TEPZZ_ _ ¥85B_T

(19)

(11) EP 1 212 385 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.:

of the grant of the patent: C09K 8/04 (2006.01) E21B 43/25 (2006.01)
30.12.2015 Bulletin 2015/53 E21B 43/26 (2006.01)

(21) Application number: 00959792.3 (86) International application number:

PCT/US2000/024142
(22) Date of filing: 01.09.2000
(87) International publication number:
WO 2001/018147 (15.03.2001 Gazette 2001/11)

(54) QUATERNARY AMMONIUM SALTS AS THICKENING AGENTS FOR AQUEOUS SYSTEMS

QUATERNÄRE AMMONIUMSALZE UND DEREN VERWENDUNG ALS VERDICKUNGSMITTEL
FÜR WÄSSERIGE SYSTEME
SELS D’AMMONIUM QUATERNAIRE EN TANT QU’AGENTS EPAISSISSANTS POUR DES
SYSTEMES AQUEUX

(84) Designated Contracting States: • Zhu, Yun-Peng

AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU Fort Lee, New Jersey 070024 (US)
MC NL PT SE • Zhu, Shawn
Dublin, Ohio 43017 (US)
(30) Priority: 07.09.1999 US 152662 P • Feuerbacher, Dave
Westerville, Ohio 43081 (US)
(43) Date of publication of application:
12.06.2002 Bulletin 2002/24 (74) Representative: van Deursen, Petrus Hubertus et
al
(73) Proprietor: Akzo Nobel Surface Chemistry Akzo Nobel N.V.
Aktiebolag Intellectual Property Department
444 85 Stenungsund (SE) P.O. Box 9300
6800 SB Arnhem (NL)
(72) Inventors:
• Subramanian, Shankar (56) References cited:
Dublin, OH 43016 (US) WO-A-99/32572 US-A- 4 725 372
• Burgazli, Cent R. US-A- 5 089 151 US-A- 5 551 516
Cardungton, OH 43315 (US)
EP 1 212 385 B1

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR)

 EP 1 212 385 B1

Description

FIELD OF THE INVENTION

5 [0001] This invention relates to the use of alkyl amido quaternary ammonium salts, and formulations thereof, as
thickening agents in aqueous based fluids, especially those used in oil field applications. In particular, the compositions
of the present invention find use as gelants in fluids used in oil recovery operations such as fracturing fluids, completion
fluids, and drilling fluids, that are used in the process of recovering hydrocarbons from subterranean formations. The
quaternary ammonium salts of the present invention exhibit improved gelling characteristics.
10
BACKGROUND OF THE INVENTION

[0002] Hydraulic fracturing is used to stimulate the production of hydrocarbons such as oil or natural gas from subter-
ranean formations. In this process, a fracturing fluid is injected through a wellbore and propelled against the formation
15 strata by high pressure sufficient to cause the strata to crack and fracture.
[0003] The fracturing fluid also carries what is referred to as a proppant to the fracture site. These proppant particles
remain in the fracture thereby "propping" the fracture open when the well is in production. The proppant material is
commonly sand, sintered bauxite, glass balls, polystyrene beads, and so forth.
[0004] Traditional fracturing fluids were polymer based fluids. Naturally occurring polysaccharides such as guar and
20 derivatized guar, upon dissolution in water, form hydrated polymers which can be crosslinked with organometallic com-
pounds such as borates, zirconates or titanates to form a crosslinked gel structure which increases the viscosity of the
fluid. However, these crosslinked polymers can ultimately form a rubbery semi-solid material that is difficult to recover
from the fracture causing reduction in the conductivity of the fracture. Peroxides and other gel breakers are therefore
often utilized to break the gelled polymeric structure into smaller molecules and facilitate clean-up of the fracture site.
25 Production of oil or gas is often dependent on the ability to clean the fracture site of such materials.
[0005] It is a widely known concept to use certain chemical agents to increase the viscosity or induce gel formation
in aqueous or hydrocarbon based fluids. These gelled or thickened fluids may be referred to as viscoelastic fluids. The
term viscoelastic is commonly understood to refer to a fluid that has the capability to partially return to its original non-
disturbed form upon release of applied stress. It is believed that under the right conditions, i.e. concentration, counter
30 ion, pH and so forth, that certain surfactants from rod-like or cylindrical micelles which can entangle to form these
gelatinous, viscoelastic fluids in aqueous solutions.
[0006] These thickened fluids are then capable of suspending the proppant particles and carrying them to the fracture
site. These gelled fluids also diminish loss of fluid into the fracture face, thereby improving the efficiency in the fracturing
process and reducing the overall cost.
35 [0007] Viscoelastic fluids can be formed with a combination of ionic and/or non-ionic surfactants and by the incorporation
of additives such as organic and/or inorganic salts. U.S. Patent No. 5,551,516 issued Sept. 3, 1996 to Norman et al.
describe surfactant based viscoelastic aqueous fluid systems useful in fracturing subterranean formations penetrated
by a wellbore, and state that the fracturing fluids are useful in high temperature, high permeability formations. Norman
et al. state that the preferred thickening agents are quaternary ammonium halide salts derived from certain waxes, fats
40 and oils. The thickening agent is used in conjunction with an inorganic water soluble salt, an organic stabilizing additive
selected from the group of organic salts such as sodium salicylate. The fluids are said to be stable to a temperature of
225° F.
[0008] Similarly, US, 4,725,372 discloses thickened aqueous fluids comprising a water-soluble electrolyte and a thick-
ener based on an amine, a salt of an amine, or a quaternary ammonium salt. Also the use of such thickened fluids in a
45 variety of applications is suggested. A preferred thickening agent is said to be a tertiary amine of the formula
C18H 35N(CH 2CH2OH)2 for aqueous solutions having a density of at least 15 ppg and comprising CaBr2 and ZnBr2.
[0009] Various problems have been encountered with these gelled fluids in oil field applications including the lack of
thermal stability of the fracturing fluids caused by the degradation of the additives or the instability of the gel upon
exposure to high temperatures and/or high shear conditions. This can result in changes in the rheological properties of
50 the gel which can ultimately affect the ability of the fluid to suspend proppant material. If proppant material is prematurely
lost from the fracturing fluid it can have a detrimental effect on the fracturing treatment. Furthermore, gel instability can
result in higher loss of fluid into the formation thereby diminishing the amount of fracturing that occurs. High temperatures
in the formation can further impact gel stability.
[0010] For high brine solutions, i.e. those having salt concentrations of about 30 wt-% or more, polymeric materials
55 have been used as thickeners but tend to precipitate from these high salt concentration solutions which can result in
plugging and formation damage. Furthermore, the high salt concentration makes it difficult to dissolve these polymeric
viscosifiers or thickeners in the solutions. Such high brine solutions are found in completion fluids used in drilling oper-
ations.

2
 EP 1 212 385 B1

SUMMARY OF THE INVENTION

[0011] The present invention relates to improved gelling agents for use in oil field applications. In particular, the
compositions find use in fracturing fluids, completion fluids and well drilling fluids.
5 [0012] The gelling agents of the present invention are cationic in nature and have the following general structure:

10

15

R1 is alkyl amine alkylene, alkyl amido alkylene, alkyl ester alkylene where the alkyl group contains 1-26 carbon atoms
and the alkylene group preferably contains 1 to 8 carbon atoms; R2 and R3 are each alkyl, hydroxy alkyl, polyalkoxy
with the degree of polymerization ranging from 2-30, alkyl sulfonate, hydroxyalkyl sulfonate or alkylaryl sulfonate; R4 is
20 hydrocarbon such as alkyl, aryl, aralkyl, or alkaryl and can be saturated or unsaturated; and X is selected from the group
consisting of halides; oxo ions of phosphorous, sulfur or chloride; and organic anionic molecules including the list of
anions according to claim 1.
[0013] The surfactants of the present invention, in combination with at least one additive which may be an inorganic
salt, organic salt, organic acid, alcohol or a mixture thereof, form stable gels in aqueous environments.
25 [0014] The present invention further relates to a method of fracturing a subterranean formation comprising the steps
of providing a thickened fracturing fluid as described above, and injecting the aqueous fracturing fluid through a wellbore
and against a subterranean formation at a pressure sufficient to initiate and or extend a fracture into the formation.
[0015] The present invention further relates to a method of suspending particles in a thickened aqueous liquid by
providing an aqueous medium and adding to the aqueous medium an effective amount of at least one surfactant and
30 at least one counterion selected from the group consisting of organic salts, inorganic salts, organic acids, alcohols, and
mixtures thereof, sufficient to increase the viscosity of said aqueous medium. The surfactant has the general structure
as provided above. The thickened aqueous fluid is capable of suspending solid paniculate matter. The thickened fluid
may then be further used to transport the solid particulate matter to a remote location.
[0016] This type of method is useful in well-drilling operations, coil-tubing operations, construction operations, mining
35 operations, and so forth, where it is desirable to remove solid matter from the site of operation.
[0017] The present invention further relates to a method of reducing the friction of an aqueous liquid as it passes
through a conduit by adding to the aqueous liquid, at least one surfactant of the present invention, and at least one
additive which is an inorganic salt, organic salt, organic acid, an alcohol, or a mixture thereof. The amount of surfactant
and additive added to the aqueous liquid are sufficient to reduce the friction of the aqueous liquid as it passes through
40 the conduit.
[0018] The present invention further relates to an oil field high brine oil completion fluid comprising 30 wt-% to 70 wt-
% of at least one inorganic or organic salt and 0.1 wt-% to 4 wt-% of at least one cationic surfactant having the following
general structure:

45

50

55 wherein R1 is alkyl amine alkylene or alkyl amido alkylene; R2 and R3 are each alkyl, hydroxy alkyl, polyalkoxy with the
degree of polymerization ranging from 2 to 30, hydroxyl alkyl sulfonate, alkyl sulfonate or alkylarylsulfonate; R4 is hy-
drocarbon, saturated or unsaturated; and X is selected from the group consisting of halides; oxo ions of phosphorous
sulfur or chloride; and organic anions.

3
 EP 1 212 385 B1

[0019] A further counterion, i.e. organic acid, alcohol, or mixture thereof, is optional in the case of the high brine
completion fluid.
[0020] These compositions have been found to provide a reversible thickening phenomenon whereby with increasing
temperature, the viscosity increases. However, when the heat source is removed, and the temperature drops, the
5 viscosity will again decrease.

DETAILED DESCRIPTIONS OF THE PREFERRED EMBODIMENTS

[0021] The monomeric surfactants of the present invention in the presence of organic or inorganic activators or gel
10 promoters, can be used as thickening agents in aqueous based systems.
[0022] The surfactant ions of the present invention are preferably cationic and have the following general structure:

15

20

where R1 is alkyl amine alkylene, alkyl amido alkylene or alkyl ester alkylene where the alkyl group contains 1-26 carbon
25 atoms and the alkylene group preferably contains 1 to 8 carbon atoms; R2 and R3 are each alkyl, hydroxy alkyl, polyalkoxy
with the degree of polymerization ranging from 2-30, alkyl sulfonate, hydroxyalkyl sulfonate or alkylaryl sulfonate; R1 is
hydrocarbon such as alkyl, aryl, aralkyl, alkaryl and can be saturated or unsaturated; or wherein any two of R2, R3 and
R4, together with the nitrogen atom to which they are attached, form a heterocyclic ring containing 2 to 5 carbon atoms
and 1 to 6 sulfur atoms such as sulfur (S), nitrogen (N), oxygen (O) or silicon (Si); and X is selected from the group
30 consisting of halides; oxo ions of phosphorous, sulfur or chloride; and various organic molecules.
[0023] In some preferred embodiments of the present invention, R1 is alkyl amine alkylene or alkyl amido alkylene,
and/or R2 and R3 are each alkyl or hydroxy alkyl.
[0024] Examples of suitable alkyl groups, R 2, R3 or R4 include methyl, ethyl, propyl, butyl, hexyl, allyl, benzyl, vinyl
benzyl, and the like, including iso-propyl, isobutyl, sec-butyl, tert-butyl, and so forth. Examples of suitable hydroxy alkyl
35 groups include 2-hydroxyethyl-2-hydroxypropyl and 2,3-dihydroxypropyl. Polyalkoxy groups are preferably ethyl, propyl
or butyl.
[0025] Alkyl sulfonate may also be referred to as sulfobetaines and hydroxyalkyl sulfonates may also be referred to
as sultaines. An example of a sulfobetaine is propyl sulfonate and an example of a sultaine is 2-hydroxypropyl sulfonate.
[0026] The thickening agent is employed in an amount which in combination with the other ingredients is sufficient to
40 increase the viscosity of the aqueous fluid enough to maintain proppant in suspension during fluid placement.
[0027] Preferably, the surfactants of the present invention are alkyl amidoalkyltrialkyl ammonium quaternary salts and
have the following general structure:

45

50

[0028] R2 and R3 are alkyl and preferably have from 1 to 8 carbon atoms; hydroxy alkyl preferably having from 1 to 8
carbon atoms; polyalkoxy including ethyl, propyl and butyl with the degree of polymerization ranging from 2 to 30;
55 hydroxyalkyl sulfonate, i.e. sultaine; alkyl sulfonate, i.e. sulfobetaine; alkylarylsulfonate; R4 is hydrocarbon and can be
alkyl, aryl, aralkyl, alkaryl, saturated or unsaturated; or wherein any of R2, R3 and R4, together with the nitrogen atom
to which they are attached, form a heterocyclic ring containing 2-5 carbon atoms and 1-6 hetero atoms such as sulfur
(S), nitrogen (N), oxygen (O), and silicon (Si); R is a saturated or unsaturated alkyl having from 1 to 30 carbon atoms,

4
 EP 1 212 385 B1

preferably from about 6 to 26 carbon atoms and most preferably from about 12 to 22 carbon atoms; y is an integer from
0 to 12, and preferably from 1 to 12; and X is defined above. Suitable R groups include coco, palmityl, stearyl, oleyl,
erucyl, as well as other saturated or unsaturated moieties. As a general rule, although other factors affect stability as
well, the higher the number of carbon atoms in R, the better the stability of the resultant gel.
5 [0029] In a specific preferred embodiment y is 1 and X is chloride, and the surfactant is an alkylamidopropyltrialkyl
ammonium quaternary chloride having the following general structure:

10

15
where R is erucyl (22 carbon unsaturated fatty acid chain); R2, R 3, and R4 are methyl; and y is 1. X is preferably chloride.
[0030] These types of compounds are obtained by quaternization of a corresponding alkylamidopropyltrimethylamide
with methylene chloride, ethyl chloride, benzyl chloride, vinyl chloride, butyl chloride, methyl sulfate, chlorohydroxyalkyl-
sulfonate, chloroalkylsulfonates and so forth, and mixtures thereof.
20 [0031] The long chain alkyl groups, R, are hydrophobic in nature and are generally derived from a fatty acid. The fatty
carboxylic acid is reacted with an amine to form the amide. These long chain alkyl groups are generally derived from
the fatty acids and include cetyl, oleyl, stearyl, erucyl, and the derivatives of tallow, coco, soya and rapeseed oils.
[0032] In a preferred embodiment of the present invention, the quaternary ammonium salt is erucyl amidopropyltrimethyl
ammonium quaternary salt.
25 [0033] Examples of other useful quaternary salts generally include the following structures:

30

35

40

45

50 [0034] R, R2, R3, R 4 and X are as defined above. Preferably, R has about 6 to about 26 carbons and most preferably
R has about 12 to 24 carbon atoms. As stated above, it has been found to be a general rule that R groups having a
higher number of carbon atoms, result in a gel having better thermal stability. A specific example of structure VII, above,
is dimethylalkylglycerolammonium chloride.

55

5
 EP 1 212 385 B1

10

15

20

25

30

35 [0035] Where R, R 2, R3 and R4 are defined as above.

[0036] X may be halides; oxo ions of phosphorous, sulfur or chloride; and various organic anions, including chlorides,
bromides, iodides, oxides of phosphorous, hypochlorides, phosphates, phosphites, oxides of sulfur, sulfates, sulfites,
sulfonates, phosphates, acetates, carboxylates, chlorates, perchlorates, salicylates, phthalates, lactates, maleates, gly-
cinates, citrates, citric acid, lactic acid, salicylic acid, phthalic acid, benzoic acid, naphthoic acid, amino acids, and so forth.
40 [0037] The concentration of the surfactant is preferably from 0.05% to 10% by weight of the fluid, more preferably
from 0.05% to 6%, even more preferably from 0.1% to 5%, even more preferably from 0.2% to 4% and most preferably
from 0.5% to 4%.
[0038] The surfactants of the present invention are rheologically stable up to temperatures of about 300° F (about
149° C). In some specific embodiments, the surfactants are stable up to temperatures of about 110° C or 225° F, to
45 about 275° F (about 135° C). It is important to note, however, that the gels can be used at low temperatures, i.e. 25° C,
as well as in the operations where the temperature is high.
[0039] The gelation is assisted by the presence of an activator or gel promoter. These are often referred to in the art
as counterions or additives. An organic acid, a salt, either organic or inorganic, an alcohol, or any combination thereof,
may be added as an activator or gel promoter so as to increase the viscosity of the fluid or in the development of the
50 gel. Such additives can also aid in maintaining the stability of the geologic formation to which the fluid is exposed. The
use of such compounds to improve the thickening characteristics of the fluid, are known to one of skill in the art. The
compounds are chosen such that the thickening agent is compatible with the electrolyte to avoid the formation of unde-
sirable precipitates. While some gelants, such as the sultaines or sulfobetaines, have been found to thicken or gel the
aqueous fluids without the presence of the counterions, the gel stability has been found to be poor.
55 [0040] The organic salts useful herein are typically water soluble compounds involving a metal or an amine salt of an
organic anion. Organic anions include salicylates, phthalates, naphthalates, sulfates, sulfonates, lactates, glycinates,
citrates, carboxylates, benzoates, chlorobenzoates, phenates, acetates, sulfobetaines, hydroxysultaines, and so forth.
Preferably, sulfates and sulfonates are used in the present invention, and in particular, those having aromatic groups

6
 EP 1 212 385 B1

such as xylene or toluene are preferred. Specific examples include xylene sulfonate, p-toluene sulfonate, naphthalene
sulfonate, hydroxynaphthalene sulfonate, ethoxylauryl sulfate, methyl sulfate, ethyl sulfate, and so forth.
[0041] The organic acids useful herein include citric acids, lactic acids, salicylic acids, sulfonic acids, carboxylic acids,
salicylic acids, benzoic acids, phthalic acids, naphthoic acids, and so forth. Specific examples include 3-hydroxy 2-
5 naphthoic acid, 5-hydroxy-1-naphthoic acid, 7-hydroxy-2-naphthoic acid, 1,3-dihydroxy-2-naphthoic acid, 4-amino-5-
hydroxy-1-naphthalene sulfonic acid, 2-amino-1-naphthalene sulfonic acid, and so forth.
[0042] The organic acids or salts may be modified with alkyl, ether, alpha-olefin, alkoxylates including ethoxylates,
aromatic groups, hydroxyl, amino, thio and so forth. A preferably class of organic counter ion is the sulfonate ion. These
organic acids or salts are useful in the aqueous medium from 0.1% to 5% by weight of the composition and preferably
10 from 0.2% to 1% by weight of the composition.
[0043] The alcohols useful herein are preferably medium to long chain alcohols and may be alkanols or alcohol
alkoxylates, i.e. alcohol ethoxylates. Alcohols are useful at a concentration in the aqueous medium of 0.1% to 4% by
weight of the composition and preferably from 0.2% to 2% by weight of the composition.
[0044] Inorganic salts or small quaternary ammonium salts such as tetramethyl ammonium chloride, are also useful
15 to the present invention. Preferably, the salts will be salts of sodium, potassium, ammonium, calcium, magnesium, zinc
and so forth. These ions preferably will be in combination with a halide ion. More specifically, the inorganic salt may
include potassium chloride, ammonium chloride, sodium chloride, magnesium chloride, calcium chloride, calcium bro-
mide, and so forth. These inorganic salts both aid in the development of the gel, and assist in maintaining stability of the
geologic formation to which the fluid is exposed. These inorganic salts are useful at a concentration in the aqueous
20 medium from 0% to 10% by weight, preferably from 1% to 6%. The concentration of the counterion or additive appears
to be somewhat dependent on the size of the molecule, and that larger molecules may be added in lower concentrations.
[0045] Specific examples of such counter ions include chloride, bromide, methyl sulfate, ethyl sulfate, xylene sulfonate,
p-toiuene sulfonate, naphthalene sulfonate, hydroxynaphthalene sulfonates and carboxylates, 4-amino-5-hydroxy-1-
naphthalene sulfonic acid, 2-amino-1-naphthalene sulfonic acid, 3-hydroxy-2-naphthenic acid, ethoxylated lauryl sulfate,
25 sulfobetaines, 5-hydroxy-1-naphthoic acid, 6-hydroxy-1-naphthoic acid, 7-hydroxy-1-naphthoic acid, 3-hydroxy-2-naph-
thoic acid, 5-hydroxy-2-naphthoic acid, 7-hydroxy-2-naphthoic acid, 1,3-dihydroxy-2-naphthoic acid, 3,4-dichloroben-
zoate, and so forth.
[0046] Preferably, at least one organic counterion will be present in the compositions of the present invention. Although,
in some preferred embodiments of the present invention both an inorganic salt and an organic salt, or acid, are utilized
30 together with the quaternary ammonium cationic surfactant of the present invention. Preferably, the organic salt utilized
is from the sulfonate family.
[0047] The total amount of the additives present will preferably range anywhere from 0.1% to 10% by weight of the
total composition.
[0048] It is envisioned that the cationic surfactants of the present invention may also be used in combination with other
35 surfactants such as anionic, non-ionic, amphoteric (or zwitterionic) surfactants.
[0049] To prepare the aqueous fracturing fluid of the present invention, the viscoelastic surfactant is added to an
aqueous solution in which has been dissolved at least one water soluble inorganic salt (i.e. NaCl, KCl, NH4Cl, NH4NO3,
etc.), and/or at least one organic salt, organic acid, or alcohol, to provide formation stability, or to provide selective control
of the loss of particle suspension properties. As stated above, the salts both aid in the development of the gel, and assist
40 in maintaining stability of the geological formation to which the fluid is exposed.
[0050] Standard mixing procedures known to one of skill in the art may be employed in the present invention.
[0051] Other ingredients may also be added to the fluids of the present invention including defoamers, fluid loss
additives, breakers, demulsifiers, and so forth, as well as other polymeric materials such as guar, guar derivatives,
starch, cellulose, polyacrylates, and so forth. Additives such as these are known to one of skill in the art.
45 [0052] In some instances, it may be preferable to foam the fluids of the present invention by adding air, nitrogen,
carbon dioxide, and a foaming agent.
[0053] These gelled or thickened fluids may be referred to as viscoelastic fluids. The term viscoelastic is commonly
understood to refer to a fluid that has the capability to partially return to its original non-disturbed form upon release of
applied stress. It is believed that under the right conditions, i.e. concentration, counter ion, pH and so forth, that certain
50 surfactants form rod-like or cylindrical micelles which can entangle to form these gelatinous, viscoelastic fluids in aqueous
solutions.
[0054] The gelled or thickened fluids of the present invention may exhibit a reversible thickening phenomenon. The
fluids of the present invention may exhibit an increase in viscosity as the temperature is increased as opposed to most
fluids which exhibit a decrease in viscosity as the temperature is increased. Furthermore, when the heat source is
55 removed and the temperature decreases, the viscosity will also decrease. This phenomena, for instance, is illustrated
in Table 11 of the Examples section where the viscosity of a high brine oil field completion fluid increases as the
temperature is increased from about 170° F to about 250° F (about 76.7° C to about 121.1° C).
[0055] The thickened fluids of the present invention find particular utility as fracturing fluids, in compositions used in

7
 EP 1 212 385 B1

well drilling operations, for proppant and cutting transportation to and from the fracture site, any drilling fluids. These
compositions have also found excellent utility in completion fluids. Completion fluids are often used in high brine situations
where the salt concentration (divalent salts such as CaCl2, CaBr2, ZnBr2, and so forth) may be as high as 30 wt% to 70
wt-%. Polymeric thickeners are not as advantageously used in such high brine fluids because the polymers tend to be
5 incompatible in these high salt environments. The polymers often precipitate from the solutions which can result in
damage to the subterranean formation.
[0056] Fracturing of a subterranean formation involves pumping or injecting the aqueous fluid through a wellbore and
against a subterranean formation at a flow rate and pressure sufficient to initiate and or extend a fracture into the
formation. The thickened fluid also acts as a transportation vehicle for the proppant particles. These particles are carried
10 to the fracture where they will remain in order to "prop" the fracture site open after the pressure is removed and the well
goes into production. Keeping the fracture open allows for better flow of hydrocarbons from the site.
[0057] The gels of the present invention have excellent thermal stability of greater than about 65° C, preferably greater
than about 80° C, more preferably greater than about 90° C, even more preferably greater than about 95° C, and most
preferably greater than about 105° C. Many of the preferred surfactants have been found to have thermal stability in
15 excess of about 225° F (about 107° C), although in some instances the surfactants exhibit thermal stability in the 275°
F (about 135° C) to 300° F (about 149° C) range. It is preferred that the compositions exhibit stability of at least about
185° F (about 85° C) to about 230° F (about 110° C).
[0058] The gels of the present invention exhibit excellent viscosity stability to shear forces and high pressure and do
not readily degrade upon exposure to high shear. This decreases the amount of fluid lost to the formation during the
20 fracturing process when they are exposed to extreme pressures, and subsequently, leakoff rates for these fluids are low.
[0059] The excellent thermal and shear stability of the thickened fluids of the present invention make them particularly
useful for fracturing operations where the temperature is high and/or the fracture site has high permeability. If the viscosity
of the fluid is susceptible to decrease at high temperatures, more fluid can be lost to the formation resulting in less
efficiency in the fracturing process, and more fluid lost in the formation.
25 [0060] The gel-like structure formed by the surfactants of the present invention may be disrupted on contact with
hydrocarbon liquids, resulting in loss of viscosity. This can be advantageous for removal of the gel from the fracture
once the fracturing process is complete and the well goes into production.
[0061] The gels of the present invention also find utility in other various other oil field and non-oil field applications
including gravel-pack applications, in acidizing treatments, as diverting agents or lost-circulation agents, in pipeline drag
30 reduction, in coil-tubing operations, in drilling operations as drilling fluids, as completion fluids, as foamed underbalance
drilling fluids, and so forth.
[0062] The use of polymer-free viscoelastic gels in gravel-pack applications is discussed in Society of Petroleum
Engineers (SPE) 17168, W.L. Nehmer, "Viscoelastic Gravel-Pack Carrier Fluids," incorporated by reference herein. The
gels of the present invention provide excellent rheological properties making the especially useful in gravel-pack treat-
35 ments where the rheology of the fluid is essential to achieving a good "pack". As opposed to polymer gels, the surfactant
based gels of the present invention are not as susceptible to high shear forces. Further, they are less likely to damage
the formation than those gels which utilize polymeric materials.
[0063] The surfactants of the present invention find utility in gelled acid systems for use in acidizing carbonate and
dolamite formations for prevention of loss of fluid in the formation due to the presence of natural fissures and cracks.
40 The systems of the present invention provide a cleaner system than the polymeric based gels.
[0064] The gels of the present invention find utility as diverting agents or lost-circulation agents which aid in preventing
loss of treating fluid into the natural fissures and cracks in the formation. Again, as opposed to polymeric gels, the gels
of the present invention impart less damage to the formation and are easier to clean out of the formation upon completion
of the treatment.
45 [0065] The gels of the present invention also find utility in reducing drag in pipelines. Pipeline drag reduction is discussed
in U.S. Patent No. 4,615,825 to Teot et al. incorporated by reference herein. Surprisingly, the surfactants of the present
invention provide more shear stability and greater reduction in frictional forces than polymeric additives. In a preferred
embodiment of the present invention, a salicylate is utilized as the counterion in the composition, providing excellent
drag reduction.
50 [0066] The amount of surfactant and additive added to the aqueous fluid to reduce the friction as it passes through a
conduit will depend on a variety of factors including the particular aqueous liquid, the surfactant chosen, as well as the
type of additive chosen. In general, the concentration of the surfactant is preferably from about 0.01% to about 10% by
weight of the fluid, and more preferably from about 0.05% to about 5%. The additive is preferably from about 0.1% to
about 10% by weight of the total composition.
55 [0067] The gels of the present invention find utility in both coil-tubing and drilling operations which involve the circulation
of the thickened fluids through wells. The primary function of the gels in this instance is to transport cuttings or other fine
debris including the filtered proppant out of the well bore. The gels of the present invention provide excellent rheological
properties for such applications, and contribute minimally to the friction pressure. The thickened fluids are reusable upon

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 EP 1 212 385 B1

removal of the cuttings from the fluid. These applications are discussed in U.S. Patent No. 4,735,731 to Rose et al.
[0068] In drilling operations, in addition to the transportation of cuttings, the compositions of the present invention also
find utility as drilling fluids to maintain the integrity of the wellbore and to lubricate the drill bit. Typically in these drilling
operations, the fluids are referred to as drilling mud.
5 [0069] The compositions of the present invention also find utility as completion fluids for drilling operations and for
work over rigs. Viscosifiers are necessary in completion fluids in order to prevent too much water from filtering out into
the porous surface of the formation, a phenomenon referred to in the industry as fluid loss. These viscosifiers are
necessary both during the actual drilling process, and for preventing settling of the solids later on.
[0070] The completion fluids are typically heavy brine solutions having a density in the range of about 11 pounds per
10 gallon (~1099 kg/m3) to about 19 pounds per gallon (∼1896 kg/m3) as compared to water which is about 8.32 lbs/gallon.
The gelants of the present invention are excellent thickeners for these high salt concentration fluids. The resultant
completion fluids exhibit excellent thermal stability of at least about 250° F (about 120° C) to about 350° F (about 177°
C). For these completion fluids, a small amount of surfactant in an amount of about 0.5 wt-% to about 4 wt-% facilitates
gel formation. Furthermore, the use of counterions, e.g. inorganic salts, organic salts, organic acids, alcohols, and so
15 forth, is not necessary. However, a small amount of counterion may be desirable. If a counterion is used, the desirable
range is about 0.10% to about 5%. The addition of the counterions can improve gel stability but the gelants of the present
invention function without the presence of such counterions.
[0071] In a particular embodiment, sodium salicylate in an amount of less than about 0.2 wt-% was added in addition
to the gelant.
20 [0072] Non-oil field applications include applications in the mining and metal cutting industries. The compositions of
the present invention may also be used in the construction industry during excavation, digging, tunneling, drilling, and
so forth. They may also be used for dust control. The compositions of the present invention may also be used in the
masonry, cement and concrete industries.
[0073] The compositions of the present invention also find use as rheology modifiers, and may be used in household
25 products including shampoos, detergents, cleaning products, and so forth.
[0074] The viscoelastic surfactants of the present invention also exhibit drag reducing properties.

EXAMPLES

30 [0075] KCl solution, 2% by weight, was stirred in a 500 ml stainless steel blender at an rpm of 200-300. To this solution,
approximately 4 ml (∼60% by weight concentration in ethylene glycol) of the quaternary ammonium salt (dimethylami-
dopropyltrimethyl ammonium chloride) was added to the KCl solution(forming a 3% by weight concentration of surfactant).
Witconate® SXS, xylene sulfonate, was added (2 ml, ∼40% concentration) and the resulting mixture was stirred for about
5 minutes at an rpm of 2000 to 3000 (Variact set at about 25). The resultant gel was defoamed using a sonicator and/or
35 heating to 80°C. Rheological performance was evaluated using a model 50 rheometer (a Fann 50 Rheometer). The
results may be found in the following tables.
[0076] The quaternary compound found in Table I has the following general structure:

40

45

[0077] R is erucyl, (22 carbon, unsaturated fatty acid chain), R2, R3 and R4 are each methyl, y is 1, and X is chloride.
This compound will be referred to hereinafter as erucyl-DMAPA quat.
50 [0078] Preblending of the quaternary salt and the xylene sulfonate before addition to the water appeared to delay gel
formation more than adding each ingredient to the water separately.

Example 1

55 [0079]

9
 EP 1 212 385 B1

Table 1
Rheological Performance of a Gelled Fluid
Viscosity
5 Temperature ° F (° C)
40 sec-1 100 sec-1 170 see-1
80 (26.7) 740 430 200
10 (37.8) 745 435 215

10 125 (51.7) 408 312 180

150 (65.6) 274 150 100
175 (79.4) 310 167 80
200 (93.3) 247 170 76
15
225 (107.2) 120 90 60
250(121.1) 60 -- 27

[0080] Gel Composition: 2% KCL; 4% erucyl-DMAPA quat, 60% active (gelling agent); 2% Witconate® SXS (40%
20
solution) sodium xylene sulfonate available from Witco Corp.
[0081] Example 1 illustrates the rheological performance of a viscoelastic gel of the present invention. The gels exhibits
high viscosity at low shear rates thereby providing excellent proppant transportation and control of fluid penetration into
the formation when the fluid is forced at high pressure into the fracture face.

25
Example 2

[0082]

Table 2
30
Effect of Gellant Concentration on Viscosity
Temperature ° F (° C) Viscosity (cPs) @ 100 sec-1
2.5% gelant 4% gelant (60% active) 6% gelant
35 8 (∼27) 260 430 590
100 (∼ 38) 215 435 600
125 (-52) 142 312 542
150 (∼ 66) 70 150 283
40
175 (∼ 79) 77 167 231
200 (∼ 93) 80 170 182
225 (∼ 107) 61 90 100
45

[0083] The gel composition contained 2% KCL, 2% Witconate® SXS (40% solution), and erucyl-DMAPA quat gelant.
[0084] Example 2 illustrates the effect of the concentration of the gelant on the rheological performance of the fluid.
The amount of gelant may be tailored to the physical characteristics of the geological formation such as temperature
and permeability. For instance, a fluid with a high concentration of surfactant thereby providing higher viscosity, would
50 find utility in a high temperature formation.

Example 3

[0085]
55

10
 EP 1 212 385 B1

Table 3
Effect of Chain Length of R on Stability

5 No. of carbon atoms Group Stability

22 erucyl (unsaturated) ∼ 225° F (∼ 107° C)
22 saturated C22 <150° F (65.5° C)
18 oleyl <150° F(65.5° C)
10
16 palmityl <150° F (65.5° C)
12 lauryl weak gel
*Each of the compositions contained 2% KCL; 4% gelant; and 2% Witconate® SXS.

15
Comparative Examples A and B

[0086] Comparative example A was composed of 2% KCL; 4% Kemamine® EX-300 erucyl-amine gelant; and 5 lbs
sodium salicylate/1000 gallons. The heat stability was approximately 200° F (∼93° C).
20 [0087] Comparative example B was composed of 2% KCL; 4% erucylamidopropylamine oxide (45% active) gelant;
2% Witconate® SXS; and 1% Adogen® 471. Comparative B had heat stability of <175° F (79.4° C).
[0088] Example 3 as compared to comparative examples A and B illustrates that surprisingly, comparable heat sta-
bilities are being obtained with the gelants of the present invention as compared to commercially available gelants which
are standards in the industry, even though the chemical structures are different.
25
Example 4

[0089]

30 Table 4
Effect of Counter Ion Concentration on Gel Stability
Viscosity (cPs) @ 100 sec-1
Temp ° F (° C)
1% SXS 2% SXS 3% SXS 4% SXS 6% SXS
35
80 (∼27) 300 430 360 370 -
100 (∼ 38) 220 435 340 400 285
125 (∼ 52) 250 310 220 200 170
40 150 (∼ 66) 230 150 150 166 105
175 (∼ 79) 150 165 145 115 75
200 (∼ 93) 110 170 90 90 -
225 (∼107) 80 90 - - -
45
*The gel composition was 2% KCl, 4% erucyl-DMAPA quat gelling agent (60% active); and Witconate® SXS (40%
solution) varied as shown in Table 4.

Example 5
50

[0090]

55

11
 EP 1 212 385 B1

Table 5
Effect of Counter Ion Concentration on Gel Stability

5 Temp ° F (° C) Viscosity (cPs) @ 100 sec-1

1% salicylate 2% salicylate 3% salicylate 4% salicylate 6% salicylate
80 (∼27) 110 300 310 330 250
10 (∼38) 95 380 300 350 280
10
125 (∼ 52) 75 260 320 325 245
150 (∼ 66) 50 215 360 275 175
175 (∼ 79) - 160 155 165 130

15 200 (∼ 93) - 115 140 130 90

*The gel composition was 2% KCl; 4% erucyl-DMAPA quat gelling agent (60% active); and the concentration of the
sodium salicylate counter ion (25% solution) varied as shown in Table 5.

20 Example 6

[0091]

Table 6
25 Effect of Type of Counter Ion on Stability
Counter Ion Counter Ion Concentration Stability
Witconate® SXS sodium xylene sulfonate (40% solution) 2% ∼ 225° F (∼ 107° C)
sodium salicylate (25% solution.) 2% ∼200° F (∼ 93° C)
30
Witconate® 1247H ammonium alcohol ether sulfonate 0.6% ∼ 225° F (∼ 107° C)
Witco® TX Acid (sodium salt, 20% soln) 5% ∼210° F (∼ 99° C)
sodium 3-hydroxy-2-naphthanoate 4% <150° F (∼ 65.5° C)
35
sodium 2-amino-1-naphthalene sulfonate (10% soln.) 4% <150° F (∼ 65.5° C)
*Each of the compositions in Table 6 contained 2% KCl and 4% erucyl-DMAPA quat gelling agent (60% active). The
sodium xylene sulfonate counter ion and the ammonium alcohol ether sulfate counter ion produced the most stable
gels, while those counter ions having naphthalene groups decreased the stability of the gel. The amount of counterion
40 utilized to aid in gel formation appears to be somewhat dependent on the size of the counterion, and the larger the
counterion, the less required.

Example 7

45
[0092]

Table 7
Effect of Substitution on the Amine on the Stability of the Gel
50 R2 Stability
methyl ∼225° F (∼ 107° C)
allyl ∼ 200° F (∼ 93° C)
benzyl ∼ 150° F (∼ 65.5° C)
55
vinyl benzyl ∼ 150° F (∼ 65.5° C)
propylsulfonate ∼ 200° F (∼ 93° C)

12
 EP 1 212 385 B1

(continued)

Effect of Substitution on the Amine on the Stability of the Gel

R2 Stability
5
dihydroxypropyl ∼ 210° F (∼ 99° C)
*Each composition contained 2% KCl; 4% erucyl-DMAPA quat gelant (60% active); and 2% Witconate® SXS sodium
xylene sulfonate counterion. R2 was varied on the erucyl-DMAPA quat gelant. The smaller alkyl groups and the
hydroxyalkyl groups appear to increase the stability of the gelled fluid.
10

Example 8

[0093] Example 8 illustrates the use of the gelants system of the present invention for use in a completion fluid. A
15
completion fluid brine, 100 mL, was added to a blender fitted with a 200 mL stainless steel biender jar. Surfactant was
added in amount of 4 wt-%. The resultant solution was stirred at low shear for (less than 1000 rpm) for 10 minutes. A
erucyl-DMAPA quat gelling agent was added and each solution was heated at 75° F (23.8° C) for 1 hour. A counterion,
sodium salicylate, was added to one solution in order to determine its effect on gel formation.

Table 8
20
Completion Fluids
Brine Density (kg/m3) Gel Formation/Comments Gel Stability at 121° C
(1157) *0.1875 wt-% sodium salicylate counterion not measured
25 11.6 lbs/gallon
(1507) gel formed when heat was applied at 75° F for 1 hour stable
15.1 lbs/gallon
(1716) gel formed rapidly at room temperature stable
30 17.2 lbs/gallon
(1916) gel formed at room temperature stable
19.2 lbs/gallon
*The gel composition was 4% gelant (∼ 2% active).
35

[0094] It can be noted that the gel formation time can be reduced for fluids less than 16 ppg when a counterion such
as sodium salicylates are added. However, counterions are not necessary for the compositions of the present invention.
For the gels which formed at room temperature, gel thickness could be increased with the addition of heat. In many
40
instances, this is reversible.
[0095] The rheological performance of the completion fluid brine prepared with the completion fluid having a density
of 19.2 lbs/gallon was determined. The viscosity was measured using a Fann 50 modified rheometer with a R1B5
configuration. The results are shown in Table 9 below.

Table 9
45
Time Temp vise @ 1 sec-1 n’ K(ind) K’slot R2 Calculated Viscosity (cP) @
(Min) °F (° C) 40 sec-1 100 sec-1 170 sec-1
2 76 (~24) --- 0.293 0.3868 0.4598 0.941 1622 848 583
50 40 95 (35) 20237 0.282 0.3838 0.4564 0.992 1549 803 548
74 121 (~49) 13274 0.364 0.2541 0.3003 0.990 1375 767 548
102 146 (~63) 9327 0.384 0.1787 0.2107 0.990 1041 592 427
127 170 (~77) 4495 0.480 0.0871 0.1010 0.974 710 441 335
55
150 195 (~90.5) 2450 0.508 0.0476 0.0548 0.956 427 272 210
179 221 (105) 2154 0.390 0.0414 0.0487 0.942 246 141 102

13
 EP 1 212 385 B1

(continued)

Time Temp vise @ 1 sec-1 n’ K(ind) K’slot R2 Calculated Viscosity (cP) @

(Min) °F (° C) 40 sec-1 100 sec-1 170 sec-1
5
199 245 (~118) 2421 0.250 0.0458 0.0544 0.902 164 82 55

[0096] The rheological performance of the completion fluid brine prepared with the brine solution having a density of
17.2 lbs/gallon was determined. The results are shown in the following Table 10.
10

Table 10
Time Temp vise @ 1 sec-1 n’ K(ind) K’slot R2 Calculated Viscosity (cP) @
(Min) °F (°C) 40sec-1 100sec-1 170sec-1
15
2 76 (~24) 6900 0.466 0.1337 0.1554 0.996 1039 637 480
44 95 (35) 6597 0.474 0.1280 0.1485 0.955 1023 632 478
79 120 (~49) 13217 0.368 0.2533 0.2992 0.927 1394 782 559

20 108 146 (~63) 18889 0.312 0.3600 0.4276 0.907 1618 862 598
133 170 (~77) 8814 0.502 0.1715 0.1980 0.922 1512 958 736
156 195 (90.5) 8194 0.412 0.1581 10.1855 0.904 1016 593 434
183 221 (105) 13124 0.167 0.2474 0.2913 0.805 646 301 193
25
203 245 (~118) 7117 0.316 0.1355 0.1608 0.939 617 330 229

[0097] The rheological performance of the completion fluid brine prepared with the brine solution having a density of
15.1 was determined. The results are shown in the following Tables 11 and 12. The viscosity data found in Table 11
30 was determined using a Fann 50 rheometer.

Table 11
(viscosity measured using a Fann 50 Rheometer)

35 Time Temp Vise @ 1 sec-1 n’ K(ind) K’slot R2 Calculated Viscosity (cP) @

(Min) °F (° C) 40 sec-1 100sec-1 170sec-1
2 82 (~28) 5069 0.339 0.0968 0.1147 0.976 479 261 184
33 96 (35.5) 4989 0.319 0.0948 0.1126 0.957 438 235 163
40
65 121 (~49) 5010 0.286 0.0950 0.1129 0.965 388 202 138
93 145 (~62) 4991 0.272 0.0945 0.1124 0.966 367 188 128
118 171 (~77) 2812 0.425 0.0542 0.0635 0.931 365 215 159

45 139 195 (90.5) 4244 0.412 0.0818 0.0961 0.965 525 306 224
166 220 (~104) 9391 0.259 0.1783 0.2120 0.916 660 335 226
186 245 (~118) 11322 0.289 0.2154 0.2561 0.917 890 464 318

50
[0098] The viscosity data found in the following Table 12 was determined using a Constien & Associates Reciprocating
Capillary Viscometer (RCV). The viscous properties are determined by displacing fluids at selected shear rates through
a calibrated section of tubing. Flow direction is reversed at 1/3 of the tubing volume in order to maintain the fluid under
shear for the entire test. Tubing and displacement accumulators are maintained at preselected temperatures in an oil
bath. The entire system is pressurized at 200 psi. The shear rates are ramped at each temperature over about a 25
55
minute interval at rates of 3.4, 5.1, 6.8, 12.9, 25 and 50 sec-1. The temperature is then raised and the shear rate is
maintained at 97 sec-1 while the temperature is equilibrating between ramping intervals. The fluid parameters n and K
were determined using a Power Law Model.

14
 EP 1 212 385 B1

Table 12
(viscosity measured using an RCV)

5 Ramp Temp °F (° C) n1 K (ind) K’ slot R2 Calculated Viscosity (cPs) @

1 sec-1 40 sec-1 100sec-1
ambient 0.458 0.061 0.071 0.910 3420 464 282
100 (~38) 0.420 0.055 0.065 0.995 3091 364 214
10
125 (~52) 0.375 0.059 0.070 0.992 3345 334 188
150 (65.5) 0.294 0.069 0.082 0.984 3909 289 151
175 (~79) 0.396 0.039 0.046 0.870 2193 236 136

15 200 (~93) 0.380 0.096 0.113 0.999 5422 551 312

225 (~107) 0.330 0.181 0.214 0.992 10258 865 468
250 (~121) 0.429 0.161 0.189 0.995 9046 1100 652
275 (135) 0.427 0.074 0.087 0.977 4175 504 298
20

[0099] The rheological performance of the 19.2 lb/gallon density completion fluid brine was measured with a Brook
field viscometer (#2 Disc at 0.3 rpm). The results are found in the following Table 13.
[0100] As can be noted from the viscosity data, in particular the data collected from 118 minutes to 186 minutes, the
25 viscosity increased with an increase in temperature. In contrast, most fluids exhibit a decrease in viscosity with increasing
temperature.

Table 13
Temperature High Viscosity (cps) Low Viscosity (cps)
30
122°F (50° C) 100,000 100,000
140°F (60° C) 36,000 16,000
149°F (65° C) 29,000 19,000

35 158°F (70° C) 25,000 6,000

167°F (75° C) 23,000 8,300
176°F (80° C) 17,000 2,500

40
[0101] The completion fluid brine having a density of 15.1 lbs/gallon was tested for settling using the barite. The
concentration of the erucyl-DMAPA quat was varied from 1% to 4%. The gelled fluid was mixed with the barite (37 grams
per 150 mL of gel) in a covered graduated cylinder, and the amount of settling was observed at 100° C. The results are
found in the following Table 14.

45
Table 14
Erucyl-DMAPA quat concentration % Settling
4 wt-% (60% active) none
2 wt-% (60% active) <1%
50
1 wt-% (60% active) <2%

[0102] The results found in Table 13 indicate that the amount of settling improves as the amount of the gelant of the
present invention is increased from 1 wt-% to 4 wt-%.
55

15
 EP 1 212 385 B1

Claims

1. An aqueous based fluid useful in oil field applications comprising:

5 a) at least one cationic surfactant having the following general structure:

10

15

wherein R1 is alkyl amine alkylene, alkyl amido alkylene or alkyl ester alkylene where the alkyl group contains
1-26 carbon atoms; R2 and R3 are each alkyl, hydroxy alkyl, polyalkoxy with the degree of polymerization ranging
from 2 to 30, hydroxyl alkyl sulfonate, alkyl sulfonate or alkylarylsulfonate; R4 is hydrocarbon, saturated or
20 unsaturated; and X is selected from the group consisting of halides; oxo ions of phosphorous, sulfur or chloride;
and organic anions; including chlorides, bromides, iodides, hypochlorides, phosphites, sulfates, sulfites, sul-
fonates, phosphates, acetates, carboxylates, chlorates, perchlorates, salicylates, phthalates, lactates, maleates,
glycinates, citrates, citric acid, lactic acid, salicylic acid, phthalic acid, benzoic acid, naphthoic acid, and amino
acids; and
25 b) at least one additive selected from the group consisting of inorganic salts, organic salts, organic acids,
alcohols, and mixtures thereof

2. The aqueous based fluid of Claim 1 wherein said fluid comprises at least one additive selected from the group
consisting of organic salts and organic acids.
30
3. The aqueous based fluid of Claim 1 wherein said fluid comprises at least one additive selected from the group
consisting of sulfates, sulfonates and salicylates.

4. The aqueous based fluid of Claim 2 wherein said additive comprises at least one aromatic group.
35
5. The aqueous based fluid of Claim 1 wherein said additive is an aromatic sulfonate.

6. The aqueous based fluid of Claim 1 wherein said fluid comprises from 0.1% to 5% by weight of the additive.

40 7. The aqueous based fluid of Claim 1 wherein said cationic surfactant has the following general structure:

45

50

wherein R is saturated or unsaturated alkyl and y is an integer from 0 to 12.

8. The aqueous based fluid of Claim 7 wherein R has from 6 to 26 carbon atoms.
55
9. The aqueous based fluid of Claim 7 wherein R has from 12 to 22 carbon atoms.

10. The aqueous based fluid of Claim 7 wherein the moiety R is erucyl.

16
 EP 1 212 385 B1

11. The aqueous based fluid of Claim 7 wherein y is 1.

12. The aqueous based fluid of Claim 1, wherein said surfactant is present in said fluid at a concentration of 0.05 % to
10 % by weight of said fluid.
5
13. The aqueous based fluid of Claim 1 wherein said fluid has thermal stability of greater than about 85 °C.

14. The aqueous based fluid of Claim 1 in combination with a high brine liquid comprising from 30 wt-% to 70 wt-% salt.

10 15. A method of fracturing a subterranean formation comprising the steps of

I) providing a thickened aqueous based hydraulic fracturing fluid, comprising:

a) an aqueous medium; and

15 b) an effective amount of at least one cationic surfactant having the following general structure:

20

25

wherein R1 is alkyl amine alkylene, alkyl amido alkylene or alkyl ester alkylene where the alkyl group contains
1-26 carbon atoms, R2 and R3 are each alkyl, hydroxy alkyl, polyalkoxy with the degree of polymerization
ranging from 2 to 30, hydroxyl alkyl sulfonate, alkyl sulfonate or alkylarylsulfonate; R4 is hydrocarbon,
30 saturated or unsaturated; and X is selected from the group consisting of halides; oxo ions of phosphorous,
sulfur or chloride, and organic anions, including chlorides, bromides, iodides, hypochlorides, phosphites,
sulfates, sulfites, sulfonates, phosphates, acetates, carboxylates, chlorates, perchlorates, salicylates,
phthalates, lactates, maleates, glycinates, citrates, citric acid, lactic acid, salicylic acid, phthalic acid, benzoic
acid, naphthoic acid, and amino acids; and
35 c) at least one additive selected from the group consisting of organic salts, inorganic salts, organic acids,
alcohols, and mixtures thereof, and

II) pumping the aqueous fracturing fluid through a wellbore and into a subterranean formation at a pressure
sufficient to fracture the formation.
40
16. The method of Claim 15 wherein said fracturing, fluid comprises at least one additive selected from the group
consisting of organic acids and organic salts.

17. The method of Claim 15 wherein said additive is selected from the group consisting of sulfates, sulfonates and
45 salicylates.

18. The method of Claim 16 wherein said additive comprises at least one aromatic group.

19. The method of Claim 16 wherein said additive is an aromatic sulfonate.

50
20. The method of Claim 15 wherein said gel has a thermal stability up to temperatures of about 110 °C.

21. The method of Claim 15 wherein said fracturing fluid has thermal stability of greater than about 90 °C.

55 22. The method of Claim 15 wherein said fracturing fluid comprises from 0.05% to 10% by weight of said cationic
surfactant.

23. A method of suspending particles in a thickened aqueous liquid the method comprising the steps of:

17
 EP 1 212 385 B1

I) providing an aqueous medium; and

II) adding to said aqueous medium, an effective amount of at least one cationic surfactant and at least one
additive selected from the group consisting of organic salts, inorganic salts, organic acids, alcohols, and mixtures
thereof, sufficient to increase the viscosity of said aqueous medium wherein said cationic surfactant has the
5 following having the following general structure:

10

15

wherein R1 is alkyl amine alkylene, alkyl amido alkylene or alkyl ester alkylene where the alkyl group contains
1-26 carbon atoms, R2 and R3 are each alkyl, hydroxyalkyl, polyalkoxy with the degree of polymerization ranging
from 2 to 30, hydroxyl alkyl sulfonate, alkyl sulfonate or alkylarylsulfonate, R4 is hydrocarbon, saturated or
20 unsaturated; and X is selected from the group consisting of halides; oxo ions of phosphorous, sulfur or chloride;
and organic anions, including chlorides, bromides, iodides, hypochlorides, phosphites, sulfates, sulfites, sul-
fonates, phosphates, acetates, carboxylates, chlorates, perchlorates, salicylates, phthalates, lactates, maleates,
glycinates, citrates, citric acid, lactic acid, salicylic acid, phthalic acid, benzoic acid, naphthoic acid, and amino
acids; and,
25 wherein said aqueous liquid is sufficiently thickened to suspend solid particulate matter.

24. The method of Claim 23 further comprising transporting the suspension of said solid particulate matter in said
aqueous liquid to a remote location.

30 25. The method of Claim 23 wherein said solid particulate matter is selected from the group consisting of cuttings and
proppants.

26. The method of Claim 23 wherein said method is implemented in a well drilling operation.

35 27. The method of Claim 23 wherein said method is implemented in a coil-tubing operation.

28. The method of Claim 23 wherein said method is implemented in a construction operation.

29. The method of Claim 23 wherein said method is implemented in a mining operation.
40
30. A method of reducing the friction exhibited by an aqueous liquid during flow through a conduit comprising the steps of:

a) providing an aqueous medium;

b) contacting said aqueous medium with a friction reducing amount of a viscoelastic surfactant having the
45 following general structure:

50

55

wherein R is saturated or unsaturated alkyl and y is an integer from 0 to 12, R2 and R3 are each alkyl, hydroxy

18
 EP 1 212 385 B1

alkyl, polyalkoxy with the degree of polymerization ranging from 2 to 30, hydroxyl alkyl sulfonate, alkyl sulfonate
or alkylarylsulfonate; R4 is hydrocarbon, saturated or unsaturated; and X is selected from the group consisting
of halides; oxo ions of phosphorous, sulfur or chloride; and organic anions; including chlorides, bromides,
iodides, hypochlorides, phosphites, sulfates, sulfites, sulfonates, phosphates, acetates, carboxylates, chlorates,
5 perchlorates, salicylates, phthalates, lactates, maleates, glycinates, citrates, citric acid, lactic acid, salicylic acid,
phthalic acid, benzoic acid, naphthoic acid, and amino acids; and an additive selected from the group consisting
of inorganic salts, organic salts, organic acids, alcohols, and mixtures thereof, and
c) passing, said aqueous fluid through said conduit: wherein said viscoelastic surfactant and said additive are
present in an amount capable of reducing the friction exhibited by said aqueous liquid as said aqueous liquid
10 passes through said conduit.

31. An oil field high brine completion fluid comprising:

a) 30 wt-% to 70 wt-% of at least one inorganic or organic salt; and

15 b) 0.1 wt-% to 4 wt-% of at least one cationic surfactant having the following general structure:

20

25

wherein R1 is alkyl alkyl amine alkylene, alkyl amido alkylene or alkyl ester alkylene where the alkyl group
contains 1-26 carbon atoms; R2 and R3 are each alkyl, hydroxy alkyl, polyalkoxy with the degree of polymerization
ranging from 2 to 30, hydroxyl alkyl sulfonate, alkyl sulfonate or alkylarylsulfonate; R4 is hydrocarbon, saturated
30 or unsaturated; and X is selected from the group consisting of halides; oxo ions of phosphorous, sulfur or
chloride; and organic anions, including chlorides, bromides, iodides, hypochlorides, phosphites, sulfates, sulfites,
sulfonates, phosphates, acetates, carboxylates, chlorates, perchlorates, salicylates, phthalates, lactates,
maleates, glycinates, citrates, citric acid, lactic acid, salicylic acid, phthalic acid, benzoic acid, naphthoic acid,
and amino acids.
35
32. The fluid of Claim 31 further comprising at least one additive selected from the group consisting of organic acids,
alcohols, and mixtures thereof

33. The fluid of Claim 31 wherein the viscosity of said fluid increases when the temperature is increased and decreases
40 when the temperature is decreased.

34. The method of claim 15 wherein said cationic surfactant is erucyl amidopropyltrimethyl ammonium quaternary salt,
and said additive is sodium xylene sulfonate.

45 35. The method of claim 23 wherein said cationic surfactant is erucyl amidopropyltrimethyl ammonium quaternary salt,
and said additive is sodium xylene sulfonate.

36. The high brine completion fluid of claim 31 wherein said cationic surfactant is erucyl amidopropyltrimethyl ammonium
quaternary salt, and said additive is sodium xylene sulfonate.
50

Patentansprüche

1. Wasserbasiertes Fluid, nützlich in Ölfeld-Anwendungen, umfassend:

55
a) mindestens ein kationisches Tensid mit der folgenden allgemeinen Struktur:

19
 EP 1 212 385 B1

10

wobei R1 Alkylamin-Alkylen, Alkylamido-Alkylen oder Alkylester-Alkylen ist, wobei die Alkylgruppe 1-26 Koh-
lenstoffatome enthält; R2 und R3 jeweils Alkyl, Hydroxyalkyl, Polyalkoxy mit dem Polymerisationsgrad von 2
bis 30, Hydroxylalkylsulfonat, Alkylsulfonat oder Alkylarylsulfonat sind; R4 Kohlenwasserstoff, gesättigt oder
15 ungesättigt, ist; und X aus der Gruppe ausgewählt ist, aufweisend Halide; Oxo-Ionen von Phosphor, Schwefel
oder Chlorid und organische Anionen, einschließlich Chloride, Bromide, Iodide, Hypochloride, Phosphite, Sul-
fate, Sulfite, Sulfonate, Phosphate, Acetate, Carboxylate, Chlorate, Perchlorate, Salicylate, Phthalate, Lactate,
Maleate, Glycinate, Citrate, Zitronensäure, Milchsäure, Salicylsäure, Phthalsäure, Benzoesäure, Naphthoesäu-
re und Aminosäuren; und
20 b) mindestens ein Additiv, ausgewählt aus der Gruppe aufweisend anorganische Salze, organische Salze,
organische Säuren, Alkohole und Mischungen daraus.

2. Wasserbasiertes Fluid nach Anspruch 1, wobei das Fluid mindestens ein Additiv umfasst, ausgewählt aus der
Gruppe aufweisend organische Salze und organische Säuren.
25
3. Wasserbasiertes Fluid nach Anspruch 1, wobei das Fluid mindestens ein Additiv umfasst, ausgewählt aus der
Gruppe aufweisend Sulfate, Sulfonate und Salicylate.

4. Wasserbasiertes Fluid nach Anspruch 2, wobei das Additiv mindestens eine aromatische Gruppe umfasst.
30
5. Wasserbasiertes Fluid nach Anspruch 1, wobei das Additiv ein aromatisches Sulfonat ist.

6. Wasserbasiertes Fluid nach Anspruch 1, wobei das Fluid von 0,1 bis 5 Gew.-% des Additivs umfasst.

35 7. Wasserbasiertes Fluid nach Anspruch 1, wobei das kationische Tensid die folgende allgemeine Struktur hat:

40

45

wobei R ein gesättigtes oder ungesättigtes Alkyl und y eine ganze Zahl von 0 bis 12 ist.

50 8. Wasserbasiertes Fluid nach Anspruch 7, wobei R von 6 bis 26 Kohlenstofifatome besitzt.

9. Wasserbasiertes Fluid nach Anspruch 7, wobei R von 12 bis 22 Kohlenstofifatome besitzt.

10. Wasserbasiertes Fluid nach Anspruch 7, wobei der Teil R gleich Erucyl ist.
55
11. Wasserbasiertes Fluid nach Anspruch 7, wobei y gleich 1 ist.

12. Wasserbasiertes Fluid nach Anspruch 1, wobei das Tensid in dem Fluid in einer Konzentration von 0,05 bis 10

20
 EP 1 212 385 B1

Gew.-% des Fluids vorhanden ist.

13. Wasserbasiertes Fluid nach Anspruch 1, wobei das Fluid eine thermische Stabilität von mehr als etwa 85°C besitzt.

5 14. Wasserbasiertes Fluid nach Anspruch 1 in Kombination mit einer Flüssigkeit mit hohem Laugengehalt, umfassend
von 30 bis 70 Gew.-% Salz.

15. Verfahren des Fracturing einer unterirdischen Formation, aufweisend die folgenden Schritte:

10 I) Bereitstellen eines verdickten, wasserbasierten, hydraulischen Fracturing-Fluids umfassend:

a) ein wässriges Medium; und

b) eine wirksame Menge von mindestens einem kationischen Tensid mit der folgenden allgemeinen Struktur:

15

20

25
wobei R1 Alkylamin-Alkylen, Alkylamido-Alkylen oder Alkylester-Alkylen ist, wobei die Alkylgruppe 1-26
Kohlenstoffatome enthält; R 2 und R3 jeweils Alkyl, Hydroxyalkyl, Polyalkoxy mit dem Polymerisationsgrad
von 2 bis 30, Hydroxylalkylsulfonat, Alkylsulfonat oder Alkylarylsulfonat sind; R4 Kohlenwasserstoff, gesät-
tigt oder ungesättigt, ist; und X aus der Gruppe ausgewählt ist, aufweisend Halide; Oxo-Ionen von Phosphor,
30 Schwefel oder Chlorid und organische Anionen, einschließlich Chloride, Bromide, Iodide, Hypochloride,
Phosphite, Sulfate, Sulfite, Sulfonate, Phosphate, Acetate, Carboxylate, Chlorate, Perchlorate, Salicylate,
Phthalate, Lactate, Maleate, Glycinate, Citrate, Zitronensäure, Milchsäure, Salicylsäure, Phthalsäure, Ben-
zoesäure, Naphthoesäure und Aminosäuren; und
c) mindestens ein Additiv, ausgewählt aus der Gruppe aufweisend organische Salze, anorganische Salze,
35 organische Säuren, Alkohole und Mischungen daraus, und

II) Pumpen des wässrigen Fracturing-Fluids durch ein Bohrloch und in eine unterirdische Formation bei einem
Druck, der ausreicht, um die Formation aufzubrechen.

40 16. Verfahren nach Anspruch 15, wobei das Fracturing-Fluid mindestens ein Additiv umfasst, ausgewählt aus der
Gruppe aufweisend organische Säuren und organische Salze.

17. Verfahren nach Anspruch 15, wobei das Additiv aus der Gruppe ausgewählt ist, aufweisend Sulfate, Sulfonate und
Salicylate.
45
18. Verfahren nach Anspruch 16, wobei das Additiv mindestens eine aromatische Gruppe umfasst.

19. Verfahren nach Anspruch 16, wobei das Additiv ein aromatisches Sulfonat ist.

50 20. Verfahren nach Anspruch 15, wobei das Gel eine thermische Stabilität bis zu Temperaturen von etwa 110°C hat.

21. Verfahren nach Anspruch 15, wobei das Fracturing-Fluid eine thermische Stabilität von mehr als etwa 90°C hat.

22. Verfahren nach Anspruch 15, wobei das Fracturing-Fluid von 0,05 bis 10 Gew.-% des kationischen Tensids umfasst.
55
23. Verfahren des Suspendierens von Partikeln in einer verdickten, wässrigen Flüssigkeit, wobei das Verfahren die
folgenden Schritte umfasst:

21
 EP 1 212 385 B1

I) Bereitstellen eines wässrigen Mediums; und

II) Hinzufügen einer wirksamen Menge von mindestens einem kationischen Tensid und mindestens einem
Additiv zu dem wässrigen Medium, ausgewählt aus der Gruppe aufweisend organische Salze, anorganische
Salze, organische Säuren, Alkohole und Mischungen daraus, die ausreicht, um die Viskosität des wässrigen
5 Mediums zu erhöhen, wobei das kationische Tensid die folgende allgemeine Struktur aufweist:

10

15

wobei R1 Alkylamin-Alkylen, Alkylamido-Alkylen oder Alkylester-Alkylen ist, wobei die Alkylgruppe 1-26 Koh-
lenstoffatome enthält; R2 und R3 jeweils Alkyl, Hydroxyalkyl, Polyalkoxy mit dem Polymerisationsgrad von 2
20 bis 30, Hydroxylalkylsulfonat, Alkylsulfonat oder Alkylarylsulfonat sind; R4 Kohlenwasserstoff, gesättigt oder
ungesättigt, ist; und X aus der Gruppe ausgewählt ist, aufweisend Halide; Oxo-Ionen von Phosphor, Schwefel
oder Chlorid und organische Anionen einschließlich Chloride, Bromide, Iodide, Hypochloride, Phosphite, Sulfate,
Sulfite, Sulfonate, Phosphate, Acetate, Carboxylate, Chlorate, Perchlorate, Salicylate, Phthalate, Lactate, Ma-
leate, Glycinate, Citrate, Zitronensäure, Milchsäure, Salicylsäure, Phthalsäure, Benzoesäure, Naphthoesäure
25 und Aminosäuren; und
wobei die wässrige Flüssigkeit ausreichend verdickt ist, um die Feststoffpartikel zu suspendieren.

24. Verfahren nach Anspruch 23, weiterhin umfassend das Transportieren der Suspension aus Feststoffpartikeln in der
wässrigen Flüssigkeit zu einem entfernten Standort.
30
25. Verfahren nach Anspruch 23, wobei die Feststoffpartikel aus der Gruppe ausgewählt sind aufweisend Bohrklein
und Stützmittel.

26. Verfahren nach Anspruch 23, wobei das Verfahren beim Bohren eingesetzt wird.
35
27. Verfahren nach Anspruch 23, wobei das Verfahren im Coil Tubing eingesetzt wird.

28. Verfahren nach Anspruch 23, wobei das Verfahren bei einem Bauvorgang eingesetzt wird.

40 29. Verfahren nach Anspruch 23, wobei das Verfahren im Bergbau eingesetzt wird.

30. Verfahren zum Reduzieren der Reibung durch eine wässrige Flüssigkeit während des Fließens durch eine Leitung,
umfassend die folgenden Schritte:

45 a) Bereitstellen eines wässrigen Mediums;

b) Inkontaktbringen des wässrigen Mediums mit einer reibungsreduzierenden Menge eines viskoelastischen
Tensids mit der folgenden allgemeinen Struktur:

50

55

22
 EP 1 212 385 B1

10

wobei R ein gesättigtes oder ungesättigtes Alkyl und y eine ganze Zahl von 0 bis 12 ist, R2 und R3 jeweils Alkyl,
Hydroxyalkyl, Polyalkoxy mit dem Polymerisationsgrad von 2 bis 30, Hydroxylalkylsulfonat, Alkylsulfonat oder
15 Alkylarylsulfonat sind; R 4 Kohlenwasserstoff, gesättigt oder ungesättigt, ist; und X aus der Gruppe ausgewählt
ist, aufweisend Halide; Oxo-Ionen von Phosphor, Schwefel oder Chlorid und organische Anionen einschließlich
Chloride, Bromide, Iodide, Hypochloride, Phosphite, Sulfate, Sulfite, Sulfonate, Phosphate, Acetate, Carboxy-
late, Chlorate, Perchlorate, Salicylate, Phthalate, Lactate, Maleate, Glycinate, Citrate, Zitronensäure, Milchsäu-
re, Salicylsäure, Phthalsäure, Benzoesäure, Naphthoesäure und Aminosäuren; und ein Additiv, ausgewählt
20 aus der Gruppe aufweisend anorganische Salze, organische Salze, organische Säuren, Alkohole und Mischun-
gen daraus, und
c) Leiten des wässrigen Fluids durch die Leitung, wobei das viskoelastische Tensid und das Additiv in einer
Menge vorhanden sind, die die Reibung durch die wässrige Flüssigkeit reduzieren kann, während die wässrige
Flüssigkeit durch die Leitung fließt.
25
31. Ölfeld-Stabilisierungsfluid mit hohem Laugengehalt umfassend:

a) 30 bis 70 Gew.-% von mindestens einem anorganischen oder organischen Salz; und
b) 0,1 bis 4 Gew.-% von mindestens einem kationischen Tensid mit der folgenden allgemeinen Struktur:
30

35

40

wobei R1 Alkylamin-Alkylen, Alkylamido-Alkylen oder Alkylester-Alkylen ist, wobei die Alkylgruppe 1-26 Koh-
lenstoffatome enthält; R2 und R3 jeweils Alkyl, Hydroxyalkyl, Polyalkoxy mit dem Polymerisationsgrad von 2
bis 30, Hydroxylalkylsulfonat, Alkylsulfonat oder Alkylarylsulfonat sind; R4 Kohlenwasserstoff, gesättigt oder
45 ungesättigt, ist; und X aus der Gruppe ausgewählt ist, aufweisend Halide; Oxo-Ionen von Phosphor, Schwefel
oder Chlorid und organische Anionen einschließlich Chloride, Bromide, Iodide, Hypochloride, Phosphite, Sulfate,
Sulfite, Sulfonate, Phosphate, Acetate, Carboxylate, Chlorate, Perchlorate, Salicylate, Phthalate, Lactate, Ma-
leate, Glycinate, Citrate, Zitronensäure, Milchsäure, Salicylsäure, Phthalsäure, Benzoesäure, Naphthoesäure
und Aminosäuren;
50
32. Fluid nach Anspruch 31, weiterhin umfassend mindestens ein Additiv, ausgewählt aus der Gruppe aufweisend
organische Säuren, Alkohole und Mischungen daraus.

33. Fluid nach Anspruch 31, wobei sich die Viskosität des Fluids erhöht, wenn die Temperatur erhöht wird, und sinkt,
55 wenn die Temperatur gesenkt wird.

34. Verfahren nach Anspruch 15, wobei das kationische Tensid quaternäres Ammoniumsalz von Erucyl-Amidopropyl-
trimethyl ist und das Additiv Natriumxylensulfonat ist.

23
 EP 1 212 385 B1

35. Verfahren nach Anspruch 23, wobei das kationische Tensid quaternäres Ammoniumsalz von Erucyl-Amidopropyl-
trimethyl ist und das Additiv Natriumxylensulfonat ist.

36. Stabilisierungsfluid mit hohem Laugengehalt nach Anspruch 31, wobei das kationische Tensid quaternäres Ammo-
5 niumsalz von Erucyl-Amidopropyltrimethyl ist und das Additiv Natriumxylensulfonat ist.

Revendications

10 1. Fluide à base aqueuse utile dans des applications de champ pétrolifère comprenant :

a) au moins un tensioactif cationique présentant la structure générale suivante :

15

20

dans laquelle R1 représente un alkylamine alkylène, un alkylamido alkylène ou un alkyl ester alkylène où le
25 groupe alkyle contient de 1 à 26 atome(s) de carbone ; R2 et R3 représentent chacun un alkyle, un hydroxyalkyle,
un polyalcoxy avec le degré de polymérisation se situant dans la plage allant de 2 à 30, un hydroxyalkylsulfonate,
un alkylsulfonate ou un alkylarylsulfonate ; R4 représente un hydrocarbure, saturé ou insaturé ; et X est choisi
dans le groupe constitué d’halogénures ; d’ions oxo de phosphore, de soufre ou de chlorure ; et d’anions
organiques ; y compris des chlorures, des bromures, des iodures, des hypochlorures, des phosphites, des
30 sulfates, des sulfites, des sulfonates, des phosphates, des acétates, des carboxylates, des chlorates, des
perchlorates, des salicylates, des phtalates, des lactates, des maléates, des glycinates, des citrates, de l’acide
citrique, de l’acide lactique, de l’acide salicylique, de l’acide phtalique, de l’acide benzoïque, de l’acide naphtoïque
et des acides aminés ; et
b) au moins un additif choisi dans le groupe constitué de sels inorganiques, de sels organiques, d’acides
35 organiques, d’alcools, et de mélanges de ceux-ci.

2. Fluide à base aqueuse de la revendication 1, dans lequel ledit fluide comprend au moins un additif choisi dans le
groupe constitué de sels organiques et d’acides organiques.

40 3. Fluide à base aqueuse de la revendication 1, dans lequel ledit fluide comprend au moins un additif choisi dans le
groupe constitué de sulfates, de sulfonates et de salicylates.

4. Fluide à base aqueuse de la revendication 2, dans lequel ledit additif comprend au moins un groupe aromatique.

45 5. Fluide à base aqueuse de la revendication 1, dans lequel ledit additif est un sulfonate aromatique.

6. Fluide à base aqueuse de la revendication 1, dans lequel ledit fluide comprend de 0,1% à 5% en poids de l’additif.

7. Fluide à base aqueuse de la revendication 1, dans lequel ledit tensioactif cationique présente la structure générale
50 suivante :

55

24
 EP 1 212 385 B1

10
dans laquelle R représente un alkyle saturé ou insaturé et y est un nombre entier allant de 0 à 12.

8. Fluide à base aqueuse de la revendication 7, dans lequel R a de 6 à 26 atomes de carbone.

15 9. Fluide à base aqueuse de la revendication 7, dans lequel R a de 12 à 22 atomes de carbone.

10. Fluide à base aqueuse de la revendication 7, dans lequel le groupe fonctionnel R représente l’érucyle.

11. Fluide à base aqueuse de la revendication 7, dans lequel y est égal à 1.

20
12. Fluide à base aqueuse de la revendication 1, dans lequel ledit tensioactif est présent dans ledit fluide à une con-
centration allant de 0,05% à 10% en poids dudit fluide.

13. Fluide à base aqueuse de la revendication 1, dans lequel ledit fluide a une stabilité thermique supérieure à environ
25 85°C.

14. Fluide à base aqueuse de la revendication 1, en combinaison avec un liquide à teneur élevée en saumure comprenant
de 30% en poids à 70% en poids de sel.

30 15. Procédé de fracturation d’une formation souterraine comprenant les étapes qui consistent

I) à fournir un fluide de fracturation hydraulique épaissi à base aqueuse, comprenant :

a) un milieu aqueux ; et
35 b) une quantité effective d’au moins un tensioactif cationique présentant la structure générale suivante :

40

45

dans laquelle R1 représente un alkylamine alkylène, un alkylamido alkylène ou un alkyl ester alkylène où
le groupe alkyle contient de 1 à 26 atome(s) de carbone ; R2 et R3 représentent chacun un alkyle, un
50 hydroxyalkyle, un polyalcoxy avec le degré de polymérisation se situant dans la plage allant de 2 à 30, un
hydroxyalkylsulfonate, un alkylsulfonate ou un alkylarylsulfonate ; R4 représente un hydrocarbure, saturé
ou insaturé ; et X est choisi dans le groupe constitué d’halogénures ; d’ions oxo de phosphore, de soufre
ou de chlorure, et d’anions organiques ; y compris des chlorures, des bromures, des iodures, des hypo-
chlorures, des phosphites, des sulfates, des sulfites, des sulfonates, des phosphates, des acétates, des
55 carboxylates, des chlorates, des perchlorates, des salicylates, des phtalates, des lactates, des maléates,
des glycinates, des citrates, de l’acide citrique, de l’acide lactique, de l’acide salicylique, de l’acide phtalique,
de l’acide benzoïque, de l’acide naphtoïque et des acides aminés ; et
c) au moins un additif choisi dans le groupe constitué de sels organiques, de sels inorganiques, d’acides

25
 EP 1 212 385 B1

organiques, d’alcools, et de mélanges de ceux-ci,

et

II) à pomper le fluide de fracturation aqueux à travers un puits de forage et dans une formation souterraine à
5 une pression suffisante pour fracturer la formation.

16. Procédé de la revendication 15, dans lequel ledit fluide de fracturation comprend au moins un additif choisi dans le
groupe constitué d’acides organiques et de sels organiques.

10 17. Procédé de la revendication 15, dans lequel ledit additif est choisi dans le groupe constitué de sulfates, de sulfonates
et de salicylates.

18. Procédé de la revendication 16, dans lequel ledit additif comprend au moins un groupe aromatique.

15 19. Procédé de la revendication 16, dans lequel ledit additif est un sulfonate aromatique.

20. Procédé de la revendication 15, dans lequel ledit gel a une stabilité thermique allant jusqu’à des températures
d’environ 110°C.

20 21. Procédé de la revendication 15, dans lequel ledit fluide de fracturation a une stabilité thermique supérieure à environ
90°C.

22. Procédé de la revendication 15, dans lequel ledit fluide de fracturation comprend de 0,05% à 10% en poids dudit
tensioactif cationique.
25
23. Procédé de mise en suspension de particules dans un liquide aqueux épaissi, le procédé comprenant les étapes
qui consistent :

I) à fournir un milieu aqueux ; et

30 II) à ajouter audit milieu aqueux, une quantité efficace d’au moins un tensioactif cationique et d’au moins un
additif choisi dans le groupe constitué de sels organiques, de sels inorganiques, d’acides organiques, d’alcools,
et de mélanges de ceux-ci, suffisante pour augmenter la viscosité dudit milieu aqueux où ledit tensioactif
cationique a la structure générale suivante :

35

40

45

dans laquelle R1 représente un alkylamine alkylène, un alkylamido alkylène ou un alkyl ester alkylène où le
groupe alkyle contient de 1 à 26 atome(s) de carbone ; R2 et R3 représentent chacun un alkyle, un hydroxyalkyle,
un polyalcoxy avec le degré de polymérisation se situant dans la plage allant de 2 à 30, un hydroxyalkylsulfonate,
50 un alkylsulfonate ou un alkylarylsulfonate ; R4 représente un hydrocarbure, saturé ou insaturé ; et X est choisi
dans le groupe constitué d’halogénures ; d’ions oxo de phosphore, de soufre ou de chlorure; et d’anions orga-
niques, y compris des chlorures, des bromures, des iodures, des hypochlorures, des phosphites, des sulfates,
des sulfites, des sulfonates, des phosphates, des acétates, des carboxylates, des chlorates, des perchlorates,
des salicylates, des phtalates, des lactates, des maléates, des glycinates, des citrates, de l’acide citrique, de
55 l’acide lactique, de l’acide salicylique, de l’acide phtalique, de l’acide benzoïque, de l’acide naphtoïque et des
acides aminés ; et,
où ledit liquide aqueux est suffisamment épaissi pour mettre en suspension la matière particulaire solide.

26
 EP 1 212 385 B1

24. Procédé de la revendication 23, comprenant en outre le fait de transporter la suspension de ladite matière particulaire
solide dans ledit liquide aqueux à un emplacement distant.

25. Procédé de la revendication 23, dans lequel ladite matière particulaire solide est choisie dans le groupe constitué
5 de déblais de forage et d’agents de soutènement.

26. Procédé de la revendication 23, dans lequel ledit procédé est mis en oeuvre dans une opération de forage de puits.

27. Procédé de la revendication 23, dans lequel ledit procédé est mis en oeuvre dans une opération d’introduction de
10 tube enroulé.

28. Procédé de la revendication 23, dans lequel ledit procédé est mis en oeuvre dans une opération de construction.

29. Procédé de la revendication 23, dans lequel ledit procédé est mis en oeuvre dans une opération d’exploitation minière.
15
30. Procédé de réduction du frottement présenté par un liquide aqueux au cours de l’écoulement à travers un conduit,
comprenant les étapes qui consistent :

a) à fournir un milieu aqueux ;

20 b) à mettre en contact ledit milieu aqueux avec une quantité de réduction de frottement d’un tensioactif viscoé-
lastique présentant la structure générale suivante

25

30

35
dans laquelle R représente un alkyle saturé ou insaturé, et y est un nombre entier de 0 à 12, R2 et R3 représentent
chacun un alkyle, un hydroxyalkyle, un polyalcoxy avec le degré de polymérisation se situant dans la plage
allant de 2 à 30, un hydroxyalkylsulfonate, un alkylsulfonate ou un alkylarylsulfonate ; R 4 représente un hydro-
carbure, saturé ou insaturé ; et X est choisi dans le groupe constitué d’halogénures ; d’ions oxo de phosphore,
40 de soufre ou de chlorure; et d’anions organiques ; y compris des chlorures, des bromures, des iodures, des
hypochlorures, des phosphites, des sulfates, des sulfites, des sulfonates, des phosphates, des acétates, des
carboxylates, des chlorates, des perchlorates, des salicylates, des phtalates, des lactates, des maléates, des
glycinates, des citrates, de l’acide citrique, de l’acide lactique, de l’acide salicylique, de l’acide phtalique, de
l’acide benzoïque, de l’acide naphtoïque et des acides aminés ; et un additif choisi dans le groupe constitué de
45 sels inorganiques, de sels organiques, et d’acides organiques, d’alcools et de mélanges de ceux-ci, et
c) à faire passer, ledit fluide aqueux à travers ledit conduit ; où ledit tensioactif viscoélastique et ledit additif sont
présents en une quantité capable de réduire le frottement présenté par ledit liquide aqueux à mesure que ledit
liquide aqueux passe à travers ledit conduit.

50 31. Fluide de complétion de champ pétrolifère à teneur élevée en saumure comprenant :

a) de 30% en poids à 70% en poids d’au moins un sel inorganique ou organique ; et

b) de 0,1% en poids à 4% en poids d’au moins un tensioactif cationique présentant la structure générale suivante :

55

27
 EP 1 212 385 B1

10

dans laquelle R1 représente un alkylamine alkylène, un alkylamido alkylène ou un alkyl ester alkylène où le
groupe alkyle contient de 1 à 26 atome(s) de carbone ; R2 et R3 représentent chacun un alkyle, un hydroxyalkyle,
15 un polyalcoxy avec le degré de polymérisation se situant dans la plage allant de 2 à 30, un hydroxyalkylsulfonate,
un alkylsulfonate ou un alkylarylsulfonate ; R4 représente un hydrocarbure, saturé ou insaturé ; et X est choisi
dans le groupe constitué d’halogénures ; d’ions oxo de phosphore, de soufre ou de chlorure; et d’anions
organiques ; y compris des chlorures, des bromures, des iodures, des hypochlorures, des phosphites, des
sulfates, des sulfites, sulfonates, des phosphates, des acétates, des carboxylates, des chlorates, des perchlo-
20 rates, des salicylates, des phtalates, des lactates, des maléates, des glycinates, des citrates, de l’acide citrique,
de l’acide lactique, de l’acide salicylique, de l’acide phtalique, de l’acide benzoïque, de l’acide naphtoïque et
des acides aminés.

32. Fluide de la revendication 31, comprenant en outre au moins un additif choisi dans le groupe constitué d’acides
25 organiques, d’alcools, et de mélanges de ceux-ci.

33. Fluide de la revendication 31, dans lequel la viscosité dudit fluide augmente lorsque la température augmente et
diminue lorsque la température diminue.

30 34. Procédé de la revendication 15, dans lequel ledit tensioactif cationique est un sel quaternaire d’érucyl amidopro-
pyltriméthylammonium, et ledit additif est le xylènesulfonate de sodium.

35. Procédé de la revendication 23, dans lequel ledit tensioactif cationique est un sel quaternaire d’érucyl amidopro-
pyltriméthylammonium, et ledit additif est le xylènesulfonate de sodium.
35
36. Fluide de complétion à teneur élevée en saumure de la revendication 31, dans lequel ledit tensioactif cationique
est un sel quaternaire d’érucyl amidopropyltriméthylammonium, et ledit additif est le xylènesulfonate de sodium.

40

45

50

55

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 EP 1 212 385 B1

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• US 5551516 A, Norman [0007] • US 4615825 A, Teot [0065]

• US 4725372 A [0008] • US 4735731 A, Rose [0067]

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