CA2862135A1 - Invert drilling fluids having enhanced rheology and methods of drilling boreholes - Google Patents

Abstract

An invert emulsion drilling fluid, and a method of drilling with such fluid, having improved rheology at low mud weights and high temperatures. The improved rheology is effected with addition of hydrophobic amines, most preferably dimer diamines.

Description

INVERT DRILLING FLUIDS HAVING ENHANCED RHEOLOGY AND METHODS
OF DRILLING BOREHOLES
RELATED APPLICATION
(00011 This application is a continuation-in-part of United States Patent Application Serial No. 12/660,873, filed March 6, 2010, pending.
BACKGROUND OF THE INVENTION
1. Field of the Invention [00021 The present invention relates to compositions and methods for drilling, cementing and casing boreholes in subterranean formations, particularly hydrocarbon bearing formations. More particularly, the present invention relates to methods for improving the rheology of invert emulsion drilling fluids, particularly at high temperatures, and to compositions for low mud weight, invert emulsion drilling fluids, with good stability and hid.) performance properties.

2. Description of Relevant Art 100031 A drilling fluid or mud is a specially designed fluid that is circulated through a wellbore as the wellbore is being drilled to facilitate the drilling operation. The various functions of a drilling fluid include removing drill cuttings from the wellbore, cooling and lubricating the drill bit, aiding in support of the drill pipe and drill bit, and providing a hydrostatic head to maintain the integrity of the wellbore walls and prevent well blowouts.
[00041 An important property of the drilling fluid is its rheology, and specific rheolo2ical parameters are intended for drilling and circulating the fluid through the well bore. The fluid should be sufficiently viscous to suspend barite and drilled cuttings and to carry the cuttings to the well surface. However, the fluid should not be so viscous as to interfere with the drilling operation.
10005] Specific drilling fluid systems are selected to optimize a drilling operation in accordance with the characteristics of a particular geological formation. Oil based muds are normally used to drill swelling or sloughing shales, salt, gypsum, anhydrite and other evaporate formations, hydrogen sulfide-containing formations, and hot (greater than about 300 degrees Fahrenheit (" 17") holes, but may he used in other holes penetrating a subterranean formation as well.
100061 An oil-based invert emulsion-based drilling fluid may commonly comprise between about 50:50 to about 95:5 by volume oil phase to water phase. Such oil-based muds used in drilling typically comprise: a base oil comprising the external phase of an invert emulsion; a saline, aqueous solution (typically a solution comprising about 30% calcium chloride) comprising the internal phase of the invert emulsion; emulsifiers at the interface of the internal and external phases; and other agents or additives for suspension, weight or density, oil-wetting, fluid loss or filtration control, and rheology control.
In the past, such additives commonly included organophilic clays and organophilic lignites. See ITCH.
Darley and George R. Gray, Composition and Properties of Drilling and Completion Fluids 66-67, 561-562 (.5th ed. 1988). However, recent technology as described for example in U.S.
Patent Nos. 7,462,580 and 7,488,704 to Kirsner, et al., introduced "clay-free"
invert emulsion-based drilling fluids, which offer significant advantages over drilling fluids containing organophilic clays.
[0007] As used herein and for the purposes of the present invention, the term "clay-free" (or "clayless) means a drilling fluid made without addition of any organophilic clays or organophilic lignites to the drilling fluid composition. During drilling, such "clay-free"
drilling fluids may acquire clays and/or lignites from the formation or from mixing with recycled fluids containing clays and/or lignites. However, such contamination of "clay-free"
drilling fluids is preferably avoided and organophilic clays and organophilic lignites should not be deliberately added to "clay-free" drilling fluids during drilling.
[0008] Invert emulsion-based muds or drilling fluids (also called invert drilling muds or invert muds or fluids) comprise a key segment of the drilling fluids industry, and "clay-free" invert emulsion-based muds, particularly those capable of "fragile gel"
behavior as described in U.S. Patent Nos. 7,462,580 and 7,488,704 to Kirsner, et al., are becoming increasingly popular.
[00091 Clay-free invert emulsion drilling fluids, like INNOVERTO drilling fluid available from Halliburton Energy Services, Inc., in Duncan, Oklahoma and Houston, Texas, for example, have been shown to yield high performance in drilling, with "fragile eel"
strengths and rheology leading to lower equivalent circulating density (ECDs) and improved rate of penetration ROP.
[00101 A limiting factor in drilling a particular portion of a well is the mud weight (density of the drilling fluid) that can be used. If too high a mud weight is used, fractures are created in lost-circulation zones with resulting loss of drilling fluid and other operating problems. If too low a mud weight is used, formation fluids can encroach into the well, borehole collapse may occur due to insufficient hydrostatic support, and in extreme cases safety can be compromised due to the possibility of a well blowout. Many times, wells are drilled through weak or lost-circulation-prone zones prior to reaching a potential producing zone, requiring use of a low mud weight and installation of sequential casing strings to protect weaker zones above the potential producing zone. A particularly critical drilling scenario is one that combines deepwater and shallow overburden, as is typical of ultra deepwater fields in Brazil. This scenario is characterized by high pore fluid pressure, low effective stresses, low fracturing gradients and narrow mud weight windows.
[0011]
Commercially available clay-free invert emulsion drilling fluids may have less than preferred rheology at low mud weights, that is, mud weights ranging from about 9 ppg to about 12 ppg, with temperatures up to about 375 F or higher. Addition of inert solids may improve the rheology, but result in a decreased rate of penetration during drilling and loss of or decline in other benefits seen with a clay free system. Such inert solids include for example, fine sized calcium carbonate, and the term as used herein is not meant to be understood to include or refer to drill cuttings. Low mud weight or reduced density clay-free oil based invert emulsion drilling fluids also may show a decline in the desired "fragile gel"
strength characteristic of clay-free invert emulsion drilling fluids. "Fragile gel" strength generally refers to the ability of the drilling fluid to both suspend drill cuttings at rest and show a lack of a pressure spike upon resumption of drilling.

Increasingly invert emulsion-based drilling fluids are being subjected to ever greater performance and cost demands as well as environmental restrictions.
Consequently, there is a continuing need and industry-wide interest in new drilling fluids that provide improved performance while still affording environmental and economical acceptance.
SUMMARY OF THE INVENTION
100131 The present invention provides oil-based invert emulsion drilling fluids with improved rheology without the addition of inert solids, and at temperatures ranging from about 100 F to about 375 F or higher. The present invention also provides improved methods of drilling wellbores in subterranean formations employing oil-based invert emulsion muds or drilling fluids having low mud weight. As used herein, the term "drilling"
or "drilling wellbores" shall be understood in the broader sense of drilling operations, which include running casing and cementing as well as drilling, unless specifically indicated otherwise.
[00141 The invert emulsion drilling fluid of the present invention, or used in methods of the present invention, comprises an oil:water ratio preferably in the range of 50:50 to 95:5 and preferably employs a natural oil, such as for example without limitation diesel oil or mineral oil, or a synthetic base, as the oil phase and water comprising calcium chloride as the aqueous phase. The rheology modifier or additive for theology stability is a hydrophobic amine additive, having the following general structure:

¨
R R ¨ X.
where R represents a hydrophobic or partially hydrophobic group with carbon atoms from 16 ¨ 54 which can he straight chained or branched and can be aliphatic, cycloaliphatic and aryl aliphatic; N is a primary, secondary or tertiary amine wherein the R1 and R2 groups may he the same or different and are selected from the group consisting of a hydrogen group, alkyl group, eyano alkyl group, amino alkyl group, amino aryl group, hydroxyl alkyl group or a derivative thereof; alternatively the Ri and R2 can he a carbonyl group, carbonate group, alkoxy group, hydroxyl group or a derivative thereof; X comprises a hydrophilic group such as an amine which can he primary, secondary or tertiary with substituents being a hydrogen group, alkyl group, cyano alkyl group, amino alkyl group, amino aryl group, hydroxyl alkyl group or a derivative thereof; alternatively the X group can he an amide group, amine oxide group, betaine group, ester group, carboxylic acid group, ether group, hydroxyl group, phosphate group, phosphonate group, pyrrolidone group, haloformyl group, nitrate group, nitrite group, sulfate group, sulfonate group, imidazoline group, pyridine group, sugar group, or a combination or derivative thereof. Most preferably, the hydrophobic amine used in the present invention is a C36 fatty dither diamine having the following molecular structure:

A preferred commercially available C36 (linter diamine contains C18 fatty monoamine and C54 fatty trimer triamine which are obtained during the commercial production of the (linter diamine. Generally, quantities of such hydrophobic amine ranging from about 1 pph to about 6 pph are preferred and are effective even when the mud weight is low, that is, is in the range of about 9 to about 12 ppg.
100151 Addition of the hydrophobic amine additive to the drilling fluid increases the Low Shear Yield Point (LSYP), Yield Point (YP). and the 10 minute Gel Strength but limits the increase in the Plastic Viscosity (PV) to about 60% or less, relative to the drilling fluid not having the hydrophobic amine additive, when measured at 120 F. At High Pressure High Temperature (HPHT) conditions, the invert emulsion drilling fluid of the present invention comprising the hydrophobic amine additive has increased I,SYP. YP, and 10 minute Gel Strength but similar or lower PV, relative to the drilling fluid without the hydrophobic amine additive. Such a lower PV seen with the invert emulsion drilling fluid of the invention is believed to help minimize the amount of density increase caused by pumping of the fluid.
Invert emulsion drilling fluids of the invention may also demonstrate "fragile gel" behavior when the drilling fluid is "clay-free."
BRIEF DESCRIPTION OF THE DRAWINGS
100161 Figure 1 is a bar graph comparing the plastic viscosity, yield point and low shear yield point of example 9 ppg drilling fluid formulations of the invention having various concentrations of a hydrophobic amine rheology modifier, with a formulation without that additive.
[0017] Figure 2a is a graph comparing, at high temperature and pressure, the low shear yield point of an example drilling fluid formulation of the invention having 3 ppb hydrophobic amine rheology modifier, with a base or control fluid not containing a hydrophobic amine rheology modifier.
[0018] Figure 2b is a graph comparing, at high temperature and pressure, the yield point of an example drilling fluid formulation of the invention having 3 ppb hydrophobic amine rheology modifier, with a base or control fluid not containing a hydrophobic amine rheology modifier.
[0019] Figure 2c is a graph comparing, at high temperature and pressure, the plastic viscosity of an example drilling fluid of the invention having 3 ppb hydrophobic amine 'theology modifier, with a base or control fluid not containing a hydrophobic amine rheology modifier.
[0020] Figure 3 is a graph showing the effect of a hydrophobic amine rheology modifier on an example drilling fluid of the invention not containing any inert solids additive.
[ 0021] Figure 4 is bar graph comparing rheological characteristics of example drilling fluids of the invention having different mineral oil bases.
100221 Figure 5 is a bar graph comparing the rheology of an example 12 ppg drilling fluid of the invention with a base or control drilling fluid not having a hydrophobic amine rheology modifier, after hot rolling for 16 hours at 350T.

100231 Figure 6 is a graph showing fragile gel behavior of an example 9 ppg drilling fluid of the invention compared to the behavior of a 9 ppg drilling fluid not having a hydrophobic amine rheology modifier.
100241 Figure 7a is a graph showing fragile gel behavior of an example drilling fluid of the invention having a mud weight of 16 ppg.
100251 Figure 7b is a graph showing fragile gel behavior of an example drilling fluid of the invention having a mud weight of 18 ppg DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[00261 The present invention provides an oil-based, invert emulsion drilling fluid with improved performance in the field at mud weights in the range of about 9 ppg to about 18 ppg, and a method of drilling employing that drilling fluid. The oil base may be a natural oil such as for example diesel oil, Or a synthetic base such as, for example, ACCOLADE
base comprising esters or ENCORE base comprising isomerized olefins, both available from Halliburton Energy Services, Inc., in Houston, Texas and Duncan, Oklahoma. A
mineral oil may even be successfully used as the oil base in the present invention, even though in the prior art some difficulties have been experienced in obtaining desirable rheological properties with mineral oils under certain conditions such as low mud weights, that is, mud weights ranging from about 9 to about 12 ppg, and particularly at high temperatures (greater than 225 F). Mineral oils particularly suitable for use in the invention are selected from the group consisting of n-paraffins, iso-paraffins, cyclic alkanes, branched alkanes, and mixtures thereof.
[00271 An aqueous solution containing a water activity lowering compound, composition or material, comprises the internal phase of the invert emulsion.
Such solution is preferably a saline solution comprising calcium chloride (typically about 25%
to about 30%, depending on the subterranean formation water salinity or activity), although other salts or water activity lowering materials such as for example glycerol or sugar known in the art may alternatively or additionally be used. Such other salts may include for example sodium chloride, sodium bromide, calcium bromide and formate salts. Water preferably comprises less than 50%, or as much as about 50%, of the drilling fluid and the oil:water ratio preferably ranges from about 50:50 to about 95:5.
[00281 Drilling fluids of the present invention uniquely include a hydrophobic amine additive as a rheology modifier, as will he discussed further below. Further, the drilling fluids of, or for use in, the present invention, have added to them or mixed with their invert emulsion oil base, other fluids or materials needed to comprise complete drilling fluids. Such other materials optionally may include, for example: additives to reduce or control low temperature rheology or to provide thinning, for example, additives having the trade names COLDTROLO, ATCO, and OMC2Tm; additives for enhancing viscosity, for example, an additive having the trade name RHEMOD LI'm (modified fatty acid); additives for providing temporary increased viscosity for shipping (transport to the well site) and for use in sweeps, for example, an additive having the trade name TEMPERUSTm (modified fatty acid);
additives for filtration control, for example, additives having the trade names ADAPTA and BDF-366; an emulsifier activator, such as, for example, lime; additives for high temperature high pressure control (HTHP) and emulsion stability, for example, an additive having the trade name FACTANTrm (highly concentrated tall oil derivative); and additives for emulsification, for example, an additive having the trade name EZ MULO NT
(polyaminated fatty acid). All of the aforementioned trademarked products are available from Halliburton Energy Services, Inc. in Houston, Texas, and Duncan, Oklahoma, U.S.A. As with all drilling fluids, the exact formulations of the fluids of the invention vary with the particular requirements of the subterranean formation.
[0029] A preferred commercially available drilling fluid system for use in the invention is the INNOVERTO drilling fluid system, having a paraffin/mineral oil base, available front Baroid, a Halliburton Company, in Houston, Texas and Duncan, Oklahoma.
The INNOVERTO drilling fluid system typically comprises the following additives, in addition to the paraffin/mineral oil base and brine, for use as an invert emulsion drilling fluid:
RHEMODTm L modified fatty acid suspension and viscosifying agent, BDF-366Thi or ADAPTAThl copolymer for HPFIT filtration control, particularly for use at high temperatures, and EZ MULO NT polyaminated fatty acid emulsifier/oil wetting agent, also particularly for use at high temperatures. Commercially available INNOVERT drilling fluid systems also typically include TAU-MOW.'" amorphous/fibrous material as a viscosifier and suspension agent. However, with the present invention, where the drilling fluid system has uniquely added thereto a hydrophobic amine additive as a rheology modifer, TAU-MOD
material is optional.
[0030] Invert emulsion drilling fluids of the present invention, comprising the hydrophobic amine additive, maintain acceptable and even preferred rheology measurements at low mud weights and do not experience a decreased rate of penetration (and with clay-free invert emulsion drilling fluids, also do not experience a decline in desired fragile gel strength) when in use in drilling even at high temperatures and pressures. At lIPI IF
conditions, the invert emulsion drilling fluids of the present invention, comprising the hydrophobic amine additive, has increased LSYP, YP, and 10 minute Gel Strength but similar or lower PV
relative to the drilling fluid without the hydrophobic amine additive. These advantages of the present invention are believed to be due to the addition of the hydrophobic amine additive to the drilling fluid. The advantages of the present invention are especially appreciated where the drilling fluid does not also contain organophilic clay or lignite.
[00311 Preferred commercially available hydrophobic amines suitable for use in the present invention include without limitation VERSAMINEO 552 hydrogenated fatty dimer diamine, and VERSAMINE 551 fatty C36 dimer diamine, both available from Cognis Corporation (functional products) of Monheim, Germany and Cincinnati, Ohio and PRIAMINETm 1073 and PRIAMINETm1074 fatty C36 (linter diamine, both available from Croda Internationale Plc of Goole East Yorkshire, United Kingdom and New Castle, Delaware. Typically, an amount of such dimer diamine in the range of about 1 pound per barrel (ppb) to about 3 ppb is sufficient for purposes of the invention. These fatty dimer diamines are prepared commercially from fatty dimer diacids which have been produced from dimerisation of vegetable oleic acid or tall oil fatty acid by thermal or acid catalyzed methods.
[00321 The dimerisation of C18 tall oil fatty acids produces the material leading to the C36 dimer acids. This material is a mixture of monocyclic dicarboxylic acid, acyclic dicarboxylic acid and bicyclic dicarboxylic acid along with small quantities of trimeric triacids. These diacids are converted into diamines via the reaction scheme given below:
H4t1 o 0 R ______________________ < R _______________ R
\H
H
Reaction Scheme I.
These diamines are further converted into compounds that fall under the scope of hydrophobic amine additives. These diamines are converted into cyanoethyl derivatives via cyanoethylation with acrylonitrile; these cyanoethyl derivatives are further reduced into aminopropyl amines via reduction as shown in the reaction scheme II below, as taught in United States Patent No. 4,250,045, issued February 10, 1981 to Coupland, et al.

H Cyanoethylation via acrylonitrile Reduction R¨N ______________________ R ___________________ 0- R¨N' \H
HN
Reaction Scheme II
Dicyanoethylated dimer diamine is available commercially as Kemarnine DC 3680 and 3695 and di N-aminopropylated dimer diamine is available commercially as Kemamine and 3695 from Cheintura Corporation USA. Different structures of the dimeric hydrophobic amine additives are given below:

H,Nc Mono,cyclif. (Hiner diomine \
\/

Bicyclic dialer tliamine ,NH, H N
Aromatic diner tliamine ( Acyclic clinwt diamine _______________________________________________________ CH

1() [00331 Laboratory tests demonstrate the effectiveness of the present invention. Referring to experiments whose results are graphed in Figure 1, a 9 ppg INNOVERTO invert emulsion drilling fluid was prepared using paraffin/mineral oil base in a 60:40 oil to water ratio with calcium chloride brine having a water phase salinity of 200,000 parts per million (ppm). To this, additives were mixed in for a drilling fluid having the components as indicated in Table 1 below:

Components Control Invention Formulations containing C36 dimer diamine Mud weight (ppe) 9 9 9 9 _ Oil water ratio 60/40 60/40 60/40 60/40 EDC 99 DWO paraffin/mineral oil (bbl) 0.505 0.505 0.505 0.505 EZ-MEIL NT emulsifier (lb) 8 8 8 8 Lime (lb) 3 3 3 3 RI-IEMOD L suspension and viscosifyine 3 3 3 3 agent (lb) ADAVI'ACO filtration control agent (lb) 1.5 1.5 1.5 1.5 20% CaC12 Brine (1b/bbl) 164.2 164.2 164.2 164.2 .
TAU- MOD '1 material (lb) 5 5 5 5 REV DUST (lb) 20 20 20 10 Barite (lb) 9.9 9.9 9.9 9.9 BARACARBC) 5 sized calcium carbonate 10 20 20 20 (lb) C36 climer diamine (lb) 1 3 6 16 hr. hot roll (temp. GE) 250 250 250 250 Properties 600 rpm 43 58 68 74 300 rpm 25 35 43 49 200 rpm 19 28 34 38 100 rpm 12 18 23 17 6 rpm 4 6.0 9.0 11.0 3 rpm 3.5 5.0 8.0 10.0 PLASTIC VISCOSITY (cP) 18 23 25 25 YHA]) POINT (1b/100112) 7 11 18 24 GELS 10 sec 3.5 6.0 11.0 11.0 GELS 10 min 5 15 20 21 I ,SY P 3 4.0 _ 7.0 9.0 TAU() 3.26 4.52 7.18 8.60 E.S. @ 120 F 168 143 150 200 1111 IT @ 250 `)F, ml 2.0 1.6 1.4 1.2 All trademarked products above and in other tables below are available from Halliburton Energy Services, Inc., in Houston, Texas and Duncan, Oklahoma, except that REV
DUST is an artificial drill solid available from Milwhite Inc, in Houston Texas. These compositions set forth in Table I were hot rolled at 250 F for 16 hours. The fluids were then further mixed for 5 minutes and evaluated on a FANN 35 rheometer at 120 F, testing Plastic Viscosity (PV), Yield Point (YP), yield stress (Tau zero) and Low Shear Yield Point (LSYP).
[0034] The Plastic Viscosity (PV), Yield Point (YP), Yield Stress (Tau zero) and Low Shear Yield Point (LSYP) of the invert emulsion drilling fluid were determined on a direct-indicating rheometer, a FANN 35 rheometer, powered by an electric motor. The rheometer consists of two concentric cylinders, the inner cylinder is called a bob, while the outer cylinder is called a rotor sleeve. The drilling fluid sample is placed in a thermostatically controlled cup and the temperature of the fluid is adjusted to 120 ( 2) F.
The drilling fluid in the thermostatically controlled cup is then placed in the annular space between the two concentric cylinders of the FANN 35. The outer cylinder or rotor sleeve is driven at a constant rotational velocity. The rotation of the rotor sleeve in the fluid produces a torque on the inner cylinder or bob. A torsion spring restrains the movement of the bob, and a dial attached to the bob indicates displacement of the bob. The dial readings are measured at different rotor sleeve speeds of 3, 6, 100, 200, 300 and 600 revolutions per minute (rpm).
[0035] Generally, Yield Point (YP) is defined as the value obtained from the Bingham-Plastic rheological model when extrapolated to a shear rate of zero. It may be calculated using 300 rpm and 600 rpm shear rate readings as noted above on a standard oilfield rheometer, such as a FANN 35 or a FANN 75 rheometer. Similarly, Yield Stress or Tau zero is the stress that must be applied to a material to make it begin to flow (or yield), and may commonly he calculated from rheometer readings measured at rates of 3, 6, 100, 200, 300 and 600 rpm. The extrapolation may be performed by applying a least-squares fit or curve fit to the Herchel-Bulkley rheological model. A more convenient means of estimating the Yield Stress is by calculating the Low-Shear Yield Point (1,SYP) by the formula shown below in Equation 2 except with the 6 rpm and 3 rpm readings substituted for the 600-rpm and 300-rpm readings. respectively. Plastic Viscosity (PV) is obtained from the Bingham-Plastic theological model and represents the viscosity of a fluid when extrapolated to infinite shear rate. The PV is obtained from the 600 rpm and the 300 rpm readings as given below in Equation I. A low PV may indicate that a fluid is capable of being used in rapid drilling because, amona other things, the fluid has low viscosity upon exiting the drill bit and has an increased flow rate. A high PV may be caused by a viscous base fluid, excess colloidal solids, or both. The PV and YP are calculated by the following set of equations:
PV = (600 rpm reading) ¨ (300 rpm reading) (Equation 1) YP = (300 rpm reading) ¨ PV (Equation 2) .More particularly, each of these tests were conducted in accordance with standard procedures set forth in Recommended Practice 13B-2, Recotnmended Practice for Field Testing of Oil-based Drilling Fluids, Fourth Edition, American Petroleum Institute, March 1, 2005, the contents of which is hereby incorporated herein by reference.
(00361 The results of the tests graphed in Figure 1 demonstrate that 1 to 3 ppb of C36 dimer diamine (hydrophobic amine) additive was sufficient to impart adequate low end rheology to the 9 ppe INNOVERT invert emulsion drilling fluid. The results in Table show that the PV increased by 60 % whereas the YP, LSYP and Gel Strength at 10 mins increased by 250, 200 and 300 % respectively with addition of 6 ppb of the hydrophobic amine additive (invention formulation 4) relative to the control (formulation 1).
[0037] Samples of 9 ppg INNOVERT invert emulsion drilling fluid containing 3 pph C36 dimer diamine were evaluated further with a FANN 75 rheometer using simulated down hole conditions, and particularly testing high temperature and high pressure rheology. The FANN 75 rheometer measures similarly as the FANN 35 rheometer but can measure rheology under high temperature and pressure. The compositions of these samples (formulation samples 6) are set forth in Table 2(a) below and the results of these tests are graphed in Figures 2(a), 2(b) and 2(c). Before testing, the samples were hot rolled at 325 F.
Formulation sample 5 in 'fable 2(a) was a "control," the drilling fluid without a dimer diamine (hydrophobic amine) additive. The data for these figures is provided in Table 2(h) (control formulation sample 5) and Table 2(c) (invention formulation sample 6) below.
Tables 2(b) and 2(c) show that the addition of the hydrophobic amine additive increased the YP and LSYP of the invert emulsion drilling fluid, but maintained similar or lower PV
relative to the control (formulation 5), under Mel) Pressure High Temperature (11111T) conditions.

TABLE 2(a)--Formulations Components Control Invention Formulation containing C36 dimer diamine Mud Weight (pp2) 9 9 Oil water ratio 60/40 60/40 EDC 99 DW paraffin/mineral oil (bbl) 0.51 0.51 EZ-MULO NT emulsifier (lb) 8 8 Lime (lb) 3 3 RHEMOD L suspension and viscosifying agent (lb) 3 3 ADAPT/VD filtration control agent (lb) 9.5 9.5 20% CaC12 Brine (lb/bbl) 162.2 162.2 TAU- MOD I M material (lb) 5 5 REV DUST (lb) 20 20 Barite (lb) 27.3 27.3 BARACARBO 5 sized calcium carbonate (lb) NIL NIL
C36 dimer diamine (lb) NIL 3 110T ROLL TEMPERATURE ( E) 325 325 E.S. 0_7) 120 F 101 130 HPIIT @ 325 F, ml 3.6 2.4 TABLE 2(b)¨Rheology Test Results (Control¨Formulation 5) FANN

_______ Psi psi psi psi psi psi psi psi psi psi psi psi 600 ____ 52 53 67 54 33 37 44 54 26 29 34 200 21 - 23 29 24 _ 17 19 , 22 27 15 ' 17 19 - 24 3 4 3 _ 4 4 4 5 5 6 6 6 7 7 PV 23 22 29 23 _ 12 14 17 21 9 10 12 15 YP 6 9 9 8 8 9 11 13 , 8 9 10_ 12 I,SYP 3 3 - 4 4 4 4 _ 5 5 6 6 7 7 TABLE 2(c)¨Rheology Test Results (Formulation 6) FANN

psi psi psi psi psi psi psi psi psi psi I,SYP 6 8 7 8 11 19 10 10 11 6 [0038] Figure 3 shows results of tests of the effect of C36 dimer diamine (hydrophobic amine) additive on the rheology of 10 ppg mud weight INNOVERTO
base oil invert emulsion drilling fluid formulated without TAU-MOD' amorphous/fibrous material or a fine grind bridging agent such as BARACARBO 5 material. The exact formulation of the drilling fluid and the test data is shown in Table 3. These tests indicated that the 1() ppg INNOVERT invert emulsion drilling fluid containing 6 ppb C36 dimer diamine has effective low end rheology, that is, effective rheology even at low mud weights, and even without viscosifier/suspension agent additives such as TAIT-MODTm amorphous/fibrous material and BARACARB(0 5 fine grind bridging agent. Addition of C36 (linter diamine increased the PV by about 30% and increased the YP, ISYP and 10 minute Cie]
Strength by about 250% relative to the control (formulation 7).

Formulation 7 8 Control Invention formulation containing C36 dimer diamine Mud Weight (ppe) 10 10 Oil water ratio 70/30 70/30 XP-07 oil base, bbl 0.57 0.57 EZ MULO NT emulsifier, ppb 8.00 8.00 LIME, ppb 1.50 1.50 RHEMODO L suspension & viscosifyine agent, ppb 3.00 3.00 ADAPTA filtration control agent, ppb 1.50 1.50 CaC17 soln, ppb 120.90 120.90 REVDUST, ppb 20.00 20.00 BAROID, ppb 105.90 105.90 C36 dimer diamine, ppb 0 6.00 Hot roll at 250F for 16 hours FANN 35 Rheology at 120F
600 rpm 34 58 300 rpm 20 40 200 rpm 15 33 100 rpm 10 23 6 rpm 4 9 3 rpm 3 8 Tau 0 3.2 5.9 sec.gel 5 10 10 min. gel 5 18 -TABLE 3 continued FANN 75 RHEOLOGY¨for Formulation 8 Pressure in psi 0 1000 3000 6000 10,000 Temperature in 120 250 ()F
600 rpm 55 37 35 39 46 300 rpm 38 25 26 30 36 200 rpm 37 77 23 76 37 100 rpm 24 19 20 77 28 6 rpm 8 11 13 14 19 3 rpm 8 10 17 13 18 Tau 0 8.6 8.7 12.3 12.5 17.7 sec.gel - 9 9 10 14 I() min. gel - 8 9 19 16 10039]
Invert emulsion drilling fluids of the present invention were also prepared and laboratory tested with other commercially available mineral oil invert emulsion bases, particularly EDC 99-DVV mineral oil base, available from Total in Paris, France, ESCAID(0-110 mineral oil base, available from ExxonMobil, in IIouston, Texas, and XP-07 mineral oil base, available from Petrochem Carless in Wynnewood, Oklahoma and the United Kingdom.
More particularly, these samples had the formulations set forth in Table 4 below. Each formulation had a mud weight of 9 ppg and an oil:water ratio of 60:40. After hot rolling at 250"F for 16 hours, the sample theologies were evaluated with a FANN 35 rheomoter at I 20 F. Test data are shown in Table 4 and these results are graphed in Figure 4, showing the invention to be effective with a variety of commercially available mineral oil invert emulsion drilling fluid bases.

Formulation 9 10 11 Mud weight (ppg) 9 9 9 Oil water ratio 60/40 60/40 60/40 -EDC 99 DWI", oil base, (bbl) 0.51 ESCAIDO 110 oil base (bbl) 0.502 - _ XP-07 oil base (bbl)- 0.5 EZ-MULC) NT (lb) emulsifier 9 9 9 Lime (lb) 3 3 3 RHEMOD L suspension & viscosifying agent, (lb) 3 3 3 ADAPTAO (lb) filtration control agent 2.5 2.5 2.5 20% Ca09 Brine (lb/bbl) 162.2 161.7 161.1 TAU-MODTm material, (lb) 5 5 5 REV DUST (lb) 20 20 20 Barite (lb) 27.3 31.8 36.25 BARACARBO 5 sized calcium carbonate (lb) 0 0 0 C36 dimer diamineõ (lb) 3 3 3 IIot roll temp ( F) 250 250 250 600 rpm 73 87 72 300 rpm 44 54 49 200 rpm 34 42 40 100 rpm 23 28 30 6 rpm 8.0 10.0 13.0 3 rpm 7.0 9.0 12.0 YIEI.D POINT 15 21 26 GELS 10 sec 8.0 10.0 13.0 GELS 10 min/30 min. 14/15 25/25 20/21 LSYP 6.0 8.0 11.0 TAU 6.5 7.82 10.2 ES. at 120 F 164 , 145 121 IIPHT 250 F, ml <1.0 I .8 2.0 100401 Haire 5 compares results from tests of the performance of 12 pp2 1NNOVERT invert emulsion drilling fluid (having an oil:water ratio of 70:30), with (Formulation 13) and without C36 dimer diamine (Formulation 12), hot rolled for 16 hours at 359 F. These results demonstrate the superior performance obtained with inclusion of a hydrophobic amine additive such as C36 dimer diamine. The formulation of the samples tested and the test results are set forth in Table 5 below. These results indicate that with the addition of the C36 dimer diamine, the PV increased by about 12.5% whereas the YP. LSYP

and the 10 min Gel Strength increased by about 200% relative to the fluids with out the additive.

Formulation number 12 13 Mud weight 12 12 Oil water ratio 70/30 70/30 EDC 99 DWTM oil base (bbl) 0.48 0.48 EZ-MUL0 NT emulsifier (lb) 9 9 FACTANTTm highly concentrated tall oil derivative (lb) 1 1 Lime (lb) 3 3 RHEMOD L suspension Sz. viscosifying agent, (lb) 3 3 ADAPTA(R) filtration control agent (lb) 3 3 20% CaC12 Brine (lb) 110.9 110.9 TAU-MOD "1 material (lb) 5 5 REV DUST (lb) 20 20 Barite (lb) 159.2 159.2 BARACARB05 sized calcium carbonate (lb) 50 50 C36 dimer diamine (lb) Nil 16 hour hot roll temperature F 350 350 600 rpm 71 92 300 rpm 39 56 200 rpm 28 43 100 rpm 18 29 6 min 5 11 3 rpm 4 10 GELS 10 sec 5 13 GELS 10 min/30 min. 9/12 25/27 TAU() 4.06 9./1 ES. 120 F 199 292 11P11'1 at 350 F, ml 3.2 2.4 100411 Figure 6 provides a graph showing the favorable characteristic "fragile gel"
"L" shape curve obtained in testing a 9 ppg INNOVERTO invert emulsion fluid formulated with C36 dimer diarnine. This Figure shows that even a low mud weight drilling fluid with a hydrophobic amine additive of the present invention demonstrates "fragile gel"
behavior relative to the fluid without the hydrophobic amine additive.
100421 Figures 7a and 7b provide graphs showing "fragile eel" behavior of example clay-free drilling fluids of the invention having mud weights of 16 and 18 ppg, respectively.
These graphs show that even at high mud weight and higher hot roll temperatures, a clay-free invert emulsion drilling fluid with the hydrophobic amine additive of the present invention demonstrates "fragile gel" behavior. Table 6 also shows another advantage of the invention¨that HPHT fluid losses of high mud weight drilling fluids with a hydrophobic amine additive of the invention are lower than otherwise comparable drilling fluids without the hydrophobic amine additive. In addition, the HPHT filtrate of these fluids without the hydrophobic amine additive showed an undesirable presence of a solid mass.
(00431 The formulations for the 16 and 18 ppg fluids, whose test results are graphed in Figures 7a and 7b, are shown in Table 6 below, along with the test data.

Formulation number 14 15 16 17 Invention Invention ControlControl Formulation Formulation Mud weight (ppg) 18 18 16 16 Oil water ratio 90/10 90/10 80/20 80/20 EDC 99 1)WT19 base oil, bbl 0.468 0.468 0.45 0.45 EZ MULO NT emulsifier, ppb 14 14 14 14 FACTANTTm ppb ? ? 9 9 Lime, ppb 3 3 3 3 RHEMODO L suspension &

viscosifying agent, ppb ADAPTAO filtration control 0 (1 3 3 agent, ppb BDF 366, ppb 3 3 0 0 CaCti brine, bbl 0.066 0.066 0.139 0.139 Rev Dust, ppb 20 20 20 20 BARACARBO 5 sized calcium carbonate, ppb I3AROID, ppb 546.2 546.2 387.4 387. 4 C36 climer diamine, ppb - 1 _ - 1 Hot Roll for 16 hours 375 F 375 l' 350 F 350 F

20f) 51 51 60 68 yp 11 16 ?-, _,-) 28 1() sec. act 1(1 16 24 -y) -_ min. gel 18 26 30 31 IIII1P nil in 30 min l0044] The advantages of the methods of the invention may be obtained by employing a drilling fluid of the invention in drilling operations. The drilling operations¨
whether drilling a vertical or directional or horizontal borehole, conducting a sweep, or running casing and cementing _____________________________________ may he conducted as known to those skilled in the art with other drilling fluids. That is, a drilling fluid of the invention is prepared or obtained and circulated through a wellbore as the wellbore is being drilled (or swept or cemented and cased) to facilitate the drilling operation. The drilling fluid removes drill cuttings from the wellbore, cools and lubricates the drill bit, aids in support of the drill pipe and drill bit, and provides a hydrostatic head to maintain the integrity of the wellbore walls and prevent well blowouts. The specific formulation of the drilling fluid in accordance with the present invention is optimized for the particular drilling operation and for the particular subterranean formation characteristics and conditions (such as temperatures). For example, the fluid is weighted as appropriate for the formation pressures and thinned as appropriate for the formation temperatures. The fluids of the invention afford real-time monitoring and rapid adjustment of the fluid to accommodate changes in such subterranean formation conditions.
Further, the fluids of the invention may be recycled during a drilling operation such that fluids circulated in a wellbore may be recirculated in the wellbore after returning to the surface for removal of drill cuttings for example. The drilling fluid of the invention may even be selected for use in a drilling operation to reduce loss of drilling mud during the drilling operation and/or to comply with environmental regulations governing drilling operations in a particular subterranean formation.
[0045] The foregoing description of the invention is intended to be a description of preferred embodiments. Various changes in the details of the described fluids and methods of use can be made without departing from the intended scope of this invention as defined by the appended claims.

Claims (17)

1. A method for drilling in a subterranean formation comprising providing or using in the drilling an invert emulsion drilling fluid having an oleaginous continuous phase, a non-oleaginous discontinuous phase, and a hydrophobic amine additive having the following general structure:
where R is a hydrophobic or partially hydrophobic group with carbon atoms ranging from about 16 to about 54, straight chained or branched, and aliphatic, cycloaliphatic or aryl aliphatic; N is a primary, secondary or tertiary amine wherein the R1 and R2 groups may be the same or different and are selected from the group consisting of a hydrogen group, alkyl group, cyano alkyl group, amino alkyl group, amino aryl group, hydroxyl alkyl group or a derivative thereof; alternatively the R1 and R2 can be a carbonyl group, carbonate group, alkoxy group, hydroxyl group or a derivative thereof; X comprises a hydrophilic group such as an amine which can be primary, secondary or tertiary with substituents being a hydrogen group, alkyl group, cyano alkyl group, amino alkyl group, amino aryl group, hydroxyl alkyl group or a derivative thereof; alternatively the X group can be an amide group, amine oxide group, betaine group, ester group, carboxylic acid group, ether group, hydroxyl group, phosphate group, phosphonate group, pyrrolidone group, haloformyl group, nitrate group, nitrite group, sulfate group, sulfonate group, imidazoline group, pyridine group, sugar group, or a combination or derivative thereof, wherein the drilling fluid with the hydrophobic amine additive, when compared to the drilling fluid without the hydrophobic amine additive, restricts the increase in plastic viscosity to 60% or less and has a characteristic selected from the group consisting of: an increased yield point; an increased low shear yield point; an increased gel strength; and any combination thereof.

2. The method of claim 1 wherein the drilling fluid is clay-free.

3. The method of claim 1 wherein the oleaginous phase comprises: a synthetic oil comprising an ester or olefin; a diesel oil; or a mineral oil selected from the group consisting of n-paraffins, iso-paraffins, cyclic alkanes, branched alkanes, and mixtures thereof.

4. The method of claim 1 wherein the drilling fluid has mud weight in the range of about 9 to about 18 ppg.

5. The method of claim 1 wherein the drilling fluid comprises from about 0.25 ppb to about 18 ppb of the hydrophobic amine additive.

6.. The method of claim 1 wherein the drilling fluid has an oil:water ratio in the range of about 50:50 to about 95:5.

7. The method of claim 1 wherein the aqueous solution contains a water activity lowering material selected from the group consisting of: sugar; glycerol;
salts selected from the group consisting of calcium chloride, calcium bromide, sodium chloride, sodium bromide, and formate; and combinations thereof.

8. The method of claim 1 wherein the drilling fluid with the hydrophobic amine additive, when compared to the drilling fluid without the hydrophobic amine additive, has a lower HPIIT fluid loss.

9. The method of claim 1 wherein the drilling fluid with the hydrophobic amine additive, under HPHT conditions, has enhanced YP, LSYP and gel strength but similar or lower PV, when compared to the drilling fluid without the hydrophobic amine additive.

10. The method of claim 1 where the invert emulsion fluid comprises at least one additive from the group consistina of: weiahting agents, inert solids, fluid loss control agents, emulsifiers, salts, dispersion aids, corrosion inhibitors, emulsion thinners, emulsion thickeners, viscosifier, HPHT emulsifier-filtration control agents, and any combination thereof.

11. The method of claim 1 further comprising drilling, running casing and/or cementing a wellbore in the subterranean formation.

12. An invert emulsion drillina fluid having a mud weight in the range of about 9 ppg to about 18 ppg, comprisina:
a natural or synthetic oil base;
an aqueous solution; and a rheology modifier comprising a hydrophobic amine having the following general structure:
where R is a hydrophobic or partially hydrophobic group with carbon atoms ranging in number from about 16 to about 54, straight chained or branched, and aliphatic, cycloaliphatic or aryl aliphatic; N is a primary, secondary or tertiary amine wherein the R1 and R2 groups may be the same or different and are selected from the group consisting of a hydrogen group, alkyl group, cyano alkyl group, amino alkyl group, amino aryl group, hydroxyl alkyl group or a derivative thereof; alternatively the R1 and R2 can be a carbonyl group, carbonate group, alkoxy group, hydroxyl group or a derivative thereof; X comprises a hydrophilic group such as an amine which can be primary, secondary or tertiary with substituents being a hydrogen group, alkyl group, cyano alkyl group, amino alkyl group, amino aryl group, hydroxyl alkyl group or a derivative thereof;
alternatively the X group can be an amide group, amine oxide group, betaine group, ester group, carboxylic acid 2roup, ether group, hydroxyl group, phosphate group, phosphonate group, pyrrolidone group, haloformyl group, nitrate group, nitrite group, sulfate group, sulfonate group, imidazoline group, pyridine group, sugar group, or a combination or derivative thereofõ
wherein the invert emulsion has an oil:water ratio of at least about 50:50;
wherein the drilling fluid with the hydrophobic amine rheology modifier, when compared to the drilling fluid without the hydrophobic amine rheology modifier, restricts the increase in plastic viscosity to 60% or less and has a characteristic selected from the group consisting of: an increased yield point; an increased low shear yield point; an increased gel strength; and any combination thereof.

13. The drilling fluid of claim 12 wherein the base oil comprises: a synthetic oil comprising an ester or olefin; a diesel oil; or a mineral oil selected from the group consisting of n-paraffins, iso-paraffins, cyclic alkanes, branched alkanes, and any mixture thereof.

14. The drilling fluid of claim 12 wherein the aqueous solution contains a water activity lowering material selected front the group consisting of: sugar; glycerol;
salts selected from the group consisting of calcium chloride, calcium bromide, sodium chloride, sodium bromide, and formate; and any combination thereof.

15. The drilling fluid of claim 12 comprising about 1 ppb to about 6 ppb of the rheoloey modifier.

16. A method for drilling in a high temperature subterranean formation comprising providing or using in the drilling an invert emulsion drilling fluid having a mud weight in the range of about 9 ppg to about 18 ppe, wherein the drilling fluid comprises a continuous oleaginous phase and a discontinuous non-oleaginous phase in an oil:water ratio in the range of about 50:50 to about 95:5, and a rheology modifier having the following general structure:
where R is a hydrophobic or partially hydrophobic group with carbon atoms ranging from about 16 to about 54, straight chained or branched, and aliphatic, cycloaliphatic or aryl aliphatic; N is a primary, secondary or tertiary amine wherein the R1 and R2 groups may be the same or different and are selected from the group consisting of a hydrogen group, alkyl group, cyano alkyl group, amino alkyl group, amino aryl group, hydroxyl alkyl group or a derivative thereof; alternatively the R1 and R2 can be a carbonyl group, carbonate group, alkoxy group, hydroxyl group or a derivative thereof; X
comprises a hydrophilic group such as an amine which can be primary, secondary or tertiary with substituents being a hydrogen group, alkyl group, cyano alkyl group, amino alkyl group, amino aryl group, hydroxyl alkyl group or a derivative thereof; alternatively the X group can he an amide group, amine oxide group, betaine group, ester group, carboxylic acid group, ether group, hydroxyl group, phosphate group, phosphonate group, pyrrolidone group, haloformyl group, nitrate group, nitrite group, sulfate group, sulfonate group, imidazoline group, pyridine group, sugar group, or a combination or derivative thereof, wherein the drilling fluid with the rheology modifier, when compared to the drilling fluid without the rheology modifier, restricts the increase in plastic viscosity to 60% or less and has a characteristic selected from the group consisting of: an increased yield point; an increased low shear yield point; an increased gel strength; and any combination thereof.

17. The method of claim 16 wherein the drilling fluid has an oleaginous phase selected front the group of oils consisting of: diesel oils; ester oils; olefins; and mineral oils selected front the group consisting of n-paraffins, iso-paraffins, cyclic alkanes, branched alkanes, and mixtures thereof.