METHOD FOR BREAKING PETROLEUM EMULSIONS AND THE LIKE USING MICELLAR SOLUTIONS OF THIN FILM SPREADING AGENTS COMPRISING AN ACYLATED POLYETHER POLYOL

METHODE POUR BRISER DES EMULSIONS DE PETROLE OU DE PRODUITS APPARENTES AU MOYEN DE SOLUTIONS MICELLAIRES D'AGENTS TENSIO-ACTIFS CONTENANT UN POLYOL DE POLYETHER ACYLE

English Abstract

ABSTRACT OF THE INVENTION
The invention relates to the use of a homogeneous,
micellar solution of a water-insoluble thin film spreading
agent for the breaking of petroleum emulsions, and the like,
comprising: (a) from between about 5% and about 75% by
weight of an acylated polyether polyol; (b) from between
about 2% and about 30% by weight of a hydrotropic agent;
(c) from between about 2% and about 30% by weight of an
amphipathic agent; and (d) from between about 15% and about
90% by weight of water.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method for breaking petroleum emulsions of the
water-in-oil type characterized by subjecting the emulsion to
the action of a homogeneous micellar solution of a thin film
spreading agent, said micellar solution comprising: (1) from
between about 5% and about 75% by weight of an acyl ted poly-
ether polyol having the formula:
<IMG>
wherein:
A is an alkylene oxide group, -CiH2iO-;
O is oxygen;
i is a positive integer from 2 to about 10;
j is a positive integer no greater than about 100;
k is a positive integer no greater than about 100;
N is nitrogen;
R1 is one Of hydrogen, a monovalent hydrocarbon group
containing less than about C11 or [ALH];
L is a positive integer no greater than about 100;
R is a hydrocarbon moiety of a polyol, a primary or
secondary amine, a primary or secondary polyamine,
a primary or secondary amino alcohol, or hydrogen; and
m+n is no greater than about 4 when R is other than
hydrogen and one of m and n is zero and the other
is unity when R is hydrogen, said acylated polyether
polyol being the reaction product of said polyether
polyol and a member selected from the class consisting
of mono- and polybasic carboxylic acids, acid anhydrides,

and iso-, diiso-, and polyisocyanates, said
acylated polyether polyol at about 25°C.:
(a) being less than about 1% by volume soluble
in water and in isooctane; (b) having a solu-
bility parameter in the range of between about
6.9 and about 8.5; and (c) spreading at the
interface between distilled water and refined
mineral oil to form a film having a thickness
no greater than about 20 Angstroms at a spread-
ing pressure of about 16 dynes per cm; (2) from
between about 2% about 30% by weight of a hydro-
tropic agent having one of the formulas:
X-Z (A)
wherein X is an alkyl, alicyclic, aromatic, alkyl-
alicyclic, alkylaryl, arylalkyl, alicyclicalkyl,
heterocyclic or substituted heterocyclic radical
having 2 to 13 carbon atoms; and wherein Z is one
of: OH;
<IMG> ; <IMG> ; -COOH;
and -OCH3; and U and V are hydrogen or hydrocarbon
substituents;
- X - Y - R - (Z)n'
wherein:
Z is one of - OH;
<IMG> ; - CHO; <IMG> ; - COOH;
and - OCH3;
46

X is an alkyl, alicyclic, aromatic, alkylalicyclic,
alkylaryl, arylalkyl, alicyclicalkyl, heterocyclic
or substituted heterocyclic radical having 2 to 12
carbon atoms;
R is a member selected from the class consisting of,
-CH2-,-C2H4-,C3H5=,C3H6,and -C2-
H4-O-C2H4-;
n is either a one or two integer, the integer
dependent upon the selection of R; U and V are
hydrogen or hydrocarbon substituents; and
Y is a member selected from the class consisting of:
<IMG> , <IMG> , <IMG> , <IMG> ,
- O - , and - S - ;
(3) from between about 2% and about 30% by weight
of an amphipathic agent having at least one radical
having from between about 10 and about 64 carbon
atoms per molecule; and
(4) from between about 15% and about 90% by weight,
water.
2. The method of claim 1 wherein said acylated poly-
ether polyol is the reaction product of a difunctional poly-
ether polyol and a difunctional member of the class consisting
of carboxylic acids, acid anhydrides and isocyanates.
3. The method of claim 1 wherein said acylated poly-
ether polyol is the reaction product of a polyether polyol and
an acylating agent selected from the class consisting of di-
and mono-basic acids and anhydrides having C13 or less.
47

4. The method of claim 1 wherein said acylated poly-
ether polyol is the reaction product of a polyether polyol an
a polyisocyanate containing at least two isocyanate groups.
5. The method of claim 1 wherein the hydrotropic
agent is an alcohol.
6. The method of claim 1 wherein the hydrotropic
agent is an aldehyde.
7. The method of claim 1 wherein the hydrotropic
agent is a semi-polar oxygen-containing compound capable of
forming hydrogen bonds.
8. The method of claim 1 wherein the hydrotropic
agent is an amine.
9. The method of claim 1 wherein the hydrotropic
agent is a carboxy amide.
10. The method of claim 1 wherein the amphipathic
agent is a hydrophobic hydrocarbon residue-containing compo-
sition wherein the hydrocarbon residue is aliphatic, alkyl-
alicyclic, aromatic, arylalkyl or alkylaromatic.
11. The method of claim 1 wherein the amphipathic
agent comprises mahogany or green sulfonates of petroleum,
petroleum fractions, or petroleum extracts.
12. The method of claim 1 wherein the amphipathic
agent is anionic.
13. The method of claim 1 wherein the amphipathic
agent is cationic.
48

14. The method of claim 1 wherein the amphipathic
agent is nonionic.
15. A method for breaking petroleum emulsions of the
water-in-oil type characterized by subjecting the emulsion to
the action of a micellar solution of a thin film spreading
agent, said homogeneous micellar solution comprising: (1) from
between about 5% and about 75% by weight of an acylated poly-
ether polyol wherein said polyether polyol has an average mole-
cular weight of 15,000 or less and is derived from the reaction
of an alkylene oxide containing less than about 10 carbon atoms
with a member of the group consisting of polyols, amines, poly-
amines and amino alcohols containing from about 2 to about 10
active hydrogen groups capable of reaction with alkylene oxides,
said member having 18 or less carbon atoms, and the acylating
agent being a member selected from the class consisting of mono-
and polybasic carboxylic acids, açid anhydrides and iso-, di-
iso-, and polyisocyanates, said acylated polyether polyol, at
about 25°C.: (A) having a solubility in water and isooctane of
less than about 1%, by volume; (B) having a solubility para-
meter from between about 6.8 and about 8.5; and (C) spreading
at the interface between white, refined mineral oil and dis-
tilled water to form a film having a calculated thickness no
greater than about 20 Angstroms, at a spreading pressure of
about 16 dynes per cm; (2) from between about 2% and about 30%
by weight of a hydrotropic agent comprising a semi-polar hydro-
gen bond forming compound containing at least one of oxygen,
nitrogen and sulfur and from between about 2 and about 12 carbon
atoms; (3) from between about 2% and about 20% by weight of an
amphipathic agent having at least one radical having from be-
tween about 10 and about 64 carbon atoms per molecule; and (4)
from between about 15% and about 90% by weight, water.
49

16. The method of claim 15 wherein the amphipathic
agent is a hydrophobic hydrocarbon residue-containing composi-
tion wherein the hydrocarbon residue is aliphatic, alkyl-
alicyclic, aromatic, arylalkyl or alkylaromatic.
17. The method of claim 15 wherein the amphipathic
agent comprises mahogany or green sulfonates of petroleum,
petroleum fractions, or petroleum extracts.
18. The method of claim 15 wherein the amphipathic
agent is anionic.
19. The method of claim 15 wherein the amphipathic
agent is cationic.
20. The method of claim 15 wherein the amphipathic
agent is nonionic.
21. A method of recovering oil from an oil-bearing
formation into which a well bore extends, comprising the steps
of: (I) generating steam at the surface; (II) supplying said
steam to said oil-bearing formation by way of said well bore;
(III) supplying a homogeneous micellar solution of a thin film
spreading agent to said oil-bearing formation to inhibit the
production of oil-water emulsion as a result of the interaction
of said steam with the oil and water in the formation said
agent comprising: (1) from between about 5% and about 75% by
weight of an acylated polyether polyol having the formula:
<IMG>
wherein:
A is an alkylene oxide group, -CiH2iO-;
O is oxygen;

i is a positive integer from 2 to about 10;
j is a positive integer no greater than about 100;
k is a positive integer no greater than about 100;
N is nitrogen:
R is one of hydrogen, a monovalent hydrocarbon group
group containing less than about C11, or [ALH];
L is a positive integer no greater than about 100;
R is a hydrocarbon moiety of a polyol, a primary or
secondary amine, a primary or secondary polyamine,
a primary or secondary amino alcohol, or hydrogen; and
m+n is no greater than about 4 when R is other than hydro-
gen and one of m and n is zero and the other is unity
when R is hydrogen, said acylated polyether being the
reaction product of said polyether polyol and a member
selected from the class consisting of mono- and poly-
basic carboxylic acids, acid anhydrides, and iso-, or
diiso-, and polyisocyanates, said acylated polyether
polyol at about 25°C.: (a) being less than about 1%
by volume soluble in water and in isooctane; (b) having
a solubility parameter in the range of between about 6.9
and about 8.5; and (c) spreading at the interface between
distilled water and refined mineral oil to form a film
having a thickness no greater than about 20 Angstroms at
a spreading pressure of about 16 dynes per cm; (2) from
between about 2% and about 30% by weight of a hydrotropic
agent having one of the formulas:
X--Z (A)
wherein X is an alkyl, alicyclic, aromatic, alkyl-
alicyclic, alkylaryl, arylalkyl, alicyclicalkyl, hetero-
cyclic or substituted heterocyclic radical having 2 to
13 carbon atoms; and wherein Z is one of: -OH;

<IMG> ; . <IMG> ; COOH;
and - OCH3; and U and V are hydrogen or hydrocarbon
substituents;
X - Y - R (Z)n'
wherein:
Z is one of - OH;
<IMG> ; <IMG> ; --COOH;
and - OCH3;
X is an alkyl, alicyclic, aromatic, alkylalicyclic, alkyl-
aryl, arylalkyl, alicyclicalkyl, heterocyclic or sub-
stituted heterocyclic radical having 2 to 12 carbon
atoms;
R is a member selected from the class consisting of,
-CH2-,-C2H4-,C3H5=,-C3H6,and -C2-
H4 - O - C2H4 - ;
n is either a one or two integer, the integex dependent
upon the selection of R; U and V are hydrogen or hydro-
carbon substituents; and
Y is a member selected from the class consisting of:
<IMG> , <IMG> , <IMG> , <IMG> ,
- O - , and - S - ;
(3) from between about 2% and about 30% by weight of an
amphipathic agent having at least one radical having
from between about 10 and about 64 carbon atoms per
molecule; (4) from between about 15% and about 90%
52

by weight, water; and (IV) recovering from said formation
oil and water which was subjected to the action of said
steam.
22. The method of claim 21, wherein said acylated
polyether polyol is the reaction product of a difunctional
polyether polyol and a difunctional member of the class con-
sisting of carboxylic acids, acid anhydrides and isocyanates.
23. The method of claim 21, wherein said acylated
polyether polyol is the reaction product of a polyether polyol
and an acylating agent selected from the class consisting of
di- and mono-basic acids and anhydrides having C13 or less.
24. The method of claim 21, wherein said acylated
polyether polyol is the reaction product of a polyether polyol
and a polyisocyanate containing at least two isocyanate groups.
25. The method of claim 21, wherein the hydrotropic
agent is an alcohol.
26. The method of claim 21, wherein the hydrotropic
agent is an hydroxy ester of a polyol.
27. The method of claim 21, wherein the hydrotropic
agent is an aldehyde.
28. The method of claim 21, wherein the hydrotropic
agent is a semi-polar oxygen-containing compound capable of
forming hydrogen bonds.
29. The method of claim 21, wherein the amphipathic
agent is a hydrophobic hydrocarbon residue-containing compo-
sition wherein the hydrocarbon residue is aliphatic, alkyl-
alicyclic, aromatic, arylalkyl or alkylaromatic.
53

30. The method of claim 21, wherein the amphipathic
agent comprises mahogany or green sulfonates of petroleum,
petroleum fractions, or petroleum extracts.
31. The method of claim 21, wherein the amphipathic
agent is anionic.
32. The method of claim 21, wherein the amphipathic
agent is cationic.
33. The method of claim 21, wherein the amphipathic
agent is nonionic.
34. A method of recovering oil from an oil-bearing
formation into which a well bore extends, comprising the steps
of: (I) generating steam at the surface; (II) supplying said
steam to said oil-bearing formation by way of said well bore;
(III) supplying a homogeneous micellar solution of a thin film
spreading agent to said oil-bearing formation to inhibit the
production of oil-water emulsion as a result of the interaction
of said steam with the oil and water in the formation, said
micellar solution comprising: (1) from between about 5% and
about 75% by weight of an acylated polyether polyol wherein
said polyether polyol has an average molecular weight of 15,000
or less and is derived from the reaction of an alkylene oxide
containing less than about 10 carbon atoms with a member of
the group consisting of polyols, amines, polyamines and amino
alcohols containing from about 2 to about 10 active hydrogen
groups capable of reaction with alkylene oxides, said member
having 18 or less carbon atoms and the acylating agent being a
member selected from the class consisting of mono- and poly-
basic carboxylic acids, acid anhydrides and iso-, diiso-, and
polyisocyanates, said acylated polyether polyol, at about 25°C:
54

(A) having a solubility in water and isooctane of less than
about 1% by volume; (B) having a solubility parameter from
between about 6.8 and about 8.5; and (C) spreading at the
interface between white, refined mineral oil and distilled
water to form a film having a calculated thickness no greater
than about 20 Angstroms, at a spreading pressure of about 16
dynes per cm; (2) from between about 2% and about 30% by weight
of a hydrotropic agent comprising a semi-polar hydrogen bond
forming compound containing at least one of oxygen, nitrogen
and sulfur and from between about 2 and about 12 carbon atoms;
(3) from between about 2% and about 20% by weight of an amphi-
pathic agent having at least one radical having from between
about 10 and about 64 carbon atoms per molecule; (4) from
between about 15% and about 90% by weight, water and (IV)
recovering from said formation oil and water which was sub-
jected to the action of said steam.
35. A method of breaking petroleum or bitumen emul-
sions of water comprising contacting the emulsion with a
sufficient emulsion-breaking amount of a homogeneous micellar
solution of a thin film spreading agent said micellar solution
comprising: (l) from between about 5% and about 75% by weight
of an acylated polyether polyol wherein said polyether polyol
has an average molecular weight of 15,000 or less and is de-
rived from the reaction of an alkylene oxide containing less
than about 10 carbon atoms with a member of the group consist-
ing of polyols, amines, polyamines and amino alcohols contain-
ing from about 2 to about 10 active hydrogen groups capable of
reaction with alkylene oxides, said member having 18 or less
carbon atoms, and the acylating agent being a member selected
from the class consisting of mono- and polybasic carboxylic
acids, said anhydrides and iso-, diiso-, and polyisocyanates,

said acylated polyether polyol, at about 25°C.:
(A) having a solubility in water and isooctane of less than
about 1%, by volume; (B) having a solubility parameter from
between about 6.8 and 8.5; and (C) spreading at the interface
between white, refined mineral oil and distilled water to form
a film having a calculated thickness no greater than about 20
Angstroms, at a spreading pressure of about 16 dynes per cm;
(2) from between about 2% and about 30% by weight of a hydro-
tropic agent comprising a semi-polar hydrogen bond forming
compound containing at least one of oxygen, nitrogen and sul-
fur and from between about 2 and about 12 carbon atoms; (3)
from between about 2% and about 20% by weight of an amphipathic
agent having at least one radical having from between about 10
and about 64 carbon atoms per molecule; and (4) from between
about 15% and about 90% by weight, water.
36. In the method of preventing the formation of
emulsions of an aqueous phase and a petroleum oil or bitumen
phase, the improvement comprising: contacting said petroleum
oil or bitumen phase prior to or coincident with its contact
with the aqueous phase with an effective emulsion preventing
amount of a homogeneous micellar solution of a thin film spread-
ing agent, said micellar solution comprising: (1) from between
about 5% and about 75% by weight of an acylated polyether
polyol wherein said polyether polyol has an average molecular
weight of 15,000 or less and is derived from the reaction of
an alkylene oxide containing less than about 10 carbon atoms
with a member of the group consisting of polyols, amines, poly-
amines and amino alcohols containing from about 2 to about 10
active hydrogen groups capable of reaction with alkylene oxides,
said member having 18 or less carbon atoms, and the acylating
agent being a member selected from the class consisting of mono-
56

and polybasic carboxylic acids, acid anhydrides and iso-,
diiso-, and polyisocyanates, said acylated polyether polyol,
at about 25°C: (A) having a solubility in water and isooctane
of less than about 1% by volume; (B) having a solubility para-
meter of from between about 6.8 and about 8.5; and (C) spread-
ing at the interface between white, refined mineral oil and
distilled water to form a film having a calculated thickness
no greater than about 20 Angstroms, at a spreading pressure
of about 16 dynes per cm; (2) from between about 2% and about
30% by weight of a hydrotropic agent comprising a semi-polar
hydrogen bond forming compound containing at least one of
oxygen, nitrogen and sulfur and from between about 2 and about
12 carbon atoms; (3) from between about 2% and about 20% by
weight of an amphipathic agent having at least one radical
having from between about 10 and about 64 carbon atoms per
molecule; and (4) from between about 15% and about 90% by
weight, water.
37. In the method of breaking and preventing emulsions
of water in bitumen during the recovery of bitumen or heavy
oil from tar sands and subterranean deposits by steaming,
flooding, and combinations thereof, the improvement comprising:
contacting said bitumen or heavy oil with a homogeneous mi-
cellar solution of a thin film spreading agent, comprising:
(1) from between about 5% and about 75% by weight of an
acylated polyether polyol wherein said polyether polyol has an
average molecular weight of 15,000 or less and is derived from
the reaction of an alkylene oxide containing less than about
10 carbon atoms with a member of the group consisting of
polyols, amines, polyamines and amino alcohols containing from
about 2 to about 10 active hydrogen groups capable of reaction
with alkylene oxides, said member having 18 or less carbon
57

atoms, and the acylating agent being a member selected from
the class consisting of mono- and polybasic carboxylic acids,
acid anhydrides and iso-, diiso-, and polyisocyanates, said
acylated polyether polyol, at about 25°C.: (A) having a
solubility in water and isooctane of less than about 1%, by
volume; (B) having a solubility parameter from between about
6.8 and about 8.5; and (C) spreading at the interface between
white, refined mineral oil and distilled water to form a film
having a calculated thickness no greater than about 20 Ang-
stroms, at a spreading pressure of about 16 dynes per cm;
(2) from between about 2% and about 30% by weight of a hydro-
tropic agent comprising a semi-polar hydrogen bond forming
compound containing at least one of oxygen, nitrogen and sulfur
and from between about 2 and about 12 carbon atoms; (3) from
between about 2% and about 20% by weight of an amphipathic
agent having at least one radical having from between about
10 and about 64 carbon atoms per molecule; and (4) from between
about 15% and about 90% by weight, water.
38. The method of claim 34 or 35 wherein the acylated
polyether polyol is the reaction product of a difunctional
polyether polyol and a difunctional member of the class con-
sisting of carboxylic acids, acid anhydrides and isocyanates.
39. The method of claim 34 or 35 wherein said acylated
polyether polyol is the reaction product of a polyether polyol
and a polyisocyanate containing at least two isocyanate groups.
40. The method of claim 34 or 35 wherein the hydro-
tropic agent is an alcohol.
41. The method of claim 34 or 35 wherein the hydro-
tropic agent is an hydroxy ester of a polyol.
58

42. The method of claim 34 or 35 wherein the hydro-
tropic agent is an aldehyde.
43. The method of claim 34 or 35 wherein the hydro-
tropic agent is a semi-polar oxygen-containing compound capable
of forming hydrogen bonds.
44. The method of claim 34 or 35 wherein the hydro-
tropic agent is an amine.
45. The method of claim 34 or 35 wherein the hydro-
tropic agent is a carboxy amide.
46. The method of claim 34 or 35 wherein the hydro-
tropic agent is a phenolate.
47. The method of claim 34 or 35 wherein the amphi-
pathic agent is a hydrophobic hydrocarbon residue-containing
composition wherein the hydrocarbon residue is aliphatic,
alkylalicyclic, aromatic, arylalkyl or alkylaromatic.
48. The method of claim 34 or 35 wherein the amphi-
pathic agent contains an uninterrupted chain of from between
about 10 and about 22 carbons.
49. The method of claim 34 or 35 wherein the amphi-
pathic agent is an anion-active soap.
50. The method of claim 34 or 35 wherein the amphi-
pathic agent comprises mahogany or green sulfonates of petro-
leum, petroleum fractions, or petroleum extracts.
51. The method of claim 34 or 35 wherein the amphi-
pathic agent is anionic.
59

52. The method of claim 34 or 35 wherein the amphi-
pathic agent is cationic.
53. The method of claim 34 or 35 wherein the amphi-
pathic agent is nonionic.
54. The method of claim 36 or 37 wherein said acylated
polyether polyol is the reaction product of a difunctional
polyether polyol and a difunctional member of the class con-
sisting of carboxyliç acids, acid anhydrides and isocyanates.
55. The method of claim 36 or 37 wherein said acylated
polyether polyol is the reaction product of a polyether polyol
and a polyisocyanate containing at least two isocyanate groups.
56. The method of claim 36 or 37 wherein the hydro-
tropic agent is an alcohol.
57. The method of claim 36 or 37 wherein the hydro-
tropic agent is an hydroxy ester of a polyol.
58. The method of claim 36 or 37 wherein the hydro-
tropic agent is an aldehyde.
59. The method of claim 36 or 37 wherein the hydro-
tropic agent is a semi-polar oxygen-containing compound capable
of forming hydrogen bonds.
60. The method of claim 36 or 37 wherein the hydro-
tropic agent is an amine.
61. The method of claim 36 or 37 wherein the hydro-
tropic agent is a carboxy amide.
62. The method of claim 36 or 37 wherein the hydro-
tropic agent is a phenolate.

63. The method of claim 36 or 37 wherein the amphi-
pathic agent is a hydrophobic hydrocarbon residue-containing
composition wherein the hydrocarbon residue is aliphatic,
alkylalicyclic, aromatic, arylalkyl or alkylaromatic.
64. The method of claim 36 or 37 wherein the amphi-
pathic agent contains an uninterrupted chain of from between
about 10 and about 22 carbons.
65. The method of claim 36 or 37 wherein the amphi-
pathic agent is an anion-active soap.
66. The method of claim 36 or 37 wherein the amphi-
pathic agent comprises mahogany or green sulfonates of petro-
leum, petroleum fractions, or petroleum extracts.
67. The method of claim 36 or 37 wherein the amphi-
pathic agent is anionic.
68. The method of claim 36 or 37 wherein the amphi-
pathic agent is cationic.
69. The method of claim 36 or 37 wherein the amphi-
pathic agent is nonionic.
61

Description

l~S3273
BACKGROUND OF THE INVENTION
1. FIELD OF THE INVENTION: The invention relates to the
use of a micellar solution of a thin film spreading agent
comprising an acylated polyether polyol in the breaking or
prevention of petroleum emulsions. More specifically, the
invention relates to a composition in which water replaces
all or a substantial part of the organic solvents formerly
required for preparation of li~uid solutions of this inter-
facially active compound.
2. DESCRIPTION OF THE PRICR ART: One of the principal
uses of the present composition is in the breaking of petro-
leum emulsions to permit the separation thereof into two ~ulk
phases. Much of the crude petroleum oil produced throughout
the world is accompanied by some water or brine which origi-
nates in or adjacent to the geological formation from which
the oil is produced. The amount of aqueous phase accompany-
ing the oil may vary from a trace to a very large percentage
of the total fluid produced. Due to the natural occurrence
in most petroleum of oil-soluble or dispersible emulsifying
agents, much of the aqueous phase produced with oil is emul-
sified therein, ~orming stable water-in-oil emulsions.
The literature contains numerous references to such
emulsions, the problems resulting from their occurrence, and
the methods employed to break them and separate salable
petroleum. See, for example, "The Technology of Resolving
Petroleum Emulsions" by L.T. Monson and R.W. Stenzel, p. 535
et seq in Colloid Chemistry Vol VI, Ed. by Jerome Alexander,
Rheinhold Publishing Corp., New York (1946) and "Interfacial
Films Affecting the Stability of Petroleum Emulsions" by
Chas. M. Blair, Jr. in ChemistrY and IndustrY (London), p.53
et seq (1960).
~ . ' ,
,~

~lS3273
Early demulsifiers used to resolve petroleum emul-
sions were water-soluble soaps, Twitchell reagents, and sul-
fonated glycerides. These products were readily compounded
with water to form easily pumpable liquids and were con-
veniently applied by pumping into flow lines at the well head
or by washing down the casing annulus with water to commingle
with well fluids prior to their flow to the surface. These
products, however, were effective only at relatively high
concentrations and their use added substantially to the cost
of production.
Some time ago, it was discovered that certain lightly
sulfonated oils, acetylated caster oils and various poly-
esters, all of which were insoluble in water but soluble in
alcohols and aromatic hydrocarbons, were much more effective
in breaking emulsiQns. Accordingly, essentially all com-
mercial demulsifier development has led to production of
agents which are insoluble in both water and petroleum oils
and have other properties to be described below which cause
them to spread at oil-water interfaces to form very thin,
mobile films which displace any emulsifying agent present in
the oil to allow coalesaence of dispersed water droplets.
Generally, such interfacially active compounds are hereafter
referred to as Thin Film Spreading Agents, or "TFSA's". In
the past, these have had to be compounded with and dissolved
Ln alcohols or highly aromatic hydrocarbon solvents in order
to produce readily applied liquid compositions. A wide
variety of such compositions are required to treat the many
different emulsions encountered throughout the world.
While present TFSA compositions are highly effective,
being, perhaps, up to fifty to a hundred times more effective
per unit volume than the original water-soluble demulsifiers,
~;r
p~

~1532~3
they suffer serious practical deficiencies because of their
solu~ility characteristics. For example, alcohols and the
aromatic hydrocarbons, which are required for preparation of
liquid, pumpable compositions, are q~ite expensive, today
approaching in cost that of the active demulsifier ingredient
itself. Further, such solvents are flammable and thus create
safety problems and entail more expense in shipping, stQring
and use. The low flash point flammability can be improved by
using high boiling aromatic solvents, but these are increas-
ingly rare, expensive and dangerous from the standpoint of
carcinogenicity and dermatological effects.
Still further, present demulsifiers cannot generally
be used in a subterranean Qil or gas well, injection well, or
the like~ since they cannot be washed down with either water
(or brine) or a portion of the produced oil, and, being vis-
cous liquids which are re~uired in very small amo~nts, they
cannot be reliably and continuously delivered several thousand
feet down at the fluid level in a typical well without use of
elaborate and expensive delivery means.
Other applications of TFSA cqmpositions would be
facilitated if they were readily soluble or dispersi~le in
water. For example, much heavy, viscous oil is prod~ced in
the United States by steam injection procedures. Typically,
wet steam is injected into the oil producing strata for
several weeks in order to heat the oil, lower its viscosity
and increase reservoir energy. Steam injection is then
stopped and oil is flowed or pumped from the ~ore hole which
was used for steam injection. Much of the water resulting
from condensation of the steam is also produced with the oil
in emulsified form. Since emulsions are more viscous than
the external phase at the same temperature, and thus create
- 3 -
'

1153273
increased resistance to flow, productivity of the steamed
wells can be improved by injecting a water-soluble ~emulsifier
into the wet steam during the steam injection period to pre-
vent: emulsion formation. See, for example, U.S. Patent
3,396,792, dated April 1, 1966, to F.D. Muggee. At present,
the requirsment of water solubility seriously limits the
choice of demulsifiers for use in steam or water in~ection to
the relatively inefficient compositions.
As disclosed in my co-pending Canadian applications,
Serial Number 353,251, filed June 3, 1980 and entitled "Method
of Recovering Petroleum From A Subterranean ReservQir Incor-
porating A Polyether PQlyol", Serial Number 353,232, filed
June 3, 1980, and entitled "Method of Recovering Petroleum
From A Subterranean Reservoir Incorporating Resinous Poly-
alkylene Oxide Adduct$", Serial Number 353,35~, filed June 3,
1980, and entitled "~ethod of Recovering Petroleum From A
Subterranean Reservoir Incorporating An Acylated Polyether
Polyol", and Serial Number 353,233, filed June 3, 198Q, and
entitled "Method of Recovering Petroleum From A Subterranean
Reservoir Incorporating Polyepoxide Condensates Of Resinous
Polyalkylene Oxide Adducts and Polyether Polyols", TFSA's are
useful in processes for enhanced recovery of petroleum. Used
in s~ch processes involving displacement of residual oil by
aqueous solutions, polymer solutions and other aqueous systems
these agents act to increase the amount of oil recovered.
Such action possibly arises from their ability to further
water wetting of reservoir rock, lessen the viscosity of the
oil-water interfacial layer and promote coalescence of dis-
persed droplets of either water or oil in the other phase.
By use of the present aqueous micellar solutions, the
introduction of TFSA into aqueous displacement or flooding
-- 4 --

llS32~3
fll~ids is greatly facilitated. In addition, the present
micellar solutions, per se, or in combination with other
components, can be used as the flooding agent or as a pre-
treating bank or slug ahead of other aqueous fluids.
Other applications for the present TFSA micellar
solutions include their use as flocculation aids for finely
ground hematite and magnetite ores during the desliming step
of ore beneficiation, as additives for improving the oil re-
moval and detergent action of cleaning compositions and deter-
gents designed for use on polar materials, for the improve-
ment of solvent extraction processes such as those used in
extraction of antibiotic products from aqueous fermentation
broths with organic solvents, for the improvement of effi-
ciency and phase separation in the purification and con-
centration of metals by solvent extraction with organic solu-
tions of metal complex-forming agents, and as assistants to
improve the wetting and dying of natural and synthetic fibers
and f.or other processes normally involving the in erface
between surfaces of differing polarity or wetting charac-
teristics.
SUMMARY OF TH~ INVENTION
A primary object of the present invention iQ to pro-
vide aqueous, li~uid compositions of these TFSA's having new
and useful characteristics which allow production of: petro-
leum emulsion breakers and emulsion preventing compositions
free or relatively free of highly flammable and envirQn-
mentally objectionable aromatic hydrocarbons; compositions
having a comparatively low cost; compositions which are solu-
ble or dispersible in water and which, therefore, can often
be applied by more effective methods than can existing
products; compositions which can be used in enhanced recovery
-- 5 --
~,
. , . ~
- .

llS3273
operations such as steam flooding and aqueous medium flooding
where present products cannot be readily applied; and compo-
sitions which can be compounded with water-soluble reagents
of other types, such as corrosion inhibitors, wetting agents,
scale inhibitors, biocides, acids, e~c., to provide multi-
purpose compounds for use in solving many oil well completion,
production, transportation and refining problems.
In accordance with the present invention, these aims
are accomplished by means of amphipathic agents which are
capable of forming micellar solutions and which by this
mechanism or other undefined actions, combined with those of
a second essential component which will be referred to as a
hydrotropic agent, are able to form homogeneous aqueous solu-
tions containing a relatively wide range of concentrations of
TFSA.
DESCRIPTION OF THE PREF~RRED ~MBO~IMENT$
,, , ; . -
The TFSA compositions of the present invention can
be broadly categorized by the following general characteris-
tics:
l. SQluhility in water and isooctane at about 25QC
is less than about 1~ by volume;
2. Solubility parameter at about 25C is in the
range of from between about 6.8 to about 8.5,
with a majority in the range of from between
7.0 and about 7.9; and
3. Spread at the interface between white, refined
mineral oil and distilled water to form films
having a calculated thickness no greater than
about 20 Angstroms at a spreading pressure of
about 16 dynes per cm.
: - 6 -

l~S3273
TFSA compositions having these properties are
generally organic polymers or semi-polymers having molecular
weights ranging from about 2,000 to about 100,000 and having
structures containing a multiplicity of distributed hydro-
philic and hydrophopic moieties arranged in linear or planar
arrays which make them surface active and lead to their ad-
sorption at oil-water interfaces to form very thin films.
Unlike most commonly encountered surface-active com-
pounds, the present TFSA appears to be incapable of forming
a micelle in either oil or water. The distributed and alter-
nating occurrence of polar and nonpolar or hydrophilic and
hydrophobic groups in the molecule apparently prevents the
kind of organization required for micelle formation and thus
impairs dispersion or solution in either water or low polarity
organic solvents.
The TFSA's ~seful in the present invention have the
previously recited properties:
1. The solu~ility in water and;in isooctane at abo~t
25~ is less than about 1% by volume.
Solubility tests may be run by placing a 1 ml
sample (or the weight of solid product calculated to
have a volume of 1 ml) in a graduated cylinder ~f the
type which may be closed with a ground glass stopper.
Thereafter place 99 ml of water in the cylinder,
; close, place in a 25C water bath until thermal
equilibrium is reached, and remove from the bath and
shake vigorously for one minute. Return the sample
to the bath for five minutes and then repeat the
shaking procedure. Finally, return the sample to
the bath and allow it to stand quietly for one hour.
7 ~
, . . . .

~lS3273
The cylinder contents should be carefully examined
and any cloudiness or opacity of the liquid phase
or the appearance of any sediment or undissolved
material in the cylinder noted, thus indicating that
the sample satisfied the requirement for insolu-
bility in water.
Isooctane solubility is determined similarly by
substituting this hydrocarbon for the water used
above.
2. The $olubility Parameter (S.P.) at a~ou~ 25~ is
from between_ab_ut 6.9 and about 8.5, inclusive.
Methods of determination of sol~bility parameter
are disclosed in Joel H. Hildebrand, "The Solubility
of Nonelectrolytes", Third Edition, pgs. 425 et se~.
However, a simplified procedure, sufficiently ac-
curate for qualification of a useful TFSA composition
may be utilized. Components of a given solubility
parameter are generally insoluble in hydrocarbon
(non-hydrogen-bonding) solvents having a lower solu-
bility ~arameter than themselves. Therefore, ~he
present c~mposition should be insoluble in a hydro-
carbon solvent of a solubility parameter of about
6.8. $ince the solubility parameter of mixtures of
solvents is an additive function of volume percentage
of components in the mixture, test solutions of the
desire~ solubility parameters may be easily prepared
by blending, for example, benzene ~S.P. ~.15) and
isooctane (S.P. 6.85) or perfluoro-n-heptane (S.P.
5.7).
3o ! A mixture of about 72 parts of benzene with
about 28 parts of isooctane will provide a solvent
.
.
.

~iS3Z73
having a solubility parameter of about 8.5 at room
temperature (about 25C). Perfluoro-n-heptane has
a solubility parameter of about 5.7 at 25C, SQ a
mixture of 68 parts of this solvent with 32 parts
of benzene provides a solvent with a solubility
parameter of about 6.8, or isooctane of a solubility
parameter 6.85 may be used.
When 5 ml of the TFSA are mixed with 95 ml of
an 8.5 solubility parameter sol~ent at room tempçra-
ture, a clear solution should result. When 5 ml of
TFSA is mixed with a 6.85 solubility parameter sol-
vent, a cloudy mixture or one showing phase separa-
tion should result. Solvent mixtures have a solu-
bility parameter between about 7.0 and about 7.9 may
be prepared as described above and utilized in a
similar test procedure.
In interpreting the solubility parameter and
other tests, it should be recognized that the TFSA
consists not of a single material or compound but a
cogeneric mixture of products containing a range of
products of molecular weights distributed around the
average molecular weight and even containing small
amounts of the starting compounds employed in the
synthesis. AS a result, in running solubility and
solubility parameter tests, very slight appearances
of cloudiness or lack of absolute clarity should not
be interpreted as a pass or a failure to pass the
criteria. The intent of the test is to ensure that
the bulk of the cogeneric mixture, i.e., 75% or more,
meets the requirement. When the result is in doubt,
the solubility tests may be run in centrifuge tubes
_ g _
,

~iS3Z7;~
allowing subsequent rapid phase separation by centri-
fuging, after which the separated non-solvent phase
can be removed, any solvent contained in it can be
evaporated, and the actual weight or volume of
separated phase can be determined.
3. The TFSA should spread at the interface between
distilled water and refined mineral oil to form
~ ,, , . , , ;. _ . .
films with thickness no greater than about 20
Angstroms (0.0020 micrometer:? at a film ~ressure
of about 16 dYnes Per cm (-0.016 Newton Per meter).
Suitable methods of determining film pressure
are disclosed in N. K. Adam, I'Physics and Chemistry
of Surfaces", Third Edition, ~xford ~niversity Press,
London, 1941, pgs. 20 et seq, and C. M. Blair, Jr.,
.
"Interfacial Films Affecting The Stability of Petro-
leum Emulsions", Chemistry _nd Industry (London),
1960, pgs. 538 et seq. Film thickness is calculated
on the assumption that all of the TFSA remains on
the area of interface between ~il and water on which
the pr~duct or its solution in a volatile solvent
has been placed. Since spreading pressure is numeri-
cally eq~al to the change in interfacial tensi~n
resulting from spreading of a film, it is con~eni-
ently determined by making interfacial tension
measurements before and after adding a known amount
of TFSA to an interface of known area.
Alternatively, one may utilize an interfacial
film balance of the Langmuir type such as that
described by J. H. Brooks and B. A. Pethica,
Transactlons of the Faraday Society (1964), p. 20
et seq, or other methods which have been qualified
-- 10 --
- ~ .
,~
... . ~.

11532~3
for such interfacial spreading pressure determinations.
In determining the interfacial spreading pressure of
the TFSA products, I prefer to use as the oil phase a fairly
available and reproducible oil such as a clear, refined
mineral oil. Such oils are derived from petroleum and have
been treated with sulfuric acid and other agents to remove non-
hydrocarbon and aromatic constituents. ~ypical of such oils
is "Nujol", distributed by Plough, Inc. This oil ranges in
density from about 0.85 to 0.89 and usually has a solubility
parameter between about 6.9 and about 7.5. Numerous similar
oils of greater or smaller density and viscosity are commonly
available from chemical supply houses and pharmacies.
Other essentially aliphatic or naphthenic hydrocarbons
of low volatility are eq~ally usable and will yield similar
values of spreading pressure. Suitable hydrocarbon oils appear
in commercial trade as refined "white oils", "textile lubri-
cants", "paraffin oil", and the like. Frequently, they may
contain very small quantities of alpha-tocQpherol (Vitamin E)
or similar antioxidants which are oil-soluble and do not
interfere with the spreading measurements.
While the existence of micelles and of oily or aqueous
micellar solutions have been known for some time (see, e.g.,
"Surface Activity", Moilliet, Collie and Black, ~. Van Nostrand
& Co., New York (1961)) and are probably involved in many
operations involving detergency where either oily ~nonpolar)
or earthy (highly polar) soil particles are to ~e removed,
their utility in cooperation with hydrotropic agents for the
present purposes is an unexpected and unpredictable discovery.
In U.$. Patent No. 2,356,205, issued August 22, 1944,
to Chas. M. Blair, Jr. ~ Sears Lehman, Jr., a wide variety of
micellar solutions designed to dissolve petroleum oils, bitumen,

1153273
wax, and other relatively nonpolar compounds are described for
purposes of cleaning oil formation faces and for effecting
enhanced recovery of petroleum by solution thereof. At this
earLy date, however, the use of micellar principles was not
contemplated for the preparation of solutions of the relatively
high molecular weight demulsifiers.
However, some of the principles disclosed in the above
patent, omitting the main objective therein of dissolving
relatively large amounts of hydrocarbons, chlorinated hydro-
carbons, and the like, are applicable to preparation of the
present compositions.
The four necessary components of the micellar solu-
tions of TFSA are:
1. A micelle-forming amphipathic agent. Such may be
anionic, cationic, or nonionic and, if anionic or
cationic, may be either in salt form or as ~he free
acid or free base or mixt~res thereof.
2. A hy~rotr~pic agent. This is a small to medium
molecular weight semi-polar compound containing
oxygen, nitrogen or sulfur and capable of forming
hydrogen bonds. It is believed that such agents co-
operate in some manner with the amphipathic agent to
form clear or opalescent, stable compositions.
3. Water.
4. TFSA, having the properties recited above.
In addition to these components, the micellar solu-
tions may contain, but are not required to contain, salts,
hydrocarbons, or small amounts of other inorganic or organic
material. Such constitUents may be impurities, solvents, or
by-products of syntheses used in forming the hydrotropiç agent,
or may be additions found useful in forming the composition of
- 12 -

~153273
this invention. As an example of the latter, small amounts of
inorganic salts such as NaCl, Na2SO4, KNO3, CaC12, and the
like, are sometimes helpful in promoting homogeneity with a
minimum of amphipathic and hydrotropic agents. They may also
yield compositions of lower freezing point, a property useful
when the composition is employed in cold climates. Similarly,
ethylene glycol, methanol, ethanol, acetic acid, or similar
organic compounds may be incorporated into the compositions
to improve physical properties such as freezing point, ~is-
cosity, and density, or to improve stability.
As stated above, the micelle-forming amphipathic
agents which may be used in preparing the aqueous solutions
herein con~emplated may be either cation-active, anion-active,
or of the nonelectrolytic type. Amphipathic agents generally
have present at least one radical containing about 10 or more
carbon atoms and not more than about 64 carbon atoms per
molecule. This is true of the amphipathic agents employed in
the present invention as a component of the vehicle or solvent
or dispersant employed in the present compositions. The hydro-
phobic portion5 of these agents may be aliphatic, alicyçlic,alkylalicyclic, aromatic, arylalkyl, ~r alkylaromatic. The
preferred type of agents are those in which the molecule
contains a long, uninterrupted carbon chain containing from
10 to 22 carbon atoms in length. Examples of suitable anion-
active amphipa~hic agents include the common soaps, as well as
materials such as sodium cetyl sulfate, ammoni~m lauryl sul-
fonate, ammonium di-isopropyl naphthalene sulfonate, sodium
oleyl glyceryl sulfate, mahogany and green sulfonates from
petroleum or petroleum fractions or extracts, sodium stearami-
coethyl sulfonate, do-decylbenzene sulfonate, dioctyl sodium
sulfosuccinate, sodium naphthenate, and the like. Other
- 13 -

1153273
suitable sul~onates are disclosed and taught in U.S. Patent No.
2,278,171, issued February 17, 1942, to De Groote and Keiser.
Suitable cation-active compounds include cetyl
pyridinium chloride, stearamidoethyl pyridinium chloride, tri-
methyl-heptadecyl ammonium chloride, dimethyl-pentadecyl
sulfonium bromide, octadecylamine acetate, and 2-heptadecyl-3-
diethylene diaminoimidazoline diacetate.
Suitable nonelectrolytic amphipathic agents include
the oleic acid ester of nonaethylene glycol, the steric acid
ester of polyglycerol, oxyethylated alkylphenols, and long
chain alcohol ethers of polyethylene glycols.
It is of course, well known that amphipathic compounds
are readily and commercially available, or can be readily pre-
pared to exhibit the characteristic of more than one of the
above mentioned types. Such compounds are disclosed in U.S.
Patent No. 2,262,743, dated November 11, 1941, to De Groote,
Keiser and Blair. For convenience, in such instances where a
surface-active material may show the characteristics ~f more
than one of the above described types, it is understoo~ that
it may be classified under either or both types.
The mutual solvent or hydrotropic agents of the solu-
tion utilized in the present invention are characterizable as
compounds of a hydrophobic hydrocarbon residue of comparatively
low molecular weight combined with a hydrophilic group of low
molecular weight and are free from surface-active properties.
The hydrophobic residue may contain from 2 to 12 carbon atoms
and may be alkyl, alicyclic, aromatic, or alkyl substituted
alicyclic or aromatic, or may be the hydrocarbon portion of a
heterocyclic or hydrocarbon substituted heterocyclic group.
The hydrocarbon residue may have branched or normal chain
s~ructure, but no branch may h~ve a length of more than 7
-~ - 14 -

~1 53273
carbon atoms from the point of attachment to the hydrophilic
residue, counting a benzene or cyclohexyl group as bein~ equi-
valent in length to an aliphatic chain of three carbon atoms.
Where the hydrocarbon residue consists of not more than 4
carbon atoms, structures of the normal primary alkyl type are
preferred. Where the residue is made up of more than four
carbon atoms, then structures of secondary and tertiary types
are also good where the second and third branches may be methyl
or ethyl groups.
This hydrophobic hydrocarbon residue is combined
either directly or indirectly with a hydrophilic group of one
of the following groups:
(a) A hydroxyl group which may be alcoholic,
phenolic, or carboxylic;
(b) An aldehyde group;
(c) A carboxy amide group;
(d) An amine salt group;
(e) An amine group; and
(f) An alkali phenolate group.
By "indirectedly combined with one of these groups"
is meant that the hydrocarbon residue is combined as by
etherification, esterification, or amidification, or the like,
with another organic residue which contains not more than four
carbon atoms and also one or more of the hydrophilic groups
named above, provided that after said com~ination, at least
one of the hydrophile groups remains free. Specific examples
illustrating this class of compounds are: Ethyl alcohol, n-
amyl alcohol, alphaterpineol, p-cresol, cyclohexanol, n-buty-
raldehyde, benzaldehyde, n-butyric acid, glycol mono-butyrate,
propyl lactate, mono n-butyl amine hydrochloride, n-propionamid,
ethylene glycol mono n-butyl amine hydrochloride, n-propionamid,
- 15 -
~, ,- , . .

1153273
ethylene glycol mono n-butyl ether, pyridine, methylated
pyridine, piperidine, or methylated piperidines.
The solubilizer (mutual solvent or hydrotropic com-
pound above described) is essentially a semi-polar liquid in
the sense that any liquid whose polar character is no greater
than that of ethyl alcohol and which shows at least some
tendency to dissolve in water, or have water dissolved in it,
is properly designated as semi-polar.
The solubilizer or semi-polar liquid indicated may be
illustrated by the formula X - Z, in which X is a radical
having 2 to 12 carbon atoms, and which may be alkyl, alicyclic,
aromatic, alkylalicyclic, alkylaryl, arylalkyl, or ali~yclic-
alkyl in nature, and may, furthermore, include heterocyclic
compounds and substituted heterocyclic compo~n~s. There is the
added limitation that the longest carbon atQm chain must be
less than eight carbon atoms, and that, in such characteri-
zation, cyclic carbon atoms must be counted as one-half.
Z represents:
U H O U
11 /
- OH:-N ; - C ; --CN ; - COOH; or - OMe
\V ~0 \V
where U and V are hydrogen or a hydrocarbon substituent and Me
is an alkalie metal;
N
if X is a cyclic teritary amine nucleus;
NH
if X is a cyclic secondaLy amine nucleus.
The sPmi-polar liquid also may be indicated by the
following formula: - X -Y - R -(Z)n' Here X and Z have their
- 16 -

llS3273
previous significance, R is - CH2 - , - C2H4 - , - C3H5 - ;
- C3H6 - or - C2H4 O C2 4
and n is either one or two as the choice of R demands. Y is
one of the following:
O H H O O O
Il l l 11 11 11
- C -N -; - N -C -; - C - O -; - O -C - ; - O-; - S - .
In general, these hydrotropic agents are liquids
having di-electric constant values between about 6 and about
26, and have at least one polar group containing one or more
atoms of oxygen, and/or nitrogen. It is significant, perhaps,
that all of the solubilizers are of types known tQ be able to
form hydrogen bonds.
The choice of solubilizer or common solvent and its
propor~ion in the mixture depends somewhat upon the amphipathic
agent used, the amount and kind of TFSA used, and the propor-
tion of water used, and is best determined by preparing experi-
mental mixtures on a small scale.
In some cases, it is desirable to include in the solu-
tion small amounts of acid, alkali, or inorganic salts, as it
has been found that the presence of these electrolytes often
gives solutions having greater stability and a wider range of
miscibility with water and organic material. Excess acid, when
used, will usually be in solutions containing a cation-active
or nonelectrolytic wetting agent, but not exclusively so.
Excess alkali, when used, will usually be in a solution contain-
ing anion-active wetting agents, but, again, not exclusively.
The acylated polyether polyol or TFSA utilized in this
invention is generally ar. organic polymer or semi-polymer with
an average molecular weight above about 800 and below about
30,000 and has a structure which will allow orientation on
polar surfaces with much or most of the elements of the molecule
- 17 -
~ ~ .
.

1153273
in a thin plane. To be effectively adsorbed at oil-water or
oil-rock interfaces and subsequently to be desorbed at wa~er-
rock interfaces, the TFSA must generally contain constituents
which give it a highly distributed hydrophile and hydrophobe
character, and without such concentrations of either hydro-
philic or hydrophobic groups as to producç water solubility or
oil solubility, in the ordinary macroscopic sense. The TFSA
also appears to differ from formerly used surfactants in that
the effects on oil-water interfacial tensions as a function of
concentration are limited. While spreading efficiently at such
interfaces to form thin films with spreading pressures up to
about 35 to 40 dynes per cm, addition or larger amounts of TFSA
have relatively little effect on interfacial tension. Also,
the present TFSA constituent of the micellar solution in con-
trast to formerly used surfactants, has relatively little or
no tendency to stabilize either oil-in-water or water-in-oil
emulsions when present in normal use amounts.
The acylated polyether polyol or TFSA utilized in this
invention is generally an organic polymer or semi-polymer with
an average molecular weight above about 800 and below abo~t
30,000 and has a structure which will allow orientation on
polar surfaces with much or most of the elements of the mole-
cule in a thin plane. To be effectively adsorbed at oil-water
or oil-rock interfaces and subsequently to be desorbed at water-
rock interfaces, the TFSA must generally contain constituents
which give it a highly distributed hydrophile and hydrophobe
character, and without such concentrations of either hydro-
philic or hydrophobic groups as to produce water solubility or
oil solubility, in the ordinary macroscopic sense. The TFSA
also appears to differ from formerly used surfactants in that
the effects on oil-water interfacial tensions as a function of
- 18 -

llS3Z73
concentration are limited. While spreading efficiently at
such interfaces to form thin films with spreading pressures up
to about 35 to 40 dynes per cm, addition or larger amounts of
TFSA have relatively little effect on interfacial tension.
Also, the present TFSA constituent of the micellar solution in
contrast to formerly used surfactants, has relatively little
or no tendency to stabilize either oil-in-water or water-in-oil
emulsions when present in normal use amounts.
Usually the TFSA constituents applicable to the
practice of the invention are organic molecules containing
carbon, hydrogen and oxygen, although in some instances they
may also contain sulfur, nitrogen, silicon, chlorine, phos-
phorous or other elements. Small amounts of inorganic material
such as alkalies, acids or salts may appear in the compositions
as neutralizing agents, catalyst residues or otherwise. The
critical requirements for the TFSA compositions are not so
much compositional as structural an~ physical. They must be
made up of hydrophilic (polar) moieties, usually ones capable
of forming hydrogen bonds, such as hydroxyl, carbonyl, ester,
ether, sulfonium, amino, ammonium, phospho or similar hydrogen
bonding groups, connected by or to hydrophobic groups, such as
alkylene, alkyl, cycloalkyl, aryl, arylene, aralkyl, poly-
alkylene, polyalkylyne, combinations of such groups and such
groups containing relatively non-polar substituents, such as
hydrocarbon, chlorine, fluorine and the like. Sometimes the
hydrophobic moieties are larger and contain more atoms than
the polar groups in the molecule, having a minimum of two
carbon atoms in each group and up to as many as 36 carbon atoms,
although the actual ratio of sizes depends greatly on the
structure of the hydrophilic moiety. Most commonly, the hydro-
phobic groups will contain 14 to 22 carbon atoms and will have
-- 19 --
. .

llS3273
linear or sheet-like conformations allowing for relatively flat
orientation on surfaces.
Polar moieties other than hydrogen bonding ones are
not excluded from these compositions and, indeed, may be de-
liberately included in some structures to improve adsorption
and interfacial spreading tendencies. For example, quaternary
ammonium groups, while incapable of forming hydrogen bonds, can
improve spreading and interfacial adsorption in some appli-
cations by way of their highly ionized form which imparts
cationic character to the molecules in which they occur and,
via coulombic repulsion effects, can improve spreading in a
film.
Generally, the TFSA constituents will contain at least
two each of the required hydrophilic (polar) and hydrophobic
moieties per molecule and commonly will contain many mQre of
each. The effective products, however, must have the three
properties described above.
While, as pointed out above, the effective TFSA may be
derived from a wide variety of chemical reactants and may
contain numerous different groups or moieties, I have fo~nd
that particularly effective products are those which are
described as an acylated polyether polyol having the form~la:
/ [ j ]n
{~ [(A)kH~ } m
wherein:
A is an alkylene oxide group, -CiH2iO-;
O is oxygen;
i is a positive integer no greater than about lQ;
j is a positive integer no greater than about 100;
- 20 -

1~53273
k is a positive integer no greater than about 100;
N is nitrogen;
Rl is one of hydrogen, a monovalent hydrocarbon group contain-
ing less than about Cll, or [~ H];
L is a positive integer no greater than about 100;
R is a hydrocarbon moiety of a polyol, a primary or secondary
amine, a primary or secondary polyamine, a primary or
secondary amino alcohol, or hydrogen; and
m + n is no greater than about 4 when R is other than hydrogen
and one of m and n is zero and the other is unity when R
is hydrogen,
said acylated polyether polyol being the reaction product of
said polyether polyol and a member selected from the class
consisting of mono- and polybasic carboxylic acids, acid an-
hydrides, and iso-, diiso-, and polyisocyanates, said acylated
polyether polyol at about 25C: (a) being less than abo~t 1%
by volume soluble in water and in isooctane; (b) having a solu-
bility parameter in the range of between about 6.9 and about
8.5; and (c) spreading at the interface between distilled water
and refined mineral oil to form a film having a thickness no
greater than about 20 Angstroms at a film pressure of about
16 dynes per cm.
Alternatively, the TFSA constit~ents may be described
as acylated polyether polyols derivable by the reaction of an
alkylene oxide containing less than about 10 carbon atoms with
a member of the group consisting of polyols, amines, polyamines
and amino alcohols containing from between about 2 to about 10
active hydrogen groups capable of reaction with alkylene oxides
and the acylating agent being a member selected from the class
consisting of mono- and polybasic carboxylic acids, acid an-
hydrides and iso-, diiso- and polyisocyanates.
- 21 -

~lS3273
Compositions incorporated within the scope of the
formula set forth above contain an average of about 1~ or more
hydroxyl groups per molecule and are generally composed of a
cogeneric mixture of products obtained by condensing alkylene
oxides with smaller molecules containing two or more reactive
hydrogens as part of hydroxyl or amino groups.
Representative of these compositions is polypropylene
glycol, having an average molecular weight of about 1,200, to
which about 20% by weight of ethylene oxide has been added.
Such a polyether glycol is theoretically obtainable by condens-
ing about 20 moles of propylene oxide with about one mole of
water, followed by addition of about six moles of ethylene
oxids. Alternatively, one may condense about 20 moles of
propylene oxide with a previously prepared polyethylene glycol
of about 240 average molecular weight.
Alkylene oxides suitable for use in preparing the
TFSA constituents used in the present solutions include
ethylene oxide, propylene oxide, butylene oxide, 2-3-epoxy-2-
methyl butane, tri-methylene oxide, tetrahydrofuran, glycidol,
and similar oxide~ containing less than about 10 carbon atoms.
Because of their reactivity and relatively low cost, the pre-
ferred alkylene oxides for preparing ef~ective TF$A CQnStitUentS
are the 1,2-alkylene oxides (oxiranes) exemplified by ethylene
oxide, propylene oxide and butylene oxide. In the preparation
of many TFSA constituents, more than one alkylene Qxide may be
employed either as mixtures of oxides or sequentially to form
block additions of individual alkylene oxide groups.
Other suitable dihydric alcohols may be obtained by
condensing alkylene oxides or mixtures of oxides or in
successive steps (blocks) with difunctional (with respect to
oxide addition) compounds, such as ethylene glycol, methyl
- 22 -

1~53273
amine, propylene glycol, hexamethylene glycol, ethyl ethanol-
amine, analine, resorcinol, hydroquinone and the like.
Trihydric ether alcohols may be prepared by condensa-
tion of ethylene, propylene or butylene oxides with, for
example, glycerin, ammonia, triethanolamine, diethanolamine,
ethyl ethylene diamine or similar smaller molecules containing
three hydrogens capable of reacting with alkylene oxides.
Similarly, polyether alcohols with a multiplicity of hydroxyl
groups may be obtained by condensing alkylene oxides with multi-
reactive starting compounds, such as pentaerythritol, glycerol,
N-monobutyl ethylene diamine, trishydroxymethylaminomethane,
ethylene diamine, diethylenetriamine, diglycerol, hexamethylene
diamine, decylamine and cyclohexylamine. DeGroote, in U.S.
Patent No. 2,679,511, describes a number of amino derived
polyols which he subsequently esterfies. Product 15-200, manu-
factured and sold by the Dow Chemical Company, and derived ~y
oxyalkylation of glycerol with a mixture of ethylPne and pro-
pylene oxides, is an example of a commercially availa~le polyol
of the kind contemplated herein.
Generally, these compositions will have average mole-
cular weights of 15,000 or less and will he deri~ed from
reactive hydrogen compounds having 18 or fewer carbon at~ms and
10 or fewer reactive hydrogens.
Other general descriptions of suitable compounds coming
within the scope of the structure detailed above, along with
methods for carrying out the actual manuacturing steps, are
disclosed in "High Polymers, Vol. XIII, Polyethers," edited by
N.G. Gaylord, John Wiley & Sons, New York, 1963.
Effective TFSA with improved performance may be pre-
pared by acylation of the polyether polyol described above with
a mono- or polybasic carboxylic acid, acid anhydride, isocyanate,
- 23 -

~153Z~3
diisocyanate or other polyisocyanate. An especially useful
TFSA may be made by reacting an approximately difunctional
polyether polyol with a difunctional carboxylylic acid, acid
anhydride or isocyanate to form a polymeric ester or urethane.
However, polymerization is not always required, and where
effected is usually not carried to the point of including a
very large number of monomer units in the molecule. Frequently,
effective reagents are obtained where residual, unreacted
hydroxyl or carboxyl groups remain the product or, where a
polyisocyanate is used, one or more residual isocyanate groups
or amino or substituted urea groups which result from reaction
of residual end groups with water, followed by decarboxylation,
may remain.
Examples of acylating agents suitable for preparing
useful esters include acetic acid, acetic anhydride, butyric
acid, benzoic acid, abietic acid, adipic acid, ~iglycollic acid,
phthallic anhydride, fumaric acid, hydroxyacetic acid, itaconic
acid, succinic acid, dimerized fatty acids and the like. I
have found the most generally useful acylating agents to be
the di- and mono-basic acids and anhydrides containing less
than 13 carbon atoms.
Examples of isocyanates useful for the acylation of a
polyether polyol to produce an effective TFSA include methyl-
isocyanate, phenyl isocyanate, cyclohexylmethylene isocyanate,
and the like. Especially useful reactants are polyisocyanates
containing two or more isocyanate groups and including phenylene
diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate
hexame~hylene diisocyanate, 1,5-Naphthalene diisocyanate and
polymethylene-polyphenyl isocyanates.
Following acylation reactions of polyether polyols
with polyisocyanates, where a stoichiometric excess of the
- 24 -
~ .
. . . .~

liS3Z73
latter reactant is employed, remaining isocyanate groups may
be left as such or may, by appropriate addition of water or
monohydric alcohol, be converted to carbamic acid groups,
whic:h immediately mdergo decarboxylation to yield residual
amino groups, or carbamate groups.
Examples of acylated polyether polyols and their manu-
facturing procedures are well known to the art, as disclosed in
U.S. Patent No. 2,45~,808, issued November 30, 1948, to
Kirkpatrick, U.S. Patent No. 2,562,878, issued August 7, 1951,
to Blair, U.S. Patent No. 2,679,511, issued May 25, 1954, to
DeGroote, U.S. Patent No. 2,602,061, issued July 1, 1952, also
to DeGroote, "Chemical Process Industries" by R. N. Shreve,
McGraw Hill Publishing Co., 1967, page 654 et seq., and "High
Polymers", Vol. XIII, edited by N. G. Gaylord, John Wiley &
Sons, 1963, page 317 et seq.
As to the limits of the various constituents ~f the
micellar solutions containing TFSA, the following will serve
as a guide, the percentages being by weight:
Percent
, ~ r ~
TF5A Constituents about 5 to about 75
Hydrotropic Agent about 2 to about 30
Amphipathic Agent about 2 to about 30
Water about 15 to about 90
Although the exact function of the electrolytes pre-
viously referred to is not completely understood, the effect,
in part, may be due to the ability to bind water, i.e., to
become hydrated. This suggests that certain other materials
which are highly hydrophile in character and clearly differ-
entiated from the classes of non-polar solvents and semi-polar
solubilizers may be the functional equivalent of an electrolyte.
Substances of this class which ordinarily do not dissociate
- 25 -

1153273
include glycerol, ethylene glycol, diglycerol, sugar, glucose,
sorbitol, mannitol, and the like.
Also, as stated above, these solutions may contain
other organic constituents such as hydrocarbons. These fre-
~uently are used as thinning agents, azetropic distillation
aids or reflux temperature controllers in the manufacture of
the TFSA constituent and may be left-therein when the present
micellar solutions are prepared. To the extent that such com-
pounds are present they appear to compete somewhat with the
TFSA constituent for micelle space, thus limiting, to some
extent, the maximum amount of TFSA constituent which can be
brought into homogeneous solution.
Selection of an effective TFSA composition for a given
petroleum emulsion and determination of the amount required is
usually made by so-called "bottle tests", conducted, in a
typical situation, as follows:
A sample of fresh emulsion is obtained and 100 ml
portions are poured into each of several 180 ml screw tQp pre-
scription or similar graduated bottles. Dilute solutions (1%
or 2%) of various TFSA constituents are prepared in isopropyl
alcohol. By means of a graduated pipette, a small ~olume of a
TFSA solution is added to a bottle. A similar vQlume of each
composition is added to other bottles containing emulsion. The
bottles are then closed and transferred to a water ~ath held
at the same temperature as that employed in the field treating
plant. After reaching this temperature, the bottles are shaken
briskly for several minutes.
After the shaking period, the bottles are placed up-
~; right in the water bath and allowed to stand quietly. Perio-
dically, the volume of the separated water layer is recorded
along with observations on the sharpness of tha oil-water
- 26 -
$

1153Z73
interface, appearance of the oil and clarity of the water
phase.
After the standing period, which may range from 30
minutes to several hours, depending upon the temperature, the
viscosity of the emulsion and the amount of TFSA compositions
used, small samples of the oil are removed by pipette or
syringe and centrifuged to determine the amount of ~ree and
emulsified water left in the oil. The pipette or syringe used
to remove the test samples should be fitted through a stopper
or other device which acts as a position guide to insure that
all bottles are sampled at the same fluid level.
The combined information on residual water and emul-
sion, speed of the water separation and interface appearance
provides the basis for selection of the generally most effec-
tive TFSA constituent. Where none of the results are satis-
factory, the tests should be repeated using higher c~ncentra-
tions of TFSA constituents and, conversely, where all results
are good and similar, the tests should be repeated at lower
concentrations until good discrimination is possi~le.
In practicing the process for resolving petroleum
emulsions of the water-in-oil type with the present micellar
solution, such solution is brought into contact with ~r caused
! to act upon the emulsion to be treated, in any of the various
methods or apparatus now generally used to resolve or break
petroleum emulsions with a chemical reagent, the above pro-
cedure being used alone or in combination with other demulsify-
ing procedure, such as the electxical dehydration process.
One type of procedure is to accumulate a volume of
emulsified oil in a tank and conduct a batch treatment type of
demulsification procedure to recover clean oil. In this
procedure, the emulsion is admixed with the micellar TFSA
- 27 -

~153273
solution, for example, by agitating the tank of emulsion and
slowly dripping the micellar TFSA solution into the emulsion.
In some cases, mixing is achieved by heating the emulsion while
dripping in the micellar TFSA solution, depending upon the
convection currents in the emulsion to produce satisfactory
admixture. In a third modification of this type of treatment,
a circulating pump withdraws emulsion from, e.g., the bottom
of the tank and reintroduces it into the top of the tank, the
micellar TFSA solution being added, for example, at the suction
side of said circulating pump.
In a second type of treating procedure, the micellar
TFSA solution is introduced into the well fluids at the well-
head, or at some point between the wellhead and the final oil
storage tank, by means of an adjustable proportioning mechanism
or proportioning pump. Ordinarily, the flow of fluids through
the subsequen~ lines and fittings suffices to produce the
desired degree of mixing of micellar TFSA solution and emulsion,
although, in some instances, additional mixing devices may be
introduced into the flow system. In this general procedure,
the system may include various mechanical devices for with-
drawing free water, separating entrained water, or accomplish-
ing quiescent settling of the chemically treated emulsion.
Heating devices may likewise be incorporated in any of the
treating procedures described herein.
A third type of application (down-the-hole~ of mi-
cellar TFSA solution to emulsion is to introduce the micellar
solution either periodically or continuously in dil~ted form
into the well and to allow it to come to the surface with the
well fluids, and then to flow the chemical-containing emulsion
through any desirable surface equipment, such as employed in
the other treating procedures. This particular type of appli-
- 28 -
._

llS3273
cation is especially useful when the micellar solution is used
in connection with acidification of calcareous oil-bearing
strata, especially if dissolved in the acid employed for
acidification.
In all cases, it will be apparent from the foregoing
description, the broad process consists simply in introducing
a relatively small proportion of micellar TFSA solution into a
relatively large proportion of emulsion, admixing the chemical
and emulsion either through natural flow, or through special
apparatus, with or without the application of heat, and allow-
ing the mixture to stand quiescent until the undesirable water
content of the emulsion separates and settles from the mass.
Besides their utility for breaking petroleum em~lsions,
the present micellar TFSA splutions~ as mentioned earlier, may
be used to prevent emulsion forma~ion in steam flooding, in
secondary waterflooding, in acidiæing of oil-producing forma-
tions, an~ the like.
Petroleum oils, even after demulsification, may contain
substantial amounts ~f inorganic salts, either in solid form
or as small remaining brine droplets. For this reason, most
petroleum oils are desalted prior to refining. The desalting
step is effected by adding and mixing with the oil a few volume
percentages of fresh water to contact the ~rine and salt. In
the absence of demulsifier, such added water would also become
emulsified without effecting its washing action. The p~esent
micellar solutions may be added to the fresh water to prevent
its emulsification and to aid in phase separation and removal
of salt by the desalting process. Alternatively, if desired,
they may be added to the oil phase as are present aromatic
solvent compositions.
Most petroleum oil, along with its accpmpanying brines
- 29 -

~153273
and gases, is corrosive to steel and other metallic structures
with which it comes in contact. Well tubing~ casing, flow
lines, separators and lease tanks are often seriously attacked
by well fluids, especially where acidic gases such as H2S or
C2 are produced with the liquids, but also in systems free of
such gases.
It has been known for some time, and as exemplified
in U.S. Patent 2,466,517, issued April 5, 1949, to Chas. M.
Blair and Wm. F. Gross, that such corrosive attack of crude oil
fluids can be mitigated or prevented by addition to the fluids
of small amounts of organic inhibitors. Effective inhibitors
compositions for this use are usually semi-polar, surface
active compounds containing a nonpolar hydrocarbon moiety
attached to one or more polar groups containing nitrogen,
oxygen or sulfur or combinations of such elements. Generally
these inhibitors or their salts are soluble in oil and/or water
(brine) and frequently appear to be able to form mic~lles in
one or both of these phases. Typical inhibitors include amines
such as octyl amine, dodecyl amine, dioctodecyl amine, butyl
naphthyl amine, dicyclohexyl amine, benzyl dimethyldodecyl
ammonium chloride, hexadecylaminopropyl amine, decyloxypropyl
amine, mixed amines prepared by hydrogenation of nitrile deri-
vatives of tall oil fatty acids, soya acid esters of mono-
ethanol amine, 2~undecyl, l-amino ethyl imidazoline and a wide
variety of cationic nitrogen compounds of semi-polar character.
Also effective in some applications are nonyl succinic acid,
diocylnaphthalene sulfonic acid, trimeric and dimeric fatty
acids, propargyl alcohol, mercaptobenzothiozole, 2, 4, 6-tri-
methyl-l, 3, 5-trithiaane, hexadecyldimethyl benzimidazolium
bromide, 2-thiobutyl-N-tetrodecylpyridinium chloride, tetra-
hydronaphthylthiomorpholine, and the like.
- 30 -
~r~

1153Z73
In contrast to the TFSA, corrosion inhibitors appear
to function by forming on the metal surface strongly adherent,
thick, closely packed films which prevent or lessen contact of
corrosive fluids and gases with the metal and interfere with
ionic and electron transfer reactions involved in the corrosion
process.
Corrosion inhibitors are quite commonly introduced
down the casing annulus of oil wells where they commingle with
the well fluids before their travel up the well tubing and thus
can effectively prevent corrosion of well equipment. Where
corrosive attack occurs at the surface, the inhibitor may be
introduced at or near the well head, allowing it to adsorb on
the flow lines and surface equipment to insure protection.
Addition of inhibitor at either downhole or surface
locations may be com~ined conveniently with demulsifier addi-
tion since the latter is also frequently introduced in one of
these locations.
Inhibitors such as those mentioned above, may generally
be incorporated into the TFSA micellar solutions, replacing a
portion of or in addition to the TFSA constit~ent. AlsQ, since
many of these inhibitors are themselves micelle-forming amphi-
pathic agents, they may be included in the micellar sol~tion as
such, replacing other amphipathic agents which might be other-
wise utiliæed. Combining the micellar solu~ion with corrosion
inhibitor permits more economic chemical treatment by reducing
inventory to one compound, requiring only one chemical injec-
tion system rather than two and lessening the labor and super-
vision required.
Still another important effect of using the micellar
solution of TF$A and corrosion inhibitor results from the pre-
vention of emulsification by the inhibitor. Frequently, it has
- 31 -

llS3Z73
been found that inhibitor in the amount required for effective
protection causes the formation of very refractive emulsions
of water and hydrocarbon, especially in systems containing
light, normally nonemulsifying hydrocarbons such as distillate,
casing head gasoline, kerosene, diesel fuel and various re-
finery fractions. Inhibitors are commonly used in refinery
systems where emulsification is highly objectionable and where
the compositions could be designed to include an effective
emulsion preventative micellar solution of TFSA.
Inhibitor use may range from a few to several hundred
parts per million based on the oil to be treated, depending
upon the severity of corrosion. For a given oil field or group
of wells, tests will normally be run to determine the require-
ment for micellar solution of TFSA and for inhibitor and a
composition incorporating these components in approximately the
desired ratio will be prepared. In some instances, the require-
ment for micellar solution of TFSA in the best concentration
may result in use of corrosion inhibitor, employed as micelle-
former, in some excess over that required for inhibition. This
will not affect the utility of the micellar solution and will
provide a comfortable excess of inhibition which can be helpful
during the periods when higher corrosivity may be ~ncountered.
Examples of micellar solutions employing TFSA with
inhibitor in water ~ispersible, micellar sol~tions are given
below.
Selection of the proper corrosion inhibitox for a
~iven system or oil is usually made by conducting laboratory
tests under conditions simulating those encountered in the well
or flowline. Such tests are exemplified by that described in
Item No. lK155, "Proposed Standardized Laboratory Procedure for
Screening Corrosion Inhibitors for Oil and Gas Wells", published
- 32

1153Z73
by the National Association of Corrosion Engineers, Houston,
Texas.
EXAMPLES OF THIN FILM SPREADING AGENTS
EXAMPLE I
Reference is made to U.S. Patent No. 2,562,878, dated
August 7, 1951, to Chas. M. Blair, Jr., which describes the
preparation of demulsifiers which are polyesters of dicar-
boxylic acids and polyhydric alkylene ether glycols. Using the
procedure described therein, 150 lbs. of diglycolic acid was
reacted with 2,000 lbs. of "Pluronic ~-62" manufactured by
Wyandotte Chemical Corporation of Wyandotte, Michigan.
"Pluronic L-62" is described as a polypropylene glycol having
a molecular weight of about 1,650 to which has been added and
condensed therewith about 25% by weight of ethylene oxide.
The esterification reaction was continued until the
acid number of the reaction mixture had dropped to about 15.
The resulting product was a moderately viscous liquid,
insoluble to the extent of 1% in either water or isooctane, had
a Solubility Parameter of 8.1, and spread at the interface
between white mineral oil and water at 25~C to yield a film
pressure of 22 dynes per cm at a calculated thickness of 14
Angstroms.
EXAMPLE II
Using the procedure described by C. H. M. Roberts in
U.S. Patent No. 1,977,146, dated October 23, 1934, one mole
each of the mono- and diglycerides of ricinoleic acid were
reacted with three moles of phthallic anhydride. The reaction
was stopped short of gelation to yield a viscous, reddish
polymer, insoluble in water and isooctane, having a solubility
parameter of 8.4 and spreading at the white oil-distilled water
interface with a pressure of 20 dynes per cm at a calculated
*Trademark
- 33 -

1;~532~3
thickness of 10 Angstroms,
EXAMPLE III
:
To 1,000 parts of commercial polyoxypropylene glycol
of molecular weight of about 2,000 was added 200 parts of
ethylene oxide. Reaction was conducted as in Example I. After
completion of the ethylene oxide addition, a mild vacuum was
applied for 30 minutes to remove any unreacted oxide. The
temperature was lowered to 40C and 5 parts of dodecylbenzene
sulfonic acid were added to the reaction mass while stirring.
Eighty parts of phenyacetic acid were then introduced and heat-
ing and stirring were commenced under a take-off condensor.
The temperature was slowly raised to about 160C over a three-
hour period and was held at this temperature for an additional
2 hours.
The product was then cooled and drummed. It was an
effective demulsifier especially for petroleum emulsions en-
countered in southern Louisiana, and met the criteria recited
previously for such interfacially active compounds.
EXAMPLE IV
~ , .
Two and one-half parts of tris-hydroxymethylamino-
methane was added with stirring 5 parts of maleic anhydride.
The temperature was then raised to 130QC while the ~essel was
open to take-off condensor. Stirring and heating were con-
tinued until a sample of the reaction mass had a viscosity in
the range of 900 tQ 1,100 centipoises at 80C.
This product was an effective thin film spreading
agent and especially useful as a demulsifier for petroleum
emulsions occurring in western Kansas and in Kuwait.
EXAMPLE V
,
Using the apparatus and procedure of Example I, 4,000
lbs. of polypropylene glycol of average molecular weight 1,200
- 34 -

liS3;~73
was condensed with 700 lbs. of ethylene oxide. Forty pounds
of potassium hydroxide was dissolved in the polypropylene
glycol prior to oxide addition, which was carried out within
the temperature range of about 140 - 160C under a maximum
pressure of about 75 psi.
After completion of the above reaction, the tempera-
ture was lowered to about 60C and the reaction vessel was
connected to a take-off condensor. Fifty pounds of 85% phos-
phoric acid was slowly added to the reaction mass with stirring
followed by 314 lbs. of adipic acid. The temperature was then
slowly brought to 145 - 155C while continuing to stir and to
distill water from the reaction mixture. The acid number of
the product was periodically determined. When a valve between
10 and 15 mg. KOH per gm. was reached, heating was stopped r
the product was cooled to r~om temperature and filled into
55-gallon drums.
This product has a calculated equivalent weight in
excess of 4,000, is insoluble to the extent of 1% in water and
isooctane, has a solubility parameter of 7.9 and rapidly
spreads at the interface between white oil and distilled water,
at 25C, to give a film pressure of 18 dynes per cm at a cal-
culated thickness of 18 Angstroms.
EXAMPLE VI
~ ~ . .
Into a 1,000 gal. stainless steel autoclave, equipped
with steam jacket, internal cooling coils, stirrer, condensor
and several inlet feed lines were place 92 lbs. Qf glycerol.
2,750 lbs. of a mixture of 2,250 lbs. of propylene oxide and
500 lbs. of ethylene oxide was prepared in a separate weighed
feed tank. Twelve pounds of a 50% aqueous solution of
potassium hydroxide was stirred into the glycerol while heating
to about 120C. During this period, the vessel was connected
- 35 -

1~53273
to a steam jet vacuum system through the condensor, arranged
in take-off position. Stirring under vacuum was continued
until the evolution of water had effectively ceased.
The vessel was then closed and the mixed oxides were
introduced slowly. The resulting exothermic reaction was
controlled by the oxide addition rate such as to allow a slow
increase in temperature to about 150C. After the addition of
about 800 lbs. of oxides the rate of reaction declined. The
oxide addition line was then closed, the temperature lowered
to 110C, the vessel was vented briefly to the ~acuum jet, and
an additional 25 lbs. of 50% aqueous solution of potassium
hydroxide was introduced into the reaction mass which was then
stirred under vacu~m at 120 - 140C until water evolution
ceased.
The vessel was closed, the oxide inlet line was again
opened and reaction was continued with the fresh catalyst,
holding the t~mperature at about 150C under a maximum pressure
of about 50 psi until the whole of the 2,750 lbs. of mixed
oxide had bee~ reacted.
After cooling this batch to about 120C, 1,~60 lbs. of
commercial mixed xylene was pumped into the autoclave and the
whole was stirred and adjusted to a temperature of about 95C.
A solution of 125 lbs. of toluene diisocyanate in 200 lbs. of
xylene was then slowly pumped into the vessel while maintaining
; the temperature at 100 ~ 5C for approximately the two hours
re~uired for the addition. The temperature was then raised to
140C and stirring was continued until the viscosity at 100~
was within the range of 1,000 to 1,500 centipoises. Heating
was then discontinued and the batch was cooled ~uickly to allow
transfer to storage.
- 36 -

1153;~73
A sample of this product, after removal of xylene by
vacuum distillation was found to meet the three criteria for
a TFSA.
EXAMPLES OF MICELLAR SOLUTIONS OF TFSA's
EXAMPLE A
Wt. %
Product of Example II 40
2-heptadecyl-3-triethylene triaminoimidazoline 6
Acetic Acid 1.5
10 Phenol 2.5
n-Butanol 10
Water 40
Besides having good demulsification action, this
product is an effective corrosion inhibitor for down-the-hole
use, the imidazoline used as the amphipathic agent being a
strongly adsorbed inhibitor for steel in anaerobic systems.
EX~MPLE B
Wt. %
Pxoduct of Example IV 20
20 n-Dodecylbenzene sulfonic acid 6
Methanol 14
Ethylene glycol monobutyl ether 10
Water 50
This clear, homogeneous solution is quite acidic.
It can be combined with 15% hydrochloric acid used for acidiz-
ing calcareous oil-producing formations and acts therein to
prevent emulsification of acid and spen~ acid.
EXAMPLE C
. ~..,
Wt %
30 Product of Example II 70
Oleyl amine 10
- 37 -
~ .

1153273
Acetic Acid 3
n-Propanol 2
Water 15
This is a clear, homogeneous but viscous solution.
EXAMPLE ~
Wt. %
Product of Example III 35
Dinonylphenolsulfonic acid 8
50% Aqueous NaOH 2
Isopropanol g
Methanol 10
Water 36
EXAMPLE E
Wt. %
Product of Example I 28
Ethyleneglycol monobutyl ether 14
5-mole ethylene adduct of p-nonyl phenol 14
Water 44
ThiS product may be diluted further with water to
form clear to slightly opalescent solutions.
EXAMPLE F
Wt. %
Product of Example VI 41.0
! Ammonium dodecylbenzene sulfonate 17.5
Isopropanol 24.0
Water 17.5
This product is an efective micellar compasition for
numerous petroleum emulsions, bllt is especially effective as a
component in synergistic blends with the composition of Example
B and with other compositions such as those disclosed in my
co-pending applications.
$ - 38
~,.

1153273
The product of Example F has also been found to be an
effective waterflood additive, especially in combination with
aqueous micellar solutions of resinous polyoxide adducts such
as those described in my co-pending application, Serial No.
361,787, filed October 8, 1980, and entitled, "Micellar Solu-
tions of Thin Film Spreading Agents Comprising Resinous Poly-
alkylene Oxide Adducts".
EXAMPLE G
Wt. %
10 Product of Example IV 35
Octaethyleneglycol Monooleate 10
Ethylene glycol monobutyl ether 12
"Polyox" coagulant grade (a commercial
polyethylene oxide of about
5 million molecular weight) 2
Water 41
This product is a very viscous, redish liquid, readilydispersible in water to form slightly opalescent solutions. It
is effective alone or in combination with other aqueous systems
or dilu~ed in water as a flooding agent for oil recovery,
especially where a higher viscosity agent is needed for mobility
control.
Further, it is an effective demulsifier for heavy oil
emulsion produce~ in the McKittrick, Ca.field and is even more
effective in a 50-50 blend with the composition of Example E.
Still further, this product is found to assist in the
flocculation and sedimentation of finely ground hematite
particles during the decantation of aqueous slurries of the
ground ore to remove sand and clay minerals and effect bene-
ficiation of the iron-containing values.
Among procedures which have been found usef~l in
selecting effective micellar TFSA solutions for this use, one
*Trademark
- 39 -
,

liS3273
involves a determination of oil displacement efficiency from
prepared oil-containing rock cores in equipment described below.
A tube of glass or transparent polymethacrylate ester, having
an inside diameter of about 3.5 cm (1~ in.) and a length of
about 45 cm (18 in~), is fitted with inlet connections and
appropriate valves at each end. The tube is mounted vertically
on a rack in an air bath equipped with a fan, heater and thermo-
stat which allows selection and maintenance of temperatures in
the range of between about 25 - 130C.
To select an effective micellar TFSA solution for use
in a given oil formation, samples of the Qil, of the producing
rock formation and of the water to be used in the flooding
operation were obtained. The formation rock is extracted with
toluene to remove oil, is dried and is then ground in a ball
mill to the point where a large percentage passes a 4Q mesh
sieve. The fraction between 60 and 100 mesh in size is re-
tained. The tube described above is removed from the air bath,
opened and, after insertion of a glass wool retaine~ at the
lower end, is packed with the ground formation rock. The tube
is tapped gently from time-to-time during filling to ensure
close packing and is visually inspected to assure absence of
voids.
The tube is then returned to the air bath, connected
to the inlet tubing, the temperature is adjusted to the oil
formation temperature and water representative of that produced
from the formation is admitted slowly through the bottom line
from a calibrated reservoir in an amount just sufficient to fill
the packed rock plug in the tube. This volume is determined
from the calibrations and is referred to as the "pore volume",
being that volume of water just sufficient to fill the pores
of interstices of the pacXed plug rock.
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1~3Z73
The upper line to the reservoir is then connected to
a calibrated reservoir containing the oil representing that
from the formation to be flooded. By proper manipulation of
valves, the line is filled with oil which is then slowly pumped
into the core from the reservoir after the lower valve is
opened to allow displacement of the formation water.
As breakthrough of oil at the bottom is noted, pumping
is stopped and the ~olume of oil introduced into the sand is
determined from the reservoir readings. This is referred to as
the volume of oil in place. The tube of sand containing oil is
then left in the ai~ bath at the temperature of the formation
for a period of three days to allow establishment of equili-
brium between the ground formation rock and the oil with respect
to adsorption of oil constituents on the rock and lowering of
interfacial tension. The time allowed for equilibrium may be
varied widely. At higher temperat~res, the time required to
reach equilibrium is probably reduced. ~sually, for compara-
tive tests, three days are allowed to age the oil-rock plug.
Results with this procedure closely simulate work with actual
cores of oil-bearing rock.
The oil and water samples used for test Purpose9 are
preferably taken under an inert gas such as high purity
nitrogen, and axe maintained oUt of contact with air during all
minipulations in order to prevent oxidation of the oil and con-
comitant introduction of spurious polar, surface-active con-
stituents in the oil. At this point, the rock-oil system
simulates the original oil formation before primary production
oil has commenced and well befora any secondary waterflood
operation.
The upper inlet line to the tube is now connected to
the sample of water used in the flooding of the oil formation

1153273
and, by means of a syringe pump or similar very small volume
posLtive displacement ~ump, the water is pumped into the sand
body from the top to displace fluids out of the bottom tubing
connection into a calibrated receiver. The pumping rate is
adjusted to one simulating the rate of flood water advance in
an actual operation, which is usually in a range of 1 to 50 cm
per day. Pumping is maintained at this rate ~ntil two pore
volumes of water have been pumped through the sand.
The volumes of fluids collected in the receiver are
measured and the relative amount of oil and water ~isplaced
from the rock sample are determined and recorded. Of special
interest is the volume of oil displaced as a fraction of the
original pore volume. This information may be viewed as an
indication of the approximate percentage of oil originally in
place which is produced by natural water drive following drill-
ing of a well into the rock formation followed by the primary
phase cf field production carried to the approximate economic
limit.
Following this step, one to three additional pore
volumes of water containing the TFSA micellar solution to be
tested are pumped sl~wly through the plug and the volumes of
additional oil and water displaced are determined. Typically,
where such an initial "slug" of micellar TFSA solution is
introduced, it may be contained in a volume of fluid ranging
from 1% to 100~ of the pore volume, b~t most frequently it will
be in a slug volume of 10~ to 50% of pore volume.
After this final displacement step, the produced oil
and water are again measured. By comparing the amount ~f oil
produced by this additional injection of water containing, or
preceded by a solution, of micellar TFSA solution with the
amount produced when the same volume of water containing no
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1~53Z73
TFSA solution is injected, one can evaluate the effectiveness
of the particular micellar TFSA solution used for enhancing
the recovery of additional oil over and above that obtained by
ordinary waterflooding.
Generally, six or more sand columns of the kind
described above are mounted in the heated air bath. Test of a
given micellar TFSA solution is then run in triplicate, using
identical conditions and concentrations, simultaneously with
three blank tests run similarly but without addition of mi-
cellar TFSA solution to the water.
The composition of Example F was tested by this pro-
cedure with the following conditions:
Oil -- Ranger Zone, Wilmington, Calif.,
field API Gravity approximately
13.5
Water -- Mixed water used in flood operations
Airbath Temperature -- 150F (Same as formation tempera-
ture)
Oil was displaced by pumping two pore vQlumes of
water into the sand. After measuring the volumes of oil and
water produced through the bottom line, a further 0.2 pore
volumes of water containing 2,600 ppm of the composition of
Example F was injected followed by 2.~ volumes of water contain-
ing 175 ppm of the composition of Example D. Measurement of
the volumes of oil and water p~o~uced were read after each 0.2
pore volumes of water was injected.
Results of this test at the points of 2,3 and 5 pore
; volumes of injected water are given in the table below wherein
averages of three duplicate determinations are presented.
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~lS3~'Z73
Oil Recovery as % of
Oil in Pl;ace
Composition of Ratio of Increment
Example F of Oil Production
Pore Volumes No Chemical Added to Water After Initial 2
(P.V.) of Water Addition after Initial P.V. Chemical/No
Injected 2 P.V. of Water chemical
2 36.5 36.5
3 40.0 43.7 2.1
43.1 53.0 2.5
Use of the composition of Example F in the amounts
given above resulted in the production of 110% more oil from
injection of one incremental pore volume of water than was
produced by water injection alone and gave 150% more oil after
three incremental pore volumes of treated water injection.
Althou~h the invention has been described in terms of
specified embodiments which are set forth in detail, it should
be understood that this is by illustration only anq that the .
invention is not necessarily limited thereto, since alternative
embodiments and operating techniques will become apparent to
those skilled in the art in view of the disclosure. Accor-
dingly, modifications are contemplated which can be made with-
out departing from the spirit of the describe~ invention.
~ - 44 -