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Патент USA US2110837

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Patented Mar. 8, 1938 -
I
_'
291
Q‘ UNITED STATES PATENT-OFFICE
PROCESS FOR BREAKING PETROLEUM
EMULSIONS
‘
I
Charles M. Blair, Webster Groves, Mo., assignor
to The Tret-O-Lite Company, Webster Groves,
Mo., a corporation of Missouri
No Drawing. Application June 21, 1937,
Serial No. 149,476
16 Claims.
(Cl. 196-4)
This invention relates to'the treatment of naphthalene, and the like. I have found, how
emulsions of mineral oil and water, such as ever, that the most desirable reagents are pro
petroleum emulsions, for the purpose of separat- ' duced from alkvlated polycyclic aromatic com
ing the oil from the water.
pounds in which the alkyl group contains not less
5
Petroleum emulsions are of the water-in-oil than three carbon atoms and not more than ten 5
type, and comprise ?ne droplets of naturallyoccurring waters or brines, dispersed in a more
or lessperinanent state throughout the oil which
constitutes the continuous phase of- the emul10 sion. They are obtained from producing wells
and from the bottom of oil storage tanks, and are
commonly referred to as “cut oil”, “roily oil”,
carbon atoms. For sake of brevity in the various
illustrations hereinafter described, I shall refer
to the use of or the preparation of compounds‘
derived from naphthalene in which the alkyl
‘radical contains not less than three carbon atoms 10
and not more than ten. It is understood, how
ever, that one may employ alkylated monocyclic
“emulsi?ed oil”, and “bottom settlings”.
compounds and also alkylated polycyclic com
The object of my invention ‘is to provide a
pounds in which the alkyl‘ group contains not
15 novel and inexpensive process for separating
more than two carbon atoms.
emulsions of the character referred to into their
_
l5
It is well known that if a secondary amine, par-'
component parts of oil and water or brine.
ticularly the kind containing less than 24 carbon .
Brie?y described, my process consists in subatoms is condensed with a phenol and an alde- .
jecting a petroleum emulsion of the water-in-oil - 'hyde, there results a complex amine or a mix
20 type to the action of a treating agent or de- ture of. complex amines. ‘The composition of 20
mulsifying agent of the kind hereinafter de- ' such amine or mixture of amines is not fully
scribed, thereby causing the emulsion to break
understood, but apparently at least the follow
down and separate into its component parts of
ing types of amines are present:
oil and water'or brine, when the emulsion is‘
-' on
25 permitted vto remain in a quiescent state after
.‘
treatment, or'is subjected to other equivalent
separatory procedures.
.
.
of a complex-amine salt of the kind hereinafter
described. The alkylated aromatic compounds
are nuclear substituted products.
_
1]
'Y
N/
x“ -°H—
‘
.
_
-
_
I
It is understood that the, compounds used as
lodemulsitying agents in the present process may
>
.
'
inst-[i
.
cyclic aromatic sulfonic acids or their saltsI Al-
salt, sodium salt, etc.
Y’
and
[on],
03 GH_
.
fonic acids, and particularly substituted poly-
45 the corrosiveness of the sultonic acid-‘it is the
usual practice to employ the reagent in the form
of a salt, such as an ammonium salt, potassium
30
. /
' among other substances, alkylated aromatic sul-
or more alkyl groups into a naphthalene residuev
' and then producing the sulfonic acid. Due to
'
Y
-
35 breaking or resolving oil ?eld emulsions include
plicatlcn is obtained by introducing one, two,
.»
\
'
I
_
though the alkylated monocyclic aromatic sul-
25
y’
on
{I
Commercial demulsifying agents employed for
40 tonic acids find some application in demulsi?ca~
tion, yet the type which ?nds most frequent ap-
a
-
K- -°H- \
30 an alkylated aromatic sultonic acid inthe form
_
~
{I
-
rll'he treating agent or demulsifying agent contemplated by- my process consists of or comprises
'
Y
'
]
'
Y
-
. _"
.
_
C
35
-
s/
._
t \Y,
'
.
.
'
'
_
‘where R is the'aromatic nucleus, X is a hydrogen 4;)
atom or a nuclear substitutent, Z is either a
hydrogen atom or the group originally attached
to the ---CH0 group oi.’ the aldehyde and Y and Y’ are the groups, other than hydrogen, 0118!‘
nally attached to the non-aromatic secondary‘ 45
amine. The —-CI-I—\group is attached at a pod
tion either ortho or para to the phenolic hy
droxyl, ora functionally equivalent position.
n
and m are small whole numbers, such as 1, 2, 3,
4 J'or 5, and less than 10, q is a whole number 50
be obtained from any alkylated nucleus, includ- ' which may have any value from 1 up to and in-
ing such-materials as toluene, xylene, ethyl ben-'
'
eluding [n(m—1)+1], and p .is zero or a yhole
zene, trimethylbenzene, propylbenzene, cymene, number having any value up to and including .
etc. such compoundsmay als'obeproduced from . n(m—1), with the provision that in all cases the .
u methyl naphthalene, ethyl naphthalene, dimethyl
sum of pond q must total [Mm-1) +1].
I
'55
2
2,110,837
For the sake of convenience, these complex thymol, carvacol, resorcinol, naphthol, nitrophe
_ nol, chlorphenol, and chlorcresol. The simpler
amines may be represented by the formula:
(OHM
where T is the phenolic residue, D is the aldehydo
linkage and B is the monovalent secondary amino
10 radical.
m is a small whole number such as 1,
2, 3, 4 or 5, and less than 10; n is a whole num
ber having any value from m to m+10; 1; may
be zero or any whole number up to and includ
ing (n--m) ; q may be any whole number from‘ 1
15 up to and-including (n-m+1), with the pro
vision that in all cases the sum of p and q must
total (n-—m+1).
,
In addition to amines of the types above de
scribed, other complex amines or associated com
20 pounds may be present, and for this reason, as
well as for convenience, the amines are advan
tageously described by the means of producing
the same.
Phenols which may be employed to form the
25
complex aldehydic amine may be indicated by
the general formula X—R—-0H, where R is an
aromatic monocyclic or polycyclic nucleus having
at least one free nuclear position, ortho or para '
to the phenolic hydroxyl group available for con
30 densation; and X is a hydrogen atom or. a nu
clear substituent of R, and particularly of the
type where X represents a long alkyl chain, that
is, a monovalent hydrocarbon radical containing
particularly six or more carbon atoms.
It is
understood herein that the aromatic nucleus B
may contain other nuclear substituents in addi
tion to X, such as additional hydroxyl groups,
halogen atoms, or alkyl, alkoxy, nitro, amino or
alkylol groups; but R should be free from acidic
40 or acid-forming substituents, such as sulfonic,
aldehydo or carboxyl groups, whose presence
amines, which are employed to combine with a
phenol and an aldehyde to form the complex
amines which subsequently form the alkylated
aromatic sulfonic acid salt, or the strongly basic
non-aromatic amines, and have the general for
mula' type RF—NH—R1, where R and R1 are alkyl,
alkylol or allcyclic groups, or where R and R1 to
gether form an‘ alkylene ring, substituted alkylene 10
ring, or an alkylene ring interrupted by oxygen.
These amines must also be free from interfering‘
groups, such as carboxyl, nitrile, or aIc/iehydo
groups. Secondary amines which are particu—
larly suitable for the formation of the more com
methylethylamine, diethylamine, dipropylamine,
piperidine, piperazine, diethanolamine, dibutyl
amine, diamylamine, dihexylamine, dioctylamine,
didodecylamine, etc. As to the manufacture of 20
secondary aliphatic amines of fairlyhigh molec
ular weight, see U. S. Patent No. 2,078,922, to
Arnold, dated May 4, 1937.
The aldehydes which may be employed in ‘the
manufacture of the complex, phenolic alkylene
amines may vary from low molecular weight al
dehydes, such as formaldehyde, to aldehydes of
high molecular weights, derived from fatty acids
such as aleyl aldehyde, stearyl aldehyde, and the
like: As to the manufacture of these aldehydes 30
of high molecular weights derived from fatty
acids of commerce, see U. S. Patent No. 2,033,539,
to Ralston and Jackson, dated March 10, 1936.
The aldehydes may be saturated or unsaturated
and may be heterocylic and aromatic, as well as
aliphatic.
Benzaldehyde, crotonaldehyde, fur
fural, stearal, cinnamic aldehyde, etc., may be
employed, as well as acetaldehyde, propionalde
hyde, butyraldehyde, isobutyraldehyde, methyl
ethyl acetaldehyde, valeraldehyde, trimethyl
acetaldehyde, heptaldehyd'e, caprylic aldehyde
prevents the desired condensation from taking
(Ca), pelargonic aldehyde (C9), margaric alde
place.
hyde, etc. Phenyacetaldehyde may also be em
ployed.
'.
The manufacture of the complex ‘phenolic
amines.._may be illustrated by the following ex
The hydrocarbon group X is a mono
valent aromatic, hydroaromatic, alicyclic, or
45 aliphatic radical, and as previously stated, pref
erably contains six or more carbon atoms.
Phenols, such. as butylphenol, butylbromphenol,
butylcresol,
butylchlorphenol,
amples:
butylresorcinol,
butyliodophenol, butylnaphthol and their respec
tive higher homologues, such as the‘ correspond
ing amyl-, hexyl-, heptyl-, octyl-, duodecyl-,
hexadecyl-, or octa-decylphenols and the corre-
.
To a solution of 94 g. of phenol in 100 cc. of
water containing 103 g. of diethanolamine, 100 g.
of aqueous,30% formaldehyde are added while
sponding cresols, hydroquinones, resorcinols, and‘
cooling and stirring. After 24 hours standing,»
the water is stirred off in vacuo, using a tem
groups in all of these phenols can be'elther
straight-chain or branched-chain in character,
and may be in either the ortho, meta, or para
60 position to the phenolic hydroxyl group, pro
vided a free position ortho or para to the‘phenolic
’ hydroxyl group remains available for condensa
tion. Furthermore, phenols such as cyclo hexyl
ph‘enol, bornylphenol, tetrahydronaphthaylphe-'.
40
,Eazample 1
naphthols are particularly suitable as phenolic
bodies to be employed to, form the demulsifying
agents used in the present process. The alkyl
15
plex amines include morpholine, dimethylamine,
perature of not'over 25° C. A pale yellow vis 55
cous oil is obtained which is employed to neu
tralize dipropylated naphthalene sulfonic acid,
so as to get a demulsifying agent of excellent
quality.
_.
'
'
60
Example 2 - -
10' g. of acetaldehyde and 29 g. of dinormal
butyl amine are mixed and to this is added 25
g. of p-tertiary butyl phenol. The mixture is 65
heated
under re?ux at 94° C. for three hours.
responding cresol, resorcinol, hydroquinone, or After evaporating
off volatile products on the
naphthol analogues can be used.
steam
plate,
a
clear,
thin, reddish oil is obtained.
In producing the’ amine of the kind employed
oil is insoluble in water, but soluble in benzol
to combine with suitable alkylated aromatic sul ' This
and kerosene. It combines with triisopropyl
70 fonic acids to yield a demulsifying agent of the naphthalene sulfonic acid with evolution of heat
kind employed in the present process, one may
to yield a dark, viscous oil which is only‘very
employ a phenol which contains no, nuclear sub
stituent of more than three carbon atoms; as, slightly soluble in water, but soluble in benzol.
for instance, phenol itself (hydroxy benzene), This salt has a powerful demulsifying action on
.
75
75 resols, xylenols, ethyl phenol, isopropyl phenol, certain emulsions.
.65 nol, phenylphenol, benzylphenol, and their cor
3
2,1 10,887
Example 3
19 g. of heptaldehyde and I75 g. of diethanol-w
amine are mixed and. to this is added 30 g. 95%
ethanol and 25 g. of p-tertiarybutyl phenol. This
mixture is placed under re?ux at 77° C. for 18
hours. After evaporating off volatile material
on ‘the steam plate, 53g. of a light yellow ,oil are
obtained. This material is soluble in water. It
combines with triisopropyl naphthalene sulfonic
10 acid- with evolution of heat to yield a viscous red
oil soluble in benzol and having quite appreciable
demulsifying action on certain emulsions.
The proportions of aldehydev and amine ‘used
should be at least one mole of each per mole of
15 phenol. An excess of either or both the alde
hyde and amine may also be employed. The de
sired condensation takes place only in basic or
neutral solution, and in some cases the yield may
tionship between the complex phenolic alkylene '
amine residue and the sulfo-aromatic residue.
The neutralization of other conventional acidic
demulsifying reagents with complex‘ phenolic‘
alkylene amine does not seem to produce any
marked ‘improvement over the corresponding so
dium or ammonium salts, and in many cases,‘
yields an inferior product, thus indicating that
apparently the increased value does not reside -
in an additive e?ect, due to the complex phenolic
alkylene amine residue.‘ Furthermore, the ef
fectiveness of complex phenolic alkylene amine
apparently is not enjoyed by various other amines 15
which bear some similarity to this material, such‘
as aniline, toluidine, propylamine, diamylamine,
etc. In other words, if the same alkylated'naph
be improved by adding small amounts of anal
thalene sulfonic acids which are employed to
producethe treating agent or demulsifying agent
bonate to the reaction mixture.
other apparently kindred amines, one does not
20 kali such as, potassium hydroxide or sodium car
.
>
In some instances, it is desirable that the com
plex amine be produced by reacting a phenolic
formaldehyde resin or its equivalent with addi
25 tional formaldehyde, or some other aldehyde,
and then reacting said components with a strong
ly basic, non-aromatic secondary amine in the
manner previously described. 'Under such cir
30
Apparently, there is some unlocked-for co-op
eration or chemical or' physical-chemical rela
cumstances, at least one mole of a secondary
amine and at least one mole of additional form
aldehyde or the like should-‘be used for each
molecular equivalent of the phenolic formalde
used in my process are neutralized with many
obtain a reagent that even begins to approach
the‘eifectiveness of thedemulsifying agent used
in my process. Similarly, if one neutralizes other
sulfonic acids, which are known to be eifecti've
25"
demulsifying agents, such as petroleum sulfonic'
acids of the mahogany acid type, with complex
phenolic alkylene amine, one does not obtain a
more e?ectivedemulsifying agent, and indeed, 30
one is more likely to obtain a demulsifying agent
which is less e?'ective. ' Based on the results of
actual tests obtained in‘ a variety of ' emulsi?ed
hyde resin or the like, which‘is employed as a ' crudes occurring in a number of the major oil
raw material. As to procedure relating to the ?elds of the United States, the conclusion‘ one 35
35
manufacture of this‘particular type of complex must inevitably reach is,‘ that the result obtained
amine. reference. is made'to U. S.'Patent No. by uniting the two residues, 1. e., the complex
2,037,557, dated February 18, 1936, to Bruson.
phenolic alkylene amine residue, and the de
For further information as to the manufac
scribed sulfo-aromatic residue in ‘a single mole
ture of the complex phenolic alkylene amines, cule, results‘ in an unlocked-for, unique quality,
40
reference is made to U. S. Patent No.‘ 2,033,092, which could not be foreseen by the present knowl-'
edge of the art, and which produces a demulsi
'to Bruson, dated March 3, 1936,'and U. S. Pat
ent No. 2,036,916, to Bruson, dated April 7, 1936. fying agent that is particularly effective for. a
For sake of convenience, I will refer to the
45
complex phenolic amines as"complex phenolic
alkylene amine, because .when derived from sim
pler saturated aldehyde's, such as formaldehyde,
,
Alkylated naphthalene sulfonic acids are pro 45
duced commercially, and the salts are used for
link. However, when derived from some‘other
a variety of purposes, They are generally pro
duced from naphthalene, because there does not appear to be any advantage in the use of a
type of aldehyde, there might be some radical
other than the alkylene radical forming the link
age. An effort to include nomenclature of such
scope as to include all the possible linkages might
naphthalene derivative, such as chlor-naphtha 50
lene, alpha and beta naphthol, etc. In other
words, one could. introduce the sulfonic acid
residue and the alkyl residues into a substituted
there is present an alkylene radical acting as a
50
large number of emulsi?ed crude oils. '
add to‘ confusion rather than clarity. For this naphthalene, such as 'chlor-naphthalene, 1 etc.,
reason, the expression “alkylene” when used in _ just as readily perhaps as in the case of naphtha
connection with the term “complex phenolic al
kylene amine” is to be used in a generic sense, as
described.
‘
‘
_
~
I have discovered that if a suitable alkylated
60 aromatic sulfonic acid, and particularly an al
kylated naphthalene sulfonic acid having at least
three carbbn atoms in the alkyl group, is neu
tralized with a complex phenolic alkylene amine,
one obtains a reagent of unusual effectiveness.
There does not appear to be anyvsuitable expla
nation of this unusual superiority, and similarly,
there does not seen to be any basis by which one
could anticipate or foresee this unusual effective
ness. Apparently, this marked improvement is
70 not directly related to oil or water solubility, in‘
sofar that similar neutralization with other
amines may yield compounds which’ ,have a
greater solubility in oily materials or in water,
and yet are not nearly as suitable and not nearly
" 75 as e?fective in their demulsifying action.
lene. However, such derivatives are more ex
pensive and no advantage is obtained. Such
simple derivatives, of course, are thecheinical,
equivalent of naphthalene in the manufacture
of such 'sulfonic acids as vare employed in the 60
manufacture of the present reagent. It is un
derstood that the word “naphthalene” is here
inafter employed to include these derivatives, al
though, as pointed out, there is no advantage in
using them, and the expense usually would be 65
prohibitive.
_
a
.
The general process of manufacturing the de
mulsifying agent contemplated by my process,
consists in converting the naphthalene into either;
the alpha or beta naphthalene sulfonic acid, or-v
in some instances, into a di---or even tri-sulf?nic. 1 '
acid.
in introducing
In most more
instances
than,;.one
theresulfonic
fis no advantage}
acid
due. In many instances itg'is unnecessary to use
particular care to prepare either only the alpha
75."
2,110,887
sulfonic acid, or only the beta sulfonic acid, be
cause a mixture in which either one or the other
predominates, or a mixture in which the alpha
and beta sulfonic acids are present in approxi
mately equal amounts, is just as satisfactory as
one sulfonic acid completely freed from the other
type.
.
The alcohol employed, such as propyl alcohol,
butyl alcohol, amyl alcohol, hexyl alcohol, decyl
10 alcohol, etc., is converted into the acid sulfate,
such as propyl hydrogen sulfate. The naphtha
lene sulfonic acid and the alkyl hydrogen sulfate
are combined in proportions so that one, two,
three, or even four alkyl groups are introduced
15 into the aromatic residue. This condensation re
action is generally carried out in the presence
of an excess of sulfuric acid. In some instances,
the various reactions, such as sulfonation, sul
fation, condensation, etc., are carried out simul
20
taneously.
Generally‘ speaking, the dialkylated
and trialkylated material appear to yield the
most desirable type of reagent. The presence of
some monoalkylated _material, or some tetra
alkylated material is not objectionable, and may
reagents from these alcohols, and in some in
stances, it is desirable to introduce different alkyl
' groups, such as a propyl group and butyl group
into the same sulfo-naphthalene residue.
\
In the actual manufacture of alkylated naph
thalene sulfonic acids, the completion of the
desired chemical reactions is followed by a
washing process, which removes the excess of
sulfuric acid or other sulfonation, sulfation, or
condensation reagent employed. The acidic .10
mass thus obtained is neutralized with complex
phenolic alkylene amine in the same manner that
sodium or potassium or ammonium hydroxides
might usually be employed. The ?nal product,
if it represents a pasty or semi-solid or a solid 15
mass, is rendered suitable for industrial use by the
addition of a solvent, such as water, an alcohol, a
coal tar solvent, a petroleum hydrocarbon solvent,
or in any similar manner.
.
The demulsifying agent that I prefer to use 20
in practicing my process is obtained by a reac
tion in which three moles of isopropyl alcohol
are united with one mole of naphthalene by the
customary sulfation, sulfonation and conden
25 even be desirable.
sation reactions. The resulting mixture consists 25
It is obvious, of course, that the alkylated
groups introduced might be derived from ole?nes,
such as butylene, propylene, amylene, etc., insofar
that such ole?nes react directly with sulfuric
30 acid, to produce the alkyl hydrogen sulfates. Of
course, in addition to introducing such alkyl resi
largely of dipropyl naphthalene, sulfonic acids
and tripropyl naphthalene sulfonic acids, with
possibly small amounts of monopropyl sulfonic
dues of the kind described into the aromatic
nucleus, one could also introduce an alkyl resi
due from some other alcohol, as, for example, an
35 alkylated group derived from ethyl or methyl al
cohol, or one might introduce a group derived
from an aryl, aralkyl, or cyclo-alcohol, but re
gardless of whether or not one introduces such
other residues, it is necessary that at least one
40 alkyl residue of the kind described, 1. e., having
at least three carbon atoms and not more than
ten carbon atoms, be introduced into the naph
thalene ring. Such compounds having some other
residue present, such as a methyl residue, might
45 be considered as being derived from methyl
acids and tetrapropyl sulfonic acids present.
Generally speaking, it is ‘easier to conduct the 30
reaction so that the bulk ofithe sulfonic acid
represents‘ the beta type, although the alpha
type may be produced, if desired. The neutral
ized product is diluted with one or more solvents,
so as to reduce its viscosity to that of ordinary 35
castor oil, or slightly greater. The solvents
which I preferably employ, are 'a- mixture of two
or more of the following: Water, denatured alco
hol, kerosene, or tar acid oil.
Among the reagents which are particularly ef 40
fective are the complex phenolic alkylene amine
salts of the following alkylated naphthalene sul
fonic acids, i. e., monoisopropyl naphthalene sul
55 mal butyl or isobutyl alcohol. It is immaterial
whether the alcohol be a primary alcohol, or a
secondary alcohol, or a tertiary alcohol, or the
like.
It is obvious that a large number of isomers
60 can be produced in the manufacture of the re
fonic acid, diisopropyl naphthalene sulfonic acid,
triisopropyl naphthalene sulfonic acid, mono
normal butyl naphthalenesulfonic acid, dinormal
butyl naphthalene sulfonic'acid, monoisobutyl
naphthalene sulfonic acid, diisobutyl naphtha
lene sulfonic acid, diamyl naphthalene sulfonic
acid, triamyl naphthalene sulfonic acid, mono
hexyl naphthalene sulfonic acid, dihexyl naph
thalene sulfonic acid, trihexyl naphthalene sul
fonic acid, mono-octyl naphthalene sulfonic
acid, dioctyl naphthalene sulfonic acid, mono
decyl naphthalene sulfonic acid, didecyl naph
thalene sulfonic acid, monoisopropyl dinormal
butyl naphthalene sulfonic acid, diisopropyl,
monoamyl naphthalene sulfonic acid, monoiso
propyl, monohexyl naphthalene sulfonic. acid,
is. manifest that the alkyl group or groups can
65 be introduced into various positions in regard to
various amines.
naphthalene, instead of naphthalene, and thus,
would fall within the class of chemical equiva
lents previously noted. It is immaterial as to the
50
particular alcohol employed, or the particular
isomeric form of the alcohol employed, although
generally speaking, it is most desirable to use
the one lowest in cost. It is immaterial whether
one uses normal propyl alcohol or isopropyl al
cohol. It is immaterial whether one uses a nor
etc.
agent employed in the present process. For in
It may be desirable to indicate that there is
stance, although the sulfonic group may be in
troduced into either the alpha or beta position, it - sometimes some variation in nomenclature in
the position of the sulfonic acid residue.
Ap
parently, as far as I am aware, one isomeric form
is as eifective as the other. Reference to the
compounds is not intended to indicate any par
70 ticular isomer, unless the text clearly-indicates
some speci?c position.
‘
Insofar that the most readily available alcohols,
from the standpoint of cost, are isopropyl alco
hol, normal butyl alcohol, isobutyl alcohol, and
75 amyl alcohol, it is my preference to produce my
45
50
55
60
regard to the salts derived from strong acids and
For instance, the combination 65
of aniline and hydrochloric acid, isoften referred
to as aniline hydrochloride. When aniline hy~
drochloride is treated with caustic soda, aniline
is regenerated and sodium chloride formed. For
this reason, and perhaps for other reasons, struc 70
tural conditions are best expressed by referring
to the compound as a hydrochloride, in order
to indicate that one does not obtain the chloride
of a quaternary ammonium compound.
Simi
larly, the reaction of complex phenolic alkylene 75
5
2,110,887
tying agent comprising a salt of the kind de
rived by reaction between an alkylated aromatic
amine salt, although .‘for reasons‘pointed out, sulfonic acid and a complex amine; said'complex
such salt might be looked upon as, a complex amine being derived by reaction between an alde
phenolic alkylene amine hydrogen sulfonate, as . hyde having not over 22 carbon atoms, a strongly
. well as being considered as a complex phenolic basic, non-aromatic secondary amine having not
over 44;‘ carbon atoms and free from carboxyl,
'alkylene amine sulfonate. Insofarv that it is. nitrile,
and aldehydo groups, and-a ‘phenol of
perfectly clear asato the chemical composition of
the type X-R-.OH', where R is an aromatic '
the compound, it is immaterial which nomencla ’ nucleus having at least one free nuclear position,
amine with a sulfonic acid may be‘ considered
as producing the. complex phenolic alkylene
ture is employed.
.
-
In such instances where there is present more
than one sulfonic acid residue, as inthe forma
tion of a disulfonic acid, or a trisulfonic acid, if
desired, all the sulfonic acid hydrogen may be
15 neutralized _ with complex phenolic alkylene
amine,‘ orif desired, only one s'ulfonic hydrogen
may be neutralized withfcomplex phenolic alkyl
ene amine, and the other sulfonic hydrogen atom
or atoms may be neutralized ,with some other
suitable base, such as sodium hydroxide, potas
sium hydroxide, ammonium hydroxide,'etc.
Complex phenolic alkylene amine salts, such
as the hydrochloride, may react by double de
composition'with alkali salt sulfonates in a suit
25 able medium to produce the complex phenolic
_ alkylene amine sulfonate.
Conventional demulsifying agents employed in
the treatment of oil ?eld emulsions are used as
30 such, or after dilution with any suitable solvent,
such as water, petroleum hydrocarbons, such as
gasoline, kerosene, stove oil, a coal tar product,
such as benzene, toluene,‘xylene, tar acid oil,
cresol, anthracene. oil, etc. Alcohols, particu
larly aliphatic alcohols, such as methyl‘v alcohol,
ethyl alcohol, denatured alcohol, propyl alcohol,
butyl alcohol, hexyl alcohol, octyl alcohol,_etc.,
may be employed as dlluents. Miscellaneous
solvents, such as pine oil, carbon tetrachloride,
sulfur dioxide extract obtained in the re?ning ‘of
petroleum, etc. may be employed as dlluents.
Similarly, the material or- materials employed
as the demulsifying agent ‘of my process may be
admixed with one or more of the solvents cus
v45
tomarily used; in connection with conventional
demulsifying agents. Moreover, said material or
materials may be 'used alone .or iii-admixture
with other suitable well known classes of demul
sifying agentsgsuch‘ as demulsifylng agents of
50
the modi?ed fatty'acid type, the petroleum sul
fonate type, the alkylated sulfa-aromatic type,
in which the sulfonic hydrogen is neutralized by
the use of ‘some base other than complex phe
' nolic alkylene' amine.
55
It is well known that conventional demulsify
ing agents’ inay be used in a water-soluble form,
or in an oil-soluble form, or in a form exhibit
ing both oil and water solubility. Sometimes
_they may be used ina form which exhibits rela
tively limited water solubility and relatively lim
ited oil solubility. However, since such reagents
are sometimes'used in a ratio of 1 to" 10,000, or
' 1 to-20,000, or even 1 to 30,000, such an apparent
10
ortho or para, to the phenolic hydroxyl available
for condensation, or an equivalent position, if in
a polycyclic nucleus; and X is a hydrogen atom
or a nuclear substituent of R and consisting of a
monovalent hydrocarbon radical; and R is addi 15
tionally characterized by the fact that other sub
stituents selected from the class? consisting of
halogen atoms, alkyl, alkoxy, nitro, amino, ‘and
alkylolradicals, ‘may be present, but R must be
free from acidic or acid-forming constituents se
lected from'the class of sulfonic, aldehydo or car
boxyl radicals.
20
\, .
2. A-process for breaking petroleum emulsions
of’the water-in-oil type, which consists in ,sub
jecting the emulsion to the action of a demulsify 25
ing agent comprising a salt of the kind derived
by reaction between an alkylated aromatic sul- .
fonic acid and a complex amine; said complex
amine being derived by reaction between asatu
rated aldehyde having not over 22 carbon atoms, 30
a strongly basic non-aromatic secondary amine
having not ever ‘My carbon atoms, and free
from carboxyl, nitrile, and aldehydo groups, and
a phenol of’the type X-Rr-OH, where R is‘ an
aromatic nucleus having at least one free nuclear 35
position, ortho or para, to the phenolic hydroxyl
available for condensation, or an equivalent posi-'
tion, if in a polycyclic nucleus; and X is a hydro- ‘
gen atomor a nuclear substituent of R and con
sisting' of a monovalent hydrocarbon ‘radical; 40
and R is additionally characterized by’ the fact
that other substituents selected from the class'
consisting of halogen atoms, alkyl, alkoxy, nitro,
amino, and alkylol radicals, may be present, but
R must be free from acidic or acid-forming con
45
stituents selected from the class of sulfonic,
aldehydo or carboxyl radicals.
3. A process for breaking petroleum emulsions
of the water-in-oil type, which consists in sub
jecting the emulsionto the action of a demulsify
ing agent comprising a salt of the kind derived _
by reaction between an alkylated aromatic sul
i’onic acid and a complex‘ amine; ,said complex
amine being, derived by reaction between a satu
rated aldehyde having not over 22 carbon atoms,
a strongly basic non-aromatic secondary amine
having not over 44 carbon atoms, and free from
carboxyl, nitrile, and aldehydo groups, and a
phenol of the type X-R—OH, where R is an
aromatic monocyclic nucleus having at least one 60
free nuclear position, ortho or para, to the
phenolic hydroxyl available for condensation, and f
X is a hydrogen atom or a nuclear substituent of
R and consisting of-a monovalent hydrocarbon
radical; and R is additionallycharacterized by 65
bility within the concentration employed. This,_ the fact that-other substituents selected from the
insolubility in oil and water‘ is not significant
because said reagents undqpbtedly have solu
- same fact is true in regard to the materialv or
‘materials employed as the demulsifylng agent
of my process.
,
Having thus described my invention, what I
to.claim
as new and desire to secure by Letters
Patent is:
.
'
1. A process for breaking petroleum emulsions
of the water-in-oil type, which consists in sub
a class consisting of halogen atoms, alkyl, alkoxy,
nitro, amino, and alkylol. radicals, may be pres
ent, but R must be free from acidic or acid-form
ing constituents selected from the class of 70
sulfonic, aldehydo or carboxyl radicals.
‘
.,
4. A process for breaking‘ petroleum emulsions
of the water-in-oil type, which consists *in' sub—
jecting the emulsion to the action of a demulsify
jectingthe emulsion to the action of 8. (168111159 ing agent comprising a salt of the ldnd derived by 75
6
2,110,887
reaction between an alkylated aromatic sulfonic
acid and a complex amine; said complex amine
being derived by reaction between‘ a saturated
aldehyde having not over 22 carbon atoms, a
strongly basic non-aromatic secondary amine
having not over 44 carbon atoms, and free from
carboxyl, nitrile, and aldehydo groups, and a
phenol of the type X—R—OH, where R is an
aromatic monocyclic nucleus having at least one
10 free nuclear position, ortho or para, to the
_ phenolic hydroxyl available for condensation, and
X is a hydrogen atom or a nuclear substituent
of R and consisting of a monovalent hydrocarbon
radical containing at, least 6 carbon atoms; and
15 R is additionally characterized by the fact that
other substituents selected from the class con
fying agent comprising a salt of the kind derived
by reaction between an alkylated aromatic poly-'
cyclic sulfonic acid derived from naphthalene,
and characterized by the fact that the alkyl rad
ical introduced into the naphthalene nucleus con
tains at least 3 carbon atoms and not more than
10 carbon atoms, and a complex amine; said com
plex amine being derived by reaction between a
saturated aldehyde having not overv 22 carbon
atoms, a strongly basic non-aromatic secondary 10
amine having not over 44 carbon atoms, and free ~
from carboxyl, nitrile, and aldehydo groups, and
a phenol of the type ~X-—R—OH, where R is an
aromatic monocyclic nucleus having at least one
free nuclear position, ortho or para, to the phe 15
nolic hydroxyl available for condensation; and
sisting of halogen atoms, alkyl, alkoxy, nitro,
X is a hydrogen atom ‘or a nuclear substituent of
amino and alkylol radicals, may be present, but
R and consisting of a monovalent hydrocarbon
radical containing at least 6 carbon atoms; and R‘
is additionally characterized by the fact that other 20
substituents selected from the class consisting
R must be free from acidic or acid-forming con
20 stituents selected from the class of sulfonic alde
hydo or carboxyl radicals.
5. A process for breaking petroleum emulsions
of the water-in-oil type, which consists in sub
jecting the emulsion to the action of a demulsify
25 ing agent comprising a salt of the kind derived
by reaction between an alkylated aromatic poly
cyclic sulfonlc acid and a complex amine; said
complex amine being derived by reaction between
a saturated aldehyde having not over 22 carbon
atoms, a strongly basic non-aromatic secondary
amine having not over 44 carbon atoms, and free
from carboxyl, nitrile, and aldehydo groups, and
a phenol of the type X—R—OH, where R is an
aromatic monocyclic nucleus having at least one
35 free nuclear position, ortho or para, to the
phenolic hydroxyl available for condensation, and
X is a hydrogen atom or a nuclear substituent of
R and consisting of a monovalent hydrocarbon
radical containing at least 6 carbon atoms; and
40 R is additionally characterized by the fact that
other substituents selected from the class con
sisting of halogen atoms, alkyl, alkoxy, nitro,
amino, and alkylol radicals, may be present, but
R must be free from acidic or acid-forming con
45 stituents selected from the class of sulfonic,
of halogen atoms, alkyl,- alkoxy, nitro, amino, and
alkylcl radicals, may be present, but R must be
free from acidic or acid-formingconstituents se
lected from the class of sulfonic, aldehydo or car
boxyl radicals.
25
'
8; A process for breaking petroleum emulsions
of the water-in-oil type, which consists in sub
jecting the emulsion to the action of a demulsi
fying agent comprising a salt of the kind derived 30
by reaction between an alkylated aromatic poly
cyclic suli'onic acid derived from naphthalene, and
characterized by the fact that the alkyl radical
introduced into the naphthalene nucleus contains
at least 3 carbon atoms and not more than 10 35
carbon atoms, and a complex amine; said complex
amine being derived by reaction between a satu
rated aldehyde having not over 22 carbon atoms,
a strongly basic non-aromatic secondary amine
having not over 44 carbon atoms, and free from 40
carboxyl, nitrile, and aldehydo groups, and a
phenol of the type X-R-OH,‘ where R is an aro
matic monocyclic nucleus having at least one free
nuclear position, ortho or para, to the phenolic
' hydroxyl available for condensation; and X is a
hydrogen atom or‘ a nuclear substituent of R and
consisting of an alkyl radical containing at least
6 carbon atoms; and R is additionally charac
terized by the fact that other substituents se
50 fying agent comprising a salt of the kind derived ' lected from the class consisting of halogen atoms,
aldehydo or carboxylic radicals.
6. A process for breaking petroleum emulsions
of the water-in-oil type, which consists insub
jecting the emulsion to the action of a demulsi
by reaction between an alkylated aromatic poly
cyclic sulfonic acid derived from naphthalene and
a complex amine; said complex amine being de
rived by reaction between a saturatedaldehyde
alkyl, alkoxy, nitro, amino, and alkylol radicals,
may be present, but R must be free from acidic or
acid-forming constituents selected from the class
of sulfonic, aldehydo or carboxyl radicals. ,
9. A process for breaking petroleum emulsions
non-aromatic secondary amine having not over oi’ the water-in-oil type, which consists in sub
44 carbon atoms, and free from carboxyl, nitrile, iecting the emulsion to the action of a demulsi
and aldehydo groups, and a phenol of the type tying agent comprising a salt of the kind derived
X—R—OH, where R is an aromatic monocyclic by reaction between an alkylated aromatic poly
nucleus having at least one free nuclear posi mcyclic sultonic acid derived from naphthalene, 60
tion, ortho ‘or para, to the phenolic hydroxyl and characterized by the fact that the alkyl rad
available for condensation; and X is a hydrogen ical introduced into the naphthalene nucleus con- ’
tains at least 3 carbon atoms and not more than
‘ atom or a nuclear substituent of R and consisting
of a monovalent hydrocarbon radical containing 10 carbon atoms, and a complex amine; said com
65 at least 6 carbon atoms; and -R is additionally plex amine being derived by reaction, in the equiv 65
characterized by the fact that other substituents alent molecular proportion of 1:1:1, between a
selected from the class consisting of halogen saturated aldehyde having not over 22 carbon
atoms,’ alkyl, alkoxy, nitro, amino, and alkylol atoms, a strongly basic non-aromatic secondary
radicals, may be present, but R must be free from amine having not over 44 carbon atoms, and free
70 acidic or ‘acid-forming constituents selected from from carboxyl, nitrile, and aldehydo groups, and
the class of sulfonic, aldehydo or carboxyl radi . a phenol oi the type X-'-R—OH, where R is an
aromatic monocyclic nucleus having at least one
cals.
'
7. A process for breaking petroleum emulsions free nuclear position, ‘ortho, or para, to the phe
nolic hydroxyl available for condensation; and X
of the water-in-foil type, which consists in sub
is a hydrogen atom or a nuclear substituent of
75 jecting the emulsion to the action of a demulsi
55 having not over 22 carbon atoms, a strongly basic
u
7
2,110,837
R ‘and consisting of an alkyl radical containing
at least 6 carbon atoms; and R is additionally
a phenolic residue, D is an aldehydo linkage, and
B is a monovalent secondary amino radical, m
characterized by the fact that other substituents
selected from the class consisting of halogen at
oms, alkyl, alkoxy, nitro, amino, and alkylol rad
is a small whole number such asl, 2,3, 4 or 5,’; ,
and less than 10; n is a whole number having any
value from m to m+10; p may be zero or any
icals, may be present, but R must be free from
acidic or acid-forming constituents selected from
the class of sulfonic, aldehydic or carboxyl radi
,cluding (n-m+1-), with the provision that in
cals.
whole number up to and including (n—m); q
may be any whole number from 1 up to and in
all instances the sum of p and q must total
r
10. A process for breaking petroleum emulsions
10 of the water-in-oil type, which consists in sub
jecting the emulsion to the action of a demulsi
iying agent comprising a salt of- the kind derived
by reaction between an alkylated aromatic poly
cyclic sulfonic acid derived from naphthalene,
and characterized by the fact that the alkyl rad
ical introduced into the naphthalene nucleus con
tains atleast 3 carbon atoms and not more than
10 carbon atoms, and a complex amine; said com,
20 plex amine being derived by reaction, in the equiv- '
alent molecular proportion of 1:1:1, between a
saturated aldehyde having not over 22 carbon
atoms, a strongly basic non-aromatic secondary
amine of the aliphatic type, having not over 44
25 carbon atoms, and free from carboxyl, nitrile,_
and aldehydo groups, and a phenol of the type
X—Rr-OH, where R is an aromatic monocyclic
nucleus having at least one free'nuclear position,
ortho or para, to the phenolic hydroxyl available
30 for condensation; and X is a hydrogen atom or
a nuclear substituent of R and consisting of an
(n-m+1).
-
~
‘
13. A, process for breaking ~petroleum emul- _
sions of the water-in-oil type, which consists in
subjecting the emulsion to the action of a demul
10
sifying agent comprising aechemical compoun
oi the formula type:
>
15
(011)’;
Rso 11.01‘ ..
)Y (ID) ..\
a
-
-
(B):
where R is an alkylated' aromatic nucleus, T is a ' 20
phenolic residue, D is- an aldehydo linkage de
rived from a saturated aldehyde, and B is a. _
monovalent secondary amino ‘radical, m is a
small whole number such as 1, 2, 3, 4 or 5, and
less than’ 10; n is a whole number having any 25
value from m to m+10; p may be zero or any
whole 1number up to and including (n-m); q
may be any-whole number from 1 up to and in
cluding (n—m+1), with the ‘provision that in
all instances the s’um’of p and q must total 30
(n—-m+1).
_
.
14. A process for breaking petroleum emul
and R is additionally characterized by the fact sions of the water-in-oil type, which consists in
that other substituents selected from the class subjecting the emulsion to the action of a demul-.
consisting of halogen atoms, alkyl, alkoxy, nitro, ‘ sifying agent comprising a chemical compoun
alkyl radical containing at least 6 carbon'atoms;
amino, and alkylol radicals, may be present, but
R must be free from acidic or acid-forming con
of the formula type:
I
-
stituents selected from the class of sulfonic, alde- hydo or carboxyl radicals. ‘
s
11. A process for breaking petroleum emulsions
40'
of the water-in-oil type, which consists in sub
jecting the emulsion to the action of a demulsi
\ fying agent comprising a salt of the kind derived
40
where R is an alkylated polycyclic aromatic nu
cleus, T is a‘ phenolic residue, D is an aldehydo
linkage derived from a saturated aldehyde, and .
by reaction'between an alkylated aromatic poly
B is a monovalent secondary amino radical, m
cyclic sulfonic acid derived from naphthalene,‘ is a small whole number such as 1, 2, 3, 4 or 5, 45
and characterized by the ‘fact that the alkyl radi
and less than 10; n is a whole number having anyv
cal introduced into the naphthalene nucleus con
tains at least 3 carbon atoms and not more than
10 carbon atoms, and a complex amine being de
rived by reaction, in the equivalent molecular
50 proportion 1:1:1 between formaldehyde, dieth
anolamine, and a phenol oi’ the type X-R-OH,
where R is an aromatic monocyclic nucleus hav
ing at least one free ‘nuclear position, ortho or
para, to the phenolic hydroxyl available for con
densation; and X is a hydrogen atom or a nu
clear substituent of R and consisting of an alkyl
radical containing'at least 6 carbon atoms; and
R is additionally characterized by the fact that
60 other substituents selected from the class con
._ sisting of halogen atoms, alkyl, alkoxy, nitro,
amino, and alkylol radicals, may be present, but
R must be free from acidic or acid-forming con
stituents selected from the class of sulfonic, alde
hydo or carboxyl radicals.
,
-
‘
12. A process for breaking petroleum emul
sions of the water-in-oil type, which consists in
subjecting the emulsion to the action of a demul
sifying agent comprising a chemical compound of
the formula type:
-
‘ .
value from m to m+1o; p may be zero or any
whole number up to and including (n—m) ; q
may be‘any whole number from 1 up to and in
cluding (n—m+1), with the provision that in 50
all instances the sum ofp and ,q must total
(n-m+1).
_
15. A process ‘for breaking petroleum emulsions
oi the water-in-oil type, which consists in sub
jecting the emulsion to the action of a demulsi 55
fying agent comprising a chemical compound of
the formula type:
-
"
'
(0H),
BHBOIHxT) n(D)n
60
(B).
u
where R is an .alkylated naphthalene nucleus, T
is a phenolic residue, D is an aldehydo linkage
derivedefrom a saturated aldehyde, and B is a
monovalent secondary amino radical, mlis a 65
small whole number such as 1, 2, 3, 4 ,or 5, and
less than 10; n is a whole number having any
value from m to m+10; p may be zero or any
whole number up to and including (11-112.); :1
may be any whole number from 1 up to and. in
70
cluding- (n-m-I-l), with the provision that in
all instances. the sum of p and. q ‘must total
'
(B),
75 where R, is an alkylated aromatic nucleus, T is
(n—,m+1).
4
.
16.v A process for breaking petroleum emulsions
of the water-in-oil type, which consists in sub 76
8
a.
‘jecting the emulsion to the action 01.’ a demulsi
fying agent comprising a chemical compound of
the formula. type:
.
(0H),
linkage derived from a‘saturated aldehyde, and
B is a monovalent secondary amino radical, m
is a small whole number such as 1, 2, 3, 4 or 5,
and less than 10; n is a whole number having any
value from m to m+10; p may be zero or any
whole number up to and including (n-—m,); q
. may be any whole number from 1 up to and in
where R is an alkylated naphthalene nucleus,
characterized by the fact that the alkyl radicals
10 contain at least 3 carbon atoms and not more
than 10, T is a phenolic residue, D is an aldehydo
cluding (n-m-i-l), with the provision that in
all instances the sum of p and q must total
(n—m+1).
10
CHARLES M. BLAIR.
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