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Патент USA US3056758

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1
3,056,748
Patented Oct. 2, 1962
2
molecular weight polycarboxy acid having at least eight
3,056,748
carbons;
PROCESS FOR BREAKING PETROLEUIVI OIL
EMULSIONS WITH COMPLEX POLYESTER
CONDENSATION PRODUCTS
(d) 15-60% of an ethylene oxide adduct of an alkali
insoluble, organic-solvent-soluble alkyl phenol-formal
Earl Theodore Kocher, Lakewood, Calif., assignor to 5
Nalco Chemical Company, a corporation of Delaware
No Drawing. Filed Apr. 8, 1958, Ser. No. 727,056
10 Claims. (Cl. 252-342)
dehyde condensation product having about 4 to 15
phenolic nuclei, said alkyl group having 5-15 carbons,
inclusive, said condensation product being oxyethyl
ated at a weight ratio of ethylene oxide to condensation
product of about 2:3 to 9:1, respectively; and
This invention, in general, relates to new compositions 10 (e) 15-60% of an oxyalkylated, alkali-insoluble, organic
of matter and their use in the treatment of water-in
solvent-soluble phenol-formaldehyde condensation prod
petroleum oil emulsions, such as petroleum emulsions
commonly encountered in the production, handling and
re?ning of crude mineral oil.
clei, the alkyl group having between 5 and 15 carbons,
uct of a monoalkyl phenol having 4-15 phenolic nu
Petroleum emulsions are, in general, of the water-hr 15
oil type wherein oil acts as the continuous phase for dis
persal of the ?nely-divided particles of naturally occur
ring waters or brines.
These emulsions are often ex
inclusive, the weight ratio of alkylene oxide to con
densation product falling between about 2:3 and 9:1,
respectively, the phenol-formaldehyde condensation
product being oxyalkylated with both ethylene oxide
and propylene oxide, the weight ratio of propylene
tremely stable and will not resolve into the oil and Water
oxide to ethylene oxide being in the range of 1:9 to 9: 1.
components even on long standing. The emulsions ob 20
The foregoing condensation products are prepared by
tained from producing wells and from the bottom of
heating in a process kettle a mixture of the components
crude oil storage tanks are commonly referred to as “cut
(a) to (e) to a temperature in the range of 400° to 550°
oil,” “emulsi?ed oil,” “bottom settlings” and “B.S.” It
F.,
in an inert organic solvent such as S02 extract. The
is also to be understood that water-in-oil emulsions may
reaction is essentially one of esteri?cation between the
occur arti?cially, resulting from any one or more of 25
free carboxy groups and the free hydroxyl groups in the
numerous operations encountered in various industries.
oxyalkylene chains. The water of reaction is distilled off
The emulsion breaking chemicals of this invention are
and collected. The reaction is stopped short of the for
particularly effective in demulsi?cation of certain low
mation of insoluble gelatinous resins, and the solutions of
gravity crudes and have proved to Work effectively on
vexacious low gravity, high viscosity crudes upon which 30 the polyesters herein contemplated may range from vis
cosities of 100 or slightly less to several thousand centi
a relatively large number of demulsi?ers proved to be in
poises.
effective at economical dosages.
(a) Dicarboxy acid esters of oxyethylated polyoxypro
One type of process involves subjection emulsions of
pylene
glycoL-In practicing the invention, an intermedi
the Water-in-oil type to the action of a demulsifying agent
ate composition comprising the esters of a dicarboxy acid
of the kind hereinafter described, thereby causing the
and the terminally oxyethylated polyoxypropylene glycol,
emulsion to resolve and stratify into its component parts
of oil and water or brine after emulsion has been allowed
to stand in a relatively quiescent state.
One object of the invention is to provide novel and
economical e?ective processes for resolving emulsions of
the character referred to into their component parts of
the resulting ester having free carboxy groups, is ?rst pre
pared by heating in an inert solvent such as S02 extract
between 250° F. and 500° F. a dicarboxy acid and the
oxyethylated polyoxypropylene glycol to form the partial
ester. The water of reaction is distilled off and removed
from the reaction zone. “Partial ester” is intended to
oil and water or brine.
mean an ester of the dicarboxylic acid in which some of
Another object is to provide novel chemicals which are
surface-active in order to enable their use as demulsi?ers
or for such uses Where surface-active characteristics are 4
necessary or desirable.
Another object is to provide novel processes for re
solving naturally occurring water-in-oil emulsions in low
gravity, high viscosity crudes into their component parts
of oil and water. Other objects will appear hereinafter.
In accordance with the invention, the demulsifying
chemicals are complex compounds prepared by esteri?
cation of mono- and polycarboxylic acids With polyhy
droxy organic polymers. They are condensation reaction
products of the following compounds, the percentage
indicated being calculated on a Weight basis and totaling
the carboxy groups of the dicarboxylic acid remain un
reacted and thus remain as free carboxy groups. This is
‘accomplished by reacting at least one mol, preferably at
least 1.5 mols, of the dicarboxy acid per mol of the oxy
ethylated polyoxypropylene glycol and usually not greater
than about two mols. The preparation of this intermedi
0 ate ester is essential in the practice of the invention. If
the dicarboxy acid and the oxyethylated polyoxypropyl
ene glycol are charged without ?rst esterifying the two
chemicals into a reaction mixture with the remaining com
ponents, the products are rubbery gels unsuitable for pur
5 poses of this invention.
The esteri?cation process described above is continued
100%:
until at least one mol of water of reaction is liberated. A
(a) 4—60% of a partial ester of a dicarboxylic acid and
esteri?cation is to collect and measure the Water distilled
convenient way to determine the termination point for the
a terminally oxyethylated polyoxypropylene glycol, the 60 from the reaction mixture. By taking into account any
polyoxypropylene glycol nucleus having a molecular
water introduced in the reactant chemicals, the degree of
Weight in the range of 1,000 to 4,500, the ethylene
esteri?cation can be reasonably accurately determined by
oxide being adducted on said polyoxypropylene glycol
the amount of water formed in the reaction and collected
in amounts in the range of 1 to 12 mols of ethylene
upon distillation.
oxide per mol of polyoxypropylene glycol, the partial 6
The intermediate partial esters are preferably products
ester resulting from esteri?cation of l to 2 mols of di
which are substantially entirely dicarboxylic acid diesters
carboxylic acid per mol of the oxyethylated polyoxy
of the dihydric oxyethylated polyoxypropylene glycol.
propylene glycol;
_ (b) 6~36% of a monocarboxylic acid having at least six
carbons, preferably a monocarboxylic fatty acid having
11-18 carbons;
(a) 41-24% of a polycarboxy acid, preferably a higher
They, however, may contain substantial quantities of
polyesters of the two reactants of low orders of conden
sation and in many instances the intermediate ester may
consist of both the diesters and polyesters of a low order
of condensation. The formation of diesters is favored
3,056,748
3
.
as the ratio of the mols of the dicarboxy acid per mol of
oxyethylated polypropylene glycol increases. It is par
ticularly favored where the dicarboxy acid is at least two
mols per mol of glycol or where the dicarboxy acid is
present in excess, such as a mol ratio of 3: 1.
4
oil acids of the linoleic acid series, including, for example,
the polymers of sorbic acid, geranic acid, palmitolic acid,
linoleic acid and humoceric acid.
It will be understood
that these polymers may include cogeneric mixtures of
polycarboxy acids.
A number of these polymer acids are available as by—
product materials. Thus, one source of the polymeric
acids suitable for the purposes of this invention is the
least about one free carboxy group per mol of dicarboxy
still residue of the dry distillation of castor oil in the
acid esteri?ed, and, in the most preferred form of the
invention, the intermediate product will consist essen 10 presence of sodium hydroxide. VR~1 acid is an acid of
In other words, the intermediate should have a sub
stantial quantity of free carboxy groups-preferably at
tially of the dicarboxylic acid diester of oxyethylated poly
oxypropylene glycol, which may be illustrated by the fol
lowing formula:
this type.
VR-l acid is a mixture of polybasic acids, with an
average molecular weight of about 1,000. It has an
average of slightly more than two carboxylic acid groups
15 per molecule. It is a by-product acid, and is a dark
amber, rather viscous liquid. A typical sample of VR-l
wherein R is a bivalent organic radical, either aliphatic
acid gave the following analysis:
or aromatic, of the dicarboxy acid and R1 is the oxyethyl
ated polyoxypropylene glycol nucleus. In all probability,
Acid number ______________________________ __
150
the most preferred intermediate product will also contain
Iodine number ___________ __.. _______________ __
36
minor amounts of polycondensates of a low order, which 20 Saponi?cation number ______________________ __ 172
polycondensates may be illustrated by the following for
Unsaponi?able matter, percent _______________ __
3.7
mula:
Moisture content, percent ___________________ __
0.86
Alternatively, there may be used a commercial prod
wherein R and R1 have the signi?cance indicated above, 25 uct containing both the monocarboxylic acidv and the di
carboxylic acid. An example of a product containing
and n is a small integer.
both the monocarboxylic acid and the polycarboxy acids
The acids used to prepare the above described inter
is a product marketed by the Hardesty Division of Wal
mediate ester are relatively low molecular weight acids
lace & Tiernan under the name Roleic Acid. Roleic Acid
such as phthalic acid, diglycolic acid, tartaric acid, maleic
acid, malic acid, and like dicarboxy acids not exceeding 30 is reported to comprise about 60% by weight of mono
basic acids, chie?y myristic and oleic acids, and 40% by
eight carbons and in the case of the aliphatic acids, pref
weight of polybasic acids, principally fatty dimer acids.
erably not exceeding six carbons. In this instance, my
purpose is to use the shorter chain aliphatic or simple
The product has a titer of 24° to 28° C., an iodine value
of 40-50, free fatty acid value, as oleic acid, of 100-105,
aromatic dicarboxy acids to avoid reduction of the hydro
philic portions of the ultimate complex molecules by in 35 an acid number of 201—210, and less than 1% unsaponi
?ables.
creasing the hydrophilic portions too greatly by the. use
(d) Ethylene oxide adducts of phenol-formaldehyde
of long chain dicarboxy acids such as dilinoleic acid, etc.
resins.—-The phenol-formaldehyde resins are the alkali
(b) Monocarboxylic acids.—Turning now to the mono
insoluble, organic-solvent-soluble reaction products of
carboxylic acids used as one of the reactants, these acids
are used to control the degree of condensation of the 40 formaldehyde with a monoalkyl phenol, the alkyl group
ultimate, complex polyester condensate and also to pro
vide hydrophobic or lipophilic portions to the complex
molecule. They may be aliphatic acids such as caproic
having between 5-15 carbons inclusive. Dialkyl phenols
are not suitable for compositions of this invention, but
amounts up to 25% dialkyl phenol in the monoalkyl
phenol reactant may be tolerated. The weight ratio of
45 ethylene oxide to the phenol-formaldehyde condensation
product will, for most applications, fall between about
2:3 and 9:1, respectively, preferably the range of 2:3 to
linolenic acid, arachidic acid, behenic acid or mixtures
2:1. It is also possible to use in a similar manner in
thereof; resin acids such as abietic acid and the like; or
this intermediate product, instead of solely ethylene oxide,
aryl monocarboxylic acids such as naphthenic acid, or
even mixtures of these classes of acids such as the mixture 50 both propylene oxide and ethylene oxide wherein the
oxides are added sequentially—the 1,2-propylene oxide
of fatty acids and resin acids in tall oil. In most in
being added to the resin ?rst and the ethylene oxide being
stances, monocarboxylic acids having 11-24 carbons are
added to the oxypropylene groups. The ethylene oxide
preferred.
will be at least 1 part by weight per 40 parts of propylene
(0) Polycarboxy acids.—-The polycarboxy acids em
oxide adducted.
ployed as one of the reactants also contribute hydrophobic
In this manner, the terminal oxyalkylation groups are
portions to the ultimate, complex molecule. To this end,
those of oXyethylene, which have primary hydroxyl
the polycarboxy acids should have at least eight carbons.
groups. Primary hydroxyl groups are easier to esterify
They may be such polycarboxy acids as suberic acid,
than secondary hydroxyl groups resulting from 1,2-prop
azelaic acid, or polycarboxy polymer acids such as those
obtained as by-products or those obtained by polymeriz 60 ylene oxide.
ing a drying oil monocarboxylic acid in dimerized and
Phenol-Formaldehyde Condensation
acid, caprylic acid, capric acid, 2-ethyl hexanoic acid,
lauric acid, myristic acid, myristoleic acid, palmitic acid,
palmitoleic acid, stearic acid, oleic acid, linoleic acid,
trimerized form.
Examples of such polymerized acids
The phenol-formaldehyde condensation products are
prepared by reacting formaldehyde or a substance which
Emery dimer acid is essentially dilinoleic acid and is
a polymer made by polymerizing an unsaturated fatty 65 breaks down to formaldehyde under the reaction condi
tions, e.g., paraformaldehyde and trioxane, and a mono
acid containing at least two nonconjugated double bonds.
alkyl phenol, preferably crude alkylated phenol for eco
Such acids may also be described as polymerized drying
nomic reasons, by heating the reactants in the presence
oil acids. The term “drying oil acid” is used herein to
are Emery’s dimer acid and VR-l acid.
of a small amount of an acid catalyst such as sulfamic
mean an unsaturated monocarboxylic fatty acid contain
ing at least two double bonds and at least six carbon 70 acid or hydrochloric acid under substantially anhydrous
conditions—excepting the water produced during the reac~
atoms. The polymer acids employed for the purpose of
tion. The aqueous distillate which begins to form is col
the invention preferably consist predominantly of dimer
lected and removed from the reaction mixture. After
acids but may contain trimers and higher polymers. The
several hours of heating at temperatures slightly above
preferred polymer acids are those containing 12 to 40
carbon atoms and especially the polymers of the drying 75 the boiling point of water, the mass becomes viscous and
3,056,748
5
6
is permitted to cool to about 100° to 105° C. At this
used in place of sulfamic acid are mineral acids such as
point a suitable hydrocarbon fraction is added, and heat
ing is resumed. ‘Further aqueous distillate begins to
sulfuric acid, hydrochloric acid, phosphoric acid, etc.
The preparation of a phenol-formaldehyde resin where
in the catalyst is hydrochloric acid is illustrated in the
form and heating is continued for an additional number
of hours until at least about one mol of aqueous distillate
per mol of reactants has been secured. The product is
permitted to cool to yield the phenol-formaldehyde con
densation product in a hydrocarbon solvent. The molec~
following example.
EXAMPLE D
Six thousand parts of the crude alkylated phenol of
Example A, 900 parts of paraformaldehyde, and 45
ular weight of these intermediate condensation products
cannot be ascertained with certainty, but we would‘ ap
10 parts of 35% hydrochloric acid are heated to 65 to 70°
proximate that the resins employed herein should contain
‘about 4 to 15, preferably 4 to 10, phenolic nuclei per
resin molecule. The solubility of the condensation prod
uct in hydrocarbon solvent would indicate that the resin
is a linear type polymer, thus distinguishing them from 15
the more common phenol-formaldehyde resins of the
cross linked type.
C. ‘without external heating.
The reaction mixture is held at 95 to 100° C. for three
hours. The temperature is slowly raised to about 115°
C., at which point 2400 parts of S02 extract are added.
The heating is continued slowly until a temperature of
210° C. is reached. The product is then cooled to yield
This aspect of the invention is illustrated in the follow
ing examples but is not limited thereto. The parts are
by weight.
C. The heating is reduced, and a temperature of 100°
C. is approached slowly because the exothermic reac
tion may be su?icient to raise the temperature to 100°
20 the phenol-formaldehyde resin solution.
EXAMPLE A
In a three-necked reaction ?ask provided with means
of mechanical stirring anda return condenser ‘system
permitting the removal of any aqueous phase formed in 25
the course of reaction, there is added 1500 parts of a
crude alkylate phenol which comprises an undistilled
nonyl phenol containing approximately 10% of dinonyl
phenol, 225 parts paraformaldehyde and 3 parts sulfamic
acid which is present at a catalyst in the reaction. The 30
reaction mass is heated, and at 108° C. an aqueous distil
late begins to form. After three hours heating at approxi
As stated heretofore, intermediate phenol-formalde
hyde resin should contain a minimum of about 4 phenolic
nuclei and should not exceed about 15 phenolic nuclei.
It is extremely dif?cult, if not impossible, to accurately
determine the molecular weight of the intermediate resin
products. However, it is believed that the resin of
Example A contains about 10 phenolic nuclei per resin
molecule, Example B, about 7 phenolic nuclei, and Ex
ample C, about 4 phenolic nuclei per resin molecule.
Oxyalkylation of the Condensation Products
Having prepared the intermediate phenol-formalde
mately 110° C. the mass becomes quite viscous and is
hyde products, the next step is the oxyalkylation of the
permitted to cool to about 100° C. At this point 600
condensation products. This is achieved by mixing the
parts of S02 extract is added, and heating is resumed.
intermediate phenol-formaldehyde condensation product
Again at 110° C. further aqueous distillate begins to
in a hydrocarbon solvent with a small amount of sodium
form, and heating is continued for an additional three
hydroxide in an autoclave. The condensation product is
hours, or until approximately 141 parts of aqueous dis
heated above 100° C., and ethylene oxide, or ?rst the
tillate has been secured at a maximum temperature of
propylene oxide until it is completely reacted and then
212° C. The product is permitted to ‘cool to yield the fin 40 the ethylene oxide, is charged into the autoclave until
ished phenol-formaldehyde resin solution in hydrocarbon
solvent.
the pressure is in the vicinity of 75 to 100 psi.
The reaction mixture is gradually heated until an exo
thermic reaction begins.
The external heating is then
EXAMPLE B
removed and alkylene oxide is added as such a rate that
In a manner similar to Example A, 1000 parts of the 45 the temperature is maintained between about 150 to 160°
C. in a pressure range of 80 to 100 psi. After all of
crude alkylate phenol, 120 parts of paraformaldehyde
the alkylene oxide has been added, the temperature is
and 2 parts sulfamic acid are heated 2 hours at 105 to
maintained for an additional 10 to 20 minutes to assure
110° C. to permit reaction of the phenol and formalde
hyde under conditions minimizing formaldehyde loss.
substantially complete reaction of the alkylene oxide.
At temperatures above 110° C. vigorous reaction sets 50 The resulting product is the alkylene oxide adduct of an
alkyl phenol-formaldehyde condensation product, in
in which must be controlled by cooling. After about
which the weight ratio of the oxide to the condensation
27 parts of aqueous distillate have been secured, the reac
product is between about 2:3 and 9:1, respectively, or
tion comes under control and becomes exceedingly vis
even slightly higher. The molecular weight of the oxy
cous. At this point the resin is cooled to 105° C., and
alkylated phenol~formaldehyde condensation products
400 parts of S02 extract are added. Heating is continued
of this invention range from as low as about 1100 to as
for an additional three hours, or until a total of about 75
high as about 50,000.
parts of aqueous distillate have been removed at max
imum temperature of 212° C. to yield the ?nished phenol
formaldehyde resin solution in hydrocarbon solvent.
Some preferred embodiments of the oxyalkylated,
alkyl phenol-formaldehyde condensation products and
60 methods of their preparation are illustrated in the follow
EXAMPLE C
ing examples wherein all parts are by Weight unless other
wise stated, but the invention is not limited thereto.
In a manner similar to Examples A and B, 1000 parts
of the crude alkylate phenol, 90 par-ts paraformaldehyde
EXAMPLE E
and 2 parts sulfamic acid are carefully reacted at tem 65
In an autoclave having a two-liter capacity equipped
peratures of 100 to 110° C. When the reaction mass
with a means of external electric heating, internal cooling
becomes quite viscous, the reaction is permitted to cool,
coils and mechanical agitation, there is charged 950 parts
of the resin solution of Example A, and 1.5‘ parts of
sodium hydroxide. Into a transfer bomb there is intro
duced 575 parts ethylene oxide. The resin is heated to
temperature of 213° C. to yield the ?nished phenol
135° C., and the ethylene oxide is charged into the reac
formaldehyde resin solution in hydrocarbon solvent.
tor until reactor pressure is 80 psi. The reaction mix
In the preceding examples, sulfamic acid has been
ture is gradually heated until an exothermic rection be
used as the acid catalyst to assist in the condensation
gins to take place. The external heating is then removed
reaction. Other suitable equivalent acids which may be 75 and ethylene oxide is then added at such a rate that the
and 400 parts of S02 extract are added. Heating is re
sumed for an additional hour, or until a total of 55 parts
of aqueous distillate have been secured at maximum
3,056,748
E
7
manner as the resins described in the previous section,
and reference is made thereto.
The weight ratio of alkylene oxide to the phenol
formaldehyde condensation product will, for most ap
temperature is maintained between 150 to 160° C. with
a pressure range of 80 to 100 p.s.i. After approximately
two hours all of the oxide has been added to the auto
clave, and the temperature is maintained for an additional
15 ‘minutes to make certain that the unreacted oxide is
reduced to a minimum. The resulting product is the
plications, fall between about 2:3 and 9: 1, or even slightly
higher, respectively. The alkylene oxides are ethylene
oxide and propylene oxide and are added as mixtures.
ethylene oxide adduct of a phenol-formaldehyde resin,
The weight ratio of ethylene oxide to propylene oxide
in which the weight ratio of oxide to resin by Weight is
ranges from 4:1 to 1:4.
2 to 3. The oxyalkylated phenol-formaldehyde condensa
The oxyalkylation of the phenol-formaldehyde con
tion product had a hydroxyl equivalent weight of about 10
densation products is achieved by mixing the intermedi
620 and contained about ten oxyalkylene chains per resin
ate phenol-formaldehyde condensation product in a hy
molecule.
drocarbon solvent with a small amount of sodium hy
EXAMPLE F
droxide in an autoclave. The condensation product is
In a manner similar to Example E, the ethylene oxide 15 heated above 100° C., and a mixture of ethylene oxide
and propylene oxide is charged into the autoclave until
adduct of the resin of Example B was prepared in which
the pressure is in the vicinity of 75 to 100 p.s.i.
the ratio of ethylene oxide to resin was 1% to 1 by
The reaction mixture is gradually heated until an ex
weight. The oxyalkylated phenol-formaldehyde con
othermic reaction begins. The external heating is then
densation product had a hydroxyl equivalent weight of
about 840 and contained about four oxya‘lkylene chains 20 removed, and alkylene oxide mixture is added at such a
rate that the temperature is maintained between about
per resin molecule.
150 to 160° C. in a pressure range of 80 to 100 p.s.i.
EXAMPLE G
After all of the alky'lene oxide mixture has been added,
In a manner similar to Example E there is prepared a
the temperature is maintained for an additional 10 to
propylene oxide adduct of the resin of Example A in 25 20 minutes to assure substantially complete reaction of
the alkylene oxide. The resulting product is the mixed
alkylene oxide adduct of an alkyl phenol-formaldehyde
condensation product, in which the weight ratio of the
which the ratio of propylene oxide to resin by weight is
1 to 1. The oxypropylated phenol-formaldehyde resin
was then reacted further with ethylene oxide until the
oxide to the condensation product is between about 2:3
?nished product contained 10% by weight of ethylene
oxide. The oxyalklylated phenol-formaldehyde condensa 30 and 9: 1, respectively, or even slightly higher. The molecu
tion product had a hydroxyl equivalent weight of about
lar weight of the oxyalkylated phenol-formaldehyde con
750 and contained about ten oxyalkylene chains per resin
molecule.
densation products of this invention range from as low as
about 1100 to as high as about 50,000.
Some preferred embodiments of the oxyalkylated, alkyl
EXAMPLE H
35 phenol-formaldehyde condensation products and methods
of their preparation are illustrated in the following exam
In a manner similar to Example G a propylene oxide
ples wherein all parts are by weight unless otherwise
adduct of the resin of Example C was prepared in which
stated, but the invention is not limited thereto.
the ratio of propylene oxide to resin was 6 to 1 by
weight. Ethylene oxide was then added to this oxy
EXAMPLE L
propylated phenol-formaldehyde resin until the ?nished 40
In
an
autoclave
having
a two-liter capacity equipped
product contained 20% by Weight of ethylene oxide. The
with means of external electrical heating, internal cool
oxyalkylated phenol-formaldehyde condensation product
ing coils and mechanical agitation, there is charged 18
had a hydroxyl equivalent weight of about 1200 and
parts
of the resin solution of Example B and 1.5 parts
contained about four oxyalkylene chains per resin mole
of sodium hydroxide. Into a transfer bomb there is
cule.
introduced 23 parts of mixed oxides prepared by mixing
equal parts of ethylene and propylene oxide by weight.
EXAMPLE I
The intermediate is heated to 135° C. and the oxide mix
ture is charged into the reactor until reactor pressure is
In a manner similar to Example G a propylene oxide
adduct of the resin of Example A was prepared in which 50 80 p.s.i. The reaction mixutre is gradually heated until
the ratio of propylene oxide to resin was 9 to 1 by weight.
an exothermic reaction begins to take place. The external
This oxypropylated phenol-formaldehyde resin was then
heating is removed and the mixed oxides are then added
further reacted with ethylene oxide until the ?nished
at such a rate that the temperature is maintained between
material contained 5% by weight of ethylene oxide. The
150 to 160° C. with a pressure range of 80 to 100 p.s.i.
oxyalkylated phenol-formaldehyde condensation product
At various stages in the reaction small samples of the
had a hydroxyl equivalent weight of about 1400 and con
reaction product were removed. After approximately 2
tained about ten oxyalkylene chains per resin molecule.
hours all of the oxide has been added to the autoclave
and the temperature is maintained for an additional period
EXAMPLE K
of time so that the reactor pressure drops to a constant
In a manner similar to Example G a propylene oxide 60 value. This may require from 15 minutes to 2 hours to
adduct of the resin of Example C was prepared in which
make certain that the unreacted oxide is reduced to a
minimum. The resultant product is the mixed oxide
the ratio of propylene oxide to resin was 2 to 1 by weight.
This oxypropylated phenol-formaldehyde resin was then
adduct of a phenol-formaldehyde resin in which the
ratio of oxide to resin by weight is 4 to 1.
further reacted with ethylene oxide until the ?nished
material contained 30% by weight of ethylene oxide. The
oxyalkylated phenol-formaldehyde condensation prod
uct had a hydroxyl equivalent weight of about 1200 and
contained about four oxyalkylene chains per resin mole
65
EXAMPLE M
In a manner similar to Example L a mixed oxide ad
duct of the resin of Example A was prepared in which
the ratio of ethylene oxide to propylene oxide was 1 part
cule.
Mixed Alkylene Oxide Adducts of Organic-Solvent-Soluble 70 to 2 parts. The ?nished product is an oxyalkylated resin
in which the ratio of mixed oxides to resin is 4 to 1.
Phenol-Formaldehyde Resins
EXAMPLE N
The phenol-formaldehyde resins in the intermediate
products constituting mixed oxyethylated and oxypropylat
In the same facilities as used in Example L, there is
ed phenol-formaldehyde resins are prepared in the same 75 charged 172 parts of the resin solution of Example A and
3,056,748
10
1 part of sodium hydroxide. Into a transfer bomb there
useful as demulsi?ers. Unless otherwise-indicated, the
is introduced 250 parts by weight of ethylene oxide
parts are by weight.
and 250 parts of propylene oxide. The intermediate is
EXAMPLE 1
heated to 135° C. and the mixed oxides are charged into
the reactor until the reactor pressure is 80 p.s.i. The re 5
Nine thousand pounds of a terminally oxethylated
action conditions from here on were identical with those
polyoxypropyleene glycol (6 mols ethylene oxide per
employed in Example L. The resulting product is the
mixed oxide adduct of a phenol-formaldehyde resin in
which the ratio of oxide to resin by weight is approxi
mately 4 to 1.
10
EXAMPLE 0
In a manner similar to Example ‘N, using a 1 to 1 by
weight ratio of ethylene oxide and propylene oxide, a
mixed oxide adduct of the resin of Example C Was pre
pared in which the ratio of oxide to resin was 6 to 1.
EXAMPLE P
In a manner similar to Example N, using ‘a 1 to 3 by
weight ratio of ethylene oxide to propylene oxide, a 20
mixed oxide adduct of the resin of Example C was pre
pared in which the ratio of oxide to resin was 6 to 1.
mol of polyoxypropylene glycol, the latter having a mole~
cular weight of about 2700) and 220 gallons of S02 ex
tract are charged into a process kettle equipped with a
stirrer and heated to 300° F. Then, the 1200 pounds of
diglycolic acid are added. The mixture is heated slowly
and uniformly, and the water of reaction is distilled 0E
and collected until 18 gallons of water have been dis
tilled off. This requires about four hours. The ?nal
temperature rises to about 500° F. The mixture is then
cooled, and 220 gallons of S02 extract are added. The
product is then drummed without delay.
Two drums (about 900 lbs.) of the foregoing prod
uct, 1400 pounds of roleic acid, described supra, 1800
pounds of the product of Example E, 1800 pounds of
the product of Example S, and 330 gallons of S02 ex
tract are charged into a process kettle.
The mixture
is heated slowly with the distillation of water until 12
gallons of water have been distilled off. This takes about
In a manner similar to Example N, using a 1 to 3
?ve hours, and the ?nal temperature is in the range of
by weight ratio of ethylene oxide to propylene oxide, 25 480° to 500° F. The product becomes viscous toward
a mixed oxide adduct of the resin of Example B was
the end of the reaction, and care is exercised to avoid
prepared in which the ratio of oxide to resin was 2 to 1.
gelation.
When twelve gallons of water have distilled off, the
EXAMPLE R
30 product is cooled quickly by dropping it into a thinning
kettle, and 330 gallons of S02 extract are added. The
In a manner similar to Example N, using a 3 to 1
Warm product is pumped to storage and allowed to settle
by weight of ethylene oxide to propylene oxide, a mixed
while cooling.
oxide adduct of the resin of Example A was prepared
in which the ratio of oxide to resin was 1 to 1.
FURTHER EXAMPLES
EXAMPLE Q
EXAMPLE S
In an autoclave equipped with external heating means,
internal cooling coils and a mechanical agitator, there
is charged 1750 parts of the resin solution of Example
Other examples of compositions contemplated by this
invention and their preparation are outlined in the fol
lowing table. The preparatory technique of Example 1
was followed in each instance, and the parts are reported
on a weight basis:
D and 7 parts of ?ake caustic. Into a charge vessel are
pumped 3500 parts of ethylene oxide and 3500 parts
of propylene oxide, which are intimately mixed by re
circulating the oxirane gases through a recirculating pump
for two hours. The autoclave is purged with natural
gas, and heating is begun. At 140° C., the mixed oxides 45
are added until the pressure reaches 40 p.s.i. The addi
tion is stopped at this point, and as the mixture is grad
ually heated, an exothermic reaction begins. The ex
Parts in Formulation
Components
Example
2
3
4
5
6
7
8
9
Composition A ____ __
Crude Roleic AcicL _
150
50
I00
100
100
100
100
100
50
150
50
150
20
200
20
200
Example E ________ __
Example S . __
__
S02 extract ________ __
oxides are added at a rate to maintain the temperature 50 Aqueous distillate___
150
150
200
225
75
200
150
150
200
75
225
200
75
225
200
150
150
200
150
150
200
180
120
200
5. 2
8. 0
7. 6
7. 8
6.0
6.2
6.4
7. 0
between 150° and 160° C. When all of the mixed oxides
have been added to the autoclave, the contents of the
tillation, ° C ____ __
196
164
163
187
192
197
188
190
Final temp., ° O____
Reaction time, hrs_ _
245
4
255
4%
253
4%
262
4%
246
5
257
5
261
4
261
4
ternal heating is discontinued, and the remaining mixed
autoclave are recycled for two hours at 150° to 160° C.
Initial temp. of dis
S02 extract added
The product is then cooled. The resultant product is
at end of reaction.. 200
150
150
150
150
200
150 150
the mixed oxide adduct of a phenol-formaldehyde resin 55
in which the ratio of oxide to resin by weight is 4:1.
Composition A in the above table is the diglycolic acid
The hydrocarbon fraction in the foregoing examples
ester of the oxyethylated polyoxypropylene glycol de
is sulfur dioxide extract. This material is a by-product
scribed in Example 1.
from the Edeleanu process of re?ning petroleum in which
Demulsi?cation
the undesirable fractions are removed by extraction with 60
liquid sulfur dioxide. After removal of the sulfur di
The compositions of this invention are surface-active
oxide a mixture of hydrocarbons is substantially aro
and are particularly suitable for demulsi?cation of crude
matic in character, remains and is designated in the trade
oil emulsions. Demulsi?cation is achieved by mixing
as sulfur dioxide extract or S02 extract. Examples of
the demulsifying chemicals of this invention with the
other suitable hydrocarbon vehicles are toluene, xylene, 65 crude oil emulsion at a Weight ratio of one part of the
gas oil, diesel fuel, bunker fuel and coal tar solvents.
active chemical to 1000 to 50,000 parts of the emulsion,
The above cited examples of solvents are adaptable to
and thereafter allowing the emulsion to remain in a rela-v
azeotropic distillation as would also be any other solvent
tively quiescent state during which separation of the
which is immiscible with water, miscible with the react
water or brine and oil occurs. While the invention herein
ing mass and has a boiling point or boiling range in 70 disclosed is not limited thereto, the demulsi?ers of this
excess of the boiling point of water.
invention have been particularly successful, as com
pared with known demulsi?ers, in the treatment of low
Surface Active Complex Polyesters
gravity, high viscosity crude oils which are generally
The following examples are illustrative of the complex
treated in the upper portion of the 150° to 200° F. treat
polyesters which are surface active and are particularly 75 ing temperature range. These low gravity crudes are
3,056,748
11
12
solvent-soluble phenol-formaldehyde condensation prod
predominantly asphaltic base oils, containing appreciable
uct of a monoalkyl phenol having 4-15 phenolic nuclei,
the alkyl group having between 5 and 15 carbons, inclu
sive, the weight ratio of alkylene oxide to condensation
product falling between about 2:3 and 9:1, respectively,
amounts of asphaltenes, asphaltanes, bitumen, and pyro
litic residuum.
For example, treatment of low gravity crudes from
California (12-13 API) with the chemical of Example
the phenol-formaldehyde condensation product being oxy
alkylated with both ethylene oxide and propylene oxide,
the Weight ratio of propylene oxide to ethylene oxide being
1 was successful at dosages of almost 40% in one in
stance, and 50% in another instance, less than the com
petitive chemical used commercially with these crudes.
in the range of 1:9 to 9:1; and thereafter separating the
Improvements in water clarity were also noted-the
water released by treatment with the chemical of Ex 10 water from the petroleum oil.
3. In a process for breaking petroleum oil emulsions
ample 1 being crystal clear whereas the water released
of the water-in-oil type, adding to said emulsion a suffi
by treatment with the competitive chemical had been
cient quantity to break the emulsion into its water and
turbid. Also, settling time (the period of relative quies
petroleum components of a surface-active, polyester con
cence) was reduced from 36 hours to 18 hours.
15 densation product of the following compounds, the per‘
The invention is hereby claimed as follows:
centages enumerated being calculated on a weight basis
1. In a process for breaking petroleum oil emulsions
and totaling 100%: (a) 4-60% of a partial ester of a
of the water-in-oil type, adding to said emulsion a suffi
dicarboxylic acid and a terminally oxyethylated polyoxy
cient quantity to break the emulsion into its water and
propylene glycol, the polyoxypropylene glycol nucleus
petroleum components of a surface-active, polyetser con
densation product of the following compounds, the per 20 having a molecular weight in the range of 1,000 to 4,500,
the ethylene oxide being adducted on said polyoxypro
centages enumerated being calculated on a weight basis
pylene glycol in amounts in the range of 1 to 12 mols of
and totaling 100%: (a) 4-60% of a partial ester of a
ethylene oxide per mol of polyoxypropylene glycol, the
dicarboxylic acid and a terminally oxyethylated polyoxy
partial ester resulting from esteri?cation of 1 to 2 mols
having a molecular weight in the range of 1,000 to 4,500, 25 of dicarboxylic acid per mol of the oxyethylated poly
oxypropylene glycol; (b) 6-36% of a monocarboxylic
the ethylene oxide being adducted on said polyoxypro
acid having at least six carbons; (0) 4—24% of a poly
pylene glycol in amounts in the range of 1 to 12 mols of
propylene glycol, the polyoxypropylene glycol nucleus
carboxy acid having at least eight carbons; (d) 15-60%
ethylene oxide per mol of polyoxypropylene glycol, the
of an alkylene oxide adduct containing terminal oxy
ethylene groups of an alkali-insoluble, organic-solvent
partial ester resulting from esteri?cation of "1 to 2 mols
of dicarboxylic acid per mol of the oxyethylated polyoxy
soluble alkyl phenol-formaldehyde condensation product
propylene glycol; (b) 6—36% of a monocarboxylic acid
having about 4 to 15 phenolic nuclei, said alkyl group
having at least six carbons; (c) 4-24% of a polycarboxy
acid having at least eight carbons; (d) 15-60% of an
ethylene oxide adduct of an alkali-insoluble, organic-sol
vent-soluble alkyl phenol-formaldehyde condensation
having 5-15 carbons, inclusive, said condensation prod
uct being oxyalkylated with alkylene oxides from the
group consisting of ethylene oxide and both ethylene oxide
product having about 4 to 15 phenolic nuclei, said alkyl
group having 5-15 carbons, inclusive, said condensation
product being oxyethylated at a weight ratio of ethylene
oxyalkylation being oxypropylation of the condensation
product followed by oxyethylation of the oxypropylated
and propylene oxide, in the latter instance the order of
oxide to condensation product of about 2:3 to 9:1, re
condensation product, at a weight ratio of total oxides to
insoluble, organic-solvent-soluble phenol-formaldehyde
and (e) 15-60% of an oxyalkylated, alkali-insoluble, or
condensation product of a monoalkyl phenol having 4-15
phenolic nuclei, the alkyl group having between 5 and 15
carbons, inclusive, the weight ratio of alkylene oxide to
condensation product falling between about 2:3 and 9:1,
product of a monoalkyl phenol having 4-15 phenolic
nuclei, the alkyl group having between 5 and 15 carbons,
inclusive, the weight ratio of alkylene oxide to condensa
spectively; and (e) 15-60% of an oxyalkylated, alkali 40 condensation product of about 2:3 to 9:1, respectively;
ganic-solvent-soluble phenol-formaldehyde condensation
tion product falling between about 2:3 and 9:1 respec
respectively, the phenol-formaldehyde condensation prod
uct being oxyalkylated with both ethylene oxide and pro
pylene oxide, the weight ratio of propylene oxide to
ethylene oxide being in the range of 1:9 to 9:1; and
50
thereafter separating the water from the petroleum oil.
2. In a process for breaking petroleum oil emulsions
of the water-in-oil type, adding to said emulsion a su?i
cient quantity to break the emulsion into its water and
petroleum components of a surface active, polyester con
densation product of the following compounds, the per
centages enumerated being calculated on a weight basis
and totaling 100%: (a) 4-60% of a partial ester of a
dicarboxylic acid and a terminally oxyethylated polyoxy
tively, the phenol-formaldehyde condensation product
being oxyalkylated with a premixture of ethylene oxide
and propylene oxide, the weight ratio of propylene oxide
to ethylene oxide being in the range of 1:9 to 9:1; and
thereafter separating the water from the petroleum oil.
4. In a process for breaking petroleum oil emulsions
of the Water-in-oil type, adding to said emulsion a suffi
cient quantity to break the emulsion into its water and
‘ petroleum components of a surface active, polyester con
densation product of the following compounds, the per
centages enumerated being calculated on a weight basis
and totaling 100%: (a) 4-60% of a partial ester of a di
propylene glycol, the polyoxypropylene glycol nucleus
carboxylic acid and a terminally oxyethylated polyoxy
carbons, inclusive, said condensation product being oxy
formaldehyde condensation product having about 4 to
15 phenolic nuclei, said alkyl group having 5-15 carbons,
having a molecular weight in the range of 1,000 to 4,500, 60 propylene glycol, the polyoxypropylene glycol nucleus
having a molecular weight in the range of 1,000 to 4,500,
the ethylene oxide being adducted on said polyoxypro
the ethylene oxide being adducted on said polyoxypro
pylene glycol in amounts in the range of 1 to 12 mols of
pylene glycol in amounts in the range of 1 to 12 mols of
ethylene oxide per mol of polyoxypropylene glycol, the
ethylene oxide per mol of polyoxypropylene glycol, the
partial ester resulting from esteri?cation of 1 to 2 mols
partial ester resulting from esteri?cation of 1 to 2 mols
of dicarboxylic acid per mol of the oxyethylated poly~
of dicarboxylic acid per mol of the oxyethylated poly
oxypropylene glycol; (b) a monocarboxylic acid having
oxypropylene glycol; (b) a monocarboxylic acid having
11 to 18 carbons; (c) a dicarboxylic fatty dimer acid
11 to 18 carbons; (c) a dicarboxylic fatty dimer acid
having 12 to 40 carbons; (d) 15-60% of an ethylene oxide
having 12 to 40 carbons; (d) 15-60% of an alkylene oxide
adduct of an alkali-insoluble, organic-solvent-soluble alkyl
adduct containing terminal oxyethylene groups of an
phenol-formaldehyde condensation product having about 70 alkali-insoluble,
organic-solvent-soluble alkyl phenol
4 to 15 phenolic nuclei, said alkyl group having 5-15
ethylated at a weight ratio of ethylene oxide to condensa
inclusive, said condensation product being oxyalkylated
tion product of about 2:3 to 9:1, respectively; and (e)
15-60% of an oxyalkylated, alkali-insoluble, organic 75 with alkylene oxides from the group consisting of ethylene
3,056,748
13
14
oxide and both ethylene oxide and propylene oxide, in the
latter instance the order of oxyalkylation being oxypro
pylation of the condensation product followed by oxy
ethylation of the oxypropylated condensation product, at
per mol of polyoxypropylene glycol, the partial ester re—
sulting from esteri?cation of l to 2 mols of dicarboxylic
acid per mol of the oxyethylated polyoxypropylene gly
col; (b) a monocarboxylic acid having 11 to 18 carbons;
a weight ratio of total oxides to condensation product of 5 (c) a dicarboxylic fatty dimer acid having 12 to 40 car
about 2:3 to 9:1, respectively; and (e) 15-60% of an
bons; (d) 15-60% of an ethylene oxide adduct of an al
oxyalkylated, alkali-insoluble, organic-solvent-soluble phe
kali-insoluble, organic-solvent-soluble alkyl phenol-form
nol-formaldehyde condensation product of a monoalkyl
aldehyde condensation product having about 4 to 15
phenol having 4-15 phenolic nuclei, the alkyl group hav
phenolic nuclei, said alkyl group having 5-15 carbons,
ing between 5 and 15 carbons, inclusive, the Weight ratio 10 inclusive, said condensation product being oxyethylated at
of alkylene oxide to condensation product falling between
a weight ratio of ethylene oxide to condensation prod
about 2:3 and 9:1, respectively, the phenol-formaldehyde
uct of about 2:3 to 9:1, respectively; and (e) 15-60%
condensation product being oxyalkylated with a premix
of an oxyalkylated, alkali-insoluble, organic-solvent-sol
ture of ethylene oxide and propylene oxide, the Weight
uble phenol-formaldehyde condensation product of a
ratio of propylene oxide to ethylene oxide being in the 15 monoalkyl phenol having 4-15 phenolic nuclei, the alkyl
range of 1:9 to 9:1; and thereafter separating the water
group having between 5 and 15 carbons, inclusive, the
from the petroleum oil.
weight ratio of alkylene oxide to condensation product
5. In a process for breaking petroleum oil emulsions,
falling between about 2:3 and 9:1, respectively, the phe
adding to a water-in-petroleum oil emulsion, the petro
nol-formaldehyde condensation product being oxyalkyl
leum oil being a low gravity, high viscosity crude which 20 ated with both ethylene oxide and propylene oxide, the
is predominantly asphaltic base oils, a su?icient quantity
weight ratio of propylene oxide to ethylene oxide being
to break the emulsion into its water and petroleum com~
in the range of 1:9 to 9:1; and thereafter separating the
water and the petroleum oil.
uct of the following compounds, the percentages enum
7. In a process for breaking petroleum oil emulsions,
erated being calculated on a Weight basis and totaling 25 heating to a temperature between 150 and 200° F. and
100%: (a) 4-60% of a partial ester of a dicarboxylic
adding to a water-in-petroleum oil emulsion, the petro
ponents of a surface-active, polyester condensation prod
acid and a terminally oxyethylated polyoxypropylene
glycol, the polyoxypropylene glycol nucleus having a mo
lecular weight in the range of 1,000 to 4,500, the ethyl
ene oxide being adducted on said polyoxypropylene gly 30
col in amounts in the range of 1 to 12 mols of ethylene
oxide per mol of polyoxypropylene glycol, the partial
ester resulting from esteri?cation of 1 to 2 mols of di
leum oil being a low gravity, high viscosity crude which
is predominantly asphaltic base oils, a su?icient quantity
to break the emulsion into its Water and petroleum com
ponents of a surface-active, polyester condensation prod
uct of the following compounds, the percentages enum
erated being calculated on a weight basis and totaling
100%: (a) 4-60% of a dicarboxylic acid and a ter
carboxylic acid per mol of the oxyethylated polyoxypro
minally oxyethylated polyoxypropylene glycol, the poly
pylene glycol; (b) 6-36% of a monocarboxylic acid hav 35 oxypropylene glycol nucleus having a molecular weight
ing at least six carbons; (0) 4-24% of a polycarboxy
in the range of 1,000 to 4.500, the ethylene oxide being
acid having at least eight carbons; (d) 15-60% of al
adducted on said polyoxypropylene glycol in amounts
kylene oxide adduct containing terminal oxyethylene
groups of an alkali-insoluble, organic-solvent-soluble al
kyl phenol-formaldehyde condensation product having
in the range of 1 to 12 mols of ethylene oxide per mol
of polyoxypropylene glycol, the partial ester resulting
40 from esteri?cation of 1 to 2 mols of dicarboxylic acid
about 4 to 15 phenolic nuclei, said alkyl group having
per mol of the oxyethylated polyoxypropylene glycol;
—l5 carbons, inclusive, said condensation product be
(b) 6-36 % of a monocarboxylic acid having. at least six
ing oxyalkylated with alkylene oxides from the group
carbons; (0) 4-24% of a polycarboxy acid having at least
consisting of ethylene oxide and both ethylene oxide and
eight carbons; (at) 15-60% of an ethylene oxide adduct
propylene oxide, in the latter instance the order of oxy 45 of an alkali-insoluble, organic-solvent-soluble alkyl phe
alkylation being oxypropylation of the condensation prod
uct followed by oxyethylation of the oxypropylated con
densation product, at a weight ratio of total oxides to
condensation product of about 2:3 to 9:1, respectively;
and (e) 15-60% of an oxyalkylated, alkali-insoluble, or-
ganic-solvent-soluble phenol-formaldehyde condensation
product of a monoalkyl phenol having 4-15 phenolic
nuclei, the alkyl group having between 5 and 15 carbons,
inclusive, the weight ratio of alkylene oxide to conden
sation product falling between about 2:3 and 9: 1, respec
tively, the phenol-formaldehyde condensation product
being oxyalkylated with a premixture of ethylene oxide
and propylene oxide, the weight ratio of propylene oxide
to ethylene oxide being in the range of 1:9 to 9:1; and
thereafter separating the water and the petroleum oil.
6. In a process for breaking petroleum oil emulsions,
adding to a water-in-petroleum oil emulsion, the petro—
leum oil being a low gravity, high viscosity crude which
is predominantly asphaltic base oils, a suf?cient quantity
to break the emulsion into its water and petroleum com
ponents of a surface active, polyester condensation prod
uct of the following compounds, the percentages enum
erated being calculated on a weight basis and totaling
100%: (a) 4-60% of a partial ester of dicarboxylic acid
and a terminally oxyethylated polyoxypropylene glycol,
the polyoxypropylene glycol nucleus having a molecular
Weight in the range of 1,000 to 4.500, the ethylene oxide
being adducted on said polyoxypropylene glycol in
nol-formaldehyde condensation product having about 4
to 15 phenolic nuclei, said alkyl group having 5-15 car
bons, inclusive, said condensation product being oxy
ethylated at a weight ratio of ethylene oxide to conden
sation product of about 2:3 to 9:1, respectively; and
(2) 15-60% of an oxyalkylated, alkali-insoluble, organ
ic-solvent-soluble
phenol - formaldehyde
condensation
product of a monoalkyl phenol having 4-15 phenolic
nuclei, the alkyl group having between 5 and 15 carbons,
inclusive, the weight ratio of alkylene oxide to conden
sation product falling between about 2:3 and 9: 1, respec
tively, the phenol-formaldehyde condensation product be
ing oxyalkylated with both ethylene oxide and propylene
oxide, the weight ratio of propylene oxide to ethylene
oxide being in the range of 1:9 to 9:1.
8. In a process for breaking petroleum oil emulsions,
heating to a temperature between 150 and 200° F. and
adding to a water-in-petroleum oil emulsion, the petro
leum oil being a low gravity, high viscosity crude which
is predominantly asphaltic base oils, a sufficient quantity
to break the emulsion into its water and petroleum com
ponents of a surface active, polyester condensation prod
uct of the following compounds, the percentages enum
erated being calculated on a weight basis and totaling
100%: (a) 4-60% of a partial ester of a dicarboxylic
acid and a terminally oxyethylated polyoxypropylene gly
col, the polyoxypropylene glycol nucleus having a molec
ular weight in the range of 1,000 to 4,500, the ethylene
oxide being adducted on said polyoxypropylene glycol in
amounts in the range of 1 to 12 mols of ethylene oxide 75
amounts in the range of l to 12 mols of ethylene oxide
3,056,748
per mol of polyoxypropylene glycol, the partial ester re
sulting from esteri?cation of 1 to 2 mols of dicarboxylic
acid per mol of the oxyethylated polyoxypropylene gly
col; (b) a monocarboxylic acid having 11 to 18 carbons;
(c) a dicarboxylic fatty dimer acid having 12 to 40 car
bons; (d) 15-60% of an ethylene oxide adduct of an al
kali-insoluble, organic-solvent-soluble alkyl phenol~form~
16
ated with a premixture of ethylene oxide and propylene
oxide, the weight ratio of propylene oxide to ethylene
oxide being in the range of 1:9 to 9:1.
10. In a process for breaking petroleum oil emulsions,
heating to a temperature between 150 and 200° F. and
adding to a water-in-petroleum oil emulsion, the petro
leurn oil being a low gravity, high viscosity crude which
is predominantly asphaltic base oils, a sufficient quantity
aldehyde condensation product having about 4 to 15 phe
to break the emulsion into its water and petroleum com
nolic nuclei, said alkyl group having 5-15 carbons, in
clusive, said condensation product being oxyethylated at 10 ponents of a surface active, polyester condensation prod
uct of the following compounds, the percentages enum
erated being calculated on a Weight basis and totaling
100%: (a) 4-60% of a partial ester of a dicarboxylic
a weight ratio of ethylene oxide to condensation product
of about 2:3 to 9:1, respectively; and (e) 15-60% of an
oxyalkylated, alkali - insoluble, organic - solvent - soluble
acid and a terminally oxyethylated polyoxypropylene gly
col, the polyoxypropylene glycol nucleus having a mo
lecular weight in the range of 1,000 to 4-,500, the ethyl—
phenol-formaldehyde condensation product of a monoal
kyl phenol having 4-15 phenolic nuclei, the alkyl group
having between 5 and 15 carbons, inclusive, the weight
ratio of alkylene oxide to condensation product falling
between about 2:3 and 9:1, respectively, the phenol
formaldehyde condensation product being oxyalkylated
with both ethylene oxide and propylene oxide, the weight
ene oxide being adducted on said polyoxypropylene gly
col in amounts in the range of 1 to 12 mols of ethylene
oxide per mol of polyoxypropylene glycol, the partial
20 ester resulting from esteri?cation of 1 to 2 mols of di
carboxylic acid per mol of the oxyethylated polyoxypro
pylene glycol; (b) a monocarboxylic acid having 11 to
18 carbons; (c) a dicarboxylic fatty dimer acid having
ratio of propylene oxide to ethylene oxide being in the
range of 1:9 to 9:1.
9. In a process for breaking petroleum oil emulsions,
12 to 40 carbons; (d) 15-60% of an alkylene oxide ad
heating to a temperature between 150 and 200° F. and
adding to a water-in-petroleum oil emulsion, the petrole 25 duct containing terminal oxyethylene groups of an al
kali-insoluble, organic-solvent-soluble alkyl phenol-form
um oil being a low gravity, high viscosity crude which is
aldehyde condensation product having about 4 to 15 phe
predominantly asphaltic base oils, a sui?cient quantity to
nolic nuclei, said alkyl group having 5-15 carbons, in
break the emulsion into its water and petroleum C0111
clusive, said condensation product being oxyalkylated
ponents of a surface-active, polyester condensation prod
uct of the following compounds, the percentages enum 30 with alkylene oxides from the group consisting of ethyl
ene oxide and both ethylene oxide and propylene oxide,
erated being calculated on a weight basis and totaling
in the latter instance the order of oxyalikylation being
100%: (a) 41-60% of a partial ester of a dicarboxylic
oxypropylation of the condensation product followed by
acid and a terminally oxyethylated polyoxypropylene gly
oxyethylation
of the oxypropylated condensation prod
col, the polyoxypropylene glycol nucleus having a mo 35
uct at a weight ratio of total oxides to condensation
lecular weight in the range of 1,000 to 4,500, the ethylene
product of about 2:3 to 9:1, respectively; and (e) 15
oxide being adducted on said polyoxypropylene glycol in
60% of an oxyalkylated, alkali-insoluble, organic—sol
amounts in the range of 1 to 12 mols of ethylene oxide
Vent-soluble phenol-formaldehyde condensation product
per mol of polyoxypropylene glycol, the partial ester re
sulting from esteri?cation of 1 to 2 mols of dicarboxylic 40 of a monoalkyl phenol having 4-15 phenolic nuclei, the
alkyl group having between 5 and 15 carbons, inclusive,
acid per mol of the oxyethylated polyoxypropylene gly
the weight ratio of alkylene oxide to condensation prod
col; (1)) 6-36% of a monocarboxylic acid having at least
not falling between about 2:3 and 9:1, respectively, the
six carbons; (c) 4-24% of a dicarboxy acid having at
phenol-formaldehyde condensation product being oxy
least eight carbons; (d) 15-60% of an alkylene oxide
alkylated with a premixture of ethylene oxide and pro
adduct containing terminal oxyethylene groups of an al
pylene oxide, the weight ratio of propylene oxide to ethyl
kali-insoluble, organic-solvent-soluble alkyl phenol-form
ene oxide being in the range of 1:9 to 9:1.
aldehyde condensation product having about 4 to 15 phe
nolic nuclei, said alkyl group having 5-15 carbons, in
References Cited in the ?le of this patent
clusive, said condensation product being oxyalkylated
UNITED STATES PATENTS
with alkylene oxides from the group consisting of ethyl
ene oxide and both ethylene oxide and propylene oxide,
2,354,993
Harlan ______________ __ Aug. 1, 1944
in the latter instance the order of oxyalkylation being
2,454,808
Kirkpatrick et al. ____ __ Nov. 30, 1948
oxypropylation of the condensation product followed by
2,542,012
De Groote et al _______ __ Feb. 20, 1951
oxyethylation of the oxypropylated condensation product
at a weight ratio of total oxides to condensation prod
uct of about 2:3 to 9:1, respectively; and (e) 15—60%
of an oxyalkylated, alkali-insoluble, organic-solvent-sol—
uble phenol-formaldehyde condensation product of a
monoalkyl phenol having 4-15 phenolic nuclei, the alkyl
55
2,542,013
2,557,081
2,562,878
2,574,538
2,581,380
De Groote et a1. ______ __ Feb. 20,
De Groote et al. ______ __ June 19,
Blair _______________ __ Aug. 7,
De Groote et al. ______ __ Nov. 13,
De Groote et al _________ __ Jan. 8,
1951
1951
1951
1951
1952
2,606,882
De Groote et al _______ __ Aug. 12,
Hoenel ______________ __ June 22,
Dickson ______________ __ Oct. 9,
Kirkpatrick __________ __ Aug. 23,
1952
1954
1956
1960
group having between 5 and 15 carbons, inclusive, the 60 2,681,894
weight ratio of alkylene oxide to condensation product
2,766,213
falling between about 2:3 and 9:1, respectively, the phe
2,950,299
mol-formaldehyde condensation product being oxyalkyl
UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No. 8vO56E748
October 2, 1962-,
Earl Theodore Kocher
It is hereby certified that erro r appears in the above numbered pat
ent requiring correction and that the said Letters Patent should read as
corrected below.
Column 5v line 3Ov for "at" read —— as ——; column 60 line
73, for "rection" read —— reaction -=-—; column 10, line 6G for
"polyoxypropyleene" read —— polyoxypropylene »—; line/l0Q
strike out "the"; column 14, line 36' for "4500" read
--=
4,500
'
“a
Signed and sealed this 26th day of March 1963.,
(SEAL)
Attest:
ESTON G. JOHNSON
Attesting Officer
DAVID L. LADD
Commissioner of Patents
UNITED STATES PATENT OFFICE
vCERTIFICATE OF CORRECTION
Patent Noo 3vO56V748
October 2, 1962-1
Earl Theodore Kocher
It is hereby certified that error appears in the above numbered pat
ent requiring correction and that the said Letters Patent should read as
corrected below.
Column 5v line 30, for "at" read —- as ——; column 6V line
73., for "rection" read —— reaction —-; column 10, line 6U for
"polyoxypropyleene" read —— polyoxypropylene ——g line 1Oq
strike out "the"; column 14, line 367 for "4500" read
—¢-
I
4,500
——‘.
Signed and sealed this 26th day of March 1963.,
(SEAL)
Attest:
ESTON Ga JOHNSON
Attcsting Officer
DAVID L. LADD
Commissioner of Patents
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