METHOD FOR BREAKING PETROLEUM EMULSIONS AND THE LIKE USING THIN FILM SPREADING AGENTS COMPRISING A POLYETHER POLYOL

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

English Abstract

TITLE: METHOD FOR BREAKING PETROLEUM EMULSIONS AND THE
LIKE USING THIN FILM SPREADING AGENTS
COMPRISING a POLYETHER POLYOL
ABSTRACT OF THE INVENTION
The invention relates to a method of breaking petroleum
emulsions, by utilization of a homogeneous, micellar solution
of a water-insoluble thin film spreading agent comprising:
(a) from between about 5% and about 75% by weight of a poly-
ether 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, comprising: (1) from between about 5% and
about 75% by weight of a 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;
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 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
41

about 8.5; and (c) spreading at the interface between distilled
water and refined mineral oil to form a film having a thick-
ness no greater than about 20 Angstoms 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 formu-
las:
X - Z (A)
wherein X is an alkyl, alicyclic, aromatic, alkylalicyclic,
alkylaryl, arylalkyl, alicyclicalkyl, heterocyclic or sub-
stituted heterocyclic radical having 2 to 13 carbon atoms;
and wherein Z is one of: -OH;
<IMG> ; -CHO; <IMG>
- COOH, and - OCH3; and U and V are hydrogen or hydrocarbon
substituents;
X - Y - R - (Z)n, (B)
wherein:
Z is one of - OH;
<IMG> ; -CHO; <IMG> ;
- COOH; and - OCH3;
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 depend-
ent upon the selection of R;
42

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 polyether
polyol contains an average of at least about 11/2 hydroxyl
groups per molecule and is the condensation reaction product
of at least one alkylene oxide with a reactant having two or
more reactive hydrogens of one or more hydroxyl or amino
groups.
3. The method of claim 1 wherein said polyether
polyol is an ethylene oxide condensate of polypropylene glycol
having an average molecular weight of at least about 800.
4. The method of claim 1 wherein R is the hydro-
carbon residue of a dihydric alcohol.
5. The method of claim 1 wherein said polyether
polyol is a trihydric ether alcohol.
6. The method of claim 1 wherein the hydrophobic
portion of the amphipathic agent is aliphatic, alkylalicy-
clic, aromatic, arylalkyl or alkylaromatic.
7. The method of claim 1 wherein the amphipathic
agent contains an uninterrupted chain of from between about
10 and about 22 carbons.
8. The method of claim 1 wherein the amphipathic
agent is an anion-active soap.
43

9. The method of claim 1 wherein the amphipathic agent
comprises mahogany or green sulfonates of petroleum, petroleum
fractions, or petroleum extracts.
10. The method of claim 1 wherein the amphipathic agent
is anionic.
11. The method of claim 1 wherein the amphipathic agent
is cationic.
12. The method of claim 1 wherein the amphipathic agent
is nonionic.
13. 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, comprising: (1) from between about 5% and
about 75% by weight of a polyether polyol 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 polyether polyol having an average
molecular weight of about 15,000 or less, said member being
derived from reactive hydrogen compounds having 18 or less
carbon atoms, said 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. a 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;
44

(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.
14. The method of claim 13 wherein the hydrotropic
agent is an alcohol.
15. The method of claim 13 wherein the hydrotropic
agent is an hydroxy ester of a polyol.
16. The method of claim 13 wherein the hydrotropic
agent is an aldehyde.
17. The method of claim 13 wherein the hydrotropic
agent is an amine.
18. The method of claim 13 wherein the hydrotropic
agent is a carboxy amide.
19. The method of claim 13 wherein the hydrotropic
agent is a phenolate.
20. The method of claim 13 wherein the hydrophobic
portion of the amphipathic agent is aliphatic, alkylalicyclic,
aromatic, arylalkyl or alkylaromatic.
21. The method of claim 13 wherein the amphipathic
agent contains an uninterrupted chain of from between about 10
and about 22 carbons.
22, The method of claim 13 wherein the amphipathic
agent comprises mahogany or green sulfonates of petroleum,
petroleum fractions, or petroleum extracts.
23. The method of claim 13 wherein the amphipathic
agent is anionic.
24. The method of claim 13 wherein the amphipathic
agent is cationic.
25. The method of claim 13 wherein the amphipathic
agent is nonionic.
26. 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 a 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;
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 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
46

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; (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, alkylalicyclic,
alkylaryl, arylalkyl, alicyclicalkyl, heterocyclic or sub-
stituted heterocyclic radical having 2 to 13 carbon atoms;
and wherein Z is one of: - OH;
<IMG> ; -CHO; <IMG> ;
- COOH; and - OCH3; and U and V are hydrogen or hydrocarbon
substituents;
X - Y - R - (Z) , (B)
wherein;
Z is one of - OH;
<IMG> ;-CHO; <IMG> ;
- COOH; and - OCH3;
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-;
47

n is either a one or two integer; the integer depend-
ent 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; (4)
from between about 15% and about 90% by weight, water; and
(IV) recovering from said formation oil and water which was
subjected to the action of said steam.
27. The method of claim 26, wherein said polyether
polyol contains an average of about 11/2 or more hydroxyl groups
per molecule and is the condensation reaction product of at
least one alkylene oxide with a reactant having two or more
reactive hydrogens of one or more hydroxyl or amino groups.
28. The method of claim 26, wherein said polyether
polyol is an ethylene oxide condensate of polypropylene glycol.
29. The method of claim 26, wherein said polyether
polyol is a trihydric ether alcohol condensation product of
at least one of ethylene, propylene and butylene oxide and a
polyol, amine or amino alcohol having present therein hydrogens
for reaction with said oxide.
30. The method of claim 26, wherein said polyether
polyol is the oxyalkylation reaction product of glycerol
and at least one of ethylene and propylene oxide.
31. The method of claim 26, wherein the hydrotropic
agent is an amine.
48

32 The method of claim 26, wherein the amphipathic
agent is a hydrophobic hydrocarbon residue-containing composi-
tion wherein the hydrocarbon residue is aliphatic, alkylali-
cyclic, aromatic, arylalkyl or alkylaromatic.
33. The method of claim 26, wherein the amphipathic
agent comprises 2-heptadecyl-3-diethylene diaminoimidazoline
diacetate.
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 a polyether polyol 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 polyether polyol having an
average molecular weight of about 15,000 or less, said member
being derived from reactive hydrogen compounds having 18 or
less carbon atoms, said 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 Angstroms, at a spreading pressure of about
16 dynes per cm; (2) from between about 2% and about 30% by
49

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 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;
and (IV) recovering from said formation oil and water which
was subjected 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 solu-
tion comprising: (1) from between about 5% and about 75% by
weight of a polyether polyol 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 polyether polyol having an average molecular weight of
about 15,000 or less said member being derived from reactive
hydrogen compounds having 18 or less carbon atoms, said poly-
ether 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 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 to

about 12 carbon atoms; (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.
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 at least one of
said petroleum, bitumen or water phases with an effective
emulsion preventing amount of a homogeneous micellar solution
of a thin film spreading agent, said micellar solution of a
thin film spreading agent, said micellar solution comprising:
(1) from between about 5% and about 75% by weight of a poly-
ether polyol 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 poly-
ether polyol having an average molecular weight of about 15,000
or less, said member being derived from reactive hydrogen
compounds having 18 or less carbon atoms, said 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 8.57 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
51

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.
37, 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 spreading agent, said micellar solution com-
prising: (1) from between about 5% and about 75% by weight of
a polyether polyol derived from the reaction of an alkylene
oxide containing from about 2 to 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
polyether polyol having an average molecular weight of about
15,000 or less, said member being derived from reactive hydro-
gen compounds having 18 or less carbon atoms, said 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 8.51 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 1% carbon atoms; (3) from between about 2% and about
30% by weight of an amphipathic agent having at least one
52

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. In the method of breaking and preventing emulsions
of water in bitumen during the recovery of bitumen from tar
sands of subterranean deposits by steaming, flooding or
combinations thereof, the improvement comprising: contacting
said bitumen with 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 a poly-
ether polyol 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 poly-
ether polyol having an average molecular weight of about
15,000 or less, said member being derived from reactive hydro-
gen compounds having 18 or less carbon atoms, said 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 calcu-
lated 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 com-
prising 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 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
53

about 90% by weight, water.
39. The method of claim 34, 35, or 36 wherein said
polyether polyol contains an average of about 1? or more
hydroxyl groups per molecule and is the condensation reaction
product of at least one alkylene oxide with a reactant having
two or more reactive hydrogens of one or more hydroxyl or
amino groups.
40. The method of claim 34, 35, or 36 wherein said poly-
ether polyol is an ethylene oxide condensate of polypropylene
glycol.
41. The method of claim 34, 35 or 36 wherein said
polyether polyol is a condensation product of a dihydric
alcohol and at least one alkylene oxide.
42. The method of claim 34, 35, or 36 wherein said
polyether polyol is a trihydric ether alcohol.
43. The method of claim 34, 35, or 36 wherein said
polyether polyol is a trihydric ether alcohol condensation
product of at least one of ethylene, propylene and butylene
oxide and a polyol, amine or amino alcohol having present
therein hydrogens for reaction with said oxide.
44. The method of claim 34, 35, or 36 wherein said
polyether polyol is the oxyalkylation reaction production of
glycerol and at least one of ethylene and propylene oxide.
45. The method of claim 34, 35, or 36 wherein the
hydrotropic agent is an alcohol.
46. The method of claim 34, 35, or 36 wherein the
hydrotropic agent is an hydroxy ester of a polyol.
47. The method of claim 34, 35, or 36 wherein the
hydrotropic agent is an aldehyde.
48. The method of claim 34, 35, or 36 wherein the
hydrotropic agent is an amine.

49. The method of claim 34, 35, or 36 wherein the
hydrotropic agent is a carboxy amide.
50. The method of claim 34, 35, or 36 wherein the
hydrotropic agent is a phenolate.
51. The method of claim 34, 35, or 36 wherein the
amphipathic agent is a hydrophobic hydrocarbon residue-contain-
ing composition wherein the hydrocarbon residue is aliphatic,
alkylalicyclic, aromatic, arylalkyl or alkylaromatic.
52. The method of claim 34, 35, or 36 wherein the
amphipathic agent is anionic.
53. The method of claim 34, 35, or 36 wherein the
amphipathic agent is cationic.
54. The method of claim 34, 35, or 36 wherein the
amphipathic agent is nonionic.
55. The method of claim 37 or 38 wherein said poly-
ether polyol contains an average of about 1? or more hydroxyl
groups per molecule and is the condensation reaction product
of at least one alkylene oxide with a reactant having two or
more reactive hydrogens of one or more hydroxyl or amino
groups.
56. The method of claim 37 or 38 wherein said poly-
ether polyol is an ethylene oxide condensate of polypropylene
glycol.
57. The method of claim 37 or 38 wherein said poly-
ether polyol is a condensation product of a dihydric alcohol
and at least one alkylene oxide.
58. The method of claim 37 or 38 wherein said poly-
ether polyol is a trihydric ether alcohol.
59. The method of claim 37 or 38 wherein said poly-
ether polyol is a trihydric ether alcohol condensation product
of at least one of ethylene, propylene and butylene oxide and
a polyol, amine or amino alcohol having present therein

hydrogens for reaction with said oxide.
60. The method of claim 37 or 38 wherein said poly-
ether polyol is the oxyalkylation reaction product of glycerol
and at least one of ethylene and propylene oxide.
61. The method of claim 37 or 38 wherein the hydro-
tropic agent is an alcohol.
62. The method of claim 37 or 38 wherein the hydro-
tropic agent is an hydroxy ester of a polyol.
63. The method of claim 37 or 38 wherein the hydro-
tropic agent is an aldehyde.
64. The method of claim 37 or 38 wherein the hydro-
tropic agent is an amine.
65. The method of claim 37 or 38 wherein the hydro-
tropic agent is a carboxy amide.
66. The method of claim 37 or 38 wherein the hydro-
tropic agent is a phenolate.
67. The method of claim 37 or 38 wherein the amphi-
pathic agent is a hydrophobic hydrocarbon residue-containing
composition wherein the hydrocarbon residue is aliphatic,
alkylalicyclic, aromatic, arylalkyl or alkylaromatic.
68. The method of claim 37 or 38 wherein the amphi-
pathic agent is anionic.
69. The method of claim 37 or 38 wherein the amphi-
pathic agent is cationic.
70. The method of claim 37 or 38 wherein the amphi-
pathic agent is nonionic.
56

Description

llS327~
BACKGROUND OF THE INVENTI ON
1. FIELD OF THE INVENTION: The invention relates to a
new and improved micellar solution of a thin film spreading
agent comprising a polyether polyol which is particularly
useful for breaking or preventing petroleum emulsions. More
specifically, the invention relates to the use of a composition
in which water replaces all or a substantial part of the
organic solvents formerly required for preparation of liquid
solutions of this interfacially active compound.
2. DESCRIPTION OF THE PRIOR ART: One of the principal
uses of the present composition is in the breaking of petroleum
emulsions to permit the separation thereof into two bulk phases.
Much of the crude petroleum oil produced throughout the world
is accompanied by some water or brine which originates in or
adjacent to the geological formation from which the oil is
produced. The amount of aqueous phase accompanying the oil
may vary from a trace to a very large percentage of the total
fluid produced. Due to the natural occurrence in most petro-
leum of oil-soluble or dispersible emulsifying agents, much of
the aqueous phase produced with oil is emulsified therein,
forming 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 petro-
leum. 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. 538 et seq.
(1960L.
Early demulsifiers used to resolve petroleum emulsions
-- 2 --

~153274
were water-soluble soaps, Twitchell reagents, and sulfonated
glycerides. These products were readily compounded with water
to Eorm easily pumpable liquids and were conveniently 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 polyesters,
all of which were insoluble in water but soluble in alcohols
and aromatic hydrocarbons, were much more effective in breaking
emulsions. Accordingly, essentially all commercial 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 coalescence of
dispersed water droplets. Generally, such interfacially active
~O compounds are hereafter referred to as Thin Film Spreading
Agents, or "TFSA's". In the past, these have had to be com-
pounded with and dissolved in alcohols or hlghly aromatic
hydrocarbon olvents 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,
they suffer serious practical deficiencies because of their
solubility characteristics. For example, alcohols and the
aromatic hydrocarbons, which are required for preparation of

~lS;~;~7~
liquid, pumpable compositions, are quite 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, storing
and use. The low flash point flammability can be improved by
using high boiling aromatic solvents, but these are increasing-
ly rare, expensive and dangerous from the standpoint of car-
cinogenicity and dermatological effects.
S~ill further, present demulsifiers cannot generally be
used in a subterranean oil 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 viscous
liquids which are required in very small amounts, 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 compositions would be facili-
tated if they were readily soluble or dispersible in water.
For example, much heavy, viscous oil is produced 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 bore 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 increased resistance to
flow, productivity of the steamed wells can be improved by
injecting a water-soluble demulsifier into the wet steam
during the steam injection period to prevent emulsion forma-
tion. See, for example, U.S. Patent 3,396,792, dated April 1,

~153274
1966, to F. D. Muggee. At present, the requirement of water
solubility seriously limits the choice of demulsifiers for use
in steam or water injection to the relatively inefficient
compositions.
- 4a -
~'

1153274
As disclosed in my co-pending Canadian applications, Serial
Number 353,Z51, filed June 3, 1980 and entitled "Met~od of Recover-
ing Petroleum From A Subterranean Reservoir Incorporating A Polyether
Polyol", Serial Number 353,232, filed June 4, 1980, and entitled
"Method of Recovering Petroleum From A Subterranean Reservoir
Incorporating Resinous Polyalkylene Oxide Adducts", Serial Number
353,250, filed June 3, 1980, and entitled "Method Of Recovering
Petroleum From A Subterranean Reservoir Incorporating An Acylated
Polyether Polyol", and Serial Number 353,233, filed June 3, 1980,
and entitled " Method of Recoveirng Petroleum From A
Subterranean Reservoir Incorporating Polyepoxide Condensates Of
Resinous Polyalkylene Oxide Adducts And Polyether Polyols",
TFSA's are useful in processçs for enhanced recovery of petroleum.
Used in such 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 inter-
facial layer and promote coalescence of dispersed droplets of
either water or oil in the other phase.
By use of the present aqueous micellar solutions, the intro-
duction of TFSA into aqueous displacement or flooding fluids is
greatly facilitated. In addition, the present micellar solu~ions,
per se, or in combination with other components, can be used as
;;~75 the flooding agent or as a pretreating bank or slug ahead of
other aqueous fluids.
Other applications for the present TFSA micellar solutions in-
clude their use as flocculation aids for finely ground hematite and
~agnetite ores during the desliming step of ore beneficiation, as
additives for improving the oil removal and detergcnt action of
cleanin~ compositions and detergents designed for use on polar
:.
--5--
~.,~~~

~153274
materials, for the improvement of solvent extraction processes
such as those used in extraction of antibiotic products from
aqueous fermentation broths with organic solvents, for the
improvement of efficiency and phase separation in the purifica-
tion and concentration of metals by solvent extraction with
organic solutions of metal complex-forming agents, and as :-
assistants to improve the wetting and dying of natural and
synthetic fibers and for other processes normally involving
the interface between surfaces of differing polarity or wetting
characteristics.
SUMMARY OF THE INVENTION
A primary object of the present invention is to provide
aqueous, liquid compositions of these TFSA' s having new and
useful characteristics which allow production of: petroleum
emulsion breakers and emulsion preventing compositions free or
relatively free of highly flammable and environmentally
objectionable aromatic hydrocarbons; compositions having a
comparatively low cost; compositions which are soluble or
dispersible in water and which, therefore, can often be applied
by more effective methods than can existing products; composi-
tions which can be used in enhanced recovery operations such as
steam flooding and aqueous medium flooding where present
products cannot be readily applied; and compositions which can
, :-
: be compounded with water-soluble reagents of other types, such
as corrosion inhibitors, wetting agents, scale inhibitors,
biocides, acids, etc., to provide multipurpose compounds for
i~
~ use in solving many oil well completion, production, trans-
portation 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
- 6 -
. .

llS3274
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 solutions contain-
ing a relatively wide range of concentrations of TFSA.
DESCRI~TION OF THE PREFERRED EMBODIMENTS
The TFSA compositions of the present invention can be
broadly categorized by the following general characteristics:
1. Solubility in water and isooctane at about 25C
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.
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 stru¢-
tures containing a multiplicity of distributed hydrophilic and
hydrophopic moieties arranged in linear or planar arrays which
make them surface active and lead to their adsorption at
oil-water interfaces to form very thin films.
Unlike most commonly encountered surface-active compounds,
the present TFSA appears to be incapable of forming a micelle
in either oil or water. The distributed and alternating
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
- 7 -
. ~

1~53274
dispersion or solution in either water or low polarity organic
sol~rents .
The TFSA's useful in the present invention have thepreviously recited properties:
l The solubilitY in water and in isooctane at about
.
25C is less than about 1% by volume.
Solubility tests may be run by placing a l ml
sample (or the weight of solid product calculated
to have a volume of l ml) in a graduated cylinder
o of 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 hour. 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. The cylinder contents should be
carefully examined and any cloudiness or opacity
~o 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 insolubility in water.
Isooctane solubility is determined similarly
by substituting this hydrocarbon for the water used
above.
2. The Solubi_it~ Parameter (S.P.) at about 25C is
from between about 6,9 and about 8.5, inclusive.
_
Methods of de~ermination of solubility parameter
;O are disclosed in Joel H. Hildebrand, "The Solubility
of Nonelectrolytes", Third Edition, pgs. 425 et seq.
However, simplified procedure, sufficiently accurate
- 8 -
:.. -

1153;~74
for qualification of a useful TFSA composition
may be utilized. Components of a give solubility
parameter are generally insoluble in hydrocarbon
(non-hydrogen-bonding) solvents having a lower
solubility parameter
- 8a -
: ,

llS32~4
l than thcmselves. :Cherefore, the present composition
should be~oluble in a hydrocarbon solvent of a solu-
~t, ?4 -bility parameter of about 6.8. Since the solubility
parameter o.f mixtures of solvents is an additive`func-
tion of volume percenta~e of components in the mixture,
test solutions of the desired solubility parameters may
be easlly prepared by blending, for example, benzene
(S.P. 9.15~ and isooctane (S.P. 6.8S) or perfluor~-n-
heptbne (S.P. 5.7).
10~ A mixture~of about 72~parts of benzene with about
28.parts~o~f~isooc~ane will~provide~a solvent having a
; solubil~ity~par~a~eter~of about 8.5~at~room temperature
(abQùt~25C~ Per~luoro n-heptane~11as~ a~so~lub:Llity :
pQrameter~of~about~5.7~at~25C, so~a mixture~o:f 68 ~ :
5~ p~art~s:~of~th~is ~solvent with 32 parts of benzene pr~ovides
` a~solvent~with~a;~sol~ lity~parQme~ter.o~about~6.8,~o :~ ;
isooc ~e f: ~s~ paramete~ 85~ma`~be~used.: ~:
When.~5~ `o~ the:~TF ~`~are~mix~éd wi~th~95:ml ~ an ~ :
, u~l~b~ y~parametQr solvent at roo te~pe,ratur~, a
f~ mixsd~wi:~h a~6.85~s~ol:u~ility parameter sol~ent,;a
;c:lou~.~mix:~ure:~or~one s~owing phase~:separation:shoul~:
r~s ~ ` ~ n~mixt es;have a s~ illty par ~eter
r~ th~r
tes ~ ~ ~ ~ e~`:?re~gnized~thàt~the TFSA~consists
n :t ~f~ ~ mà~e~ ` r~co ` ?but~a,cogen ~lc
y:r~ ~ s~c`ontainin~ a~r ~ e of:products of
r`~we ~ s di~s~trlbuted-around~the:average~
ole ~ ar~ e:~i ~ t`and~ ~en;containin~:small amounts of
i~$ ~
,'~:,: : ;

llS3Z74
,
1 ~he s~r~in~ colnl~>llotls elnl~loy~ e syntllesis. ~s a
rcs~lt, in l~lnning solubility .~nd ~so~ub;lity parameter
tests, very slight ~ppearances of clo~diness 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, ~he solubility tcsts may he run in
~ cen~rifuge tubes allowing subsequent rapid phase separà-
~ tion by centrifuging, after whicb ~he'scp.~rated non-
solvent phase'can be removed, any solv~ent contained in
. it can be evaporated, and the actual weight or volume
~::: . . . ..
'' of sep'arated p~iase can be'determined. ~'
3. The TFSA'should spr~ead at the interface betwe'en
dist-illed water and refLned mineral oil to form films
with;';thi~cknes~s~no~p,~eater~than about;ZO Angstroms-
(O.OOZO~mi~crometer)~ at~a film pressure o~ about 16
dynes~per~cm~(O,~016 Ne'w~ton per ~eter). ~ ~
Suitàble~methods~of~determining;f~ilm pressure are
disclo~sèd'~in~N. K.~Adamj '`Physics and Chemistry of
Surfacesl'l Third Edition,' Oxor~ University Press, London~
1941~ pg's~. 20;et seq, and~C. M. Blair, Jr., "Inter-
fa~ial~Films~Aff'eoting The Stability~o~ Petroleum
ETnulsions"~,'Chemis~try~and Tndu'stry (London3, 1960, pgs.
5~38 ~''s~eq~ Film~thicknes~s~is~calculated on-the
assumption~hat'~all of the TFSA remains on the area of
inter~aoe~between;;oil~and~`water~on~which the product or
its solutionl ~ a;voLst}le~solvent has been placed.
Since~9pre9ding~pressure~is numerically equal to the
3~ Ghange'in~interfaoisl tension resulting from spreading
of a~film,~ t~is~oonveniently de~rmined by makin~
`1'' ~: ~ ., . :
:: ,

~53274
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,
Transactions of the Faraday Society (1964), p. 20
et seq, or other methods which have been qualified
for such interfacial spreading pressure determina-
tions.
In determining the interfacial spreadingpressure 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 nonhydrocarbon and aromatic constituents.
Typical of such oils is "Nujol", distributed by
Plough, Inc. This oil ranges in density from about
'0 0.85 to 0.89 and usual}y 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 rom chemical supply houses
and pharmacies.
Other essentially aliphatic or naphthenic
hydrocarbons of low volatility are equally usable
and will yield similar values of spreading pressure.
.~
Suitable hydrocarbon oils appear in commexcial
trade as refined "white oils", "textile lubricants",
"paraffin oil", and the like. Fre~uently, they
may contain very small quantities of alpha-tocopherol
(Vitamin E) or similar antioxidants which are
-- 11 --

115327~
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, D. 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 be removed, their
utility in cooperation with hydrotropic agents for the present
o purposes is an unexpected and unpredictable discovery.
In U.S. 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,
wax, and other relatively nonpolar compounds are described for
purposes of cleaning oil formation faces and for effecting en-
hanced 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.
~o However, some of the principles disclosed in the above
patent, omitting the main objective therein of dissolving rela-
tively large amounts of hydrocarbons, chlorinated hydrocarbons,
and the like, are applicable to preparation of the present com-
positions.
The four necessary components of the micellar solutions
~` 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 the
o free acid or free base or mixtures thereof.
2. A hy-drotropic agent~ This is a small to medium mole-
cular weight semi-polar compound containing oxygen,
- 12 -

llS3274
nitrogen or sulfur and capable of forming hydrogen
bonds. It is believed that such agents cooperate
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 solutions
may contain, but are not required to contain, salts, hydro-
carbons, or small amounts of other inorganic or organic material.
Such constituents may be impurities, solvents, or by-products of
syntheses used in forming the hydrotropic agent, or may be
additions found useful in forming the composition of this
invention. As an example of the latter, small amounts of
inorganic salts such as NaCl, Na2SO4, RNO3, 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, viscosity,
and den~ity, or to improve stability.
As stated above, the micelle-forming amphipathic agents
which may be used in preparing the aqueous solutions herein
contemplated may be either cation-active, anion-active, or of
the nonelectrolytlc 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
30 invention as alcomponent of the vehicle or solvent or dis-
persant employed in the present compositions. The hydrophobic
portions of these agents may be aliphatic, alicyclic,
- 13 -
, r

1153274
alkylalicyclic, aromatic, arylalkyl, or alkylaromatic. The
preferred type of agents are those in which the molecule con-
tains a long, uninterrupted carbon chain containing from 10 to
22 carbon atoms in length. Examples of suitable anion-active
amph:ipathic agents include the common soaps, as well as mater-
ials such as sodium cetyl sulfate, ammonium lauryl sulfonate,
ammonium di-isopropyl naphthalene sulfonate, sodium oleyl
glyceryl sulfate, mahogany and green sulfonates from petroleum
or petroleum fractions or extracts, sodium stearamidoethyl
!0 sulfonate, dodecylbenzene sulfonate, dioctyl sodium sulfo-
succinate, sodium naphthenate, and the like. Other suitable
sulfonates 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, trimethyl-hepta-
decyl ammonium chloride, dimethyl-pentadecyl sulfonium bromide,
octadecylamine acetatet and 2-heptadecyl-3-diethylene diamino-
imidazoline diacetate.
Suitable nonelectrolytic amphipathic agents include the
'0 oleic acid ester of nonaethylene glycol, the steric acid ester
of polyglycerol, oxyethylated alkylphenols, and long chain
alcohol ethers of polyethylene glycols.
It i8 0~ course, well known that amphipathic aompoundQ
are readily and commercially available, or can be readily
prepared to exhibit the characteristics of more than one of the
above mentioned types. 5uch 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 instance where a
surface-active material may show the characteristics of more
than one of the above described types, it is understood that it
may be classified under either or both types.
The mutual solvent or hydrotropic agents of the solution
- 14 -
\, _, A

1153274
utilized in the present invention are characterizable as com-
pounds 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
structure, but no branch may have a length of more than 7 car-
bon atoms from the point of attachment to the hydrophilic
residue, counting a benzene or cyclohexyl group as being equiv-
alent in length to an aliphatic chain of three carbon atoms.
Where the hydrocarbon residue consists of not more than 4 car-
bon 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 etherifi-
cation, esterification, or amidification, or the like, with
- 15 -
%

1153274
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 combination, 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-butyr-
aldehyde, 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,
ethylene glycol mono n-butyl ether, pyridine, methylated pyri-
dine, piperidine, or methylated piperidines.
The solubilizer (mutual solvent or hydrotropic compound
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 ox semi-polar liquid indicated may be
illustrated by the formula X -Z, in which X is a radical hav-
ing 2 to 12 carbon atoms, and which may be alkyl, alicyclic,aromatic, alkylalicyclic, alkylaryl, arylalkyl, or alicyclic-
alkyl in nature, and may, ~urthermore, include heterocyclic
compounds and substituted heterocyclic compounds. There is
the added limitation that the longest carbon atom chain must be
less than eight carbon atoms, and that, in such characteriza-
tion, cyclic carbon atoms must be counted as one-half. Z
represents:
U / H O / U
OH;- N \ ; - C ~ ; - CN ; - COOH; or - OMe
- 16 -

~iS3274
where U and V are hydrogen or a hydrocarbon s~bstituent and Me
is an alkalie metal;
~ '
N
if X is a cyclic tertiary amine nucleus;
- 16a -

~153274
NH
if X is a cyclic secondary amine nucleus.
The semi-polar liquid also may be indicated by the
following formula: - X - Y - R - (Z)n Here X and Z have
their previous significance, R is - CH2 - , - C2H4 - , - C3H5- ;
- C3H6- or C2H4 C2 4
and n is either one or two as the choice of R demands. Y is
one of the following:
o H H 0 o 0
Il I I 11 11 11
- C- N ~ C -; - C- 0 -; - 0 -C -; - 0-; -S - .
In general, these hydrotropic agents are liquids having
dielectric 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 to be able to form
hydrogen bonds.
The choice of solubilizer or common solvent and its pro-
portion 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 ex-
perimental mixtures on a small ~cale.
In some cases, it is desirable to include in the solution
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 mis-
cibility 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.
- 17 -
.

1153274
The polyether polyol or TFSA utilized in this invention
is genexally an 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 in a thin
plane. To be effectively adsorbed at oil-water or oil-rock
interfaces and subsequently to be desorbed at water-rock inter-
faces, the TFSA must generally contain constituents which give
it a highly distributed hydrophile and hydrophobe character,
and without such concentrations of either hydrophilic or hydro-
phobic groups as to produce water solubility or oil solubility,
in the ordinary macroscopic sense. The TFSA also appears to
differ from formly 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 o~ 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 s~me instances they may also
contain sulfur, nitrogen, silicon, chlorine, phosphorous 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 and physical. They must be made up
of hydrophilic (polar) moieties, usually onescapable of forming
- 18 -

1~53274
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 alkyl-
ene, alkyl, cycloalkyl, aryl, arylene, aralkyl, polyalkylene,
polyalkylyne, combinations of such groups and such groups
containing relatively non-polar substituents, such as hydro-
carbon, chlorine, fluorine and the like. Sometimes the hydro-
phobic 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
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 deliberate-
ly included in some structures to improve adsorption and inter-
facial spreading tendencies. For example, quaternary ammonium
groups, while incapable of foxming hydrogen bonds, can improve
spreading and interfacial adsorption in some applications by
way of their highly ionized form whlch imparts cationic charac-
ter 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 more 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 con-
tain numerous different groups or moieties, I have found that
-- 19 --

llS327g
particularly effective products are those which are described
as a polyether polyol having the formula:
[O~A)jH~
{NR ~(A)kHl} m
wherein:
A is an alkylene oxide group, -CiH2iO-;
O is oxygen;
i is a positive integer no greater than about 10;
j is a positive integex no greater than about 100;
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 l~ 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 ~reater 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 polyether polyol at about 25C: (a) being less than about
1% by volume soluble in water and in isooctane; (b) having a
~olubility 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 thick-
ness no greater than about 20 Angstroms at a film pressure of
about }6 dynes per cm.
AlternateIy, the TFSA constituents may be described as
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
- 20 -
~; ~
: `

1153274
amino alcohols containing fro~ between about 2 to about 10 active
hydrogen groups capable of reaction with alkylene oxides.
Compositions incorporated within the scope of the formula
set forth above contain an average of about l~ 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
oxide. Alternatively, one may condense about 20 moles of
popylene 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
hutane, trimethylene oxide, tetrahydrofuran, glycidol, and
similar oxides containing less than about 10 carbon atoms.
Because of their reactivity and relatively low cost, the pre-
ferred alkylene oxides for preparing effective TFSA constitu-
ents are the 1,2-alkylene oxides (oxiranes) exempliied by
ethylene oxide, propylene oxide and butylene oxide. In the
preparation of many TFSA constituents, more than one alkylene
oxide may he employed either as mixtures o oxides or sequen-
tially to form block additions of individual alkylene oxide
groups.
Other suitables dihydric alcohols may be obtained by
condensing alkylene oxides or mixtures of oxides or in
- 21 -

~lS3Z74
successive steps (blocks) with difunctional (with respect to
oxide addition) compounds, such as ethylene glycol, methyl
amine, propylene glycol, hexamethylene glycol, ethyl ethanol-
amine, analine, resorcinol, hydroquinone and the like.
Trihydric ether alcohols may be prepared by condensation
of ethylene, propylene or butylene oxides with, for example,
glycerin, ammonia, triethanolamine, diethanolamine, ethyl
ethylene diamine or similar smaller molecules containing three
hydrogens capable o~ reacting with alkylene oxides. Similarly,
polyether alcohols with a multiplicity of hydroxyl groups may
be obtained by condensing alkylene oxides with multireactive
starting compounds, such as pentaerythritol, glycerol, N-mono-
butyl 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 esterifies Product 15-200, manufactured
and sold by the Dow Chemical Company, and derived by oxyalkyla-
tion of glycerol with a mixture of ethylene and propylene
oxides, is an example of a commercially available polyol of
the kind contemplated herein.
Generally, these composltions will have average molecular
weights of 15,000 or less and will be derived from reactive
hydrogen compounds having 18 or fewer carbon atoms 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 manufacturing steps, are
: disclosed in "High Polymers, Vol. XIII, Polyethers," edited by
N. G. Gaylord, John Wiley ~ Sons, New~York, 1963.
As to the limits o~ the various constituents of the
micellar solutions containing TFSA, the following will serve
- 22 -

1~53274
as a guide, the percentages being by weight:
Percent
TFSA Constituents about 5 to about 75
~ydrotropic 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 previous- -
ly 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 differentiated
from the classes of non-polar solvents and semi-polar solu-
bilizers may be the functional equivalent of an electrolyte. ~ -
Substances of this class which ordinarily do not dissociate
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 frequently
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 compounds
are present they appear to compete somewhat with the ~FSA
constituent for micelle space, thus limiting, to some extent,
the maximum amount of TFSA constituent which can be brought
into homogeneous solutlon.
Selection of an efective 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 por-
tions are poured into each of several 180 ml screw top
- 23 -
. .. i . . . .

115;~274
prescription or similar graduated bottles, Dilute solutions(1% or 2%) of various TFSA constituents are prepared in iso-
propyl alcohol. By means of a graduated pipette, a small
volume of a TFSA solution is added to a bottle. A similar
volume of each composition is added to other bottles contain-
ing emulsion. The bottles are then closed and transferred to
a water bath 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 upright
in the water bath and allowed to stand quietly. Periodically,
the volume of the separated water layer is recorded along with
observations on the sharpness of the oil-water interface,
appearance of the oil and clarity of the water phase.
After the standing period, which may range from 30 min-
utes 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 free 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 emulsion,
speed of the water separation and interface appearance provides
the basis for selection of the generally most effective TFSA
constituent. Where none of the results are satisfactory, the
tests should be repeated using higher concentrations of TFSA
constituents and, conversely, where all results are good and
similar, the tests should be repeated at lower concentrations
until good discrimination is possible.
In practicing the process for resolving petroleum
- 24 -
`

1153Z74
emulsions o~ the water-in-oil type with the present micellar
solution, such solution is brought into contact with or caused
to ~ct 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 demulsi-
fying procedure, such as the electrical dehydration process.
One type of procedure is to accumulate a volume of emul-
sified oil in a tank and conduct a batch treatment type of
demulsification procedure to recover clean oil. In this pro-
cedure, the emulsion is admixed with the micellar TFSA solu-
tion, for example, by agitating the tank of emulsion and slow-
ly dripping the micellar TFSA solution into the emulsion. In
some cases, mixing is achieved by heating tha 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 i8 introduced into the well fluids at the wellhead,
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 subsequent lines and fittings-sufficas to produce the
desired dagree 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 accomplishing
- 25 -
~r
\~.

~lS327~
quiescent settling of the chemically treated emulsion. Heatingdevices may likewise be incorporated in any of the treating
procedures described herein.
A third type of application (down-the-hole) of micellar
TFSA solution to emulsion is to introduce the micellar solution
either periodically or continuously in diluted 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 e~uipment, such as employed in
the other treating procedures. This particular type of
application 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 T~SA 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
allowing 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 emulsions,
the present micellar TFSA solutions, as mentioned earlier,
may be used to prevent emulsion formation in steam flooding,
; in secondary waterflooding, in acidizing of oil-producing
formations, and the like.
Petroleum oils, even after demulsification, may contain
substantial amounts of 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
- 26 -
X

~:lS3274
step is effected by adding and mixing with the oil a few volumepercentages of fresh water to contact the brine and salt. In
the absence of demulsifier, such added water would also become
emulsified without effecting its washing action. The present
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 accompanying brines
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 micelles
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 dimethyldo-
decyl ammonium chloride, hexadecylaminopropyl amine, decycloxy-
propyl amine, mixed amines prepared by hydrogenation of nitrile
- 27 -
X

llS3274
derivatives of tall oil fatty acids, soya acid esters ~f mono-
ethanol amine, 2-undecyl, l-amino ethyl imidazoline and a wide
variety of cationic nitrogen compounds of semi-polar charac-
ter. Also effective in some applications are nonyl succinic
acid, diocylnaphthalene sulfonic acid, trimeric and dimeric
fatty acids, propargyl alcohol, mercaptobenzothiozole,
2, 4, 6-trimethyl-1, 3, 5-trithiaane, hexadecyldimethyl benz-
imidazolium bromide, 2-thiobutyl-N-tetrodecylpyridinium chlor-
ide, tetrahydronaphthylthiomorpholine, and the like.
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 o~ inhibitor at either downhole or surface
locations may be combined 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 constituent. Also, since
many of these inhibitors are themselves micelle-forming amphi-
pathic agents, they may be included in the micellar solution
as such, replacing other amphipathic agents which might be
- 28 -

llS3~74
otherwise utilized. Combining the micellar solution with
corrosion inhibitor permits more economic chemical treatment
by reducing inventory to one compound, requiring only one
chemical injection system rather than two and lessening the
labor and supervision required.
Still another important effect of using the micellar
solution of TFSA and corrosion inhibitor results from the
prevention of emulsification by the lnhibitor. Frequently,
it has 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 refinery 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
requirement for micellar solution of TFSA and for inhibitor
and a composition incorporating these components in approxi-
mately the deslred ratio will be prepared. In some instances,
the requirement for micellar solution of TFSA in the best
-~ concentration may result in use of corrosion inhibitor,
employed as micelle-formerl 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 helpul during the periods when higher
corrosivity may be encountered.
Examples of micellar solutions employing TFSA with
- 29 -

- 1153274
inhibitor in water dispersible, micellar solutions are given
below.
Selection of the proper corrosion inhibitor for a given
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 by the National Association of Corrosion Engineers,
Houston, Texas.
EXAMPLES OF THIN FILM SPREADING AGENTS
EXAMPLE I
To an autoclave equipped with a means of mechanical
stirring, heating, and cooling, 4.7 parts of dipropylene
glycol and 0.25 parts potassium hydroxide were added. The
contents of the autoclave were heated to 125C. At this
temperature, 1,2-propylene oxide was slowly introduced from
a transfer bomb which contained 200 parts of 1,2-propylene
oxide. Cooling was applied during the addition to maintain
the temperature below 130C with a pressure of 60 - 75 psi.
Approximately two hours were required to introduce the 1,2-
propylene oxide. The reaction mass was maintained at 130C
for four hours to ensure that the unreacted 1,2-propylene
oxide was at a minimum. Five parts of ethylene oxide were
then added from a transfer bomb at such a rate that the
` temperature was maintained between 150 - 160C with a pressure
of 60 - 75 psi. After all of the ethylene oxide had been
added, the temperature was held at 150C for an additional
hour to complete the reaction. The molecular wei~ht of the
final product was approximately 4,000.
- 30 -

1153Z74
This product is insoluble in water and diisobutylene,
has a Solubility Parameter of 7.2 and spreads at the distilled
water-mineral oil interface to yield a spreading pressure of
21 dynes per cm at a calculated thickness of 10 Angstroms.
EXAMPLE II
In an apparatus similar to that of Example I, 9.2 parts
of glycerol were reacted with 275 parts of a mixture of 225
propylene
~ 30a -

~lS3Z7~
oxide and 50 parts of ~thylene oxide, uslng the same procedure as
t:hat employed in Example II of my co-pending application filed on
June 3, 1980, having Serial number 353,232, entitled "Method of
Recovering Petroleum From A Subterranean Reservoir Incorporating
Resinous Polyalkylene Oxide Adducts 11 . The final product
was a clear, almost colorless viscous oil having a molecular
weight of about 3,000. This product was not soluble to the
extent of 1% in water or diisobutylene. It has a solubility
parameter of 7.5 and spread at the distilled water-mineral oil
in~erface to yield a pressure of 20 dynes per cm with a calculated
film thickness of 12 Angstroms.
EXAMPLE III
: Using the apparatus and procedure of Example I, 4,000 lbs. of
polypropylene glycol of average molecular weight 1,200 was condensed
with 700 lbs. of ethylene oxide. Forty pounds of potassium hydro-
ide was dissolved in the polypropylene glycol prior to oxide addi-
tion, which was carried out within the temperature range of about
, 140 - 160C under a maximum pressure of about 75 psi.
: This product, on cooling to room temperature, was found.to be
insoluble to the extent of 1% in water and isooctane, to have a
solubility parameter of 8.0 and to spread at a whi~e oil-distilled
water interface at 25C to form a ~ilm exerting a spreading
~'. pressure of 16 dynes per cm with a calculated film thickness of
20 Angstroms.
. EXAMPLE IV
To a 200 gal. vesseI equipped like the larger one of Example
I, was placed 175 lbs. of diethylene triamine. The temperature
was raised to 110C and propylene oxide was slowly admitted at a
-31-

13L532~
rate sufficient to raise the temperature by way of the heat of
reaction to about 140C. Cooling was then applied to maintain
this temperature until 700 lbs. of propylene oxide had been
added. At this point the contents of the vessel were cooled
to 70C and pumped into a 2,000 gal. stainless steel vessel
similar to that of Example I.
Nine pounds of flake caustic potash was stirred into the
vessel contents. Pure nitrogen was blown through the liquid
contents to remove water and the temperature was raised to
110C. The vessel was then closed, the nitrogen valve was
closed and propylene oxide was again pumped into the reaction
mass at a rate sufficient to bring the temperature to about
140 - 160C. Such addition was continued until the rate of
oxide addition fell to two lbs. per minute. The vessel was
then opened briefly and an additional 25 lbs. of flake caustic
potash was introduced followed by 30 minutes of nitrogen
spraging.
Propylene oxide was again pumped into the reaction mass
until the total of all propylene oxide additions came to
8,000 lbs. At this point the propylene oxide addition was
stopped and ethylene oxide was introduced at a rate sufficient
to maintain a liquid temperature of about 140 - 150C or
until a total of 900 lbs. had been added.
The cooling system was then activated to reduce the
temperature to about 40 C at which point the product was
pumped to storage.
This product met the three criteria for a suitable TFSA
recited above.
EXAMPLE V
Two Hundred pounds of triethanolamine were substituted
for the diethylene triamine of Example IV. The synthesis
- 32 -

1153~74
procedure was followed except that the 9 lbs. of flake caustic
potash was stirred into the triethanolamine prior to the
addition of propylene oxide.
The final product met the required criteria for the TFSA.
EXAMPLES OF MICELLAR SOLUTIONS OF TFSA's
EXAMPLE A
Wt. %
Product of Example III 40
2-heptadecyl-3-triethylene triaminoimidazoline 6
o Acetic Acid 1.5
Phenol 2.5
n-Butanol 10
Water 40
Besides having good demulsification action, this product
has been found to be an effective corrosion inhibitor for
down-the-hole use, the imidazoline used as the amphipathic
agent being a strongly adsorbed inhibitor for steel in anaero-
bic systems.
EX~MPLE B
Wt.
Product of Example I 40
Sodium Mahogany Sulfonate
(M. W. of about 470) 15
Methanol 5
Alpha Terpineol 10
Water 30
This product has substantial corrosion inhibiting actionin aerated systems as well as being a useful demulsifier.
This product was tested to determine its effective in enhancing
- 33 -
`

1~53274
the recovery of oil by waterflooding.
Among procedures which have been found useful in select-
ing effective micellar TFSA solutions for this use, one
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 connec--
tions and appropriate valves at each end. The tube is mounted
vertically on a rack in an air bath equipped with a fan, heat-
er and thermostat 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 oil, of the producing
rock formation and of the water to be used in the flooding
operation were obtained. The formation rock is extracted
with tolu~ne to remove oil, is dried and is then ground in a
ball mill to the point where a large percentage passes a 40
mesh sieve. The fraction between 60 and 100 mesh in size is
retained. The tube described above is removed from the air
bath, opened and, after insertion of a glass wool retainer at
the lower end, is packed with the ground formation rock. The
tube i9 tapped gently from time-to-time during filling toensure
close packing and is visually inspected to assure absence of
voids.
The tube is then returned to the air bath, connected to
the ~nlet tubing, the temperature is adjusted to the oil
formation temperature and water representative of that produc-
ed 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
- 34 -
~ ~ .

llS3Z7~
"pore volume", being that volume of water just sufficient tofill the pores or interstices of the packed plug rock.
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 volume 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 air bath at the temperature of the
formation for a period of three days to allow establishment
of equilibrium 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 temperatures,
the time required to reach equilibrium is probably reduced.
Usually, for comparative tests, three days are allowed to age
the oil-rock plug. Results with this procedure closely simu-
late work with actual cores of oil-bearing rock.
The oil and water samples used for test purposes are
preferably taken under an inert gas such as high purity nitro-
gen, and are maintained out of contact with air during all
miniuplations in order to prevent oxidation of the oil and
concomitant introduction of spurious polar, surface-active
constitutents in the oil. At this point, the rock-oil system
simulates the original oil formation before primary production
oil has commenced and well before any secondary waterflood
operation.
The upper inlet line to the tube is now connected to the
- 35 - .
q~ r

~lS3274
sample of water used in the flooding of the oil formation and,
by means of a syringe pump or similar very small volume posi-
tive displacement pump, 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 until 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 displaced
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
drilling of a well into the rock formation followed by the
primary phase of field production carried to the approximate
economic limit.
Following this step, one to three additional pore vol-
umes of water containing the TFSA micellar solution to be
tested are pumped slowly through the plug and the volume3 o~
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, but 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 of 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
- 36 -
.~

llS;~Z74
TF~A 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 micellar TFSA solution to the water.
The composition of Example ~ was tested by this procedure
with the following conditions;
Oil --Ranger Zone, Wilmington, Calif.,
field API Gravity approximately
13.5
Water --Mixed water used in flood opera-
tions
Airbath Temperature --150F (Same as formation tempera-
ture)
Oil was displaced by pumping two pore volumes 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 3,500 ppm of the composition of Example B
was injected followed by 2.8 volumes o water containing 200
ppm of the composition of Example ~ Measurement of the
volumes of oil and water produced 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.
~ .
- 37 -

1153Z74
Oil Recovery as % of
Oil in Place
Composition of Ration of Incre-
Example B ment of Oil
Added to Production After
Pore Volumes Water after Initial 2
(P.V.) of No Chemical Initial 2 P.V. P.V. Chemical/
Water Injected Addition of Water No Chemical
2 36.5 36.5
3 40.0 44.5 2.3
43.1 54.8 2.8
Use of the composition of Example B in the amounts given
above resulted in the production of 130% more oil from injec-
tion of one incremental pore volume of water than was produced
by water injection alone and gave 180% more oil after three
incremental pore volumes of treated water injection.
EXAMPLE C
Wt.
Product of Example III 70
Oleyl amine 10
Acetic Acid 3
n-Propanol 2
Water 15
This is a clear, homogeneous but viscous solution. This
product was found to be an effective demulsifier for emulsion
produced in the Swan Hills, Alberta, field and was especially
~,
helpful in causing a clear water phase to separate from the
oil phase in the field treating plant.
;
- 3~ -

1153274
EXAMPLE D
Wt.
Product of Example IV 27.3
Dodecyldimethylbenzyl
Ammonium Chloride 27.3
N-Butanol 9.1
Mixed cresylic acids 13.6
Water 22.7
This product in addition to having strong demulsifica-
tion on East Texas crude oil emulsions, is an effective
bacteriacide with the quarternary ammonium salt and the cresy-
lic acids which are sufficiently soluble in the aqueous phase
separating from the emulsion to prevent bacterial growth
therein and thus insure its ready injectability for disposal
or enhanced recovery. In this composition the dodecyldimethyl-
benzyl ammonium chloride functions both as a micelle-forming
amphipathic agent and as a biocide. The utility of this
product for the breaking and resolution of a petroleum emulsion
was demonstrated by the following test:
100 ml of an emulsion from the Taching field, People's
Republic of China, was placed into each of two 6 oz. graduated,
screw cap bottles. The emulsion contained 42% water as
determined by azetropic distillation with xylene. The bottles
were placed in a water bath and held at a temperature of 130F.
After 30 minutes in the bath, one bottle (No. 1) was opened
and 0.8 ml of a 1% isopropanol solution of the composition of
~i Example D was placed in the bottle by means of a calibrated
1.0 ml pipette. 0.8 ml of pure isopropanol was placed into
the other bottle (No. 2) with a similar pipette. Both bottles
were closed tightly, shaken in a mechanical shaking machine
for five minutes at a rate of 134 four-inch oscillations per
minute and then returned to the water bath.
- 39 -
~, .

1153Z74
After one hour of quiet standing at 130F the bottles
were examined. In Bottle No. 1 a clear phase separation was
apparent with a sharp interface at approximately the 40 ml
graduation. Bottle No. 1 showed no free water or other phase
separation.
The bottles were allowed to stand for another hour after
which they were opened and 6 ml samples were pipetted from the
60 ml of each level and mixed with 6 ml portions of xylene in
12 ml API calibrated centrifuge tubes. The tubes were shaken
for a few seconds to insure mixing of oil and xylene and then
centrifuged for five minutes at 1800 rpm. The sample from
Bottle No. 1 contained 0.2% free water and 0.1% sedimented
emulsion. The sample from Bottle No. 2 contained 52% of a
sedimented emulsion layer and no free water.
,,
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274
1 EXAMPLE E
I Wt. %
Product of Example III 30
Isopropanol 10
Ammonium nonylphenoxyethoxy
sulfate 8
"Polyox" *coagulant (PQlyethyleneoxide
of Mol. Wt. about 5 million) 2
Water 50
This product was found to be an effective demulsifier for
emulsions produced in the Salem, Illinois field and was further
found to give a clear separated water phase, free of oil and other
suspended matter, which could be reinjected for pressure mainten-
ance with minimal contamination of filters and producing formation:
This product has a high viscosity and can be used as such
or mixed with an approximate equal quantity of water as the drive
fluid for secondary or tertiary oil recovery where mobility con-
trol, as well as improved water wetting and oil removal, is an
important consideration.
Although 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 and that the inven-
tion 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. Accordingly, modi-
fications are contemplated which can be made without departing
~- 25~ from the spirit of the described invention.
' ~ .
i~
`~ .
-40-
$