Patented June 29, 1954

2,682,549

UNITED STATES PATENT OFFICE v

PRODUCTION OF PALMITIC ACID
Hans George Kirschenbauer, Allendale, N. L, as
signor to Colgate-Palmolive Company, Jersey
City, N. J., a corporation of Delaware
No Drawing. ApplicationJanuary 31, 1951,
. 1 Serial No. 208,835

11 Claims. (0]. 260—409)

2
Palmitic acid isan excellent raw material for the Varrentrapp reaction to convert the oleic
the manufacture of soap, particularly hard acid component to the desired palmitic acid.
soaps.‘ It is also employed as an intermediate The polyunsaturated fatty acids such as linoleic
in making compounds suitable for many other and linolenic acids are hydrogenated during the
industrial uses. It is present in rather substan selective hydogenation step to an oleic acid that
tial quantities among the component acids of may be present as such or in one or more‘of its
many vegetable and animal oils including other isomeric forms, while at the same time the oleic
fatty acids of an unsaturated nature such as acid originally present in combination as glyc
oleic and linoleic. Tall oil obtained as a by erides in the starting material remains substan
product derived from the waste liquor of pine 10 tially unaffected. The selectively hydrogenated
oil pulp is a rich sourceof palmitic acid but this material, in which most of the acids that were
type of oil contains not only palmitic acid but morehighly unsaturated than oleic have been
other miscellaneous acids in solution therewith. converted to oleic acids, is then subjected to a
Processes have been used for treatment of oil heat treatment in the presence of excess alkali
such as tall oil to produce palmitic acid. One 15 such as caustic potash or caustic soda, whereupon
such process is known as the Varrentrapp reac the resultant product consists essentially of a
tion, which per se has been known to chemists relatively highv percentage of palmitic acid soap
since about 1841. This reaction involves heat resulting from the Varrentrapp reaction, which
ing the vegetable oil containing the fatty acid is conjectured as involving the migration of the
radicals (such as the oleic acid radical) which it 20 double bond of the oleic acid toward the 16,117
is designed to convert to palmitic acid in the position with subsequent cracking of the fatty
presence of excess caustic such as KOI-I or NaOI-I. acid between C16 and Cu to give the desired (he
The temperature of heating is preferably of the saturated acid component as a major reaction
order of about 320° C. when substantially an product.
hydrous conditions are employed, but may be ap 25 In order to indicate still more fully the nature
preciably lower, such as of the order of about of the present invention, the following examples
260° 0., if carried out in an autoclave in the pres of typical procedure are set forth with the un
ence of a substantial quantity of water. The derstanding that this is by way of illustration
conversion of the oleic to palmitic acid is accom only, and not by way of limiting the scope of
panied by the generation of hydrogen. the invention.
It has been found that if the fatty oil used as a Example I
starting material in a process of the above-men
tioned nature contains glyceride esters of other An example of the process, carried out under
unsaturated acids besides oleic, such as linoleic, substantially anhydrous conditions, is as fol
lows: ‘
linolenic and similar unsaturated acids, the at
tempted conversion to palmitic acid is very small A cottonseed oil containing as component acids
because in such cases the more highly unsatu the following: 20% palmitic, 30% oleic, 45%
rated'acids are broken down to saturated acids linoleic and 5% miscellaneous acids including
of shorter chain length, such as myristic from some linolenic acid, is subjected to selective hy
linoleic and lauric from linolenic acid. drogenation in order to convert the linoleic and
It is therefore an object of this invention to 40 linolenic acids present into oleic acids. By selec
provide a process which substantially increases tive hydrogenation, it is to be understood that
the yields of the relatively more desirable the conditions of hydrogenation under other
palmitic acid resulting from the treatment of wise conventional conditions are carefully con
vegetable oils in the aforesaid manner. trolled so as to terminate the hydrogenation when
Generally speaking, the process comprises two 45 substantially all the polyunsaturated acids have
steps. First, the vegetable oil starting mate been converted to the monounsaturated oleic
rial is seletcively hydrogenated under conditions acid. The selective hydrogenation may be
such that the relatively more highly unsatu carried out at atmospheric or slightly elevated
rated fatty acids such as linoleic and linolenic pressures, using known nickel hydrogenation
50 catalysts of the “selective” type such as are com
acids normally present therein are largely 01‘
substantially completely converted to oleic acid
mercially available. The temperatures of hy
drogenation are preferably of the order of, 160°
without at the same time substantially affecting
180° (3., although variations somewhat on either
the oleic acid content; and second, the product end of this range may be resorted to without sace
of the selective hydrogenation is ‘subjected to 55 ri?cing all the advantages thereof.
 2,682,549
Following the selective hydrogenation step, the action results surprisingly in high yields of pal
hydrogenation catalyst is removed and the ma mitic acid. The combination of the two steps
terial is then subjected to reaction with excess thus provides industry with a process which is
caustic alkali, such as caustic soda or caustic very e?icient and which eliminates the disadvan
potash or mixtures thereof, at elevated tempera tages in the processes already known in the art.
tures such as of the order of 300°—400° C‘. al The major disadvantage of all prior art processes
though preferably temperatures near the lower was that the ?nal product was relatively low in
end of this range, such as 320° C., are employed. palmitic acid and relatively high in the shorter
This results in a high yield of an alkali metal chain degradation products of the original fatty
soap of palmitic acid. Upon separating this soap 10 oil material. The present process on the other
from the crude reaction mixture, and acidifying hand gives high yields of palmitic and low yields
the soap, a water-insoluble fatty acid mixture is of the less desired shorter chain degradation
obtained which contains about 90 % palmitic acid. products.
Example II While speci?c examples of preferred methods
15 embodying the present invention have been set
An example of the process, carried out under forth above, it will be apparent that many changes
hydrous conditions, is as follows: and modi?cations may be made in the methods
A corn oil having an iodine value of 126.4, and of procedure without departing from the spirit
in which the major acid components are 8% of the invention. It will therefore be Iunderstood
palmitic, 4% stearic, 45% oleic, 41% linoleic and that the examples cited and the particular pro
2% miscellaneous, is subjected to selective hy portions and methods of operation set forth
drogenation at 165° 0., using a conventional se above are intended to be illustrative only, and
lective-type nickel hydrogenation catalyst in a are not intended to limit the scope of the inven-'
hydrogenating vessel of the shaking type at a tion. '
pressure slightly above 10 atmospheres. When 25 -What is claimed is: ' '
the iodine value of- the corn oil is substantially 1. In a process for the production of palmitic
lowered, namely, to a value corresponding to that acid from a fatty material containing polyun
for the substantially complete conversion of the saturated soap-forming fatty acid components,
polyunsaturated acid components to monoun the steps that comprise selectively hydrogenating
saturated acid components (i. e., to an iodine the fatty material to hydrogenate the polyun
value of 70.8), the selective hydrogenation is dis saturated fatty acid components to oleic acid
continued. The hydrogenation catalyst is re components, heating the resulting product con-L
moved by ?ltration and 100 parts of the selec taining oleic acid components produced by the
tively hydrogenated corn oil product is trans selective hydrogenation to an elevated tempera
ferred to a reaction vessel provided with external ture in the presence of excess alkali to convert
heating means and equipped with agitating said oleic acid material to palmitic acid material,
means. 50 parts of an aqueous potash lye con and recovering a palmitic acid-containing re
taining approximately 20 parts of anhydrous action product from the reaction mixture.
KOH are then added to the contents of this ves 2. In a process for the production of palmitic
sel. The mixture is agitated and the tempera- ' acid from a fatty oil material containing high
ture is gradually increased to 320° C.', to elimin molecular weight polyunsaturated soap-forming
ate the water from the reaction mixture. To the fatty acid components of which the fatty acid
molten mixture there is now‘ added with con radicals are of 18 carbon atom chain length, the
stant agitation 150 parts of powdered anhydrous steps that comprise selectively hydrogenating the
KOH. Heating is continued for 2 hours after all fatty oil material to hydrogenate the polyunsatu
of the caustic has :been added. The reaction mix rated fatty acid components to oleic acid com
ture is cooled and taken up in about 400 parts of ponents, heating the resulting selectively hydro
water. The grained-out soap, consisting princi genated product containing oleic acid components
pally of potassium palmitate is recovered by produced by the selective hydrogenation to a
skimming, leaving the bulk of the unreacted caus temperature of about 260° to 400“ C. in the pres
tic as well as the major portion of the potassium ence of excess alkali to convert said oleic acid
acetate produced during the Varrentrapp reaction material to palmitic acid material, and recover
in the lower aqueous layer. The soap thus ob ing a palmitic acid-containing reaction product
tained may be used, as such, or if desired it may from the reaction mixture.
be readily converted to palmitic acid by acidi? 3. in a process for the production of palmitic
cation followed by distillation. The potassium acid from a fatty oil material containing oleic
palmitate reaction product is obtained in high acid and more highly unsaturated soap-forming
yield. fatty acid components of the group consisting of
Other vegetable and animal oils having a sub linoleic and linolenic acids, the steps that com
stantial content of polyunsaturated acids of 18 prise selectively hydrogenating the fatty oil ma
carbon atoms or more, such as palm, soy bean, terial to hydrogenate the more highly unsat
perilla, peanut, avocado, olive, olive oil foots and urated fatty acid components to oleic acid com
red oil, are suitable as starting materials. Also, ponents without substantially further hydrogen
any higher fatty acid mixture of suitable com
position may be employed including soap stocks ating the latter, heating the resulting selectively.
hydrogenated product containing oleic acid com
and acidulated soap stocks, or any other suit 65
able higher fatty acid mixtures obtained by ponents produced by the selective hydrogenae
known processes, so long as these contain the tion in admixture with the originally present oleic
polyunsaturated acids as just mentioned. Ad acid components to an elevated temperature in
ditionally, any known technique for obtaining the presence of excess caustic alkali to convert
high selectivity during hydrogenation in convert 70 said oleic acid material to palmitic. acid material,
ing linoleic or linolenic acid to oleic acids may and recovering a palmitic acid-containing reac‘-'
be used. Additionally, any suitable alkali besides tion product from the reaction mixture. '_
caustic potash may be used such as caustic soda 4. In a process for the production‘of palmitic
or mixtures of the two. The combination of se acid from a fatty oil material comprising glyc
lective hydrogenation and the Varrentrapp re 75 eride esters of oleic, linoleic and linolenic acids,
 2,682,649
-5 6
the steps that comprise selectively hydrogenat heating the selective hydrogenated product to
ing the fatty oil material in the presence of a about 300° to 320° C‘. in the presence of excess
selective hydrogenation nickel catalyst to hydro caustic potash to convert said oleic acid material
genate the glyceride esters of linoleic and lino to potassium palmitate, and acidifying the re
lenic acids to glyceride ester of oleic acid, heat— sultant reaction product to produce palmitic acid.
ing the selectively hydrogenated product contain 9. A process for the production of palmitic acid
ing augmented oleic acid produced by the selec that comprises selectively hydrogenating a vege
tive hydrogenation to a temperature of about 260° table oil containing an oleic acid together with
to 400° C. in the presence of excess alkali to con acids more highly unsaturated than oleic acid to
vert said oleic acid material to palmitic acid ma 10 selectively hydrogenate only the more highly un
terial, and recovering a palmitic acid-containing saturated acids to an oleic acid, heating the selec- '
reaction product from the reaction mixture. tively hydrogenated product in the presence of
5. A process for the production of palmitic acid excess alkali to convert said oleic acid material to
that comprises selectively hydrogenating a vege palmitic acid soap, and acidifying the resultant
table oil containing fatty acids therein to hydro 15 reaction product to produce palmitic acid.
genate only the more highly unsaturated fatty 10. A process for the production of palmitic
acids therein to an oleic acid, heating the selec acid that comprises selectively hydrogenating a
tively hydrogenated product in the presence of vegetable oil containing an oleic acid together
excess alkali to convert oleic acid to palmitic acid with acids more highly unsaturated than oleic
soap, and acidifying the resultant reaction prod acid to selectively hydrogenate only the more
uct to produce palmitic acid. highly unsaturated acids to an oleic acid, heat
6. A process for the production of palmitic acid ing the selectively hydrogenated product in the
that comprises selectively hydrogenating a fatty presence of excess caustic potash to convert said
acid mixture containing an oleic acid together oleic acid material to potassium palmitate, and
with acids more highly unsaturated than oleic 25 acidifying the resultant reaction product to pro
acid to hydrogenate only said more highly unsat duce palmitic acid.
urated acids to an oleic acid, heating the selec 11. A process for the production of palmitic
tively hydrogenated product in the presence of acid that comprises selectively hydrogenating a
excess alkali to convert oleic acid to palmitic acid cottonseed oil containing an oleic acid together
soap, and acidifying the resultant reaction prod 30 with acids more highly unsaturated than oleic
uct to produce palmitic acid. acid, including linoleic and linolenic acids, to hy
'7. A process for the production of palmitic acid drogenate only the more highly unsaturated acids
that comprises selectively hydrogenating a cot to an oleic acid, heating the selectively hydro
tonseed oil to hydrogenate the more highly un genated product in the presence of excess caustic
saturated fatty acids therein to an oleic acid, ‘ potash to convert said oleic acid material to po
heating the selectively hydrogenated product in tassium palmitate, and acidifying the resultant
the presence of excess alkali to convert said oleic reaction product to produce palmitic acid.
acid material to palmitic acid soap, and acidify
ing the resultant reaction product to produce References Cited in the ?le of this patent
palmitic acid. 40
8. A process for the production of palmitic acid UNITED STATES PATENTS
that comprises selectively hydrogenating a cot Number Name Date
tonseed oil to hydrogenate the more highly un 1,429,114. Stiepel __________ __ Sept. 12, 1922
saturated fatty acids therein to an oleic acid, 2,457,611 Swern et al _______ __ Dec. 28, 1948