RU2751621C2 - Friction-reducing compositions for use in drilling operations - Google Patents

Abstract

FIELD: drilling operations.SUBSTANCE: group of inventions relates to drilling for the development of natural resources. The friction-reducing composition includes one or more compounds described by the formula Xm-Ar-Rn, where Ar is mono- or a polycyclic aromatic fragment, each group X means a polar functional group that is not -(OC2H4)z, where z is an integer at least equal to 1, each group R is independently selected from a branched or unbranched, saturated or unsaturated, substituted or unsubstituted C1-C50hydrocarbon group, where n is an integer greater than or equal to 1, and where m is an integer greater than or equal to 0, if at least one group R is replaced by a functional group and/or the Ar group contains a heteroatom, and in other cases it is an integer greater than or equal to 1.EFFECT: reduced torque and coefficient of friction during drilling operations, which leads to an easier drilling process, especially drilling long boreholes.25 cl, 1 dwg, 4 tbl, 23 ex

Description

Priority claim

This application claims priority and advantage according to US patent application No. 62/439653, filed December 28, 2016, and European application No. 17160013.3, filed March 9, 2017, which are incorporated herein by reference in their entirety.

Cross-references to related claims

The present invention relates to US Application Nos. 2017-0002251 "Glycerol Carbamate Based Lubricant Compositions And Methods Of Making And Using Same", 2017-0002254 "Lubricant Compositions and Methods of Making and Using Same", 2017-0002252 "Lubricant Compositions and Methods of Making and Using Same ", 2017-0002253" Lubricant Compositions Containing Phosphates and / or Phosphites and Methods of Making and Using Same ", 2017-0002250" Lubricant Compositions Comprising Diol Functional Groups and Methods of Making and Using Same ", concurrently applied for US patent No. 62/439660 "Friction-Reducing Compositions for Use in Drilling Operations" and concurrently filed partially ongoing US patent application No. 2017-0107417 "Lubricant Compositions and Methods of Making and Using Same".

Scope of the present invention

The present invention relates to friction-reducing compositions suitable for drilling operations.

Background of the present invention

When drilling operations to develop natural resources in order to remove cuttings from the wellbore, lubricate and cool the drill bit, it is necessary to use a fluid that controls the pressure in the formation and maintains the stability of the well. Problems arise during drilling operations in many formations. For example, the horizontal displacement that occurs during extended reach drilling (ERD) is often limited by torsional and axial frictional losses. It is believed that such frictional losses are contributed by surface interactions such as rotation of the drill string. During extended reach drilling, frictional losses can be reduced by using a hydrocarbon-based drilling fluid such as an oil-based drilling fluid. Such drilling fluids are commonly used for many wells and for several years. Components are often added during use to replenish volume due to loss, component degradation and / or to correct properties. For example, additives can be added to the drilling fluid to further reduce frictional losses.

However, extended reach drilling may be more suitable if longer wellbores are effectively drilled. Thus, there is a need for the development of new friction-reducing compositions, for example, for use in drilling operations, especially in extended reach drilling.

References of interest include Suresh et al., "Synthesis, Structure, and Properties of Novel Polyols from Cardanol and Developed Polyurethanes," Ind. Eng. Chem. Res., Vol. 44, pp. 4504-4512 (2005), Ionescu et al., "Polyols and Rigid Polyurethane Foams from Cashew Nut Shell Liquid," J. Polym. Environ., V. 20, cc. 647-658 (2012) and Vorin et al, "Functionalization of Cardanol: Towards Biobased Polymers and Additives," Polym. Chem., Vol. 5, cc. 3142-3162 (2014), Gupta et al., "Preparation and characterization of electrically conducting Langmuir-Blodgett films of poly (N-octadecylaniline)," J. Coll. Int. Sci. 285, cc. 67 (2005), and Ito et al., "N-Alkyl Group-Substituted Poly (m-aniline) s: Synthesis and Magnetic Properties," Macromolecules 28 (16), cc. 5618-5626 (1995).

Brief Description of the Present Invention

It is an object of the present invention, in part, to discover that certain compositions, when added to an oil-based drilling composition, can significantly reduce the coefficient of friction observed in drilling operations. It is believed that such a reduction in the coefficient of friction could lead to improved drilling, especially long hole drilling.

Thus, in one aspect, the present application relates to methods for conducting drilling operations using an oil-based drilling composition. Such methods generally involve drilling for a period of time using an oil-based drilling composition followed by the addition of a friction-reducing composition comprising one or more compounds of Formula I:

where Ar is a mono- or polycyclic aromatic residue, each X group is a polar functional group, each R group is independently selected from a branched or unbranched, saturated or unsaturated C ₁ -C ₅₀ hydrocarbon group, n is an integer greater than or equal to 1, and where m is an integer greater than or equal to 0 if at least one R group is substituted with a functional group and / or the Ar group contains a heteroatom, and in another embodiment is an integer greater than or equal to 1. Basically, the friction-reducing composition is at least partially dispersible in the oil-based drilling composition during drilling operations. Preferably, the methods further comprise determining a torque limit for the drilling operation. In such objects, the friction reducing composition is generally added at a drilling torque of approximately ≥90% of the torque limit.

In another aspect, the present application relates to the targeted use of a friction reducing composition to reduce the torque of a drilling operation by at least 1%, more preferably at least 5%, and ideally preferably at least 10%. In yet another aspect, the present application relates to lubricating compositions comprising a blend product of an oil-based drilling composition and a friction-reducing composition.

Brief description of the figure

The figure is a schematic representation of the test protocol used to determine the coefficient of friction in examples 1-20.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE PRESENT INVENTION

All numerical values included in the detailed description and the appended claims are given in conjunction with the term "approximately" or "within" taking into account experimental errors and variance expected of one of ordinary skill in the art. Unless otherwise indicated, room temperature was approximately 23 ° C.

The terms "well" and "wellbore" as used herein are used interchangeably and may include, but are not limited to, an oil, gas or water well, injection well, or geothermal well. The term "wellbore" as used herein includes at least one wellbore. The wellbore can include vertical, deviated and horizontal sections, and can be straight, curved, or branched. The term "wellbore" as used herein means any cased and any uncased, open section of a wellbore. The near-wellbore area is the subterranean material and rock of the subterranean formation that surrounds the wellbore. The term "well" as used herein also includes the wellbore area. A near-wellbore area is generally approximately 10 feet from the wellbore. The term "downhole" as used herein means and includes penetration into any part of the wellbore, including the wellbore or near-wellbore area.

A portion of the wellbore can be an open hole or a cased hole. In an open section of a wellbore, a pipe or drill string may be positioned within the wellbore. The pipe or drill string circulates in the wellbore. In a cased section of a wellbore, casing is anchored and cemented into a wellbore, which may also contain tubing or drill string. The space between the two cylindrical shapes is called the annulus. Examples of annular space include, but are not limited to, the space between the wellbore and the outside of the pipe or drill string in the open section of the wellbore, the space between the wellbore and the outside of the casing in the open section of the wellbore, and the space between the interior of the casing. pipes and the outside of the pipes and drill string in the cased section of the wellbore.

The term "friction" as used in the present invention and the appended claims means the mechanical resistance and friction of the drill string against a cased hole and an open hole as the string and pipes move up and down, as well as when they rotate. In addition, the term also refers to the mechanical resistance of coiled tubing within a cased and open hole, insertion of casing, insertion of filters, insertion of clean-up, fracturing and perforating devices, rotation of the pipeline, advancement through the wellbore, removal of the pipeline and / or removal of coiled tubing. The term "drilling operations" as used in the present invention and the appended claims means the interaction of the cased hole and open hole drill string as the drill string and pipe is rotated forward and backward. In addition, the term also includes the movement of coiled tubing within a cased hole and an open hole, insertion of casing, insertion of filters, insertion of cleaners, fracturing and perforating devices, rotation of the drill string, advancing through the wellbore, removing the drill string and / or removal of flexible pipes.

The present invention and the appended claims used a new numbering scheme for the groups of the periodic system, as described in Chemical and Engineering News, vol. 63 (5), p. 27 (1985).

One of ordinary skill in the art knows that the hydroxyl groups in the compounds described herein are deprotonated. Thus, alcohols and / or phenols described in this context, for example, alkyl phenols and polyols, include salts formed by their reaction with a suitable counterion. Some suitable counterions include, but are not limited to, metals from groups 1-2, organic cations, for example, groups NR ₄ ⁺ and PR ₄ ⁺ , where each R group is independently selected from H and hydrocarbon groups.

In any embodiment of the present invention described in this context, the metals of groups 1-2 include Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, preferably Li, Na, K, Cs , Mg and Ca.

The terms "hydrocarbon radical", "hydrocarbon" and "hydrocarbon group" are used interchangeably in this context. Likewise, the terms "alkyl radical" and "alkyl" are used interchangeably in this context. Likewise, the terms "group", "radical" and "substituent" are used interchangeably in this context. The term "hydrocarbon radical" as used in the present invention means C ₁ -C ₅₀ radicals, which may be linear, branched or cyclic, and if cyclic, may be aromatic or non-aromatic. Substituted hydrocarbon radicals are radicals in which at least one hydrogen atom of the hydrocarbon radical is replaced by at least one functional group such as NR ₂ , OR, SeR, TeR, PR ₂ , AsR ₂ , SbR ₂ , SR, BR ₂ , SiR ₃ , GeR ₃ , SnR ₃ , PbR ₃ , etc., or at least one carbon atom of the hydrocarbon radical is replaced by at least one heteroatom or heteroatom containing a functional group.

The term "alkyl radical" used in the present invention and its interchangeable terms, for example, "alkyl", means substituted or unsubstituted aliphatic hydrocarbon radicals. For the avoidance of doubt, the term "alkyl radicals" includes both saturated hydrocarbon radicals and radicals with some degree of unsaturation, such as the presence of one or more double bonds. First of all, the term "alkyl radicals" used in this context means radicals that can be obtained from alkanes, alkenes and / or alkynes. Examples of such radicals include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl , cyclooctyl and the like, including substituted analogs thereof. Examples of suitable unsaturated radicals include, but are not limited to, ethenyl, propenyl, allyl, 1,4-butadienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, and the like, including substituted analogs thereof. The term "thioalkyl" means an alkyl group in which at least one carbon atom is replaced by a sulfur atom.

The term "aromatic" or "aromatic residue" means a stable mono- or polycyclic unsaturated residue, preferably containing from 3 to 14 carbon atoms, each of which may be substituted or unsubstituted. Basically, the term "aromatic" or "aromatic residue" means one or more cycles, each of which contains π-orbitals at each atom in the cycle, perpendicular to the plane of the cycle, and satisfies the Hückel rule. The term "aryl" or "aryl group" means an aromatic ring of 6 carbon atoms and their substituted analogs, including but not limited to phenyl, 2-methylphenyl, xylyl, and the like. Similarly, the term "heteroaryl" means an aryl group in which the ring carbon (or 2 or 3 ring carbon atoms) is replaced by a heteroatom, preferably N, O or S. The term "aromatic" as used herein also means substituted aromatic compounds. The term "substituted aromatic" means aromatic groups in which at least one hydrogen atom is replaced by a hydrocarbon group or by a substituted hydrocarbon group, or by a heteroatom or a group containing a heteroatom.

In the case of the existence of isomers of the indicated alkyl, alkoxide, aromatic groups (for example, n-butyl, iso-butyl, sec-butyl and tert-butyl), reference to one member of the group (for example, n-butyl) explicitly means the remaining isomers (for example , iso-butyl, sec-butyl and tert-butyl) families. Likewise, reference to an alkyl, alkoxide, aromatic or aryl group without specifying a specific isomer (eg, butyl) explicitly means all isomers (eg, n-butyl, iso-butyl, sec-butyl, and tert-butyl).

The term "primary carbon atom" used in this context means a carbon atom bonded to one carbon atom, the term "secondary carbon atom" means a carbon atom bonded to two carbon atoms, "tertiary carbon atom" means a carbon atom bonded to three carbon atoms, and "quaternary carbon atom" means a carbon atom bonded to four carbon atoms.

The term "cashew nut shell liquid (Cashew nut shell liquid)" means the liquid extracted from the cashew nut shell.

The term "heterogeneous mixture" used in this context means a composition containing two or more morphological phases in the same state. For example, a mixture of immiscible components, for example, oil and water, is considered heterogeneous, in which one component forms discrete inclusions dispersed in the matrix of the other component. By continuous phase is meant the matrix phase in a heterogeneous mixture. Discontinuous phase means a dispersed phase in a heterogeneous mixture.

Suitable friction-reducing compositions and / or compounds in friction-reducing compositions described in this context and in the appended claims may be described as "at least partially dispersible in an oil-based drilling composition under bulk drilling conditions". This description, as used in this context, refers to materials that are at least partially soluble and / or existing in a liquid state as a heterogeneous mixture in the bulk conditions of drilling operations. Such bulk conditions include temperatures from about 50 ° C, 60 ° C, 70 ° C, 80 ° C, 90 ° C, 100 ° C, or 125 ° C to about 170 ° C, pressures from atmospheric pressure to about 100 bar (10,000 kPa), 200 bar (20,000 kPa), 300 bar (30,000 kPa), 400 bar (40,000 kPa), 500 bar (50,000 kPa), or 600 bar (60,000 kPa). Desirably, at least 10% of the friction-reducing composition and / or compounds included in its composition is dispersible, and, for example, at least 20%, 30%, 40%, 50%, 60%, 70%, 80 %, 90%, 95%, 99%, or even 100%.

Kinematic viscosity (also called viscosity, Kv) was determined under standard ASTM D445 conditions, and is usually measured at 40 ° C (Kv40) or 100 ° C (Kv100). If no temperature is specified, the viscosity is KB100.

Friction-reducing composition

The friction-reducing compositions of the present invention comprise one or more compounds of Formula I:

where Ar is a mono- or polycyclic aromatic residue, each X group is a polar functional group, each R group is independently selected from a branched or unbranched, saturated or unsaturated, substituted or unsubstituted C ₁ -C ₅₀ hydrocarbon group, for example, C ₅ -C ₄₀ , C ₁₀ -C ₃₀ , C ₁₅ -C ₂₅ or C ₁₅ -C ₂₀ , where n is an integer greater than or equal to 1, and where m is an integer greater than or equal to 0, if at least one R group is substituted polar functional group and / or the Ar group contains a heteroatom, and in other cases m is an integer greater than or equal to 1. Preferably X is greater than or equal to 1. As known to those skilled in the art, although each m and n is an integer, suitable mixtures of two or more compounds with different numbers of X and / or R groups can be prepared. In such mixtures, the average value of m and n for the compound may not be an integer. Without wishing to be bound by theory, it is believed that the polar functional group (s) contained in the compound of Formula I promotes the adsorption of the compound to the surface in such a way that aromatic residues interact and thereby strengthen the adsorbed film, and the R group (s) promotes the formation of a lubricant. films with nearby adsorbed compounds.

Preferably, Ar is selected from the group consisting of an aryl group, a heteroaryl group, a biphenyl group, deprotonated cyclic C ₅ diolefins, and a polycyclic aromatic group. Suitable heteroaryl groups include, but are not limited to, pyridine, quinolone, acridine, pyrazine, imidazoline, thiophene, and benzothiophene. Suitable polycyclic aromatic groups include, but are not limited to, naphthalene, anthracene, indan, indene, and tetralin. Ar is often a phenyl group or a polycyclic aromatic group. First of all, preferably Ar is a phenyl group.

Preferably, each X group is individually selected from the group consisting of —OH (hydroxyl group), —OCH ₃ (methoxy group), —NH ₂ (amino group), —NO ₂ (nitro group), —CHO (aldehyde group), —CH ₃ OH (methanol group), —SO ₂ R (sulfonyl group), amines (eg polyamines), polyols, oxazolidines, metals of groups 1-2, NR ₄ ⁺ groups, PR ₄ ⁺ groups and a glycosyl group. First of all, preferably at least one X group is —OH. Preferably, each X group has a polarity of at least the same polarity as the —OCH ₃ group, more preferably a polarity higher than the —OCH ₃ group. For example, each X group may have a polarity in the range of the polarity of the —OCH ₃ group and the polarity of the —OH group. In most cases, the compound of Formula I is not an ethoxylate. For example, in most cases, each X group is not selected from groups of the structure - (OC ₂ H ₄ ) _z OH, where z is an integer of at least 1, generally in the range from 1 to 10. In most cases, if Ar is naphthalene group, then each X does not mean -OH.

Preferred R groups include ethyl, branched and unbranched isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octyladecyl, docadecyl, docyl tricosyl, tetracosyl and their unsaturated variants, primarily with unsaturation in the form of one or more double bonds. Particularly preferred R groups contain a carbon chain containing at least 10 carbon atoms, more preferably at least 15 carbon atoms. Optionally, one or more R groups may also include mixtures of alkyl groups, cycloalkyl groups, aromatic groups, and other similar hydrocarbon groups.

It was found that the number of carbon atoms adjacent to the α-carbon atom with respect to Ar affects the oxidative stability of the R group, while the R groups containing a quaternary α-carbon atom with respect to Ar were the most stable, and the R groups containing a tertiary the α carbon atom with respect to Ar were less stable. Accordingly, branched R groups preferably contain a quaternary carbon atom with respect to Ar (i.e., a quaternary carbon atom directly bonded to Ar).

In most cases, at least one R group is substituted. For example, preferably at least one hydrogen atom in the hydrocarbon radical may be substituted with a polar functional group selected from the group consisting of —OH, —OCH _3, —NH ₂ , —NO ₂ , —CHO, —CH ₃ OH, —SO ₂ R, polyamines, polyols, oxazolidines, metals of groups 1–2, NR ₄ ⁺ groups, PR ₄ ⁺ groups and a glycosyl group, more preferably an —OH group. Preferably, the polar functional group is bonded to either the α or β carbon atom with respect to Ar, more preferably the α carbon atom. Alternatively or additionally, at least one carbon atom of the hydrocarbon radical (preferably an α or β carbon atom with respect to Ar, more preferably an α carbon atom) may be a substituted at least a heteroatom or a heteroatom-containing functional group. Preferred heteroatoms include S (sulfur), O (oxygen), N (nitrogen), and P (phosphorus). Preferred heteroatom-containing functional groups include carbonyl and amide.

The combination of an Ar moiety and an X group (s) in a compound of Formula I may be generally referred to as the "polar head" of the compound, and each R group (s) may be called an "alkyl tail". Preferably, the cross-sectional area of the polar head is proportional to the cross-sectional area of each alkyl tail. For example, the cross-sectional area of the polar head is preferably no more than 3 times the cross-sectional area of each alkyl tail, more preferably no more than 2 times.

In general, a compound of formula I may include several X groups and / or several R groups, for example, at least one of m or n is greater than or equal to 2. Preferably m may be 2, 3 or 4. Additionally or alternatively, n may be equal to 2, 3 or 4.

Preferably, the friction-reducing composition comprises at least one compound of formulas Ia, Ib or Ic:

where R, X, m and n are each as described above for Formula I. First of all, preferably, the friction-reducing composition comprises at least a compound of Formula Ia. Preferably, in a compound of formula Ia, one or more R groups are located in the meta or para position with respect to the X group, more preferably in the para position.

Suitable compounds of formulas Ia, Ib or Ic can be synthesized from petroleum-based precursors or derivatives from natural sources. Preferred compounds of formulas Ia, Ib or Ic include alkylphenols, alkylanisoles, alkylnaphthols, cashew shell liquid (CGS) components, thioalkylphenols, alkylbenzamides, alkylanilines and derivatives thereof. Particularly preferred are alkyl phenols and their derivatives, in particular containing at least 10 carbon atoms in the alkyl chain, i. E. C ₁₀ + alkylphenols. For example, especially the compounds of formula Ia include 4-dodecylphenol, 3-pentadecylphenol and cardanol.

In general, the compound of Formula I is at least partially dispersed in the oil-based drilling composition under the volumetric conditions of drilling operations. More preferably, the compound of Formula I is in a liquid state under volumetric drilling conditions. In addition, the compound of Formula I is generally reactively stable under the volumetric conditions of the drilling operation, that is, substantially no material is formed that is at least partially non-dispersible in the oil-based drilling composition under the volumetric conditions of the drilling operations. For example, in bulk drilling operations, a compound of Formula I typically reacts to form a material that is at least partially non-dispersed in an oil-based drilling composition at a rate of less than about 10 mol%. % per day, based on the total moles of the compound in the friction-reducing composition, more preferably less than about 5 mol. % per day and most preferably less than about 1 mol. % per day, such as about 0 mol. % per day. Additionally or alternatively, the compound of Formula 1 is typically not polymerized and / or crosslinked under bulk drilling conditions. For example, in bulk drilling operations, a compound of Formula 1 will typically crosslink and / or polymerize at a rate of less than about 10 mole percent. % per day, based on the total moles of the compound in the friction-reducing composition, more preferably less than about 5 mol. % per day and most preferably less than about 1 mol. % per day, such as about 0 mol. % per day. In another embodiment, the compound of Formula 1 does not include a crosslinking functional group, such as by reacting with a crosslinking agent or gelling agent, or otherwise allowing the compound to react to form a polymer structure, such as a gel. For example, preferably the compound of Formula 1 does not contain an epoxy group. More preferably, typically, the X group (s) of the compound of Formula 1 are not epoxy groups. In addition, typically the R group (s) of the compound of Formula 1 is not substituted with an epoxy group. Additionally or alternatively, the friction-reducing composition generally contains no or substantially no epoxy-functional compounds of Formula 1. More preferably, the friction-reducing composition generally contains no or substantially no epoxy-functional LSC components such as epoxy-functional cardanol. For example, the friction-reducing composition typically comprises less than about 0.5 wt. % epoxy-functional compounds of Formula 1, such as epoxy-functional cardanol, based on the weight of the friction reducing composition, more preferably less than about 0.1 wt. %, for example, about 0 wt. %.

Especially suitable compounds and / or classes of compounds of the formulas Ia, Ib or Ic are described below. The present invention is not limited to these compounds, and the use of other compounds within the broader scope of the invention is not excluded.

Components of ZhSOK

Suitable components of LSS of formulas Ia are represented by the following structures:

where w is 0, 2, 4, or 6.

Basically, each component of the LSS represented by the above formulas includes a mixture of compounds with varying degrees of saturation of the alkyl chain. For example, each component generally comprises from about 35 to about 60 wt. % monoene alkyl chains (w = 2) based on the total weight of the component, from about 45 to about 50 wt. %, about 15 to about 40 wt. % triene alkyl chains (w = 6) based on the total weight of the component, from about 25 to 30 wt. %, about 10 to about 20 wt. % diene alkyl chains (w = 4) based on the total weight of the component, from about 13 to about 18 wt. % and from about 3 to about 10 wt. % saturated alkyl chains (w = 0) based on the total weight of the component, for example, from about 4 to about 9 wt. %. The components of the LFA can be hydrogenated to increase the degree of saturation, i. E. increasing the proportion of molecules with w = 0 and decreasing the proportion of molecules with w> 0, preferably the number of molecules with w = 0 may be greater than about 10%, about more than 50%, about more than about 90%, or about more than about 99%.

Typically, the friction-reducing composition may contain a mixture of two or more LSC components. Suitable mixtures may include technical LSS. Typical examples, for example, technical LSS, include from about 50 to about 80 wt. % cardanol based on the total weight of the mixture, for example, from about 60 to about 75 wt. %, from 5 to 15 wt. % cardol based on the total weight of the mixture, for example, from about 10 to about 12 wt. %, and from about 0.5 to about 5 wt. % 2-methylcardol based on the total weight of the mixture, for example, from about 1 to about 3 wt. %. Additionally or alternatively, suitable mixtures may include cardanol and cardol in a ratio of from about 4: 1 to about 15: 1, for example, about 6: 1. Preferred mixtures include little or no anacardic acid, for example, less than about 5 wt. %, more preferably less than about 1 wt. % and ideally less than about 0.5 wt. % based on the total weight of the mixture. Suitable technical grade LSCs are available from Cardolite Corporation and Palmer International, Inc., such as NC-603 from Cardolite Corporation. Alternatively, the friction-reducing composition may contain purified cardanol, cardol and / or 2-methylcardol, preferably cardanol, isolated from LSC, for example, using vacuum distillation or solvent extraction. In most cases, the purified cardanol is hydrogenated. Examples of suitable commercially available purified cardanol include NX-2023 and NX-2024, both from Cardolite Corporation, and 1500-1 from Palmer International, Inc. A suitable product containing hydrogenated cardanol is NC-510 from Cardolite Corporation.

LAO and PAO based compounds

Suitable compounds of formulas Ia, Ib or Ic may contain linear α-olefin (LAO) or poly-α-olefin (PAO), especially functionalized aromatic compounds alkylated with LAO and / or PAO. The term "functionalized aromatic compound" used in the present invention means an aromatic residue functionalized with one or more polar functional groups. Preferred functionalized aromatics include phenol, anisole, and naphthol (resulting in alkylphenol, alkylanisole, or alkylnaphthol, respectively) after alkylation. Alkylation of functionalized aromatics using LAO and / or PAO can be accomplished by standard alkylation methods. The alkylation is often carried out in the presence of a catalyst, for example using an acidic ion exchange resin or zeolite. Preferred zeolites are alkylated at the para position. Examples of suitable LAO or PAO based compounds are represented by the following structures.

Particularly preferred PAOs containing one olefinic unsaturation, namely unhydrogenated PAOs, ngPAOs, are useful for preparing a compound of formulas Ia, Ib or Ic. ngPAO can be obtained by oligomerization of α-olefins with a number of carbon atoms in the range of C ₃ -C ₂₄ and with combinations thereof. The number average molecular weight of ngPAO Mn is in the range from 84 to 7000 Da, and the number of carbon atoms is from C ₆ to C ₅₀₀ . ngPAOs can be composed of dimers, trimers, tetramers, α-olefin pentamers, and the like. The oligomerization catalyst used to make ngPAO can be similar to any oligomerization catalyst used to make synthetic PAO-based lubricant base compositions. Examples include a metallocene oligomerization catalyst (U.S. Patent Nos. 2013/0090277 or 5,688,887 and 6,043401, each of which is incorporated by reference in its entirety), a supported chromium catalyst (U.S. Patent No. 5,171,915, which is incorporated herein by reference in its entirety ) or a Lewis acid catalyst including, but not limited to, catalysts BF ₃ or AlCl ₃ . Unsaturation in ngPAO can be characterized by vinylidene, trisubstituted, or vinyl olefin geometry. Alkylation of a functionalized aromatic compound can lead to the formation of a new carbon-carbon bond at the tertiary, secondary, or primary carbon atom in the PAO residue. Preferably, alkylation occurs at the tertiary carbon atom to form a compound with a quaternary α carbon atom with respect to the aromatic moiety. Such compounds are usually characterized by increased oxidation stability. The functionalized aromatic compounds alkylated with PAO may contain from 1 to 5 PAO residues. ngPAO or functionalized aromatic compounds alkylated with PAO can be any combination of the variants described in this context.

Alkylbenzamides and alkylanilines

Additional suitable compounds of formula Ia may include alkylbenzamides and / or alkylanilines. In most cases, suitable alkylbenzamides contain a nitro functionality, such as those represented by the following structures:

Compounds represented by the formulas above can be synthesized by amidation of benzoyl chloride with an alkylamine, for example oleylamine.

Especially suitable alkylanilines are compounds of the formulas Ia (i) and Ia (ii):

where R has the meaning described above for formula I. Alkylanilines with the structure represented by formula Ia (i) above can be synthesized according to the methods described in Gupta et al., "Preparation and characterization of electrically conducting Langmuir-Blodgett films of poly ( N-octadecylaniline), "J. Coll. Int. Sci. 285, 67 (2005). A particularly preferred alkylaniline of formula Ia (i) is N-octadecylaniline. Alkylanilines with the structure represented by formula Ia (ii) above can be synthesized first by the formation of halogenated alkylanilines according to the methods described in Ito et al., "N-Alkyl Group-Substituted Poly (m-aniline) s: Synthesis and Magnetic Properties. "Macromolecules, Vol. 28 (16), pp. 5618-5626, (1995), and then with the elimination of the halogen atom according to methods known in the art.

Thioalkylphenols

Additional suitable compounds of formula Ia may include thioalkylphenols. An example of a suitable thioalkylphenol includes BNX ™ 1037 from Mayzo, Inc. and is represented by the following formula:

Derivatives of compounds

Preferred compounds of formula Ia may be derivatives of any of the compounds described above, preferably derivatives derived from alkyl phenols, more preferably from cardanol. Suitable derivatives of cardanol include aminated cardanols, for example phenalkamines, polyols and Mannich base precursors, nitrated cardanols, sulfonated cardanols, and glycosyl-modified cardanols. Suitable analogous derivatives can be obtained from alkyl phenols with the exception of cardanol.

Suitable aminated cardanols can be synthesized by a Mannich base reaction between an aldehyde such as formaldehyde, cardanol and an amine. Preferred aminated cardanols are phenalkamines, i. E. compounds in which the amine used to form the aminated cardanol is a polyamine, for example ethylenediamine or diethyltriamine. An example of a suitable commercial phenalkamine is RAC-951LV from Palmer International Inc. following structure:

where w is 0, 2, 4, or 6.

Additional examples of suitable aminated cardanols are provided by the structures below:

where w is 0, 2, 4, and 6.

In general, suitable polyols contain at least 2 hydroxyl groups, for example 2, 3 or 4 hydroxyl groups. Suitable polyols can be synthesized according to the procedures described in Suresh et al., "Synthesis, Structure, and Properties of Novel Polyols from Cardanol and Developed Polyurethanes," Ind. Eng. Chem. Res., Vol. 44, pp. 4504-4512 (2005), primarily diols represented by the structure:

where w is 0, 2, 4, or 6.

Alternative methods for preparing polyols from Mannich base precursors are described in Ionescu et al., "Polyols and Rigid Polyurethane Foams from Cashew Nut Shell Liquid," J. Polym. Environ, vol. 20, cc. 647-658 (2012). These processes are usually carried out by reacting cardanol with an oxazolidine, for example N- (2-hydroxyethyl) -1,3-oxazolidine, to form a Mannich base (which itself is a suitable cardanol derivative of Formula Ia), followed by alkoxylation to form a polyol ...

Suitable glycosyl-modified cardanols can be represented by the following structure:

where w is 0, 2, 4, or 6. Glycosyl-modified cardanols, the structures shown above, can be synthesized by reacting cardanol with glucose pentaacetate in the presence of a Lewis acid, for example

BF ₃ -OEt ₂ .

Secondary component

The friction-reducing composition may optionally contain one or more secondary friction-reducing components. Secondary friction reducing components can be selected from nitrogen-containing compounds, esters, substituted imidazolines and amides (described in US patent No. 2017-0002252 "Lubricant Compositions and Methods of Making and Using Same"), from alkyldiols, especially alkyldiols in which an alkyl group is selected from C ₁₀ -C ₂₅ alkyl groups, for example, octadecane-1-2-diol (described in US patent No. 2017-0002254 "Lubricant Compositions and Methods of Making and Using Same"), glycerol carbamates, for example, oleylglycerol carbamates (described in the patent US No. 2017-0002251 "Glycerol Carbamate Based Lubricant Compositions and Methods of Making and Using Same"), alkylthioglycerols, for example, octadecylthioglycerol, and alkyl-substituted glycerols, for example, glycerol monostearate (described in US patent No. 2017-0002250 Groups and Methods of Making and Using Same "), phosphoric acid esters and dialkyl hydrogen phosphites such as trioleyloxy phosphate, and pegyliro a bath alkyl ester of a phosphoric acid ester (described in US patent No. 2017-0002253 "Lubricant Compositions Containing Phosphates and / or Phosphites and Methods of Making and Using Same") and oligomers / polymers derived from compounds described in this context, for example, phenolic resins (US patent application No. 62/439660 (serial number), patent register number 2017EM351 "Friction-Reducing Compositions for Use in Drilling Operations"), each of which is incorporated herein by reference in its entirety.

Suitable secondary friction reducing components include products such as Vikinol ™ 18, ColaLube ™ 3410, ColaLube ™ 3407, and additives under the trade name ColaMid ™. One or more secondary friction reducing components may be present in the friction reducing composition in an amount of ≥ about 5.0 wt. %, for example, ≥ about 10.0 wt. %), ≥ approximately 20.0 wt. %, ≥ approximately 50.0 wt. %, ≥ approximately 70.0 wt. % or ≥ approximately 90 wt. % based on the total weight of the friction reducing composition. Additionally or alternatively, one or more secondary friction reducing components may be present in the friction reducing composition in an amount of ≤ about 95 wt. %, for example, ≤ about 75.0 wt. %, ≤ approximately 50.0 wt. %, ≤ approximately 25.0 wt. %, ≤ approximately 20.0 wt. % or ≤ approximately 10.0 wt. % based on the total weight of the friction reducing composition. The ranges of the amounts of the secondary friction reducing component, which are explicitly set forth in this context, include ranges obtained from any combination of the above-described individual values, for example, from about 5.0 to about 95.0 wt. %, from about 10.0 to about 90.0 wt. %, from about 15.0 to about 85.0 wt. %, from about 20.0 to about 80.0 wt. %, from about 25.0 to about 75.0 wt. %, from about 30.0 to about 70.0 wt. %, from about 35.0 to about 65.0 wt. %, from about 40.0 to about 60.0 wt. %, from about 45.0 to about 55.0 wt. %, etc.

In another embodiment, the secondary friction reducing components may be absent or substantially absent from the friction reducing composition. For example, one or more secondary friction reducing components may be present in an amount of ≤ about 10 wt. %, or ≤ about 5 wt. %, or ≤ approximately 1 wt. %, or ≤ about 0.5 wt. %, ≤ approximately 0.1 wt. %, or about 0.0 wt. %. Additionally or alternatively, each of the following secondary friction reducing components may or may not be present in the friction reducing composition: substituted imidazolines, substituted amides, alkyldiols, glycerol carbamates, alkylthioglycerols, phosphates, and phosphites. For example, each of substituted imidazolines, substituted amides, alkyldiols, glycerol carbamates, alkylthioglycerols, phosphates, and phosphites may be present in an amount of ≤ about 10 wt. %, or ≤ about 5 wt. %, or ≤ approximately 1 wt. %, or ≤ about 0.5 wt. %, ≤ approximately 0.1 wt. %, or about 0.0 wt. %. Additionally or alternatively, combinations of the following secondary friction reducing components may or may not be present in the friction reducing composition: substituted imidazolines, substituted amides, alkyldiols, glycerol carbamates, alkylthioglycerols, phosphates, and phosphites. For example, combinations of substituted imidazolines, substituted amides, alkyldiols, glycerol carbamates, alkylthioglycerols, phosphates, and phosphites can be present in an amount of ≤ about 10 wt. %, or ≤ about 5 wt. %, or ≤ approximately 1 wt. %, or ≤ about 0.5 wt. %, ≤ approximately 0.1 wt. %, or about 0.0 wt. %.

Oil-based drilling composition

In general, a petroleum-based drilling composition may include a petroleum base and one or more oil-based additives. Preferably, the friction-reducing compositions described herein are absent or substantially absent from the oil-based drilling composition. Although the mechanisms are not fully understood, it is believed that such friction-reducing compositions included in an oil-based drilling composition will be lost over time through chemical decomposition, chemical interaction with other additives and / or adsorption on rock and cuttings. ... It has been found that some of these friction-reducing compositions present in an oil-based drilling composition may even degrade or interact with the formation over a period of time of components that can lead to an increase in the coefficient of friction compared to the coefficient of friction of the oil-based drilling composition. containing a friction-reducing composition.

Oil base

A large number of petroleum bases are known in the art. Specific base oils used in the present invention include natural oils and synthetic oils, as well as unconventional oils (or mixtures thereof) that can be used unrefined, refined, or doubly refined (the latter is also known as recovered or refined oils) ... Crude oil is oil obtained directly from a natural or artificial source and used without further refining. Such oils include direct dry distillation shale oil, direct first distillation oil and ester oil obtained directly from the esterification process. Refined oil is similar to the described crude oil except that the refined oil has been subjected to one or more refining stages to improve at least one basic property of the oil. Many purification methods are known to those skilled in the art. Such methods include solvent extraction, secondary distillation, acid extraction, base extraction, filtration, and gravity filtration. Re-refined oil is produced by methods similar to those that produce refined oil, but using oil that was previously used as a feedstock.

Groups I, II, III, IV, and V are broad categories of base oils developed and defined by the American Petroleum Institute (API Publication 1509; www.API.org) to develop guidelines for the use of base oils. The Group I base oil is characterized by a viscosity index of 80 to 120 and contains more than 0.03% sulfur and / or less than 90% saturated hydrocarbons. The Group II base oil is characterized by a viscosity index of 80 to 120 and contains ≤ 0.03% sulfur and / or ≥ 90% saturated hydrocarbons. The group III base oil is characterized by a viscosity index of more than 120 and contains ≤ 0.03% sulfur and / or more than 90% saturated hydrocarbons. Group IV base oils include polyolefins (PAO) and gas-to-liquid (GOL) materials. The Group V petroleum base includes bases not included in the bases of Groups I-IV. The table below summarizes the properties of each of these 5 groups.

Typical properties of base oils

Used GORs include petroleum bases described as highly refined hydrocarbon feeds, paragraphs [0245] - [0303] in US patent No. 2008/0045638. PAOs used in the present invention include PAOs described in paragraphs [0243] - [0266] in US patent No. 2008/0045638. Suitable Group III petroleum bases include those described in paragraphs [0304] - [0306] of US patent No. 2008/0045638.

Natural oils include animal oils, vegetable oils (eg castor oil and lard oil), and mineral oils. You can use animal and vegetable oils that are highly resistant to thermal oxidation. Among natural oils, mineral oils are preferred. Mineral oils vary widely in their source of origin, for example, they can be paraffinic, naphthenic or mixed paraffin-naphthenic. You can also use oils from coal or shale. Natural oils also differ in the way they are made and refined, for example in their distillation range and in their first distillation or cracking, hydroprocessing or solvent extraction methods. Petroleum bases of group II and / or group III, treated with hydroprocessing or hydrocracking, including synthetic oils, are also well known petroleum bases.

Synthetic oils include hydrocarbon oil. Hydrocarbon oils include oils such as polymerizable and copolymerizable olefins (eg, polybutylenes, polypropylenes, propylene-isobutylene copolymers, ethylene-olefin copolymers, and ethylene-α-olefin copolymers). Poly-α-olefinic (PAO) petroleum base is a well-known hydrocarbon synthetic oil. For example, you can use PAO from olefins C ₈ -C ₁₄ , for example, olefins C ₈ , C ₁₀ , C ₁₂ , C ₁₄ or mixtures thereof. Certain such PAOs are described in US Pat. Nos. 4,956,122, 4,827,064 and 4,827,073, each of which is incorporated herein by reference in its entirety.

The number average molecular weights of PAO, which are known materials and usually commercial products from suppliers such as ExxonMobil Chemical Company, Chevron Phillips Chemical Company, BP, etc., generally range from 250 to 3000 g / mol, although the kinematic viscosity of PAO typically up to 3500 cSt (100 ° C). PAOs typically include relatively low molecular weight hydrogenated α-olefin polymers or oligomers, which include, but are not limited to, C ₂ -C ₃₂ , C ₈ -C ₁₆ α-olefins such as 1-octene, 1-decene, 1 β-dodecene and the like, which are preferred. Preferred poly-α-olefins are poly-1-octene, poly-1-decene and poly-1-dodecene and mixtures thereof and polyolefins of mixed origin. However, dimers of higher olefins in the C ₁₄ -C ₁₈ range can be used to produce a base oil with low viscosity and acceptable low volatility. Depending on the degree of viscosity and the starting oligomer, PAO can be mainly trimers and / or tetramers of starting olefins with a trace amount of higher oligomers, characterized by a kinematic viscosity range from 1.5 to 3500 cSt (Kv100), such as from 1.5 to 12 cSt.

PAO fluids can be obtained in a simple manner by polymerizing an α-olefin in the presence of a polymerization catalyst such as Friedel-Crafts catalysts, including, for example, aluminum trichloride, boron trifluoride or complexes of boron trifluoride with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters such as ethyl acetate or ethyl propionate. For example, you can use the methods described in US patent No. 4149178 or 3382291. Other methods for the synthesis of PAO are described in US patent No. 3742082, 3769363, 3876720, 4239930, 4367352, 4413156, 4434408, 4910355, 4956122 and 5068487. Dimers C ₁₄ - C ₁₈ olefins are described in US Pat. No. 4,218,330. PAO can be prepared using a metallocene catalyst as described in Patent Nos. 8535514 and 8247358. Other suitable base fluids include non-standard base oils that have been processed, preferably catalytically, or synthesized to provide high performance.

Non-standard base oils / petroleum bases include one or more blends of oils derived from one or more HHI materials, as well as isomerate / isodewaxate based petroleum bases that are derived from natural wax or wax sources, sources of mineral and / or non-mineral oil wax, such as crude paraffin, natural waxes, and sources of waxes such as gas oil, oil from the bottom of the hydrocracker, wax raffinates, hydrocracking products, thermal cracked products or other mineral, mineral oil or even wax materials of non-petroleum origin, such as wax materials obtained from liquefied coal or shale oil, and mixtures of such raw materials.

GHL materials are materials resulting from one or more syntheses, combinations, transformations, rearrangements and / or destruction / degradation processes from gaseous carbon-containing materials, hydrogen-containing materials and / or elements as raw materials such as hydrogen, carbon dioxide , carbon monoxide, water, methane, ethane, ethylene, acetylene, propane, propylene, propyne, butane, butylenes and butynes. GHL base oils and / or base oils are base oils with a base oil viscosity that are typically derived from hydrocarbons, for example, waxy synthesized hydrocarbons derived from simpler gaseous carbon-containing compounds, hydrogen-containing compounds and / or elements as feedstocks. The HHF feedstock and / or petroleum base includes oils with a boiling point in the boiling range of the lubricating oil: (1) isolated / fractionated from synthesized HHF materials, such as, for example, materials obtained by distillation and which are then subjected to a final wax treatment step, which includes one of two or both catalyst dewaxing processes, or solvent dewaxing process to obtain low pour point / low pour point lubricating oils, (2) synthesized wax isomerizates, including, for example, hydrodewaxed or hydroisomerized catalyst and / or solvent dewaxed synthesized waxes or waxy hydrocarbons, and (3) dewaxed or hydroisomerized in the presence of a catalyst and / or solvent, Fischer-Tropsch (FT) materials (i.e. hydrocarbons, waxy hydrocarbons, waxes and possible similar oxidation products), preferably hydrodeparaffin dewaxed or hydroisomerized / followed by dewaxing in the presence of a catalyst and / or solvent of dewaxed waxy hydrocarbons FT, or hydrodewaxed or hydroisomerized, followed by dewaxing in the presence of a catalyst (or solvent) of dewaxed waxes FT or their mixtures.

GHL feedstock and / or base oil obtained from HHF materials, primarily from hydrodewaxed or hydroisomerized / dewaxed using a catalyst and / or solvent, wax or waxy feedstock, preferably feedstock and / or base oil obtained from FT materials, is usually characterized by kinematic viscosity at 100 ° C from 2 cSt to 50 cSt (ASTM D445). In addition, their pour point is -5 ° C to -40 ° C or less (ASTM D97). They are also characterized as having a viscosity index of 80 to 140 or more (ASTM D2270).

In addition, the GHL feedstock and / or base oil are usually highly paraffinic (more than 90% saturated hydrocarbons) and may contain mixtures of monocycloparaffins and polycycloparaffins in combination with non-cyclic isoparaffins. The ratio of naphthenic content (ie cycloparaffins) in such combinations varies depending on the catalyst used and the temperature. In addition, the GHL and / or base oil feeds are typically very low in sulfur and nitrogen, typically less than 10 ppm and more typically less than 5 ppm of each of these elements. The content of sulfur and nitrogen in the feedstock of GHL and / or petroleum base obtained from FT materials, primarily FT wax, is practically zero. In addition, the absence of phosphorus and aromatics makes these materials particularly suitable for the formation of products with a low content of sulphated ash and phosphorus (low SAP content).

The term "GHL feedstock and / or petroleum base and / or wax isomerate feedstock and / or petroleum base" encompasses individual fractions of such materials with viscosities in a wide range, recovered in the process of their production, as well as mixtures of one or two or more fractions with low viscosity with one, two or more fractions with high viscosity, characterized by the required kinematic viscosity.

The GHL material from which the HHF feedstock and / or base oil was (are) obtained is preferably an FT material (i.e., hydrocarbons, wax-like hydrocarbons, wax). In addition, the GHL feedstock and / or base oil are usually highly paraffinic (more than 90% saturated hydrocarbons) and may contain mixtures of monocycloparaffins and polycycloparaffins in combination with non-cyclic isoparaffins. The ratio of naphthenic content (ie cycloparaffins) in such combinations varies depending on the catalyst used and the temperature. In addition, the GHL and / or base oil feedstock and hydrodewaxed or hydroisomerized / catalytically (and / or solvent-based) dewaxed feedstock and / or base oil are usually very low in sulfur and nitrogen, generally less than 10 ppm or more. typically less than 5 ppm of each of these elements. The content of sulfur and nitrogen in the raw materials for hot liquids and / or base oils (petroleum base) obtained from FT materials, primarily FT wax, is practically zero. In addition, the absence of phosphorus and aromatics makes these materials particularly suitable for the formation of products with low sulfur content, sulphated ash and phosphorus (low SAP content).

Petroleum bases for use in the formed petroleum-based drilling compositions used in the present invention are any oils corresponding to API Groups I, II, III, IV and V oils and mixtures thereof, preferably oils of Groups II, III, IV and V, and mixtures thereof, more preferably oils of groups III-V, and mixtures thereof due to their exceptional volatility, stability, viscosity properties and purity. The presence of minor amounts of Group I feedstock, such as the amount used to dilute the additives for mixing with the formed lubricating oils, is acceptable, but should be present in a minimum amount, i.e. only those quantities are allowed which are associated with their use as diluents / carriers of additives for petroleum used as a basis "on a working weight basis". Even with respect to the group II feedstock, it is preferred that the group II feedstock is in the range of higher quality associated with the feedstock, i. E. raw materials of group II with a viscosity index in the range from 100 to 120.

Some petroleum bases may have an ester content of approximately ≤ 50 wt. %, for example, approximately ≤ 40 wt. %, approximately ≤ 30 wt. %, approximately ≤ 5.0 wt. % or approximately ≤ 1.0 wt. %. Additionally or alternatively, some petroleum bases may have an ester content of about ≥ 40 wt. %, approximately ≥ 50 wt. %, approximately ≥ 70 wt. % or approximately ≥90 wt. %.

Some petroleum bases may have an aromatics content of approximately ≤ 15.0 wt. %, for example, approximately ≤ 10.0 wt. %, approximately ≤ 5.0 wt. %, approximately ≤ 1.0 wt. %), approximately ≤ 0.50 wt. %, approximately ≤ 0.10 wt. %, approximately ≤ 0.05 wt. %, approximately ≤ 0.01 wt. % or approximately ≤ 0.005 wt. %. Additionally or alternatively, the aromatic content may be approximately ≥ 0.005 wt. %, for example, approximately ≥ 0.01 wt. %, approximately ≥ 0.05 wt. %, approximately ≥ 0.1 wt. %, approximately ≥ 0.5 wt. %, approximately ≥ 0.1 wt. %, approximately ≥ 1.0 wt. %, approximately ≥ 5.0 wt. % or approximately ≥ 10.0 wt. %. Ranges of aromatics content, explicitly given in this context, include all combinations of the above values, for example, from about 0.005 to about 15.0 wt. %, from about 0.01 to about 10.0 wt. %, from about 0.05 to about 5.0 wt. %, from about 0.10 to about 1.0 wt. % etc.

Some typical petroleum bases are characterized by their kinematic viscosity at 40 ° C (CV40). For example, petroleum bases may have a viscosity of approximately ≥ 1.0 cSt, for example, approximately ≥ 1.3 cSt, approximately ≥ 1.5 cSt, approximately ≥ 1.7 cSt, approximately ≥ 1.9 cSt, approximately ≥ 2.1 cSt , approximately ≥ 2.3 cSt, approximately ≥ 2.5 cSt, approximately ≥ 2.7 cSt, approximately ≥ 2.9 cSt, approximately ≥ 3.1 cSt, approximately ≥ 3.3 cSt, approximately ≥ 3.5 cSt, approximately ≥3.7 cSt, approximately ≥ 4.0 cSt, approximately ≥ 4.5 cSt, or approximately ≥4.8 cSt at 40 ° C. Additionally or alternatively, the viscosity at 40 ° C can be about 5.0 cSt, for example, about 4.8 cSt, about 4.5 cSt, about 4.0 cSt, about 3.7 cSt, approximately ≤ 3.5 cSt, approximately ≤ 3.3 cSt, approximately ≤ 3.1 cSt, approximately ≤ 2.9 cSt, approximately ≤ 2.7 cSt, approximately ≤ 2.5 cSt, approximately ≤ 2.3 cSt, approximately ≤ 2.1 cSt, approximately ≤ 1.9 cSt, approximately ≤ 1.7 cSt, approximately ≤ 1.5 cSt, approximately ≤ 1.3 cSt, or approximately ≤ 1.1 cSt at 40 ° C. Certain such base oils are marketed by ExxonMobil Chemical Company under the trade name Escaid ™, for example, Escaid ™ 110 includes a desulfurized hydrogenated hydrocarbon containing less than 0.50 wt. % aromatics and having a viscosity of approximately 1.7 cSt at 40 ° C, Escaid ™ 115 with a viscosity of approximately 2.1 cSt at 40 ° C, Escaid ™ 120 with a flash point above 100 ° C and Escaid ™ 120 ULA with an aromatics content less than 0.01 wt. %. Petroleum base additives

In most cases, oil-based drilling compositions contain additional additives. Preferably one or more additional additives form a heterogeneous mixture with the petroleum base. In such objects, the oil-based drilling composition is preferably a heterogeneous mixture containing the oil base as the continuous phase and one or more additional additives as the dispersed or internal phase. Alternatively, or additionally, one or more additional additives can be solubilized in the petroleum base.

For example, the oil-based drilling composition may include additional additives including, but not limited to, an internal phase, which is typically water or brine (i.e., the oil-based drilling composition is an inverse emulsion), a buffering agent for pH control, thickener and / or rheological modifier, emulsifier, wetting agent, weighting agent, fluid loss reducing agent, and friction reducing agent. Preferably, the oil-based drilling composition does not contain additives, especially thickeners and / or rheological modifiers containing amides and / or amines.

For example, a petroleum based drilling composition may include a pH control buffering agent selected from the group consisting of magnesium oxide, potassium hydroxide, calcium oxide, and calcium hydroxide. Commercial pH buffering products include lime. The pH buffering agent may be present at a concentration ranging from about 0.5 to 10.0 pounds per barrel (lb) of the oil-based drilling composition. The pH of a suitable oil-based drilling composition can range from about 7, 8, 9, 10, 11, or 12 to about 14, such as from 10 to 14.

The oil-based drilling composition may optionally include a thickener and / or rheology modifier. Suitable thickeners are selected from the group consisting of an inorganic thickener, fatty acids including, but not limited to, polycarboxylic fatty acid dimer and trimer, diamines, polyamines, organophilic clays, and combinations thereof. Suitable thickener commercial products include, but are not limited to, VG-PLUS ™ products from M-I Swaco and Schlumberger Company, RHEMOD L ™, TAU-MOD ™, RM-63 ™, and combinations thereof from Halliburton Energy Services, Inc. In one embodiment, the thickener and / or rheology modifier is present at a concentration of at least 0.5 lb. of the oil-based drilling composition. The thickener and / or rheology modifier may also be present in a concentration ranging from about 0.5 to about 20 lb, in another embodiment from about 0.5 to 10 lb of the oil-based drilling composition.

An oil-based drilling composition may also include a lubricant in addition to the friction-reducing composition described herein. In certain embodiments, the additional lubricant comprises a particulate material such as graphite such as Halliburton's Steelseal ™ product.

The oil-based drilling composition may also include an emulsifier. The emulsifier can be selected from the group consisting of tall oil fatty acid ester derivatives such as amides, amines, amidoamines and imidazolines obtained by reaction of fatty acids and various ethanolamine compounds, vegetable oil derivatives, and combinations thereof. Commercial products of a suitable emulsifier include, but are not limited to, EZ MUL ™ NT, INVERMUL ™ NT, LE SUPERMUL ™ and combinations thereof from Halliburton Energy Services, Inc., MEGAMUL ™, VersaMul ™, VersaCoat ™ from MISwaco, Schlumberger Company. In one embodiment, the emulsifier is present in at least a sufficient concentration such as to maintain the oil-based drilling composition in a stable emulsion or inverse emulsion state. In another embodiment, the emulsifier is present at a concentration of at least 1 lbf of the oil-based drilling composition. The emulsifier may also be present in a concentration ranging from about 1 to about 20 lb of the oil-based drilling composition.

The oil-based drilling composition may also contain a weighting additive. The weighting agent can be selected from the group consisting of barite, hematite, manganese tetroxide, calcium carbonate, and combinations thereof. Commercial weighting agent products include, but are not limited to, BAROID ™, BARACARB ™, BARODENSE ™ and combinations thereof from Halliburton Energy Services, Inc. and MICROMAX ™ from Elkem. In one embodiment, the weighting agent is present at a concentration of at least 10 lbf of the oil-based drilling composition. The weighting agent may also be present in a concentration in the range of about 10 to about 1000 lb, such as 10-800 lb of oil-based drilling composition.

The oil-based drilling composition may also contain a fluid loss reducing agent. The fluid loss reducing agent can be selected from the group consisting of oleophilic polymers, including crosslinked oleophilic polymers, particles. Commercial products of a suitable fluid loss agent include, but are not limited to, VERSATROL ™ from M-I Swaco, N-DRIL ™ HT PLUS, ADAPTA ™ from Halliburton Energy Services, Inc. The fluid loss reducing agent can be present at a concentration of from about 0.5 to about 10 lb of the oil-based drilling composition.

The oil-based drilling composition may also contain an ether additive. The ester additive can be present in a concentration ranging from about 1% to about 20%.

The oil-based drilling composition may optionally also contain one or more metal salts, MX _y , where M is a Group 1 or 2 metal, X is halogen, and y is 1 to 2. Examples of such salts include NaCl, KCl, CaCl ₂ , MgCl ₂ and the like. The total amount of such salts in an oil-based drilling composition is typically about 10-35 wt. % in the aqueous phase. Organic additives can also be used to reduce the activity of the water.

Water can also be present in the oil-based drilling composition at any suitable concentration, usually at a relatively low concentration, for example, about ≤ 15.0 wt. %, approximately ≤ 12.5 wt. %, approximately ≤ 10.0 wt. %, approximately ≤ 7.5 wt. %, approximately ≤ 5.0 wt. %, approximately ≤ 2.5 wt. % or approximately ≤ 1.0 wt. %, where the value of wt. % is based on the total weight of the base oil and water. In addition or in another embodiment, the concentration of water can be approximately ≥ 0.5 wt. %, for example, approximately ≥ 1.0 wt. %, approximately ≥ 2.5 wt. %, approximately ≥ 5.0 wt. %, approximately ≥ 7.5 wt. %, approximately ≥ 10.0 wt. %, approximately ≥ 12.5 wt. % or approximately ≥ 15.0 wt. %. In certain embodiments, the amount of water can be from about 1 to about 21 gallons per barrel of oil-based drilling composition, such as from about 1 to about 10 gallons per barrel of oil-based drilling composition. The explicit range of water content includes any of the above values, for example, from about 0.5 to about 20.0 wt. %, from about 0.5 to about 15.0 wt. %, from about 0.5 to about 12.5 wt. %, from about 0.5 to about 10.0 wt. %, from about 0.5 to about 7.5 wt. %, from about 0.5 to about 5.0 wt. %, from about 0.5 to about 2.5 wt. %, from about 0.5 to about 1.0 wt. %, from about 1.0 to about 10.0 wt. %, from about 1.0 to about 7.5 wt. %, from about 1.0 to about 5.0 wt. %, from about 1.0 to about 2.5 wt. %, from about 2.5 to about 10.0 wt. %, from about 2.5 to about 7.5 wt. %, from about 2.5 to about 5.0 wt. %, from about 5.0 to about 10.0 wt. %, from about 5.0 to about 7.5 wt. % etc.

The oil-based drilling composition may also include wetting agents. Wetting agents can be selected from the group consisting of tall oil fatty acid ester derivatives such as amides, amines, amidoamines and imidazolines obtained from the reaction of fatty acids and various ethanolamine compounds, vegetable oil derivatives, and combinations thereof. Commercial products of a suitable wetting agent include, but are not limited to, DrillTreat ™, OMC, Halliburton Energy Services, Inc., VersaWet ™ from MISwaco, Schlumberger Company. In one embodiment, the wetting agent is present in at least a sufficient concentration such as to maintain the oil-based drilling composition in a stable emulsion or inverse emulsion state. In another embodiment, the wetting agent is present at a concentration of at least 0.25 lbb of the oil-based drilling composition. The wetting agent may also be present in a concentration in the range of about 0.05 to about 20 lb, such as about 0.25 to about 20 lb of the oil-based drilling composition. In yet another embodiment, the oil-based drilling composition does not contain a wetting agent.

Lubricating compositions

The friction-reducing composition can be mixed with an oil-based drilling fluid to form a lubricating composition. In general, the friction-reducing composition is at least partially dispersed in the oil-based drilling composition under volumetric drilling conditions.

The oil-based drilling composition is usually present in the lubricant composition in an amount of about ≥ 50.0 wt. %, approximately ≥ 55.0 wt. %, approximately ≥ 60.0 wt. %, approximately ≥ 65.0 wt. %, approximately ≥ 70.0 wt. %, approximately ≥ 75.0 wt. %, approximately ≥ 80.0 wt. %, approximately ≥ 85.0 wt. %, approximately ≥ 90.0 wt. %, approximately ≥ 95.0 wt. % or approximately ≥ 97.0 wt. % based on the weight of the lubricant composition. In addition, or in another embodiment, the lubricating composition comprises about 99.0 wt. %, approximately ≤ 97.0 wt. %, approximately ≤ 95.0 wt. %, approximately ≤ 90.0 wt. %, approximately ≤ 80.0 wt. %, approximately ≤ 75.0 wt. %, approximately ≤ 70.0 wt. %, approximately ≤ 65.0 wt. %, approximately ≤ 60.0 wt. %, or approximately ≤ 55.0 wt. % oil-based drilling composition. Ranges for the amounts of an oil-based drilling composition in a lubricant composition include ranges obtained from any combination of the above values, for example, from about 50.0 to 99.0 wt. %, about 55.0 to 97.0 wt. %, about 60.0 to 95.0 wt. %, about 65.0 to 90.0 wt. %, about 70.0 to 85.0 wt. %, about 75.0 to 80.0 wt. %, about 70.0 to 95.0 wt. %, about 80.0 to 95.0 wt. % etc.

Preferably, the petroleum base is present in the lubricating composition in the ranges from about 50.0 to about 99.0 wt. %, from about 55.0 to about 97.0 wt. %, from about 60.0 to about 95.0 wt. %, from about 65.0 to about 90.0 wt. %, from about 70.0 to about 85.0 wt. %, from about 75.0 to about 80.0 wt. %, from about 70.0 to about 95.0 wt. %, from about 80.0 to about 95.0 wt. %. The friction-reducing composition is usually present in the lubricating composition in an amount of about ≥ 0.1 wt. %, for example, approximately ≥ 0.5 wt. %, approximately ≥ 1.0 wt. %, approximately ≥ 5.0 wt. %, approximately ≥ 10.0 wt. %, approximately ≥ 15.0 wt. %, or approximately ≥ 19.0 wt. %. In addition, or in another embodiment, the lubricating composition comprises about 20 wt. %, for example, approximately ≤ 19 wt. %, approximately ≤ 15 wt. %, approximately ≤ 10 wt. %, approximately ≤ 5.0 wt. %, approximately ≤ 1.0 wt. % or approximately ≤ 1.0 wt. % friction reducing composition. The ranges for the amounts of the friction-reducing composition in the lubricating composition include ranges derived from any combination of the above values, for example, from about 0.1 to about 20 wt. %, from about 1.0 to about 15 wt. %, from about 5.0 to about 10 wt. % etc. All weight percentages are based on the total weight of the oil-based drilling composition and the friction-reducing composition.

Lubricating compositions generally have a lower friction coefficient than an oil-based drilling composition. Some lubricating compositions have a coefficient of friction of approximately ≤ 0.40, for example, approximately ≤ 0.30, approximately ≤ 0.25, approximately ≤ 0.20, approximately ≤ 0.15, or approximately ≤ 0.10, or approximately ≤ 0.05 ... Additionally or alternatively, the coefficient of friction can be about ≥ 0.01, for example, about ≥ 0.03, about ≥ 0.05, about ≥ 0.10, about ≥ 0.20, or about ≥ 0.25, or about ≥ 0.30. The ranges of the coefficients of friction of the lubricant composition include ranges obtained from any combination of the above values, for example, from about 0.01 to about 0.40, from about 0.05 to about 0.30, from about 0.10 to about 0.25. , about 0.15 to about 0.20, and the like.

Additionally or alternatively, the lubricant composition can be characterized by a change in the coefficient of friction compared to the coefficient of friction of an oil-based drilling composition that does not contain a friction-reducing composition. In other words, the lubricating composition containing the friction-reducing composition has a coefficient of friction of at least about 5.0%, for example, at least about 10.0%, at least about 15.0%, at least about 20.0%, at least about 25.0%, at least about 30.0%, at least about 35.0%, at least about 40.0%, at least about 45.0%, at least about 45.0%, at least about 55.0%, at least about 60.0% less than the coefficient of friction of the drilling composition in the absence of the additive composition. Decrease in the coefficient of friction of a lubricant composition as compared to the coefficient of friction of an oil-based drilling composition that does not contain a friction-reducing composition include ranges derived from any combination of the above values, for example, less than about 5.0% to about 60%, less than about 10.0 to about 50.0%, less than about 15.0 to about 40.0%, less than about 20.0 to about 35.0%, less than about 25.0 to about 30.0%. For better understanding, a typical lubricant composition may contain 4.0 g of a friction reducing agent and 96.0 g of a petroleum-based drilling composition containing 86.0 g of a petroleum base and 10.0 g of other additives. The reduction in the coefficient of friction can be determined by comparing the coefficient of friction of this typical composition with the coefficient of friction of a composition comprising 86.0 g of a base oil and 10.0 g of other additives.

Typically, the lubricating composition contains no or substantially no crosslinking agents and / or gelling agents, for example, amines, and / or other compounds that accelerate the crosslinking and / or polymerization of the compound of Formula 1 present in the friction reducing composition. For example, preferably the lubricating composition comprises less than about 0.5 wt. % crosslinking and / or gelling agents based on the weight of the lubricating composition, more preferably less than about 0.1 wt. %, approximately 0 wt. %.

Drilling operations

The friction-reducing compositions described herein are suitable for any drilling operation. Friction reducing compositions are particularly useful in drilling operations characterized by operational and / or mechanical constraints. For example, drilling operations may be limited due to the torque limitations of the drilling rig. These torque limits may be due to the maximum torque that the drive can provide and / or the maximum torque that the drill string can withstand before metal damage begins, therefore, these limits differ from drill string to drill string due to either the size of the drive and / or used drill string. Torque can be measured using a special device (such as a torque tester) and / or by measuring the electrical energy consumed by the drive. Typically, drilling operations are performed using at least 10% safety factor between torque and torque limitation. When the torque approaches or exceeds an acceptable value, the achievable borehole length is limited. Operational changes can be made to reduce torque, such as slowing the penetration rate (forward drilling rate), removing accumulated cuttings from the wellbore, removing the drill string from the wellbore, and replacing / rebuilding worn components and / or reducing solids low density (crushed cuttings) from a circulating oil-based drilling composition. Such steps to reduce torque can be costly and time consuming, and can lead to only marginal benefits. Therefore, in certain applications, the addition of the friction-reducing compositions described herein is beneficial to reduce torque to increase penetration rates and / or to provide longer wellbore lengths.

It has been found that the friction-reducing compositions described in this context should be used in drilling operations only when it is necessary to reduce friction due to operational and / or mechanical constraints, such as torque constraints. Thus, preferred methods according to an aspect of the invention include introducing an oil-based drilling composition into the well, drilling the oil-based composition for a period of time, and sequentially injecting a friction-reducing composition into the well. In such objects, the torque limitation for drilling operations is usually defined. Basically, the torque limitation corresponds to the maximum torque that the drive can provide and / or the maximum torque that the drill string can handle before metal breaks. Preferably, the friction-reducing composition is injected into the wellbore at a drilling torque of approximately ≥ 90% of the torque limit, or approximately ≥ 95% of the torque limit, or approximately ≥ 99% of the torque limit.

Alternatively, or in addition in some aspects, it is preferred to use the friction-reducing compositions described herein to reduce torque. Preferably, the use is the targeted use of a friction-reducing composition comprising at least one compound of Formula I for reducing the torque of drilling operations when the torque reaches a threshold, for example, approximately ≥ 90% of the torque limitation or approximately ≥ 95% of the torque limitation, or approximately ≥ 99% of torque limitation. Preferably, the use of a friction-reducing composition reduces drilling torque by at least about 1%, more preferably at least about 2%, more preferably at least about 3%, more preferably at least about 5%, and more preferably at least about 10%. In other words, preferably, the drilling torque is about 99%, more preferably about 98%, more preferably about 97%, more preferably about 95%, and most preferably about 90% of the torque of similar drilling operations performed with using an oil-based drilling composition, but in the absence of a friction-reducing composition.

Typical methods of administering the friction-reducing compositions in drilling operations include mixing a friction-reducing composition comprising at least one compound of Formula I and at least one petroleum base composition to form a lubricating composition, and injecting the lubricating composition into the well. The injection steps may include pumping the lubricant composition down the well. Pumping can be done continuously, i.e. provide a continuous flow of lubricant composition, intermittently or cyclically, i. e. with alternating periods of the flow of the lubricant composition or its absence. Preferred methods further include continuously, intermittently, or cyclically providing a second amount of the friction-reducing composition in a lubricant composition already present in the wellbore. In some methods, the continuous supply of the friction-reducing composition provides an overall reduction in the amount of friction-reducing agent used in the drilling operation. Alternatively, a continuous supply of a friction-reducing agent may result in milder drilling operations. The well can be, but is not limited to, an oil production, gas production or water supply well, or an injection well. The methods may further include one or more of the steps of inserting the downhole tool into the wellbore.

The added lubricant composition can be maintained at temperatures ranging from about 50 ° C, 60 ° C, 70 ° C, 80 ° C, 90 ° C, 100 ° C or 125 ° C to about 170 ° C, and pressures from ambient pressure up to approx. 100 bar (10,000 kPa), 200 bar (20,000 kPa), 300 bar (30,000 kPa), 400 bar (40,000 kPa), 500 bar (50,000 kPa) or 600 bar (60,000 kPa). The introduced lubricating composition can be used while rotating the system elements at a speed of about ≤ 1000 rpm, for example, about ≤ 800 rpm, about ≤ 700 rpm, and about ≥ 0 rpm, such as from 1 to 1000 rpm min. The introduced lubricant composition can also be used with minimal rotation, but with longitudinal motion at a speed of ≤ 10000 m / h (meters per hour), ≤ 1000 m / h, ≤ 100 m / h and / or ≤ 10 m / h.

In an embodiment of the present invention, the well penetrates or is located adjacent to the formation. The drilling operations may further include the step of removing at least a portion of the lubricating composition after the insertion step. Drilling operations can include any number of additional optional steps. For example, some drilling operations include one or more of the following optional steps: installing and cementing drill pipes in the first well; installing a blowout preventer or lubricator in the upper part of the well, drilling at a distance from the well, the second well near the section of the first well so that the second well comes into working contact with the first well; installation and cementing of well pipes in the second well; installation of a blowout preventer or lubricator in the upper part of the second well; whereupon drilling from one first or second well continues down into the formation, and another well, which has not yet been drilled, is completely or partially filled with fluid, and the drilling tool is located in another well and the other well was sequentially closed so that access is possible to another borehole later, and the tool is left in the other borehole so that the tool can be used to connect to one first or second borehole in which drilling continues.

Other additional steps include one or more of the following steps: calculating the required fluid path for the well of interest versus the reference well, measuring the location of the well of interest versus the reference well along the wellbore, calculating the actual path of the well of interest based on at least at least a portion of the measured location of the borehole of interest compared to at least one reference borehole, comparing the actual path of the at least one borehole of interest to the desired path for the borehole of interest, and adjusting the drilling system to change the actual path in the borehole of interest based on the at least a portion of the deviation between the actual path of the well of interest and the desired path of the well of interest.

experimental part

The viscosity index was determined by the value of the kinematic viscosity according to the instructions of ASTM D2270-10e 1.

Kinematic viscosity was determined according to ASTM D445 guidelines.

The coefficient of friction (CT) was determined using a Falex Block-on-Ring instrument. The block is made of SAE 01 tool steel and the ring is made of SAE 4620 carbon steel. The block was 15.76 mm (0.620 in) long and 6.35 mm (0.250 in) wide. The outer diameter of the ring was 35 mm (1.377 inches) and the thickness was 8.15 mm (0.321 inches). The roughness of the _{block surface R a} was in the range from 0.10 μm to 0.20 μm. The roughness of the surface R _{a of the} ring was in the range from 0.15 μm to 0.30 μm. For each test, a new pair of block and ring was used.

For each example of a friction-reducing composition, a mixture was prepared containing an oil-based drilling composition and a friction-reducing composition. The mixture was then placed in a test cell of the Falex Block-on-Ring device, into which a new pair of block and ring was pre-installed. The interface between the block and the ring is completely immersed in the oil-based drilling composition.

Each test was started with an initial start-up period with a ring speed of 400 rpm, during which the block load applied to the ring gradually increased from 0 to 5 lbf, and then from 5 to 15 lbf, while the system was heated from ambient temperature to 75 ° C. Then, a series of three ramping cycles was carried out, consisting of a decreasing stage and an increasing stage. In the course of each stage of decreasing, the rotation speed of the ring decreased from 400 to 0 rpm at a rotation speed of 1 rpm, and in the course of each stage of the increase, the rotation speed of the ring increased from 0 rpm to 400 rpm at a rotation speed of 1 rpm. with. During some of these transitions, the rotation of the ring was stopped for 2 min to relax the system. The characteristics of the dependence of the coefficient of friction on the rotation speed in rpm, obtained at the stages of increasing, were quantitatively similar to the dependences obtained at the stages of decreasing. The characteristics of the dependence of the friction coefficient on the rotational speed in rpm, obtained in three stages of reduction, were averaged to obtain the registered relationship between the friction coefficient and the rotational speed in rpm. In some cases, the friction-reducing compositions investigated were tested several times, with the average being given. The test protocol is shown schematically in the figure.

Examples of

Amidation procedure for examples 15-18

Benzoyl chloride (1 eq.) And pyridine (1 eq.) Were dissolved in methylene chloride to give a solution with a concentration of 0.5 M. and the mixture was stirred for 5 hours. The reaction was stopped by adding 5% HCl over 30 minutes and extracted with methylene chloride. The organic portion was dried over MgSO ₄ , filtered and concentrated.

Example 1

In Example 1, a mixture was prepared containing 200 ml of a petroleum based drilling composition (Versaclean from M-I SWACO, Schlumberger company) and 6 ml of a standard friction reducing agent (Ultralube II from Integrity Industries, Inc., Kingsville, TX USA). The mixture was prepared by adding 6 ml of Ultralube II in 200 ml of an oil-based drilling composition at room temperature, after which the mixture was mixed on a Hamilton Beach 936-2 mixer at 10,000 rpm until complete mixing. As shown in table. 1, at 30 rpm, the mixture showed a 5% reduction in the friction coefficient compared to the oil-based drilling composition.

Example 2

Example 2 largely repeated Example 1, except that the composition contained approximately 200 ml of the oil-based drilling composition of Example 1 and 5.55 g of 3-pentadecylphenol from Sigma Aldrich (technical grade, 90%). As shown in table. 1, at 30 rpm, the mixture showed a 44% decrease in the friction coefficient compared to the oil-based drilling composition.

Example 3

Example 3 largely repeated Example 1 except that the composition contained approximately 200 ml of the oil-based drilling composition of Example 1 and 4.78 g of 4-dodecylphenol from Sigma Aldrich (isomer mixture). As shown in table. 1, at 30 rpm, the mixture had a 22% reduction in the friction coefficient compared to the oil-based drilling composition.

Example 4

Example 4 largely repeated Example 1, except that the composition contained approximately 200 ml of the oil-based drilling composition of Example 1 and 5.44 grams of Cardolite NX-2023, a high cardanol CNSL derivative from Cardolite Corporation. As shown in table. 1, at 30 rpm, the mixture had a 22% reduction in the friction coefficient compared to the oil-based drilling composition.

Example 5

Example 5 largely repeated Example 1, except that the composition contained approximately 200 ml of the oil-based drilling composition of Example 1 and 5.44 g of Cardolite NX-2024, a high cardanol CNSL derivative from Cardolite Corporation. As shown in table. 1, at 30 rpm, the mixture showed a 23% reduction in the friction coefficient compared to the oil-based drilling composition.

Example 6

Example 6 largely repeated Example 1 except that the composition contained approximately 200 ml of the oil-based drilling composition of Example 1 and 5.44 g of product 1500-1, a high cardanol CNSL derivative from Palmer International, Inc. As shown in table. 1, at 30 rpm, the mixture had a 38% reduction in the friction coefficient compared to the oil-based drilling composition.

Example 7

Example 7 largely repeated Example 1, except that the composition contained approximately 200 ml of the oil-based drilling composition of Examples 1 and 6, 11 grams of RAC-951LV, phenalkamine, obtained from the amination of Palmer's high cardanol CNSL derivative. International, Inc. As shown in table. 1, at 30 rpm, the mixture had a 12% reduction in the friction coefficient compared to the oil-based drilling composition.

Example 8

Example 8 largely repeated Example 1, except that the composition contained approximately 200 ml of the oil-based drilling composition of Example 1 and 7.61 g of a mixture of Mannich base isomers with the following structure:

The Mannich base of the structure shown above was synthesized according to the following procedure: the Mannich precursor N- (2-hydroxyethyl-1,3-oxazolidine) was prepared as described in the article Russian Journal of Applied Chemistry, vol. 85, cc. 81-84 (2012). Oxazolidine (5.0 g, 42.7 mmol) and cardanol (13.3 ml, 42.7 mmol) were heated at 70 ° C. for 2.5 hours. After cooling, the product was obtained as a viscous yellow liquid.

As shown in table. 1, at 30 rpm, the mixture of an oil-based drilling composition and a Mannich base showed a 12% reduction in the friction coefficient compared to an oil-based drilling composition.

Example 9

Example 9 largely repeated Example 1, except that the composition contained approximately 200 ml of the oil-based drilling composition of Example 1 and 8.42 g of glycosyl-modified cardanol prepared by the following procedure: pentaacylated glucose (20 g, 51.3 mmol) and pentadecylphenol (15.6 g, 51.3 mmol, Cardolite NX-2023) were dissolved in 100 ml of methylene chloride over molecular sieves with a pore diameter of 4 A. Boron trifluoride etherate catalyst (6.3 ml, 51.3 mmol) and the reaction mixture was stirred at room temperature for 24 h, then the reaction was stopped by adding 5% sodium bicarbonate solution. The organic layer was dried (MgSO ₄ ), filtered and concentrated.

As shown in table. 1, at 30 rpm, a mixture of an oil-based drilling composition and glycosyl-modified cardanol had a 14% reduction in friction coefficient compared to an oil-based drilling composition.

Example 10

Example 10 largely repeated Example 1, except that the composition contained approximately 200 ml of the oil base drilling composition of Example 1 and 6.25 g of Cardelox 1, ethoxylated cardanol, containing 1 mole of ethylene oxide per mole of cardanol from K2P Chemicals. As shown in table. 1, at 30 rpm, the mixture showed a -13% reduction in the friction coefficient compared to the oil-based drilling composition.

Example 11

Example 11 largely repeated Example 1 except that the composition contained approximately 200 ml of the oil-based drilling composition of Example 1 and 10.29 grams of Cardelox 6, ethoxylated cardanol, containing 6 moles of ethylene oxide per mole of cardanol from K2P Chemicals. As shown in table. 1, at 30 rpm, the mixture showed a -5% reduction in the friction coefficient compared to the oil-based drilling composition.

Example 12

Example 12 largely repeated Example 1, except that the composition contained approximately 200 ml of the oil-based drilling composition of Example 1 and 6.38 g of C14 LAO, an alkylated naphthol product, prepared by the procedure below. To a round bottom flask under nitrogen was added 2-naphthol (101.78 g, 0.71 mol), Amberlyst ™ 15H (2.34 g, 0.94 wt%) and 1-tetradecene (145.58 g, 0, 75 mol), LAO. This mixture was heated with stirring at 120 ° C for 3 days. The mixture was then cooled to 100 ° C, treated with activated carbon (5.0 g), stirred for 30 min, and filtered through a Celite ™ bed of diatomaceous earth to remove catalyst and carbon. The filtrate was distilled under vacuum on an oil pump at 200 ° C to remove unreacted 2-naphthol and tetradecene. The distillation residue was collected to give a red-brown viscous liquid. According to gas chromatographic analysis, the product was mainly monoalkylated, with a ratio of monoalkylated units to dialkylated units: 75/25.

As shown in table. 1, at 30 rpm, a mixture of an oil-based drilling composition and an alkylated naphthol showed a 12% reduction in the friction coefficient compared to an oil-based drilling composition.

Example 13

Example 13 largely repeated Example 1, except that the composition contained approximately 200 ml of the oil-based drilling composition of Example 1 and 6.06 grams of C16 LAO, an alkylated anisole, prepared by the procedure below. In a round bottom flask equipped with a separatory funnel, anisole (108.15 g, 1.00 mol) and a USY zeolite catalyst (5.01 g, 1.5 wt%) were added under nitrogen. The mixture was heated with stirring at 165 ° C. To the mixture, 1-hexadecene (230.03 g, 1.02 mol), LAO was added dropwise over 1 hour and the reaction was continued for 1 hour. The mixture was then cooled to 100 ° C and filtered through a pad of Celite ™ diatomite to removing the catalyst. The filtrate was distilled under vacuum on an oil pump at 190 ° C to remove unreacted anisole and 1-hexadecene. The distillation residue was collected to give 274.46 g of a light yellow viscous liquid. According to gas chromatographic analysis, the product was mainly monoalkylated, with a ratio of monoalkylated units to dialkylated units: 93/7.

As shown in table. 1, at 30 rpm, a mixture of an oil-based drilling composition and an alkylated anisole LAO was characterized by a 5% reduction in the value of the friction coefficient compared to an oil-based drilling composition.

Example 14

Example 14 largely repeated Example 1, except that the composition contained approximately 200 ml of the oil-based drilling composition of Example 1 and 7.08 g of C20 ngPAO, alkylated anisole, prepared by the procedure below. Anisole (800.15 g, 1.40 mol) and zeolite MCM-49 catalyst (44.0 g, 1.62 wt%) were added to a round bottom flask equipped with a separating funnel under nitrogen atmosphere. The mixture was heated with stirring at 150 ° C. To the mixture was added C20 ngPAO olefin (1875 g, 6.68 mol) dropwise over 1 hour and the reaction continued for an additional 2 hours. The reaction mixture was filtered through a bed of Celite ™ diatomite to remove the catalyst. The filtrate was distilled under vacuum on an oil pump at 200 ° C to remove unreacted anisole and olefin. The distillation residue was collected to give a light yellow viscous liquid (yield 1731 g). According to gas chromatographic analysis, the product was mainly monoalkylated, with a ratio of monoalkylated units to dialkylated units: 95/5.

As shown in table. 1, at 30 rpm, the mixture of an oil-based drilling composition and an alkylated ngPAO anisole was characterized by a -5% reduction in the value of the friction coefficient compared to an oil-based drilling composition.

Example 15

Example 15 largely repeated Example 1, except that the composition contained approximately 200 ml of the oil-based drilling composition of Example 1 and 7.55 g of 3-nitro-N-octadecylbenzamide. As shown in table. 1, at 30 rpm, the mixture showed a 15% reduction in the friction coefficient compared to the oil-based drilling composition.

Example 16

Example 16 largely repeated Example 1, except that the composition contained approximately 200 ml of the oil-based drilling composition of Example 1 and 4.26 grams of 4-nitro-N-octadecylbenzamide. As shown in table. 1, at 30 rpm, the mixture showed a 5% reduction in the friction coefficient compared to the oil-based drilling composition.

Example 17

Example 17 largely repeated Example 1, except that the composition contained approximately 200 ml of the oil-based drilling composition from Example 1 and 7.58 g of 4-nitro-N-octadecylbenzamide product made using 18.5 g (100 mmol) 4-nitrobenzoyl, 8 ml of pyridine and 26.8 g (100 mmol) of oleylamine. As shown in table. 1, at 30 rpm, the mixture showed a 6% reduction in the friction coefficient compared to the oil-based drilling composition.

Example 18

Example 18 largely repeated Example 1, except that the composition contained approximately 200 ml of the oil-based drilling composition of Example 1 and 6.5 g (Z) -4-nitro-N- (octadec-9-en-1 -yl) benzamide prepared using 18.5 g (100 mmol) of 4-nitrobenzoyl, 8 ml of pyridine and 26.7 g (100 mmol) of oleylamine. As shown in Table 1, at 30 rpm, the mixture showed a 6% reduction in friction coefficient compared to the oil-based drilling composition.

Example 19

Example 19 largely repeated Example 1, except that the composition contained approximately 200 ml of the oil-based drilling composition of Example 1 and 5.37 g of BNX ™ 565,4 - [[4,6-bis (octylthio) - 1,3,5-triazin-2-yl] amino] -2,6-bis (1,1-dimethylethyl) phenol from Mayzo, Inc. As shown in table. 1, at 30 rpm, the mixture showed a 6% reduction in the friction coefficient compared to the oil-based drilling composition.

Example 20

Example 20 largely repeated Example 1, except that the composition contained approximately 200 ml of the oil-based drilling composition of Example 1 and 4.89 g of BNX ™ 1037, 2,4-bis [(dodecylthio) methyl] -6 -methylphenol from Mayzo, Inc. As shown in table. 1, at 30 rpm, the mixture showed a 24% decrease in the friction coefficient compared to the oil-based drilling composition.

Examples 21-23

Examples 21-23 studied the aging of an oil-based drilling composition on a laboratory scale and blends made from the friction-reducing compositions of Examples 2 and 6 and an oil-based drilling composition. In each of Examples 21-23, 200 ml of oil-based drilling composition was used. The oil-based drilling composition included a sample of Megadril drilling mud from M-I SWACO, Schlumberger company. The sample was in industrial use for an extended period of time, so its exact composition could not be determined. In addition, the drilling fluid contained drill cuttings, formation oil and accumulated degradation products.

Blends of the oil-based drilling composition with the friction-reducing composition were prepared in Examples 22-23 using the procedures described in Example 1. The identity and amount of the friction-reducing composition used for each of Examples 22-23 are described in Table II. 2.

For samples from each example 21-23, the initial coefficient of friction was measured first. Samples from examples 21-23 were subjected to thermal aging at 75 ° C for 7 days in closed capsules with constant shaking, after which the relative coefficient of friction was measured again. The initial values of the relative coefficients of friction of the materials from the examples and after thermal aging are given in table. 3.

As can be seen from the data in Table 3, Examples 22 and 23, which present the friction-reducing compositions described as useful in this context, show a significant increase in the coefficient of friction after thermal aging compared to Example 21 (oil-based drilling composition ). These results are specific to this particular used formation drilling fluid sample, similar deterioration may or may not occur with other used formation drilling fluids depending on the exact formulation, but the findings suggest that the friction-reducing compositions of the present invention degrade over time or interact with the formation of residues, which leads to an increase in the coefficient of friction compared to an oil-based drilling composition that does not contain a friction-reducing composition.

As shown above, embodiments of the present invention provide novel friction-reducing compositions that can be used in a variety of lubrication operations, for example, wellbore reaming, well completion, and the like. New friction-reducing compositions can have one or more of the following benefits. For example, the compositions can have a lower coefficient of friction than conventional compositions, making it easier to achieve previously unattainable shaft lengths. Some compositions described in this context may allow drilling operations to be performed at lower torque and / or total friction factor (also called total friction factor). The overall friction factor for a particular drilling operation is a complex factor that combines many factors specific to each well, the drilling operation, and a point in time for each well, reflecting the changes observed in the wells. The general friction factor is described in the following papers: "Friction Factor Model and Interpretation of Real Time Data (Thesis)," Christine Frafjord, Petroleum Geoscience and Engineering, Department of Petroleum Engineering and Applied Geophysics, Norwegian Univ. of Sci. and Tech. (May 2013), "Improvement of Torque-and-Drag Modeling in Long-Reach Wells," Seyed Ahmad Mirhaj, Eirik Kaarstad, Bernt S. Aadnoy, Modern Applied Sci., vol. 5, no. 5, 10 ISSN 1913-1844 E-ISSN 1913-1852 (October 2011); "Real Time Torque and Drag Analysis during Directional Drilling (Thesis)," Mohammad Fazaelizadeh, Univ. of Calgary, Dept. of Chemical and Petroleum Engineering, Calgary, Alberta, CA (March 2013), each of which is incorporated herein by reference in its entirety. Torque and total friction factor each represent a measure of the load that the drilling operation places on the equipment. Decreasing one or more of these values can provide a longer lasting improvement in any property that is adversely affected by higher values, such as longer wellbores, longer production times between maintenance periods, higher efficiency, and the like. Other properties and additional benefits will be apparent to those skilled in the art.

All documents described in this context are incorporated by reference to comply with all jurisdictions where such practice is permitted, including any priority documents and / or testing methodology to the extent that they do not conflict with this context. As follows from the above basic description and specific embodiments of the present invention, although the forms of the invention have been illustrated and described, various modifications can be made without departing from the spirit and scope of the invention. Accordingly, the invention is therefore not limited to these modifications. For example, compositions described in this context may not contain any component or composition not expressly indicated or disclosed in this context. Any method may not contain any step not cited or described in this context. Likewise, the term "including" is considered synonymous with the term "comprising". Wherever a method, composition, element or group of elements is preceded by the definition "including", it should be understood that the authors also contemplate a similar composition or group of elements with the definitions "mainly consisting of", "consisting of", "selected from the group consisting of ", or the verb" is "preceding a description of a composition, element or elements, and vice versa.

Claims (43)

1. A method for reducing friction during drilling operations, including the following stages: a) providing at least one oil-based drilling composition for the drilling operation, b) carrying out the drilling operation for a period of time using an oil-based drilling composition, and c) adding a friction-reducing composition for the drilling operation, the friction-reducing composition comprising one or more compounds represented by formula I:

where Ar is a mono- or polycyclic aromatic moiety, each X group is a polar functional group that is not - (OC ₂ H ₄ ) _z , where z is an integer of at least 1, each R group is independently selected from a branched or an unbranched, saturated or unsaturated, substituted or unsubstituted C ₁ -C ₅₀ hydrocarbon group, where n is an integer greater than or equal to 1, and where m is an integer greater than or equal to 0, if at least one R group is substituted with a functional group and / or group Ar contains a heteroatom, and in other cases means an integer greater than or equal to 1. 2. The method of claim 1, wherein the friction-reducing composition is at least partially dispersed in the oil-based drilling composition during the bulk drilling operation. 3. The method of claim 1 or 2, wherein the friction-reducing composition is in a liquid state under a well drilling operation. 4. A method according to any one of claims. 1-3, wherein the step of providing at least one oil-based drilling composition comprises introducing at least one oil-based drilling composition into the wellbore, and wherein the step of adding a friction-reducing composition comprises introducing a friction-reducing composition into the wellbore. 5. The method according to any one of claims. 1-4, wherein the step of adding the friction-reducing composition further comprises the steps of mixing the friction-reducing composition with an oil-based drilling composition to form a lubricating composition, and providing a lubricating composition for the drilling operation, where optionally the friction-reducing composition is blended with the oil-based drilling composition to such an extent that the concentration of the friction reducing composition in the lubricating composition is from about 0.1 wt% to about 20 wt% based on the weight of the lubricant composition. 6. The method according to any one of claims. 1-5, wherein one or more of the compounds represented by Formula I do not contain an epoxy group. 7. A method according to any one of claims. 1-6, wherein the step of adding the friction-reducing composition comprises periodically adding the friction-reducing composition to maintain the required torque. 8. The method according to any one of claims. 1-7, further comprising the step of determining a torque limiter for the drilling operation, and wherein the step of adding a friction-reducing composition for the drilling operation is performed at a drilling operation torque of ≥ about 90% of the torque limiter. 9. A method according to any one of claims. 1-8, where the drilling operation has a working torque of <95% of the torque in the same drilling operation as performed using an oil-based drilling composition but no friction-reducing composition. 10. The method according to any one of claims. 1-9, where Ar is selected from the group consisting of an aryl group, a heteroaryl group, a biphenyl group, deprotonated cyclic C ₅ diolefins, and a multinucleated aromatic group, and combinations thereof, and / or each X group is independently selected from the group consisting of —OH, -OCH ₃ ; -NH ₂ , -NO ₂ , -CHO, -CH ₃ OH, -SO ₂ R, polyamines, polyols, oxazolidines, metals of groups 1-2, NR ₄ ⁺ groups, PR ₄ ⁺ groups and glycosyl groups and combinations thereof. 11. The method according to any one of claims. 1-10, where at least one R group contains a chain containing at least 10 carbon atoms, and / or where at least one R group contains a quaternary carbon atom directly attached to the Ar group. 12. The method according to any one of claims. 1-11, where at least one m or n is greater than or equal to 2. 13. The method according to any one of claims. 1-12, wherein the friction-reducing composition comprises one or more compounds represented by at least one of formulas Ia, Ib, or Ic:

where each R, X, m and n are as defined in claim 1. 14. The method of claim 13, wherein the friction-reducing composition comprises one or more compounds represented by at least one of formulas Ia or Ic, and wherein at least one R group is located in the meta or para position with respect to the X group ... 15. A method according to claim 13 or 14, wherein one or more of the compounds represented by at least one of formulas Ia, Ib or Ic is selected from the group consisting of alkylphenols, alkylanisoles, alkylnaphthols, cashew nut shell liquid (CGS) components , thioalkylphenols, alkylbenzamides, alkylanilines and any derivatives and mixtures thereof. 16. The method of claim 15, wherein one or more of the compounds represented by at least one of formulas Ia, Ib or Ic comprises functionalized aromatic compounds alkylated with a linear alpha olefin and / or a poly alpha olefin. 17. The method of claim 15, wherein one or more of the compounds represented by at least one of formulas Ia, Ib or Ic comprises an alkyl phenol and / or an alkyl phenol derivative. 18. The method of claim 17, wherein one or more of the compounds represented by at least one of formulas Ia, Ib, or Ic comprises cardanol. 19. The method of claim 17, wherein the alkyl phenol derivative is selected from the group consisting of phenalkamines, polyols, Mannich base precursor polyols, glycosyl-modified cardanol, and combinations or mixtures thereof. 20. The method according to any one of claims. 1-19, where the drilling operation includes one or more operations: insertion of a drill string, insertion of coiled pipes, insertion of casing pipes, insertion of filters, insertion of devices for cleaning, fracturing and perforating, rotation of the drill string, completion of the wellbore, removal of the drill string, and / or removal of coiled pipes. 21. Use of a friction-reducing composition for reducing torque in a drilling operation, wherein the friction-reducing composition comprises one or more compounds represented by formula I:

where Ar is a mono- or polycyclic aromatic moiety, each X group is a polar functional group that is not - (OC ₂ H ₄ ) _z , where z is an integer of at least 1, each R group is independently selected from a branched or an unbranched, saturated or unsaturated, substituted or unsubstituted C ₁ -C ₅₀ hydrocarbon group, where n is an integer greater than or equal to 1, and where m is an integer greater than or equal to 0, if at least one R group is substituted with a functional group and / or group Ar contains a heteroatom, and in other cases means an integer greater than or equal to 1, where the drilling operation optionally has a working torque <99% of the torque during the same drilling operation as performed using an oil-based drilling composition but no friction-reducing composition. 22. A lubricating composition suitable for use in drilling operations, including: a) ≥ about 80 wt% of at least one oil-based drilling composition based on the weight of the lubricating composition, wherein the oil-based drilling composition comprises from about 1.0 to about 15.0 wt% water, and b) from about 0.1 to about 20.0 wt% of a friction reducing composition based on the weight of the lubricating composition, wherein the friction reducing composition comprises one or more compounds represented by Formula I:

where Ar is a mono- or multinuclear polycyclic aromatic moiety, each X group is a polar functional group that is not - (OC ₂ H ₄ ) _z , where z is an integer of at least 1, each R group is independently selected from branched or unbranched, saturated or unsaturated, substituted or unsubstituted C ₁ -C ₅₀ hydrocarbon group, where n is an integer greater than or equal to 1, and where m is an integer greater than or equal to 0, if at least one R group is substituted functional group and / or the Ar group contains a heteroatom, and in other cases m means an integer greater than or equal to 1, and otherwise means an integer greater than or equal to 1, provided that if Ar means a naphthalene moiety, each X group does not mean -OH. 23. The composition of claim 22, wherein the friction-reducing composition comprises one or more compounds represented by formula Ia:

where each R, X, m and n have the meanings defined in clause 22. 24. The lubricating composition of claim 23, wherein one or more of the compounds represented by formula Ia is selected from the group consisting of alkylphenols, alkylanisoles, cashew nut shell liquid (CGS) components, thioalkylphenols, alkylbenzamides, alkylanilines and any derivatives and mixtures thereof ... 25. Lubricating composition according to any one of paragraphs. 22-24, wherein the lubricating composition contains no or substantially no gelling and / or crosslinking agents.

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