FLAVOUR AND FRAGRANCE JOURNAL WATER-SOLUBLE CONSTITUENTS OF ROSE OIL 555

Flavour Fragr. J. 2005; 20: 555–558

Published online 1 February 2005 in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/ffj.1482

Recovery of water-soluble constituents of rose oil using

simultaneous distillation–extraction
Mohammad H. Eikani,1* Fereshteh Golmohammad,1 Soosan Rowshanzamir 2 and Mehdi Mirza3
1
Chemical Industries Research Center, Iranian Research Organization for Science and Technology, PO Box 15815-3538, Tehran,
Iran
2
Green Research Center, Iran University of Science and Technology, Tehran, Iran
3
Department of Phytochemistry, Research Institute of Forests and Rangelands, Tehran, Iran
Received 8 December 2003; Revised 17 April 2004; Accepted 1 May 2004

ABSTRACT: Recovery of water-soluble constituents of rose oil from aqueous solutions using simultaneous distillation–
extraction was studied. Experiments were carried out using a modified Likens–Nickerson apparatus. A preliminary study
was first performed on aqueous 2-phenylethanol solutions. Using n-butyl acetate as the solvent, the effects of extraction
time, solvent volume and solute concentration on recovery yields were investigated. The optimum experimental conditions
obtained from the preliminary study were applied to extract rose oil constituents from actual aqueous solutions, such as
rose water, second distillation water and residual water of Iranian rose (Rosa damascena Mill). The results show that a
representative extract with recovery of the most valuable constituents of rose oil was carried out successfully. Copyright
© 2005 John Wiley & Sons, Ltd.
KEY WORDS: simultaneous distillation–extraction; 2-phenylethanol; n-butyl acetate; rose water; Rosa damascena Mill

Introduction of the valuable oxygenated constituents, such as 2-

Simultaneous distillation–extraction (SDE) has been one
of the most often cited methods for the isolation of
volatiles since its first report by Likens and Nickerson
in 1964.1 This method combines steam distillation with
simultaneous extraction of the volatiles into a small quan-
tity of a water-immiscible organic solvent. Taking into
account its possibilities and limitations as a sample pre-
paration method, it is often the best way to get the most
representative extract with the highest overall recoveries
from a wide range of constituents.2–4
An interesting field of application of SDE is the re-
covery of water-soluble rose oil constituents from aque-
ous solutions obtained during rose oil production. The
most common aroma concentrates of rose are rose oil and
rose water, derived from steam distillation, and rose con-
crete and rose absolute from solvent extraction.5–6 In the
two former processes, the water which forms the major
portion of the distillate may contain in solution an appre-
ciable amount of the valuable part of the oil. Among
over 500 chemical ingredients found in rose oil, some
* Correspondence to: M. H. Eikani, Chemical Industries Research Center,
Iranian Research Organization for Science and Technology, PO Box 15815-
3538, Tehran, Iran.
E-mail: Eikani@irost.org
Contract/grant sponsor: Golkaran-Taghtiran-Barij Essence Group, Iran;
Contract/grant number: 630-2274-10040.
phenylethanol, may be dissolved in the water used for
hydrodistillation of rose petals. It is estimated that the oil
produced by distillation with water contains only about
one-third of the 2-phenylethanol of the oil as it occurs in
nature, over two-thirds passing into solution in the water.
The solubility of 2-phenylethanol in water is a well-
known problem in the industrial preparation of rose
fragrance.7 In order to recover the water-soluble con-
stituents of rose oil in high amounts, a conventional way
is redistillation of rose water. Both the rose water and
the second distillation water have a pleasant odour of
Rosa damascena Mill. petals. These are mainly used for
high-quality food flavouring, soaps, cosmetics, toiletries
and perfumes. At the end of rose water redistillation,
the water remaining inside the distillation still is called
‘residual water’. It is a low quality by-product and its
application is more limited.
From the academic and industrial point of view, it is
interesting to perform a SDE using a suitable solvent
on the aqueous solutions of rose water, the second dis-
tillation water and the residual water. The results may be
applied to determine and identify the rose oil composi-
tion in the actual aqueous solutions obtained in both
small- and large-scale rose oil production. The aim of the
present study is to investigate the recovery and identifi-
cation of rose oil constituents from the above-mentioned
aqueous solutions using atmospheric SDE methodology.
To the best of our knowledge, no studies on SDE of such
aqueous solutions have been reported so far.

Copyright © 2005 John Wiley & Sons, Ltd. Flavour Fragr. J. 2005; 20: 555–558
556 M. H. EIKANI ET AL.
Experimental
Materials
n-Butyl acetate (Merck) was used as the solvent for ex-
traction. Rose oil extracted by hydrodistillation of Iranian
rose flowers (Rosa damascena Mill.), rose oil obtained by
redistillation of rose water, as well as rose water, second
distillation water and residual water, were supplied fresh
by Golkaran-Taghtiran-Barij Essence Co. (Kashan, Iran).
Dichloromethane (Merck) was used to determine the
essential oil content of the actual aqueous solutions.
Apparatus and Procedures
A modified version of the Likens and Nickerson appara-
tus designed by Flath and Forrey8 was used to perform
SDE experiments. It was constructed with minor changes
(Ashke Shisheh Co., Tehran, Iran) for the present work.
The feed and solvent flasks were round-bottomed. The
apparatus arms were insulated to prevent undesirable
heat loss. In all of the runs, the feed flask was filled with
250 ml aqueous solution. The solvent flask was filled
with a measured volume of n-butyl acetate. The initial
solvent was fresh and free of the solute in all experi-
ments. Tap water, at about 15 °C temperature and 2 l/min
flow rate, was used in the condenser. The feed and sol-
vent flasks were heated separately using two heating
mantles. The heating rates of the heaters were kept con-
stant in all of the experiments. The SDE procedure pro-
posed by Schultz et al.9 to run Flath’s apparatus was
used to perform the experiments. Two replications of the
extraction and analysis procedure were performed for
each of the runs.
Analysis
The concentration of 2-phenylethanol in the extract and
the raffinate phases for the experiments performed on the
aqueous 2-phenylethanol solutions were determined by
GC and UV analyses, respectively. The GC apparatus
was a Phillips Model PU-4500, equipped with FID detec-
tor. The column was filled with carbowax 20M 10%
on chromosorb W-AW-100–120 mesh. Helium was used
as the carrier gas (30 ml/min). The detector, injector and
column temperatures were 250 °C, 200 °C and 100 °C,
respectively. The UV apparatus was a Pye Unicam Model
SP4000 spectrophotometer. Absorbance was measured in
a 1 cm quartz cell at 257.5 nm.
GC–MS analysis on the actual aqueous solutions
was conducted on a Varian Saturn Model 3400 GC–MS
system equipped with a DB-5 fused silica column (30 m
× 0.25 mm i.d., film thickness 0.25 µm), interfaced with
a Varian ion trap detector. The GC conditions were: oven
Copyright © 2005 John Wiley & Sons, Ltd.
temperature from 60 °C to 240 °C at 3 °C/min; injector
and transfer line temperatures, 250 °C and 260 °C, re-
spectively; carrier gas, helium at a flow rate of 1 ml/min;
split ratio, 1:13. The detector temperature was maintained
at 240 °C. The MS conditions were: ionization energy,
70 eV; mass range, 40–400 amu; scan mode, EI. The
percentage composition of the identified constituents was
computed from the GC (Varian CP3800) peak area. The
constituents were identified by comparing their retention
times and mass spectra with those of pure reference con-
stituents. Mass spectra were also compared with those in
the NIST (National Institute of Standards and Techno-
logy), WILEY5 and TERPENOIDES mass spectra librar-
ies, and our own created library.
Results and Discussion
Aqueous 2-Phenylethanol Solution
The major water-soluble rose oil constituent is 2-
phenylethanol. Thus, it is reasonable to suppose the ac-
tual aqueous solutions to be a mixture of 2-phenylethanol
and water. Based on this simplifying assumption, a set
of preliminary experiments using a test mixture of 2-
phenylethanol and distilled water were carried out at
atmospheric pressure to obtain the optimum conditions
for performing SDE on the actual aqueous solutions. The
extraction solvent was selected to be n-butyl acetate be-
cause of its high efficiency to recover 2-phenylethanol
(partition coefficient of 34), its near-immiscibility with
water, and the fact that it is permitted as a solvent for
extraction for ingredients in food and pharmaceutical in-
dustries.10 The experiments were carried out with respect
to the extraction time, the solvent volume and the feed
concentration. Results are listed in Tables 1–3. The re-
covery yields as percentages of the initial amounts were
considered to be the mean value of the yields obtained by
GC and UV analyses. The average differences between
the yields obtained by GC and UV were about 10%.
Recoveries for various times of SDE were determined
first. Table 1 shows that the recovery of 2-phenylethanol
as a hydrophilic alcohol with intermediate volatility
reached nearly 100% after 3 h. Other researchers have
reported similar findings using other solvents, such as
dichloromethane.3 In this work, the extraction time of 3 h
was selected to be suitable for performing SDE on the
aqueous solutions.
The results presented in Table 2 show that increasing
the solvent volume leads to slightly higher values of
extraction yields. The result of higher heat transfer is
a higher flow rate of the solvent vapour. It has been
established that increasing the solvent vapour flow rate
improves the recovery rate.3 The minimum operation-
ally permitted volume of the solvent in the apparatus
was about 20 ml and this quantity was selected to be
Flavour Fragr. J. 2005; 20: 555–558
 WATER-SOLUBLE CONSTITUENTS OF ROSE OIL 557

Table 1. Effect of extraction time on the recovery Table 4. The percentage composition of rose oil con-
stituents of the first oil and the second oil obtained by
Time (h) Yield (%) industrial-scale hydrodistillation
1 64.15 Constituents First oil Second oil (RI)*
2 91.11
3 98.90
α-Pinene 2.24 t 942
β -Pinene 0.39 t 983
Solvent volume, 20 ml; initial feed concentration, 1000 mg/ l.
Myrcene 0.83 t 995
o-Cresol t t 1053
Linalool 1.12 5.28 1098
Table 2. Effect of solvent volume on the recovery 2-Phenylethanol 0.60 1.73 1117
Terpinene-4-ol t 0.27 1180
Solvent volume (ml) Yield (%) α -Terpineol t 1.07 1192
Citronellol 20.59 47.35 1230
20 91.11 Neral t 0.50 1243
50 94.35 Geraniol 8.19 22.57 1260
100 94.50 Citral t 0.81 1274
Eugenol 0.36 1.54 1362
Initial feed concentration, 1000 mg/l; extraction time, 2 h. Geranyl acetate 2.10 1.65 1385
Methyl eugenol 0.60 1.88 1406
β -Caryophyllene 1.28 0.20 1423
Table 3. Effect of initial feed concentration on the α -Guaiene 0.88 0.14 1442
recovery α -Humulene 0.78 0.13 1460
Germacrene D 2.54 0.27 1482
Pentadecane 0.88 0.24 1490
Initial concentration (mg/l) Yield (%) n-Heptadecane 5.93 1.46 1682
Hexadecan-1-ol 8.29 2.14 1870
50 100 n-Nonadecane 42.40 10.78 1893
100 100
250 99.10 * Retention indices on the DB-5 column.
500 91.20 t, trace (<0.1%).
1000 91.11

Solvent volume, 20 ml; extraction time, 2 h.
applied for SDE experiments on the actual aqueous
solutions.
To study the effect of concentration variation within
the range of concentration of the actual aqueous solu-
tions, five aqueous 2-phenylethanol solutions with con-
centrations of 50, 100, 250, 500 and 1000 mg/l were
prepared. The results of the SDE experiments are given
in Table 3. It should be mentioned that in such a broad
range of concentrations, the quantitative precision of the
GC and UV analyses might be poor.9 The results gener-
ally showed that the main goal of recovery of the solute
from the aqueous 2-phenylethanol solutions was obtained
successfully in the range 90–100%.
Actual Aqueous Solutions
SDE experiments using n-butyl acetate was investigated
on the actual aqueous solutions. To have a quantitative
measure of the essential oil content of the rose water, the
second distillation water and the residual water, 250 ml
of each of the samples were extracted with 50 ml
dichloromethane by liquid–liquid extraction. The extract
was dried over anhydrous Na2SO4 and filtered. The sol-
vent was evaporated in an oven at 40 °C. The remaining
oily phase was weighed and the concentration reported
as mg oil solution. Two replications were carried out.
The average concentrations obtained for the rose water,
the second distillation water and the residual water were
about 350, 330 and 130 mg/l, respectively.
The percentage composition of the first oil and the
second oil of Iranian rose (R. damascena Mill) obtained
by hydrodistillation of rose petals and the rose water
redistillation is worth mentioning. To perform GC–MS,
1 µl of each sample was run in dichloromethane with a
dilution of 0.05% by weight. Two replications were per-
formed for each of the samples. The mean relative stand-
ard deviation per peak was calculated to be 10%.
The results are presented in Table 4. As can be seen,
the first and the second oil contained 0.60% and 1.73%
of 2-phenylethanol. The citronellol and geraniol percent-
ages as two major odorous constituents were, respect-
ively, 20.59% and 8.19% in the first oil, and 47.35% and
22.57% in the second oil. The odour quality of the first
oil and the second oil was very high. This could be due
to the low content of esters in the R. damascena Mill.
essential oil and minor changes in their odour quality by
ester hydrolysis during the distillation process.
Table 5 shows the rose oil constituents identified in
the actual aqueous solutions extracted by n-butyl acetate
using SDE, together with their percentage concentrations.
The extract was dried over anhydrous Na2SO4, filtered
and analysed by GC–MS. Two replications of the extrac-
tion and analysis procedure were performed for each of
the samples and the mean relative standard deviation
per peak was calculated to be 8%. In the present work,
the actual aqueous solutions showed recoveries of over
95% after 3 h.

Copyright © 2005 John Wiley & Sons, Ltd. Flavour Fragr. J. 2005; 20: 555–558
558 M. H. EIKANI ET AL.
Table 5. The percentage composition of rose oil con-
stituents of the actual aqueous solutions obtained by
SDE with n-butyl acetate as solvent
Constituents Rose Second distillation
water water
o-Cresol 2.43 1.99
Linalool 1.42 1.06
2-Phenylethanol 81.27 79.43
α-Terpineol 0.69 0.34
Citronellol 5.73 6.15
Geraniol 4.43 7.10
Eugenol 1.32 3.55
Geranyl acetate 0.11 t t
Methyl eugenol 0.29 0.38
n-Heptadecane 0.34 — t
Hexadecan-1-ol 0.89 — t
n-Nonadecane 1.06 — 0.4
t, trace (<0.1%). Operating conditions: solvent volume, 20 ml; feed volume,
250 ml; extraction time, 180 min.
As expected, 2-phenylethanol (81.27%, 79.43%,
75.03%) was the major constituent of the actual aqueous
solutions and it strengthens the assumption of using aque-
ous 2-phenylethanol solutions in the preliminary study.
Babu et al.11 reported concentrations of 63.12% and
2.49% of 2-phenylethanol in the rose oil of R. damascena
Mill. extracted from rose water by dichloromethane and
redistilled in a Clevenger apparatus. It is important to
say that a main source of 2-phenylethanol in the first
oil, the second oil and the actual aqueous solutions is
2-phenylethyl β -D-glucopyranoside. This compound is
accumulated in the oil at the harvest time and can be
hydrolysed easily during the hydrodistillation of petals
inside the distillation still. The results reported here are
mainly due to hydrolysis of this compound to yield the
aglycone part. There are several reports on the accumu-
lation of the glucoside in the flowers of R. damascena
Mill.12–14
The other odorous constituents of the rose water,
the second distillation water and the residual water were,
respectively, o-cresol (2.43%, 1.99%, 1.87%), linalool
(1.42%, 1.06%, 0.90%), α-terpineol (0.69%, 0.34%,
1.14%), citronellol (5.73%, 6.15%, 7.09%), geraniol
(4.43%, 7.10%, 8.51%), eugenol (1.32%, 3.55%, 4.19%),
geranyl acetate (0.11%, <0.1%, <0.1%) and methyl
eugenol (0.29%, 0.38%, 0.87%). In the rose water, higher
alkanes were present, e.g. n-heptadecane (0.34%) and n-
nonadecane (1.06%), and hexadecane-1-ol (0.89%) as
a steropten. The result showed that after redistillation
of the rose water, the major higher alkane remaining in
the residual water was n-nonadecane (0.4%). Moreover,
the second distillation water was totally free of higher
alkanes and steroptens. As can be seen, some of the rose
oil constituents still remain in the residual water. Using
efficient distillation columns and appropriate operating
conditions, it is possible to minimize the concentration of
rose oil constituents in the residual water.
Copyright © 2005 John Wiley & Sons, Ltd.
The most important drawback inherent in SDE is
the presence of artifacts in its extracts. This may be due
to oxidation and/or thermal reactions. Many constituents
are sensitive to oxidation or other undesirable reactions,
Residual
water such as ester hydrolysis. It has been reported that the
total rose alcohols as chemically stable constituents are
1.87 very high in the rose oil extracted and redistilled from
0.90
75.03
rose water compared with rose oil distilled directly from
1.14 the rose petals.11 Based on the data presented in Table 4,
7.09 the total rose alcohols of the first oil and second oil were
8.51
4.19
31.46% and 81.69%, respectively. In Table 5, the total
rose alcohols of the rose water, the distillation water
0.87 and the residual water were as high as 97.6%, 100% and
99.6%, respectively. It may be concluded that the high
concentration of stable alcohols and low ester content of
the rose oils led to no remarkable generation of artifacts
in SDE experiments.
The smell of each extract is overshadowed by the
smell of the solvent. As a result, utilization of the extracts
may be limited to determine and identify the rose oil
composition in the aqueous solutions.
Conclusion
SDE experiments on the actual aqueous solutions
obtained in the industrial preparation of rose fragrance
using n-butyl acetate as solvent gave rise to the excellent
recovery and appropriate identification of rose oil con-
stituents. The results showed that the extracts were rep-
resentative and the artifact generation was not remarkable.
Acknowledgements—The financial support of the Golkaran-Taghtiran-
Barij Essence Group (km 44 Kashan-Delijan Road, Kashan, Iran), Con-
tract No. 630-2274-10040, is gratefully acknowledged.
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