2ðri  qi Þ  ðri  1Þ ð6Þ when process pressure increased. Data in Fig. 2 showed
 A. Pozderović et al. / Journal of Food Engineering 76 (2006) 387–395 391

60 were lower with the solution concentration by the mem-

brane HR 98 PP than HR 95 PP membrane. Concentra-
Organic components passage (%)

50 tion factor of esters in the retentate increased with

higher-pressure application by esters concentration be-
40
ethyl acetate cause of membrane selectivity increase (Fig. 3). That re-
butyl acetate
ethyl butyrate sulted in greater retention of esters in the retentate than
30 in the permeate.
Calculated values of thermodynamics parameters,
20
activity coefficient (c) and activity (a) for water model
solutions of esters and aldehydes at 20 °C temperature
10
obtained by UNIFAC method, are given in Table 2.
5 10 15 20 25 30 35 Data in that table showed that ester and aldehyde por-
Pressure (bar)
tion in solution, molecular mass and molecule structure
Fig. 1. The influence of pressure on the concentration of different affected activity coefficient (c) and activity (a). Higher
esters in permeate (membrane HR 95 PP, feed solution 0.1% v/v). concentration of esters and aldehydes in the water solu-
tion caused an increase of activity and decrease of activ-
40
ity coefficient. It was also observed that molecular mass
Organic components passage (%)

ethyl acetate increase, at the identical ester and aldehyde portion in

35 butyl acetate
ethyl butyrate
the solution, caused an increase of activity and activity
30
coefficient. Carelli and Sancho indicated that an increase
25 of molecular mass of esters and aldehydes in the water
20 solution and temperature increase resulted in their high-
15 er activity coefficient (Carelli, Crapiste, & Lozano, 1991;
Sancho, Rao, & Downing, 1997). Table 2 showed that
10
the ester molecule structure affected thermodynamic
5
parameters and because of that the n-form ester (by
0 identical portion) had lower activity and activity coeffi-
5 10 15 20 25 30 35 40 45
Pressure (bar) cient than the iso-form.
Calculated values of osmotic pressure of ester and
Fig. 2. The influence of pressure on the concentration of different
esters in permeate (membrane HR 98 PP, feed solution 0.1% v/v).
aldehyde solutions at 18 °C are shown in Table 3. Table
showed that smaller molecular weight substances exert
greater osmotic pressure than larger molecules, and
higher concentrations give higher osmotic pressures.
Concentration factor of component in retentate (%)

190
In Figs. 4–8 are presented the research results of
180
molecular mass and molecule structure effect on ester
170 and aldehyde organic components passage (OCP) in
160 the permeate during RO concentration by the mem-
150 branes HR 95 PP and HR 98 PP. Data in Fig. 4 showed
140 that ester organic components passage (OCP) increased
130
in the permeate during the ester concentration of acetate
group, using feed solution concentration of 0.01% v/v
120 ethyl acetate
butyl acetate
by 40 bar pressure and by both membrane application.
110
ethyl butyrate It was observed in Fig. 4 that esters, ethyl acetate and
100 butyl acetate, had higher permeability through the mem-
5 10 15 20 25 30 35
Pressure (bar) brane HR 95 PP (bigger portion of esters in the perme-
ate) than through the membrane HR 98 PP. Esters, amyl
Fig. 3. The influence of pressure on the concentration of different acetate and hexyl acetate, have the greater permeability
esters in retentate (feed solution 0.1% v/v, membranes HR 95 PP and
HR 98 PP).
through the membrane HR 98 PP. It was shown for
both membranes that the organic components passage
(OCP) of esters in the permeate was greater and concen-
that the same phenomenon of portion decrease in the tration factor in the retentate was lower when esters of
permeate was observed in the concentration with the lower molecular mass, ethyl acetate and butyl acetate,
membrane HR 98 PP for ethyl acetate and butyl acetate. were concentrated (lower activity and activity coeffi-
That phenomenon was not expressed that much for cient, higher osmotic pressure) compared to esters of
ethyl butyrate. It was also noticed that values of esters greater molecular mass, amyl acetate and hexyl acetate,
organic components passage (OCP) in the permeate (greater activity and activity coefficient, lower osmotic
392 A. Pozderović et al. / Journal of Food Engineering 76 (2006) 387–395

Table 2
Calculated values of activity coefficient (c) and activity (a) for model solutions of ester and aldehyde at 20 °C with UNIFAC method
Concentration % (v/v) Activity coefficient (c) Activity (a)
Ester, aldehyde Water Ester, aldehyde Water
Ethyl acetate 0.01 10.1854 1.0000 0.001019 0.9999
0.05 10.1718 1.0000 0.005086 0.9995
0.1 10.1547 1.0000 0.010155 0.999002
Butyl acetate 0.01 13.7732 1.0000 0.001377 0.9999
0.05 13.7547 1.0000 0.006877 0.9995
0.1 13.7316 1.0000 0.013732 0.999002
Hexyl acetate 0.01 16.9945 1.0000 0.0016994 0.9999
0.05 16.9718 1.0000 0.0084858 0.9995
0.1 16.9435 1.0000 0.0169435 0.999002
Ethyl butyrate 0.01 18.7888 1.0000 0.001879 0.9999
0.05 18.7567 1.0000 0.009378 0.999501
0.1 18.7168 1.0000 0.018717 0.999002
Iso-amyl propionate 0.01 23.1215 1.0000 0.0023121 0.9999
0.05 23.0825 1.0000 0.0115413 0.999501
0.1 23.034 1.0000 0.023034 0.999002
Ethyl-2-methyl butyrate 0.01 21.0412 1.0000 0.0021041 0.9999
0.05 21.0055 1.0000 0.0105028 0.999501
0.1 20.961 1.0000 0.020961 0.999002
Amyl acetate 0.01 15.4305 1.0000 0.0015430 0.9999
0.05 15.4098 1.0000 0.0077048 0.9995
0.1 15.3839 1.0000 0.0153839 0.999002
Iso-amyl acetate 0.01 15.4445 1.0000 0.0015444 0.9999
0.05 15.4238 1.0000 0.0077119 0.9995
0.1 15.398 1.0000 0.015398 0.999002
Hexanal 0.01 34.5312 1.0000 0.003453 0.9999
0.05 34.3301 1.0000 0.017165 0.999502
trans-2-Hexenal 0.01 11.055 1.0000 0.001106 0.9999
0.05 11.037 1.0000 0.005518 0.999501

Table 3
Osmotic pressure of ester and aldehyde solutions at 18 °C
Concentration Ethyl Butyl Hexyl Ethyl-2-methyl Amyl Iso-amyl Iso-amyl Ethyl Hexanal trans-2-Hexenal
% (v/v) acetate acetate acetate butyrate acetate acetate propionate butyrate (kPa) (kPa)
(kPa) (kPa) (kPa) (kPa) (kPa) (kPa) (kPa) (kPa)
0.01% 2.74 2.083 1.678 1.859 1.859 1.859 1.678 2.083 2.416 2.466
0.05% 13.72 10.419 8.392 9.297 9.297 9.297 8.392 10.419 12.083 12.331
0.1% 27.47 20.838 16.780 18.590 18.590 18.590 16.780 20.838

pressure). It was also shown for both membranes, that
permeability of ethyl acetate was greater compared to
other esters of acetate group when 0.01% v/v ethyl ace-
tate solution (the lowest molecular mass) was conducted
by 40 bar pressure. It was seen that molecular mass,
activity and activity coefficient of esters affected on or-
ganic components passage in the permeate, while osmo-
tic pressure did not has any influence. Data in Figs. 5
and 6 showed that the ester molecule structure affected
more membrane permeability during concentration of
0.01% v/v ester solution by 40 bar pressure than the es-
ter molecular mass. The ester solution concentration of
the identical molecular mass (ethyl-2-methyl butyrate,
amyl acetate, iso-amyl acetate) with the membranes
HR 95 PP and HR 98 PP showed that ethyl 2-methyl
butyrate had the smallest retention on the membrane
(greater portion in the permeate and OCP) because it
had the most branched molecule and the smallest alco-
hol radical in molecule structure. It was shown in both
membrane concentration that iso-amyl acetate, ester of
iso-structural form (bigger activity and activity coeffi-
cient), had lower retention on the membrane in the
retentate and greater organic components passage
(OCP) in the permeate as compared to amyl acetate con-
 A. Pozderović et al. / Journal of Food Engineering 76 (2006) 387–395 393

ethyl acetate HR 95 PP amyl acetate HR 95 PP 100

40 ethyl acetate HR 98 PP amyl acetate HR 98 PP 90

Organic components passage (%)

butyl acetate HR 95 PP hexyl acetate HR 95 PP
80
35 butyl acetate HR 98 PP hexyl acetate HR 98 PP
Organic components passage (%)

70
30 60
50
25
40
20 30
20
15 hexanal
10
trans-2-hexenal
10 0
1 1.5 2 2.5 3 3.5
5 Volume reduction

0 Fig. 7. The influence of the molecule structure on different aldehyde

1 1.5 2 2.5 3 3.5
portions in permeate during concentration (membrane HR 95 PP, feed
Volume reduction
solution 0.01% v/v, pressure 40 bar).
Fig. 4. The influence of molecular mass on different ester portions in
permeate during concentration (membranes HR 95 PP and HR 98 PP,
feed solution 0.1% v/v, pressure 40 bar).
90

80

Organic components passage (%) 70

70
60
60
Organic components passage (%)

50
ethyl butyrate isoamyl acetate
50 amyl acetate
ethyl-2-methyl butyrate 40
isoamyl propionate
40 30

30 20
hexanal
10 trans-2-hexenal
20
0
10 1 1.5 2 2.5 3 3.5
Volume reduction
0
1 1.5 2 2.5 3 3.5 Fig. 8. The influence of the molecule structure on different aldehyde
Volume reduction portions in permeate during concentration (membrane HR 98 PP, feed
solution 0.01% v/v, pressure 40 bar).
Fig. 5. The influence of molecular mass and molecule structure on
different ester portions in permeate during concentration (membrane
HR 95 PP, feed solution 0.01% v/v, pressure 40 bar). centration. Membrane HR 98 PP had greater permeabil-
ity for these esters having, therefore, a higher portion of
esters in the permeate than the membrane HR 95 PP.
Ethyl butyrate has a greater alcohol radical (smaller
70
molecular mass) than ethyl-2-methyl butyrate and it
60 has been found that smaller organic components pas-
Organic components passage (%)

ethyl butyrate isoamyl acetate sage (OCP) realised in permeate, in concentration by

50 ethyl-2-methyl butyrate amyl acetate both membranes. The greater concentration factor in
isoamyl propionate
40
the retentate as well as smaller organic components pas-
sage (OCP) in the permeate were received by iso-amyl
30 propionate concentration, ester with the greatest molec-
ular mass, and both membrane application.
20
Results of the molecule structure effect on the alde-
10 hyde portion in the permeate during the concentration
of 0.01% v/v solution by 40 bar pressure with the mem-
0
1 1.5 2 2.5 3 3.5 branes HR 95 PP and HR 98 PP were shown in Figs. 7
Volume reduction and 8. The figures indicated, for both membrane con-
centration of aldehyde solutions, bigger retention of
Fig. 6. The influence of molecular mass and molecule structure on
different ester portions in permeate during concentration (membrane trans-2-hexenal (smaller activity and activity coefficient,
HR 98 PP, feed solution 0.01% v/v, pressure 40 bar). higher osmotic pressure) in the retentate and lower in
394
the permeate than it was with hexanal (bigger activity
and activity coefficient, lower osmotic pressure). Better
retention of trans-2-hexenal on the membrane is due to
different molecule structure, i.e. double bond in the alde-
hyde molecule; activity, activity coefficient and osmotic
pressure did not have any influence.
At the beginning of the process, organic components
passage (OCP) was 11.27% by concentrating 0.01% v/v
solution of trans-2-hexenal with the HR 95 PP mem-
brane, while at the end of the process organic compo-
nents passage (OCP) was 25.34%. Concentration with
the membrane HR 98 PP showed higher OCP (organic
components passage) values (from 14.49% to 29.65%).
In Table 4 is shown an influence of initial portion of
esters and aldehydes in binary system on organic
components passage (OCP) in the final permeate with
membrane HR 95 PP and 40 bar pressure. Organic com-
ponents passage (OCP) in final permeate was insignifi-
cantly smaller by greater initial portion of aldehyde
and ester in binary solution (greater activity, smaller
activity coefficient, greater osmotic pressure).
Fig. 9 showed the effect of different initial portion of
esters on organic components passage (OCP) in the final
permeate at both membrane applications. The organic
components passage (OCP) in the final permeate was
insignificantly lower by greater initial portion and
Table 4
Effect of initial portion of aldehyde (initial concentration) on organic
components passage (OCP) in final permeate with membrane HR 95
PP at 40 bar
Compounds
Hexanal
trans-2-Hexenal
70
0.01% 0.05%
Organic components passage (%)
60
50
40
0.05%
0.01%
30
20
10
0 cess pressure in ester and aldehyde concentration in-
0 0.005
Fig. 9. The influence of initial portion and activity of ester solutions
on portion in the final permeate (water solutions 0.01% v/v, 0.05% v/v
and 0.1% v/v, both membranes, pressure 30 bar).
A. Pozderović et al. / Journal of Food Engineering 76 (2006) 387–395
activity of esters in the solution. It was pointed out that
organic components passage in the permeate was lower
at greater activity, osmotic pressure and greater portion
of esters and aldehydes in the feed solution.
4. Conclusion
Ester and aldehyde water solutions can be concen-
trated with the composite membranes HR 95 PP and
HR 98 PP. Retention was greater on the membrane
HR 98 PP in the retentate than on the membrane HR
95 PP by concentration of the following ester water solu-
tions: ethyl acetate, butyl acetate, ethyl butyrate, ethyl 2-
methyl butyrate. Higher retention of hexyl acetate, amyl
acetate, iso-amyl acetate, hexanal and trans-2-hexenal
was on the membrane HR 95 PP. Activity and activity
coefficient of esters in water solutions affected their
retention in the retentate. Concentration factor was
higher in the retentate, organic components passage
(OCP) was lower in the permeate when ester and alde-
hyde activity in feed solution was bigger. Greater ester
and aldehyde portion in feed solution increased their
activity (a) and osmotic pressure but decreased activity
coefficient (c). While concentration factor was higher
in the retentate, organic components passage (OCP)
was lower in the permeate when ester and aldehyde por-
tion was bigger in feed solution (higher activity (a) and
lower activity coefficient (c)). Ester concentration factor
was greater in the retentate, organic components pas-
sage (OCP) was lower in the permeate by the concentrat-
Concentration % (v/v) OCP (%)
ing ester solution of the higher molecular mass in n-form
(greater activity and activity coefficient, lower osmotic
0.01 77.25
0.05 63.74
pressure) due to lower membrane permeability. An in-
crease of molecular mass of esters and aldehydes in-
0.01 17.74
creased their activity (a) and activity coefficient (c) and
0.05 16.77
decreased osmotic pressure in water solution. Ester con-
centration of n-structural form, in case of both mem-
brane applications, showed better membrane retention
in the retentate in relation to the iso-form. Ester iso-
Ethyl acetate HR 98
form had greater activity and activity coefficient in the
Butyl acetate HR 98
0.1% Ethyl butyrate HR 98 water solution. The alcohol radical sharp of ester mole-
Ethyl acetate HR 95 cule affected membrane retention during concentration.
Ethyl butyrate HR 95
Ester with a smaller alcohol radical in the molecule had
higher permeability through the membrane and higher
0.1%
portion in the permeate. The branched ester molecule
(ethyl 2-methylbutyrat) had lower retention in the reten-
tate. Retention was greater in the permeate by the con-
0.05%
0.05%
0.1% centration of aldehyde solutions with the double bond in
0.1% the molecule (lower activity). Application of higher pro-
0.01 0.015 0.02
creased selectivity of the composite HR membranes
Activity having, therefore, better ester and aldehyde retention
in the retentate than in the permeate. Osmotic pressure
was not affect on esters and aldehydes retention on
membrane and in the retentate.
 A. Pozderović et al. / Journal of Food Engineering 76 (2006) 387–395
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