March 14, 1961

A. B. HERRICK ET Al.

2,975,170

PROCESS FOR MANUFACTURING TERPENELESS ESSENTIAL OILS

Filed May 14, 1958

4.0
A
n

9. 3-0

S
X
0)

E
a,

2.0

.2

e
"a
O:

U
.C.

I
LOO

I
2.00

I
3.00

I
4.00

Volume of Methanol Eluent Collected (liters)

SEPARATION OF TERPENES FROM OXYGENATED
COMPOUNDS OF ESSENTIAL OIL OF PETITGRAIN
(ELUTION WITH ALCOHOL AFTER ABSORPTION BY

RUBBER)

Bale-14:?ATTORNEY
W

United States

2,975,170

atent 0 " 1C@

Patented Mar. 14, 1961\

2

compounds, and recovering essential oil from which

terpenes have been'removed.

2,975,170

'

A'number of commercially important essential oils has

ESSENTIAL OILS

been listed above. The present process is applicable to!

removal of terpene hydrocarbons from those oils but

Aaron 'Brown Herrick, Cedar Grove, and James R. Trow

removing terpenes and preparing terpeneless products

PROCESS FOR MANUFACTURING TERPENELESS

is not to be restricted thereto since it ?nds general use in

bridge, Glen Rock, N.J., assignors to Colgate-Palm

olive Company, New York, N.Y., a corporation of

Delaware

Filed May 14, 1958, Ser. 'No. 735,213

7 Claims. (Cl. 260-2366)

from a wide variety of terpene-containing essential oils.

By the term terpene it is meant those hydrocarbons of
10 empirical formula C1oH16 and C15H24, the mono-terpenes
and sesquiterpenes which are considered to be the major
insoluble and unsuitable constituents of the essential oils.
As examples of these compounds may be mentioned alpha
and beta pinenes, myrcene, dipentene, ocimene, terpino

This invention relates to a process for removing terpene 15

hydrocarbons from essential oils. More particularly the

lene, d-limonene, gamma-terpinene, phellandrene, thujene,

sesquicitronellene, bisabolene, beta-caryophyllene and
cadinene.

invented process is one in which terpene hydrocarbons

are preferentially absorbed from an essential oil by a'
I particulate solid material, terpeneless essential oil being

Essential oils usually consist substantially of

mixtures of the terpenes and several more oxygenated

odoriferous compounds. In the present process the
20 terpenes are removed from the other constituents of the
obtained as the desired product.
,
essential oil due to the action of a solid absorbent,
The essential oils of commerce comprise a distinct
The solid material having a greater a?inity for the
class of organic chemical mixtures found in nature. They
terpene hydrocarbons than for the other odoriferous com
include those liquid or near liquid mixtures of odoriferous
ponents of the natural essential oils is one which perfer-.
compounds obtained by pressing, maceration, extraction,

en?eurage or distillation of dried, ?owers, berries, fruits, 25 entially absorbs the terpenes. The mechanism oflthis

absorption is apparently one in which the solid acts as a

preferential solvent for the terpene molecules. Such ~

nuts, seeds, rinds, leaves, stems, buds and roots from

plants, trees, shrubs, vines and vegetables. These oils are

action is evidenced by the pronounced swelling of some

absorbents when in contact with terpenes. For the sake
Almost all of the essential oils contain a signi?cant 30 of simplicity the term absorption will be employed in this
speci?cation to denote the act-ionof the solid employed
proportion of terpenes. In the cases of citrus oils, such
even though'adsorption may also take place. The solid
as lemon, orange, grapefruit, lime and mandarin oils,
generally pleasantly odoriferous and are of perceptible

' volatility at room temperature.

to name a few, the terpenes constitute a major propor

tion of the essential oil. Other oils, such as petitgrain

(bigarade, Paraguayan, South American), bergamot,

will be characterized as an absorbent.

pounds.

'

40 or may be of larger size but of porous, perforated or_ '

spongy structure, possessing many intercornmunicating

Terpenes are generally of lower solubility in aqueous

or alcoholic compositions thanare the oxygenated components of the essential oils. In ?avors intended for vuse

("I

components of the essential oils. , To obtain a high sur-

face/volume ratio the absorbent may be in ?ne particles '

In some perfumery, cosmetic and ?avor applications

of essential oils the terpene content performs a useful
function and is a desirable constituent of the essential oil
employed. However, there is a large number of products
and applications in which the terpenes are either harmful 45
or undesirable.

and absorbent and thereby obtain high effectiveness of'

the absorbent in separating terpenes from the oxygenated

lavender, pirnenta berry, leaf, stem and bud clove oils,

bay leaf, Sassafras and geranium, for examples, are com
para-tively low in terpene content, having a minor pro
portion, generally less than about 30% of such com

, The solid absorbent material has a high surface/ volume ,

35 ratio to promote intimate contact between essential oil' ~

voids or passageways through which essential oil solu-

tion may ?ow and on and through thewalls of which

terpenes may be absorbed. Whether the absorbent is in
particulate or other useful form it is su?iciently form-'7

retaining to leave interstices adequate for passage

aof column.
essential Where
oil when
the absorbent
the absorbent
is controllably
is packediin
com- 1
pressible the sizes of interstices can be regulated by the ~

in aqueous mixture, solution oremulsion, the terpenes 60 packing

column of
force
various
applied,
regulatable
thereby?ow
resulting
rates and
in adegrees
versatile
of
are often insu?iciently dispersible and usually rise to the
top of the product, e.g., a soft drink. or fruit juice, and
It has been found that those absorbents which are non;
form an unsightly oily layer, often of unpleasant taste.
polar exert a preferential a?inity for terpenes inessen-
The oxygenated constituents of the essential oils, which
absorbency.

'_

'

'. a ,

are much more readily- emulsi?ed or otherwise dispersed, 55 tial oils. ' Unlike the polar adsorbents, such as alumina, .

do not give rise to this problem. Additionally, these

silica
do notgel,tend
magnesia
to react
andwith
so forth,
the oils
the being
non-polar
processed
absorbents
and ._ '
essential oil constituents, such as alcohols, esters, ketones, ,.
,aldehydes, acids and others, contribute to the more de
do
constituents.
not preferentially
Among sorb
the non-polar
the oxygenated,odoriferouskv
absorbents highly; _ Q '
sirable perfume or ?avor note of the oils, and are not as
polymeric
products,such
asi-rubbers
and
non-polar'mem- - _
60
strong, harsh or bitter as the terpenes. The terpenes are
bers of the class commonly referred to as plasticsv are '
not of satisfactory stability for many Perfumery, and
suitable in the present processes. 7These materials are ,
?avor applications and natural oils containing themtend '
characterized as non-polar in this speci?cation although
to be oxidized causing the production of unwanted odors >
they are sometimes considered as being of low polarity
and ?avors. The oxidationiof ,the?terpenes may some
times result in products which very'se'riously detract from .65 when compared with the highly polar adsorbents'men'
the value and utility of the essential oils.

According to the present invention there is provided a

process for removing terpenes from essential oils which

comp'risescontacting'k an essential oil containing OdOI'lfr.

erous compounds and terpenes with a solid absorbent. 70
material of high surface/volume ratio, whichmaterial has

a greater a?inity. for'the terpenes than for the odoriferous

tioned above. Azfew examples of suitablejjpolymeri

absorbents are processed natural rubber, prefer-ably only;

slightly vulcanized, Buna S, neoprene and siliconerubbers

Various
vinyl chloride,
plastics'may
polyvinylidene
alsov be employed,
chloride, such;
apolyethv
as 7
other lower alkylene polymers, polystyrene,
such as Dacron, and so'forthL Usually it'is preferable

~ ~

2,975,170

to use the softer, more elastorneric forms of these organic

polymers, which often are more absorbent and have a

Often these solvents can be usedif polarity is increased

by mixing with lower alcohol or other suitable polar

greater a?inity for terpenes, but harder plastics may also

be usefully employed providing that they are of sut?cient

with which it is miscible also satisfactorily increases the

absorbency.

solvent.

Addition of a small amount of water to solvents

polarity thereof and makes them useful in the present

processes. Usually the water present in such adjusted
solvents will be less than 5% but more may be used if it

Usually the polymeric absorbent is granulated or other

wise reduced in size to particles having a maximum di

ameter of about 0.1 inch. Generally, the ground ab

is miscible with the solvent and does not render insoluble

the essential oil components.
To facilitate regular ?ow without channelling the par 10
Before contacting the solution of natural essential oil
ticles should be of about the same size. However, so
with the absorbent it is usually advantageous to wet the
long as the powdered solid is separable from the liquid
absorbent with polar solvent and displace air or other
media employed and su?ioient contact is obtained with
gas from the absorbing surface. The presence of gas
the essential oil being treated sizes outside the range given
bubbles within the absorbent interstices is generally un
may ?nd use. Grinding of the elastomeric polymers and 15 desirable since it both limits free ?ow of the liquid phase
the thermoplastic absorbents may be facilitated by lower
and diminishes the area of contact of absorbent with
ing the temperature of the absorbent before size reduc
solution of essential oil.
.
tion, as by chilling with Dry Ice.
The choice of solvent is to some extent dependent on
The particulate absorbent is preferably packed in a
the character of the absorbent material itself, particularly
container through which the natural essential oil can be 20 its solubility. It has been found that the comparatively
passed. In this packed container the absorbent may be
polar solvents usually do not dissolve or plasticize the
considered to act as if it were a multiplicity of plates in
elastomers or other polymeric absorbents and the various
a distilling column, each successive layer of absorbent
granules do not coalesce or adhere too strongly. On the
tending to hold back the ?ow of some of the terpene
other hand the relatively non-polar solvents, such as
content of the feed to that layer. Thus, after passing
petroleum ether, and other hydrocarbons, either aliphatic
sorbent should be no smaller than 0.001 inch in diameter.

the natural essential oil through a packed tower or column

or aromatic, tend to dissolve or fuse the usual non-polar

of polymeric non-polar absorbent the terpene has been

absorbents, which action will make the column inoperative

stripped from the valuable odoriferous oxygenated com

ponents of the oil. In many instances the terpene is so

for the present processes.

If used as a sponge having interconnecting voids the

resilient and elastomeric absorbents can be inserted and
removed as a unit and, as previously mentioned, can be

separated into 'a multiplicity of cuts which can later be

analyzed and re-blended as desired. Alternatively, a
chemical or physical test may be applied to the effluent
to determine when the ?rst terpenes are removed from

The oxygenated polar solvents aid in keeping the

strongly 'attracted by the non-polar absorbent that a 30 odoriferous essential oil components in solution and un
batch-type separation may be carried out successfully.
absorbed by the polymeric absorbent. Where some ab
This typeof process is especially applicable when the
sorption has taken place, they assist in removal of these
essential oil is comparatively low in terpene content.
desired aromatic essences, allowing the terpenes to be
When the non-polar absorbent employed possesses some
held back by the absorbent. After the solution of essen
adhesive properties particles thereof tend to be loosely
tial oil in polar solvent has been brought into contact
held together and are sometimes removable from an
with a packed column of absorbent, additional solvent
absorption column as a unit. Providing that the com
may be passed through the container to completely re
pacting of the absorbent is'not. so great as to make it
move the oxygenated components of the oil. By flow of
into an impenetrable mass this light cementing action
even more solvent the terpenes themselves can he re
is of advantage because it promotes retention of the
moved.
'
packing in position and diminishes settling of the ab
The point of demarkation in the ?ow of desired oxy
sorbent during use. The resiliency of the non-polar pack
genated compounds and terpenes may be established by
ing also causes it to resist sifting.
any suitable detection method. The effluent may be

easily adjusted in solid/void ratio by regulated compres

sion, giving various controllable ?ow rates and degrees

the column, at which point the separation of solution of

of absorption. , Such unitary absorbents can be partially

desired essences from terpene solution is made. Prefer

freed of terpenes and solvent after the deterpenation of

essential oil, by squeezing, or alternate compression and

ably, the e?luent is passed through a continuous record

ing refractometer and the desired oxygenated essences

relaxation of the sponge absorbent in a desorbing solvent.

are collected as indicated by the variations in refractive

They are easier to handle during regenerative operations

and require a minimum of effort to be re-set in the

column for use in another absorption.

The speed of flow of essentialoil through a column

index charted by this instrument.

Other instruments,

such as infrared and ultraviolet spectrometers; may be

55 adapted to the described processes. In some instances it

of absorbent may be increased and the degree of contact

with the absorbent may beirnproved by ?rst dissolving

or dispersing the oil in a suitablesolvent or other liquid

medium. The medium employed is one that is_at_ least

comparatively polar in nature and preferably is strongly
polar, comparable in polarity to methanol. Of the sol-V
vents which may be used included among the best are,

the lower aliphatic organic alcohols, e.g., methanol, etha

no], isopropanol, although those of up to 6 carbonatoms
are useful. The lower ketones, e.g.,' acetone, methyl
ethyl ketone, ethyl ketone and the lower etherrs, e.g.,
ethyl ether, also usually having no more than 6 carbon
atoms to the molecule, are useful solvents (in mixture
with the lower alcohols. The lower ketones, ethers and 70
other solvents of lower polarity than the lower aliphatic
alcohols, such as chlorinatedhydrocarbons, aromatic V
ethers, lower esters and so forth, when employedalone

may also be advantageous to make separations of the

.various oxygenated components, e.g., alcohols from es
' ters and the described techniques lend themselves readily

to such applications.
In a preferred embodiment of the invented process the
essential oil employed contains a minor proportion of

terpene hydrocarbon. Minor amounts of other hydrocar

bons may also be present but the essential oil itself prefer
ably possesses a major proportion of odoriferous oxy
genated constituents. This natural oil is ?rst dissolved
in a suf?cient amount of suitable polar solvent, selected

because of its compatibility with the absorbent and solutes

and its utility in improving the separation of terpenes
from the desired components of the essential oil. The
comparatively broad range of polarities of alcohols and

mixed solvents previously described and their gradations

of absorption characteristics assure the availability of a

solvent. particularly adapted to et?ciently separate the

do, not give satisfactory separations hof'terpenes. and the
essential oil-fractions.v After the absorbent has been se
other constituents of essential oils by the present processes. 75 lectd'it may be slulrriedwith'a'polar solvent, usually the

2,975,170

of very high purity. Where distillation techniques or

solvent extraction methods are utilized in deterpenating
essential oils it is often extremely di?icult, if not im

same as that employed to dissolve theessential oil, and

then packed in a column or alternatively it may be wet

down after packing. To allow for expansion of elas

possible, to obtain a completely terpeneless oil or toire-

tomeric absorbents due to the swelling action of absorbed '

terpenes columns are packed loosely enough. to allow

good ?ow throughout the process. The solution of oil is

cover the oxygenated essences without losing some with

> the unwanted terpenes.

In those cases where the mono- '

terpenes can be economically separated often thehigher

boiling sesquiterpenes remain with the oxygenated com

allowed to pass through the container of absorbent and '

ef?uent is collected. Additional quantities of solvent are

pounds. On the other hand, even when the invented , "
added and the ?ow through the column is maintained at
a desirable rate. A continuously registering instrument 10 process is applied to greatly different types of essential .

oils, it will be found that the oxygenated components"

thereof will be removed from the absorbent sufficiently

for measuring physical characteristics is employed on the

e?luent to ascertain when the desired separations have

ahead of the terpenes to permit a sharp separation. In '

the comparatively few cases where the terpene and a por
desorption may be speeded by addition of a less polar 15 tion of the desired essence tend to ?ow from the column
together it will be found that this condition can be easily
solvent. ' The oxygenated essential oil constituents may

been effected and the e?iuent is collected accordingly.

Afterward, if any terpenes remain on the column their

corrected by changing the solvent or increasing the eifec

tive length of column. The wide range of solvent polar
ities possible assures that solvents will be readily avail
used directly as solvent solutions. For example, when
able which will allow easy puri?cation of a large num
20
ethanol is the solvent there will often be no need to re
ber of naturalessential oils. As is indicated by the
move it completely from the terpeneless oils useful in
curve of the drawing, if it is desired sometimes oxy
perfumery.
genated components of essential oils can also be sepa
The following example is given to'illustrate the in
rated from one another by the described method and such
vented process. It is typical of the sharpness of the sep

be recovered from the polar solvent by careful dis-tilla

tion or evaporation.

In some instances they may be

arations obtained by this particular method of reverse 25 operations have been effected. Similarly, the terpene

portion of e?luent may be classi?ed into different frac

tions to segregate individual terpenes. For example, in

phase partition chromatographic puri?cation of natural

essential oils and must not be taken as limitative of the

other work with the same process it has been found pos

invention. All proportions in the example, speci?cation

and claims are by weight unless otherwise indicated.

Example
A quantity ofgum rubber (Davolbrand) was chilled
with Dry Ice and was ground to an average particle size

sible to separate d-limonene and alpha pinene from para

30

cymene.

'

The present process is most advantageously applied to

essential oils having only minor amounts of terpenes
present.

In such cases the amount of absorbent that

needs to be employed is less than where the absorbent, ~

of about 0.02 inch in diameter, as evidenced by the fact
that it passed a 20 mesh U.S. sieve and'was partlyre 35 takes up a major proportion of the oil. In the latter 1?
instance the throughput of desired odoriferous coni
tained by a 40' mesh U_.S. sieve. This powder was sub
pounds per unit weight of absorbent will be less than that "
jected to a continuous extraction with methanol at 64
when the oil contains only a minor part of terpenes and
C. for a period of about 24 hours, 450 gramsof the
the column will have to be regenerated more frequently.
extracted rubber powder, from which soluble plasticizers
The
efficiency of deterpenating essential oils of .high
40
and lower polymers had been removed, were slurried in
methanol and packed into a column of desired degree of , ' te'rpene content may be increased by first subjecting these '
oils to a conventional deterpenating process, such as dis? I
compression in a uniform absorbent bed 18 inches long

and 2% inches in diameter. 5.1 grams of oil of petit

grain (South American, like'Paraguayan). dissolved in 25 ~

tillation or solvent extraction. ' Terpeneless oil of high

quality can be obtained by this combined method because 1 .

milliliters of methanol were applied to the top of ,the 45 the- conditions of the distillation or solvent extraction"
column after which additional methanol was added, the
entire process being conducted at about room tempera

processes need not be severe since only a gross separation '

is required.
Although the invented process is best applied to-es- ,i
sential oils low in terpenes it is also distinctly advan
and the e?luent was passed through a continuously
recording differential refractometer of sensitivity of 50 tageous in removing the valuable oxygenated odor and
?avor essences from those essential oils which contain
4><10-6 refractive index units.
_
a high proportion of terpenes. In such cases only the
In the drawing there is plotted the recorded curve of
initial solvent ?ow need be collected because in that
the diiferential refractometer showing the separation of
portion will be contained all the desired oxygenated
the natural essential oil into 4 components. The two
initial higher peaks A and B indicate oxygenated mate 55 compounds. The terpenes, if offnegligible commercial
value, may be removed from the absorbent by any: suit
rials 'analyzing as linalool and linalool acetate, respec
able solvent, it being unnecessary to save these com- ;"
tively, and the smaller peaks C and D are indicative of
In such instances the only consideration is to pounds.
the comparatively non-polar compounds, terpenes and
hydrocarbons present in this oil, the latter peak corre
regenerate
taken to prevent
the absorbent
decomposition
and no
of the
special
absorbed
care vneedrbe
material '
ture. The ?ow rate was regulated at one liter per hour

,. ,,

sponding to ocimene. In this process the terpenes were 60 or to assure that it will be obtained in solution. in a

separated from the desired aromatic essences by collect

ing the ?rst 1.85 liters of eflluent apart from the subse
quent 1.15 liters. To obtain concentrated oxygenated
essences these are recovered from the solvent by a low

desirable solvent.

The non-polar absorbents used in the invented process " "

.do not strongly absorb, the desired oxygenated 'com->v

of the essential oils. Were adsorbents of the ,,.;:

temperature evaporation or distillation, preferably con 65 ponents
polar type to be employed the odoriferous components, f
ducted at or below room temperature tominimize degra
would be held by the adsorbent.
dation of the delicate essences. The resultant terpeneless
could
V
then more easily react withThe
the polar
odor adsorbent
essences,w
oil of petitgrain may be employed in the formulation of
causing some degradation thereof. For example, it has _ I
perfumes and ?avors, or in scenting the better cosmetics.
been found that the odoriferous esters, e.g., the esters of
As illustrated by the refractometer curve obtained 70 higher alcohols and lower organic acids, tend to' deconi, :-'
during the process described in the example the oxy
pose when in contact with polar adsorbents 'suchly'asijl
genated odoriferous essences of the essential oilsare re
alumina. Other reactions can result'due to the alkalinity: a

moved from, the absorbent well ahead of the terpenes.

This allows an operator to make a clean separation with

out di?iculty andto produce a terpeneless essential oil

or acidity of some polar adsorbents. Even if there is

no degradation of the perfume essence by the

at .

2,975,170
7

sorbent alone the desorptive and regenerative processes

5. A processpfor removing terpene hydrocarbons from

necessary may have an adverse eifect on the oxygenated

essential oils containing ,odoriferous oxygenated com

pounds from the group consisting of'organic alcohols,

odoriferous compounds of the essential oil. The in

vented process obviates the di?iculties of such unsatisfac

~ esters and mixtures thereof, which comprises mixing the

tory techniques.

essential oil with an organic polar solvent, adding the

The above invention has been described in conjunction

with an illustrative example and detailed descriptions of

essential oil in such a solvent to a column of particulate

non-polar highly polymeric solid absorbent material and

the invented process. It will be obvious to one skilled

?owing through the column of absorbent containing es
in the art that other variations and modi?cations of the
sential oil a suitable low molecular weight polar solvent
invention can be made and equivalents can be substituted 10 to remove the odoriferous oxygenated compounds free

therein without departing from the principles revealed

of terpenes.

or being outside the purview of the claims or the process

of the speci?cation.
What is claimed is:
1. A process for removing terpenes from essential oils
which comprises contacting an essential oil containing
odoriferous compounds and terpenes with a solid absorb
ent material of high surface/volume ratio, which mate
rial has a greater a?inity for the terpenes than for the
odoriferous compounds, and recovering essential oil
from which terpenes have been removed.
2. A process for removing terpenes from essential, oils
which comprises contacting an essential oil containing
odoriferous compounds and terpenes with a particulate
solid absorbent material which has a greater a?inity for
the terpenes than for the odoriferous compounds and
recovering essential oil from which the terpenes have been
removed.
3. A process for removing terpenes from essential oils
which comprises contacting an essential oil containing
odoriferous oxygenated compounds and terpenes with a
comparatively non-polar particulate solid absorbent ma
terial which has a greater af?nity for the terpenes than
for the oxygenated compounds and contacting the mix

6. A process for removing undesirable terpene hydro

carbons from essential oils containing oxygenated odor

iferous compounds from the group consisting of higher

15 organic alcohols, esters and mixtures thereof which com

prises dissolving the essential oil in a suitable volatile

organic alcohol of 1-3 carbon atoms, adding the solution
of essential oil to a packed column of granular non~

polar highly polymeric solid absorbent material, ?ow

20 ing through the column of absorbent containing essential

oil a suitable volatile organic alcohol of 1-3 carbon

atoms to remove the terpene-free oxygenated odoriferous
compounds from the absorbent and then making a low
temperature separation of solvent from the odoriferous
25

terpene-free alcohol.
7. A process according to claim 5 in which the essen

tial oil contains a minor proportion of terpene hydro

carbons, the absorbent is a granulated rubber and meth
anol is the solvent for the essential oil.
30

ture of absorbent and essential oil with a comparatively 35

References Cited in the ?le of this patent

UNITED STATES PATENTS
1,786,630
2,712,008

Reid ________________ __ Dec. 30, 1930

Kirchner et a1 _________ __ June 28, 1955

488,359
977,373
619,545

France _______________ __ May 7, 1917

France ______________ __ Dec. 17, 1948
France ______________ __ July 30, 1955

polar solvent to remove the terpeneless odoriferous oxy

FOREIGN PATENTS

genated compounds.

4. A process for removing terpenes from essential oils

containing odoriferous oxygenated compounds which

comprises contacting a mass of particulate non-polar 40
polymeric solid absorbent material with a solution of

OTHER REFERENCES
terpene-containing essential oil in a comparatively polar
Plachenov
et
al.: Chem. Abs., vol. 48, p. 3638 (1954),
solvent and subsequently contacting the absorbent with
abstracting
Zuhr.
Priklad Khim., vol. 26, pp. 482-494
polar solvent to remove the odoriferous oxygenated
(1953).
compounds free of terpenes.
45

1.: