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Патент USA US2106243

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' . _ itentqdiiap. 55, 1938 ‘
~
2,106,243
“UNITED STATES PATENT OFFICE,
2,106,243
PROCESS FOR BREAKING PETROLEUM
EMULSIONS
Melvin De Groote, St. Louis, Mo., assignor to The
'l'rct-O-Lite Company, Webster Groves, M0» a
corporation of Missouri"
‘No Drawing. Application June 21, 1937,
.
/
Serial No. 149,472
10 Claims.~ (0!. 196-4)
This invention relates to the treatment of
emulsions of mineral oil and water, such as pe
troleum emulsions, for the purpose of separating
the oil from the water.
the formation of a detergent as abietic acid it
self, and such functional derivatives are consid
ered as detergent-forming acids.
.
Reference is made to U. S. Patent #1,988,835,
.
Petroleum emulsions are of the water-in-oil to De Groote and Wirtel, dated January 22, 1935. 5
‘ type, and comprise ?ne droplets of naturally-oc
This particular patent describes a process’ for
curring waters or brines, dispersed in a more or breaking petroleum emulsions of the water-in-oil
less permanent state throughout the oil which type, which consists in subjecting the emulsion
constitutes the continuous phase of the emulsion. to the action of a demulsifying agent containing >
10 They are obtained from producing wells and from a sulfo-aliphatic ester of a fatty ‘acid of the type 10
the bottom of oil storage tanks, and are com
R".C00(T.SO3.Z), in which R" is a: fatty acid‘
monly referred to as f‘cut oil", "roily oil”, “emul
radical, C00 is a carboxyl residue, T is the
5
slfled;oil” and “bottom settlings”.
_ The/object of my invention is to provide a novel
15 and inexpensive process for separating emulsions
of the character referred to into their component’
parts of oil and water or brine.
‘
‘
,
aliphatic residue, 5031s the conventional sul
fonic acid residue, Z represents the acidic hy-'
drogen atom of thesulfonic acid or its equiva- 15
lentwand (T.SOa.Z) replaces the carboxylic hy- .
drogen.
Brie?y described, ,my process consists in sub
. Reference is also made to U. S. Patent #2,077,
jecting a petroleum emulsion of the water-in
20 011 type to the action of a treating agent or de
745, to De Groote, dated April 20, 1937. This par
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 per
25 mitted to remain in a quiescent state after treat
ment, or is subjected to other equivalent separa
Vtory procedures.
_
'
v
.
¢ The treating agent or demulsifying agent con
templated by ‘my process consists of a sulfopoly
30 hydric alcohol ester of a detergent-forming car
boxy acid, of the kind hereinafter described in
detail.
It has long been known that various organic
acids of fairly high molecular weight, combine
"35 with alkalis to produce soap or detergent-like
materials. Such acids include the higher fatty
ticular patent describes a process for breaking 20
petroleum emulsions of the water-in-oil type,
which consists in subjecting the emulsion to the
. action of a demulsifying agent of the kind in-
k _
dicated by the type formula:
R.COO.T(OH)1i(SO4.Z_)m
in which RG00 is the carboxy acid radical de
rived from a detergent-forming carboxy acid;
T(OH)» is the residue from a polyhydric al
cohol; S04 is the ‘sulfate radical; and Z is the 30
ionizable hydrogen equivalent; 1!. represents the
numeral 0, 1 or more; and m represents the
numeral 1 or more.
'
‘
Reference is also made to U. S. Patent #2,052,
284, to De Groote, dated August 25, 1936, which 7 35
describes a process for breaking petroleum emul
acids derived from animal or vegetable sources, ‘sions by the action of “a demulsifying agent com
such as oleic acid, stearic acid, palmitic acid, prising a chemical compound of the formula type‘:
rlcinoleic acid, etc. Acids derived from rosins (R1100) m.T.(OH) m, in which R.COO represents
40 such as .abietic acid represents another class. - a non-sulfo, detergent-forming, monocarboxy 4°
‘Similarly, carboxy acids derived‘ from petroleum,_ acid radical, T represents a polyhydric alcohol
such as various naphthenic acids, represent a
third class. It is also well known that these
various detergent-forming acids can be modi?ed
45 so as to produce equivalent derivatives, which
have the same. functional properties. For in
stance, chlorinated or brominated oleic acid pro
residue, and m indicates the numeral 1 or more,
and R and T being additionally characterized by
freedom from an extraneous acid residue.
I have found that certain oil ?eld emulsions 45
which, although susceptible tog-1 or more of .the
types of demulsifying agent previously described,
duces detergent-like materials, and such an acid
are even more susceptible to a reagent characmr
is- classi?ed as a detergent-forming acid. Simi
ized by being of the following type formula:
50 larly, fatty sulfonic acids, fatty acid sulfates, or
sulfa-aromatic fatty acids represent detergent
forming carboxy acids which combine with alkalis
to produce detergents or detergent-like materials.
Similarly, hydrogenated abietic acid or sulfon
55 ated abietic acid willserve as satisfactorily for
50
in which R.COO is a carboxy acid radical de
rived from a detergent-forming carboxy acid,
vT(0H)1l is a residue derived from a polyhydric
alcohol, of the kind which in unaltered form con- 55
2,106,243
a3.
tains at least three hydroxyls, n being the nu
meral 1, 2, or 3, and SO3Z being the typical sul
fonic acid radical, in which Z represents 'an
containat least three alcoholic hydroxyls. For
instance, one could prepare the monbchlorhydrin
or the dichlorhydrin from diglyc'erol, which is
ionizable hydrogen atom equivalent.
an ether alcohol, and employ such material just
Compounds of the kind contemplated for use
as demulsifying agents in the present process
may be prepared in any suitable manner. Vari
derived from glycerol. Similarly, onelcouldt pre
ous methods are known for the preparation of
soluble salts of 1:2 dihydroxy propane :3 sul~
10 fonic acid. Such material can be esteri?ed with
a mole of any suitable detergent-forming car
boxy acid, and particularly various fatty acids
or modi?ed fatty acids of the kind previously de
scribed. Another suitable procedure is to treat
15 the soluble salts of l halogen :2 hydroxy pro
pane :3 sulfonic acid with suitable fatty acid
salts or the like, so as to eliminate an inorganic
halide, such as sodium chloride.
Examples of well known procedures for pro
20 ducing reagents of the kind herein contemplated
as demulsifying agents include the following: ‘
Example 1
180 parts of the sodium salt of glycerol sulfonic
25 acid (sodium 1:2-dihydroxy propane 3-sulfonate,
prepared by heating alpha-chlorohyclrin derived
as advantageously as a corresponding compound
pare an ether alcohol from diglycerolf and -a
monohydric alcohoL-such as ethyl alcohol, and
employ such ether alcohol in place of glycerol,
provided that the compound contained at least
three alcoholic hydroxyls and provided that it
could be converted readily so as to yield amono
chlorhydrin and a dichlorhydrin. Similarly,
ether alcohols could be obtained by reaction be
tween a glycol, such as ethylene glycol, propylene
glycol, or the like, and glycerol. The ether alco
hols so obtained could be converted into a mono
chlorhydrin or a dichlorhydrin and these mate
rials employed in the manner previously de
20
scribed.
It is understood that reference to a polyhydric
alcohol or a polyhydric alcohol residue refers to
the ether type as well as the non-ether type.
Whenever it is intended torlimit the meaning to
polyhydric alcohols or polyhydric alcohol resi
dues, as differentiated from the polyhydric alco
hol ethers or polyhydric alcohol ether residues,
the expression‘ “free from an ether linkage” will
from glycerol with aqueous NazSOa solution and
subsequent removal of water) are heatedv at 150°
to 225° C. for 6 hours with stirring with 210
be employed.
droxy propane: 3-sulfonic acid (prepared by ?rst
These acids are commonly referred to as “modi~
Although it has been pointed out that the 30
30 parts of the fatty acids from cocoanut oil, the
detergent-forming carboxy acid may be supplied
water evolved in the reaction being allowed to
by a resin acid, such as abietic acid, chlorabietic
escape and the fatty acids being returned to the
acid, sulfoabetic acid, or the like, or may be fur
reacting chamber by suitable reflux condensa
nished by a petroleum carboxy acid, such as
tion. The product of this reaction is then puri
35 ?ed by washing with cold ethyl alcohol or other 'naphthenic acid, sulfonaphthenic acid, or the
low-boiling alcohol, or preferably by dissolving like, I prefer to employ detergent-forming car
boxy acids derived from fatty acids, and particu
in hot ethyl alcohol, ?ltering to remove insolu
ble inorganic salts, or other insoluble matter and larly, modi?ed fatty acids, which are nothing more
nor less than equivalent functional derivatives of
crystallizing from the acoholic solution.
a. simple unchanged fatty acid, and which still 40
Example 2
have the characteristic quality of combining with
an alkali to give a soap or soap-like detergent.
200 parts of the sodium salt of 1-chloro 2-hy
treating one mole of glycerine with two moles of
4:5 chlorine to
form CH2Cl—CHOH-—CH2C1, and
then reacting one mole of this product with one
mole of sodium sul?te to form
50 are heated at 100° to 200° C. with stirring for 5
hours with 300 parts of sodium soap prepared
from tallow. The product of the reaction may
then be puri?ed as in Example 1.
Example 3
55
materials.
Brie?y described, modi?ed fatty
acids are modi?cations of fatty acids obtained
by chemical reaction on a fatty acid or its equiva
lent, so as to result in an addition product or
A triethanolammonium (sometimes called tri
ethanolamine) compound may be formed as
follows:
290 parts of the sodium salt of commercial
60 stearic acid are heated at about 125° C., with stir
ring for 4 hours with 325 parts of the triethanol
ammonium salt of l-chloro 2-hydroxy propane
3-su1fonic acid (prepared by heating 1:3 dichloro
hydrin with triethanolammonium sul?te). The
65 product of the reaction may be puri?ed as in
Example 1.
In some instances it is more economical to
employ the dichlorhydrin as the raw material
rather than the monochlorhydrin. The reason is
70 that the dichlorhydrin can be prepared very eco
nomically by means of sulfur monochloride. See
“Systematic Organic Chemistry”,
Hopper, Wheeler, 1931, p. 335.‘
?ed fatty acids". I prefer to prepare my demul
sifying agent, which is a sulfopolyhydric alcohol
ester, from modi?ed fatty acids.
The expression “modi?ed fatty acids" is well
understood by those skilled in the art of resolv
ing petroleum emulsions of the water-in-oil type,
and has been used frequently in the patent litera
ture to designate a certain Well known class of
Cumming,
It is obvious that other polyhydroxylated ma
75 terials may replace glycerol provided that they
substitution‘ product, and they bear a simple
genetic relationship to each other or to the parent
fatty acid or fatty acid compound from which
they were derived. Modi?ed fatty acids do not
include salts of unmodi?ed fatty acids, such as (30
soaps, because a salt of a fatty acid is not an
addition product. Likewise, it is not a substitu
tion product, because “substitution products" in
the sense that such term is used. in organic chem
istry, is applied not to salts, but to undissociable
or indiiferent compounds. Furthermore, whereas
the acid hydrogen involved in salt formation can
be replaced only by metals or metal-like groups,
that is, elements or radicals which are electro
positive, substitution may replace the hydrogen
of organic compounds by a variety of elements
and groups which may be electro-negative.
The treating agent or demulsifying agent con
templated by my process includes esters of the
speci?c kind described, and may be derived from
aioacas
employed as the demulsifying agent of my
process.
I desire to point out that the superiority of
the reagent or demulsifying agent contemplated
in my process is based upon its ability to treat cer
tain emulsions more advantageously and at a
somewhat lower cost than is possible with other
available demulsi?ers, or conventional mixtures
thereof. It is believed that the particular de
10 mulsifying ‘agent or treating agent herein de
scribed will ?nd comparatively limited applica
tion, so far as the majority of oil ?eld emulsions
are concerned; but I have found that such a de
mulsifying agent has commercial value, as it will
15 economically break or resolve oil field emulsions
in a number of cases which cannot be treated as
easily or at so low a cost with the demulsifying
agents heretofore available.
In practising my process, a treating agent or
demulsifying agent of the kind described above
may be brought in contact with the emulsion to
be treated in any of the numerous ways now em
ployed in the treatment of petroleum emulsions
of the water-ln-oil type with chemical demulsi
25 fying agents, such, for example, as by intro~
ducing the treating agent into the well in which
the emulsion is produced; introducing the treat
ing agent into a conduit through which the emul
sion is ?owing; introducing the treating agent
30 into a tank in which the emulsion is stored; or
introducing the treating agent into a container
that holds a sludge obtained from the bottom of
an oil storage tank. In some instances, it may
be advisable to introduce the treating agent into
35 at producing well in such a way that it will be
come mixed with water and oil that are emerg
ing from the surrounding strata, before said
water and oil enter the barrel of the well pump
or the tubing up through which said water and
oil ?ow to the surface of the ground. After
treatment, the emulsion is allowed to stand in a
quiescent state, usually in a settling tank, and
usually at a temperature varying from atmos
pheric temperature to about 200° 0., so as to
permit the water or brine to separate from the
oil, it being preferable to keep the temperature
low enough to prevent the volatilization of val
uable constituents of the oil. If desired, the
treated emulsion may be acted upon by one or
more of the various kinds of apparatus now used
in the operation of breaking petroleum. emulsions,
such as homogenizers, hay tanks, gun barrels,
?lters, centrifuges, or electrical dehydrators.
The amount of treating agent that may be re
55 quired to break, the emulsion may vary from ap
proximately one part of treating agent to 500
parts of emulsion, up to one part of treating
agent to 20,000, or even 30,000 parts of emulsion.
The proportion depends on the type of emulsion
60
being treated, and also upon the equipment be
ing used, and the temperature employed.
In
treating exceptionally refractory emulsions of
the kinds known as “tank bottoms” and “resid
65 ual pit oils”, the ratio of 1:500, above referred to,
may be required. In treating fresh emulsion,
l. e., emulsions that will yield readily to the ac
tion of chemical demulsifying agents, the ratio
of 1:30,000, above referred to, may be su?lcient
70 to produce highly satisfactory results. In gen
eral, I have found that for an average petroleum
emulsion a ratio of one part of treating agent to
5,000 parts or 10,000 parts of emulsion will usually
be found to produce commercially satisfactory
75 results.
Having thus described my invention, what I
claim
out is:
new and desire to secure by Letters Pat—
1. A process for breaking petroleum emulsions
of the water-in-oil type, which consists in sub in
jecting the emulsion to the action of a demulsi
fying agent comprising a compound of the form
ula type:
‘
10
in which H.000 is a carboxy acid radical derived
from a detergent~forming carboxy acid; T(OH)7=
is a residue derived from a polyhydric alcohol of
the kind which in unaltered form contains at
least three hydroxyl groups; n is the numeral 1,
2 or 3; and S032; is the typical sulfonic acid radi
cal in which Z represents an ionizable hydrogen
atom equivalent.
2. A process for breaking petroleum emulsions
of the water~in~oil type, which consists in sub 20
jecting the emulsion to the action of a demuisi
fying agent comprising a compound of the for
mula
25
in w‘.ich RG00
a carboxy acid radical de
rived ircm a rosin acid; ‘ITOHM is a residue tie
rived from a polyhydric alcohol of the kind
which in unaltered form contains at least three
hydroxyl groups; n is the numeral 1, 2 or 3; and
S032 is the typical sulfonic acid radical in which
Z represents an ionizable hydrogen atom equiv
alent.
3. A process for breaking petroleum emulsions
of the water~in-oil type, which consists in sub 35
jecting the emulsion to the action of a demulsi~
lying agent comprising a compound oi.’ the for
mula type:
‘
RCOQIJKOH) 1&(3032)
in which H.600 is a carboxy acid radical derived 40
from a petroleum acid; T<OH>n is a residue de
rived from a polyhydric alcohol of the kind which
in unaltered form contains at least three hy
droxyl groups; n is the numeral 1, 2 or 3; and
S032 is the typical. sulfonic acid radical in which 45
Z represents an ionizable hydrogen atom equiva
lent.
4. A process for breaking petroleum emulsions
of the water~in~oil type, which consists in sub
jecting t-
emulsion to the action of a demulsify
50
ing agent ccunprising a compound of the formula
type:
HJFJOO.T(OH) 12(8032)
in which. H.600 is a carlooxy acid radical de 55
rived from a higher fatty acid; T<OH)n is a resi
due derived from a polyhydric' alcohol of the kind
.Which in unaltered form contains at least three
hydroxyl groups; n is the numeral 1, 2 or 3; and
S032 is the ‘typical sulfonic acid radical in which
Z represents an icnizable hydrogen atom equiva
lent.
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 demulsi 65
fying agent comprising a compound of the for
mula type:
in which 13.000 is a carboxy acid radical derived 70
from a higherfatty acid; T(OH)n is a residue,
free from an ether linkage, and derived from a
polyhydric alcohol of the kind which in unaltered
form contains at least three hydroxyl groups: n
is the numeral 1, 2 or 3; and S032 is the typical
5
2,106,248
ionizable hydrogen atom equivalent.
ing agent comprising a compound of the for
mula type:
6. A process for breaking petroleum emulsions
of the waterl-in-oil type, which consists in sub
in which R.COO is a carboxy acid radical de
sulfonic acid radical in which Z‘represents an
a jecting the emulsion to the action of a demulsi
fying agent comprising a compound of the for
mula type:
R.COO.T(OH) "($032)
in which R.COO is a carboxy‘acid radical de
10
rived from a higher fatty acid; T(-0H)n is the
bivalent radical CaH5OH; and SOaZ is the typical
sulfonic‘ acid radical in which Z represents an
‘ionizable hydrogen atom equivalent.
7. A process for breaking petroleum emulsions
voi’ the water-in-oil type, which consists in sub
jecting the emulsion to the action of a demulsify
ing agent comprising a compound of the formula
'
type:
R.COO.T(OH)1.(SO3Z)
20
in which R.COO is a carboxy acid radical de-'
J rived from a hydroxylated higher fatty acid;
T(0H)n is the bivalent radical CaHsOI-I; and
SOaZ is the typical sulfonic acid radical in which
25 Z represents an ionizable hydrogen atom equiva
lent.
»
8. A process for breaking petroleum emulsions
of the water-in-oil type, which consists in sub
jecting the emulsion to the action oi’ a demulsii'y
R.CO0.T (OH) MSOaZ)
rived from a hydroxylated higher fatty acid;
T(O.H)n is the bivalent radical CaHsOH; and
SOaZ is the typical sulfonic acid radical in which
Z represents a metallic atom.
9. A process for breaking petroleum emulsions
of the water-in-oil type, which consists in sub
jecting the emulsion to the action of a demulsii’y
ing agent of the water-soluble type comprising a
compound of the formula type:
15
in which R.COO is a carboxy acid radical de
rived from a hydroxylated higher fatty acid;
T(OH)11 is the bivalent radical CsHsOH; and
S032 is the typical sulfonic acid radical in which
20
Z represents a metallic atom.
10. 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
ing agent comprising a compound of the formula
type:
OH.C3H5.CmHrizOI-IQOOSOaNa
MELVIN DE GROO'I'E.
25
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