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Патент USA US2025805

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Patented Dec. 31, 1935
Melvin De Groote, St. Louis, Bernhard Keiser,
Webster Groves, and Arthur F. WirteL'Bich
mond Heights, Mo., assignors to Tretolite Com
pany, Webster Groves, Mo., a corporation of
No Drawing. Application December 31, 1934,
Serial No. 760,033
6 Claims. (Cl. 196-4)
broadly speaking, polyricinoleic acids are more‘
This invention relates to the treatment of e?ective demulsifying reagents than ricinoleic
emulsions of mineral oil and water, such as pe
acid. However, there are certain emulsions on
troleum emulsions, for the purpose of separating which
the unpolymerized keto fatty acid bodies,
the oil from the water.
which will be referred to more simply as “keto
Petroleum emulsions are of the water-in-oil fatty acid bodies”, are more effective than the
type, and comprise ?ne droplets of naturally-oc
polymerized keto fatty acid bodies. The present
curring waters or brines, dispersed in a more or
less permanent state throughout the oil which
constitutes the continuous phase of the emulsion.
10 They are obtained from producing wells and
from the bottom of oil storage tanks, and are
commonly referred to as “cut oil”, “roily oil”,
“emulsi?ed oil” and “bottom settlings".
The object of our invention is to provide a
15 novel and inexpensive process for separating
emulsions of the character referred to into their
component parts of oil and water or brine.
Brie?y described, our process consists in sub
jecting a petroleum emulsion of the water-in-oil'
20 type to the action of a treating agent or de
mulsifying agent of the kind hereinafter de
scribed, thereby causing the emulsion to break
down and separate into its component parts
of oil and water or brine, when the emulsion is
permitted to remain ina quiescent state after
treatment, or is subjected to other equivalent
separatory procedures.
The treating agent used in our process con
sists of an unpolymerized keto fatty body or
30 bodies. It is well known that fatty acids or
fatty bodies can be subjected to chemical treat
ment so as to yield keto fatty acids, that is, fatty
acids in which a ketonic group (a carbonyl group)
is present. One example is the conversion of
35 ricinoleic acid into ketohydroxystearic acid. (See
Lewkowitsch “Chemical Technology of Oils, Fats
and Waxes”, Gthedition, volume 1, page 242.)
In a general way, the manufacture of such ketonic
acids is dependent upon the treatment of an un
40 saturated fatty bcdy or fatty acid, such as ricin
oleic acid, oleic acid, or the like, with a halogen,
such as bromine, so as to form a halogen addi
tion product, for example, ricinoleic acid di
bromide, which. is then converted into ricin
Ricinstearolic acid, on treatment
45 stearolic acid.
process is concerned with the use of keto fatty,
acid bodies in an unpolymerized state, in those
instances where they are the most .effective de 10
mulsifying agents.
As previously indicated, the method described
in the Lewkowitsch reference forproducing keto
hydroxystearic acid bodies may be applied to va
rious unsaturated acids and the like. Such proc 15
ess can be applied to the hydroxylated unsaturat
ed materials obtained in themanner described
in co-pending application for patent of De Groote
and Keiser, Serial No. 760,025, ?led December 31,
1934. Said aforementioned application for patent. 20
discloses the oxidation of highly unsaturated fatty -
bodies having a relatively high iodine number, ‘ '
above 120, for example, so as to produce un- '
saturated, hydroxylated fatty bodies.
In our co-pending application for patent Serial
No. 760,031, ?led December 31, 1934, we have de
scribed a new composition of matter consisting of
the poly keto fatty acid bodies. These poly keto
fattyacid bodies may beobtained by the esteri?ca
tion or polymerization or condensation of a keto 30'
fatty acid with another fatty acid molecule, which.
need not contain a ketone group. In said afore
mentioned application for patent describing
these new compositions of matter, there is also
disclosed a method for producing poly keto fatty 35
acids directly without ?rst forming the‘ unpoly
merized keto fatty acids. It would appear'at least
theoretically possible to decompose‘ such poly keto
fatty acid bodies and perhaps separate from the
resultant mixture unpolymerized keto fatty acid 40
bodies. Thus far, however, we-have been unable
to accomplish this hydrolysis and separation, '
but this is immaterial ‘because the keto fatty
acids may be produced in the‘ manner previously '
We are fully aware that migration may take
with sulfuric acid, yields ketohydroxystearic acid. place
in a fatty molecule. For instance, that the
In our co-pending application for patent Serial ‘ formation of stearolactone from hydroxystearic' '
No. 760,031, ?led December 31, 1934, we have dis
acid appears to depend on the migration of the
‘closed the use of poly keto fatty acids or the salts alcoholiform hydroxyL- We are also aware that.
in the case of the-common non-fatty ketonic acid,
In a general manner we have found that fre
aceto-acetic acid, that certain reactions are‘
quently the poly keto fatty acid bodies are more known to take place which suggest that aceto
effective for breaking the majority of emulsions ~ acetic acid may, a far as these reactions are con-‘
than the unpolymerized keto fatty acid bodies.
55 This is true to the same general extent that,
cemed, react more as an aldehyde or as an alde
hyde acid than as a ketonic acid. Such wander
ing of a hydrogen atom and change in position
of a double bond, is referred to as keto-enolic
tautomerism (Bernthsen “Textbook of Organic
Chemistry”, 2nd edition, 1931, page 231). We
believe that this or a comparable change may
take place in these ketonic fatty acids or bodies
previously described. Possibly in regard to some
reactions employed in identi?cation, these keto
10 acids or salts or esters thereof act more as if
they were aldehydic acids or esters or salts there
of. In other words, if these ketonic acid bodies
are to be used in a mixture where aldehydic acids
would be incompatible, it is also likely that these
15 ketonic acids or their salts or their esters may be
incompatible, for the reason that they really
may be aldehydic acid bodies. It is to be noted
that the reagents of the kind employed for de
termining the presence of the carbonyl group in
-20 ketones also usually detect the presence of the
carbonyl group in aldehydes. It is to be under
stood that in the claims where the products are
characterized by the presence of ketonic radical,
that such acids might ultimately prove to be alde
hydic acids, or at least convertible under certain
conditions of use, or else under certain conditions
of identi?cation, possibly they become converted
into aldehydic acids, and it is not intended that
the word “ketonic” or “keto” be interpreted as
30 excluding the meaning of “aldehydic” in the sense
previously described or discussed, i. e., that both
have the carbonyl (CO) radical present, and their
ultimate composition in carbon atoms, hydrogen
atoms, and oxygen atoms, is identical.
It is understood, of course, that these keto fatty
acids or their esters may be converted into salts
or into esters in the manner generally employed
for the manufacture of salts and esters. How
ever, it should be borne in mind that saponi?ca
40 tion of the kind which would decompose or de
stroy the carbonyl radical cannot be employed.
may be employed, such as the methyl ester, ethyl
ester, propyl ester, butyl ester, amyl ester, hexyl
ester, cetyl ester, etc. Aromatic or cyclic esters
may be employed. What has been said in regard
to the use of conventional demulsifying agents 5
applies also to the materials employed as the de
mulsifying agent of our process, with the limita
tion that such materials are generally monobaslc,
although it is probable that dibasic acids, such as ,
sulfoketostearic acid might be prepared, and w
would prove to be a suitable demulsifying agent.
Conventional demulsifying agents’ employed in
the treatment of oil ?eld emulsions are used as
such, or after dilution with any suitable solvent,
such as water, petroleum hydrocarbons, such as 15
gasoline, kerosene, stove oil, a coal tar product,
such as benzene, toluene, xylene, tar acid oil,
cresol, anthracene oil, etc. Alcohols, particular
ly aliphatic alcohols, such as methyl alcohol,
ethyl alcohol, denatured alcohol, propyl alcohol, 20
butyl alcohol, hexyl alcohol, octyl alcohol, etc.
may be employed as diluents. Miscellaneous sol
vents, such as pine oil, carbon tetrachloride, sul
fur dioxide, extract obtained in the re?ning of
petroleum, etc. may be employed as diluents. 35
Similarly, the material or materials employed as
the demulsifying agent of our process may be ad
mixed with one or moreof the solvents customarily
used in connection with conventional demulsifying
agents. Moreover, said material or materials may
be used alone or in admixture with other suitable
well known classes of demulsifying agents, such as
demulsifying agents of the modi?ed fatty acid
type, the petroleum sulfonate type, the alkylated
sulfo-aromatic type, etc.
It is well known that conventional demulsify
ing agents may be used in a water-soluble form, or
in an oil-soluble form, or in a form exhibiting
both oil and water solubility. Sometimes they
may be used in a form which exhibits relatively 40
limited water-solubility and relatively limited oil
In such instances where it is desirable to elimi
nate the residual acidity, it is best accomplished
by means of a relatively weak base, such as tri
solubility. However, since such reagents are
sometimes used in a ratio of 1 to 10,000, or 1 to
20,000, or 1 to 30,000, such an apparent insolu
means of a stronger base, such as ammonium
said reagents undoubtedly have solubility with
45 ethanolamine, or it may be accomplished by
hydroxide or caustic soda, provided the neutrali
zation is conducted with care. In some instances
it is desirable to mix an alcohol, particularly a
50 polyhydric alcohol, such as glycerine or ethylene
glycol with a keto fatty acid body and then heat
so as to eliminate the carboxylic hydrogen. In
any event, the ketonic bodies may be converted
into any suitable form by means of conventional
55 reactions, provided that the material is not de
composed to destroy the carbonyl radical.
Our preferred reagent consists of unneutralized
ketohydroxystearic acid obtained from ricinoleic
acid in the manner previously described. For the
60 sake of convenience we prefer to dilute the keto
bility in oil and water is not signi?cant, because 15
in the concentration employed.
This same fact is
true in regard to the material or materials em- ,
ployed as the demulsifying agent of our process.
As stated previously, it has been so common to 50
use a conventional demulsifying agent derived
from an acid in the form of the acid itself, or in
the form of a salt, or in the form of an ester.
that the expression “acid body” is frequently em
ployed to mean' the acid itself, or an ester thereof, 56
or salt thereof. The word “body” is herein em
ployed in this same sense in conformity with its
prior usage in the trade, and particularly in va
rious patents of the prior art. Half salts and
half esters are considered as'salts, and esters, re
hydroxystearic acid with 50%, by weight, of a spectively.
solvent composed of equal volumes of methyl al
In practising our process a treating agent or de
cohol and solvent naphtha.
The use of demulsifying agents consisting of' mulsifying agent of the kind above‘ described is
65 various sulfo acids, or carboxy acids, or com
brought into contact with or caused to act upon
pounds having both a sulfo group and a carboxyl the emulsion to be treated, in any of the various 65
ways or by any of the various apparatus now gen
group, is well known in the treatment of water
erally used to resolve or break petroleum emul
in-oil emulsions. In the use of conventional de
mulsifying agents it is the common practice to sions with a chemical reagent.
70 use them, not only in the form of acids, but also
Having thus described our invention, what we
in the form of salts or esters, or half salts, or
half esters, or ester salts, in case of dibasic acids.
The salts generally employed are the sodium salt,
potassium salt, ammonium salt, ‘calcium, magne
sium, the triethanolamine salt, etc. The esters
claim as new and desire to secure by Letters Pat- 70
en 1s:
1. A process for breaking a petroleum emulsion
of the water-in-oil type, which consists in sub
jecting the emulsion to the action of a demulsify
ing agent, comprising a keto fatty acid body.
2. A process for breaking a petroleum emulsion
of the water-in-oil type, which consists in subject
in; the emulsion to the action of a demulsifying
agent, comprising a keto fatty acid body in the
form of an acid.
8. A process for breaking a petroleum emulsion
of the water-in-oil type, which consists in subject
ing the emulsion to the action of a demulsifying
agent, comprising a'keto fatty acid body derived
10 from castor oil.
4. A process for breaking a petroleum emulsion
of the water-in-oil type, which consists in subject
ing the emulsion to the action of a demulsifying
agent, comprising a keto fatty acid body in the
form of an acid and derived from castor oil.
5. A process for breaking a petroleum emulsion
of the water-in-oil type, which consists in subject
ing the emulsion to the action ' of ketohydroxy
stearic acid.
6. A process for breaking a petroleum emulsion
of» the water-in-oil type, which consists in sub
jecting the emulsion to the action of ketohydroxy
stearic acid with 50%, by weight, of a‘ solvent com- 10
posed of equal volumes of benzol and ethyl alcohol.
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