Patented May 16, 1939 2,158,670

UNETED STATES PATENT OFFICE

2,158,670
PROCESS FOR '1 RECOVERY 0F
ESSENTI OILS
Charles Douglas Barnes, Long Beach, and Wil
liam A. S. Wright, Los Angeles, Calif., assignors
to Union Oil Company oi California, Los An
geles, can, a corporation of California
No Drawing. Application February 20, 1937,
Serial No. 126,886
5 Claims. (Cl. 87-28)
This invention relates to a process for the re the essential oil at temperatures substantially
covery of essential oils, such as orange oil, lemon above 32 F. inorder to avoid freezing of oil cells
oil, lime oil or other oils from citrus fruit. which would reduce the yield of oil. The solvent
It is common practice at present to recover. and citrus pulp or slurry is then thoroughly agi
orange oil from orange peel by cold pressing the tated for a period of time su?iciently long to 11
orange rind and pulp to separatea portion of completely extract the essential oil. ' The mixture
the oil contained therein and recover the re is then permitted to settle, the heavier pulp pres
mainder of the oil present in the pressed residue cipitating to the bottom of the container. After
by steam distillation. Theoil recovered from removal of a major portion of the water and pulp
10 the pulp by steam distillation is considered in by any suitable means, the butane or other hydro
ferior to the cold pressed oil because of the in carbon solution is then separated from the re
clusion of undesirable constituents due to their mainder of the insoluble material by ordinary
volatility with the steam. Consequently, the oil decantation or by ?ltration or by a combination
which is recovered by steam distillation is of of decantation and ?ltration, or, if desired, the
inferior quality to the cold pressed oil and, there butane solution may also be separated from the 15
fore has a somewhat lower commercial value. butane insoluble materials by centrifuging the
The yield of cold pressed oil from orange peel, mass. The butane phase recovered by the fore
however, is rather low, in fact on the basis of going extraction contains the major portion of
the whole fruit, from 0.1 to 0.3% is about the the essential oil in solution as well as some unde
sirable resins. In order to remove these unde- _
20 highest yield of oil which can be recovered by
cold pressing. Therefore, the remainder of the sirable resins from the butane solution of essen
oil which may amount to 0.45 to 0.7% is recov: tial oil, this solution is cooled su?'lciently to cause
ered by steam distilling the cold pressed rind or the resins present to precipitate. The chilled
Pulp- a
butane solution is ?ltered, centrifuged or settled
25 By our process we have discovered a method by forthe separation of the precipitated resinous
which we are able to recover a major portion of I material, after which the substantially resin-free
the oil present in the citrus'pulp orpeel and at , butane solution of essential oil is distilled for the
the same time retain in the recovered oil the de-__ removal of the butane from the .oil. By the fore
sirable quality characteristics of cold pressed oil, going'proce'ss 'weare'able to recover as high as
30 The oil recovered by our process is completely "I approximately 90% of the essential-oil present
soluble in 95% ethyl alcohol, which permits its . inthe citrus fruit; ' r - - ' " '

incorporation in alcoholic ?avoring extracts " It is, thereforaan' object of the present inven- '
without the necessity of ?ltration for the prepa 'tion to recover citrus oil from citrus fruit or
ration of clear, solutions. While it ispossible products by means 'of a solvent and to purify the
35 to treat unpulped orange peel by our process it is recovered oil bynseparating'i'wax'or resinous con 35
, preferable that the citrus peel be pulped or , stituentstherefrom. ' I > _ I

ground by any suitable method into a line slurry " It is a further object of the present invention
in the presence or absence of water. vto remove wax or resinous material from citrus
or ground citrus peel is then extracted with a.v ,oilby dissolving'thecitrus'oil in an appropriate
'Ihis'slurry
:40 suitable solvent which has a high solvent power" solvent such as liquid butane, cooling the-solvent
for the oil and a minimum solvent power for the _ solutio'n'of oil to a temperature su?icie'ntly low
undesirable constituents of the peel'or'puln; "The I to precipitate the w'axlor resinous material, re
solvent solution of the citrus oil is then separated '_ moving the precipitated resinous or waxy mate
from the pulp or slurry and subjectedto distilla-jj I rial by centrifuging, settling or ?ltering and then
tion for the removal of solvent'from the oil. ~_ recovering the dewaxed or deresinated oil from
More speci?cally, the process consists in pulp-I the'solution byv removing the solventpresent by
ing the citrus peel orgrinding in the presence of distillation. _ - ~ 1 r a .

water to form a slurry containing the highest ' It is a further objectv of the presentinvention
possiblecontent of essential oil, which upon conq- ' to recover citrusfoil from citrus fruit by prepar
ce'ntration by'rejecting the juice and oil free por ing a pulp or slurry of citrus fruit andcontact
tions of the fruit may actually reach 1 to 5% of ing vthe pulp with an appropriate solvent," such '
essential oil. This pulp or slurry is- then con-g ' as liquid normal butane,_to dissolve the on, sepa-_
tacted with an appropriate solvent, such as liquid rating the normal butane solutionv or citrus oil
normal butane at a temperature of about70 F, from the pulp, chilling the'solution to precipitate
' to 80 F. We have found it preferable to extract " the resinous material present in the solution,
 2 2,168,670
separating the precipitated resinous material to permit good fractional distillation between the 1

I from the butane solution of oil and by recover oil and solvent. Furthermore the solvents should
ing the oil from the solution by removing the be free from malodorous or maltasting constitu
butane from the distillation. ents which impart to the oil a bad taste or odor.
The following is a speci?c example of the' It is also preferable that the solvent employed
method for carrying out our invention: should not be water soluble to any appreciable
Orange pulp and rind is ground or macerated extent. In some instances the solvent may be
in the presence of water to form a slurry contain treated for removal of constituents present which
ing approximately 2_1/2% orange oil. This slurry unfavorably influence the quality of the oil. For
.0 is then mixed with liquid normal butane at a example, low boiling hydrocarbon solvents may
temperature of about 70 to 80 F. in the propora be pretreated with caustlcsoda for the removal
tion of 2.75 parts by volume of liquid normal bu of hydrogen sulphide or mercaptans both of
tane to one part by volume of the orange slurry. which impart a highly undesirable odor to citrus
The mixture of orange slurry and normal butane oil. Furthermore, we have described a process in
15 is then agitated at a temperature of 70 to 80 F. which 2.75 volumes of solvent and one volume of
for a period of about thirty minutes, after which citrus are mixed together for the recovery of the
the mass is permitted to settle for a period up to oil, but we do not wish to limit ourselves to these
about twelve hours. A large portion of the water proportions since in many cases itrmay be desir
and solid pulp is then withdrawn from the ex able to alter this ratio. In some instances it may
traction vessel. The butane solution of the require three or four volumes of the liquid butane
orange oil remaining in the extraction vessel is to one volume of the citrus pulp or slurry and in
then cooled to a temperature of about 32 F. for other instances it may be desirable to use equal
the precipitation of the resinous materials in the or even smaller volumes of solvent than of pulp
solution. The chilled solution is then filtered ,or slurry. '
25 through paper or other suitable medium and We have described a process in which we have ,
thereby freed from the precipitated resinous ma employed an extraction temperature of about
~terial, after which it is heated to about 125 F. that of atmospheric, namely 70 F. to 80 F.
for the removal of the major portion of the nor However, we do not wish to limit ourselves to this
mal butane and ?nally to a maximum of 212 F. temperature since in some instances it may be
30 for not over ?fteen minutes to remove any heavy, desirable to employ temperatures which are
ends of the hydrocarbon extractant from the greatly in excess of atmospheric, for example,
orange oil. The oil recovered by the foregoing the orange slurry may be charged into a pressure
method is equal in quality to cold pressed orange bomb together with the liquid normal butane and
oil and a yield of 86% of the total orange oil this mixture may be heated to a temperature of '
35 present in the slurry is obtained. about 150 F. to 200 F. together with agitation 35
The chilling step for the separation of the in order to insure complete solution of the oil in
resinous material is subject to some variation the solvent. After complete solution, the mixture,
since certain of the oils extracted contain more may then be cooled and after removal of the
of the resinous-or waxy material than others. water and 'the resinous materials present in the
40 In general a temperature of about 32 F. is satis solution by cooling and separating, as described
factory to remove sufficient of these resinous ma above, the orange oil may then be recovered by
terials, however, .we do not wish to limit ourselves ' simply removing the normal butane present.
to this speci?c temperature since we have satis Another modi?cation of the process consists
factorily employed temperatures as low as 0 F. in leaching the slurry at a temperature at which
for precipitation of the resinous or waxy material the resinous material will not go into solution.
from the solvent solution of oil. In carrying out This temperature will be about 32 F. to 35 F.
the resin separating step it is important to note At this temperature the slurry is a solid mass
that it is desirable to leave from v2 to 5% of the due to the crystallization of the water present.
resin or wax in the oil since oil containing lower. When operating according to this cold leaching
50 concentrations than these tend to resemble method the chilled slurry at a temperature of .
arti?cial oil and has a somewhat poorer ?avor. 32 F. to 35 F. is intimately mixed with chilled
We have described liquid normal butane as be normal butane at about the same temperature.
ing the preferred solvent since it has a high After thorough agitation the chilled mixture con-
solvent power for the essential oils and amini taining the dissolved orange oil is then separated.
mum solvent power for the undesirable con from the insoluble pulp and after filtration to re-
stituents, its vapor pressure is suf?ciently low at move any solid material which may be present
70 to 80 F. that it does not necessitate the use the solvent is removed from the oil by distilla
of especiallyheavy equipment, it is available com- - tion. , . > .

mercially in a sufficiently high state of purity to It is to be understood that these disclosures are
60 prevent contamination of the essential oil, and
presented as illustrative of the generic invention CO
the boiling point is sufficiently low to permit com and not as limiting, inasmuch as other modi?ca
plete removal from the essential oil without heat tions will be obvious to those skilled in the art.
ing to temperatures high enough to impair the ' We claim: I
quality of the oil. However, we do not wish to 1. A process for the purification of citrus oil
limit ourselves to this solvent since many other containing resinous impurities whichcomprises
solvents may be employed, as for example, iso grinding citrus peel in the presence of water and
butane, liquid ethane, liquid propane, the liquid thereby forming a slurry, commingling said slurry
pentanes, a suitable fraction from casinghead or with a lique?ed normally gaseous hydrocarbon
primary gasoline and mixtures thereof. Further solvent under su?'icient pressure to maintain said ~
more, we may also employ other-solvents, as for , solvent in a liquid state, settling the ,mixture of '
example, ketones such as acetone and methyl " slurry and solvent,under pressure and thereby
acetone, and ethers such as ethyl and isopropyl forming a solvent layer containingthe citrus oil
ether or mixtures of those solvents. Preferably and a slurry layer, separating said layers, cool
the solvents which we employ should have a lower ing the solvent layer to precipitate resinous ma
75 boiling point than that of the citrus oil in order terial, removing the precipitated resinous mate
 3
2,158,670
lique?ed normally gaseous hydrocarbon solvent
rial from the solvent layer and removing the under su?icient pressure to maintain said solvent
solvent from the de-resinated oil. i in a liquid state, settling the mixture under pres
2. A process according to claim 1 in which the sure and thereby forming a liquidsolvent layer
solvent is liquid butane. , containing the citrus oil and a slurry layer, sepa
3. A process according to claim 1 in which the rating said layers, and removing the solvent from
solvent layer is cooled to a temperature between
the layer containing the citrus oil.
10 F. and 32 F. for precipitation of the resinous 5. A process according to claim 4 in which the
material. _ leaching temperature is between 0 F. and
4. A process for the puri?cation of citrus oil 10
containing resinous impurities which comprises 32 F. '
10 CHARLES DOUGLAS BARNES.
grinding citrus peel with water and thereby form WILLIAM A. S. WRIGHT.
ing a slurry, commingling said slurry with cooled