High solids tolerant invert emulsion fluids

A low gravity solid tolerant emulsifier and methods of making the same is provided. The emulsifier includes a maleated amido-amine reaction product produced by: (1) reacting a fatty acid material including rosin acid at a concentration of about 11% to about 50%, and an amine material (e.g., a amine having a amine value of about 700 to about 1300 mg/g, such as AMINE HST) to produce an amido-amine reaction product; and (2) reacting the amido-amine reaction product with maleic anhydride to produce the maleated amido-amine reaction product. Invert emulsion fluids and drilling fluids that include the emulsifier above and methods of using the same is further provided.

FIELD

The present disclosure relates to an invert emulsion fluid composition and associated methods. In particular, the disclosure provides reaction products of amine, low titer fatty acid material, and maleic anhydride as emulsifiers for invert emulsion drilling fluids, and drilling fluid compositions comprising the same. The invert emulsion fluids (IEF) is stable and has high tolerance for low gravity solids (LGS) providing controlled (low) rheology. The present disclosure also provides methods of synthesizing an economic and effective drilling fluid composition for oil and gas drilling.

BACKGROUND

A drilling fluid is a specially designed fluid that is circulated through an oil or gas wellbore as the wellbore is drilled to facilitate the drilling operation. A need exists for an improved additive for modifying and controlling the suspension properties of drilling fluids that would be efficient, easily handled, and readily dispersible in a broad range of drilling muds, and usable under a broad range of conditions.

Drilling fluids or muds are typically classified according to their base fluid or continuous phase, as water base and oil base fluids. Drilling fluids may contain a mixture of base fluids, and are typically classified by the predominating or continuous base fluid, with the fluid present in lesser quantities becoming the internal or emulsified phase. The use of oil and invert oil-based drilling fluids or muds in oil exploration is increasing rapidly owing to the more demanding requirements encountered in drilling deep and/or non-vertical and deviated wells. Compared with the longer-established water-based drilling muds, oil and invert oil-based drilling fluids possess a number of advantages, including reduced interaction with earth formations, and improved lubricity. The drilling fluids and methods of the present disclosure are particularly useful in invert emulsion systems.

Oil based invert emulsion drilling fluids are generally used throughout the world and consist of a three-phase system: oil, internal hygroscopic phase and fine particulate solids. The internal hygroscopic phase can be an aqueous phase typically a brine or it can be an organic compound like glycerol or polyglycerol either dissolved in water or neat or a combination thereof. The addition of brine reduces the overall price of the fluid, reduces the risk of combustion of the oil, builds an emulsion structure that provides suspension and improved viscosity to the fluid, provides improved shale stability by driving water out of the shale and into the fluid via osmosis, and improves the water acceptance of the mud. The brine of choice is commonly an aqueous solution of an inorganic salt, such as sodium chloride or calcium chloride.

Drilling fluids or drilling muds are pumped under pressure down through a long string of drill pipe, then through the center of the drilling bit at the hole bottom, then back up through the annulus between the outside of the string of drill pipe and up the borehole wall to the surface.

Drilling fluids provide a number of interrelated functions to satisfy the requirements of the oil industry for a commercial drilling fluid, which may be grouped as follows. (1) The drilling fluid must suspend and transport solid particles, e.g. drill cuttings, to the surface for screening out and disposal. (2) The drilling fluid must build a filter cake that can prevent the loss of downhole pressure and fluid loss to the formation, including when traversing an interval of porous formation material. (3) The drilling fluid must keep suspended an additive weighting agent (to increase specific gravity of the mud), so that uniform mud weight is maintain throughout the column of drilling fluid in the well, especially when encountering pressurized pockets of combustible gas, which otherwise would tend to reduce downhole pressure, as well as creating a “blowout” in which the fluid and even the drill stem are violently ejected from the well, with resulting catastrophic damages, such as fires. (4) The drilling fluid must constantly lubricate the drill bit so as to promote drilling efficiency and retard bit wear. (5) The drilling fluid should maintain sufficient hydrostatic pressure to manage the wellbore pressure for improved wellbore stability.

It should be noted that a drilling fluid must perform its various functions not only when the drill bit is actively encountering the bottom of the borehole, but also at times when the drill stem is inactive, or is being removed or re-inserted for some purpose. In particular, cuttings must be held in suspension in the event of shut-downs in drilling.

An ideal drilling fluid is a thixotropic system. That is, the drilling fluid (1) will exhibit low viscosity when sheared, such as during agitation or circulation (as by pumping or otherwise) but, (2) when the shearing action is halted, the fluid must gel to hold the cuttings in place, and it must become gelled relatively rapidly, reaching a sufficient gel strength before suspended materials fall any significant distance, and (3) this behavior should be almost completely reversible. In addition, even when it is a free-flowing liquid, the fluid must retain a sufficiently high viscosity to carry all unwanted particulate matter from the bottom of the hole to the surface. Moreover, upon long-term interruption of circulation, such as when drilling fluid has been ejected from the borehole into a quiescent holding vessel or pond, the gel structure should remain intact to allow the weighting agent particles to remain suspended and maintain a uniform distribution throughout the fluid.

During the drilling process, some of the drilled solids erode and become finer particles that cannot be removed via solids control equipment (at the surface) due to their small size. As drilling progresses these particles become finer to colloidal size and increase in their concentration in the drilling fluid. These colloidal fines and their concentration can negatively impact the performance of the invert emulsion fluid (IEF). The performance of the IEF can be gauged by the American Petroleum Institute (API) fluid loss test, rheology and monitoring for emulsion stability. These colloidal fines can either cause an increase in the API fluid loss, increase the overall rheology of the fluids or at the very end may even destabilize the IEF. This increase in the overall rheology of the fluid can be determined by an increase in Fann 35 rheometer readings from 600 rotations per minute (rpm) to 3 rpm. An increase in overall rheology of the fluid increases the equivalent circulating density (ECD) of the fluid. The ECD is the effective density of the circulating fluid in the wellbore resulting from the sum of the hydrostatic pressure imposed by the static fluid column and the friction pressure. APISTD65—Part2, Isolating Potential Flow Zones During Well Construction, Upstream Segment, Second Edition, December2010. Global Standards. More specifically, an increase in the rheology increases the frictional pressure component in the ECD equation, and thereby, the ECD of the fluid. The ECD is an important parameter in avoiding kicks and losses of the fluid, particularly in wells that have a narrow window between the fracture gradient and pore-pressure gradient.

When the colloidal fines in the IEF increase, the fluid may be treated in one or more of the following ways, for example, by: (i) adding a thinner to lower the rheology; (ii) adding wetting agents to maintain the water wettability of the colloidal fines; (iii) adding fresh IEF to dilute the overall drilling fluid to reduce the overall concentration of the low gravity solids (LGS); (iv) performing high speed centrifuge operations to remove the finer solids; and/or (v) adding other additives to maintain a workable fluid. However, at times these treatments may not work and the whole of the used IEF has to be discarded and fresh IEF made.

It is therefore advantageous to have emulsifiers or additives as part of the IEF that reduce the maintenance/treatments of these fluids by maintaining controlled (low) rheology profile and API fluid loss performance of the IEF. This improvement will in turn increase the overall working longevity of the IEF. Thus, there is a need for a cost effective drilling fluid that can perform all the above mentioned functions. The present disclosure provides a drilling fluid with an IEF composition having low titer low titer fatty acid material (or low titer rosin acid containing fatty acid material) based specialty emulsifier which delivers a low rheology IEF even in the presence of a high concentration of low gravity solids (LGS). A low rheology in turn leads to lower induced fluid losses in the drilling fluid formation when drilling oil and gas wells.

SUMMARY

The present disclosure provides a low gravity solids (LGS) tolerant emulsifier, maleated low titer fatty acid material, or low titer rosin containing fatty acid material based amido-amine (herein, “MDTA”) emulsifier, an invert emulsion fluid (herein, “IEF”) comprising the MDTA emulsifier (i.e., the LGS tolerant emulsifier) of the present disclosure, drilling fluids comprising the IEF of the present disclosure, and associated methods of use. Surprisingly and unexpectedly, when incorporated into IEF compositions, the emulsifier of the present disclosure reduces IEF rheology even in the presence of a high LGS concentration—i.e. the IEF has a lower rheology as compared to an IEF without the MDTA emulsifier of the present disclosure. The low rheology in turn leads to lower induced fluid losses in the drilling fluid formation when drilling oil and gas wells.

Thus, in an aspect, the present disclosure provides a LGS tolerant emulsifier or MDTA emulsifier comprising a maleated amido-amine reaction product. The maleated amido-amine reaction product can be produced by: reacting a low titer fatty acid material (e.g., a lower titer fatty acid material comprising rosin acid) and an amine material to produce an amido-amine reaction product (or amido-amine intermediate reaction product or amido-amine low-titer fatty acid material intermediate reaction product or amido-amine low-titer rosin acid containing fatty acid material intermediate reaction product), and reacting the amido-amine reaction product with maleic anhydride to produce the maleated amido-amine reaction product.

In another aspect, the present disclosure provides methods for preparing/making a LGS tolerant emulsifier or a MDTA emulsifier. The method comprises: reacting a low titer fatty acid material (i.e., a low titer fatty acid material comprising rosin acid) and an amine material to produce an amido-amine low-titer fatty acid material intermediate (or amido-amine reaction product or amido-amine intermediate reaction product); and reacting the amido-amine low-titer fatty acid material intermediate or reaction product with maleic anhydride (e.g., adding maleic anhydride) to produce a maleated amido-amine reaction product or MDTA emulsifier. In certain embodiments, the method of preparing a MDTA emulsifier comprises reacting low titer fatty acid material (i.e., low titer rosin acid containing fatty acid material) and an amine resulting in an amido-amine-low titer fatty acid material intermediate; and reacting the intermediate with maleic anhydride (i.e., maleic anhydride addition) to form the LGS tolerant emulsifier or MDTA emulsifier.

In any aspect or embodiment described herein, the LGS tolerant emulsifier or MDTA emulsifier includes at least one of: the low titer fatty acid material or low titer rosin acid containing fatty acid material is present in an amount of about 55 wt. % to about 95 wt. % (e.g., about 65 wt. % to about 75 wt. %) of the amido-amine reaction product; the amine material is present in an amount of about 5 wt. % to about 45 wt. % (e.g., about 25 wt. % to about 35 wt. %) of the amido-amine reaction product; the maleic anhydride is present in an amount of about 1 wt. % to about 20 wt. % (e.g., about 5 wt. % to about 13 wt. %) of the maleated amido-amine reaction product or the emulsifier; or a combination thereof.

In any of the aspects or embodiments described herein, the low titer fatty acid material (e.g., low titer fatty material comprising rosin acid or low titer rosin acid containing material) includes or is at least one of: a side stream from the crude tall oil (CTO) refining process collected as the bottoms product during the subsequent production of low rosin (<5%) and low Gardner Color index (<7.0) tall oil fatty acid (TOFA) from refinery columns during the distillation of crude tall oil (CTO); a mixture of a blend of the side stream and at least one of distilled tall oil, tall oil fatty acid, rosin, or a combination thereof; a product stream of the CTO refining process; a mixture or blend of TOFA and distilled tall oil; a mixture or blend of a distilled tall oil and rosin; a mixture or blend of TOFA and rosin; a disproportionated tall oil, a mixture of disproportionated tall oil and rosin, a mixture of disproportionated tall oil and TOFA, a mixture of disproportionated tall oil and distilled tall oil (DTO), or a combination thereof; or a combination thereof.

In any aspect or embodiment described herein, the low titer fatty acid material or low titer fatty acid material comprising rosin acid has at least one of: an acid number ranging from about 143 to about 200 mg/g; a rosin acid concentration of about 11% to about 50%; a titer point of less than about 14° C.; a PAN rosin acid concentration of less than or equal to about 50%; heavies present in an amount of less than or equal to about 40% of the low titer fatty acid material; a Gardner color index in a range from about 4.0 to about 17.0; or a combination thereof. For example, in certain embodiments, the low titer fatty acid material has an acid number in a range from about 155 to about 174 mg/g or about 143 to about 185 mg/g. In any aspect or embodiment described herein, the low titer fatty acid material has a Gardner color index in a range from 4 to about 14.7.

In any of the aspects or embodiments described herein, the amine HST has an amine value between about 700 mg/g and about 1300 mg/g (e.g., about 750 mg/g to about 900 mg/g or about 750 mg/g).

In any aspect or embodiment described herein, the amine material includes or is a distillation residuum bottom composition of a reaction product of monoethanolamine and ammonia in which piperazine distillate product has been recovered.

In any of the aspects or embodiments described herein, the amine material includes or is a chemical composition with the Chemical Abstracts Service Registry No. 68910-05-4. For example, in certain embodiments, the amine material is or includes at least one of AMINE HST from Dow Chemical Co. (Midland, Mich.), AMIX 1000 from BASF (Ludwigshafen, Germany), Berolamine 20 (BA-20; AkzoNobel, Illinois Chicago), or a combination thereof.

In particular embodiments, the amine material includes or is a distillation residuum bottom composition of a reaction product of monoethanolamine and ammonia in which piperazine distillate product has been recovered.

In an embodiment, the amine material is or includes a chemical composition with the Chemical Abstract Service Registry No. 68910-05-4 (e.g., AMINE HST from Dow Chemical Co., AMIX 1000 from BASF, BA-20 from Akzo Nobel, or a combination thereof).

In certain embodiments, the amine material includes at least one of: AMINE HST from Dow Chemical Co., AMIX 1000 from BASF, BA-20 from Akzo Nobel, or a combination thereof.

In any aspect or embodiment described herein, the amido-amine reaction product (i.e., the amido-amine reaction intermediate product or amido-amine low-titer fatty acid material intermediate reaction product) includes at least one of amidoamines, alkanolamides, di-amidoamine, di-ester alcohol amine, ester alcohol amine, di-ester amine, ester amido amines, amido amine alcohols, amides of the hydroxy piperazine, amide imidazoline, ester imidazoline, amine imidazoline, alkanol imidazoline or combinations thereof.

In an additional aspect, the present disclosure provides an invert emulsion fluid (IEF) comprising the LGS tolerant emulsifier or MDTA emulsifier of the present disclosure, and at least one of a non-aqueous continuous phase, a discontinuous hygroscopic phase like brine, an additive, or a combination thereof. The IEF of the present disclosure, which includes the LGS tolerant emulsifier or MDTA emulsifier of the present disclosure, demonstrates controlled (i.e., reduced) rheology even in the presence of relatively high concentration of LGS, as compared to a maleated TOFA amido-amine (herein, “MHTA”) emulsifier, which is generally recognized as the industry standard. See, for example, an emulsifier as disclosed in U.S. Pat. No. 8,927,468 B2, which is incorporated herein, as well as non-spray dried version thereof.

In any aspect or embodiment described herein, the IEF comprises between about 4 and about 12 V/V of LGS. In any aspect or embodiment described herein, the LGS have specific gravity between about 2.0 and about 3.0.

In any aspect or embodiment described herein, the IEF of the present disclosure has a low high temperature, high pressure (HTHP) fluid loss between about 1 and about 20 ml at 350° F. See, American Petroleum Institute (API) Recommended Practice 13B-2, Fourth Edition, Recommended Practice for Field Testing of Oil-based Drilling Fluids, for an exemplary test method to conduct the HTHP filtration test at the test temperature indicated above.

In any aspect or embodiment described herein, the IEF has a lower rheology than an IEF without the MDTA emulsifier (e.g., an IEF comprising a maleated TOFA amido-amine emulsifier).

In any aspect or embodiment described herein, the MDTA emulsifier of the present disclosure reduces the IEF rheology by from about 10 to about 92% (e.g., about 25 to about 85% or about 50 to about 85%), as compared to an IEF comprising a MHTA emulsifier (i.e., the industry standard). In any aspect or embodiment described herein, the IEF of the present disclosure has a low rheology having 600 rpm to 3 rpm dial readings that are lower than similarly formulated IEF with a MHTA emulsifiers at 150° F. In any aspect or embodiment described herein, the relative rheology may be determined at 100 ppb loading REVDUST® tested under standard conditions (e.g., an exemplary test method/conditions can be found at API Recommended Practice 13B-2, Fourth Edition, Recommended Practice for Field Testing of Oil-based Drilling Fluids).

In any aspect or embodiment described herein, the IEF of the present disclosure has a gel strength that is about 10 to about 92% (e.g., about 25 to about 85% or about 50 to about 85%) lower than a similarly formulated IEF without the described MDTA emulsifier (e.g., a similarly formulated IEF with a maleated TOFA amine emulsifier) at 150° F. In any aspect or embodiment described herein, the gel strength may be determined by API Recommended Practice 13B-2, Fourth Edition, Recommended Practice for Field Testing of Oil-based Drilling Fluids.

In any aspect or embodiment described herein, the IEF of the present disclosure has a low rheology having yield stress (Tau0) less than the yield stress of similarly formulated IEF without the described MDTA emulsifier (e.g., a similarly formulated IEF comprising a MHTA emulsifier) at 150° F.

In any aspect or embodiment described herein, the IEF of the present disclosure is used for gas and oil drilling.

In a further aspect, the present disclosure provides a drilling fluid comprising the IEF of the present disclosure (i.e., an IEF comprising the MDTA emulsifier of the present disclosure).

A further aspect of the present disclosure provides a method of drilling a well. The method comprises drilling a well bore and circulating the drilling fluid of the present disclosure through said well bore when drilling the well bore.

Further aspects, features, and advantages of the present disclosure will be apparent to those of ordinary skill in the art upon examining and reading the following Detailed Description of the Preferred Embodiments.

DETAILED DESCRIPTION

The following is a detailed description provided to aid those skilled in the art in practicing the present disclosure. Those of ordinary skill in the art may make modifications and variations in the embodiments described herein without departing from the spirit or scope of the present disclosure. All publications, patent applications, patents, figures and other references mentioned herein are expressly incorporated herein by reference in their entirety for all purposes.

The present description provides improved compositions and methods for drilling wells, fracturing subterranean formations, and other treatments. The drilling and fracturing compositions and methods of the present disclosure are economical and desirable properties that are surprising and unexpected. In particular, the present disclosure provides a low gravity solids (LGS) tolerant emulsifier or maleated low titer fatty acid material (also referred to herein as a low titer fatty acid material comprising rosin acid or a low titer rosin acid containing fatty acid material) based amido-amine (herein, “MDTA”) emulsifier, invert emulsion fluid (herein, “IEF”) comprising the LGS tolerant emulsifier or MDTA emulsifier of the present disclosure, drilling fluids comprising the IEF of the present disclosure, and associated methods of use of each. Surprisingly and unexpectedly, when the LGS tolerant emulsifier or MDTA emulsifier of the present disclosure is incorporated into IEF compositions, the rheology of the IEF is reduced, even in the presence of a high LGS concentration—i.e. the IEF of the present disclosure has a lower rheology as compared to an IEF formulated with a conventional MHTA emulsifier (i.e., without the emulsifier of the present disclosure). The low rheology in turn leads to lower induced fluid losses in the drilling fluid formation when drilling oil and gas wells

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. The terminology used in the description is for describing particular embodiments only and is not intended to be limiting of the disclosure.

The following terms are used to describe the present disclosure. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. The terminology used in the description is for describing particular embodiments only and is not intended to be limiting of the disclosure.

The articles “a” and “an” as used herein and in the appended claims are used herein to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article unless the context clearly indicates otherwise. By way of example, “an element” means one element or more than one element.

It should also be understood that, in certain methods described herein that include more than one step or act, the order of the steps or acts of the method is not necessarily limited to the order in which the steps or acts of the method are recited unless the context indicates otherwise.

As used herein, the term “drilling” or “drilling well bores” shall be understood in the broader sense of drilling operations, which include running casing and cementing as well as drilling, unless specifically indicated otherwise. The present disclosure also provides invert emulsion based drilling fluids for use in the methods of the disclosure to effect the advantages of the disclosure.

The present disclosure provides an invert emulsion drilling fluid that meets environmental constraints and provides improved performance in the field.

As disclosed herein, a “gel” may be defined a number of ways. One definition indicates that a “gel” is a generally colloidal suspension or a mixture of microscopic water particles (and any hydrophilic additives) approximately uniformly dispersed through the oil (and any hydrophobic additives), such that the fluid or gel has a generally homogeneous gelatinous consistency. Another definition states that a “gel” is a colloid in a more solid form than a “sol”, which is a fluid colloidal system, especially one in which the continuous phase is a liquid. Still another definition provides that a “gel” is a colloid in which the disperse phase has combined with the continuous phase to produce a viscous jelly-like product. Generally, a gel has a structure that is continually building. If the yield stress of a fluid increases over time, the fluid has gelled. “Yield stress” is the stress required to be exerted to initiate deformation.

During drilling, the fluids of the present disclosure generally maintain consistently low values for the difference in their surface density and downhole equivalent circulating density (ECD), as well as have significantly reduced fluid loss, as compared to other (e.g., conventional) drilling fluids used under comparable conditions.

Oil or synthetic fluid-based muds are normally used to drill swelling or sloughing shales, salt, gypsum, anhydrite or other evaporate formations, hydrogen sulfide-containing formations, and hot boreholes (e.g. greater than about 300° F.) holes, but may be used in other holes penetrating a subterranean formation as well. Unless indicated otherwise, the terms “oil mud” or “oil-based mud or drilling fluid” shall be understood to include synthetic oils or other synthetic fluids as well as natural or traditional oils, and such oils shall be understood to comprise invert emulsions.

Oil-based muds used in drilling typically comprise: a base oil (e.g. natural or synthetic fluid) comprising the external phase of an invert emulsion; a saline, aqueous solution (e.g. an aqueous solution comprising about 20 to about 40% calcium chloride, or about 25% to about 35% calcium chloride, or about 30% calcium chloride) comprising the internal phase of the invert emulsion; emulsifiers at the interface of the internal and external phases; and other agents or additives for suspension, weight or density, oil-wetting, fluid loss or filtration control, and rheology control. Such additives commonly include organophilic clays and organophilic lignites. See H. C. H. Darley and George R. Gray, Composition and Properties of Drilling and Completion Fluids 66-67, 561-562 (5th ed. 1988). In any aspect or embodiment described herein, the oil-based or invert emulsion-based drilling fluid comprises between about 50:50 to about 95:5 by volume oil phase to water phase. In some embodiments, the drilling fluid is a completely oil mud simply comprises 100% liquid phase oil by volume; that is, there is no aqueous internal phase.

Invert emulsion drilling fluids (also called invert drilling muds or invert muds or fluids) comprise a key segment of the drilling fluids industry. However, increasingly invert emulsion-based drilling fluids have been subjected to greater environmental restrictions, as well as performance and cost demands. There is consequently an increasing need and industry-wide interest in new drilling fluids that provide improved performance while still affording environmental and economical acceptance. Furthermore, the automotive and metalworking industries are always looking for low cost, highly efficient lubricants and lubricant additives that are environmentally friendly and that have a high thermal stability. Many lubricants and lubricant additives currently used, e.g., in these industries, do not meet these performance criteria. In addition, most of them are petroleum-based and thus, non-renewable.

The compositions of the present disclosure relate to drilling fluid additives (e.g., a LGS tolerant emulsifier or MDTA emulsifier) and drilling fluids, which are also known as drilling muds in the oil service industry, that have surprising and unexpected improvements in low gravity solids tolerance, while maintaining controlled (low) rheology. In particular, the compositions of the present disclosure relate to oil and invert oil based emulsion types of drilling fluids in which water is dispersed in an oil-based medium. Such drilling fluid compositions when prepared at a mud plant are often called mud plant formulations. The disclosure is particularly directed to providing an invert emulsion fluid with low rheology and that is tolerant to high concentrations of low gravity solids.

Maleated Low Titer Fatty Acid Material Based Amine Emulsifier

An aspect of the present disclosure provides a low gravity solid (LGS) tolerant emulsifier or MDTA emulsifier. The emulsifier of the present disclosure includes a maleated amido-amine reaction product produced by reacting a low titer fatty acid material (e.g., a low titer fatty acid material comprising rosin acid or low titer rosin acid containing fatty acid material) with an amine material to produce an amido-amine low-titer fatty acid material intermediate reaction product (or amido-amine intermediate product or amido-amine reaction product), and reacting the amido-amine low-titer fatty acid material intermediate reaction product with maleic anhydride to produce the maleated amido-amine reaction product. The reaction conditions like temperature and hold time at the highest temperature are specially engineered to derive maximum LGS tolerance. As used herein, unless the context indicates otherwise, the term low titer fatty acid material amido-amine is used inclusively of bis-amide amine, amido amines, alkanol amides, ester amido amines, amido amine alcohols, amides of the hydroxy piperazine, produced according to the methods described herein from the reaction of a low titer fatty acid material with an amine source.

Low Titer Fatty Acid Material

In any aspects or embodiment described herein, the low titer fatty acid material, low titer fatty acid material comprising rosin acid, or low titer rosin acid containing fatty acid material includes or is a side stream from the crude tall oil (CTO) refining process. For example, the low titer fatty acid material includes or is a side stream collected as the bottoms product during the subsequent production of low rosin (<5%) and low Gardner Color index (<7.0) tall oil fatty acid (TOFA) from refinery columns during the distillation of crude tall oil (CTO). For example, in any aspect or embodiment described herein, the side stream from the CTO refining process is C2-B° (available from Ingevity, Charleston, S.C.). Thus, in any aspect or embodiment described herein, the low titer fatty acid material is or includes a side stream from the CTO refining process that has at least one of: an acid number of about 143 mg/g to about 185 mg/g (e.g., about 155 mg/g to about 174 mg/g) or about 150 mg/g to about 200 mg/g, about 12% to about 40% rosin acids, a titer point of less than −2° C., about 45% fatty acids, about 14% monounsaturated fatty acids, about 34% unsaturated fatty acids, less than about 3% saturated fatty acids, or a combination thereof.

In any aspect or embodiment described herein, the low titer fatty acid material is or includes the side stream from the CTO refining process and at least one of distilled tall oil, tall oil fatty acid, rosin, or a combination thereof, wherein the rosin acid content of the low titer fatty acid material is as described herein.

In any aspect or embodiment described herein, the low titer fatty acid material is or includes a product stream of the CTO refining process, wherein the CTO refining process product stream has a rosin acid content as described herein. For example, in any aspect or embodiment described herein, the CTO refining process product stream is (1) Altapyne™ M-28B (e.g., about 26 to about 30% or about 28% rosin acid content) (Ingevity Corp., Charleston, S.C.); (2) a distilled tall oil having at least one of about 11% to about 12% rosin acid, an acid number of less than or equal to about 188 mg/g, a Gardner Color Index of less than or equal to about 8, less than or equal to about 1% palmitic acid, a titer point of less than about 14° C., or a combination thereof; or (3) a combination thereof. Thus, in any aspect or embodiment described herein, the low titer fatty acid material is or includes (1) a distilled tall oil having at least one of: about 26% to about 30% rosin acid, an acid number of at least about 180 mg/g, a Gardner Color Index of less than or equal to 10, a titer point of about 10° C. to about 12° C. (e.g., about 11° C.), or a combination thereof; (2) a distilled tall oil having at least one of about 11% to about 12% rosin acid, an acid number of less than or equal to about 188 mg/g, a Gardner Color Index of less than or equal to about 8, less than or equal to about 1% palmitic acid, a titer point of less than about 14° C., or a combination thereof; or (3) a combination thereof.

In any aspect or embodiment described herein, the low titer fatty acid material is or includes one or more distilled tall oils (e.g., 1, 2, 3, 4, 5, 6, or more distilled tall oils). For example, in any aspect or embodiment described herein, the distilled tall oil is or includes at least one of: Altapyne™ M-50B (about 45.0 to about 48.5% rosin acid content), Altapyne™ M-25 (about 12.0 to about 40.0% rosin acid content), Altapyne™ M-38 (about 37.0 to about 43.0% rosin acid content), Altapyne™ M-226 (about 25.0 to about 28.0% rosin acid content), or a combination thereof. Thus, in any aspect or embodiment described herein, the low titer fatty acid material is or includes a distilled tall oil having at least one of an acid number of about 175 mg/g to about 180 mg/g, about 45 to about 48.5% rosin acid, a Gardner Color Index of no greater than about 17 (e.g., about 17), or a combination thereof. In any aspect or embodiment described herein, the low titer fatty acid material is or includes a distilled tall oil having at least one of: an acid number of about 150 mg/g to about 200 mg/g, about 12.0 to about 40.0% rosin acid (e.g., about 20% rosin acid), a Gardner Color Index of about 10 to about 12 (e.g., about 11), a titer point of less than or equal to −2° C., about 45% fatty acids, less than about 3% saturated fatty acids, about 14% monosaturated fatty acids, about 34% unsaturated fatty acids, or a combination thereof. In any aspect or embodiment described herein, the low titer fatty acid material is or includes a distilled tall oil having at least one of: an acid number of about 175 mg/g to about 200 mg/g, about 37.0 to about 43.0% rosin acid (e.g., about 40% rosin acid), a Gardner Color Index equal to or less than 9 (e.g., about 7 to about 9), or a combination thereof. In any aspect or embodiment described herein, the low titer fatty acid material is or includes a distilled tall oil having at least one of: an acid number of about 182.0 mg/g to about 200 mg/g (e.g., about 189 mg/g), about 25.0 to about 28.0% rosin acid (e.g., about 26% rosin acids), a Gardner Color Index of equal to or less than 7 (e.g., about 5 to about 7 or about 6), about 1.0% or less palmitic acid, about 6.0% or less pimaric acid, or a combination thereof.

In any aspect or embodiment described herein, the low titer fatty acid material is or includes a mixture or blend of tall oil fatty acid and distilled tall oil, wherein the low titer fatty acid material has a rosin acid content as described herein. For example, in any aspect or embodiment described herein, the blend or mixture of tall oil fatty acid and distilled tall oil fatty acid is or includes Altapyne™ M-15 (about 10% to about 15% or about 13% rosin acid content) (Ingevity Corp., Charleston, S.C.). Thus, in any aspect or embodiment described herein, the low titer fatty acid material includes or is a distilled tall oil having at least one of: about 10 to about 15% rosin acid, an acid number of about 175 mg/g to about 195 mg/g, a Gardner Color Index equal to or less than 10, a titer point of about 9 to about 11° C. (such as about 10° C.), or a combination thereof.

In any aspect or embodiment described herein, the low titer fatty acid material is or includes a mixture or blend of distilled tall oil and rosin, wherein the low titer fatty acid material has a rosin acid content as described herein. For example, in any aspect or embodiment described herein, the blend or mixture of distilled tall oil and rosin is or includes Altapyne™ M-32 (about 30% to about 34% or about 30% rosin acid) (Ingevity Corp., Charleston, S.C.). Thus, in any aspect or embodiment described herein, the low titer fatty acid material includes or is a distilled tall oil having at least one of: about 30% to about 34% rosin acid, an acid number of about 170 mg/g to about 185 mg/g, a Gardner Color Index of less than or equal to 12, a titer point of about 10 to about 12° C. (such as about 11° C.), or a combination thereof.

In any aspect or embodiment described herein, the low titer fatty acid material is or includes a mixture or blend of TOFA and rosin, wherein the rosin acid content is as described herein. For example, in any aspect or embodiment described herein, the blend or mixture of TOFA and rosin is or includes Altapyne™ M-30D (e.g., about 26% to about 31% rosin acid) (Ingevity Corp., Charleston, S.C.). Thus, in any aspect or embodiment described herein, the low titer fatty acid material includes or is a blend or mixture of TOFA and rosin, wherein the low titer fatty acid material includes or is a blend or mixture of TOFA and rosin that has at least one of: about 26% to about 31% rosin acid, an acid number of about 180 mg/g to about 185 mg/g, about 64% to about 70% fatty acids, a Gardner Color Index equal to or less than 11, a titer point of about 8° C. to about 12° C., or a combination thereof.

In any aspect or embodiment described herein, the low titer fatty acid material is or includes a disproportionated tall oil, a mixture of disproportionated tall oil and rosin, a mixture of disproportionated tall oil and TOFA, a mixture of disproportionated tall oil and distilled tall oil (DTO), or a combination thereof, wherein the low titer acid material has a rosin acid content as described herein. For example, in any aspect or embodiment described herein, the low titer fatty acid material is or includes Altapyne™ 1430 (Ingevity Corp., Charleston, S.C.). Thus, in any aspect or embodiment described herein, the low titer fatty acid material is or includes a disproportionated tall oil, having at least one of: an acid number of about 170 to about 185 mg/g, about 24% to about 30% rosin acid, a Gardner Color Index of no greater than about 12, about 60% to about 70% fatty acids, about 30% to about 40% oleic acid, about 8 to about 30% dehydroabietic acid, less than about 1.0% abietic acid, or a combination thereof.

In any aspect or embodiment described herein, the low titer fatty acid material is or includes at least one of SYLVATAL™ D25LR (e.g., a DTO composition with an acid number of about 186 mg/g, about 70% fatty acids, about 26% rosin acids, titer point of about 2° C.; Arizona Chemicals, Jascksonville, Fla.), SYLVATAL™ D30LR (e.g., a DTO composition with an acid number of about 185 mg/g, about 66% fatty acids, about 30% rosin acids, titer point of about 2 to about 10° C. (e.g., about 10° C.); Arizona Chemicals, Jascksonville, Fla.), SYLFATAL™ D40LR (e.g., a DTO composition with an acid number of about 181 mg/g, about 58% fatty acids, about 39% rosin acids, titer point of about 2° C.; Arizona Chemicals, Jascksonville, Fla.), or a combination thereof.

In any aspect or embodiment described herein, acid number can be determined by titration. For example, in any aspect or embodiment described herein, acid number can be determined by titration with 0.5N KOH. An exemplary method to determine acid number through titration is described below in the Examples.

In any aspect or embodiment described herein, the low titer fatty acid material, low titer fatty acid material comprising rosin acid, or low titer rosin acid containing fatty acid material has a rosin acid (RA) concentration or content of about 11% to about 50% (e.g., about 11% to about 41% or about 19% to about 28%). For example, in any aspect or embodiment described herein, the RA concentration of the low titer fatty acid material is about 11% to about 50%, about 11% to about 45%, about 11% to about 41%, about 11% to about 35%, about 11% to about 30%, about 11% to about 25%, about 11% to about 20%, about 15% to about 50%, about 15% to about 45%, about 15% to about 41%, about 15% to about 35%, about 15% to about 30%, about 15% to about 25%, about 20% to about 50%, about 20% to about 45%, about 20% to about 41%, about 20% to about 35%, about 20% to about 30%, about 25% to about 50%, about 25% to about 45%, about 25% to about 41%, about 25% to about 35%, about 30% to about 50%, about 30% to about 45%, about 30% to about 41%, about 35% to about 50%, about 35% to about 45%, or about 40% to about 50%. The RA concentration can be determined by titration. For example, in certain embodiments, a modified Glidden procedure is utilized for RA concentration of about 15% or less, and for RA concentration of about 15% or greater a modified Wolfe Method is utilized. Alternatively, the RA concentration can be determined by the organic gel permeation chromatography. In any aspect or embodiment described herein, the rosin acid includes or is at least one of palustric acid, abietic acid, neoabietic acid, pimaric acid, levopimaric acid, isopimaric acid, a disproportionated rosin acid (e.g., dehydroabietic acid), or a combination thereof.

In any aspect or embodiment described herein, the low titer fatty acid material, low titer fatty acid material comprising rosin acid, or low titer rosin acid containing fatty acid material, is or includes a stream from the tall oil fatty acid distillation or processing (e.g., crude tall oil refining). In an embodiment, the low titer fatty acid material stream, low titer fatty acid material comprising rosin acid stream, or low titer rosin acid containing fatty acid material stream is or includes a by-product of crude tall oil refining process during the production of the light colored (Gardner color <7) highly pure TOFA (e.g., TOFA with a RA concentration of less than about 5% as determined by titration).

The fatty acid concentration and/or content can be determined by organic gel permeation chromatography (GPC), e.g., GPC using tetrahydrofuran (THF) as the mobile phase and refractive index detector. Since GPC alone cannot differentiate and estimate different carbon chain lengths in the fatty acid. Further determination of the fatty acid type and percentage is estimated by the combination of GPC and gas chromatography (GC) methods, wherein the correction factor for the heavies is determined by the GPC method. Thus, for example, from the GC method of analysis the fatty acid content, the low titer fatty acid material, low titer fatty acid material comprising rosin acid, or low titer rosin acid containing fatty acid material can include: predominantly C18 type fatty acid (e.g., about 25-about 89% or about 25-about 77%), less than or equal to about 34% (e.g., about 0.4 to about 34% or about 8 to about 34%) C20 type fatty acids; minor components of C16 type fatty acids (e.g., about 5%, about 4%, about 3%, about 2%, or about 0.5 to about 3%); or a combination thereof.

PAN rosin acid concentration/content can be determined by GC. For example, in any aspect or embodiment described herein, the PAN rosin acid concentration/content can be determined according to ASTM D-5974-15 or a modification thereof, which are within the general knowledge of those skilled in the art. For example, the ASTM D-5974-15 method can be modified by using, e.g., a non-polar column (e.g., SPB-5), instead of a polar column, to allow for the use of high temperatures, which allows for substances with higher boiling points to elute out from the column, and/or faster heating rates, which can accelerate the analysis. In any aspect or embodiment described herein, the correction factor for heavies estimation can be determined by the GPC method. PAN rosin acid concentration/content can alternatively be determined by GS-Mass Spectroscopy utilizing the ASTM D-5974-15 method, including modifications that one skilled in the art would appreciate (such as, a non-polar column may be utilized to allow for faster heating rates and higher temperature, which accelerates the analysis).

In any aspect or embodiment described herein, the heavies in the low titer fatty acid material (i.e., the low titer fatty acid material comprising rosin acid) is less than or equal to about 40% (e.g., about 0.5 to about 40%, about 5 to about 40%, about 5 to about 35%, or about 15 to about 28%) of the low titer fatty acid composition. In any aspect or embodiment described herein, the heavies are dimer and trimer fatty or rosin acids that have a higher boiling point than the monomer fatty and rosin acids, which are usually formed during the distillation process. In any aspect or embodiment described herein, the concentration and content of heavies in the low titer fatty acid material can be determined, e.g., by the GPC. For example, in certain embodiments, the low titer fatty acid material (i.e., the low titer rosin acid containing fatty acid material) comprises ≤about 40%, ≤about 35%, ≤about 30%, ≤about 25%, ≤about 20%, ≤about 15%, ≤about 10%, ≤about 5%, about 0.5% to about 40%, about 0.5% to about 35%, about 0.5% to about 30%, about 0.5% to about 25%, about 0.5% to about 20%, about 0.5% to about 15%, about 0.5% to about 10%, about 0.5% to about 5%, about 5% to about 40%, about 5% to about 35%, about 5% to about 30%, about 5% to about 25%, about 5% to about 20%, about 5% to about 15%, about 5% to about 10%, about 10% to about 40%, about 10% to about 35%, about 10% to about 30%, about 10% to about 25%, about 10% to about 20%, about 10% to about 15%, about 15% to about 40%, about 15% to about 35%, about 15% to about 30%, about 15% to about 25%, about 15% to about 20%, about 20% to about 50%, about 20% to about 35%, about 20% to about 30%, about 20% to about 25%, about 25% to about 40%, about 25% to about 35%, about 25% to about 30%, about 30% to about 40%, or about 35% to about 40% heavies from the tall oil distillation process or crude tall oil refining (e.g., dimers, trimmers, or other heavier components).

In any aspect or embodiment described herein, the low titer fatty acid material, low titer fatty acid material comprising rosin acid, or low titer rosin acid containing fatty acid material has a Gardner color index in a range from about 4.0 to about 17.0 (e.g., about 4.0 to about 14.7, about 6.0 to about 14.7, or about 9.0 to about 13.0). For example, in certain embodiments, the low titer fatty acid material has a Gardner color index of about 4.0 to about 17.0, about 4.0 to about 15.0, about 4.0 to about 14.7, about 4.0 to about 13.0, about 4.0 to about 12.0, about 4.0 to about 10.0, about 4.0 to about 8.0, about 4.0 to about 6.0, about 6.0 to about 17.0, about 6.0 to about 15.0, about 6.0 to about 14.7, about 6.0 to about 13.0, about 6.0 to about 12.0, about 6.0 to about 10.0, about 6.0 to about 8.0, about 8.0 to about 17.0, about 8.0 to about 15.0, about 8.0 to about 14.7, about 8.0 to about 13.0, about 8.0 to about 12.0, about 8.0 to about 10.0, about 10.0 to about 17.0, about 10.0 to about 15.0, about 10.0 to about 14.7, about 10.0 to about 13.0, about 10.0 to about 12.0, about 12.0 to about 17.0, about 12.0 to about 15.0, about 12.0 to about 14.0, or about 14.0 to about 17.0. In any aspect or embodiment described herein, the Gardner color index is determined with ASTM D6166-12 (2016).

In any aspect or embodiment described herein, the low titer fatty acid material, low titer fatty acid material comprising rosin acid, or low titer rosin acid containing fatty acid material has a Chemical Abstracts Service Registry (CAS) No. 8002-26-4; a blend or mixture of a tall oil with a CAS No. 8002-26-4 and a TOFA with a CAS No. 61790-12-3; a blend or mixture of CAS No. 8050-09-7 (Resin-95 or rosin R-24) and a TOFA with a CAS No. 61790-12-3; a blend or mixture of CAS No. 8002-26-4, CAS No. 61790-12-3, and CAS No. 8050-09-7; or a disproportionated tall oil with a CAS No. 68152-92-1 optionally blended or mixed with another low titer fatty acid material, TOFA, DTO, or tall oil.

Amine Material

In any aspect or embodiment described herein, amine value can be determined through titration. For example, in any aspect or embodiment described herein, amine value can be determined by titration with 0.5N HCl. An exemplary method that may be used to determine amine value through titration is described below in the Examples.

In any aspect or embodiments described herein, the amine material is or includes the chemical composition having Chemical Abstracts Service (CAS) Registry No. 68910-05-4. This composition is the distillation residuum bottoms composition remaining from the process wherein monoethanolamine (i.e., 2-aminoethanol) is reacted with ammonia to produce a reaction product which is then fractionated to recover a piperazine distillate product therefrom, thus leaving the remaining CAS Reg. No. 68910-05-4 distillation residuum bottoms composition. The distillation residuum bottoms composition CAS Reg. No. 68910-05-4 is commercially available, for example, from Dow® Chemical Co. (Marlborough, Mass.) under the name AMINE HST and is also available from BASF under the name AMIX 1000 or Berolamine 20 (BA-20). AMINE HST has: an estimated boiling point (760 mmHg) of 256° C., an estimated flashpoint (closed cup) of 146° C., an estimated vapor pressure of less than 0.01 mmHg at 20° C., an estimated vapor density (air=1) of 4.6, an estimated specific gravity (water=1) of 1.0-1.3 at 20° C./20° C., an estimated solubility in water of 100% by weight at 20° C., and an estimated pour point of −24° C.

Thus, in any aspect or embodiment described herein, the amine material is or includes a chemical composition having CAS Registry No. 68910-05-4, such as at least one of: AMINE HST (e.g., an amine material having at least one of: an estimated boiling point (760 mmHg) of 256° C., an estimated flashpoint (closed cup) of 146° C., an estimated vapor pressure of less than 0.01 mmHg at 20° C., an estimated vapor density (air=1) of 4.6, an estimated specific gravity (water=1) of 1.0-1.3 at 20° C./20° C., an estimated solubility in water of 100% by weight at 20° C., an estimated pour point of −24° C., or a combination thereof), BA-20 (e.g., an amine material having at least one of: an amine value of at least 1100 mg/g, a viscosity at 50° C. that is equal to or less than 100, a melting or freezing point of at 1013 hPa that is less than −30° C., a boiling point at 1013 hPa of about 254° C., a flash point at 1013 hPa of about 176° C., a viscosity (such as a dynamic viscosity) at 50° C. of about 40 mPa·s, an auto-ignition temperature at 1013 hPa of about 355° C., a relative density at 20° C. of about 1024, about 45% alkanolamines (e.g., AEEA, DEA, hydroxymethyl DETA, and higher order alkanolamines), a vapor pressure at 20° C. of about 0.00009 hPa, about 55% higher polyethylene polyamines (e.g., isomers of TETA, TEPA, PEHA, and higher order polyethylene polyamines), or AMIX 1000 (e.g., an amine material having at least one of: an amine value of about 1000 mg/g, a melting temperature of about −30° C., a boiling temperature of about 236° C. to about 310° C., a density at 20° C. of about 1.04 g/cm3, a flash point of about 132° C., an ignition temperature of about 360° C., or a combination thereof).

Method of Making the LGS Tolerant Emulsifier

The present disclosure also provides methods of making a LGS tolerant emulsifier (i.e, a MDTA emulsifier or a LGS tolerant MDTA emulsifier), the method comprising: reacting the low titer fatty acid material an amine material to produce an amido-amine reaction product; and reacting the amido-amine reaction product with maleic anhydride to produce a maleated amido-amine reaction product.

In any aspect or embodiment described herein, the method of making a LGS tolerant MDTA emulsifier comprising reacting a low titer fatty acid material and an amine material at room temperature and then elevated temperatures to produce an amido-amine reaction product; and reacting the amido-amine reaction product with maleic anhydride at elevated temperature to produce a maleated-amido-amine reaction product. In any aspect or embodiment described herein, the method of making a LGS tolerant MDTA emulsifier comprising reacting a low titer fatty acid material and an amine material at room temperature first, followed by heating to about 110 to about 150° C. (e.g., from about 130 to about 140° C.), followed by heating to about 175 to about 250° C. (e.g., from about 200 to about 225° C.), to produce an amido-amine reaction product; and reacting the amido-amine reaction product with maleic anhydride at about 60 to about 90°, and optionally hold for up to about 1 hour (e.g., ≤about 30 minutes), to produce a maleated amido-amine reaction product. In certain embodiments, the fatty acid material and amine material are incubated at the elevated temperature for up to about 4 hours (e.g., ≤about 3 hours, ≤about 2 hours, ≤about 1 hour, about 1 to about 4 hours, about 1 to about 3 hours, about 1 to about 2 hours, about 2 to about 4 hours, about 2 to about 3 hours, or about 3 hours to about 4 hours).

Invert Emulsion Fluid

Another aspect of the present disclosure provides an invert emulsion fluid (IEF) comprising the emulsifier of the present disclosure and at least one of: a non-aqueous continuous phase, a discontinuous hygroscopic phase like brine, an additive, or a combination thereof. In any aspect or embodiment described herein, the additive includes at least one of (e.g., 1, 2, 3, 4, 5, or 6, or more) a rheology modifier, emulsifier, wetting agents, viscosifiers, lime, salts, fluid loss additives, lost circulation materials, weighting agents, or a combination thereof. The IEF of the present disclosure demonstrated the surprising and unexpected ability to control (i.e., reduced) rheology even in the presence of relatively high concentrations of LGS as compared to a maleated TOFA amine emulsifier, which is generally recognized as the industry standard, as disclosed in, e.g., U.S. Pat. No. 8,927,468 B2, which is incorporated herein by reference in its entirety, including a non-spray dried version of the emulsifier (see e.g., page 4 of U.S. Pat. No. 8,927,468 B2).

In any aspect or embodiment described herein, the IEF comprises a high volume, amount, or concentration of LGS. For example, the inverted emulsion fluid can comprise from about 4% to about 12% V/V of low gravity solids. For example, in any aspect or embodiment described herein, the IEF comprises about 4% to about 12%, about 4% to about 10%, about 4% to about 8%, about 4% to about 6%, about 6% to about 12%, about 6% to about 10%, about 6% to about 8%, about 8% to about 12%, about 8% to about 10%, or about 10% to about 12% V/V of low gravity solids. In any aspect or embodiment described herein, the IEF comprises about 4%, about 4.5%, about 5%, about 5.5%, about 6%, about 6.5%, about 7%, about 7.5%, about 8%, about 8.5%, about 9%, about 9.5%, about 10%, about 10.5%, about 11%, about 11.5%, or about 12% V/V of low gravity solids.

In any aspect or embodiment described herein, the LGS have a specific gravity of about 2.0 to about 3.0. For example, in certain embodiments, the LGS has a specific gravity of about 2.0 to about 3.0, about 2.0 to about 2.9, about 2.0 to about 2.8, about 2.0 to about 2.7, about 2.0 to about 2.6, about 2.0 to about 2.5, about 2.0 to about 2.4, about 2.0 to about 2.3, about 2.0 to about 2.2, about 2.0 to about 2.1, about 2.1 to about 3.0, about 2.1 to about 2.9, about 2.1 to about 2.8, about 2.1 to about 2.7, about 2.1 to about 2.6, about 2.1 to about 2.5, about 2.1 to about 2.4, about 2.1 to about 2.3, about 2.1 to about 2.2, about 2.2 to about 3.0, about 2.2 to about 2.9, about 2.2 to about 2.8, about 2.2 to about 2.7, about 2.2 to about 2.6, about 2.2 to about 2.5, about 2.2 to about 2.4, about 2.2 to about 2.3, about 2.3 to about 3.0, about 2.3 to about 2.9, about 2.3 to about 2.8, about 2.3 to about 2.7, about 2.3 to about 2.6, about 2.3 to about 2.5, about 2.3 to about 2.4, about 2.4 to about 3.0, about 2.4 to about 2.9, about 2.4 to about 2.8, about 2.4 to about 2.7, about 2.4 to about 2.6, about 2.4 to about 2.5, about 2.5 to about 3.0, about 2.5 to about 2.9, about 2.5 to about 2.8, about 2.5 to about 2.7, about 2.5 to about 2.6, about 2.6 to about 3.0, about 2.6 to about 2.9, about 2.6 to about 2.8, about 2.6 to about 2.7, about 2.7 to about 3.0, about 2.7 to about 2.9, about 2.7 to about 2.8, about 2.8 to about 3.0, about 2.8 to about 2.9, or about 2.9 to about 30. In certain embodiments, the LGS has a specific gravity of about 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or 3.0.

In any aspect or embodiment described herein, the low gravity solids are argillaceous solids. In any aspect or embodiment described herein, the LGS are drill solids. In any aspect or embodiment described herein, the LGS is or includes calcium montmorillonite. For example, the LGS can be REV DUST® (MILWHITE, INC., Brownsville, TV).

In any aspect or embodiment described herein, the IEF of the present disclosure has a low fluid loss, e.g. a fluid loss of no greater than (i.e., less than or equal to) about 20 mL at 350° F. in about 30 minutes. Thus, the IEF of the present disclosure does not compromise on fluid loss performance and has sufficient emulsion stability for a workable fluid.

In any aspect or embodiment described herein, the IEF of the present disclosure has a low HTHP fluid loss, e.g., a fluid loss between about 1 and about 20 mL at 350° F. in about 30 minutes. See, e.g., API Recommended Practice 13B-2, Fourth Edition, Recommended Practice for Field Testing of Oil-based Drilling Fluids, for the test method to conduct the HTHP filtration test, i.e., at the test temperature indicated. Thus, the IEF of the present disclosure do not compromise on their fluid loss performance and have sufficient emulsion stability for a workable fluid. For example, in any aspect or embodiment described herein, the fluid loss of the IEF of the present disclosure is about 1 mL to about 20 mL, about 1 mL to about 15 mL, about 1 mL to about 10 mL, about 1 mL to about 5 mL, about 5 mL to about 20 mL, about 5 mL to about 15 mL, about 5 mL to about 10 mL, about 10 mL to about 20 mL, about 10 mL to about 15 mL, or about 15 mL to about 20 mL.

In any aspect or embodiment described herein, the IEF of the present disclosure has a lower rheology than a similarly formulated IEF comprising a maleated TOFA amine emulsifier. In an embodiment, the IEF of the present disclosure has a rheology that is lower than a similarly formulated IEF comprising a maleated TOFA amine emulsifier as determined by a decrease in Fann 35 rheometer readings from 600 rotations per minute (rpm) to 3 rpm, e.g., at 150° F. In certain embodiments, the IEF of the present disclosure has a rheology that is about 10-about 92% (e.g., about 10 to about 92% or about 50 to about 92%) lower than a similarly formulated IEF comprising a maleated TOFA amine emulsifier as determined by Fann 35 rheometer readings from 600 rpm to 3 rpm at 150° F. For example, in any aspect or embodiment described herein, the IEF of the present disclosure has a rheology, as determined by Fann 35 rheometer readings from 600 rpm to 3 rpm at 150° F., that is about 10 to about 92%, about 10 to about 95%, about 10 to about 80%, about 10 to about 70%, about 10 to about 60%, about 10 to about 50%, about 10 to about 40%, about 10 to about 30%, about 20 to about 92%, about 20 to about 85%, about 20 to about 80%, about 20 to about 70%, about 20 to about 60%, about 20 to about 50%, about 20 to about 40%, about 30 to about 92%, about 30 to about 85%, about 30 to about 80%, about 30 to about 70%, about 30 to about 60%, about 30 to about 50%, about 40 to about 92%, about 40 to about 85%, about 40 to about 80%, about 40 to about 70%, about 40 to about 60%, about 50 to about 92%, about 50 to about 85%, about 50 to about 80%, about 50 to about 70%, about 60 to about 92%, 60 to about 85%, about 60 to about 80%, or about 70 to about 92% lower than a similarly formulated IEF comprising a maleated TOFA amine emulsifier. In any of the aspects or embodiments described herein, the rheology of the IEF is determined at 100 ppb REVDUST tested under standard conditions. In any aspect or embodiment described herein, HPHT fluid loss and rheology are determined using the methods/conditions described in API Recommended Practice 13B-2, Fourth Edition, Recommended Practice for Field Testing of Oil-based Drilling Fluids). It should be noted that similar decreases are expected when rheology is measured at different temperatures, such as 120° F.

In any aspect or embodiment described herein, the IEF of the present disclosure has a lower gel strength than a similarly formulated IEF with a maleated TOFA amine emulsifier. In certain embodiments, the IEF of the present disclosure has a gel strength that is about 10 to about 92% (e.g., about 25 to about 85% or about 50 to about 85%) lower than a similarly formulated IEF comprising a maleated TOFA amine emulsifier at 150° F. For example, in any aspect or embodiment described herein, the IEF of the present disclosure has a gel strength at 150° F. that is about 10 to about 92%, about 10 to about 95%, about 10 to about 80%, about 10 to about 70%, about 10 to about 60%, about 10 to about 50%, about 10 to about 40%, about 10 to about 30%, about 20 to about 92%, about 20 to about 85%, about 20 to about 80%, about 20 to about 70%, about 20 to about 60%, about 20 to about 50%, about 20 to about 40%, about 30 to about 92%, about 30 to about 85%, about 30 to about 80%, about 30 to about 70%, about 30 to about 60%, about 30 to about 50%, about 40 to about 92%, about 40 to about 85%, about 40 to about 80%, about 40 to about 70%, about 40 to about 60%, about 50 to about 92%, about 50 to about 85%, about 50 to about 80%, about 50 to about 70%, about 60 to about 92%, 60 to about 85%, about 60 to about 80%, or about 70 to about 92% lower than a similarly formulated IEF comprising a maleated TOFA amine emulsifier. It should be noted that one of ordinary skill in the art would expect similar decreases in fluid gel strength when rheology is measured at a different temperature, such as 120° F.

In any aspect or embodiment described herein, the IEF of the present disclosure has a lower yield stress (Tau0) than a similarly formulated IEF with a maleated TOFA amine emulsifier. In certain embodiments, the IEF of the present disclosure has a yield stress that is about 10 to about 92% lower than a similarly formulated IEF comprising a maleated TOFA amine emulsifier at 150° F. This decrease is even observed in presence of a high volume of low gravity solids as described herein (e.g. greater than about 10% V/V). For example, in any aspect or embodiment described herein, the IEF of the present disclosure has a yield stress at 150° F. that is about 10 to about 92%, about 10 to about 85%, about 10 to about 80%, about 10 to about 70%, about 10 to about 60%, about 10 to about 50%, about 10 to about 40%, about 10 to about 30%, about 20 to about 92%, about 20 to about 85%, about 20 to about 80%, about 20 to about 70%, about 20 to about 60%, about 20 to about 50%, about 20 to about 40%, about 30 to about 92%, about 30 to about 85%, about 30 to about 80%, about 30 to about 70%, about 30 to about 60%, about 30 to about 50%, about 40 to about 92%, about 40 to about 85%, about 40 to about 80%, about 40 to about 70%, about 40 to about 60%, about 50 to about 92%, about 50 to about 85%, about 50 to about 80%, about 50 to about 70%, about 60 to about 92%, 60 to about 85%, about 60 to about 80%, or about 70 to about 92% lower than a similarly formulated IEF comprising a maleated TOFA amine emulsifier. It should be noted that similar decreases in yield stress is expected when rheology is measured at a different temperature, such as 120° F. In any aspect or embodiment described herein, the IEF of the present disclosure has a gel strength of about 10 to about 30 (e.g., about 10 to about 20, about 20 to about 30, or about 15 to about 25).

In any aspect or embodiment described herein, the IEF of the present disclosure is used for gas drilling, oil drilling, or both.

Drilling Fluid

Another aspect of the present disclosure provides a drilling fluid that comprises the IEF of the present disclosure, the LGS tolerant emulsifier of the present disclosure, or both.

In another aspect or embodiment described herein, the drilling fluid of the present disclosure has a lower gel strength than a similarly formulated drilling fluid comprising a maleated TOFA amine emulsifier, even in presence of a high volume or concentration of LGS (e.g. from about 4% to about 12% V/V of the drilling fluid).

In any aspect or embodiment described herein, the drilling fluid of the present disclosure has a lower rheology than a similarly formulated drilling fluid comprising a maleated TOFA amine emulsifier, even in presence of a high volume or concentration of LGS (e.g. from about 4% to about 12% V/V of the drilling fluid).

In any aspect or embodiment described herein, the drilling fluid is used for gas or oil drilling.

Method of Drilling a Well

A further aspect of the disclosure provides a method of drilling a well. The method comprises drilling a well bore and circulating the drilling fluid of the any aspect or embodiment described herein through said well bore when drilling the well bore.

EXAMPLES

The embodiments described above in addition to other embodiments can be further understood regarding the following examples.

RA concentration was determined by titration. A modified Glidden procedure was utilized for RA concentration of about 15% or less, and a modified Wolff Method was utilized for RA concentration of about 15% or greater. In particular, under the modified Wolff Method, 4.5-5.5 grams of the low titer fatty acid material, 90-110 mL of methanol, and 5 mL of methyl sulfuric acid (20% in methanol) was added to an Erlenmeyer flask, and under the modified Glidden Method, 39-41 grams of the low titer fatty acid material, 140-160 mL of methanol, and 10 mL of methyl sulfuric acid (20% in methanol) was added to an Erlenmeyer flask. If the solution prepared under the modified or Wolff Method or the modified Glidden method is cloudy, toluene is added (up to 30 mL) until the solution is clear. The flask of clear solution was connected to a condenser and refluxed for 20 minutes on a hotplate. The solution was then cooled. The rosin acid number was then determined through titration of the cooled solution with 0.5N KOH in methanol on a 888 Titrando Autotitrator (Metrohm, Riverview, Fla.).

Acid Number and Amine Value Determination.

Two grams of the low titer fatty acid material or amine material was added to a beaker. The low titer fatty acid material was dissolved in methanol or a mixture of methanol and Toluene or isopropanol using agitation and/or heat, as required for complete dissolution. The amine material was dissolved in 75 mL of isopropanol, using agitation and/or heat, as required for complete dissolution. Acid number was determined via titration with 0.5N KOH in methanol and the amine value was determined via titration with 0.5 HCL in methanol on a 888 Titrando Autotitrator (Metrohm, Riverview, Fla.).

Titer point of the low titer fatty acid material was determined via ASTM D1982-61. Briefly, the low titer fatty acid material was added to a test tube. A Thermometer and stirring wire was added to the test tube. The test tube assembly was placed in a frozen cold bath assembly. The stir wire completed approximately one-hundred 1-2″ up-and-down motions per minute. The temperature of the low titer fatty acid material was read every 15 seconds until the temperature remained constant for 30 seconds or until a rise in temperature was observed. Stirring was discontinued and any temperature rise was noted (exotherm portion). The titer point is the highest temperature observed during the exotherm portion before the temperature began to decrease.

Gardner Color Index Determination.

The Gardner color index was determined according to ASTM D6166-12 (2016).

Amount of Fatty Acid and Rosin Acid Determination.

The amount of fatty acid and rosin acid in the low titer fatty acid material or components thereof was determined utilized the method described in ASTM D5974-15.

Preparation of an Exemplary Emulsifier of the Present Disclosure: C2-B® based emulsifier (i.e., a maleated amido amine based on C2-B®).

C2-B® was utilized as the low titer fatty acid material and is a low titer fatty acid material collected as the bottoms product during the production of low rosin (<5%) and low Gardner Color index (<7.0) tall oil fatty acid (TOFA) from refinery columns during the distillation of crude tall oil (CTO). The acid number of the C2-B® can vary from about 143-about 185 mg/g, but typically is about 155-about 174 mg/g. Amine HST (CAS #68910-05-4) was used as the amine material and is available as an amine stream procured from Dow Chemicals, the batch used had an amine value of approximately 750 mg/g.

Preparation of the maleated amido-amine reaction product:1. About 350 grams (70% w/w) of the C2-B® (preheated) with an acid number of 167.2 mg/gm was added into to the five neck round bottom flask (1000 ml). Under stirring at 90 rpm, 150 grams (30% w/w) of Amine HST was added, which gives an exotherm.2. Once the temperature was stabilized, the reaction mixture was heated to 135° C. over 35 minutes and then held at 135° C. for 1 hour.3. The reaction mixture was ramped to 200° C. over 56 minutes and held at 200° C. temperature for 2 hours.4. After 2 hours, the reaction mixture was cooled to 100° C. The amino-amine reaction product was transferred to a sample bottle. The amine value of this C2-B® based amido-amine (i.e., the amido-amine reaction product) was determined to be 133.9 mg/gm.5. About 35.78 grams of the amido-amine reaction product was heated to 65° C. in an aluminum can and 19.8 grams of a mineral oil LVT 200 was added.6. This reaction mixture was stirred while the temperature was maintained at 65° C.7. During stirring, 4.42 grams of molten Maleic Anhydride (MA) was added dropwise. Since MA addition resulted in an exotherm, the MA addition was controlled to ensure the temperature was maintained at 85° C.8. After the addition of all the MA, the reaction mixture was stirred, while being held at 85° C., for 1 hour. The reaction mixture was then cool to room temperature.9. The resulting maleated C2-B amido-amine (i.e. the maleated amido-amine reaction product) had an amine value of 30.29 mg/gm and acid number of 52.59 mg/gm. This samples is labelled as 9160-57-11. Additional exemplary emulsifiers were prepared utilizing similar methods and will now be described in greater detail.

Exemplary and Comparative Emulsifiers utilized in the Examples are shown in Table 1. The Exemplary Emulsifiers (i.e., LGS tolerant emulsifier or MDTA emulsifier) of the disclosure were made with the indicated pure low titer distilled tall oil streams as the low titer fatty acid material and are designated 9139-70-11 (C2-B®), 9160-57-11 (C2-B®), 9177-32-11 (C2-B®), 9177-34-11 (C2-B®), 8998-75B-7 (Altapyne™ M28B) and 8998-75C-7 (Altapyne™ 1430) in Table 1. The Exemplary Emulsifiers made with low titer distilled tall oil streams having acid numbers ranging from 147.9 mg/g to 188.4 mg/g. Commercially available maleated TOFA amido-amine emulsifiers, which are the industry standard, were utilized as Comparative Emulsifiers. The emulsifiers were tested at an effective concentration of 10.7 ppb in the IEF. The formulations of the compositions and reaction conditions are shown in Table 2.

The components of the fluids were mixed, then hot rolled for 16 hours at 325° F. The fluids were then remixed on a multimixer for 5 minutes. Rheology and electrical stability (ES) were examined at 150° F. Fluid loss of the fluids was examined at 350° F., 500 psi differentials.

The rheology data of the invert emulsion fluids was measured at 150° F. and were modeled with the Herschel Buckley (HB) model. The HB model parameters—Tau0 (yield stress), K (consistency index), & n (flow index)—along with the Gel strength at 10 minutes, the Electrical Stability (ES), Fluid loss and Fann 35 rheometer readings from 600 to 3 rpm dial readings are presented in Table 3 and 4 below. All fluids tested were stable after the hot roll (as observed from their texture and appropriate ES values), gave controlled fluid loss values at 350° F., and showed water in the filtrate.

The Gel Strengths with the maleated TOFA amido-amine emulsifiers were very high at 58 units and 74 units. In comparison, the Gel strengths of the Exemplary Emulsifiers made with the low titer fatty acid material of varying acid numbers ranged from 15 to 21 units and 30-31 units. The Maleated TOFA amido-amine—1, 9139-70-11, 9160-57-11, 9177-32-11, and 9177-34-11 were analyzed with a different batch of REV DUST® than the Maleated TOFA amido-amine—2, 8998-75B-7, and 8998-75C-7. Thus, while 8998-75B-7 and 8998-75C-7 have higher Gel strengths than the other Exemplary Emulsifiers, this appears to be a result of the REV DUST batch utilized as the Maleated TOFA amido-amine—2, which is the same product as the Maleated TOFA amido-amine—1, demonstrated a higher Gel strength. Thus, a decrease in Gel strength was observed in each of the Exemplary Emulsifiers as compared to the concomitantly analyzed comparative example.

Similarly, the Tau0 (yield stress) from the HB model were in the range of 5-10 for the Exemplary Emulsifier made with low titer fatty acid material. The commercial available maleated TOFA amine emulsifier demonstrated a very high Tau0 at 39.7 and 59.3.

The appreciable gels are required for suspension whereas the low rheology will help to maintain low ECD (in this case in the presence of high LGS @ 100 ppb).

FIGS. 1 and 2present the rheology data of shear stress versus shear rate for exemplary fluids of the present disclosure, as well as comparative fluids. The rheograms ofFIGS. 1 and 2demonstrate that the fluids of the present disclosure formulated with the emulsifier of the present disclosure has low rheology, as compared to the commercially available maleated TOFA amine emulsifier. Thus, the fluids of the present disclosure comprising the emulsifier of the present disclosure were surprisingly able to tolerate the presence of 100 ppb LGS.

A low rheology typically delivers a low ECD, while drilling oil and gas wells. A low ECD generally leads to lower induced fluid losses to the formation. Since invert emulsion fluids are expensive, lower induced fluid losses to the formation are desired. A high concentration of low gravity solids (drilled solids) in the fluid typically increases the overall rheology of the fluid thereby leading to higher ECD, and therefore, higher induced fluid losses to the formation. A low rheology should be coupled with appreciable gels, since when drilling stops and fluid is in a static condition, the gels help to maintain the barite and drilled solids in suspension. A fluid with low gels can lead to barite sag and poor hole cleaning, both of which can lead to loss of precious time at the rig when drilling oil and gas wells.

While preferred embodiments of the present disclosure have been shown and described herein, it will be understood that such embodiments are provided by way of example only. Numerous variations, changes and substitutions will occur to those skilled in the art without departing from the spirit of the present disclosure. Accordingly, it is intended that the appended claims cover all such variations as fall within the spirit and scope of the invention. Furthermore, the system may comprise at least one device for charging and/or discharging the system or a plurality of devices for charging and/or discharging the system.

The contents of all references, patents, pending patent applications and published patents, cited throughout this application are hereby expressly incorporated by reference.

Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the present disclosure described herein. Such equivalents are intended to be encompassed by the following claims. It is understood that the detailed examples and embodiments described herein are given by way of example for illustrative purposes only, and are in no way considered to be limiting to the invention. Various modifications or changes in light thereof will be suggested to persons skilled in the art and are included within the spirit and purview of this application and are considered within the scope of the appended claims. For example, the relative quantities of the ingredients may be varied to optimize the desired effects, additional ingredients may be added, and/or similar ingredients may be substituted for one or more of the ingredients described. Additional advantageous features and functionalities associated with the systems, methods, and processes of the present disclosure will be apparent from the appended claims. Moreover, those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the present disclosure. Such equivalents are intended to be encompassed by the following claims.