Patent Application
20250101309
The present disclosure relates to an emulsifier composition that remains free-flowing without the use of a support material and/or a diluent. The present disclosure also relates to methods of making the emulsifier composition, drilling fluids comprising the emulsifier composition, and methods of drilling a wellbore.
A drilling fluid (also known as “mud”) is a specially designed fluid that is circulated through an oil or gas wellbore as the wellbore is drilled to facilitate the drilling operation. The drilling fluid can be a water-based drilling fluid (water-based mud) or an oil-based drilling fluid (oil-based mud).
Oil-based drilling fluid or mud is a widely used drilling fluid in the oil and gas production industry. Drilling fluids or muds are used to cool the bit, lubricate the drill string, suspend and transport cuttings, control hydrostatic pressure, and maintain stability. Oil-based drilling fluids or muds, which are also referred to as invert emulsion drilling fluids, are composed of oil as a continuous phase and water as a dispersed phase together with emulsifiers, wetting agents, gellants, etc. The oil phase typically comprises diesel, kerosene, fuel oil, crude oil, or mineral oil. Water-based drilling fluids or muds are composed of water as a continuous phase and oil as a dispersed phase together with, e.g., viscosifiers, fluid loss control agents, weighting agents, lubricants, emulsifiers, corrosion inhibitors, salts, pH control agents, etc.
Known liquid invert emulsion drilling fluid emulsifiers suffer from issues with their pour point in cooler temperatures (such as, those experienced during the winter and in cold climates), thereby limiting their use in these conditions or requiring special equipment to warm the emulsifier before use. Powdered emulsifiers avoid cold temperature issues due to their free-flowing nature, even at cold temperatures. However, all known commercial dry emulsifiers incorporate a solid support (e.g. silica) to avoid issues with the physical property of the dried emulsifier (e.g. tackiness and caking), thereby maintaining the free-flowing nature of the powder. The use of solid support results in a dilution of the emulsifier in the end product, and results in settling of the solid support in mud pits and unwelcome abrasion issues, depending on the abrasive nature of the particular solid support.
Historically, some emulsifiers for invert emulsion drilling fluids or muds incorporate tall-oil fatty acids (TOFA) as a raw material. Depending on the chemistry, some of these emulsifiers are semi-solid at room temperature, tacky, and not well suited to producing powdered products. As discussed above, these emulsifiers can be mixed with a solid support material (e.g., silica) to allow processing into powders, but this dilutes the activity of the emulsifier by the portion of support added. Furthermore, liquid emulsifiers include additives (such as diluents, pour point depressants, and the like) to address the high viscosity of some reaction products. Thus, liquid emulsifiers also dilute the activity of the emulsifier by the required additives. Indeed, for a great deal of amidoamine chemistry, a solvent package, vide supra, is required because the amidoamine reaction product is pasty and thus, not a practical or commercially viable form for an emulsifier. As a result, the dilution of solid and liquid emulsifiers requires the usage of additional emulsifier in the application, thereby increases the cost and can impact the properties and performance of the fluid/mud.
Thus, there is a need for a powdered emulsifier for invent emulsions, such as invert emulsion drilling fluid, that does not require solid supports (e.g., not required solid supports to maintain a free-flowing powder form), and delivers fully active product when viscosity would limit that feature. The present disclosure provides an emulsifier composition that does not require (e.g., does not have) solid supports. The emulsifier composition of the present disclosure maintains its form as a free-flowing powder, thereby decreasing the amount of processing required. Not including additional additives to the emulsifier (e.g., diluents, solid supports, adsorbents, pour point depressants, and the like) increases the sustainability, since it finishes a product that is only active/operative emulsifier.
Presently described are emulsifier compositions, as well as methods of making and using the same, and drilling fluids or muds comprising the emulsifier compositions of the present disclosure, as well as methods of making and using the same.
An aspect of the present disclosure provides an emulsifier composition comprising, consisting essentially of, or consisting of a blend of: (1) a first emulsifier; and (2) a second emulsifier, or a second emulsifier reaction product, made by a process comprising, consisting essentially of, or consisting of: reacting (A) a fatty acid composition with (B) one or more (e.g., 1, 2, 3, 4, 5, 6, or more) poly(alkylamine) to produce a partial amide; and reacting (a) the partial amide with (b) an acid and/or anhydride composition that includes or is a dicarboxylic acid, di-anhydride, tricarboxylic acid, tri-anhydride, or a mixture thereof, to produce the second emulsifier, wherein the fatty acid composition comprises at least about 60% C16-18 fatty acids and at least 65% saturated fatty acids (e.g., at least 85% saturated fatty acids).
Another aspect of the present disclosure provides an emulsifier composition made by a process comprising, consisting essentially of, or consisting of, blending a first emulsifier; and a second emulsifier, or second emulsifier reaction product, made by a process comprising, consisting essentially of, or consisting of: reacting (A) a fatty acid composition with (A) one or more (e.g., 1, 2, 3, 4, 5, 6, or more) poly(alkylamine) to produce a partial amide; and reacting (a) the partial amide with (b) an acid and/or anhydride composition that includes or is a dicarboxylic acid, di-anhydride, tricarboxylic acid, tri-anhydride, or a mixture thereof, to produce the second emulsifier, wherein the fatty acid composition comprises at least about 60% C16-18 fatty acids and at least 65% saturated fatty acids (e.g., at least 85% saturated fatty acids).
A further aspect of the present disclosure provides a method of making an emulsifier composition of the present disclosure, the method comprising, consisting essentially of, or consisting of, providing a first emulsifier, optionally preparing the first emulsifier; preparing a second emulsifier; and blending the first emulsifier and the second emulsifier, wherein the method of preparing the second emulsifier comprising, consisting essentially of, or consisting of: reacting (A) a fatty acid composition with (B) one or more (e.g., 1, 2, 3, 4, 5, 6, or more) poly(alkylamine) to produce a partial amide; and reacting (a) the partial amide with (b) an acid and/or anhydride composition that includes or is a dicarboxylic acid, di-anhydride, tricarboxylic acid, tri-anhydride, or a mixture thereof, to produce the second emulsifier, wherein the fatty acid composition comprises at least about 60% C16-18 fatty acids and at least 65% saturated fatty acids (e.g., at least 85% saturated fatty acids).
An additional aspect of the present disclosure provides a method of enhancing or improving at least one handling property (e.g., moisture uptake, the spray drying process, flowability after storage, etc.) of a spray dried emulsifier composition comprising of a first emulsifier, the method comprising, consisting essentially of, or consisting of: providing a first emulsifier, optionally preparing the first emulsifier; preparing a second emulsifier; and blending the first emulsifier and the second emulsifier, wherein the blend of the first emulsifier and the second emulsifier has an enhancement or improvement in at least handling property relative to an emulsifier composition comprising the first emulsifier and not the second emulsifier (e.g., consisting of the first emulsifier), wherein the method of preparing the second emulsifier comprising, consisting essentially of, or consisting of: reacting (A) a fatty acid composition with (B) one or more (e.g., 1, 2, 3, 4, 5, 6, or more) poly(alkylamine) to produce a partial amide; and reacting (a) the partial amide with (b) an acid and/or anhydride composition that includes or is a dicarboxylic acid, di-anhydride, tricarboxylic acid, tri-anhydride, or a mixture thereof, to produce the second emulsifier, wherein the fatty acid composition comprises at least about 60% C16-18 fatty acids and at least 65% saturated fatty acids (e.g., at least 85% saturated fatty acids).
In any aspect or embodiment described herein, (i) the emulsifier composition does not include a support material, a solid support, a solvent, a diluent, an adsorbent, a pour point depressant, a filler, an anti-caking agent, any additives, or a combination thereof; (ii) the emulsifier composition only includes the first emulsifier (e.g., the first emulsifier reaction product) and the second emulsifier (e.g., the second emulsifier reaction product); (iii) the emulsifier composition consists of the first emulsifier reaction product and the second emulsifier reaction product; or (iv) a combination thereof.
In any aspect or embodiment described herein, the fatty acid composition comprises, consists essentially of, or consists of, one or more (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more) C16-18 fatty acid (e.g., a mixture of C16-18 fatty acids or Alta Veg™ FA 450).
In any aspect or embodiment described herein, the fatty acid composition comprises, consists essentially of, or consists of, two or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or more) C16-18 fatty acid (e.g., a mixture of C16-18 fatty acids or Alta Veg™ FA 450).
In any aspect or embodiment described herein, the fatty acid composition comprises: at least about 60% C16 fatty acids (e.g., palmitic acid) and C18 fatty acids (e.g., stearic acid); less than about 30% unsaturated C18 fatty acids; or a combination thereof.
In any aspect or embodiment described herein, the fatty acid composition comprises: at least about 65% C16 fatty acids (e.g., palmitic acid) and C18 fatty acids (e.g., stearic acid); less than about 25% unsaturated C18 fatty acids; or a combination thereof.
In any aspect or embodiment described herein, the fatty acid composition comprises: at least 85% saturated fatty acids; the fatty acid composition includes or is palmitic acid, stearic acid, hydrogenated tallow fatty acids, or a mixture thereof; the fatty acid composition includes at least about 65% C16 fatty acids (e.g., palmitic acid) and C18 fatty acids (e.g., stearic acid), less than about 10% C18 fatty acids (e.g., stearic acid), and less than about 25% unsaturated C18 fatty acids; or a combination thereof.
In any aspect or embodiment described herein, the poly(alkylamine) includes 1 to 12 carbon atoms (e.g., 3 to 9 or 4 to 8 carbon atoms), 1 to 7 nitrogen atoms (e.g., 2 to 6 or 3 to 5 nitrogen atoms), or a combination thereof (e.g., 1 to 12 carbon atoms and 1 to 7 nitrogen atoms, 4 to 8 carbon atoms and 3 to 5 nitrogen atoms, or 3 to 9 carbon atoms and 2 to 6 nitrogen atoms).
In any aspect or embodiment described herein, (i) the dicarboxylic acid is a C2-6 dicarboxylic acid (e.g., maleic acid, fumaric acid, succinic acid, or a mixture thereof); (ii) the di-anhydride is a C2-6 di-anhydride (e.g. maleic anhydride, succinic anhydride, or a mixture thereof); (iii) the tricarboxylic acid is a C3-8 tricarboxylic acid; (iv) the tri-anhydride is a C3-8 tri-anhydride, or (v) a combination thereof.
In any aspect or embodiment described herein, (i) the one or more poly(alkylamine) includes or is diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), or a mixture thereof; (ii) the acid and/or anhydride composition includes or selected from maleic acid, fumaric acid, succinic acid, succinic anhydride, maleic anhydride, or a mixture thereof; or (iii) a combination thereof.
In any aspect or embodiment described herein, (i) the fatty acid composition is present in an amount of about 75 to about 90 wt % (e.g., about 78 to about 88 wt %) of the partial amide; (ii) the one or more poly(alkylamine) is present in an amount of about 10 to about 25 wt % (e.g., about 12 to about 22 wt %) of the partial amide; (iii) the partial amide is present in an amount of about 80 to about 95 wt % (e.g., about 85 to about 95 wt % or about 90 wt %) of the second emulsifier; (iv) the acid and/or anhydride composition is present in an amount of about 5 to about 20 wt % (e.g., about 5 to about 15 wt % or about 10 wt %) of the second emulsifier; or (v) a combination thereof.
In any aspect or embodiment described herein, (i) the molar ratio of the fatty acid composition to the poly(alkylamine) is about 1.85 to about 2.0; (ii) the molar ratio of the partial amide to the acid and/or anhydride composition is about 0.6 to about 1.0 (e.g., about 0.6 to about 0.75); or (iii) a combination thereof.
In any aspect or embodiment described herein, the second emulsifier has an acid number of about 45 to about 80, an amine number of about 5 to about 15, or a combination thereof.
In any aspect or embodiment described herein, reacting the fatty acid composition with the poly(alkylamine) comprises, consists essentially of, or consists of: (i) heating the fatty acid composition (e.g., heating the fatty acid composition to the melting point of the fatty acid composition, such as about 50° C. to about 100° C.) to produce a molten fatty acid composition; (ii) adding the acid and/or anhydride composition to the fatty acid composition (e.g., a molten fatty acid composition); (iii) agitating the fatty acid composition and the one or more poly(alkylamine) reaction mixture; (iv) reacting the fatty acid composition and the acid and/or anhydride composition at about 145° C. to about 185° C. (e.g., about 150° C. to about 180° C. or about 150° C. to about 170° C.) until the acid number (AN) is less than about 20 mg/g, less than about 15 mg/g, or less than about 10 mg/g (e.g., reacting the fatty acid composition and the acid and/or anhydride composition for about 30 minutes to about 3 hours or about 1 hour to about 2.5 hours); or (v) a combination thereof.
In any aspect or embodiment described herein, reacting the partial amide with the acid and/or anhydride composition comprises, consists essentially of, or consists of: (i) heating the partial amide to about 100° C. to about 140° C. (e.g., about 110° C. to about 130° C., or about 120° C.); (ii) adding the acid and/or anhydride composition to the partial amide (e.g., adding the acid and/or anhydride composition while maintaining the temperature of the mixture below about 140° C., or about 120° C. to about 130° C., during the addition); (iii) agitating the partial amide and the acid and/or anhydride composition reaction mixture; (iv) reacting the partial amide and the acid and/or anhydride composition at about 130° C. to about 165° C. (e.g., about 130° C. to about 150° C. or about 130° C. to about 140° C.); (v) reacting the partial amide and the acid and/or anhydride composition for about 30 minutes to about 90 minutes (e.g., about 30 minutes to about 75 minutes, about 45 minutes to about 60 minutes, or about 45 minutes); or (vi) a combination thereof.
In any aspect or embodiment described herein, blending the first emulsifier and the second emulsifier comprises, consists essentially of, or consists of: (i) heating the second emulsifier to about 60° C. to about 100° C.; (ii) heating the emulsifier blend to about 60° C. to about 100° C.; (iii) adding the first emulsifier to the second emulsifier; (iv) mixing the first emulsifier and the second emulsifier for at least 15 minutes (e.g., about 15 minutes to about 60 minutes or about 20 minutes to about 45 minutes); (v) stop heating the emulsifier blend once (1) an acid number of about 165 to about 230 mg/g is achieved, (2) an amine value of about 1 to about 12 mg/g is achieved, or (3) a combination thereof; or (vi) a combination thereof.
In any aspect or embodiment described herein, (i) the emulsifier blend has an acid number of about 165 to about 230 mg/g, an amine value of about 1 to about 12 mg/g, or a combination thereof; (ii) the emulsifier composition is a particulate (e.g., a spray dried emulsifier composition); (iii) the emulsifier composition is a soap of the emulsifier blend and/or a neutralized emulsifier blend; (iv) the emulsifier composition has a pH of about 10 to about 11 (e.g., a pH of about 10.5), a non-volatile residue (NVR) of about 45% to about 55% (e.g., about 48% to about 52% or about 50%), or a combination thereof; or; (v) a combination thereof.
In any aspect or embodiment described herein, the process or method further comprising (i) neutralizing the emulsifier blend (e.g., reacting the emulsifier blend with a caustic solution (e.g., a solution comprising LiOH, NaOH, KOH, Ca(OH)2, ammonia, alkylamine, alkanolamines, or a combination thereof) to produce a neutralized emulsifier blend or a soap of the emulsifier blend); (ii) spray drying the emulsifier blend, the neutralized emulsifier blend, or the soap of the emulsifier blend; or (iii) a combination thereof.
In any aspect or embodiment described herein, the blend of the first emulsifier and the second emulsifier comprises, consists essentially of, or consists of: the first emulsifier in an amount of about 50 wt % to about 80 wt % (e.g., about 55 wt % to about 75 wt % or about 65 wt %); the second emulsifier in an amount of about 20 wt % to about 50 wt % (e.g., about 25 wt % to about 45 wt % or about 35 wt %); or a combination thereof.
In any aspect or embodiment described herein, neutralizing the emulsifier blend comprises, consists essentially of, or consists of: (i) heating the emulsifier blend to about 60° C. to about 100° C. (e.g., about 70° C. to about 90° C. or about 80° C.); (ii) diluting the emulsifier blend with water; (iii) adding a caustic solution (e.g., a solution comprising LiOH, NaOH, KOH, Ca(OH)2, ammonia, alkylamine, alkanolamines, or a combination thereof) to the emulsifier blend or the diluted emulsifier blend (e.g., reacting the emulsifier blend or the diluted emulsifier blend with a caustic solution (e.g., a solution comprising LiOH, NaOH, KOH, Ca(OH)2, ammonia, alkylamine, alkanolamines, or a combination thereof)); (iv) adding defoamer (e.g., polyorganosilanes) to the caustic solution treated emulsifier blend or caustic solution treated diluted emulsifier blend; (v) mixing the caustic solution treated emulsifier blend or caustic solution treated diluted emulsifier blend for about 45 minutes to about 90 minutes (e.g., about 45 minutes to about 75 minutes, about 50 minutes to about 70 minutes, or about 60 minutes); (vi) mixing the caustic solution treated emulsifier blend or caustic solution treated diluted emulsifier blend at about 35° C. to about 65° C. (e.g., about 40° C. to about 60° C. or about 50° C.); (vii) adjusting the pH to about 10 to about 11 or about 10.5 (e.g., adjusting the pH to about 10 to about 11 or about 10.5 with the addition of a base, such as NaOH); (viii) adding water to the neutralized emulsifier blend or the soap of the emulsifier blend to achieve a non-volatile residue (NVR) of about 45% to about 55% (e.g., about 48% to about 52% or about 50%); or (ix) a combination thereof.
In any aspect or embodiment described herein, the emulsifier composition, the neutralized emulsifier blend, the soap of the emulsifier blend, or the salt of the emulsifier blend, comprises, consists essentially of, or consists of: (i) water in an amount of about 30 wt % to about 55 wt % (e.g., about 35 wt % to about 47 wt % or about 41.5 wt %); (ii) the caustic solution (e.g, a solution comprising LiOH, NaOH, KOH, Ca(OH)2, ammonia, alkylamine, alkanolamines, or a combination thereof and/or a 50% caustic solution) in an amount of about 7.5 wt % to about 17.5 wt % (e.g., about 10 wt % to about 15 wt % or about 12.25 wt %); (iii) defoamer (e.g., polyorganosilanes) in an amount of about 0.02 to about 0.15 wt % (e.g., about 0.02 to about 0.1 wt % or about 0.04 wt %); (iv) the blend of the first emulsifier and the second emulsifier in an amount of about 30 wt % to about 60 wt % (e.g., 40 wt % to about 52 wt % or about 46.19 wt %); or (v) a combination thereof.
In any aspect or embodiment described herein, (i) the first emulsifier is made by a process comprising, consisting essentially of, or consisting of, reacting tall oil fatty acid (TOFA), rosin (e.g., tall oil rosin or TOR), or a mixture thereof (e.g., a mixture of tall oil fatty acid and rosin, such as tall oil rosin), with an acid and/or anhydride composition that includes or is a dicarboxylic acid, di-anhydride, tricarboxylic acid, tri-anhydride, or a mixture thereof (e.g., maleic acid, fumaric acid, succinic acid, maleic anhydride, succinic anhydride, or a mixture thereof); (ii) the first emulsifier is a tall oil fatty acid (TOFA)-based emulsifier (e.g., an emulsifier comprising a modified tall oil fatty acids, a modified rosin (e.g., a modified tall oil rosin), or a combination thereof); (iii) the first emulsifier is a tall oil fatty acid (TOFA) and rosin-based emulsifier (e.g., an emulsifier comprising a modified blend of tall oil fatty acid (TOFA) and rosin, such as tall oil rosin); (iv) the first emulsifier is maleated tall oil fatty acid (TOFA) or maleated mixture of tall oil fatty acid (TOFA) and rosin (e.g., tall oil rosin); or; (v) a combination thereof.
In any aspect or embodiment described herein, (i) the emulsifier blend has an acid number of about 165 to about 230 mg/g, an amine value of about 1 to about 12 mg/g, or a combination thereof; (ii) the emulsifier composition is a particulate (e.g., spray dried emulsifier composition); (iii) the emulsifier composition is a soap of the emulsifier blend and/or a neutralized emulsifier blend; (iv) the emulsifier composition has a pH of about 10 to about 11 (e.g., about 10.5), a non-volatile residue (NVR) of about 45% to about 55% (e.g., about 48% to about 52% or about 50%), or a combination thereof; or (v) a combination thereof.
In any aspect or embodiment described herein, the process or method further comprises: (i) reacting tall oil fatty acid (TOFA), rosin (e.g., tall oil rosin or TOR), or a mixture thereof (e.g., a mixture of tall oil fatty acid and rosin, such as tall oil rosin), with an acid and/or anhydride composition that includes or is a dicarboxylic acid, di-anhydride, tricarboxylic acid, tri-anhydride, or a mixture thereof (e.g., maleic acid, fumaric acid, succinic acid, maleic anhydride, succinic anhydride, or a mixture thereof) to produce the first emulsifier; (ii) neutralizing the emulsifier blend (e.g., reacting the emulsifier blend with a caustic solution (e.g., a solution comprising LiOH, NaOH, KOH, Ca(OH)2, ammonia, alkylamine, alkanolamines, or a combination thereof) to produce a neutralized emulsifier blend or a soap of the emulsifier blend); (iii) spray drying the emulsifier composition or blend, the neutralized emulsifier blend, or the soap of the emulsifier blend; or (iv) a combination thereof.
In any aspect or embodiment described herein, the emulsifier composition is a spray dried emulsifier composition.
In any aspect or embodiment described herein, the process or method further comprises spray drying the emulsifier composition or blend, the neutralized emulsifier blend, or the soap of the emulsifier blend.
Another aspect of the present disclosure provides an oil-based drilling fluid or mud comprising, consisting essentially of, or consisting of, an invert emulsion of a hygroscopic liquid (e.g., a brine, such as CaCl2) brine), one or more emulsifier, and at least one of: an oil, mineral oil, synthetic oil (e.g., one or more of internal olefin, poly alpha olefin, and linear paraffin), or a combination thereof, wherein the one or more emulsifiers includes the emulsifier composition of the present disclosure, an emulsifier composition produced according to the process or method of the present disclosure, or a combination thereof.
In any aspect or embodiment described herein, (i) the oil is diesel; (ii) the hygroscopic liquid is CaCl2) brine, NaCl brine, NaBr brine, CaBr2 brine, a formate brine, potassium formate, an alcohol based hygroscopic liquid, lower polyhydric alcohols, glycerol, or polyglycerol (e.g., CaCl2) brine); or (iii) a combination thereof.
In any aspect or embodiment described herein, the drilling fluid or mud further comprises: (i) one or more weighting agents (e.g., barite); (ii) one or more rheological modifier (e.g., at least one of: clay, organophilic clay, bentonite clay, amine-treated clay, amine-treated bentonite clay, a polyamide, a dimer diacid, or combinations thereof); (iii) one or more alkalinity agent (e.g., lime, CaO, or Ca(OH)2); (iv) one or more wetting agent (e.g., fatty imidazolines, soya lecithin, or combinations thereof); or (v) a combination thereof.
In any aspect or embodiment described herein, the oil-based drilling fluid or mud comprises: an invert emulsion of a hygroscopic liquid (e.g., a brine, such as CaCl2) brine), an oil (e.g. diesel), mineral oil, the emulsifier composition of the present disclosure, and internal olefin.
An additional aspect of the present disclosure provides a method of drilling a wellbore, the method comprising circulating the oil-based drilling fluid of the present disclosure through the wellbore when drilling (e.g., when drilling the well to depth).
The preceding general areas of utility are given by way of example only and are not intended to be limiting on the scope of the present disclosure and appended claims. Additional objects and advantages associated with the polymers, compositions, methods, and processes of the present disclosure will be appreciated by one of ordinary skill in the art in light of the instant claims, description, and examples. For example, the various aspects and embodiments of the present disclosure can be utilized in numerous combinations, all of which are expressly contemplated by the present disclosure. These additional advantages objects and embodiments are expressly included within the scope of the present disclosure. The publications and other materials used herein to illuminate the background of the invention, and in particular cases, to provide additional details respecting the practice, are incorporated by reference.
The accompanying drawings, which are incorporated into and form a part of the specification, illustrate several embodiments of the present disclosure and, together with the description, serve to explain the principles of the disclosure. The drawings are only for the purpose of illustrating embodiments of the disclosure and are not to be construed as limiting the disclosure. Further objects, features and advantages of the disclosure will become apparent from the following detailed description taken in conjunction with the accompanying figures showing illustrative embodiments of the disclosure.
The selection of non-traditional fatty acids for the synthesis of emulsifiers for invert emulsion drilling fluids has a significant effect on the physical properties of the emulsifier compositions described herein. Historically, emulsifiers for invert emulsion drilling fluids incorporate tall-oil fatty acids (TOFA) as a raw material. These emulsifiers are semi-solid at room temperature, tacky, and not well suited to producing powdered products. It is possible to mix these emulsifiers with a solid support material like silica to allow processing into powders, but this dilutes the activity of the emulsifier by the portion of support added. The dilution requires the usage of additional weight of material in the application and may have impacts on fluid properties and performance. And while spray drying and/or solid supports are utilized to limit blocking effects on bulk powder forms of emulsifiers produced with traditional fatty acid compositions, such as tall oil fatty acids (TOFA), these traditional fatty acid composition-based emulsifiers are still plagued with clumping/blocking.
The inventors of the present disclosure have surprisingly and unexpected discovered that by blending a first emulsifier with a second emulsifier by using a non-traditional fatty acid composition comprised of saturated fatty acids and C16-18 fatty acids, instead of tall oil fatty acids (TOFA), and reacting the emulsifier blend with a caustic solution (e.g., a solution comprising LiOH, NaOH, Ca(OH)2, ammonia, alkylamine, alkanolamines, or a combination thereof) to produce a neutralized, soap, or salt of the emulsifier blend produces a stable particulate/powder emulsifier composition (e.g., a spray dried emulsifier composition) with reduced tackiness of the emulsifier composition, and allows the emulsifier composition to be stored without significant blocking effects on the bulk particulate/powder.
By using the fatty acid compositions described herein, instead of TOFA, (1) the melting temperature and thermal transitions of the second emulsifier is increased to an extent that when mixed with a first emulsifier, and (2) an increase in the thermal transition temperatures of the resultant emulsifier powder is observed, thereby leading to increased spray drier yields. The particulate or powder emulsifier compositions (e.g. spray dried emulsifier compositions) of the present disclosure are significantly more stable with reduced tackiness of the particular emulsifier composition and reduced tendency for the particulate emulsifier composition to clump/block. The combination of reduction in clumping/blocking tendency and increase in thermal transition temperatures improve the long-term storage stability of the spray dried powder.
Thus, the present disclosure provides emulsifier compositions that do not require solid supports/support material, and are not plagued with tackiness, clumping issues, and/or blocking issues. Furthermore, no processing solvent is required (e.g., or utilized) during the manufacture of the emulsifier compositions of the present disclosure. Additionally, the emulsifier compositions of the present disclosure do not require the use of other additives (e.g., one or more of a solvent, a diluent, an absorbent, a pour point depressant, an anti-caking agent, a filler, etc.) to make a workable, final product. With appropriate solids processing, as described herein, the emulsifier compositions of the present disclosure is a pourable powder that is stable. The emulsifier composition of the present disclosure maintains its form as a free-flowing particulate/powder, thereby decreasing the amount of processing required. Thus, the emulsifier compositions of the present disclosure result in emulsifier concentrations (e.g., 100% active emulsifier) that are not obtainable with (i) commercially available solid products, which includes up to 40% adsorbent/solid support, or (ii) commercially available liquid products, which include 20-40% diluent/pour point depressant to have a pourable viscosity.
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.
Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise (such as in the case of a group containing a number of carbon atoms in which case each carbon atom number falling within the range is provided), between the upper and lower limit of that range and any other stated or intervening value in that stated range is encompassed within the disclosure. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges is also encompassed within the disclosure, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either both of those included limits are also included in the disclosure.
The following terms are used to describe the present disclosure. In instances where a term is not specifically defined herein, that term is given an art-recognized meaning by those of ordinary skill applying that term in context to its use in describing the present 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.
The phrase “and/or,” as used herein in the specification and in the claims, should be understood to mean “either or both” of the elements so conjoined, i.e., elements that are conjunctively present in some cases and disjunctively present in other cases. Multiple elements listed with “and/or” should be construed in the same fashion, i.e., “one or more” of the elements so conjoined. Other elements may optionally be present other than the elements specifically identified by the “and/or” clause, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, a reference to “A and/or B”, when used in conjunction with open-ended language such as “comprising” can refer, in one embodiment, to A only (optionally including elements other than B); in another embodiment, to B only (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.
As used herein in the specification and in the claims, “or” should be understood to have the same meaning as “and/or” as defined above. For example, when separating items in a list, “or” or “and/or” shall be interpreted as being inclusive, i.e., the inclusion of at least one, but also including more than one, of a number or list of elements, and, optionally, additional unlisted items. Only terms clearly indicated to the contrary, such as “only one of” or “exactly one of,” or, when used in the claims, “consisting of,” will refer to the inclusion of exactly one element of a number or list of elements. In general, the term “or” as used herein shall only be interpreted as indicating exclusive alternatives (i.e., “one or the other but not both”) when preceded by terms of exclusivity, such as “either,” “one of,” “only one of,” or “exactly one of.”
In the claims, as well as in the specification above, all transitional phrases such as “comprising,” “including,” “carrying,” “having,” “containing,” “involving,” “holding,” “composed of,” and the like are to be understood to be open-ended, i.e., to mean including but not limited to. Only the transitional phrases “consisting of” and “consisting essentially of” shall be closed or semi-closed transitional phrases, respectively, as set forth in the United States Patent Office Manual of Patent Examining Procedures, Section 2111.03.
As used herein in the specification and in the claims, the phrase “at least one,” in reference to a list of one or more elements, should be understood to mean at least one element selected from anyone or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements. This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase “at least one” refers, whether related or unrelated to those elements specifically identified. Thus, as a nonlimiting example, “at least one of A and B” (or, equivalently, “at least one of A or B,” or, equivalently “at least one of A and/or B”) can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.
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.
The term “effective” is used to describe an amount of a compound, composition or component which, when used within the context of its intended use, effects an intended result. The term effective subsumes all other effective amount or effective concentration terms, which are otherwise described or used in the present application.
As discussed herein, the inventors of the present disclosure surprisingly and unexpected discovered that by blending a first emulsifier with a second emulsifier that is produced with a non-traditional fatty acid composition, as described herein, and reacting the emulsifier blend with a caustic solution (e.g., a solution comprising LiOH, NaOH, KOH, Ca(OH)2, ammonia, alkylamine, alkanolamines, or a combination thereof), a neutralized, soap, or salt of the emulsifier blend produces a stable particulate/powder emulsifier composition (e.g., a spray dried emulsifier composition) with reduced tackiness of the emulsifier composition and allows the emulsifier composition to be stored without significant blocking effects on the bulk particulate/powder. Thus, the present disclosure provides an emulsifier compositions that do not require solid supports (such as, silica, diatomaceous earth, zeolite, etc.), and are not plagues with tackiness, clumping issues, and/or blocking issues. The emulsifier compositions of the present disclosure maintains its form as a free-flowing particulate/powder, thereby decreasing the amount of processing required.
Emulsifiers produced with traditional fatty acid compositions, such as tall oil fatty acids (TOFA) results in compositions that required spray drying or solid support to limit blocking effects on bulk powder forms. Even then, traditional fatty acid composition-based emulsifiers are plagued with clumping/blocking. In any aspect or embodiment described herein, the fatty acid composition does not include, or is not, distilled tall oil (DTO), tall oil fatty acids (TOFA), or a combination thereof. In any aspect or embodiment described herein, the fatty acid composition does not include, or is not, distilled tall oil (DTO). In any aspect or embodiment described herein, the fatty acid composition does not include, or is not, tall oil fatty acids (TOFA).
TOFA is produced as a byproduct of the Kraft pulping process of coniferous trees. In particular, the kraft pulping process is utilized to convert wood into wood pulp, wherein crude tall oil (CTO) is produced as a byproduct. Crude tall oil can be upgraded through distillation to produce rosin-rich distillates and distilled tall oil. Distillation streams produce tall oil pitch (TOP), tall oil rosin (TOR), head streams (light ends), tall oil fatty acids (TOFA), and distilled tall oil (DTO). Pine tree-derived TOR contains several C20 acid isomers including abietic, dehydroabietic, and pimaric acids. TOFA comprises primarily C18 linear saturated and unsaturated chains (for example, linoleic acid, oleic acid, and linolenic acid). The principle composition and yields of tall oil fractions and some empirical volatility data is provided in Table 1, and exemplary data and composition of some tall oil fatty acids are provided in Table 2.
Tall oil fatty acids (TOFA) is further broken down into Type I (minimum of 98% fatty acids and a maximum of 1% rosin acids), Type II (minimum of 96% fatty acids and a maximum of 2% rosin acids), and Type III (minimum of 90% fatty acids and a maximum of 10% rosin acids), as shown in Table 3, depending upon acid value, rosin acids concentration, unsaponifiables concentration, fatty acids concentration, Gardner color, and iodine value.
The standard methods recited in Table 3 can be utilized to determine the acid number, rosin acid concentration (%), unsaponifiables concentration (%), fatty acids concentration (%), Gardner color, and iodine value of fatty acid compositions.
The inventors demonstrated herein that the selection of non-traditional fatty acids, as described herein, for the synthesis of second emulsifiers has a significant effect on the physical properties of the produced second emulsifier and the emulsifier compositions comprising the same. The composition of fatty acids used is very important to the physical properties of the second emulsifiers produced and the emulsifier composition comprising the same, thereby affecting the storage of the emulsifier compositions, the handling of the emulsifier compositions, and the performance of the emulsifier compositions (e.g., performance in a drilling fluid). Furthermore, changing the fatty acid composition described herein affects the properties of the drilling fluid, including plastic viscosity, yield point, gel strengths, and viscosity at various shear rates.
An aspect of the present disclosure provides an emulsifier composition comprising, consisting essentially of, or consisting of a blend of: (1) a first emulsifier; and (2) a second emulsifier, or a second emulsifier reaction product, made by a process comprising, consisting essentially of, or consisting of: reacting (A) a fatty acid composition with (B) one or more (e.g., 1, 2, 3, 4, 5, 6, or more) poly(alkylamine) to produce a partial amide; and reacting (a) the partial amide with (b) an acid and/or anhydride composition that includes or is a dicarboxylic acid, di-anhydride, tricarboxylic acid, tri-anhydride, or a mixture thereof, to produce the second emulsifier, wherein the fatty acid composition comprises at least about 60% C16-18 fatty acids and at least 65% saturated fatty acids (e.g., at least 85% saturated fatty acids).
Another aspect of the present disclosure provides an emulsifier composition made by a process comprising, consisting essentially of, or consisting of, blending a first emulsifier; and a second emulsifier (or second emulsifier reaction product) made by a process comprising: reacting (A) a fatty acid composition with (B) one or more (e.g., 1, 2, 3, 4, 5, 6, or more) poly(alkylamine) to produce a partial amide; and reacting (a) the partial amide with (b) an acid and/or anhydride composition that includes or is a dicarboxylic acid, di-anhydride, tricarboxylic acid, tri-anhydride, or a mixture thereof, to produce the second emulsifier, wherein the fatty acid composition comprises at least about 60% C16-18 fatty acids and at least 65% saturated fatty acids (e.g., at least 85% saturated fatty acids).
An aspect of the present disclosure provides an emulsifier composition made by a process comprising, consisting essentially of, or consisting of, blending a first emulsifier; and a second emulsifier (or second emulsifier reaction product) made by a process consisting essentially of: reacting (A) a fatty acid composition with (B) one or more (e.g., 1, 2, 3, 4, 5, 6, or more) poly(alkylamine) to produce a partial amide; and reacting (a) the partial amide with (b) an acid and/or anhydride composition that includes or is a dicarboxylic acid, di-anhydride, tricarboxylic acid, tri-anhydride, or a mixture thereof, to produce the second emulsifier, wherein the fatty acid composition comprises at least about 60% C16-18 fatty acids and at least 65% saturated fatty acids (e.g., at least 85% saturated fatty acids).
An aspect of the present disclosure provides an emulsifier composition made by a process comprising, consisting essentially of, or consisting of, blending a first emulsifier; and a second emulsifier (or second emulsifier reaction product) made by a process consisting of: reacting (A) a fatty acid composition with (B) one or more (e.g., 1, 2, 3, 4, 5, 6, or more) poly(alkylamine) to produce a partial amide; and reacting (a) the partial amide with (b) an acid and/or anhydride composition that includes or is a dicarboxylic acid, di-anhydride, tricarboxylic acid, tri-anhydride, or a mixture thereof, to produce the second emulsifier, wherein the fatty acid composition comprises at least about 60% C16-18 fatty acids and at least 65% saturated fatty acids (e.g., at least 85% saturated fatty acids).
In any aspect or embodiment described herein, the emulsifier composition is an emulsifier reaction product, a spray dried emulsifier, a spray dried emulsifier reaction product, a neutralized the blend of the first emulsifier and the second emulsifier, a soap of the blend of the first emulsifier and the second emulsifier, a salt of the blend of the first emulsifier and the second emulsifier, a spray dried neutralized the blend of the first emulsifier and the second emulsifier, a spray dried soap of the blend of the first emulsifier and the second emulsifier, or a spray dried salt of the blend of the first emulsifier and the second emulsifier.
In any aspect or embodiment described herein, the emulsifier composition (e.g., spray dried emulsifier composition) does not include a support material or a solid support (e.g., silica, diatomaceous earth, zeolite, etc.). In any aspect or embodiment described herein, the emulsifier composition (e.g., spray dried emulsifier composition) does not include an absorbent. In any aspect or embodiment described herein, the emulsifier composition (e.g., spray dried emulsifier composition) does not include any additives (e.g., one or more of a solvent, a diluent, an absorbent, a pour point depressant, a filler, an anti-caking agent, silica, diatomaceous earth, zeolite, etc.). In any aspect or embodiment described herein, the emulsifier composition (e.g., spray dried emulsifier composition) only includes a neutralized, soap, or salt of the blend of the first emulsifier and the second emulsifier reaction product, formed from the fatty acid composition, the one or more poly(alkylamine), and the acid and/or anhydride composition, as described herein. In any aspect or embodiment described herein, the emulsifier composition (e.g., spray dried emulsifier composition) consists of a neutralized, soap, or salt of the blend of the first emulsifier and the second emulsifier reaction product, formed from the fatty acid composition, the one or more poly(alkylamine), and the acid and/or anhydride composition, as described herein. In any aspect or embodiment described herein, the emulsifier composition (e.g., spray dried emulsifier composition) is entirely (i.e., 100%) the neutralized, soap, or salt of the blend of the first emulsifier and the second emulsifier reaction product formed from the fatty acid composition, the one or more poly(alkylamine), and the acid and/or anhydride composition, as described herein. In any aspect or embodiment described herein, the emulsifier composition (e.g., spray dried emulsifier composition) does not include any additional materials than the neutralized, soap, or salt of the blend of the first emulsifier and the second emulsifier reaction product formed from the fatty acid composition, the one or more poly(alkylamine), and the acid and/or anhydride composition, as described herein.
A further aspect of the present disclosure provides a method or process of making an emulsifier composition of the present disclosure. In any aspect or embodiment described herein, the method or process comprises: providing a first emulsifier, optionally preparing the first emulsifier; preparing a second emulsifier; and blending the first emulsifier and the second emulsifier, wherein the method or process of preparing the second emulsifier comprises, consisting essentially of, or consisting of: reacting (A) a fatty acid composition with (B) one or more (e.g., 1, 2, 3, 4, 5, 6, or more) poly(alkylamine) to produce a partial amide; and reacting (a) the partial amide with (b) an acid and/or anhydride composition that includes or is a dicarboxylic acid, di-anhydride, tricarboxylic acid, tri-anhydride, or a mixture thereof, to produce the second emulsifier, wherein the fatty acid composition comprises at least about 60% C16-18 fatty acids and at least 65% saturated fatty acids (e.g., at least 85% saturated fatty acids). In any aspect or embodiment described herein, the method or process consists essentially of: providing a first emulsifier, optionally preparing the first emulsifier; preparing a second emulsifier; and blending the first emulsifier and the second emulsifier, wherein the method or process of preparing the second emulsifier comprises, consisting essentially of, or consisting of: reacting (A) a fatty acid composition with (B) one or more (e.g., 1, 2, 3, 4, 5, 6, or more) poly(alkylamine) to produce a partial amide; and reacting (a) the partial amide with (b) an acid and/or anhydride composition that includes or is a dicarboxylic acid, di-anhydride, tricarboxylic acid, tri-anhydride, or a mixture thereof, to produce the second emulsifier, wherein the fatty acid composition comprises at least about 60% C16-18 fatty acids and at least 65% saturated fatty acids (e.g., at least 85% saturated fatty acids). In any aspect or embodiment described herein, the method or process consists of: providing a first emulsifier, optionally preparing the first emulsifier; preparing a second emulsifier; and blending the first emulsifier and the second emulsifier, wherein the method or process of preparing the second emulsifier comprises, consisting essentially of, or consisting of: reacting (A) a fatty acid composition with (B) one or more (e.g., 1, 2, 3, 4, 5, 6, or more) poly(alkylamine) to produce a partial amide; and reacting (a) the partial amide with (b) an acid and/or anhydride composition that includes or is a dicarboxylic acid, di-anhydride, tricarboxylic acid, tri-anhydride, or a mixture thereof, to produce the second emulsifier, wherein the fatty acid composition comprises at least about 60% C16-18 fatty acids and at least 65% saturated fatty acids (e.g., at least 85% saturated fatty acids).
An additional aspect of the present disclosure provides a method of enhancing or improving at least one handling property (e.g., moisture uptake, the spray drying process, flowability after storage, etc.) of a spray dried emulsifier composition comprising of a first emulsifier, the method comprising, consisting essentially of, or consisting of: providing a first emulsifier, optionally preparing the first emulsifier; preparing a second emulsifier; and blending the first emulsifier and the second emulsifier, wherein the blend of the first emulsifier and the second emulsifier has an enhancement or improvement in at least handling property relative to an emulsifier composition comprising the first emulsifier and not the second emulsifier (e.g., consisting of the first emulsifier), wherein the method of preparing the second emulsifier comprising, consisting essentially of, or consisting of: reacting (A) a fatty acid composition with (B) one or more (e.g., 1, 2, 3, 4, 5, 6, or more) poly(alkylamine) to produce a partial amide; and reacting (a) the partial amide with (b) an acid and/or anhydride composition that includes or is a dicarboxylic acid, di-anhydride, tricarboxylic acid, tri-anhydride, or a mixture thereof, to produce the second emulsifier, wherein the fatty acid composition comprises at least about 60% C16-18 fatty acids and at least 65% saturated fatty acids (e.g., at least 85% saturated fatty acids).
In any aspect or embodiment described herein, (i) the emulsifier composition does not include a support material, a solid support, a solvent, a diluent, an adsorbent, a pour point depressant, a filler, an anti-caking agent, any additives, or a combination thereof; (ii) the emulsifier composition only includes the first emulsifier (e.g., the first emulsifier reaction product) and the second emulsifier (e.g., the second emulsifier reaction product), or a neutralized version, soap, or salt thereof; (iii) the emulsifier composition consists of first emulsifier (e.g., the first emulsifier reaction product) and the second emulsifier (e.g., the second emulsifier reaction product), or a neutralized version, soap, or salt thereof; or (iv) a combination thereof. In any aspect or embodiment described herein, the emulsifier composition does not include a support material, a solid support, a solvent, a diluent, an adsorbent, a pour point depressant, a filler, an anti-caking agent, any additives, or a combination thereof. In any aspect or embodiment described herein, the emulsifier composition only includes the first emulsifier (e.g., the first emulsifier reaction product) and the second emulsifier (e.g., the second emulsifier reaction product), or a neutralized version, soap, or salt thereof. In any aspect or embodiment described herein, the emulsifier composition consists of the first emulsifier (e.g., the first emulsifier reaction product) and the second emulsifier (e.g., the second emulsifier reaction product), or a neutralized version, soap, or salt thereof.
In any aspect or embodiment described herein, the fatty acid composition comprises at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, at least about 98%, at least about 99%, or 100% C16-18 fatty acids.
In any aspect or embodiment described herein, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, at least about 98%, at least about 99%, or 100% saturated fatty acids (e.g., at least 85% saturated fatty acids).
In any aspect or embodiment described herein, the fatty acid composition comprises one or more (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more) C16-18 fatty acid (e.g., a mixture of C16-18 fatty acids or Alta Veg™ FA 450). In any aspect or embodiment described herein, the fatty acid composition consists essentially of one or more (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more) C16-18 fatty acid (e.g., a mixture of C16-18 fatty acids or Alta Veg™ FA 450). In any aspect or embodiment described herein, the fatty acid composition consists of one or more (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more) C16-18 fatty acid (e.g., a mixture of C16-18 fatty acids or Alta Veg™ FA 450). In any aspect or embodiment described herein, the fatty acid composition comprises two or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or more) C16-18 fatty acid (e.g., a mixture of C16-18 fatty acids or Alta Veg™ FA 450). In any aspect or embodiment described herein, the fatty acid composition consists essentially of two or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or more) C16-18 fatty acid (e.g., a mixture of C16-18 fatty acids or Alta Veg™ FA 450). In any aspect or embodiment described herein, the fatty acid composition consists of two or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or more) C16-18 fatty acid (e.g., a mixture of C16-18 fatty acids or Alta Veg™ FA 450).
In any aspect or embodiment described herein, the fatty acid composition includes or is palmitic acid, stearic acid, hydrogenated tallow fatty acids, or a mixture thereof. Alta Veg™ FA 450 contains about 70% palmitic acid, <5% stearic acid, and the remainder being unsaturated C18 fatty acids. In any aspect or embodiment described herein, the fatty acid composition comprises: at least about 60% C16 fatty acids (e.g., palmitic acid) and C18 fatty acids (e.g., stearic acid); less than about 13% C18 fatty acids (e.g., stearic acid); less than about 30% unsaturated C18 fatty acids; or a combination thereof. In any aspect or embodiment described herein, the fatty acid composition comprises: at least about 65% C16 fatty acids (e.g., palmitic acid) and C18 fatty acids (e.g., stearic acid); less than about 10% C18 fatty acids (e.g., stearic acid); less than about 25% unsaturated C18 fatty acids; or a combination thereof. In any aspect or embodiment described herein, the fatty acid composition includes at least about 65% C16 fatty acids (e.g., palmitic acid) and C18 fatty acids (e.g., stearic acid), less than about 10% C18 fatty acids (e.g., stearic acid), and less than about 25% unsaturated C18 fatty acids. In any aspect or embodiment described herein, the fatty acid composition comprises or is about 70% palmitic acid, <5% stearic acid, and the balance is unsaturated C18 fatty acids.
In any aspect or embodiment described herein, the fatty acid composition comprises at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, at least about 98%, at least about 99%, or 100% of a mixture of C16 fatty acids (e.g., palmitic acid) and C18 fatty acids (e.g., stearic acid).
In any aspect or embodiment described herein, the fatty acid composition comprises at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, at least about 98%, at least about 99%, or 100% of a mixture of saturated C16 fatty acids (e.g., palmitic acid) and saturated C18 fatty acids (e.g., stearic acid).
In any aspect or embodiment described herein, the fatty acid composition comprises at least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, at least about 98%, at least about 99%, or 100% C16 fatty acids (e.g., palmitic acid).
In any aspect or embodiment described herein, the fatty acid composition comprises at least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, at least about 98%, at least about 99%, or 100% saturated C16 fatty acids (e.g., palmitic acid).
In any aspect or embodiment described herein, the fatty acid composition comprises at least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, at least about 98%, at least about 99%, or 100% C18 fatty acids (e.g., stearic acid).
In any aspect or embodiment described herein, the fatty acid composition comprises at least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, at least about 98%, at least about 99%, or 100% saturated C18 fatty acids (e.g., stearic acid).
In any aspect or embodiment described herein, the fatty acid composition comprises less than about 30%, less than about 29%, less than about 28%, less than about 27%, less than about 26%, less than about 25%, less than about 24%, less than about 23%, less than about 22%, less than about 21%, less than about 20%, less than about 19%, less than about 18%, less than about 17%, less than about 16%, less than about 15%, less than about 14%, less than about 13%, less than about 12%, less than about 11%, less than about 10%, less than about 9%, less than about 8%, less than about 7%, less than about 6%, less than about 5%, less than about 4%, less than about 3%, less than about 2%, less than about 1%, or 0% unsaturated fatty acids.
In any aspect or embodiment described herein, the fatty acid composition comprises less than about 30%, less than about 29%, less than about 28%, less than about 27%, less than about 26%, less than about 25%, less than about 24%, less than about 23%, less than about 22%, less than about 21%, less than about 20%, less than about 19%, less than about 18%, less than about 17%, less than about 16%, less than about 15%, less than about 14%, less than about 13%, less than about 12%, less than about 11%, less than about 10%, less than about 9%, less than about 8%, less than about 7%, less than about 6%, less than about 5%, less than about 4%, less than about 3%, less than about 2%, less than about 1%, or 0% unsaturated C18 fatty acids.
In any aspect or embodiment described herein, the poly(alkylamine) includes 1 to 12 carbon atoms (e.g., 3 to 9 or 4 to 8 carbon atoms), 1 to 7 nitrogen atoms (e.g., 2 to 6 or 3 to 5 nitrogen atoms), or a combination thereof (e.g., 1 to 12 carbon atoms and 1 to 7 nitrogen atoms, 4 to 8 carbon atoms and 3 to 5 nitrogen atoms, or 3 to 9 carbon atoms and 2 to 6 nitrogen atoms). For example, in any aspect or embodiment described herein, the poly(alkamine) includes 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms. In any aspect or embodiment described herein, the poly(alkylamine) includes 1, 2, 3, 4, 5, 6, or 7 nitrogen atoms.
In any aspect or embodiment described herein, the one or more poly(alkylamine) includes or is diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), or a mixture thereof. In any aspect or embodiment described herein, the one or more poly(alkylamine) includes or is diethylenetriamine (DETA).
In any aspect or embodiment described herein, the dicarboxylic acid is a C2-6 dicarboxylic acid (e.g., maleic acid, fumaric acid, succinic acid, or a mixture thereof). For example, in any aspect or embodiment described herein, the dicarboxylic acid includes or is maleic acid, fumaric acid, succinic acid, or a mixture thereof. In any aspect or embodiment described herein, the dicarboxylic acid is a C2, C3, C4, C5, or C6 dicarboxylic acid.
In any aspect or embodiment described herein, the di-anhydride is a C2-6 di-anhydride (e.g. maleic anhydride, succinic anhydride, or a mixture thereof). For example, in any aspect or embodiment described herein, the di-anhydride includes or is maleic anhydride, succinic anhydride, or a mixture thereof. In any aspect or embodiment described herein, the di-anhydride is a C2, C3, C4, C5, or C6 di-anhydride.
In any aspect or embodiment described herein, the tricarboxylic acid is a C3-8 tricarboxylic acid. For example, in any aspect or embodiment described herein, the tricarboxylic acid is a C3, C4, C5, C6, C7, or C8,tricarboxylic acid.
In any aspect or embodiment described herein, the tri-anhydride is a C3-8 tri-anhydride. For example, in any aspect or embodiment described herein, the tricarboxylic acid is a C3, C4, C5, C6, C7, or C8 tri-anhydride.
In any aspect or embodiment described herein, the acid and/or anhydride composition includes or is maleic acid, fumaric acid, succinic acid, succinic anhydride, maleic anhydride, or a mixture thereof. In any aspect or embodiment described herein, the acid and/or anhydride composition or the di-anhydride includes or is maleic anhydride.
In any aspect or embodiment described herein, the fatty acid composition is present in an amount of about 75 to about 90 wt % (e.g., about 78 to about 88 wt %) of the partial amide. For example, in any aspect or embodiment described herein, the fatty acid composition is present in an amount of about 75 to about 90 wt %, about 75 to about 85 wt %, about 75 to about 80 wt %, about 80 to about 90 wt %, about 80 to about 85 wt %, or about 85 to about 90 wt % of the partial amide. In any aspect or embodiment described herein, the fatty acid composition is present in an amount of about 75 wt %, about 76 wt %, about 77 wt %, about 78 wt %, about 79 wt %, about 80 wt %, about 81 wt %, about 82 wt %, about 83 wt %, about 84 wt %, about 85 wt %, about 86 wt %, about 87 wt %, about 88 wt %, about 89 wt %, about 90 wt %, any values in between, or a range from any combination of the values, of the partial amide.
In any aspect or embodiment described herein, the one or more poly(alkylamine) is present in an amount of about 10 to about 25 wt % (e.g., about 12 to about 22 wt %) of the partial amide. For example, in any aspect or embodiment described herein, the one or more poly(alkylamine) is present in an amount of about 10 to about 25 wt %, about 10 to about 22.5 wt %, about 10 to about 20 wt %, about 10 to about 17.5 wt %, about 10 to about 15 wt %, about 10 to about 12.5 wt %, about 12.5 to about 25 wt %, about 12.5 to about 22.5 wt %, about 12.5 to about 20 wt %, about 12.5 to about 17.5 wt %, about 12.5 to about 15 wt %, about 15 to about 25 wt %, about 15 to about 22.5 wt %, about 15 to about 20 wt %, about 15 to about 17.5 wt %, about 17.5 to about 25 wt %, about 17.5 to about 22.5 wt %, about 17.5 to about 20 wt %, about 20 to about 25 wt %, about 20 to about 22.5 wt %, or about 22.5 to about 25 wt % of the partial amide. In any aspect or embodiment described herein, the one or more poly(alkylamine) is present in an amount of about 10 wt %, about 11 wt %, about 12 wt %, about 13 wt %, about 14 wt %, about 15 wt %, about 16 wt %, about 17 wt %, about 18 wt %, about 19 wt %, about 20 wt %, about 21 wt %, about 22 wt %, about 23 wt %, about 24 wt %, about 25 wt %, any values in between, or a range from any combination of the values, of the partial amide.
In any aspect or embodiment described herein, the partial amide is present in an amount of about 80 to about 95 wt % (e.g., about 85 to about 95 wt % or about 90 wt %) of the emulsifier. For example, in any aspect or embodiment described herein, the partial amide is present in an amount of about 80 to about 95 wt %, about 80 to about 90 wt %, about 80 to about 85 wt %, about 85 to about 95 wt %, about 85 to about 90 wt %, or about 90 to about 95 wt % of the emulsifier. In any aspect or embodiment described herein, the partial amide is present in an amount of about 80 wt %, about 81 wt %, about 82 wt %, about 83 wt %, about 84 wt %, about 85 wt %, about 86 wt %, about 87 wt %, about 88 wt %, about 89 wt %, about 90 wt %, about 91 wt %, about 92 wt %, about 93 wt %, about 94 wt %, about 95 wt %, any values in between, or a range from any combination of the values, of the emulsifier.
In any aspect or embodiment described herein, the acid and/or anhydride composition is present in an amount of about 5 to about 20 wt % (e.g., about 5 to about 15 wt % or about 10 wt %) of the emulsifier. For example, in any aspect or embodiment described herein, the acid and/or anhydride composition is present in an amount of about 5 to about 17.5 wt %, about 5 to about 15 wt %, about 5 to about 12.5 wt %, about 5 to about 10 wt %, about 5 to about 7.5 wt %, about 7.5 to about 17.5 wt %, about 7.5 to about 15 wt %, about 7.5 to about 12.5 wt %, about 7.5 to about 10 wt %, about 10 to about 17.5 wt %, about 10 to about 15 wt %, about 10 to about 12.5 wt %, about 12.5 to about 17.5 wt %, about 12.5 to about 15 wt %, about 15 to about 20 wt %, about 15 to about 17.5 wt %, or about 17.5 to about 20 wt % of the emulsifier. For example, in any aspect or embodiment described herein, the acid and/or anhydride composition is present in an amount of about 5 wt %, about 6 wt %, about 7 wt %, about 8 wt %, about 9 wt %, about 10 wt %, about 11 wt %, about 12 wt %, about 13 wt %, about 14 wt %, about 15 wt %, about 16 wt %, about 17 wt %, about 18 wt %, about 19 wt %, about 20 wt %, any values in between, or a range from any combination of the values, of the emulsifier.
In any aspect or embodiment described herein, the molar ratio of the fatty acid composition to the poly(alkylamine) is about 1.85 to about 2.0. For example, in any aspect or embodiment described herein, the molar ratio of the fatty acid composition to the poly(alkylamine) is about 1.85 to about 2.0, about 1.86 to about 2.0, about 1.87 to about 2.0, about 1.88 to about 2.0, about 1.89 to about 2.0, 1.90 to about 2.0, 1.91 to about 2.0, 1.92 to about 2.0, 1.93 to about 2.0, 1.94 to about 2.0, about 1.95 to about 2.0, 1.96 to about 2.0, 1.97 to about 2.0, 1.98 to about 2.0, or 1.91 to about 2.0.
In any aspect or embodiment described herein, the molar ratio of the partial amide to the acid and/or anhydride composition is about 0.6 to about 1.0 (e.g., about 0.6 to about 0.75). For example, in any aspect or embodiment described herein, the molar ratio of the partial amide to the acid and/or anhydride composition is about 0.6 to about 1.0, about 0.7 to about 1.0, about 0.8 to about 1.0, or about 0.9 to about 1.0.
In any aspect or embodiment described herein, the emulsifier has an acid number of about 45 to about 80. For example, in any aspect or embodiment described herein, the emulsifier has an acid number of about 45 to about 80, about 45 to about 75, about 45 to about 70, about 45 to about 65, about 45 to about 60, about 45 to about 55, about 45 to about 50, about 50 to about 80, about 50 to about 75, about 50 to about 70, about 50 to about 65, about 50 to about 60, about 50 to about 55, about 55 to about 80, about 55 to about 75, about 55 to about 70, about 55 to about 65, about 55 to about 60, about 60 to about 80, about 60 to about 75, about 60 to about 70, about 60 to about 65, about 65 to about 80, about 65 to about 75, about 65 to about 70, about 70 to about 80, about 70 to about 75, or about 75 to about 80. In any aspect or embodiment described herein, the emulsifier has an acid number of about 45, about 46, about 47, about 48, about 49, about 50, about 51, about 52, about 53, about 54, about 55, about 56, about 57, about 58, about 59, about 60, about 61, about 62, about 63, about 64, about 65, about 66, about 67, about 68, about 69, about 70, about 71, about 72, about 73, about 74, about 75, about 76, about 77, about 78, about 79, about 80, any values in between, or a range from any combination of the values.
In any aspect or embodiment described herein, the second emulsifier has an amine number of about 5 to about 15. For example, in any aspect or embodiment described herein, the second emulsifier has an amine number of about 5, about 6, about 7, about 8, about 9, about 10, about 11, about 12, about 13, about 14, about 15, any values in between, or a range from any combination of the values.
In any aspect or embodiment described herein, reacting the fatty acid composition with the poly(alkylamine) comprises heating the fatty acid composition (e.g., heating the fatty acid composition to the melting point of the fatty acid composition, such as about 50° C. to about 100° C.) to produce a molten fatty acid composition. In any aspect or embodiment described herein, reacting the fatty acid composition with the poly(alkylamine) comprises heating the fatty acid composition to the melting point of the fatty acid composition. For example, in any aspect or embodiment described here, reacting the fatty acid composition with the poly(alkylamine) comprises heating the fatty acid composition to about 50° C. to about 100° C., about 50° C. to about 95° C., about 50° C. to about 90° C., about 50° C. to about 85° C., about 50° C. to about 80° C., about 50° C. to about 75° C., about 50° C. to about 70° C., about 50° C. to about 65° C., about 50° C. to about 60° C., about 55° C. to about 100° C., about 55° C. to about 95° C., about 55° C. to about 90° C., about 55° C. to about 85° C., about 55° C. to about 80° C., about 55° C. to about 75° C., about 55° C. to about 70° C., about 55° C. to about 65° C., about 60° C. to about 100° C., about 60° C. to about 95° C., about 60° C. to about 90° C., about 60° C. to about 85° C., about 60° C. to about 80° C., about 60° C. to about 75° C., about 60° C. to about 70° C., about 65° C. to about 100° C., about 65° C. to about 95° C., about 65° C. to about 90° C., about 65° C. to about 85° C., about 65° C. to about 80° C., about 65° C. to about 75° C., about 70° C. to about 100° C., about 70° C. to about 95° C., about 70° C. to about 90° C., about 70° C. to about 85° C., about 70° C. to about 80° C., about 75° C. to about 100° C., about 75° C. to about 95° C., about 75° C. to about 90° C., about 75° C. to about 85° C., about 80° C. to about 100° C., about 80° C. to about 95° C., about 80° C. to about 90° C., about 85° C. to about 100° C., about 85° C. to about 95° C., or about 90° C. to about 100° C.
In any aspect or embodiment described herein, reacting the fatty acid composition with the poly(alkylamine) comprises adding the acid and/or anhydride composition to the fatty acid composition (e.g., a molten fatty acid composition). For example, in any aspect or embodiment described herein, reacting the fatty acid composition with the poly(alkylamine) comprises adding the acid and/or anhydride composition to a molten fatty acid composition.
In any aspect or embodiment described herein, reacting the fatty acid composition with the poly(alkylamine) comprises agitating the fatty acid composition and the one or more poly(alkylamine) reaction mixture.
In any aspect or embodiment described herein, reacting the fatty acid composition with the poly(alkylamine) comprises reacting the fatty acid composition and the acid and/or anhydride composition at about 145° C. to about 185° C. (e.g., about 150° C. to about 180° C. or about 150° C. to about 170° C.) until the acid number (AN) is less than about 20 mg/g, less than about 15 mg/g, or less than about 10 mg/g. For example, in any aspect or embodiment described herein, In any aspect or embodiment described herein, reacting the fatty acid composition with the poly(alkylamine) comprises reacting the fatty acid composition and the acid and/or anhydride composition at about 145° C. to about 185° C. (e.g., about 150° C. to about 180° C. or about 150° C. to about 170° C.). For example, in any aspect or embodiment described herein, reacting the fatty acid composition with the poly(alkylamine) comprises reacting the fatty acid composition and the acid and/or anhydride composition at about 145° C. to about 185° C., about 145° C. to about 180° C., about 145° C. to about 175° C., about 145° C. to about 170° C., about 145° C. to about 165° C., about 145° C. to about 160° C., about 145° C. to about 155° C., about 150° C. to about 185° C., about 150° C. to about 180° C., about 150° C. to about 175° C., about 150° C. to about 170° C., about 150° C. to about 165° C., about 150° C. to about 160° C., about 155° C. to about 185° C., about 155° C. to about 180° C., about 155° C. to about 175° C., about 155° C. to about 170° C., about 155° C. to about 165° C., about 160° C. to about 185° C., about 160° C. to about 180° C., about 160° C. to about 175° C., about 160° C. to about 170° C., about 165° C. to about 185° C., about 165° C. to about 180° C., about 165° C. to about 175° C., about 170° C. to about 185° C., about 170° C. to about 180° C., or about 175° C. to about 185° C. In any aspect or embodiment described herein, reacting the fatty acid composition with the poly(alkylamine) comprises reacting the fatty acid composition and the acid and/or anhydride composition until the acid number (AN) is less than about 20 mg/g, less than about 19 mg/g, less than about 18 mg/g, less than about 17 mg/g, less than about 16 mg/g, less than about 15 mg/g, less than about 14 mg/g, less than about 13 mg/g, less than about 12 mg/g, less than about 11 mg/g, or less than about 10 mg/g. For example, in any aspect or embodiment described herein, reacting the fatty acid composition with the poly(alkylamine) comprises reacting the fatty acid composition and the acid and/or anhydride composition until the acid number (AN) is about 20 mg/g to about 10 mg/g.
In any aspect or embodiment described herein, reacting the fatty acid composition with the poly(alkylamine) comprises reacting the fatty acid composition and the acid and/or anhydride composition for about 30 minutes to about 3 hours or about 1 hour to about 2.5 hours. For example, in any aspect or embodiment described herein, reacting the fatty acid composition with the poly(alkylamine) comprises reacting the fatty acid composition and the acid and/or anhydride composition for about 30 to about 180 minutes, about 30 to about 165 minutes, about 30 to about 150 minutes, about 30 to about 135 minutes, about 30 to about 120 minutes, about 30 to about 105 minutes, about 30 to about 90 minutes, about 30 to about 75 minutes, about 30 to about 60 minutes, about 30 to about 45 minutes, about 45 to about 180 minutes, about 45 to about 165 minutes, about 45 to about 150 minutes, about 45 to about 135 minutes, about 45 to about 120 minutes, about 45 to about 105 minutes, about 45 to about 90 minutes, about 45 to about 75 minutes, about 45 to about 60 minutes, about 60 to about 180 minutes, about 60 to about 165 minutes, about 60 to about 150 minutes, about 60 to about 135 minutes, about 60 to about 120 minutes, about 60 to about 105 minutes, about 60 to about 90 minutes, about 60 to about 75 minutes, about 75 to about 180 minutes, about 75 to about 165 minutes, about 75 to about 150 minutes, about 75 to about 135 minutes, about 75 to about 120 minutes, about 75 to about 105 minutes, about 75 to about 90 minutes, about 90 to about 180 minutes, about 90 to about 165 minutes, about 90 to about 150 minutes, about 90 to about 135 minutes, about 90 to about 120 minutes, about 90 to about 105 minutes, about 105 to about 180 minutes, about 105 to about 165 minutes, about 105 to about 150 minutes, about 105 to about 135 minutes, about 105 to about 120 minutes, about 120 to about 180 minutes, about 120 to about 165 minutes, about 120 to about 150 minutes, about 120 to about 135 minutes, about 135 to about 180 minutes, about 135 to about 165 minutes, about 135 to about 150 minutes, about 150 to about 180 minutes, about 150 to about 165 minutes, or about 165 to about 180 minutes.
In any aspect or embodiment described herein, reacting the partial amide with the acid and/or anhydride composition comprises heating the partial amide to about 100° C. to about 140° C. (e.g., about 110° C. to about 130° C., or about 120° C.). For example, in any aspect or embodiment described herein, reacting the partial amide with the acid and/or anhydride composition comprises heating the partial amide to about 100° C. to about 140° C., about 100° C. to about 135° C., about 100° C. to about 130° C., about 100° C. to about 125° C., about 100° C. to about 120° C., about 100° C. to about 115° C., about 100° C. to about 110° C., about 105° C. to about 140° C., about 105° C. to about 135° C., about 105° C. to about 130° C., about 105° C. to about 125° C., about 105° C. to about 120° C., about 105° C. to about 115° C., about 110° C. to about 140° C., about 110° C. to about 135° C., about 110° C. to about 130° C., about 110° C. to about 125° C., about 110° C. to about 120° C., about 115° C. to about 140° C., about 115° C. to about 135° C., about 115° C. to about 130° C., about 115° C. to about 125° C., about 120° C. to about 140° C., about 120° C. to about 135° C., about 120° C. to about 130° C., about 125° C. to about 140° C., about 125° C. to about 135° C., or about 130° C. to about 140° C.
In any aspect or embodiment described herein, reacting the partial amide with the acid and/or anhydride composition comprises adding the acid and/or anhydride composition to the partial amide. For example, in any aspect or embodiment described herein, reacting the partial amide with the acid and/or anhydride composition comprises adding the acid and/or anhydride composition while maintaining the temperature of the mixture below about 140° C. (e.g., about 120° C. to about 130° C.), about 140° C., about 139° C., about 138° C., about 137° C., about 136° C., about 135° C., about 134° C., about 133° C., about 132° C., about 131° C., about 130° C., about 129° C., about 128° C., about 127° C., about 126° C., about 125° C., about 124° C., about 123° C., about 122° C., about 121° C., about 120° C., about 119° C., about 118° C., about 117° C., about 116° C., about 115° C., any values in between, or a range from any combination of the values, during the addition.
In any aspect or embodiment described herein, reacting the partial amide with the acid and/or anhydride composition comprises agitating the partial amide and the acid and/or anhydride composition reaction mixture.
In any aspect or embodiment described herein, reacting the partial amide with the acid and/or anhydride composition comprises reacting the partial amide and the acid and/or anhydride composition at about 130° C. to about 165° C. (e.g., about 130° C. to about 150° C. or about 130° C. to about 140° C.). For example, in any aspect or embodiment described herein, reacting the partial amide with the acid and/or anhydride composition comprises reacting the partial amide and the acid and/or anhydride composition at about 130° C. to about 165° C., about 130° C. to about 160° C., about 130° C. to about 155° C., about 130° C. to about 150° C., about 130° C. to about 145° C., about 130° C. to about 140° C., about 135° C. to about 165° C., about 135° C. to about 160° C., about 135° C. to about 155° C., about 135° C. to about 150° C., about 135° C. to about 145° C., about 140° C. to about 165° C., about 140° C. to about 160° C., about 140° C. to about 155° C., about 140° C. to about 150° C., about 145° C. to about 165° C., about 145° C. to about 160° C., about 145° C. to about 155° C., about 150° C. to about 165° C., about 150° C. to about 160° C., about 150° C. to about 160° C.
In any aspect or embodiment described herein, reacting the partial amide with the acid and/or anhydride composition comprises reacting the partial amide and the acid and/or anhydride composition for about 30 minutes to about 90 minutes (e.g., about 30 minutes to about 75 minutes, about 45 minutes to about 60 minutes, or about 45 minutes). For example, in any aspect or embodiment described herein, reacting the partial amide with the acid and/or anhydride composition comprises reacting the partial amide and the acid and/or anhydride composition for about 30 minutes to about 90 minutes, about 30 minutes to about 80 minutes, about 30 minutes to about 70 minutes, about 30 minutes to about 60 minutes, about 30 minutes to about 50 minutes, about 30 minutes to about 40 minutes, about 40 minutes to about 90 minutes, about 40 minutes to about 80 minutes, about 40 minutes to about 70 minutes, about 40 minutes to about 60 minutes, about 40 minutes to about 50 minutes, about 50 minutes to about 90 minutes, about 50 minutes to about 80 minutes, about 50 minutes to about 70 minutes, about 50 minutes to about 60 minutes, about 60 minutes to about 90 minutes, about 60 minutes to about 80 minutes, about 60 minutes to about 70 minutes, about 70 minutes to about 90 minutes, about 70 minutes to about 80 minutes, or about 80 minutes to about 90 minutes.
In any aspect or embodiment described herein, reacting the partial amide with the acid and/or anhydride composition comprises reacting the partial amide and the acid and/or anhydride composition until the acid number (AN) is about 45 to about 80. For example, in any aspect or embodiment described herein, reacting the partial amide with the acid and/or anhydride composition comprises reacting the partial amide and the acid and/or anhydride composition until the acid number (AN) is about 45 to about 80, about 45 to about 75, about 45 to about 70, about 45 to about 65, about 45 to about 60, about 45 to about 55, about 45 to about 40, about 50 to about 80, about 50 to about 75, about 50 to about 70, about 50 to about 65, about 50 to about 60, about 50 to about 55, about 55 to about 80, about 55 to about 75, about 55 to about 70, about 55 to about 65, about 55 to about 60, about 60 to about 80, about 60 to about 75, about 60 to about 70, about 60 to about 65, about 65 to about 80, about 65 to about 75, about 65 to about 70, about 70 to about 80, about 70 to about 75, or about 75 to about 80.
In any aspect or embodiment described herein, reacting the partial amide with the acid and/or anhydride composition comprises reacting the partial amide and the acid and/or anhydride composition until the amine value (AV) is about 5 to about 15. For example, in any aspect or embodiment described herein, reacting the partial amide with the acid and/or anhydride composition comprises reacting the partial amide and the acid and/or anhydride composition until the amine value (AV) is about 5, about 6, about 7, about 8, about 9, about 10, about 11, about 12, about 13, about 14, about 15, any values in between, or a range from any combination of the values.
In any aspect or embodiment described herein, blending the first emulsifier and the second emulsifier comprises, consists essentially of, or consists of: (i) heating the second emulsifier to about 60° C. to about 100° C.; (ii) heating the emulsifier blend to about 60° C. to about 100° C.; (iii) adding the first emulsifier to the second emulsifier; (iv) mixing the first emulsifier and the second emulsifier for at least 15 minutes (e.g., about 15 minutes to about 60 minutes or about 20 minutes to about 45 minutes); (v) stop heating the emulsifier blend once (1) an acid number of about 165 to about 230 mg/g is achieved, (2) an amine value of about 1 to about 12 mg/g is achieved, or (3) a combination thereof; or (vi) a combination thereof.
In any aspect or embodiment described herein, blending the first emulsifier and the second emulsifier comprises heating the second emulsifier and/or the emulsifier blend to about 60° C. to about 100° C. For example, in any aspect or embodiment described herein, heating the second emulsifier and/or the emulsifier blend to about 60° C. to about 100° C., about 60° C. to about 95° C., about 60° C. to about 90° C., about 60° C. to about 85° C., about 60° C. to about 80° C., about 60° C. to about 75° C., about 60° C. to about 70° C., about 65° C. to about 100° C., about 65° C. to about 95° C., about 65° C. to about 90° C., about 65° C. to about 85° C., about 65° C. to about 80° C., about 65° C. to about 75° C., about 70° C. to about 100° C., about 70° C. to about 95° C., about 70° C. to about 90° C., about 70° C. to about 85° C., about 70° C. to about 80° C., about 75° C. to about 100° C., about 75° C. to about 95° C., about 75° C. to about 90° C., about 75° C. to about 85° C., about 80° C. to about 100° C., about 80° C. to about 95° C., about 80° C. to about 90° C., about 85° C. to about 100° C., about 85° C. to about 95° C., or about 90° C. to about 100° C.
In any aspect or embodiment described herein, blending the first emulsifier and the second emulsifier comprises, mixing the first emulsifier and the second emulsifier for at least 15 minutes. For example, in any aspect or embodiment described herein, blending the first emulsifier and the second emulsifier comprises, mixing the first emulsifier and the second emulsifier for about 15 minutes to about 60 minutes, about 15 minutes to about 55 minutes, about 15 minutes to about 50 minutes, about 15 minutes to about 45 minutes, about 15 minutes to about 40 minutes, about 15 minutes to about 35 minutes, about 15 minutes to about 30 minutes, about 15 minutes to about 25 minutes, about 20 minutes to about 60 minutes, about 20 minutes to about 55 minutes, about 20 minutes to about 50 minutes, about 20 minutes to about 45 minutes, about 20 minutes to about 40 minutes, about 20 minutes to about 35 minutes, about 20 minutes to about 30 minutes, about 25 minutes to about 60 minutes, about 25 minutes to about 55 minutes, about 25 minutes to about 50 minutes, about 25 minutes to about 45 minutes, about 25 minutes to about 40 minutes, about 25 minutes to about 35 minutes, about 30 minutes to about 60 minutes, about 30 minutes to about 55 minutes, about 30 minutes to about 50 minutes, about 30 minutes to about 45 minutes, about 30 minutes to about 40 minutes, about 35 minutes to about 60 minutes, about 35 minutes to about 55 minutes, about 35 minutes to about 50 minutes, about 35 minutes to about 45 minutes, about 40 minutes to about 60 minutes, about 40 minutes to about 55 minutes, about 40 minutes to about 50 minutes, about 45 minutes to about 60 minutes, about 45 minutes to about 55 minutes, or about 50 minutes to about 60 minutes.
In any aspect or embodiment described herein, blending the first emulsifier and the second emulsifier comprises stop heating the emulsifier blend once an acid number of about 165 to about 230 mg/g is achieved. For example, in any aspect or embodiment described herein, blending the first emulsifier and the second emulsifier comprises stop heating the emulsifier blend once an acid number of about 165 to about 230 mg/g, about 165 to about 220 mg/g, about 165 to about 210 mg/g, about 165 to about 200 mg/g, about 165 to about 190 mg/g, about 165 to about 180 mg/g, about 165 to about 175 mg/g, about 170 to about 230 mg/g, about 170 to about 220 mg/g, about 170 to about 210 mg/g, about 170 to about 200 mg/g, about 170 to about 190 mg/g, about 170 to about 180 mg/g, about 180 to about 230 mg/g, about 180 to about 220 mg/g, about 180 to about 210 mg/g, about 180 to about 200 mg/g, about 180 to about 190 mg/g, about 190 to about 230 mg/g, about 190 to about 220 mg/g, about 190 to about 210 mg/g, about 190 to about 200 mg/g, about 200 to about 230 mg/g, about 200 to about 220 mg/g, about 200 to about 210 mg/g, about 210 to about 230 mg/g, about 210 to about 220 mg/g, or about 220 to about 230 mg/g is achieved.
In any aspect or embodiment described herein, blending the first emulsifier and the second emulsifier comprises stop heating the emulsifier blend once an amine value of about 1 to about 12 mg/g is achieved. For example, in any aspect or embodiment described herein, blending the first emulsifier and the second emulsifier comprises stop heating the emulsifier blend once an amine value of about 1 to about 12 mg/g, about 1 to about 11 mg/g, about 1 to about 10 mg/g, about 1 to about 9 mg/g, about 1 to about 8 mg/g, about 1 to about 7 mg/g, about 1 to about 6 mg/g, about 1 to about 5 mg/g, about 1 to about 4 mg/g, about 2 to about 12 mg/g, about 2 to about 11 mg/g, about 2 to about 10 mg/g, about 2 to about 9 mg/g, about 2 to about 8 mg/g, about 2 to about 7 mg/g, about 2 to about 6 mg/g, about 2 to about 5 mg/g, about 3 to about 12 mg/g, about 3 to about 11 mg/g, about 3 to about 10 mg/g, about 3 to about 9 mg/g, about 3 to about 8 mg/g, about 3 to about 7 mg/g, about 3 to about 6 mg/g, about 4 to about 12 mg/g, about 4 to about 11 mg/g, about 4 to about 10 mg/g, about 4 to about 9 mg/g, about 4 to about 8 mg/g, about 4 to about 7 mg/g, about 5 to about 12 mg/g, about 5 to about 11 mg/g, about 5 to about 10 mg/g, about 5 to about 9 mg/g, about 5 to about 8 mg/g, about 6 to about 12 mg/g, about 6 to about 11 mg/g, about 6 to about 10 mg/g, about 6 to about 9 mg/g, about 7 to about 12 mg/g, about 7 to about 11 mg/g, about 7 to about 10 mg/g, about 8 to about 12 mg/g, about 8 to about 11 mg/g, about 9 to about 12 mg/g is achieved.
In any aspect or embodiment described herein, (i) the emulsifier blend has an acid number of about 165 to about 230 mg/g, an amine value of about 1 to about 12 mg/g, or a combination thereof; (ii) the emulsifier composition is a particulate (e.g., a spray dried emulsifier composition); (iii) the emulsifier composition is a soap of the emulsifier blend and/or a neutralized emulsifier blend; (iv) the emulsifier composition has a pH of about 10 to about 11 (e.g., a pH of about 10.5), a non-volatile residue (NVR) of about 45% to about 55% (e.g., about 48% to about 52% or about 50%), or a combination thereof; or; (v) a combination thereof.
In any aspect or embodiment described herein, the emulsifier blend has an acid number of about 165 to about 230 mg/g. For example, in any aspect or embodiment described herein, the emulsifier blend has an acid number of about 165 to about 230 mg/g, about 165 to about 220 mg/g, about 165 to about 210 mg/g, about 165 to about 200 mg/g, about 165 to about 190 mg/g, about 165 to about 180 mg/g, about 165 to about 175 mg/g, about 170 to about 230 mg/g, about 170 to about 220 mg/g, about 170 to about 210 mg/g, about 170 to about 200 mg/g, about 170 to about 190 mg/g, about 170 to about 180 mg/g, about 180 to about 230 mg/g, about 180 to about 220 mg/g, about 180 to about 210 mg/g, about 180 to about 200 mg/g, about 180 to about 190 mg/g, about 190 to about 230 mg/g, about 190 to about 220 mg/g, about 190 to about 210 mg/g, about 190 to about 200 mg/g, about 200 to about 230 mg/g, about 200 to about 220 mg/g, about 200 to about 210 mg/g, about 210 to about 230 mg/g, about 210 to about 220 mg/g, or about 220 to about 230 mg/g.
In any aspect or embodiment described herein, the emulsifier blend has an amine value of about 1 to about 12 mg/g. For example, in any aspect or embodiment described herein, the emulsifier blend has an amine value of about 1 to about 12 mg/g, about 1 to about 11 mg/g, about 1 to about 10 mg/g, about 1 to about 9 mg/g, about 1 to about 8 mg/g, about 1 to about 7 mg/g, about 1 to about 6 mg/g, about 1 to about 5 mg/g, about 1 to about 4 mg/g, about 2 to about 12 mg/g, about 2 to about 11 mg/g, about 2 to about 10 mg/g, about 2 to about 9 mg/g, about 2 to about 8 mg/g, about 2 to about 7 mg/g, about 2 to about 6 mg/g, about 2 to about 5 mg/g, about 3 to about 12 mg/g, about 3 to about 11 mg/g, about 3 to about 10 mg/g, about 3 to about 9 mg/g, about 3 to about 8 mg/g, about 3 to about 7 mg/g, about 3 to about 6 mg/g, about 4 to about 12 mg/g, about 4 to about 11 mg/g, about 4 to about 10 mg/g, about 4 to about 9 mg/g, about 4 to about 8 mg/g, about 4 to about 7 mg/g, about 5 to about 12 mg/g, about 5 to about 11 mg/g, about 5 to about 10 mg/g, about 5 to about 9 mg/g, about 5 to about 8 mg/g, about 6 to about 12 mg/g, about 6 to about 11 mg/g, about 6 to about 10 mg/g, about 6 to about 9 mg/g, about 7 to about 12 mg/g, about 7 to about 11 mg/g, about 7 to about 10 mg/g, about 8 to about 12 mg/g, about 8 to about 11 mg/g, about 9 to about 12 mg/g.
In any aspect or embodiment described herein, the blend of the first emulsifier and the second emulsifier comprises: the first emulsifier in an amount of about 50 wt % to about 80 wt % (e.g., about 55 wt % to about 75 wt % or about 65 wt %); the second emulsifier in an amount of about 20 wt % to about 50 wt % (e.g., about 25 wt % to about 45 wt % or about 35 wt %); or a combination thereof. In any aspect or embodiment described herein, the blend of the first emulsifier and the second emulsifier consists essentially of: the first emulsifier in an amount of about 50 wt % to about 80 wt % (e.g., about 55 wt % to about 75 wt % or about 65 wt %); the second emulsifier in an amount of about 20 wt % to about 50 wt % (e.g., about 25 wt % to about 45 wt % or about 35 wt %); or a combination thereof. In any aspect or embodiment described herein, the blend of the first emulsifier and the second emulsifier consists of: the first emulsifier in an amount of about 50 wt % to about 80 wt % (e.g., about 55 wt % to about 75 wt % or about 65 wt %); the second emulsifier in an amount of about 20 wt % to about 50 wt % (e.g., about 25 wt % to about 45 wt % or about 35 wt %); or a combination thereof.
In any aspect or embodiment described herein, the blend of the first emulsifier and the second emulsifier comprises the first emulsifier in an amount of about 50 wt % to about 80 wt % (e.g., about 55 wt % to about 75 wt % or about 65 wt %). For example, in any aspect or embodiment described herein, the blend of the first emulsifier and the second emulsifier comprises the first emulsifier in an amount of about 50 wt % to about 80 wt %, about 50 wt % to about 75 wt %, about 50 wt % to about 70 wt %, about 50 wt % to about 65 wt %, about 50 wt % to about 60 wt %, about 55 wt % to about 80 wt %, about 55 wt % to about 75 wt %, about 55 wt % to about 70 wt %, about 55 wt % to about 65 wt %, about 60 wt % to about 80 wt %, about 60 wt % to about 75 wt %, about 60 wt % to about 70 wt %, about 65 wt % to about 80 wt %, about 65 wt % to about 75 wt %, or about 70 wt % to about 80 wt %.
In any aspect or embodiment described herein, the blend of the first emulsifier and the second emulsifier comprises the second emulsifier in an amount of about 20 wt % to about 50 wt % (e.g., about 25 wt % to about 45 wt % or about 35 wt %). For example, in any aspect or embodiment described herein, the blend of the first emulsifier and the second emulsifier comprises the second emulsifier in an amount of about 20 wt % to about 50 wt %, about 20 wt % to about 45 wt %, about 20 wt % to about 40 wt %, about 20 wt % to about 35 wt %, about 20 wt % to about 30 wt %, about 25 wt % to about 50 wt %, about 25 wt % to about 45 wt %, about 25 wt % to about 40 wt %, about 25 wt % to about 35 wt %, about 30 wt % to about 50 wt %, about 30 wt % to about 45 wt %, about 30 wt % to about 40 wt %, about 35 wt % to about 50 wt %, about 35 wt % to about 45 wt %, or about 40 wt % to about 50 wt %.
In any aspect or embodiment described herein, the emulsifier composition has a non-volatile residue (NVR) of about 45% to about 55%, about 45% to about 52%, about 45% to about 50%, about 48 to about 55%, about 48% to about 52%, about 50% to about 55%, or about 50%.
In any aspect or embodiment described herein, the process or method further comprising (i) neutralizing the emulsifier blend (e.g., reacting the emulsifier blend with a caustic solution (e.g., a solution comprising LiOH, NaOH, KOH, Ca(OH)2, ammonia, alkylamine, alkanolamines, or a combination thereof) to produce a neutralized emulsifier blend or a soap of the emulsifier blend); (ii) spray drying the emulsifier blend, the neutralized emulsifier blend, or the soap of the emulsifier blend; or (iii) a combination thereof.
In any aspect or embodiment described herein, neutralizing the emulsifier blend comprises, consists essentially of, or consists of: (i) heating the emulsifier blend to about 60° C. to about 100° C. (e.g., about 70° C. to about 90° C. or about 80° C.); (ii) diluting the emulsifier blend with water; (iii) adding a caustic solution (e.g., a solution comprising LiOH, NaOH, KOH, Ca(OH)2, ammonia, alkylamine, alkanolamines, or a combination thereof) to the emulsifier blend or the diluted emulsifier blend (e.g., reacting the emulsifier blend or the diluted emulsifier blend with a caustic solution (e.g., a solution comprising LiOH, NaOH, KOH, Ca(OH)2, ammonia, alkylamine, alkanolamines, or a combination thereof)); (iv) adding defoamer (e.g., polyorganosilanes) to the caustic solution treated emulsifier blend or caustic solution treated diluted emulsifier blend; (v) mixing the caustic solution treated emulsifier blend or caustic solution treated diluted emulsifier blend for about 45 minutes to about 90 minutes (e.g., about 45 minutes to about 75 minutes, about 50 minutes to about 70 minutes, or about 60 minutes); (vi) mixing the caustic solution treated emulsifier blend or caustic solution treated diluted emulsifier blend at about 35° C. to about 65° C. (e.g., about 40° C. to about 60° C. or about 50° C.); (vii) adjusting the pH to about 10 to about 11 or about 10.5 (e.g., adjusting the pH to about 10 to about 11 or about 10.5 with the addition of a base, such as NaOH); (viii) adding water to the neutralized emulsifier blend or the soap of the emulsifier blend to achieve a non-volatile residue (NVR) of about 45% to about 55% (e.g., about 48% to about 52% or about 50%); or (ix) a combination thereof.
In any aspect or embodiment described herein, neutralizing the emulsifier blend comprises heating the emulsifier blend to about 60° C. to about 100° C., about 60° C. to about 90° C., about 60° C. to about 80° C., about 60° C. to about 70° C., about 70° C. to about 100° C., about 70° C. to about 90° C., about 70° C. to about 80° C., about 80° C. to about 100° C., about 80° C. to about 90° C., about 90° C. to about 100° C., about 77° C. to about 83° C., or about 80° C.
In any aspect or embodiment described herein, neutralizing the emulsifier blend comprises mixing the caustic solution treated emulsifier blend or caustic solution treated diluted emulsifier blend for about 45 minutes to about 90 minutes, about 45 minutes to about 85 minutes, about 45 minutes to about 80 minutes, about 45 minutes to about 75 minutes, about 45 minutes to about 70 minutes, about 45 minutes to about 65 minutes, about 45 minutes to about 60 minutes, about 45 minutes to about 55 minutes, about 50 minutes to about 90 minutes, about 50 minutes to about 85 minutes, about 50 minutes to about 80 minutes, about 50 minutes to about 75 minutes, about 50 minutes to about 70 minutes, about 50 minutes to about 65 minutes, about 50 minutes to about 60 minutes, about 55 minutes to about 90 minutes, about 55 minutes to about 85 minutes, about 55 minutes to about 80 minutes, about 55 minutes to about 75 minutes, about 55 minutes to about 70 minutes, about 55 minutes to about 65 minutes, about 60 minutes to about 90 minutes, about 60 minutes to about 85 minutes, about 60 minutes to about 80 minutes, about 60 minutes to about 75 minutes, about 60 minutes to about 70 minutes, about 65 minutes to about 90 minutes, about 65 minutes to about 85 minutes, about 65 minutes to about 80 minutes, about 65 minutes to about 75 minutes, about 70 minutes to about 90 minutes, about 70 minutes to about 85 minutes, about 70 minutes to about 80 minutes, about 75 minutes to about 90 minutes, about 75 minutes to about 85 minutes, about 80 minutes to about 90 minutes, or about 60 minutes.
In any aspect or embodiment described herein, neutralizing the emulsifier blend comprises mixing the caustic treated treated emulsifier blend or caustic treated treated diluted emulsifier blend at about 35° C. to about 65° C., about 35° C. to about 60° C., about 35° C. to about 55° C., about 35° C. to about 50° C., about 35° C. to about 45° C., about 40° C. to about 65° C., about 40° C. to about 60° C., about 40° C. to about 55° C., about 40° C. to about 50° C., about 45° C. to about 65° C., about 45° C. to about 60° C., about 45° C. to about 55° C., about 50° C. to about 65° C., about 50° C. to about 60° C., about 55° C. to about 65° C., or about 50° C.
In any aspect or embodiment described herein, neutralizing the emulsifier blend comprises adjusting the pH to about 10 to about 11 or about 10.5 (e.g., adjusting the pH to about 10 to about 11 or about 10.5 with the addition of a base, such as NaOH).
In any aspect or embodiment described herein, neutralizing the emulsifier blend comprises adding water to the neutralized emulsifier blend or the soap of the emulsifier blend to achieve a non-volatile residue (NVR) of about 45% to about 55% (e.g., about 48% to about 52% or about 50%).
In any aspect or embodiment described herein, (i) the first emulsifier is made by a process comprising, consisting essentially of, or consisting of, reacting tall oil fatty acid (TOFA), rosin (e.g., tall oil rosin or TOR), or a mixture thereof (e.g., a mixture of tall oil fatty acid and rosin, such as tall oil rosin), with an acid and/or anhydride composition that includes or is a dicarboxylic acid, di-anhydride, tricarboxylic acid, tri-anhydride, or a mixture thereof (e.g., maleic acid, fumaric acid, succinic acid, maleic anhydride, succinic anhydride, or a mixture thereof); (ii) the first emulsifier is a tall oil fatty acid (TOFA)-based emulsifier (e.g., an emulsifier comprising a modified tall oil fatty acids, a modified rosin (e.g., a modified tall oil rosin), or a combination thereof); (iii) the first emulsifier is a tall oil fatty acid (TOFA) and rosin-based emulsifier (e.g., an emulsifier comprising a modified blend of tall oil fatty acid (TOFA) and rosin, such as tall oil rosin); (iv) the first emulsifier is maleated tall oil fatty acid (TOFA) or maleated mixture of tall oil fatty acid (TOFA) and rosin (e.g., tall oil rosin); or; (v) a combination thereof.
In any aspect or embodiment described herein, (i) the emulsifier blend has an acid number of about 165 to about 230 mg/g, an amine value of about 1 to about 12 mg/g, or a combination thereof; (ii) the emulsifier composition is a particulate (e.g., spray dried emulsifier composition); (iii) the emulsifier composition is a soap of the emulsifier blend and/or a neutralized emulsifier blend; (iv) the emulsifier composition has a pH of about 10 to about 11 (e.g., about 10.5), a non-volatile residue (NVR) of about 45% to about 55% (e.g., about 48% to about 52% or about 50%), or a combination thereof; or (v) a combination thereof.
In any aspect or embodiment described herein, the emulsifier composition, the neutralized emulsifier blend, the soap of the emulsifier blend, or the salt of the emulsifier blend, comprises, consists essentially of, or consists of: (i) water in an amount of about 30 wt % to about 55 wt % (e.g., about 35 wt % to about 47 wt % or about 41.5 wt %); (ii) the caustic solution (e.g, a solution comprising LiOH, NaOH, KOH, Ca(OH)2, ammonia, alkylamine, alkanolamines, or a combination thereof and/or a 50% caustic solution) in an amount of about 7.5 wt % to about 17.5 wt % (e.g., about 10 wt % to about 15 wt % or about 12.25 wt %); (iii) defoamer (e.g., polyorganosilanes) in an amount of about 0.02 to about 0.15 wt % (e.g., about 0.02 to about 0.1 wt % or about 0.04 wt %); (iv) the blend of the first emulsifier and the second emulsifier in an amount of about 30 wt % to about 60 wt % (e.g., 40 wt % to about 52 wt % or about 46.19 wt %); or (v) a combination thereof.
In any aspect or embodiment described herein, the emulsifier composition, the neutralized emulsifier blend, the soap of the emulsifier blend, or the salt of the emulsifier blend, comprises water in an amount of about 30 wt % to about 55 wt % (e.g., about 35 wt % to about 47 wt % or about 41.5 wt %). For example, in any aspect or embodiment described herein, the emulsifier composition, the neutralized emulsifier blend, the soap of the emulsifier blend, or the salt of the emulsifier blend, comprises about 30 wt % to about 55 wt %, about 30 wt % to about 50 wt %, about 30 wt % to about 45 wt %, about 30 wt % to about 40 wt %, about 35 wt % to about 55 wt %, about 35 wt % to about 50 wt %, about 35 wt % to about 45 wt %, about 40 wt % to about 55 wt %, about 40 wt % to about 50 wt %, about 45 wt % to about 55 wt %, about 35 wt % to about 47 wt %, or about 41.5 wt %.
In any aspect or embodiment described herein, the emulsifier composition, the neutralized emulsifier blend, the soap of the emulsifier blend, or the salt of the emulsifier blend, comprises the caustic solution (e.g., a solution comprising LiOH, NaOH, KOH, Ca(OH)2, ammonia, alkylamine, alkanolamines, or a combination thereof and/or a 50% caustic solution) in an amount of about 7.5 wt % to about 17.5 wt % (e.g., about 10 wt % to about 15 wt % or about 12.25 wt %). For example, in any aspect or embodiment described herein, the emulsifier composition, the neutralized emulsifier blend, the soap of the emulsifier blend, or the salt of the emulsifier blend, comprises the caustic solution (e.g., a solution comprising LiOH, NaOH, KOH, Ca(OH)2, ammonia, alkylamine, alkanolamines, or a combination thereof and/or a 50% caustic solution) in an amount of about 7.5 wt % to about 17.5 wt %, about 7.5 wt % to about 15.0 wt %, about 7.5 wt % to about 12.5 wt %, about 7.5 wt % to about 10.0 wt %, about 10.0 wt % to about 17.5 wt %, about 10.0 wt % to about 15.0 wt %, about 10.0 wt % to about 12.5 wt %, about 12.5 wt % to about 17.5 wt %, about 12.5 wt % to about 15.0 wt %, about 15.0 wt % to about 17.5 wt %, or about 12.25 wt %.
In any aspect or embodiment described herein, the emulsifier composition, the neutralized emulsifier blend, the soap of the emulsifier blend, or the salt of the emulsifier blend, comprises defoamer (e.g., polyorganosilanes) in an amount of about 0.02 to about 0.15 wt % (e.g., about 0.02 to about 0.1 wt %, about 0.02 wt % to about 0.06 wt %, about 0.03 wt % to about 0.05 wt %, or about 0.04 wt %).
In any aspect or embodiment described herein, the emulsifier composition, the neutralized emulsifier blend, the soap of the emulsifier blend, or the salt of the emulsifier blend, comprises the blend of the first emulsifier and the second emulsifier in an amount of about 30 wt % to about 60 wt % (e.g., 40 wt % to about 52 wt % or about 46.19 wt %). For example, in any aspect or embodiment described herein, the emulsifier composition, the neutralized emulsifier blend, the soap of the emulsifier blend, or the salt of the emulsifier blend, comprises the blend of the first emulsifier and the second emulsifier in an amount of about 30 wt % to about 60 wt %, about 30 wt % to about 55 wt %, about 30 wt % to about 50 wt %, about 30 wt % to about 45 wt %, about 30 wt % to about 40 wt %, about 35 wt % to about 60 wt %, about 35 wt % to about 55 wt %, about 35 wt % to about 50 wt %, about 35 wt % to about 45 wt %, about 40 wt % to about 60 wt %, about 40 wt % to about 55 wt %, about 40 wt % to about 50 wt %, about 45 wt % to about 60 wt %, about 45 wt % to about 55 wt %, about 50 wt % to about 60 wt %, 40 wt % to about 52 wt %, or about 46.19 wt %.
In any aspect or embodiment described herein, the first emulsifier is made by a process comprising, consisting essentially of, or consisting of, reacting tall oil fatty acid (TOFA), rosin (e.g., tall oil rosin or TOR), or a mixture thereof (e.g., a mixture of tall oil fatty acid and rosin, such as tall oil rosin), with an acid and/or anhydride composition, as described herein, that includes or is a dicarboxylic acid, di-anhydride, tricarboxylic acid, tri-anhydride, or a mixture thereof (e.g., maleic acid, fumaric acid, succinic acid, maleic anhydride, succinic anhydride, or a mixture thereof).
In any aspect or embodiment described herein, the first emulsifier is a tall oil fatty acid (TOFA)-based emulsifier (e.g., an emulsifier comprising a modified tall oil fatty acids, a modified rosin (e.g., a modified tall oil rosin), or a combination thereof).
In any aspect or embodiment described herein, the first emulsifier is a tall oil fatty acid (TOFA) and rosin-based emulsifier (e.g., an emulsifier comprising a modified blend of tall oil fatty acid (TOFA) and rosin, such as tall oil rosin).
In any aspect or embodiment described herein, the first emulsifier is maleated tall oil fatty acid (TOFA) or maleated mixture of tall oil fatty acid (TOFA) and rosin (e.g., tall oil rosin).
In any aspect or embodiment described herein, the process or method further comprises: (i) reacting tall oil fatty acid (TOFA), rosin (e.g., tall oil rosin or TOR), or a mixture thereof (e.g., a mixture of tall oil fatty acid and rosin, such as tall oil rosin), with an acid and/or anhydride composition that includes or is a dicarboxylic acid, di-anhydride, tricarboxylic acid, tri-anhydride, or a mixture thereof (e.g. maleic acid, fumaric acid, succinic acid, maleic anhydride, succinic anhydride, or a mixture thereof) to produce the first emulsifier; (ii) neutralizing the emulsifier blend (e.g., reacting the emulsifier blend with a caustic solution (e.g., a solution comprising LiOH, NaOH, KOH, Ca(OH)2, ammonia, alkylamine, alkanolamines, or a combination thereof) to produce a neutralized emulsifier blend or a soap of the emulsifier blend); (iii) spray drying the emulsifier composition or blend, the neutralized emulsifier blend, or the soap of the emulsifier blend; or (iv) a combination thereof.
In any aspect or embodiment described herein, the process or method further comprises reacting tall oil fatty acid (TOFA), rosin (e.g., tall oil rosin or TOR), or a mixture thereof (e.g., a mixture of tall oil fatty acid and rosin, such as tall oil rosin), with an acid and/or anhydride composition that includes or is a dicarboxylic acid, di-anhydride, tricarboxylic acid, tri-anhydride, or a mixture thereof (e.g. maleic acid, fumaric acid, succinic acid, maleic anhydride, succinic anhydride, or a mixture thereof) to produce the first emulsifier.
In any aspect or embodiment described herein, the process or method further comprises neutralizing the emulsifier blend (e.g., reacting the emulsifier blend with a caustic solution (e.g., a solution comprising LiOH, NaOH, KOH, Ca(OH)2, ammonia, alkylamine, alkanolamines, or a combination thereof) to produce a neutralized emulsifier blend or a soap of the emulsifier blend).
In any aspect or embodiment described herein, the process or method further comprises spray drying the emulsifier composition or blend, the neutralized emulsifier blend, or the soap of the emulsifier blend.
In any aspect or embodiment described herein, the emulsifier composition is a spray dried emulsifier.
In any aspect or embodiment described herein, the process or method further comprises spray drying the emulsifier composition or blend, the neutralized emulsifier blend, or the soap of the emulsifier blend.
Another aspect of the present disclosure provides an oil-based drilling fluid or mud comprising an invert emulsion of a hygroscopic liquid (e.g., a brine, such as CaCl2) brine), one or more (e.g., 1, 2, 3, 4, 5, 6, 7, 8, or more) emulsifiers, and at least one of: an oil, mineral oil, synthetic oil, or a combination thereof, wherein the one or more emulsifiers includes one or more of the emulsifier compositions of the present disclosure, one or more of the emulsifier compositions produced according to the method or process of the present disclosure, or a combination thereof. In any aspect or embodiment described herein, the synthetic oil includes or is internal olefin, poly alpha olefin, linear paraffin, or a combination thereof. A further aspect of the present disclosure provides an oil-based drilling fluid or mud consisting essentially of an invert emulsion of a hygroscopic liquid (e.g., a brine, such as CaCl2) brine), one or more (e.g., 1, 2, 3, 4, 5, 6, 7, 8, or more) emulsifiers, and at least one of: an oil, mineral oil, synthetic oil, or a combination thereof, wherein the one or more emulsifiers includes one or more of the emulsifier compositions of the present disclosure, one or more of the emulsifier compositions produced according to the method or process of the present disclosure, or a combination thereof. In any aspect or embodiment described herein, the synthetic oil includes or is internal olefin, poly alpha olefin, linear paraffin, or a combination thereof. An additional aspect of the present disclosure provides an oil-based drilling fluid or mud consisting of, an invert emulsion of a hygroscopic liquid (e.g., a brine, such as CaCl2) brine), one or more (e.g., 1, 2, 3, 4, 5, 6, 7, 8, or more) emulsifiers, and at least one of: an oil, mineral oil, synthetic oil, or a combination thereof, wherein the one or more emulsifiers includes one or more of the emulsifier compositions of the present disclosure, one or more of the emulsifier compositions produced according to the method or process of the present disclosure, or a combination thereof. In any aspect or embodiment described herein, the synthetic oil includes or is internal olefin, poly alpha olefin, linear paraffin, or a combination thereof.
In any aspect or embodiment described herein, the first emulsifiers includes a modified tall oil and/or a modified tall oil fatty acid (TOFA)).
In any aspect or embodiment described herein, the oil is diesel.
In any aspect or embodiment described herein, the hygroscopic liquid is CaCl2) brine, NaCl brine, NaBr brine, CaBr2 brine, a formate brine, potassium formate, an alcohol based hygroscopic liquid, lower polyhydric alcohols, glycerol, or polyglycerol. In any aspect or embodiment described herein, the hygroscopic liquid is CaCl2) brine.
In any aspect or embodiment described herein, the drilling fluid or mud further comprises one or more weighting agents (e.g., barite).
In any aspect or embodiment described herein, the drilling fluid or mud further comprises one or more (e.g., 1, 2, 3, 4, 5, 6, 7, 8, or more) rheological modifier (e.g., clay, organophilic clay, bentonite clay, amine-treated clay, amine-treated bentonite clay, a polyamide, a dimer diacid, or combinations thereof).
In any aspect or embodiment described herein, the drilling fluid or mud further comprises one or more alkalinity agent (e.g., lime, CaO, or Ca(OH)2).
In any aspect or embodiment described herein, the drilling fluid or mud further comprises one or more wetting agent (e.g., fatty imidazolines, soya lecithin, or combinations thereof).
In any aspect or embodiment described herein, the oil-based drilling fluid or mud comprises: an invert emulsion of a hygroscopic liquid (e.g., a brine, such as CaCl2) brine), an oil (e.g. diesel), mineral oil, the emulsifier composition of the present disclosure, and internal olefin.
An additional aspect of the present disclosure provides a method of drilling a wellbore, the method comprising circulating the oil-based drilling fluid of the present disclosure through the wellbore when drilling.
An further aspect of the present disclosure provides a method of drilling a wellbore, the method comprising circulating the oil-based drilling fluid of the present disclosure through the wellbore when drilling the well to depth.
Emulsifiers of the present disclosure are fatty amine condensates composed of fatty acids reacted with poly(alkylamines) that are reacted with polyacids or anhydrides to form the acid terminated fatty amine condensates. By substituting TOFA for a predominantly saturated C16 or C18 fatty acid mixture to synthesize the fatty amine condensate, the melting point of the emulsifier can be significantly increased, while decreasing the tackiness of the emulsifier. This variation of the chemical structure allows improved production of a free-flowing powder by blending with a modified TOFA (e.g., maleated TOFA), as the first emulsifier, the subsequent neuralization to produce soaps of the blend, and spray drying the soap of the blend to produce a free-flowing powder without the need for solid supports/fillers or other additives such as anti-caking agents.
AltaVeg™ FA 450 (Ingevity, Inc; North Charleston, South Carolina) was substituted for TOFA in the formulation for a maleated amidoamine emulsifier. AltaVeg™ FA 450 contains about 70% palmitic acid, <5% stearic acid, and the remainder is unsaturated C18 fatty acids.
Brief Description of Procedure. The reactants for this two-step process are shown below in Table 4 (reaction 1) and Table 5 (reaction 2). Briefly, in the first step, a fatty acid mixture is reacted with poly(alkylamine) to obtain a partial amide which is subsequently reacted in step 2 with maleic anhydride or other similar di-acids/anhydrides, and/or tri-acids/anhydrides to form the second emulsifier. The procedures for these reactions are also given below. After reaction 2, the second emulsifier was blended with EnvaMul® 692 (50% to 75% modified tall oil fatty acid, 25% to 50% modified rosin, an acid value of 270 mgKOH/g to 305 mgKOH/g, a non-volatiles residue of 85% to 97%, a moisture content of 0.01% to 0.50%, and a density at 25° C. (lbs./gal.) of 8.30 to 8.40; Ingevity, Inc; North Charleston, South Carolina), a modified blend of TOFA and rosin, as a first emulsifier. The first emulsifier, second emulsifier blend was then reacted with caustic soda (50% NaOH), diluted to 50% solids, and spray dried using a BÜCHI B290 benchtop spray dryer (BÜCHI Worldwide; Saint Gallen, Switzerland). The inlet temperature of the spray dryer was maintained at 162° C., yielding an outlet temperature of about 125° C.
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 (AN) was determined via titration with 0.5 N KOH in methanol and the amine value (AV) was determined via titration with 0.5 HCL in methanol on an 888 Titrando Autotitrator (Metrohm, Riverview, FL).
Detailed Description of Procedure. The amount of each reactant for the two-step process to make an exemplary second emulsifier of the present disclosure is shown in Table 4 (reaction 1) and Table 5 (reaction 2) below. AltaVeg™ FA450 was added to a Dean-Stark apparatus with a stirrer, a N2 line, a condenser, and a temperature probe. After heating to 93° C. at 1° C. per minute, diethylenetriamine (DETA), triethylenetetramine (TETA), and tetraethylenepentamine (TEPA) was added to the apparatus (reaction exothermed to about 130° C.). The mixture was heated to 160° C. over the course of an hour, and then incubated at 160° C. for an hour. A sample was examined for its acid number (AN) every 20 minutes. Once the acid number (AN) was below 20 mg/g, the reaction mixture was cooled to 70° C.
The reaction product from reaction 1 was heated to 120° C. with agitation. Maleic anhydride was added and the temperature maintained at 130-140° C. for 45 minutes. The acid number (AN) and amine value (AV) were determined.
The amount of each component for an exemplary emulsifier blend of the present disclosure is shown in Table 6 (blending process) and the reactants for the exemplary soap of the exemplary emulsifier blend of the present disclosure is shown in Table 7 (reaction 3) below.
The second emulsifier was added to a vessel with agitation. EnvaMul® 692 (50% to 75% modified tall oil fatty acid, 25% to 50% modified rosin, an acid value of 270 mgKOH/g to 305 mgKOH/g, a non-volatiles residue of 85% to 97%, a moisture content of 0.01% to 0.50%, and a density at 25° C. (lbs./gal.) of 8.30 to 8.40; Ingevity, Inc; North Charleston, South Carolina) was added to the second emulsifier of the present disclosure, and the mixture heated to 70-90° C., and mixed for 30 minutes. The Acid Number and Amine Values of the emulsifier blend were determined to be 175 mg/g and 4 mg/g, respectively.
The emulsifier blend was pre-heated to 80° C. in preparation of blending. The water was added to an aluminum can with open top. Next, the 50% NaOH was added to the water (a small exotherm was detected), followed by the addition of the First Defoamer (SILCOLAPSE™ Silicone Antifoamer; Elkem Silicones USA Corp., East Brunswick, New Jersey) with the caustic solution being heated to 50° C. The heated emulsifier was then charged to weight, and the Second Defoamer (SILCOLAPSE™ Silicone Antifoamer) was added. The mixture was incubated for 60 minutes with mixing.
The pH was determined and 50% NaOH added until a pH of 10.5 obtained. Next, water was added until a 50% non-volatile residue (NVR as measured by an HX204 Moisture Analyzer at 150° C. until <1 mg/50 sec mass loss) was achieved.
The Alta Veg™ FA450-based spray dried composition was compared with an equivalent sample prepared using TOFA as the fatty acid for the fatty amine condensate. Compaction of the Alta Veg™ FA450-based spray dried composition and TOFA-based spray dried composition was performed with 6.5 pounds per square inch (psi) compaction pressure at 50° C. for 16 hours. A significant improvement in blocking was observed for the Alta Veg™ FA450-based spray dried composition, as compared to the TOFA-based spray dried composition. The TOFA-based spray dried composition clumped thoroughly and required crushing to remove from the test bag (see
As mentioned above, Alta Veg™ FA 450 contains about 70% palmitic acid, <5% stearic acid, and the remainder is unsaturated C18 fatty acids. Increasing the palmitic and stearic acid concentration in the fatty acid raw material further increases the melting temperature of the second emulsifier and its salt, allowing drying, handling, and storage at increased temperatures. Palmitic acid, stearic acid, hydrogenated tallow fatty acids, and other highly saturated C16 and C18 fatty acid mixtures are suitable for synthesis of these types of products.
Performance of the emulsifier composition of the present disclosure was tested in exemplary oil-based drilling fluid formulations. The details of the formulations are shown in Tables 8 and 9. The exemplary oil-based drilling fluids were prepared by sequentially adding the ingredients listed in Tables 8 and 9 and mixing for the indicated period of time with a Hamilton Beach (Glen Allen, Virginia) mixer on medium. After preparing the oil-based drilling fluids, the drilling fluids were then hot rolled at 150° F. for 16 hours. The oil-based drilling fluids where then remixed on a multi-mixer on high for 5 minutes. The 350 mL oil-based drilling fluids had a weight of 545.17 g, with an actual mud weight of 13.0 g, and oil/water ratio (OWR) of 0.80.
The rheological properties and emulsion stability(ES) were examined according to the methods described in API Recommended Practice 13B-2, Fourth Edition, Recommended Practice for Field Testing of Oil-based Drilling Fluids. Briefly, the oil-based drilling fluid was aged for 16 hours at 250° F. under 150 pounds per square inch (psi) nitrogen using a stainless-steel rolling aging cell. After aging, the fluid was remixed using a steal mixing cup and a Hamilton Beach mixer at medium mixing speed. The rheological properties of the oil-based drilling fluid were then examined using an OFITER 900 series rotational rheometer at 120° F. Emulsion stability(ES) was measured using an OFITE® ES meter with the fluid maintained at 120° F. High Temperature High Pressure Fluid Loss (HTHP) testing was conducted at 250° F. with a 500 psi differential between the top and bottom pressures. Separated fluid was collected from the bottom port of the HTHP apparatus to measure fluid loss of the mud during the test.
The performance characteristics for Drilling Fluid 1 are shown in Table 9. Rheological properties and other performance factors were within typical ranges for oil-based muds.
As mentioned above, Alta Veg™ FA 450 contains about 70% palmitic acid, <5% stearic acid, and the balance is unsaturated C18 fatty acids. It was surprising and unexpectedly discovered that increasing the palmitic and stearic acid concentration in the fatty acid raw material increased the melting temperature of the second emulsifier, which resulted in an emulsifier composition that maintains its free-flowing particulate/powder without addition of additives.
The rheological properties and emulsion stability(ES) of Drilling Fluid 2 through Drilling Fluid 5 were examined according to the methods described in API Recommended Practice 13B-2, Fourth Edition, Recommended Practice for Field Testing of Oil-based Drilling Fluids. Briefly, the oil-based drilling fluids were aged for 16 hours at 250° F. under 150 pounds per square inch (psi) nitrogen using a stainless-steel rolling aging cell. After aging, the fluids were remixed using a steal mixing cup and a Hamilton Beach mixer at medium mixing speed. The rheological properties of the oil-based drilling fluids were then examined using an OFITE® 900 series rotational rheometer at 120° F. Emulsion stability(ES) was measured using an OFITER ES meter with the fluid maintained at 120° F. High Temperature High Pressure Fluid Loss (HTHP) testing was conducted at 250° F. with a 500 psi differential between the top and bottom pressures. Separated fluids were collected from the bottom port of the HTHP apparatus to measure fluid loss of the mud during the test.
The performance characteristics of Drilling Fluid 2, Drilling Fluid 3, Drilling Fluid 4, and Drilling Fluid 5 are shown in Table 11. Rheological properties and other performance factors were within typical ranges for oil-based muds.
Commercially available liquid all-in-one emulsifier (ENVAMUL® 1699; Ingevity, Inc., North Charleston, South Carolina) and the exemplary emulsifier composition of Example 1 were tested in oil-based drilling fluids with 6% low gravity solids (Drilling Fluids 2 and 4) or without low gravity solids (Drilling Fluids 3 and 5). Shear stresses and fluid loss were higher when using the emulsifier powder (Drilling Fluid 4 and Drilling Fluid 5), as compared to the muds prepared with liquid emulsifiers (Drilling Fluid 2 and Drilling Fluid 3). However, in several cases, solid secondary emulsifiers outperformed the liquid secondary emulsifier in relation to rheology and HTHP fluid loss. For example, the addition of low gravity solids had a much smaller effect on the mud prepared using the emulsifier powder (Drilling Fluid 5) compared with the liquid emulsifiers (Drilling Fluids 3), the latter having higher shear stresses, Plastic Viscosity, and Yield Point with the addition of low gravity solids. Thus, the emulsifier powders better tolerated low gravity solid contamination.
As mentioned above, Alta Veg™ FA 450 contains about 70% palmitic acid, <5% stearic acid, and the balance is unsaturated C18 fatty acids. It was surprising and unexpectedly discovered that increasing the palmitic and stearic acid concentration in the fatty acid raw material increased the melting temperature of the second emulsifier, which resulted in an emulsifier composition that maintains its free-flowing particulate/powder without addition of additives. Overall, the emulsifier powders were demonstrated to be very effective emulsifying agents in the exemplary formulations and were comparable to their liquid emulsifier counterparts in these fluid systems.
This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to make and use the invention. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
All cited patents, patent applications, and other references or publication are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference.
All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. Each range disclosed herein constitutes a disclosure of any point or sub-range lying within the disclosed range. “Combinations” is inclusive of blends, mixtures, alloys, reaction products, and the like. The terms “first”, “second”, and the like, do not denote any order, quantity, or importance, but rather are used to denote one element from another.
The use of the terms “a” and “an” and “the” and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Further, it should further be noted that the terms “first,” “second,” and the like herein do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The modifier “about” used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context (e.g., it includes the degree of error associated with measurement of the particular quantity).
While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.
This application claims priority to, and the benefit of, U.S. Provisional Patent Application No. 63/585,851, filed 27 Sep. 2023 and titled SOLID EMULSIFIERS, DRILLING FLUIDS, AND METHODS OF MAKING AND USING THE SAME, which is incorporated by reference herein in its entirety for all purposes.
| Number | Date | Country | |
|---|---|---|---|
| 63585851 | Sep 2023 | US |
