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com lete reconstruction of the organoleptic effect An attractive alternative is provided by liquid-liquid
AfnStirdproductswas dwaysconsideredthe ideal extraction, It can be defined as a process where the con-
objective in the creation of aroma compositions. Tbe stituents of the solution are separated due to their un-
successful naturally scented goods must satis~ consum- equal distributions (different partitiOn coefficients)
ers for whom fresh fruits, vegetables, herbs, and flowers between two immiscible liquids.
are always available as unquestionable points of refer- The rate of extraction is proportional to the interracial
ence for the taste and smell of the “real thing.” contact area and the deviation of component concentra-
The growing trend of “back to nature,” combined with tions in the liquid phases from the equilibrium position.
sophistication of public taste, challenges our industry to Phase sepwation at the end of the process results in the
offer highest quality, yet reasonably priced natural ingre- desirable separation of the components of the mixture,
dients which will provide the full spectrum of aroma nu- Although liquid-liquid extraction is a relatively simple
ances. process, its industrkd application is considerably more
Distillation, being a major recove~ and separation complex than would appear at the first glance. In all in-
technique in the production of the aroma constituents, dustrially used liquid-liquid contractors, one phase is dis-
cannot alone fuklll this objective due to the following persed in the other in the form of droplets, Spherically
general drawbacks: shaped, these droplets expose a minimum surface area
1. Commonly practiced distillation techniques are for a given volume. An attempt to increase the interracial
applicable to a rather limited group of chemicals area by excessive agitation, among other problems, leads
having boiling points within a relatively narrow range. to the formation of stable emulsions which obstruct
Distillation of natural aroma material results in phase separation.
unavoidable losses of both very light and heavy A more serious problem associated with mechanical
fractions, whose organoleptic value is often dispersion of liquid phases in counter-cument extraction
irreplaceable. devices is the phenomenon known as axial mixing. It re-
2. The distillation process necessarily causes thermal sults in the broad variation of material residence times in
degradation of labile important aroma bearing the two phases, which substantially reduces the rate of
ingredients which, even when occurring on a small extraction and has a very negative effect on equipment
scale, deeply upsets the delicate sensory balances of performance.1
the recovered material A number of technological solutions effetilvely deal-
3. Distillation is an impractical means of separation of ing with the above mentioned difllculties were proposed
any closely boiling substances, regardless of and applied, resulting in sophisticated and expensive de-
differences in their chemical nature. vices.z In most cases, their applications are justifiable in
4. Distillation is inappropriate, even when the boifing industries where the numbers of separations are small,
points are markedly different if the recovery of trace but large volumes are used, as in metallurgy, or applica-
amounts from a hulk mixture is desired. tions where money is really not the object, like the nu-
5. Distillation is inefficient in recovering aroma clear industry.
materials from dilute aqueous media-the perpetual In the flavor and fragrance industry, where natural
challenge when working with natural sources of flavor products are extremely diversified, while the volumes
and fragrance ingredients. are relatively small, the wide use of conventional ef&
~zL— — —-—-—-.
.. .. ..
1
I
B
l’,
/ I ‘,
At I ‘%..
“,
vfa,ur=(va+KdvchJ
(1– *) (III)
solvent used in the described method are not different surface tension coefficient less than 23 but not wetted by
from those used for usual solvent extraction. The solvent water or water solutions.
should be water-insoluble, preferably low boiling, and The preparation of the solid support in blocks is of spe-
evaporate completely without leaving any odorous resi- cial importance for large diameter columns. The fOllOw-
due. The utilization of liquified gases, such as Freons or ing advantages, compared to powder packed columns
C02 is particularly attractive. are:
The important criteria is a reasonable value of distribu- 1. Uniformity of support particle size distribution
tion coefficients of the aroma constituents into the aque- which substantially increases column efficiency.
ous-solvent system. As can be seen from equation (III), 2. Elimination of gradual thickening of the solid
the Kd value is the major factor which determines the support which results in decreasing the organic
V,,,., value. (In practice, it is convenient to use solvents solvent volume held by the column and increasing tbe
in which Kd value of the most polar component is about column resistance to aqueous phase flow.
250-400.) 3. Good contact between the support and the column
Porous suppoti-Selecting the material and the body and elimination of channel formation inside the
method of preparation of the column packing are impor- solid support,
tant points in tbe development of the presented method. In dynamic conditions, e.g., when the aqueous phase
Porous polytetrafluorethylene (PTFE) prepared in passes through the column at a rate of ca. 15ml/cmz/ rein,
blocks7 was found to be an ideal material. This material is the volume of the solvent, held by the solid support, is
outstandhg in its chemical inertness, so any changes in about 20q0 of the column volume.
the oil chemical composition are excluded. ETFE does Column efficiency-The column efficiency is mea-
not swell in any known solvent, and thus provides the sured by the number of theoretical plates (N), or by the
possibility to work with any chosen solvent system. height equal to the theoretical plate (HETP).
The ability to hold the organic phase is based on the HETP is a complicated function of the moving phase
fact that PTFE is well wetted by organic solvents with a velocity, the support uniformity, the selected stationa~
phase, and the quantity of stationary phase on the sup-
port? For a column of about 300 mm diameter at m
aqueous phase flow rate of 15 ml/cmVmin, HETP values
of 20-50 mm were achieved. This rather high efficiency
for an industrial-scale liquid-liquid extractor is due
mainly to the column design.
From equation (III), it can be seen that the V,a, value
depends not on N but @. Thus, for the recovey of the
aroma constituents from aqueous dispersion, it is not
reasonable to work with two efficient columns, and for
practical purposes N .20-25 (column length 600-800
mm) is satisfactory enough.
Application
The poroplast extraction technique was found to be ef-
fective in the recovery of the aroma materials from a va-
riety of water dispersions, such as fermentation broth,
aqueOus reactiOn prOducts, etc. Due tO the efficiency of
the extraction process, the aroma constituents can be
quantitatively and economically recovered even from di-
lute sources ( 100-500ppm). The amounts of tbe solvents
used in the processing are small, rarely exceeding 0.1-1 %
relti]ve to the amount of treated aqueous phase.
The poroplast extraction technique is used successfully
in the recovery of the essential oil constituents from the
aqueOus ~ndensate fO~ed during oil distillation. The
detailed chemical study of the water soluble fractions
produced during essential oil preparation will be re-
ported in a separate publication.
The technique described above will be illustrated by
the following examples:
Natural benza2dehyde-In recent years, the source
and methods of preparation of natural benzaldehyde
Alcohols
oil phsae
of spple eseence
Aldehydes
benzaldehyde 0,07
decanal 0.01
n-hexanal 8.45
trans-2-hexenal 19.38
Acids
hexanoic 0.06
octanoic 0.18
Miscellaneous
methyl chavicol 0.01
methyl eugenol 0.03
,0”.. ”,,.,,.0.
ad just.,., “ml,
I .,....8
.Icohol
4 3-nay
1
I IILJ
“.,..
F-’-””--
ph.s. 11”, I -%--------
I ,md.ct
I ?=+-&+.- recover,
Y
I
Figure 3. System for the preparation of hydrocarbon-free essential oils
sesquite~enes, have been regarded as Public Enemy essential oils, especially citrus oils, in aqueous alcohol,
No. 1 by perfumers for many years now and that re- usually results in the formation of stable emulsions. A
search has been directed for several decades to finding period of several days is required to accomplish
ways and means of eliminating them as far as possible,”ls separation ,fi
Tbe utilization of aqueous alcohol to produce the 3. A necessity of multi-stage contact. Ruys shows that
deterpenated citrus oils has been known for a ve~ long five sequential equilibrations of lemon oil and 70%
time, In 1899, Mitchell described some methods for the alcohol are reauired to recover 95’% of citral,zl
determination of lemon oil in the flavoring alcohol ex- Obviously, mor~ stages are necessa~ to recover less
tracts.m It is obvious that the alcohol extracts of citms polar ingredients of lemon oil, such as esters.
oils were used before that, They are widely used by the 4. Recooey of the oxygenated constituents from the
indusby to this date. alcohol solution is dijjktdt. The problems associated
The soluhility of hydrocarbons, especially sesquiter- with this rather important and probably most delicate
penes, in aqueous alcohol is low, while oxygenated com- and expensive step in the preparation of deterpenated
ponents of essential oils are completely soluble. oils have been discussed in detail elsewhere.zz
Decrease of the alcohol concentration leads to a sharp The important contribution to the process which takes
decrease in the volubility of hydrocwbons, Tbe alcohol place when the essential oil comes in contact with the
extract, therefore, corresponds to deterpenated essential aqueOus ~cOhOl, is nOt a questiOn Of sOlubihty, but re-
oil, lates to the partitioning of the oxygenated components
Many articles have been written on tbe alcohol between the aqueous alcohol and the hydrocarbons of
deterpenation of essential oils, While referring the the essential oil. The process of the alcohol deterpena-
reader to the most important original publications on the tion, therefore, is just a particular case of liquid-liquid
~1JbjeCt,18J9.!21 .24 I ~o~d like to point out the critical diffi- extraction, and can be easily accomplished using
culties associated with this method: poroplast extraction technique,
1. Long-equilibration tirns. In a recent publication, on A schematic presentation of the system used for the
the alcohol deterpenation of citrus oils, a 24-hour preparation of hydrocarbon-free essential oils can be
a@tatiOn was cOnducted tOachieve equilibration.fi seen in Figure 3. It mnsists of the oil extraction section
2. The formation of stable emulsions leads to a A, alcohol recovery section B, and product recove~ sec-
long-separation time. Mechanical dispersion of tion C.
The poroplast extraction technique provides a conve- 8. J Van Deemter, F Zuiderweg, A Klinkenberg, Chem Eng Sd 5,
271 (1858)
nient and cost-effective way to prepare natural aroma in-
8. G Fenaroli, Fenaroli’s Hand Book of Flavor lngrtiients, 2nd
gredients, which takes ‘advantage of liquid-liquid Edtion, CRC Press Inc, Cleveland, OH (USA) (1 975)
extraction in a very practical and convenient way. 10. E Guenther, The Essential Oils, D Van Nostrand Company Inc,
New York (1949)
11. S M Lawrence, Peti& F/avorist, 10 (5), 45-48 (1985)
Aclmowledgemenk The author is gratefid to Fkmqnth 12. K Von Marilaun, Life of Plants, Sook Publ Co “Education,” St
Petersburg (1896)
Inc., and particularly to Mr. ]. N. Friedman, the
13. A Y Leung, Encyc/cp6dia of Common Natural Ingredients Used
president, and Dr. R.]. Coleman, senior vice president, in Foml, Drugs and Cosmetics, John Wiley & Sons, New York
fortheircare and suppmt of this work. (1960)
14. S Arctander, Peiiumes and Flavor Materials of Natural Origin,
References Elizabeth, NJ (USA) (1960)
Address correspondenceto Alexander Fleisher, FlorasynthInc., 15. Anon, The Merck Index, Tenth Edition, Merck & Co, Inc,
300 North Street, Teterboro, NJ 07608. Rahway, NJ (USA) (19S3)
16. J A Ouke, Hand600k of Medicinal Her6s, CRC Press, Soca
1. PJSails, CHanson and MA Hughes, Chem Eog83(2), ffi-100 Raton, FL (USA) (1985)
(1 976) 17. L Fieser and M Fieser, Advanced Organic Chemist~, Reinhold
2. J L Humphrey, J A Rocha and J R Fair, Chem EW 91 (19), Publ Corp, New York (1 984)
76-95 (1984) 18. WJD Van Oijck and A H Ruys, Perfum Essent Oil Ret, 22,
3. S Kozhin, A Fleisher, A Smirnov, USSR Patent 321860 (Feb 2, 91-84 (1837)
1972); Otkrylija, Isobretenija 6,212-213 (1972). i 9. A H Ruys, Peffum Es’sent0/ Ret, 48,584-588 (1857)
4. S Perrv.
.>. R Amos and P Srewer, PracticalLiouid 20. AS Mitchell, JAm Chem Sot, 21,1132 (1699)
Chromatogqohy, Plenum Press, New York-London (1 972)’ 21. W R Mtlejohn, Flavors, 3 (4), 7-18(1940)
5. D Destv. Vamw Phase ChromatoaraDhv. . . Academic Press. 22. Y R Naves, h4amd Chem, 18 (4), 173-176 (1947)
New Yo’k (1957) 23. D F Othemer, M B Jacobs and N Wishnefsky, U.S. Patent
6. S Kozhin, L Moskvin, A Fleisher and J Epifanova, Z Obsh Khim, 2,631,145 (applied 4/1 0/1 951 )
43,428-434 (1973) 24. J M Kiley and R T Kiley, U.S. Patent 3,809,757 (from 5f7/1974)
7. B Preobrazhensky, L Moskvin, A Kalamin, O Lilova and B 25. J Oywusu-Yaw, R F Mathews and P F West, J FocalSci, !
Usikov, Radiochimija, 10 (3), 377-379(1968) 51,1180-1182 (19S6) !J?