CA2719610A1 - Fluid composition comprising anti-accretion additives and methods of use thereof - Google Patents
Fluid composition comprising anti-accretion additives and methods of use thereof Download PDFInfo
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Abstract
Fluids useful in drilling through high oil viscosity formations containing tar, sand and oil entrained therein are disclosed. The fluids comprise standard viscosifying and fluid loss additives along with effective concentration of an additive that may prevent the adherence of heavy oil laden drill cuttings to metal surfaces of drilling equipment.
Description
FLUID COMPOSITION COMPRISING ANTI-ACCRETION ADDITIVES AND
METHODS OF USE THEREOF
FIELD OF INVENTION
The invention relates to drilling fluids, drilling fluid additives and methods and, in particular, to drilling fluids, drilling fluid additives and methods useful for drilling oil wells through formations containing heavy oil or bitumen where it is useful to limit oil sands accretion on metal surfaces.
BACKGROUND OF THE INVENTION
When drilling through bituminous formations, accretion (or sticking) of the drill cuttings to the drill-string, bottom hole assembly or surface handling and solids control equipment may occur.
Such depositions impair the drilling operations and removal of said deposits may be required for continued drilling. Removal of the bituminous material from the drilling equipment can in some instances be achieved mechanically; however this requires halting of the drilling operations with the consequent decrease in productivity. A more economical solution to the problem of accretion may be the addition of certain chemicals to the aqueous-based drilling fluid that act to limit or possibly completely eliminate the accumulation of bitumen on drill components. The patent literature refers to several additives that act as anti-accretion additives. See for example US Patent 7081438 and US Patent Applications 2006/0003899, 2008/0214413, 2008/0217064, 2008/0045420, 2009/0099046 and 2009/0011960.
A desirable anti-accretion additive may improve the bitumen or heavy oil drilling operations by preventing the accretion of heavy oil to metal surfaces, preserving or increasing the heavy oil-mineral aggregate bond and possibly avoiding foaming of the aqueous-based drilling fluid to which is being added.
SUMMARY OF THE INVENTION
Thus, in accordance with a broad aspect of the present invention, there is provided an oil sand anti-accretion additive for drilling fluids to limit accretion of oil sands on metal surfaces comprising: at least one of an amine, an amide or a nitrogen containing heterocyclic compound.
WSLegal\049190\00049\ 5887768v4 1 In a further embodiment of the present invention there is provided an aqueous drilling fluid comprising an effective amount of an oil sand anti-accretion additive comprising: an effective amount of at least one of an amine, an amide or a nitrogen containing heterocyclic compound.
In accordance with another broad aspect of the present invention, there is provided a method for drilling a wellbore through an oil sand containing formation, the method comprising: operating a drilling assembly to drill a wellbore and circulating an aqueous-based drilling fluid through the wellbore as it is drilled; the aqueous-based drilling fluid including an oil sand anti-accretion additive including at least one of an amine, an amide or a nitrogen containing heterocyclic compound in an effective amount to limit oil sand accretion on metal surfaces.
In accordance with another broad aspect of the present invention, there is provided a method for limiting accretion on metal surfaces in contact with oil sand containing formations, the method comprising: washing the metal surfaces with an aqueous based drilling fluid, the aqueous-based drilling fluid including an oil sand anti-accretion additive including at least one of an amine, an amide or a nitrogen containing heterocyclic compound in an effective amount to limit oil sand accretion on metal surfaces.
It is to be understood that other aspects of the present invention will become readily apparent to those skilled in the art from the following detailed description, wherein various embodiments of the invention are shown and described by way of illustration. As will be realized, the invention is capable for other and different embodiments and its several details are capable of modification in various other respects, all without departing from the spirit and scope of the present invention.
Accordingly the drawings and detailed description are to be regarded as illustrative in nature and not as restrictive.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGURE 1 is a photograph depicting the accretion of oil sand on a steel shim in the absence of an anti-accretion additive;
FIGURE 2 is a photograph depicting the effect of 1, 3-propanediamine, Nl-(3-(tridecyloxy) propyl)-, branched on oil sand accretion on a steel shim;
WSLegal\049190\00049\ 5887768v4 2 FIGURE 3 is a photograph depicting the effect of fatty acids, tall-oil, reaction products with diethylenetriamine on oil sand accretion on a steel shim;
FIGURE 4 is a photograph depicting the effect octadecene dimethyl amine on oil sand accretion on a steel shim;
FIGURE 5 a photograph depicting the accretion of oil sand on a steel shim in the absence of anti-accretion additive at 50 C;
FIGURE 6 a photograph depicting the effect of fatty acids, tall-oil, reaction products with diethylenetriamine on oil sand accretion at 50 C on a steel shim;
FIGURE 7 a photograph depicting the effect of a mixture of fatty acids, tall-oil, reaction products with diethylenetriamine and amino triethyl phosphate ester on bitumen accretion at 50 C on a steel screen;
FIGURE 8 a photograph depicting the accretion of oil sand on a steel screen in the absence of anti-accretion additive;
FIGURE 9 a photograph depicting the effect of hexanedinitrile, hydrogenated, high-boiling fraction on oil sand accretion on a steel screen;
FIGURE 10 a photograph depicting the effect of a mixture of hexanedinitrile, hydrogenated, high-boiling fraction and amino triethyl phosphate ester on oil sand accretion on a steel screen;
FIGURE 11 a photograph depicting the effect of heavy oil accretions on a steel sleeve;
FIGURE 12 a photograph depicting the effect of a mixture of 0.5% morpholine on heavy oil accretions on a steel sleeve;
FIGURE 13 a photograph depicting the effect of 1.0% morpholine on heavy oil accretions on a steel sleeve;
FIGURE 14 a photograph depicting the effect of 0.5% amides of rapeseed oil and dimethylaminopropyl amine on heavy oil accretions on a steel sleeve;
WSLegal\049190\00049\ 5887768v4 3 FIGURE 15 is a photograph depicting the effect of 1.0% amides of rapeseed oil and dimethylaminopropyl amine on heavy oil accretions on a steel sleeve; and FIGURE 16 is a photograph depicting the effect of 0.5% pyridinium, 1-(phenylmethyl)-, alkyl derivatives, chlorides on heavy oil accretions on a steel sleeve.
DETAILED DESCRIPTION
The detailed description set forth below in connection with the appended drawings is intended as a description of the present invention and is not intended to represent the only embodiments contemplated by the inventor. The detailed description includes specific details for the purposes of providing a comprehensive understanding of the present invention. However, it will be apparent to those skilled in the art that the present invention may be practiced without these specific details.
In horizontal drilling operations, the drill string first bores a substantially vertical well, then at some predetermined point deviates from vertical in the build section.
Eventually the borehole may deviate 90 from vertical to become a horizontal well. The horizontal section of a well is designed to have increase well bore intersection with the oil-bearing formation. The drill string in a horizontal section of the well experiences increased torque due to the increased contact between the string and the horizontal well bore. Horizontal wells are advantageous in heavy oil, oil sand or bitumen production due to the low mobility of the oil. Horizontal wells offer inherent advantages over vertical wells in steam-assisted oil production. A significant portion of heavy oil deposits are found in unconsolidated formations, such as unconsolidated sand. The mixture of heavy oil or bitumen with this unconsolidated sand, often referred to as oil sands, makes the drill cuttings from these formations malleable. For the purposes of this description, the terms oil sand, heavy oil and bitumen and may be used interchangeably.
Deformation of these drill cuttings between the drill string and the formation or the drill string and the build section results in the adherence of a coating of the bitumen and sand on the drill string and casing. This coating is often referred to as accretion.
The present invention provides several chemicals that may be useful to limit oil sand accretions on metal surfaces or remove accretions already deposited. In this application, the term "limit"
WSLegal\049190\00049\ 5887768v4 4 has been used to mean, in its broadest sense, a reduction or removal of accretions using the present additive in comparison to the reduction or removal of accretions using non-additive containing fluids. In addition, the additives of the present invention can also prevent stripping of the heavy oil from the mineral aggregate. The additives may have limited foaming abilities, a property which may be beneficial for the drilling operations. The chemicals that are useful in the present invention belong to the chemical class of: an amine, a polyamine, an oxylated polyamine, an aminosilane, a nitrogen containing heterocycle, an amide, an alkylamidopolyamine, a polyamide, a Mannich amine, a melamine formaldehyde resin, a dicyandiamide resin, a polyamideamine, a polyethyleneimine, and a polyvinylamine.
These chemical classes may be useful in the present invention as an effective additive when applied in aqueous systems that may limit oil sand accretion on metal surfaces exposed to oil sand-containing formations. In addition, the additives of the present invention may also prevent stripping of the heavy oil from the mineral aggregate. The additives may have limited foaming abilities, a property which is beneficial for the drilling operations.
Possible examples of a suitable amine anti-accretion additive may include:
= polyamine;
= oxylated polyamine;
= aminosilane;
= alkylamidopoliamine;
= Mannich amine;
= melamine formaldehyde resin; and = polyamideamine.
Possible examples of a suitable polyamine anti-accretion additive may include:
= hexanedinitrile, hydrogenated, high-boiling fraction (CAS # 68411-90-5);
= dihexylenetriamine (CAS# 143-23-7);
WSLegal\049190\00049\ 5887768v4 5 = n-coco alkyl trimethylenediamine (CAS# 61791-63-7);
= fatty acids, tall-oil, reaction products with diethylenetriamine (CAS# 61790-69-0);
= tall oil reaction products with diethylenetriamine (CAS# 68140-14-7);
= 1,3-Propanediamine, N1-(3-(tridecyloxy)propyl)-, branched (CAS# 68479-04-9);
= n-tallow alkyltripropylene-tetraamine (CAS# 68911-79-5);
= n-tallow alkyl trimethylenediamine (CAS# 61791-55-7);
= 1,2-ethandiamine, polymer with aziridine (CAS#25987-06-8);
= polyethyleneimine (CAS #9002-98-6); and = polyvinylamines.
Possible examples of a suitable amide anti-accretion additive includes:
= Amides from diethylenetriamines and tall-oil fatty acids;
= Amides of rapeseed oil and dimethylaminopropyl amine;
= Polyamides; and = Dicyandiamide resins.
A possible example of a suitable nitrogen containing heterocyclic anti-accretion additive includes 1-(2-hydroyethyl)-2-alyl-2-imidazoline, alkyl derived from tall oil fatty acid (CAS#
61791-39-7), pyridinium, 1-(phenylmethyl)-, alkyl derivative chlorides (CAS #
100765-57-9) and morpholine (CAS# 110-91-8).
As can be noted from the above examples, the anti-accretion additives of the present invention may contain in their molecular structure at least one basic nitrogen functionality. Without being limited by theory, it is believed that the amine functionality of the anti-accretion additive may serve at least one of the following functions: (i) the basic nitrogen can form a salt with the acidic functional groups present in bitumen; and (ii) the ion pairing between the anti-accretion additive WSLegal\049190\00049\ 5887768v4 6 and the bituminous material may cause an increase in the softening temperature of bitumen and consequently the bitumen becomes less sticky. In addition, the anti-accretion additive may oil wet the solid aggregates to ensure a strong bond between the bitumen and solid aggregates present in oil sands.
Quaternary ammonium salts are known to cause foaming of the drilling fluid and precipitation of anionic viscosifying and fluid loss additives such as polycarboxylated cellulose and xanthan.
The use of the anti-accretion additives of the present invention in conjunction with quaternary ammonium salts may result in reduction of foaming and precipitation by decreasing the amount of quaternary ammonium salt required for achieving the anti-accretion activity.
The anti-accretion additives of the present invention can be employed at a broad concentration range of 0.2 to 5.0% by weight of drilling fluid that is effective to limit oil sand accretion on metal surfaces. While lower concentrations may be effective, the additives are generally employed at concentrations of at least 0.5% by weight of the drilling fluid.
With economical considerations, an upper limit of 5.0% by weight of the drilling fluid has been employed but a narrower range of 0.5 to 2% has also demonstrated efficacy. However, concentrations above 5.0% can be employed if desired.
Aqueous-based drilling fluids, according to the present invention, include effective amounts of an amine, a polyamine, an oxylated polyamine, an aminosilane, a nitrogen containing heterocycle, an amide, an alkylamidopolyamine, a polyamide, a Mannich amine, a melamine formaldehyde resin, a dicyandiamide resin, a polyamideamine, a polyethyleneimine, and a polyvinylamine or mixtures thereof. While lower concentrations may be effective, the additive is generally employed at concentrations of at least 0.5% by weight of the drilling fluid. The drilling fluid may include water and additives such as, for example, viscosifying and fluid loss control additives, corrosion inhibitors, along with an oil sand anti-accretion additive according to the present invention. The anti-accretion additive can be added to the water before or after the addition of the viscosifying and fluid loss control additives. The anti-accretion additive may be dissolved in any suitable solvent prior to adding it to the drilling fluid.
The addition of defoamers may generally not be required as the anti-accretion additives of the present invention have none to very limited foaming ability. If foaming is encountered, defoamers may be added to the drilling fluid or to the anti-accretion additive. The present anti-accretion additives can be WSLegal\049190\00049\ 5887768v4 7 used in conjunction with other known anti-accretion additives such as phosphonates, phosphate esters of alkanolamines, quaternary ammonium salts, anionic polymers, cationic polymers, and nonionic polymers.
The drilling fluid may be useful to inhibit or remove oil sand accretion on metal surfaces. In one aspect, the drilling fluid can be used in a method for drilling a wellbore through an oil sand-containing formation. In such a method, without the present additive, drill cuttings can adhere as accretions to the metal surfaces of the drilling assembly, metal surfaces in the wellbore such as liners and casing and metal surfaces of the surface handling and solids control equipment. Thus, the present method includes circulating the aqueous-based drilling fluid, as described above, while operating a drilling assembly to drill the wellbore.
It will be appreciated that a drilling assembly can include, for example, a drill bit, drill string, and various control and monitoring subs.
It will also be appreciated, that it may not be necessary to use the oil sand anti-accretion additive-containing drilling fluid throughout an entire drilling operation. For example, it may not be required during drilling through over burden. The method is useful during drilling wherein oil sand drill cuttings are being produced and very useful where there is more frequent contact between metal surfaces such as, for example, during drilling of the build section and the horizontal section of a wellbore.
Where, during drilling using a drilling fluid according to the present invention, accretions are being deposited to an undesirable extent, the concentration of additive can be increased to inhibit further undesirable amounts of accretion and possibly to remove, at least to some degree, those accretions already deposited.
The drilling fluid of the present invention may also be used to reduce or remove accretions, which have already been built up on metal surfaces. Thus, in another aspect the drilling fluid can be used in a method for removing accretion from metal surfaces that have been in contact with oil sand-containing formation cuttings, the method comprising: washing the metal surfaces with an aqueous-based drilling fluid, the aqueous-based drilling fluid including an amount of at least one of an amine, a polyamine, an oxylated polyamine, an aminosilane, a nitrogen containing heterocycle, an amide, an alkylamidopolyamine, a polyamide, a Mannich amine, a melamine WSLegal\049190\00049\ 5887768v4 8 formaldehyde resin, a dicyandiamide resin, a polyamideamine, a polyethyleneimine, and a polyvinylamine in conjunction with a phosphonate, a phosphate ester of an alkanolamine, a quaternary ammonium salt, an anionic polymer, a cationic polymer and a non-ionic polymer.
In this method, the drilling fluid can be used, for example, to wash accretions from the drilling assembly such as the drill string, for the wellbore liners and casing. This method can also be used to facilitate running in of liners, such as a slotted liner into a wellbore where accretions have occurred. In so doing, the fluid may be circulated through the wellbore while the liner is run in. The removal of accretions may require washing over a period of time to remove a desired amount of accretions.
EXAMPLES
The following examples are presented to illustrate but not limit the scope of this invention. All percentages and parts are by weight unless otherwise noted.
Unless otherwise indicated, the examples are based on the following test procedure, which was developed to replicate accretion of the oil sand and heavy oil onto metal surfaces. In the test procedure, 350 mL of drilling fluid to be tested was added to a Waring commercial blender of 1L
capacity. The anti-accretion additive was added to the drilling fluid under mixing and the pH of the fluid adjusted to a range of 7 to 11 with sodium hydroxide, for example a pH of 10. The mixer was set to high speed and whilst mixing, oil sand of various oil to sand ratio or bitumen was added to the drilling fluid. The resultant drilling fluid and oil sand slurry was then mixed for a further 5 minutes to disperse the oil sand and ensure homogeneity.
The drilling fluid/tar sand mixture was then transferred into a 500 mL 316 stainless steel drilling fluid aging cell such as those supplied by Fann Instruments, having an internal diameter of 6.5 cm and a depth of 15.5. To simulate downhole assembly/shale shaker, pre-weighed mild steel shims or 130 mesh steel screen were inserted into the aging cell. The cell was sealed and placed horizontally in an aging cell roller oven similar to a Fann Instruments Model 701 Roller Oven with the temperature set at 25 C or 50 C. The rotary apparatus was turned on to rotate the cell at approximately 19rpm. After the desired aging time elapsed, the aging cells were removed from the roller oven; the steel shims of the steel screens were removed from the aging cell, rinsed under cold water to remove any loose material on the steel, then rinsed with methanol to remove WSLegal\049190\00049\ 5887768v4 9 water. The sleeves were left to dry and then reweighed. The heavy oil or bitumen adhesion was then calculated on a mass quantity per unit of exposed surface area and the level of accretion was visually verified.
Example 1 A sample of a drilling fluid was prepared using 350 mL of tap water containing 0.6% of a slurried polysaccharide and I% of a starch based fluid loss additive. A slurry was prepared using this fluid and 50g of oil sand as described in the test procedure. A steel shim of 15cm x 21cm was placed into the aging cell with the slurry and placed in a roller oven for 48 hours at 25 C.
The steel shim was removed and treated as described in the test procedure. oil sand accretion was evident on the shim as shown in Figure 1. The oil sand accretion was found to be 172 g oil sand/m2 steel, see Table 1. This example demonstrates the accretion of oil sand on simulated down-hole equipment when the drilling fluid is not treated with an anti-accretion additive.
Example 2 A drilling fluid was prepared by hydrating 0.6% of a slurried polysaccharide and 1% of a starch based drilling fluid in tap water. To 350 mL fluid 0.5% of an anti-accretion additive was added and the pH adjusted to 10. A slurry was prepared using this fluid and 50g of oil sand as described in the test procedure. A steel shim of 15cm x 21cm was placed into the aging cell with the slurry and placed in a roller oven for 48 hours at 25 C. The steel shim was removed and treated as described in the test procedure. The amount of oil sand accretion was quantified by calculating the weight difference between the steel shim before and after the test. The anti-accretion additives tested along with the amount of oil sand accretion/ m2 exposed surface area are given in Table 1. Figures 2 to 4 are photographs of the test results using various anti-accretion additives.
WSLegal\049190\00049\ 5887768v4 10 Anti-accretion additive Tar sand accretion (g/m2) No anti-accretion additive 172 1,3-Propanediamine, N 1-(3-(tridecyloxy)propyl)-, branched 0 N-tallow alkyltripropylene-tetraamine 0 N-coco alkyl trimethylenediamine 0 Fatty acids, tall-oil, reaction products with diethylenetriamine 0 Hexanedinitrile, hydrogenated, high-boiling fraction 0 Tallow trimethyl ammonium chloride* 0 Octadecene dimethyl amine ** 238 *Forms a large amount of foam.
**While not fully understood, it may be possible that a basic nitrogen group in this molecule, at the pH tested, does not have adequate oil wetting properties to facilitate limiting accretion.
Example 3 A drilling fluid was prepared by hydrating 0.6% of a slurried polysaccharide and I% of a starch based drilling fluid in tap water. To 350 mL fluid 0.25, 0.5, 1.0, and 2.0 %
of fatty acids, tall-oil, reaction products with diethylenetriamine or hexanedinitrile, hydrogenated, high-boiling fraction were added and the pH adjusted to 10. A slurry was prepared using this fluid and 50g of oil sands as described in the test procedure. A steel shim of 15cm x 21cm was placed into the aging cell with the slurry and placed in a roller oven for 48 hours at 25 C. The steel shim was removed and treated as described in the test procedure. The amount of oil sand accretion was quantified by calculating the weight difference between the steel shim before and after the test.
WSLegal\049190\00049\ 5887768v4 1 1 In both the tests with fatty acids, tall-oil, reaction products with diethylenetriamine and the tests with hexanedinitrile, hydrogenated, high-boiling fraction, all percentages tested demonstrated that the amount of accretion was Og/ m2 exposed surface area.
Example 4 A series of tests were performed to test the efficacy of the anti-accretion additives at elevated temperatures. A drilling fluid was prepared by hydrating 0.6% of a slurried polysaccharide and 1% of a starch based drilling fluid in tap water. To 350 mL fluid 0.25% of an anti-accretion additive was added and the pH adjusted to 10. A slurry was prepared using this fluid and 50g of oil sand or bitumen as described in the test procedure. A steel shim of 15cm x 21 cm was placed into the aging cell with the slurry and placed in a roller oven for 48 hours at 50 C. The steel shim was removed and treated as described in the test procedure. The amount of oil sand/bitumen accretion was quantified by calculating the weight difference between the steel shim before and after the test. The anti-accretion additives tested along with the amount of oil sand or bitumen accretion/ m2 exposed surface area are given in Table 2.
Figures 5 to 7 are photographs of the test results using various anti-accretion additives.
Anti-accretion additive Test sample Sample accretion (g/m ) No additive Tar sand 220 Fatty acids, tall-oil, reaction 4.7 products with diethylenetriamine Tar sand Fatty acids, tall-oil, reaction products with diethylenetriamine Bitumen Hexanedinitrile, hydrogenated, high-boiling fraction Tar sand N-coco alkyl trimethylenediamine Tar sand 0 WSLegal\049190\00049\ 5887768v4 12 Mixture of Fatty acids, tall-oil, reaction products with Bitumen diethylenetriamine and amino 0 triethyl phosphate ester Example 5 The same test procedure was followed as outlined in Example 2 using 130 mesh steel screen instead of the steel shim and 1% of anti-accretion additives were added. The test results are given in Table 3. Figures 8 to 10 are photographs of the test results in the absence and in the presence of the anti-accretion additive.
Anti-accretion additive Tar sand accretion (g/m ) No additive 189 hexanedinitrile, hydrogenated, high-boiling fraction 2 Mixture of hexanedinitrile, hydrogenated, high-boiling fraction and amino triethyl phosphate ester 30 Example 6 The same test procedure was followed as outlined in Example 2, except 1.0%
polyethyleneimine or 1,2-ethanediamine, polymer with aziridine were added to the fluid. For polyethyleneimine, 6 g/m2 of accretion was observed and for the 1,2-ethanediamine, polymer with aziridine, 9g/m2 of accretion was observed.
WSLegal\049190\00049\ 5887768v4 13 Example 7 A polymeric Mannich amine, the reaction product of polyacrylamide, formaldehyde and dimethylamine was also tested using the test procedure outlines in Example 2.
The additive was added at 2% and 30g/m2 accretion was observed.
Example 8 A drilling fluid was prepared by adding 0.3% xanthan gum, 0.2% polyanionic cellulose and 0.8%
starch to tap water while being mixed. The pH of the resulting fluid was adjusted to 10 using sodium hydroxide and 350 mL of the resulting fluid was placed in a Waring blender, to which 35g of an oil sand sample was added along with various amine or amide additives listed below in Table 4. The mixture was sheared at high speed for 1 minute and the resulting slurry was transferred into a 500 mL drilling fluid ageing cell lined with a mild steel sleeve. The slurry was then placed in a roller oven and aged for 16 hours at 35 C. After which the sleeves were removed and loose oil rinsed off with water. Observations made on the sleeves are summarized in Table 4. FIG. 11 to 16 are photographs of the test results observed for Example 8.
Anti-accretion additive Concentration Observation No additive N/A Heavy Oil Accretion on Sleeve morpholine 0.5% Slight Accretion on Sleeve morpholine 1.0% Slight Accretion on Sleeve amides of rapeseed oil and 0.5%
dimethylaminopropyl Slight Accretion on Sleeve amine amides of rapeseed oil and 1.0%
dimethylaminopropyl Slight Accretion on Sleeve amine pyridinium, 1- 0.5%
(phenylmethyl)-, alkyl Very Slight Accretion on Sleeve derivatives, chlorides WSLegal\049190\00049\ 5887768v4 14 The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to those embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein, but is to be accorded the full scope consistent with the claims, wherein reference to an element in the singular, such as by use of the article "a" or "an" is not intended to mean "one and only one"
unless specifically so stated, but rather "one or more". All structural and functional equivalents to the elements of the various embodiments described throughout the disclosure that are know or later come to be known to those of ordinary skill in the art are intended to be encompassed by the elements of the claims. Moreover, nothing disclosed herein is intended to be dedicated to the public regardless of whether such disclosure is explicitly recited in the claims. No claim element is to be construed under the provisions of 35 USC 112, sixth paragraph, unless the element is expressly recited using the phrase "means for" or "step for".
WSLegal\049190\00049\ 5887768v4 15
METHODS OF USE THEREOF
FIELD OF INVENTION
The invention relates to drilling fluids, drilling fluid additives and methods and, in particular, to drilling fluids, drilling fluid additives and methods useful for drilling oil wells through formations containing heavy oil or bitumen where it is useful to limit oil sands accretion on metal surfaces.
BACKGROUND OF THE INVENTION
When drilling through bituminous formations, accretion (or sticking) of the drill cuttings to the drill-string, bottom hole assembly or surface handling and solids control equipment may occur.
Such depositions impair the drilling operations and removal of said deposits may be required for continued drilling. Removal of the bituminous material from the drilling equipment can in some instances be achieved mechanically; however this requires halting of the drilling operations with the consequent decrease in productivity. A more economical solution to the problem of accretion may be the addition of certain chemicals to the aqueous-based drilling fluid that act to limit or possibly completely eliminate the accumulation of bitumen on drill components. The patent literature refers to several additives that act as anti-accretion additives. See for example US Patent 7081438 and US Patent Applications 2006/0003899, 2008/0214413, 2008/0217064, 2008/0045420, 2009/0099046 and 2009/0011960.
A desirable anti-accretion additive may improve the bitumen or heavy oil drilling operations by preventing the accretion of heavy oil to metal surfaces, preserving or increasing the heavy oil-mineral aggregate bond and possibly avoiding foaming of the aqueous-based drilling fluid to which is being added.
SUMMARY OF THE INVENTION
Thus, in accordance with a broad aspect of the present invention, there is provided an oil sand anti-accretion additive for drilling fluids to limit accretion of oil sands on metal surfaces comprising: at least one of an amine, an amide or a nitrogen containing heterocyclic compound.
WSLegal\049190\00049\ 5887768v4 1 In a further embodiment of the present invention there is provided an aqueous drilling fluid comprising an effective amount of an oil sand anti-accretion additive comprising: an effective amount of at least one of an amine, an amide or a nitrogen containing heterocyclic compound.
In accordance with another broad aspect of the present invention, there is provided a method for drilling a wellbore through an oil sand containing formation, the method comprising: operating a drilling assembly to drill a wellbore and circulating an aqueous-based drilling fluid through the wellbore as it is drilled; the aqueous-based drilling fluid including an oil sand anti-accretion additive including at least one of an amine, an amide or a nitrogen containing heterocyclic compound in an effective amount to limit oil sand accretion on metal surfaces.
In accordance with another broad aspect of the present invention, there is provided a method for limiting accretion on metal surfaces in contact with oil sand containing formations, the method comprising: washing the metal surfaces with an aqueous based drilling fluid, the aqueous-based drilling fluid including an oil sand anti-accretion additive including at least one of an amine, an amide or a nitrogen containing heterocyclic compound in an effective amount to limit oil sand accretion on metal surfaces.
It is to be understood that other aspects of the present invention will become readily apparent to those skilled in the art from the following detailed description, wherein various embodiments of the invention are shown and described by way of illustration. As will be realized, the invention is capable for other and different embodiments and its several details are capable of modification in various other respects, all without departing from the spirit and scope of the present invention.
Accordingly the drawings and detailed description are to be regarded as illustrative in nature and not as restrictive.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGURE 1 is a photograph depicting the accretion of oil sand on a steel shim in the absence of an anti-accretion additive;
FIGURE 2 is a photograph depicting the effect of 1, 3-propanediamine, Nl-(3-(tridecyloxy) propyl)-, branched on oil sand accretion on a steel shim;
WSLegal\049190\00049\ 5887768v4 2 FIGURE 3 is a photograph depicting the effect of fatty acids, tall-oil, reaction products with diethylenetriamine on oil sand accretion on a steel shim;
FIGURE 4 is a photograph depicting the effect octadecene dimethyl amine on oil sand accretion on a steel shim;
FIGURE 5 a photograph depicting the accretion of oil sand on a steel shim in the absence of anti-accretion additive at 50 C;
FIGURE 6 a photograph depicting the effect of fatty acids, tall-oil, reaction products with diethylenetriamine on oil sand accretion at 50 C on a steel shim;
FIGURE 7 a photograph depicting the effect of a mixture of fatty acids, tall-oil, reaction products with diethylenetriamine and amino triethyl phosphate ester on bitumen accretion at 50 C on a steel screen;
FIGURE 8 a photograph depicting the accretion of oil sand on a steel screen in the absence of anti-accretion additive;
FIGURE 9 a photograph depicting the effect of hexanedinitrile, hydrogenated, high-boiling fraction on oil sand accretion on a steel screen;
FIGURE 10 a photograph depicting the effect of a mixture of hexanedinitrile, hydrogenated, high-boiling fraction and amino triethyl phosphate ester on oil sand accretion on a steel screen;
FIGURE 11 a photograph depicting the effect of heavy oil accretions on a steel sleeve;
FIGURE 12 a photograph depicting the effect of a mixture of 0.5% morpholine on heavy oil accretions on a steel sleeve;
FIGURE 13 a photograph depicting the effect of 1.0% morpholine on heavy oil accretions on a steel sleeve;
FIGURE 14 a photograph depicting the effect of 0.5% amides of rapeseed oil and dimethylaminopropyl amine on heavy oil accretions on a steel sleeve;
WSLegal\049190\00049\ 5887768v4 3 FIGURE 15 is a photograph depicting the effect of 1.0% amides of rapeseed oil and dimethylaminopropyl amine on heavy oil accretions on a steel sleeve; and FIGURE 16 is a photograph depicting the effect of 0.5% pyridinium, 1-(phenylmethyl)-, alkyl derivatives, chlorides on heavy oil accretions on a steel sleeve.
DETAILED DESCRIPTION
The detailed description set forth below in connection with the appended drawings is intended as a description of the present invention and is not intended to represent the only embodiments contemplated by the inventor. The detailed description includes specific details for the purposes of providing a comprehensive understanding of the present invention. However, it will be apparent to those skilled in the art that the present invention may be practiced without these specific details.
In horizontal drilling operations, the drill string first bores a substantially vertical well, then at some predetermined point deviates from vertical in the build section.
Eventually the borehole may deviate 90 from vertical to become a horizontal well. The horizontal section of a well is designed to have increase well bore intersection with the oil-bearing formation. The drill string in a horizontal section of the well experiences increased torque due to the increased contact between the string and the horizontal well bore. Horizontal wells are advantageous in heavy oil, oil sand or bitumen production due to the low mobility of the oil. Horizontal wells offer inherent advantages over vertical wells in steam-assisted oil production. A significant portion of heavy oil deposits are found in unconsolidated formations, such as unconsolidated sand. The mixture of heavy oil or bitumen with this unconsolidated sand, often referred to as oil sands, makes the drill cuttings from these formations malleable. For the purposes of this description, the terms oil sand, heavy oil and bitumen and may be used interchangeably.
Deformation of these drill cuttings between the drill string and the formation or the drill string and the build section results in the adherence of a coating of the bitumen and sand on the drill string and casing. This coating is often referred to as accretion.
The present invention provides several chemicals that may be useful to limit oil sand accretions on metal surfaces or remove accretions already deposited. In this application, the term "limit"
WSLegal\049190\00049\ 5887768v4 4 has been used to mean, in its broadest sense, a reduction or removal of accretions using the present additive in comparison to the reduction or removal of accretions using non-additive containing fluids. In addition, the additives of the present invention can also prevent stripping of the heavy oil from the mineral aggregate. The additives may have limited foaming abilities, a property which may be beneficial for the drilling operations. The chemicals that are useful in the present invention belong to the chemical class of: an amine, a polyamine, an oxylated polyamine, an aminosilane, a nitrogen containing heterocycle, an amide, an alkylamidopolyamine, a polyamide, a Mannich amine, a melamine formaldehyde resin, a dicyandiamide resin, a polyamideamine, a polyethyleneimine, and a polyvinylamine.
These chemical classes may be useful in the present invention as an effective additive when applied in aqueous systems that may limit oil sand accretion on metal surfaces exposed to oil sand-containing formations. In addition, the additives of the present invention may also prevent stripping of the heavy oil from the mineral aggregate. The additives may have limited foaming abilities, a property which is beneficial for the drilling operations.
Possible examples of a suitable amine anti-accretion additive may include:
= polyamine;
= oxylated polyamine;
= aminosilane;
= alkylamidopoliamine;
= Mannich amine;
= melamine formaldehyde resin; and = polyamideamine.
Possible examples of a suitable polyamine anti-accretion additive may include:
= hexanedinitrile, hydrogenated, high-boiling fraction (CAS # 68411-90-5);
= dihexylenetriamine (CAS# 143-23-7);
WSLegal\049190\00049\ 5887768v4 5 = n-coco alkyl trimethylenediamine (CAS# 61791-63-7);
= fatty acids, tall-oil, reaction products with diethylenetriamine (CAS# 61790-69-0);
= tall oil reaction products with diethylenetriamine (CAS# 68140-14-7);
= 1,3-Propanediamine, N1-(3-(tridecyloxy)propyl)-, branched (CAS# 68479-04-9);
= n-tallow alkyltripropylene-tetraamine (CAS# 68911-79-5);
= n-tallow alkyl trimethylenediamine (CAS# 61791-55-7);
= 1,2-ethandiamine, polymer with aziridine (CAS#25987-06-8);
= polyethyleneimine (CAS #9002-98-6); and = polyvinylamines.
Possible examples of a suitable amide anti-accretion additive includes:
= Amides from diethylenetriamines and tall-oil fatty acids;
= Amides of rapeseed oil and dimethylaminopropyl amine;
= Polyamides; and = Dicyandiamide resins.
A possible example of a suitable nitrogen containing heterocyclic anti-accretion additive includes 1-(2-hydroyethyl)-2-alyl-2-imidazoline, alkyl derived from tall oil fatty acid (CAS#
61791-39-7), pyridinium, 1-(phenylmethyl)-, alkyl derivative chlorides (CAS #
100765-57-9) and morpholine (CAS# 110-91-8).
As can be noted from the above examples, the anti-accretion additives of the present invention may contain in their molecular structure at least one basic nitrogen functionality. Without being limited by theory, it is believed that the amine functionality of the anti-accretion additive may serve at least one of the following functions: (i) the basic nitrogen can form a salt with the acidic functional groups present in bitumen; and (ii) the ion pairing between the anti-accretion additive WSLegal\049190\00049\ 5887768v4 6 and the bituminous material may cause an increase in the softening temperature of bitumen and consequently the bitumen becomes less sticky. In addition, the anti-accretion additive may oil wet the solid aggregates to ensure a strong bond between the bitumen and solid aggregates present in oil sands.
Quaternary ammonium salts are known to cause foaming of the drilling fluid and precipitation of anionic viscosifying and fluid loss additives such as polycarboxylated cellulose and xanthan.
The use of the anti-accretion additives of the present invention in conjunction with quaternary ammonium salts may result in reduction of foaming and precipitation by decreasing the amount of quaternary ammonium salt required for achieving the anti-accretion activity.
The anti-accretion additives of the present invention can be employed at a broad concentration range of 0.2 to 5.0% by weight of drilling fluid that is effective to limit oil sand accretion on metal surfaces. While lower concentrations may be effective, the additives are generally employed at concentrations of at least 0.5% by weight of the drilling fluid.
With economical considerations, an upper limit of 5.0% by weight of the drilling fluid has been employed but a narrower range of 0.5 to 2% has also demonstrated efficacy. However, concentrations above 5.0% can be employed if desired.
Aqueous-based drilling fluids, according to the present invention, include effective amounts of an amine, a polyamine, an oxylated polyamine, an aminosilane, a nitrogen containing heterocycle, an amide, an alkylamidopolyamine, a polyamide, a Mannich amine, a melamine formaldehyde resin, a dicyandiamide resin, a polyamideamine, a polyethyleneimine, and a polyvinylamine or mixtures thereof. While lower concentrations may be effective, the additive is generally employed at concentrations of at least 0.5% by weight of the drilling fluid. The drilling fluid may include water and additives such as, for example, viscosifying and fluid loss control additives, corrosion inhibitors, along with an oil sand anti-accretion additive according to the present invention. The anti-accretion additive can be added to the water before or after the addition of the viscosifying and fluid loss control additives. The anti-accretion additive may be dissolved in any suitable solvent prior to adding it to the drilling fluid.
The addition of defoamers may generally not be required as the anti-accretion additives of the present invention have none to very limited foaming ability. If foaming is encountered, defoamers may be added to the drilling fluid or to the anti-accretion additive. The present anti-accretion additives can be WSLegal\049190\00049\ 5887768v4 7 used in conjunction with other known anti-accretion additives such as phosphonates, phosphate esters of alkanolamines, quaternary ammonium salts, anionic polymers, cationic polymers, and nonionic polymers.
The drilling fluid may be useful to inhibit or remove oil sand accretion on metal surfaces. In one aspect, the drilling fluid can be used in a method for drilling a wellbore through an oil sand-containing formation. In such a method, without the present additive, drill cuttings can adhere as accretions to the metal surfaces of the drilling assembly, metal surfaces in the wellbore such as liners and casing and metal surfaces of the surface handling and solids control equipment. Thus, the present method includes circulating the aqueous-based drilling fluid, as described above, while operating a drilling assembly to drill the wellbore.
It will be appreciated that a drilling assembly can include, for example, a drill bit, drill string, and various control and monitoring subs.
It will also be appreciated, that it may not be necessary to use the oil sand anti-accretion additive-containing drilling fluid throughout an entire drilling operation. For example, it may not be required during drilling through over burden. The method is useful during drilling wherein oil sand drill cuttings are being produced and very useful where there is more frequent contact between metal surfaces such as, for example, during drilling of the build section and the horizontal section of a wellbore.
Where, during drilling using a drilling fluid according to the present invention, accretions are being deposited to an undesirable extent, the concentration of additive can be increased to inhibit further undesirable amounts of accretion and possibly to remove, at least to some degree, those accretions already deposited.
The drilling fluid of the present invention may also be used to reduce or remove accretions, which have already been built up on metal surfaces. Thus, in another aspect the drilling fluid can be used in a method for removing accretion from metal surfaces that have been in contact with oil sand-containing formation cuttings, the method comprising: washing the metal surfaces with an aqueous-based drilling fluid, the aqueous-based drilling fluid including an amount of at least one of an amine, a polyamine, an oxylated polyamine, an aminosilane, a nitrogen containing heterocycle, an amide, an alkylamidopolyamine, a polyamide, a Mannich amine, a melamine WSLegal\049190\00049\ 5887768v4 8 formaldehyde resin, a dicyandiamide resin, a polyamideamine, a polyethyleneimine, and a polyvinylamine in conjunction with a phosphonate, a phosphate ester of an alkanolamine, a quaternary ammonium salt, an anionic polymer, a cationic polymer and a non-ionic polymer.
In this method, the drilling fluid can be used, for example, to wash accretions from the drilling assembly such as the drill string, for the wellbore liners and casing. This method can also be used to facilitate running in of liners, such as a slotted liner into a wellbore where accretions have occurred. In so doing, the fluid may be circulated through the wellbore while the liner is run in. The removal of accretions may require washing over a period of time to remove a desired amount of accretions.
EXAMPLES
The following examples are presented to illustrate but not limit the scope of this invention. All percentages and parts are by weight unless otherwise noted.
Unless otherwise indicated, the examples are based on the following test procedure, which was developed to replicate accretion of the oil sand and heavy oil onto metal surfaces. In the test procedure, 350 mL of drilling fluid to be tested was added to a Waring commercial blender of 1L
capacity. The anti-accretion additive was added to the drilling fluid under mixing and the pH of the fluid adjusted to a range of 7 to 11 with sodium hydroxide, for example a pH of 10. The mixer was set to high speed and whilst mixing, oil sand of various oil to sand ratio or bitumen was added to the drilling fluid. The resultant drilling fluid and oil sand slurry was then mixed for a further 5 minutes to disperse the oil sand and ensure homogeneity.
The drilling fluid/tar sand mixture was then transferred into a 500 mL 316 stainless steel drilling fluid aging cell such as those supplied by Fann Instruments, having an internal diameter of 6.5 cm and a depth of 15.5. To simulate downhole assembly/shale shaker, pre-weighed mild steel shims or 130 mesh steel screen were inserted into the aging cell. The cell was sealed and placed horizontally in an aging cell roller oven similar to a Fann Instruments Model 701 Roller Oven with the temperature set at 25 C or 50 C. The rotary apparatus was turned on to rotate the cell at approximately 19rpm. After the desired aging time elapsed, the aging cells were removed from the roller oven; the steel shims of the steel screens were removed from the aging cell, rinsed under cold water to remove any loose material on the steel, then rinsed with methanol to remove WSLegal\049190\00049\ 5887768v4 9 water. The sleeves were left to dry and then reweighed. The heavy oil or bitumen adhesion was then calculated on a mass quantity per unit of exposed surface area and the level of accretion was visually verified.
Example 1 A sample of a drilling fluid was prepared using 350 mL of tap water containing 0.6% of a slurried polysaccharide and I% of a starch based fluid loss additive. A slurry was prepared using this fluid and 50g of oil sand as described in the test procedure. A steel shim of 15cm x 21cm was placed into the aging cell with the slurry and placed in a roller oven for 48 hours at 25 C.
The steel shim was removed and treated as described in the test procedure. oil sand accretion was evident on the shim as shown in Figure 1. The oil sand accretion was found to be 172 g oil sand/m2 steel, see Table 1. This example demonstrates the accretion of oil sand on simulated down-hole equipment when the drilling fluid is not treated with an anti-accretion additive.
Example 2 A drilling fluid was prepared by hydrating 0.6% of a slurried polysaccharide and 1% of a starch based drilling fluid in tap water. To 350 mL fluid 0.5% of an anti-accretion additive was added and the pH adjusted to 10. A slurry was prepared using this fluid and 50g of oil sand as described in the test procedure. A steel shim of 15cm x 21cm was placed into the aging cell with the slurry and placed in a roller oven for 48 hours at 25 C. The steel shim was removed and treated as described in the test procedure. The amount of oil sand accretion was quantified by calculating the weight difference between the steel shim before and after the test. The anti-accretion additives tested along with the amount of oil sand accretion/ m2 exposed surface area are given in Table 1. Figures 2 to 4 are photographs of the test results using various anti-accretion additives.
WSLegal\049190\00049\ 5887768v4 10 Anti-accretion additive Tar sand accretion (g/m2) No anti-accretion additive 172 1,3-Propanediamine, N 1-(3-(tridecyloxy)propyl)-, branched 0 N-tallow alkyltripropylene-tetraamine 0 N-coco alkyl trimethylenediamine 0 Fatty acids, tall-oil, reaction products with diethylenetriamine 0 Hexanedinitrile, hydrogenated, high-boiling fraction 0 Tallow trimethyl ammonium chloride* 0 Octadecene dimethyl amine ** 238 *Forms a large amount of foam.
**While not fully understood, it may be possible that a basic nitrogen group in this molecule, at the pH tested, does not have adequate oil wetting properties to facilitate limiting accretion.
Example 3 A drilling fluid was prepared by hydrating 0.6% of a slurried polysaccharide and I% of a starch based drilling fluid in tap water. To 350 mL fluid 0.25, 0.5, 1.0, and 2.0 %
of fatty acids, tall-oil, reaction products with diethylenetriamine or hexanedinitrile, hydrogenated, high-boiling fraction were added and the pH adjusted to 10. A slurry was prepared using this fluid and 50g of oil sands as described in the test procedure. A steel shim of 15cm x 21cm was placed into the aging cell with the slurry and placed in a roller oven for 48 hours at 25 C. The steel shim was removed and treated as described in the test procedure. The amount of oil sand accretion was quantified by calculating the weight difference between the steel shim before and after the test.
WSLegal\049190\00049\ 5887768v4 1 1 In both the tests with fatty acids, tall-oil, reaction products with diethylenetriamine and the tests with hexanedinitrile, hydrogenated, high-boiling fraction, all percentages tested demonstrated that the amount of accretion was Og/ m2 exposed surface area.
Example 4 A series of tests were performed to test the efficacy of the anti-accretion additives at elevated temperatures. A drilling fluid was prepared by hydrating 0.6% of a slurried polysaccharide and 1% of a starch based drilling fluid in tap water. To 350 mL fluid 0.25% of an anti-accretion additive was added and the pH adjusted to 10. A slurry was prepared using this fluid and 50g of oil sand or bitumen as described in the test procedure. A steel shim of 15cm x 21 cm was placed into the aging cell with the slurry and placed in a roller oven for 48 hours at 50 C. The steel shim was removed and treated as described in the test procedure. The amount of oil sand/bitumen accretion was quantified by calculating the weight difference between the steel shim before and after the test. The anti-accretion additives tested along with the amount of oil sand or bitumen accretion/ m2 exposed surface area are given in Table 2.
Figures 5 to 7 are photographs of the test results using various anti-accretion additives.
Anti-accretion additive Test sample Sample accretion (g/m ) No additive Tar sand 220 Fatty acids, tall-oil, reaction 4.7 products with diethylenetriamine Tar sand Fatty acids, tall-oil, reaction products with diethylenetriamine Bitumen Hexanedinitrile, hydrogenated, high-boiling fraction Tar sand N-coco alkyl trimethylenediamine Tar sand 0 WSLegal\049190\00049\ 5887768v4 12 Mixture of Fatty acids, tall-oil, reaction products with Bitumen diethylenetriamine and amino 0 triethyl phosphate ester Example 5 The same test procedure was followed as outlined in Example 2 using 130 mesh steel screen instead of the steel shim and 1% of anti-accretion additives were added. The test results are given in Table 3. Figures 8 to 10 are photographs of the test results in the absence and in the presence of the anti-accretion additive.
Anti-accretion additive Tar sand accretion (g/m ) No additive 189 hexanedinitrile, hydrogenated, high-boiling fraction 2 Mixture of hexanedinitrile, hydrogenated, high-boiling fraction and amino triethyl phosphate ester 30 Example 6 The same test procedure was followed as outlined in Example 2, except 1.0%
polyethyleneimine or 1,2-ethanediamine, polymer with aziridine were added to the fluid. For polyethyleneimine, 6 g/m2 of accretion was observed and for the 1,2-ethanediamine, polymer with aziridine, 9g/m2 of accretion was observed.
WSLegal\049190\00049\ 5887768v4 13 Example 7 A polymeric Mannich amine, the reaction product of polyacrylamide, formaldehyde and dimethylamine was also tested using the test procedure outlines in Example 2.
The additive was added at 2% and 30g/m2 accretion was observed.
Example 8 A drilling fluid was prepared by adding 0.3% xanthan gum, 0.2% polyanionic cellulose and 0.8%
starch to tap water while being mixed. The pH of the resulting fluid was adjusted to 10 using sodium hydroxide and 350 mL of the resulting fluid was placed in a Waring blender, to which 35g of an oil sand sample was added along with various amine or amide additives listed below in Table 4. The mixture was sheared at high speed for 1 minute and the resulting slurry was transferred into a 500 mL drilling fluid ageing cell lined with a mild steel sleeve. The slurry was then placed in a roller oven and aged for 16 hours at 35 C. After which the sleeves were removed and loose oil rinsed off with water. Observations made on the sleeves are summarized in Table 4. FIG. 11 to 16 are photographs of the test results observed for Example 8.
Anti-accretion additive Concentration Observation No additive N/A Heavy Oil Accretion on Sleeve morpholine 0.5% Slight Accretion on Sleeve morpholine 1.0% Slight Accretion on Sleeve amides of rapeseed oil and 0.5%
dimethylaminopropyl Slight Accretion on Sleeve amine amides of rapeseed oil and 1.0%
dimethylaminopropyl Slight Accretion on Sleeve amine pyridinium, 1- 0.5%
(phenylmethyl)-, alkyl Very Slight Accretion on Sleeve derivatives, chlorides WSLegal\049190\00049\ 5887768v4 14 The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to those embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein, but is to be accorded the full scope consistent with the claims, wherein reference to an element in the singular, such as by use of the article "a" or "an" is not intended to mean "one and only one"
unless specifically so stated, but rather "one or more". All structural and functional equivalents to the elements of the various embodiments described throughout the disclosure that are know or later come to be known to those of ordinary skill in the art are intended to be encompassed by the elements of the claims. Moreover, nothing disclosed herein is intended to be dedicated to the public regardless of whether such disclosure is explicitly recited in the claims. No claim element is to be construed under the provisions of 35 USC 112, sixth paragraph, unless the element is expressly recited using the phrase "means for" or "step for".
WSLegal\049190\00049\ 5887768v4 15
Claims (116)
1. A oil sand anti-accretion additive for drilling fluids to limit accretion of oil sands on metal surfaces comprising: at least one of an amine, an amide or a nitrogen containing heterocyclic compound.
2. The additive of claim 1, wherein the amine is a polyamine.
3. The additive of claim 1, wherein the amine is an oxylated polyamine.
4. The additive of claim 1, wherein the amine is an aminosilane.
5. The additive of claim 1, wherein the amine is an alkylamidopoliamine.
6. The additive of claim 1, wherein the amine is a Mannich amine.
7. The additive of claim 1, wherein the amine is a melamine formaldehyde resin.
8. The additive of claim 1, wherein the amine is a polyamideamine.
9. The additive of claim 2, wherein the polyamine is a hexanedinitrile, hydrogenated, high-boiling fraction.
10. The additive of claim 2, wherein the polyamine is a dihexylenetriamine.
11. The additive of claim 2, wherein the polyamine is an n-coco alkyl trimethylenediamine.
12. The additive of claim 2, wherein the polyamine is a fatty acids, tall-oil, reaction products with diethylenetriamine.
13. The additive of claim 2, wherein the polyamine is a tall oil reaction products with diethylenetriamine.
14. The additive of claim 2, wherein the polyamine is a 1, 3-Propanediamine, N1-(3-(tridecyloxy) propyl)-, branched.
15. The additive of claim 2, wherein the polyamine is an n-tallow alkyltripropylene-tetraamine.
16. The additive of claim 2, wherein the polyamine is an n-tallow alkyl trimethylenediamine.
17. The additive of claim 2, wherein the polyamine is a 1, 2-ethandiamine, polymer with aziridine.
18. The additive of claim 2, wherein the polyamine is a polyethyleneimine.
19. The additive of claim 2, wherein the polyamine is a polyvinylamine.
20. The additive of claim 1, wherein the amide is an amide from diethylenetriamine and tall-oil fatty acids.
21. The additive of claim 1, wherein the amide is an amide of rapeseed oil and dimethylaminopropyl amine.
22. The additive of claim 1, wherein the amide is a polyamide.
23. The additive of claim 1, wherein the amide is a dicyandiamide resin.
24. The additive of claim 1, wherein the nitrogen containing heterocycle anti-accretion additive is 1-(2-hydroyethyl)-2-alyl-2-imidazoline, alkyl derived from tall oil fatty acid.
25. The additive of claim 1, wherein the nitrogen containing heterocycle anti-accretion additive is morpholine.
26. The additive of claim 1, wherein the nitrogen containing heterocycle anti-accretion additive is pyridinium, 1-(phenylmethyl)-, alkyl derivatives, chlorides.
27. The additive of claim 1, further comprising a quaternary ammonium salt.
28. An aqueous drilling fluid comprising an effective amount of an oil sand anti-accretion additive comprising: an effective amount of at least one of an amine, an amide or a nitrogen containing heterocyclic compound.
29. The fluid of claim 28, wherein the amine is a polyamine.
30. The fluid of claim 28, wherein the amine is an oxylated polyamine.
31. The fluid of claim 28, wherein the amine is an aminosilane.
32. The fluid of claim 28, wherein the amine is an alkylamidopoliamine.
33. The fluid of claim 28, wherein the amine is a Mannich amine.
34. The fluid of claim 28, wherein the amine is a melamine formaldehyde resin.
35. The fluid of claim 28, wherein the amine is a polyamideamine.
36. The fluid of claim 29, wherein the polyamine is a hexanedinitrile, hydrogenated, high-boiling fraction.
37. The fluid of claim 29, wherein the polyamine is a dihexylenetriamine.
38. The fluid of claim 29, wherein the polyamine is an n-coco alkyl trimethylenediamine.
39. The fluid of claim 29, wherein the polyamine is a fatty acids, tall-oil, reaction products with diethylenetriamine.
40. The fluid of claim 29, wherein the polyamine is a tall oil reaction product with diethylenetriamine.
41. The fluid of claim 29, wherein the polyamine is a 1, 3-Propanediamine, N1-(3-(tridecyloxy) propyl)-, branched.
42. The fluid of claim 29, wherein the polyamine is an n-tallow alkyltripropylene-tetraamine.
43. The fluid of claim 29, wherein the polyamine is an n-tallow alkyl trimethylenediamine.
44. The fluid of claim 29, wherein the polyamine is a 1, 2-ethandiamine, polymer with aziridine.
45. The fluid of claim 29, wherein the polyamine is a polyethyleneimine.
46. The additive of claim 29, wherein the polyamine is a polyvinylamine.
47. The fluid of claim 28, wherein the amide is an amides from diethylenetriamine and tall-oil fatty acids.
48. The fluid of claim 28, wherein the amide from amides of rapeseed oil and dimethylaminopropyl amine.
49. The additive of claim 28, wherein the amide is a polyamide.
50. The fluid of claim 28, wherein the amide is a dicyandiamide resin.
51. The fluid of claim 28, wherein the nitrogen containing heterocycle anti-accretion additive is 1-(2-hydroyethyl)-2-alyl-2-imidazoline, alkyl derived from tall oil fatty acid.
52. The fluid of claim 28, wherein the nitrogen containing heterocycle anti-accretion additive is morpholine.
53. The fluid of claim 28, wherein the nitrogen containing heterocycle anti-accretion additive is pyridinium, 1-(phenylmethyl)-, alkyl derivatives, chlorides.
54. The fluid from claim 28, wherein the anti-accretion additive is neutralized to a pH of 7 to 11.
55. The fluid from claim 28, wherein the anti-accretion additive is neutralized to a pH of 10.
56. The fluid of claim 28, wherein the effective amount of anti-accretion additive is present in the fluid at a concentration between 0.2 and 5%.
57. The fluid of claim 28, wherein the effective amount of anti-accretion additive is present in the fluid at a concentration between 0.5 and 2%.
58. A method for drilling a wellbore through an oil sand containing formation, the method comprising: operating a drilling assembly to drill a wellbore and circulating an aqueous-based drilling fluid through the wellbore as it is drilled; the aqueous-based drilling fluid including an oil sand anti-accretion additive including at least one of an amine, an amide or a nitrogen containing heterocyclic compound in an effective amount to limit oil sand accretion on metal surfaces.
59. The method of claim 58, wherein the amine is a polyamine.
60. The method of claim 58, wherein the amine is an oxylated polyamine.
61. The method of claim 58, wherein the amine is an aminosilane.
62. The method of claim 58, wherein the amine is an alkylamidopoliamine.
63. The method of claim 58, wherein the amine is a Mannich amine.
64. The method of claim 58, wherein the amine is a melamine formaldehyde resin.
65. The method of claim 58, wherein the amine is a polyamideamine.
66. The method of claim 59, wherein the polyamine is a hexanedinitrile, hydrogenated, high-boiling fraction.
67. The method of claim 59, wherein the polyamine is a dihexylenetriamine.
68. The method of claim 59, wherein the polyamine is an n-coco alkyl trimethylenediamine.
69. The method of claim 59, wherein the polyamine is a fatty acids, tall-oil, reaction products with diethylenetriamine.
70. The method of claim 59, wherein the polyamine is a tall oil reaction product with diethylenetriamine.
71. The method of claim 59, wherein the polyamine is a 1, 3-Propanediamine, N1-(3-(tridecyloxy) propyl)-, branched.
72. The method of claim 59, wherein the polyamine is an n-tallow alkyltripropylene-tetraamine.
73. The method of claim 59, wherein the polyamine is an n-tallow alkyl trimethylenediamine.
74. The method of claim 59, wherein the polyamine is a 1, 2-ethandiamine, polymer with aziridine.
75. The method of claim 59, wherein the polyamine is a polyethyleneimine.
76. The method of claim 59, wherein the polyamine is a polyvinylamine.
77. The method of claim 58, wherein the amide is an amide from diethylenetriamine and tall-oil fatty acids.
78. The method of claim 58, wherein the amide is a polyamide.
79. The method of claim 58, wherein the amide is a dicyandiamide resin.
80. The method of claim 58, wherein the nitrogen containing heterocycle anti-accretion additive is 1-(2-hydroyethyl)-2-alyl-2-imidazoline, alkyl derived from tall oil fatty acid.
81. The method of claim 58, wherein the anti-accretion additive is neutralized to a pH of 7 to 11.
82. The method of claim 58, wherein the anti-accretion additive is neutralized to a pH of 10.
83. The method of claim 58, wherein the effective amount of anti-accretion additive is present in the fluid at a concentration between 0.2 and 5%.
84. The method of claim 58, wherein the effective amount of anti-accretion additive is present in the fluid at a concentration between 0.5 and 2%.
85. The method of claim 58, the anti-accretion additive further comprises a quaternary ammonium salt.
86. A method for limiting accretion on metal surfaces in contact with oil sand containing formations, the method comprising: washing the metal surfaces with an aqueous based drilling fluid, the aqueous-based drilling fluid including an oil sand anti-accretion additive including at least one of an amine, an amide or a nitrogen containing heterocyclic compound in an effective amount to limit oil sand accretion on metal surfaces.
87. The method of claim 80, wherein the amine is a polyamine.
88. The method of claim 80, wherein the amine is an oxylated polyamines.
89. The method of claim 80, wherein the amine is an aminosilane.
90. The method of claim 80, wherein the amine is an alkylamidopoliamine.
91. The method of claim 80, wherein the amine is a Mannich amine.
92. The method of claim 80, wherein the amine is a melamine formaldehyde resin.
93. The method of claim 80, wherein the amine is a polyamideamine.
94. The method of claim 81, wherein the polyamine is a hexanedinitrile, hydrogenated, high-boiling fraction.
95. The method of claim 81, wherein the polyamine is a dihexylenetriamine.
96. The method of claim 81, wherein the polyamine is an n-coco alkyl trimethylenediamine.
97. The method of claim 81, wherein the polyamine is a fatty acids, tall-oil, reaction products with diethylenetriamine.
98. The method of claim 81, wherein the polyamine is a tall oil reaction product with diethylenetriamine.
99. The method of claim 81, wherein the polyamine is a 1, 3-Propanediamine, N1-(3-(tridecyloxy) propyl)-, branched.
100. The method of claim 81, wherein the polyamine is an n-tallow alkyltripropylene-tetraamine.
101. The method of claim 81, wherein the polyamine is an n-tallow alkyl trimethylenediamine.
102. The method of claim 81, wherein the polyamine is a 1, 2-ethandiamine, polymer with aziridine.
103. The method of claim 81, wherein the polyamine is a polyethyleneimine.
104. The method of claim 81, wherein the polyamine is a polyvinylamine.
105. The method of claim 80, wherein the amide is an amide from diethylenetriamine and tall-oil fatty acids.
106. The method of claim 80, wherein the amide is amides of rapeseed oil and dimethylaminopropyl amine.
107. The method of claim 80, wherein the amide is a polyamide.
108. The method of claim 80, wherein the amide is a dicyandiamide resin.
109. The method of claim 80, wherein the nitrogen containing heterocycle anti-accretion additive is 1-(2-hydroyethyl)-2-alyl-2-imidazoline, alkyl derived from tall oil fatty acid.
110. The method of claim 80, wherein the nitrogen containing heterocycle anti-accretion additive is morpholine.
111. The method of claim 80, wherein the nitrogen containing heterocycle anti-accretion additive is pyridinium, 1-(phenylmethyl)-, alkyl derivatives, chlorides.
112. The method of claim 80, wherein the anti-accretion additive is neutralized to a pH of 7 to 11.
113. The method of claim 80, wherein the anti-accretion additive is neutralized to a pH of 10.
114. The method of claim 80, wherein the effective amount of anti-accretion additive is present in the fluid at a concentration between 0.2 and 5%.
115. The method of claim 80, wherein the effective amount of anti-accretion additive is present in the fluid at a concentration between 0.5 and 2%.
116. The method of claim 80, the effective amount of anti-accretion additive further comprises a quaternary ammonium salt.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US26645909P | 2009-12-03 | 2009-12-03 | |
| US61/266,459 | 2009-12-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2719610A1 true CA2719610A1 (en) | 2011-06-03 |
Family
ID=44114226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2719610A Abandoned CA2719610A1 (en) | 2009-12-03 | 2010-10-29 | Fluid composition comprising anti-accretion additives and methods of use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2719610A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104781194A (en) * | 2012-10-31 | 2015-07-15 | 贝克休斯公司 | Process for reducing the viscosity of heavy residual crude oil during refining |
| WO2015200241A1 (en) * | 2014-06-24 | 2015-12-30 | Schlumberger Norge As | Methods of inhibiting salt precipitation and corrosion |
| CN107686151A (en) * | 2017-07-25 | 2018-02-13 | 上海颢羟环保科技有限公司 | A kind of preparation method of water process coagulant |
-
2010
- 2010-10-29 CA CA2719610A patent/CA2719610A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104781194A (en) * | 2012-10-31 | 2015-07-15 | 贝克休斯公司 | Process for reducing the viscosity of heavy residual crude oil during refining |
| WO2015200241A1 (en) * | 2014-06-24 | 2015-12-30 | Schlumberger Norge As | Methods of inhibiting salt precipitation and corrosion |
| CN107686151A (en) * | 2017-07-25 | 2018-02-13 | 上海颢羟环保科技有限公司 | A kind of preparation method of water process coagulant |
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