TEPZZ 8447_5B_T

(19)

(11) EP 2 844 715 B1

(12) EUROPEAN PATENT SPECIFICATION

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

of the grant of the patent: C09K 8/32 (2006.01) C09K 8/34 (2006.01)
09.03.2016 Bulletin 2016/10 C09K 8/36 (2006.01) C08G 18/10 (2006.01)
C08G 18/34 (2006.01)
(21) Application number: 13722890.4
(86) International application number:
(22) Date of filing: 22.04.2013 PCT/US2013/037598

(87) International publication number:

WO 2013/165728 (07.11.2013 Gazette 2013/45)

(54) RHEOLOGY MODIFIERS

RHEOLOGIEMODIFIKATOREN
MODIFICATEURS DE RHÉOLOGIE

(84) Designated Contracting States: (72) Inventors:

AL AT BE BG CH CY CZ DE DK EE ES FI FR GB • HARRIS, Jeffrey
GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO Tulsa, Oklahoma 74133 (US)
PL PT RO RS SE SI SK SM TR • BYERS, Jim
Bartlesville, Oklahoma 74006 (US)
(30) Priority: 30.04.2012 US 201213459677
(74) Representative: Nash, David Allan
(43) Date of publication of application: Haseltine Lake LLP
11.03.2015 Bulletin 2015/11 Redcliff Quay
120 Redcliff Street
(73) Proprietor: Chevron Phillips Chemical Company Bristol BS1 6HU (GB)
LP
The Woodlands, Texas 77380 (US) (56) References cited:
EP-A2- 0 403 437 WO-A2-2004/094522
US-A1- 2007 015 902 US-A1- 2009 227 478
EP 2 844 715 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 2 844 715 B1

Description

TECHNICAL FIELD OF THE INVENTION

5 [0001] This disclosure relates to wellbore servicing fluids. More specifically, this disclosure relates to rheology modifiers
for use in drilling muds.

BACKGROUND

10 [0002] Subterranean deposits of natural resources such as gas, water, and crude oil are commonly recovered by
drilling wellbores to tap subterranean formations or zones containing such deposits. Various fluids are employed in
drilling a wellbore and preparing the wellbore and an adjacent subterranean formation for the recovery of material
therefrom. For example, a drilling fluid or mud is usually circulated through a wellbore as it is being drilled to cool the
bit, keep deposits confined to their respective formations during the drilling process, and bring drill cuttings to the surface.
15 [0003] Increased drilling activity has continued at greater depths in challenging geographic areas such as marine
environments. Drilling fluids used during these recovery operations are often exposed to a range of temperatures as the
drilling fluid moves from a platform structure to the beginning/bottom of the ocean floor. For example, a drilling fluid
moving through a drill string or pipe from a platform structure to 30,000-40,000 feet (9,144-12,192 m) of combined water
depth and core substrata may experience temperatures ranging from 35 °F to 400 °F (1.7-204 °C). Drilling fluids are
20 designed to display a set of rheological characteristics that are suitable for a particular recovery operation. One challenge
to the use of drilling fluids in challenging geographic areas is the maintenance of desirable rheological characteristics
over the range of environmental conditions to which the fluids are exposed. Thus an ongoing need exists for improved
drilling fluids for use in challenging geographic areas.
[0004] US2009/227478 and EP0403437 describe the use of reaction products of dimer acids and polyfunctional amines
25 as additives in oil based muds. US2007/015902 and WO2004/094522 disclose compositions comprising the reaction
product of a polysulfide, a dimer acid and a polyfunctional amine but are not directed to oil field operations.

SUMMARY

30 [0005] Disclosed herein is a non-aqueous wellbore servicing fluid comprising a rheology modifier wherein the rheology
modifier comprises a reaction product of a polysulfide, a dimer acid and a polyfunctional amine, wherein the polyfunctional
amine comprises a molecule containing at least two amine groups, and wherein the nonaqueous wellbore servicing fluid
comprises an oil-based mud.
[0006] Also disclosed herein is a method of conducting an oilfield operation comprising placing an oil-based mud
35 comprising a rheology modifier into a wellbore wherein the rheology modifier comprises a reaction product of a polysulfide,
a dimer acid and a polyfunctional amine, wherein the polyfunctional amine comprises a molecule containing at least two
amine groups.

BRIEF DESCRIPTION OF THE DRAWINGS

40
[0007] For a more complete understanding of the present disclosure and the advantages thereof, reference is now
made to the following brief description, taken in connection with the accompanying drawings and detailed description:

Figures 1 and 2 are plots of yield point as a function of temperature for the samples from Example 1.
45 Figure 3 is a plot of yield point as a function of temperature for the samples from Example 2.
Figure 4 is a plot of yield point as a function of temperature for the samples from Example 3.

DETAILED DESCRIPTION

50 [0008] Disclosed herein are methods and compositions for use in wellbore servicing operations. In an embodiment,
the composition comprises a wellbore servicing fluid (WSF) and a rheology modifier. Such compositions may maintain
one or more user and/or process desired rheological characteristics over a range of conditions encountered during a
wellbore servicing operation. WSFs comprising a rheology modifier of the type disclosed herein are termed flat rheology
compositions for wellbore servicing (FRC).
55 [0009] In an embodiment, the FRC comprises a rheology modifier: In an embodiment, the rheology modifier is prepared
by the reaction of a dimer acid and a polysulfide to form a first mixture which is further reacted with a polyfunctional
amine to form the rheology modifier.
[0010] Herein, the term "dimer acid" is synonymous with the term dibasic acid and refers to an oligomeric fatty acid

2
 EP 2 844 715 B1

product that is the result of the self-condensation of two unsaturated fatty acids. In an embodiment, the two unsaturated
fatty acids involved in the self-condensation to form the dimer acid are the same, alternatively, the two unsaturated fatty
acids involved in the self-condensation to form the dimer acid are different. In an embodiment, each unsaturated fatty
acid participating in the self-condensation reaction comprises any number of carbon atoms. The unsaturated fatty acid
5 can comprise a C12-C24 unsaturated fatty acid, alternatively, a C14-C22 unsaturated fatty acid, or alternatively, a C14-
C18 unsaturated fatty acid. In an embodiment, the unsaturated fatty acid comprises a C14-18 unsaturated fatty acid. In
an embodiment, the polysulfide comprises di(hydroxyethyl)polysulfides or homopolymers thereof. Alternatively, the
polysulfide comprises a di(hydroxyethyl)disulfide, a di(hydroxyethyl)trisulfide, and/or a di(hydroxyethyl)tetrasulfide. In
an embodiment, the polysulfide can be a compound characterized by general Formula I or Formula Ia.
10

15

[0011] In an embodiment, each R, R’, and R’" can be different. In some embodiments, each R, R’, and R’" can be the
20 same. In other embodiments, at least two of the R, R’, and R"’ groups are the same. In an embodiment, each R, R’, and
R’" can be independently selected from the group consisting of hydrogen and an organyl group; or alternatively, hydrogen
and a hydrocarbyl group. In some embodiments, each non-hydrogen R group can be independently selected from the
group consisting of an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an aryl
group, a substituted aryl group, a heteroaryl group, and a substituted heteroaryl group.
25 [0012] In an embodiment, the non-hydrogen R, R’ or R’" group can be independently selected from the group consisting
of a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl
group, a nonyl group, a decyl group, a undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl
group, a hexadecyl group, a heptadecyl group, an octadecyl group, or a nonadecyl group; or alternatively, a methyl
group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a
30 nonyl group, and a decyl group.
[0013] In an embodiment, x of the polysulfide moiety can be a number ranging from 2 to 6; alternatively, 3 to 6; or
alternatively, 3 to 4. In other embodiments, the polysulfide moiety can be 2; alternatively, 3; alternatively, 4; alternatively,
5; or alternatively, 6. One having ordinary skill in the art recognizes that compositions containing compounds having a
polysulfide moiety can typically contain compounds having different values of x. For example, commercially available
35 dithiodiglycol contains the polysulfide having the formula HOC2H4S2C2H4OH and some polysulfide having the formula
HOC2H 4S3C2H4OH. Consequently, the value x for the polysulfide can be described as having an average value of x.
Generally, x can have an average of greater than 2. In some embodiments, x can have an average of greater than 2.03;
alternatively, greater than 2.25; alternatively, greater than 2.5; alternatively, greater than 3; alternatively, greater than
3.5; or alternatively, greater than 4. In some other embodiments, x can have an average value ranging from 2.03 to 6;
40 alternatively, from 2.03 to 5; alternatively, from 2.03 to 4.5; alternatively, from 2.03 to 2.15; alternatively, from 2.5 to 3.5;
alternatively, 3.5 to 4.5. In other embodiments, the average value of x for the polysulfide can be about 2.03; alternatively,
about 2.25; alternatively, about 2.5; alternatively, about 3; alternatively, about 3.5; or alternatively, about 4.
[0014] The polyfunctional amine comprises a molecule containing at least two amine groups having either primary,
secondary and/or tertiary functionalities and capable of reacting with the first mixture to form the rheology modifier. The
45 polyfunctional amine may comprise 3-ethylaminopiperazine. Methods for producing the rheology modifier are described
in more detail in U.S. Patent No. 7,087,708. As will be understood by one of ordinary skill in the art, the rheology modifier
prepared as described herein is a reaction product comprising a number of differing compounds. Further the constituents
of the reaction product may vary depending on variations in the reaction conditions used to obtain the product (e.g.,
reaction time, reaction temperature). In an embodiment, the reaction product disclosed herein may be used in wellbore
50 servicing fluids without further purification or separation of the constituent(s) of the reaction product. In an alternative
embodiment, the reaction product may be separated into constituent components. In such an embodiment, the constit-
uents of the reaction product may be separated using any suitable technique and the extent to which the individual
constituents of the reaction product are purified may vary. In some embodiments, one or more of the individual constituents
of the reaction product are characterized as having the ability to modify the rheology of a wellbore servicing fluid as
55 described herein. In an embodiment, the rheology modifier may comprise one or more of the separated constituents of
the reaction product.
[0015] In an embodiment, the rheology modifier further comprises a diluent. The diluent may be introduced to the
rheology modifier in order to give the rheology modifier a physical form suitable for use in an oilfield operation (e.g.,

3
 EP 2 844 715 B1

flowable viscosity). In an embodiment, the diluent comprises any fluid compatible with the other components of the
rheology modifier which when introduced to the material decreases the viscosity of the rheology modifier to some user
and/or process desired range. Alternatively, the rheology modifier as prepared comprises a highly viscous material that
lacks the flow properties desired for used in an oilfield operation. Diluent may be included in the rheology modifier in an
5 amount sufficient to achieve some user and/or process desired flow properties. In an embodiment, the rheology modifier
comprises diluents suitable for the environmental issues experienced offshore in the Gulf of Mexico as well as the North
Sea. Nonlimiting examples of classes of diluents that are suitable for use in the present disclosure are the internal olefins
of C16-C24 carbon length as produced by Chevron Phillips Chemical Company, as well as, the cellulosic ether derivatives
more commonly utilized in the coatings industry as diluents components. In an embodiment, the diluent comprises butyl
10 carbitol. In an embodiment, the diluent is used to dilute the rheology modifier by an amount sufficient to provide a viscosity
that meets some user and/or process goal. In an embodiment, the diluent is present in an amount that dilutes the rheology
modifier by about 30%; alternatively, by about 20%; or alternatively, by about 10%. In an embodiment, the rheology
modifier (based on 100% activity) is present in the FRC in an amount of from 0.02 weight percent (wt.%) to 2.2 wt.%
based on the total weight of the FRC, alternatively, from 0.1 wt.% to 1.4 wt.%, or alternatively, from 0.2 wt.% to 1.1 wt.%.
15 [0016] In an embodiment, the FRC comprises a non-aqueous WSF. As used herein, a non-aqueous WSF includes
fluids that are comprised entirely or substantially of non-aqueous fluids and/or invert emulsions wherein the continuous
phase is a non-aqueous fluid. In an embodiment, the non-aqueous WSF comprises less than 30%, 25%, 20%, 15%,
10% or 1% water by weight of the WSF. Alternatively, the WSF composition may contain a balance of the non-aqueous
fluid after taking other components of the fluid composition into account.
20 [0017] In an embodiment, the WSF comprises an oleaginous fluid. Alternatively, the WSF after taking other components
of the fluid composition into account may consist essentially of an oleaginous fluid. Alternatively, the WSF after taking
other components of the fluid composition into account may consist of an oleaginous fluid. Oleaginous fluids herein refer
to fluids comprising substantially no aqueous component. Examples of oleaginous fluids suitable for use in the WSF
include without limitation hydrocarbons, olefins, internal olefin based oils, mineral oil, kerosene, diesel oil, fuel oil, synthetic
25 oil, linear or branched paraffins, esters, acetals, mixtures of crude oil, derivatives thereof, or combinations thereof.
[0018] In an embodiment, the WSF is an oil-based drilling mud (OBM) of the type used in drilling operations. The OBM
may comprise an oleaginous fluid of the type disclosed herein. In some embodiments, the OBM is an invert emulsion
having a non-oleaginous fluid as the dispersed phase and an oleaginous fluid as the continuous phase. In some em-
bodiments, the WSF may comprise additional additives as deemed appropriate for improving the properties of the fluid.
30 Such additives may vary depending on the intended use of the fluid in the wellbore. Examples of such additives include,
but are not limited to, weighting agents, glass fibers, carbon fibers, suspending agents, conditioning agents, dispersants,
water softeners, oxidation and corrosion inhibitors, bacteriacides, thinners, and combinations thereof. These additives
may be introduced singularly or in combination using any suitable methodology and in amounts effective to produce the
desired improvements in fluid properties.
35 [0019] In an embodiment, the FRCs disclosed herein (e.g., OBM + rheology modifier) display a flat rheology. Herein,
"flat rheology" refers to the ability of the composition to maintain relatively stable rheological characteristics over a range
of temperatures and pressures. In an embodiment, "relatively stable" refers to variations in the disclosed parameter
(e.g., yield point) during use that are within 620% of the original value, alternatively, 6 15%, 10%, 5%., or 1% of the
original value. In an embodiment, the rheological characteristics of the FRC may be considered "relatively stable" if a
40 plot of the observed rheological parameter (e.g., yield point) as a function of temperature and/or pressure displays a
plateau. The rheological characteristics of the FRC may be considered "relatively stable" if the FRC maintains some
user and/or process desired rheological characteristics (e.g., yield point) over a broad range temperature and pressure
such that the FRC functions for its intended purpose under a range of conditions.
[0020] In an embodiment, an FRC of the type disclosed herein displays a variation in yield point of less than 20%;
45 alternatively, less than 15%; or alternatively, less than 10% over a temperature range of from 100 °F to about 430 °F
(38-221 °C), alternatively, from 50 °F to 350 °F (10-177 °C), or alternatively, from 35 °F to 400 °F (2-204 °C). The yield
point refers to the resistance of the fluid to initial flow or represents the stress required to start fluid movement. Practically,
the YP is related to the attractive force among colloidal particles in drilling mud and may be determined by a dynamic
rheometric measurement of the moving fluids. The rheometer most commonly utilized in the drilling industry (and most
50 easily related to) is the Fann 35 Rheometer. Thus, one subtracts the 300 rpm reading from the 600 rpm reading at a
particular controlled temperature to obtain the plastic viscosity (PV value). Subsequently, the PV is subtracted from the
300 rpm value to obtain the yield point (YP). Not all fluids are treated with rheology modifiers, thus, it is common for the
yield points as well as pressures in the well bore to drop up to 20% or so with increasing temperature of the greater
depths of the wellbore.
55 [0021] In an embodiment, an FRC of the type disclosed herein displays a variation in gel strength of less than 20%;
alternatively, less than 15%; or alternatively, less than 10% over a temperature range of from 100 °F to 400 °F (38-204
°C); alternatively, from 50 °F to 350 °F (10-177 °C); or alternatively, from 35 °F to about °F (2-204 °C). The gel strength
may be determined by Fann 35 Rheometric analysis. Gel Strength is a static measurement in that the measurement is

4
 EP 2 844 715 B1

determined after the fluids have been static for a defined time frame. During this time, a dynamic equilibrium based on
diffusional interfacial interactions is reached which also determines the stability of the fluid or the ability to suspend cuttings.
[0022] In an embodiment, an FRC of the type disclosed herein displays a variation in gel strength and/or yield point
of less than 20%; alternatively, less than 15%; or alternatively, less than 10% when subjected to cyclic temperature
5 changes. Particularly, an FRC of the type disclosed herein may be subjected to an initial temperature Ti, for example
when prepared at the surface of an offshore platform. The FRC when placed into the wellbore may travel from the
platform through a conduit to the ocean floor. Disposed within the conduit the FRC may experience a range of temperatures
associated with the surrounding ocean and collectively denoted Tc where Tc is less than Ti. Upon entering the conduit
and the subterranean formation via the wellbore, the FRC may experience a range of temperatures associated with the
10 formation and collectively denoted Tf where Tf is greater than Tc or greater than Ti. Thus, the FRC may be exposed to
cycles of alternating elevated and decreased temperatures and maintain a rheology consistent with the intended function
of the FRC.
[0023] In an embodiment, an FRC of the type disclosed herein displays an initial yield point and gel strength at ambient
temperature that is greater than an otherwise similar composition lacking a rheology modifier of the type disclosed herein.
15 Herein, "ambient temperature" refers to the temperature in the range of from 40 °F to 100 °F (4-38 °C). As a result, the
FRC may have improved suspension ability when compared to an otherwise similar composition lacking a rheology
modifier of the type disclosed herein. In an embodiment, a FRC of the type disclosed herein may display a yield point
of greater than 6 lbs/100 ft2 (2.9 Pa); alternatively, greater than 8 lbs/100 ft2 (3.8 Pa); or alternatively, greater than 10
lbs/100 ft2 (4.8 Pa). In an embodiment, a FRC of the type disclosed herein has a 10 minute gel strength of greater than
20 8 lbs/100 ft2 (3.8 Pa); alternatively, greater than 10 lbs/100 ft2 (4.8 Pa); or alternatively, greater than 12 lbs/100 ft2 (5.8 Pa).
[0024] In an embodiment, an FRC of the type disclosed herein may advantageously function as a corrosion inhibitor.
In such an embodiment, the FRC disposed within a piece of oilfield servicing equipment or contacted with a piece of
oilfield servicing equipment (e.g., conduit) may function to prevent corrosion of the oilfield servicing equipment when the
equipment is exposed to "free water." Herein, free water refers to water present in the form of "formation water" or water
25 present due to degradation of the surfactant package of the oil based drilling fluid over time and temperature.
[0025] The FRC can be placed into a wellbore and used to service the wellbore in accordance with suitable procedures.
For example, when the intended use of the FRC is as a drilling fluid or drilling mud (e.g., OBM), the fluid can be circulated
down through a hollow drill stem and out through a drill bit attached thereto while rotating the drill stem to thereby drill
the wellbore. The drilling fluid can be flowed back to the surface in a circulatory repetitive path such as to lubricate the
30 drill bit, deposit a filter cake on the walls of the wellbore and to continuously carry drill cuttings to the surface. In an
embodiment, the FRC is prepared at the wellsite. Alternatively, the FRC is prepared offsite and transported to the use
site before being placed downhole. FRCs of the type disclosed herein advantageously provide for theological charac-
teristics that are stable over the range of temperatures and pressures that the fluid may experience during an oil field
operation. In an embodiment, FRCs of the type disclosed herein are utilized in maritime oilfield operations. In such
35 embodiments, the FRC may be placed into a wellbore from the surface and transported via the appropriate conduit to
a subsea well disposed in a formation. FRCs transported from the platform to the subsea well formation may be subjected
to a broad range of temperatures and pressures. FRCs of the type disclosed herein may advantageously provide rhe-
ological characteristics that fluctuate within the previously disclosed ranges over the course of temperatures and pres-
sures experienced.
40
EXAMPLES

[0026] The disclosure having been generally described, the following examples are given as particular embodiments
of the disclosure and to demonstrate the practice and advantages thereof. It is understood that the examples are given
45 by way of illustration and are not intended to limit the specification or the claims in any manner.
[0027] For the examples to follow the rheology modifier was prepared by combining in a reaction vessel 1 mole of
DIHEDS and 2 moles of UNIDYME 14 to which 0.1 wt. % methanesulfonic acid was added as a catalyst. DIHEDS is
di-(2-hydroxyethyl) disulfide commercially available from Chevron Phillips Chemical Co. while UNIDYME 14 is a dimer
acid commercially available from Arizona Chemical, Dimer. The vessel was heated to between 125 °C and 130 °C with
50 constant mixing under low vacuum (10 mm Hg (1.3 kPa)) in order to remove water from the reaction mixture. The first
stage of the reaction was considered complete when an acid number of 83.58 mg KOH/gM was reached. The acid
number was determined in accordance with ASTM D 465. N-aminoethyl piperazine was then added to the products of
the reaction mixture in the amount of 2.1 mols. This mixture was then heated to between 130 °C and 135 °C for less
than 1 hour under atmospheric pressure, the pressure was then lowered to 10 mm Hg (1.3 kPa) and the reaction
55 continued, for usually another 2 hours, until the amine number was approximately 80 mg KOH/gM. No more water
evolution was observed when the amine number approached 80 mg KOH/gM. The final reaction product was cooled to
approximately 80 °C and transferred to containers. A one gallon (3.8 litres) blend of the final reaction product was mixed
with butyl carbitol at a 70:30 ratio for 3 hours at 167 °F (75 °C) and used as a rheology modifier of the type disclosed

5
 EP 2 844 715 B1

herein (designated RMX) in the following examples.

Example 1

5 [0028] The rheology of a FRC of the type disclosed herein was investigated. Oil-based muds were prepared by mixing
oleaginous fluid (2120 g), lime (75g), VG-69 Clay (87.5g), INVERMUL primary emulsifier (75g), EZMUL emulsifier (75g),
and 30% CaCl2 brine (815g). VG-69 is an organophillic clay commercially available from Mi SWACO. EZMUL emulsifier
is a polyaminated fatty acid and INVERMUL is a blend of oxidized tall oil and polyaminated fatty acid, both of which are
commercially available from Baroid Chemicals. The OBMs were prepared to a density of 14 pounds per gallon (ppg)
10 (1.7 kg per litre) and a 75:25 oil:water ratio (OWR).
[0029] Samples contained the OBM (208 g), Barite (212 g), API clay (8 g) and the indicated amount of either RMX
(Sample A) or THIXATROL rheological additive (Sample B). THIXATROL rheological additive is a modified derivative
of castor oil commercially available from Elementis Specialties. The samples were mixed for approximately 30 minutes
using a multi-mixer and subsequently hot-rolled at 300 °F (149 °C) for 16 hours. Control samples did not contain any
15 rheology modifying materials. Rheology tests were performed on the gel using a Fann 35 viscometer. The results are
given in Table 1 for samples which had a diesel (Diesel #2) as the oleaginous fluid while Table 2 gives the result when
using ESCAID 110 as the oleaginous fluid. ESCAID 110 hydrocarbon fluid is a petroleum distillate commercially available
from EXXON-MOBIL Corp.

20 Table 1
Control Sample A Sample B
Fan 35 Rheology @ 85 °F (29 °C)
600 rpm 101 137 144
25
300 rpm 66 92 96
PV 35 45 48
YP 31 47 48
30 200 rpm 53 76 79
100 rpm 38 56 55
6 rpm 7 31 30
3 rpm 6 30 26
35
Gels 10 sec, 10 min 18/25 37/48 38/56
Fan 35 Rheology @ 120 °F (49 °C)
600 rpm 78 128 140
40 300 rpm 51 87 106
PV 27 41 34
YP 24 46 72
200 rpm 41 70 87
45
100 rpm 30 52 64
6 rpm 14 29 37
3 rpm 13 27 34
50 Gels 10 sec, 10 min 15/20 34/44 44/58
Fan 35 Rheology @ 150 °F (66 °C)
600 rpm 60 113 144
300 rpm 42 80 110
55
PV 18 33 34
YP 24 47 76

6
 EP 2 844 715 B1

(continued)

Fan 35 Rheology @ 150 °F (66 °C)

200 rpm 34 67 90
5
100 rpm 24 52 69
6 rpm 11 30 44
3 rpm 10 28 42
10 Gels 10 sec, 10 min 12/17 34/41 47/56
ES @ 150 °F (66 °C) = 811 1546 1486
HTHP@ 300 °F (149 °C) 14.4 ml 17.2 ml

15
Table 2
Control Sample A Sample B
Fan 35 Rheology @ 85 °F (29 °C)
20 600 rpm 59 78 70
300 rpm 36 49 43
PV 23 29 27
YP 13 20 16
25
200 rpm 27 38 32
100 rpm 17 26 20
6 rpm 6 11 7
30
3 rpm 5 10 6
Gels 10 sec, 10 min 7/9 16/28 12/24
Fan 35 Rheology @ 120 °F (49 °C)

35
600 rpm 45 66 61
300 rpm 27 43 39
PV 18 23 22
YP 9 20 17
40
200 rpm 19 34 29
100 rpm 12 24 20
6 rpm 4 11 8

45 3 rpm 3 10 7
Gels 10 sec, 10 min 4/8 16/24 12/21
Fan 35 Rheology @ 150 °F (66 °C)
600 rpm 37 58 54
50
300 rpm 21 40 35
PV 16 18 19
YP 5 22 16

55 200 rpm 15 33 27
100 rpm 9 23 18
6 rpm 3 12 8.5

7
 EP 2 844 715 B1

(continued)

Fan 35 Rheology @ 150 °F (66 °C)

3 rpm 2.5 11 7.5
5
Gels 10 sec, 10 min 4/6 15/21 12/18
ES @ 150 °F (66 °C) = 569 1002 712
HTHP@ 300 °F (149 °C) 21.0 ml 16.2 ml 18.2 ml
10
[0030] HTHP stands for the high-temperature high-pressure (HTHP) fluid loss. The HTHP fluid loss was determined
in accordance with the Specification for Drilling Fluids Materials, ANSI/API Specification 13A, Eighteenth Edition, February
2010. ES stands for emulsion stability which was determined with an emulsion stability meter which measures the voltage
across a small gap filled with oil based mud with a aqueous discontinuous phase (at a known temperature). The higher
15 the voltage recorded the greater the stability of the emulsion.
[0031] Referring to Tables 1 and 2, it is discernible during Fann 35 rheology studies that for the control samples,
properties such as YP (yield point) and gels (gel strengths at 10 seconds, 10 minutes, and 30 minutes) decrease rather
noticeably as the temperature increased from 85 °F to 150 °F (29-66 °C) (typical testing parameters). The yield points
for the samples from Tables 1 and 2 are plotted in Figures 1 and 2 respectively. Upon the addition of approximately 2
20 lbb (pounds per barrel) (5.7 kg/m3) of RMX it was observed that the YP and gel strength increased in value over that of
the control along the temperature testing range (85 °F (29 °C), 120 °F (49 °C), and 150 °F (66 °C)). As temperature was
increased during the Fann experiment, the YP gel strength values for the samples containing a RMX did not decrease
to the extent observed for the control samples. The drop in YP and gel strength with increasing temperature is more
noticeable for the Control samples in Table 2 which contain the ESCAID 110 hydrocarbon fluid based OBM. Without
25 wishing to be limited by theory, the OBM having ESCAID 110 hydrocarbon fluid is more paraffinic in nature than the
diesel fuel (higher naphthenic character) and has less affinity for dissolution or solvent interaction with the rheology
modifiers. However, in both OBMs the RMXs of this disclosure are as effective as THIXATROL in changing rheology
such that the overall fluid properties are much improved.

30 EXAMPLE 2

[0032] The effect of varying the concentration of the RMX in the FRCs of this disclosure was investigated. Four samples
were prepared containing the ESCAID-OBM described in Example 1 and either RMX (Control), 1.8 lb (0.82 kg) of the
RMX (Sample C), 1.5 lb (0.68 kg) of the RMX (Sample D), 1.3 lb (0.59 kg) of the RMX (Sample E) or 2 lb of RMX (Sample
35 F). Rheology tests were performed and are presented in Table 3.

Table 3
Control Sample C Sample D Sample E Sample F

40 Fan 35 Rheology @ 85 °F (29 °C)

600 rpm 59 82 79 76 70
300 rpm 36 50 48 47 43
PV 23 32 31 29 27
45
YP 13 18 17 18 16
200 rpm 27 38 37 36 32
100 rpm 17 26 25 24 20

50 6 rpm 6 11 10.5 10 7
3 rpm 5 10 10 9 6
Gels 10 sec, 10 min 7/9 16/27 15/25 14/23 12/24
Fan 35 Rheology @ 120 °F (49 °C)
55
600 rpm 45 70 66 63 61
300 rpm 27 42 40 39 39

8
 EP 2 844 715 B1

(continued)

Fan 35 Rheology @ 120 °F (49 °C)

PV 18 28 26 24 22
5
YP 9 14 14 15 17
200 rpm 19 33 31 31 29
100 rpm 12 24 22 21 20
10 6 rpm 4 11 10 9 8
3 rpm 3 10 9 8 7
Gels 10 sec, 10 min 4/8 16/23 13/21 12/20 12/21
Fan 35 Rheology @ 150 °F (66 °C)
15
600 rpm 37 62 54 52 54
300 rpm 21 39 34 33 35
PV 16 23 20 19 19
20 YP 5 16 14 14 16
200 rpm 15 33 29 27 27
100 rpm 9 24 21 19 18
6 rpm 3 12 9.5 8.5 8.5
25
3 rpm 2.5 11 9 8 7.5
Gels 10 sec, 10 min, 30min 4/6/5 14/22/23 12/17/20 11/16/18 12/18/20
ES @ 150 °F (66 °C) = 569 955 960 815 712
30
HTHP@ 300 °F (149 °C) 21.0 ml 22.8 ml 19.6 ml 16.0 ml 18.2 ml

[0033] The results demonstrate the values of YP and gel strength remained relatively constant throughout the con-
centrations of RMX investigated and were similar to values observed when using THIXATROL rheological additive at 2
35 lbb (5.7 kg/m 3). The yield points for the samples from III are plotted in Figure 3. Further the results of the 30 minute gel
strengths performed at 150 °F (66 °C) samples containing a RMX yielded surprisingly beneficial and encouraging results.
Without wishing to be limited by theory, the significance of the 30 minute gel values remaining stable or unchanging
suggests that an FRC (e.g., OBM) made in accordance with the present disclosure may have sufficient suspension
capability that it may stand for some period of time (e.g., 30 minutes) without loss of the suspended particulate material.
40
Example 3

[0034] The rheological characteristics of an FRC of the type disclosed herein were compared to wellbore servicing
fluids having conventional rheological additives. Samples were prepared using the ESCAID 110 based OBM described
45 in Example 1 and the following amounts of rheological additives: VERSAMOD (2 lbb (5.7 kg/m3)) in Sample G; RM-63
(2 lbb (5.7 kg/m3)) in Sample H; RMX (2.14 lbb (6.1 kg/m3)) Sample I; RMX (1.85 lbb (5.3 kg/m3)) Sample J; and
THIXATROL (2 lbb (5.7 kg/m 3)) Sample K. RM-63 viscosifier is a rheological additive commercially available from
Halliburton Energy Services, and VERSAMOD organic gelling agent is a liquid rheology modifier commercially available
from Mi SWACO. The results of the rheological testing are presented in Table 4 and the yield points for the samples are
50 plotted in Figure 4.

Table 4
Sample G Sample H Sample I Sample J Sample K
Fan 35 Rheology @ 85 °F (29 °C)
55
600 rpm 71 63 79 76 70
300 rpm 41 37 48 47 43

9
 EP 2 844 715 B1

(continued)

Sample G Sample H Sample I Sample J Sample K

Fan 35 Rheology @ 85 °F (29 °C)
5
PV 30 26 31 29 27
YP 11 11 17 18 16
200 rpm 29 26 37 36 32
10 100 rpm 17 15 25 24 20
6 rpm 5 4 10.5 10 7
3 rpm 4 3 10 9 6
Gels 10 sec, 10 min 8/25 6/23 15/25 14/23 12/24
15
Fan 35 Rheology @ 120 °F (49 °C)
600 rpm 57 54 66 63 61
300 rpm 34 30 40 39 39
20 PV 23 24 26 24 22
YP 11 6 14 15 17
200 rpm 22 21 31 31 29
100 rpm 13 12 22 21 20
25
6 rpm 4 3 10 9 8
3 rpm 3 2 9 8 7
Gels 10 sec, 10 min 7/19 4/20 13/21 12/20 12/21
30
Fan 35 Rheology @ 150 °F (66 °C)
600 rpm 46 43 54 52 54
300 rpm 27 23 34 33 35

35
PV 19 20 20 19 19
YP 8 3 14 14 16
200 rpm 17 16 29 27 27
100 rpm 10 9 21 19 18
40
6 rpm 3 2 9.5 8.5 8.5
3 rpm 2 1 9 8 7.5
Gels 10 sec, 10 min, 30min 6/16/17 3/16/17 12/17/20 11/16/18 12/18/20

45 ES @ 150 °F (66 °C)= 520 500 960 815 712

HTHP@ 300 °F (149 °C) 19.6 ml 16.0 ml 18.2 ml

[0035] A comparison of the samples containing RMX (Samples I and J) was made to commercially available products
based on product usage rates typical for field use. The commercial species were tested at 2 lbb (5.7 kg/m3) concentration
50
against concentrations of 2.14 lbb (6.1 kg/m3) and 1.85 lbb (5.3 kg/m3) for the RMX. The object was to bracket the 2
lbb (5.7 kg/m3) range to see if there was much deviation in performance of the RMX given the slightly lower or higher
additive concentration. The results demonstrate the RMX outperformed both the VERSAMOD and RM-63 in that both
YP and gel strength values for the RMX remained fairly constant, whereas, those same values fell precipitously as the
samples containing the VERSAMOD and RM-63 products increased in temperature.
55

10
 EP 2 844 715 B1

Claims

1. A non-aqueous wellbore servicing fluid comprising a rheology modifier wherein the rheology modifier comprises a
reaction product of a polysulfide, a dimer acid and a polyfunctional amine, wherein the polyfunctional amine comprises
5 a molecule containing at least two amine groups, and wherein the nonaqueous wellbore servicing fluid comprises
an oil-based mud.

2. The fluid of claim 1 wherein the rheology modifier is present in the wellbore servicing fluid in an amount of from 0.02
wt.% to 2.2 wt.% based on the total weight of the wellbore servicing fluid.
10
3. The fluid of any preceding claim wherein the polysulfide comprises di(hydroxyethyl)polysulfides, di(hydroxyethyl)di-
sulfide, di(hydroxyethyl)trisulfide, di(hydroxyethyl)tetrasulfide or homopolymers thereof, or wherein the polysulfide
is characterized by general Formula I or Ia:

15

20

where each R, R’ and R’" can be independently selected from the group consisting of hydrogen and an organyl
group and x has an average value greater than 2.
25
4. The fluid of any preceding claim having a variation in yield point of less than 20% over a temperature range of from
100 °F to 430 °F (38-221°C).

5. The fluid of any preceding claim having a variation in gel strength of less than 20% over a temperature range of
30 from 100 °F to 430 °F (38-221°C).

6. A method of conducting an oilfield operation comprising:

placing an oil-based mud comprising a rheology modifier into a wellbore wherein the rheology modifier comprises
35 a reaction product of a polysulfide, a dimer acid and a polyfunctional amine, wherein the polyfunctional amine
comprises a molecule containing at least two amine groups.

7. The method of claim 6 wherein the oilfield operation is a maritime oilfield operation.

40 8. The method of claim 6 or 7 wherein the rheology modifier is present in the oil-based mud in an amount of from 0.02
wt.% to 2.2 wt.% based on the total weight of the wellbore servicing fluid.

9. The method of claim 6, 7, or 8 wherein the polysulfide comprises di(hydroxyethyl)polysulfides, di(hydroxyethyl)di-

sulfide, di(hydroxyethyl)trisulfide, di(hydroxyethyl)tetrasulfide or homopolymers thereof.
45
10. The method of claim 6, 7, 8, or 9 wherein the oil-based mud has a variation in yield point of less than 20% over a
temperature range of from 100 °F to 430 °F (38-221°C).

11. The method of any of claims 6-10 wherein the oil-based mud displays a flat rheology.
50
12. The method of any of claims 6-11 wherein the oil-based mud is subjected to cyclic temperature stresses.

13. The method of any of claims 6-12 wherein the oil-based mud has a variation in yield point of less than 20%.

55 14. The method of any of claims 6-13 wherein the oil-based mud has a variation in gel strength of less than 20% over
a temperature range of from 100 °F to 430 °F (38-221°C).

15. The fluid of any of claims 1 to 5 or the method of any of claims 6-14 wherein the dimer acid comprises a C12-C24

11
 EP 2 844 715 B1

unsaturated fatty acid.

Patentansprüche
5
1. Nicht-flüssiges Bohrlochwartungsfluid, das einen Rheologiemodifikator umfasst, wobei der Rheologiemodifikator
ein Reaktionsprodukt eines Polysulfids, einer Dimersäure und eines polyfunktionellen Amins umfasst, wobei das
polyfunktionelle Amin ein Molekül umfasst, das zumindest zwei Amingruppen enthält, und wobei das nicht-flüssige
Bohrlochwartungsfluid einen Schlamm auf Ölbasis umfasst.
10
2. Fluid nach Anspruch 1, wobei der Rheologiemodifikator im Bohrlochwartungsfluid in einer Menge von 0,02 Gew.-
% bis 2,2 Gew.-% auf Basis des Gesamtgewichts des Bohrlochwartungsfluids vorhanden ist.

3. Fluid nach einem vorstehenden Anspruch, wobei das Polysulfid Di(hydroxyethyl)polysulfide, Di(hydroxyethyl)disul-
15 fid, Di(hydroxyethyl)trisulfid, Di(hydroxyethyl)tetrasulfid oder Homopolymere davon umfasst, oder wobei das Poly-
sulfid durch die allgemeine Formel I oder Ia gekennzeichnet ist:

20

25
wobei R, R’ und R’" jeweils unabhängig aus der Gruppe ausgewählt sein können, bestehend aus Wasserstoff und
einer Organylgruppe, und wobei x einen Durchschnittswert von mehr als 2 aufweist.

4. Fluid nach einem vorstehenden Anspruch mit einer Schwankung der Elastizitätsgrenze von weniger als 20 % in
30 einem Temperaturbereich von 38 bis 221 °C (100 °F bis 430 °F).

5. Fluid nach einem vorstehenden Anspruch mit einer Schwankung der Gelfestigkeit von weniger als 20 % in einem
Temperaturbereich von 38 bis 221 °C (100 °F bis 430 °F).

35 6. Verfahren zum Durchführen eines Erdölfeldvorgangs, das umfasst:

Platzieren eines Schlamms auf Erdölbasis, der einen Rheologiemodifikator umfasst, in einem Bohrloch, wobei
der Rheologiemodifikator ein Reaktionsprodukt eines Polysulfids, einer Dimersäure und eines polyfunktionellen
Amins umfasst, wobei das polyfunktionelle Amin ein Molekül umfasst, das zumindest zwei Amingruppen enthält.
40
7. Verfahren nach Anspruch 6, wobei der Erdölfeldvorgang ein Erdölfeldvorgang zur See ist.

8. Verfahren nach Anspruch 6 oder 7, wobei der Rheologiemodifikator im Schlamm auf Ölbasis in einer Menge von
0,02 Gew.-% bis 2,2 Gew.-% auf Basis des Gesamtgewichts des Bohrlochwartungsfluids vorhanden ist.
45
9. Verfahren nach Anspruch 6, 7 oder 8, wobei das Polysulfid Di(hydroxyethyl)polysulfide, Di(hydroxyethyl)disulfid,
Di(hydroxyethyl)trisulfid, Di(hydroxyethyl)tetrasulfid oder Homopolymere davon umfasst.

10. Verfahren nach Anspruch 6, 7, 8 oder 9, wobei der Schlamm auf Ölbasis eine Schwankung der Elastizitätsgrenze
50 von weniger als 20 % in einem Temperaturbereich von 38 bis 221 °C (100 °F bis 430 °F) aufweist.

11. Verfahren nach einem der Ansprüche 6 bis 10, wobei der Schlamm auf Ölbasis eine flache Rheologie zeigt.

12. Verfahren nach einem der Ansprüche 6 bis 11, wobei der Schlamm auf Ölbasis zyklischen Temperaturbelastungen
55 ausgesetzt wird.

13. Verfahren nach einem der Ansprüche 6 bis 12, wobei der Schlamm auf Ölbasis eine Schwankung der Elastizitäts-
grenze von weniger als 20 % aufweist.

12
 EP 2 844 715 B1

14. Verfahren nach einem der Ansprüche 6 bis 13, wobei der Schlamm auf Ölbasis eine Schwankung der Gelfestigkeit
von weniger als 20 % in einem Temperaturbereich von 38 bis 221 °C (100 °F bis 430 °F) aufweist.

15. Verfahren nach einem der Ansprüche 1 bis 5 oder Verfahren nach einem der Ansprüche 6 bis 14, wobei die Dimer-
5 säure eine ungesättigte C12-C24-Fettsäure umfasst.

Revendications

10 1. Fluide d’entretien non-aqueux de puits de forage comprenant un modificateur de rhéologie, dans lequel le modifi-
cateur de rhéologie comprend un produit de réaction d’un polysulfure, d’un acide dimère et d’une amine polyfonc-
tionnelle, dans lequel l’amine polyfonctionnelle comprend une molécule contenant au moins deux groupes amines,
et dans lequel le fluide d’entretien non-aqueux de puits de forage comprend une suspension à base d’huile.

15 2. Fluide selon la revendication 1, dans lequel le modificateur de rhéologie est présent dans le fluide d’entretien non-
aqueux de puits de forage à hauteur de 0,02% en poids à 2,2% en poids sur la base du poids total du fluide d’entretien
non-aqueux de puits de forage.

3. Fluide selon l’une quelconque des revendications précédentes, dans lequel le polysulfure comprend des polysulfures
20 de di(hydroxyéthyle), du disulfure de di(hydroxyéthyle), du trisulfure de di(hydroxyéthyle), du tétrasulfure de di(hy-
droxyéthyle), ou des homopolymères de ceux-ci, ou dans lequel le polysulfure est caractérisé par la formule
générale I ou Ia :

25

30

où chaque R, R’ et R" peut être choisi individuellement dans le groupe consistant en un hydrogène et un groupe
organyle et x a une valeur moyenne supérieure à 2.
35
4. Fluide selon l’une quelconque des revendications précédentes ayant une variation de limite d’élasticité inférieure
à 20% sur une gamme de températures allant de 100°F à 430°F (38-221°C).

5. Fluide selon l’une quelconque des revendications précédentes ayant une variation de capacité gélifiante inférieure
40 à 20% sur une gamme de températures allant de 100°F à 430°F (38-221°C).

6. Procédé de direction des opérations d’un champ pétrolifère comprenant :

de placer une suspension à base d’huile comprenant un modificateur de rhéologie dans un puits de forage,
45 dans lequel le modificateur de rhéologie comprend un produit de réaction d’un polysulfure, d’un acide dimère
et d’une amine polyfonctionnelle, dans lequel l’amine polyfonctionnelle comprend une molécule contenant au
moins deux groupes amines.

7. Procédé selon la revendication 6, dans lequel l’opération du champ pétrolifère est une opération de champ pétrolifère
50 offshore.

8. Procédé selon la revendication 6 ou 7, dans lequel le modificateur de rhéologie est présent dans la suspension à
base d’huile à hauteur de 0,02% en poids à 2,2% en poids sur la base du poids total du fluide d’entretien non-
aqueux de puits de forage.
55
9. Procédé selon la revendication 6, 7 ou 8, dans lequel le polysulfure comprend des polysulfures de di(hydroxyéthyle),
du disulfure de di(hydroxyéthyle), du trisulfure de di(hydroxyéthyle), du tétrasulfure de di(hydroxyéthyle), ou des
homopolymères de ceux-ci.

13
 EP 2 844 715 B1

10. Procédé selon la revendication 6, 7, 8 ou 9, dans lequel la suspension à base d’huile a une variation de limite
d’élasticité inférieure à 20% sur une gamme de températures allant de 100°F à 430°F (38-221°C).

11. Procédé selon l’une quelconque des revendications 6 à 10, dans lequel la suspension à base d’huile présente un
5 comportement rhéologique plat.

12. Procédé selon l’une quelconque des revendications 6 à 11, dans lequel la suspension à base d’huile est soumise
à des stress de température cycliques.

10 13. Procédé selon l’une quelconque des revendications 6 à 12, dans lequel la suspension à base d’huile a une variation
de limite d’élasticité inférieure à 20%.

14. Procédé selon l’une quelconque des revendications 6 à 13, dans lequel la suspension à base d’huile a une variation
de capacité gélifiante inférieure à 20% sur une gamme de températures allant de 100°F à 430°F (38-221°C).
15
15. Fluide selon l’une quelconque des revendications 1 à 5 ou procédé selon l’une quelconque des revendications 6 à
14, dans lequel l’acide dimère comprend un acide gras insaturé en C12-24.

20

25

30

35

40

45

50

55

14
EP 2 844 715 B1

15
EP 2 844 715 B1

16
EP 2 844 715 B1

17
EP 2 844 715 B1

18
 EP 2 844 715 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 2009227478 A [0004] • WO 2004094522 A [0004]

• EP 0403437 A [0004] • US 7087708 B [0014]
• US 2007015902 A [0004]

Non-patent literature cited in the description

• Specification for Drilling Fluids Materials. ANSI/API

Specification 13A. February 2010 [0030]

19