Patent Application
20190284467
The present invention relates generally to microemulsions and/or diluted microemulsions that have low surface tensions in gas wells.
Diluted microemulsions may be useful for treating gas wells. However, diluted microemulsions may have undesirably high surface tensions under gas well conditions. Accordingly, improved methods of formulating microemulsions and/or diluted microemulsions with especially low surface tension and improved methods of treating gas wells with diluted microemulsions with especially low surface tension may be advantageous.
The present invention generally relates to methods related to making, manufacturing, and/or formulating microemulsions and/or diluted microemulsions with especially low surface tensions for use in in gas wells. The present subject matter of the present invention involves, in some cases, interrelated products, alternative solutions to a particular problem, and/or a plurality of different uses of one or more systems and/or articles.
In some embodiments, a method of formulating a microemulsion and/or a diluted microemulsion for treating a gas well having a wellbore is provided. The method comprises selecting a solvent or combination of solvents to form a non-aqueous phase of a microemulsion based on a temperature and pressure of the gas well, combining the non-aqueous phase with an aqueous phase and a surfactant to form the microemulsion, and diluting the microemulsion into an aqueous dilution phase. In some embodiments, the solvent or combination of solvents has a surface tension of less than or equal to 34 mN/m and greater than or equal to 15 mN/m at the temperature and pressure of the gas well. In some embodiments, the solvent or combination of solvents has a surface tension of less than or equal to 24 mN/m and greater than or equal to 15 mN/m at ambient temperature and pressure. In some embodiments, the microemulsion or the diluted microemulsion has a surface tension of less than or equal to 28 mN/m and greater than or equal to 15 mN/m at the temperature and pressure of the gas well. In some embodiments, the microemulsion or the diluted microemulsion (a microemulsion diluted to a use concentration) has a surface tension of less than or equal to 24 mN/m and greater than or equal to 15 mN/m as measured using the capillary rise technique or the rising bubble technique at ambient temperature and pressure.
In some embodiments, a method of treating a gas well having a wellbore based on the temperature and pressure of the gas well, is provided. The method comprises injecting a diluted microemulsion into the wellbore to increase formation gas production by the gas well. The diluted microemulsion comprises a microemulsion comprising an aqueous phase, a surfactant, and a non-aqueous phase comprising a solvent or combination of solvents. In some embodiments, the solvent or combination of solvents has a surface tension of less than or equal to 34 mN/m and greater than or equal to 15 mN/m at the temperature and pressure of the gas well. In some embodiments, the solvent or combination of solvents has a surface tension of less than or equal to 24 mN/m and greater than or equal to 15 mN/m at ambient temperature and pressure. In some embodiments, the diluted microemulsion has a surface tension of less than or equal to 28 mN/m and greater than or equal to 15 mN/m at the temperature and pressure of the gas well. In some embodiments, the microemulsion or a diluted microemulsion (a microemulsion diluted to a use concentration) has a surface tension of less than or equal to 24 mN/m and greater than or equal to 15 mN/m as measured using the capillary rise technique or the rising bubble technique at ambient temperature and pressure.
The method also comprises formulating or using microemulsions comprising solvents having a vapor pressure at the bottom hole temperature and pressure of the gas well best suited to provide especially low surface tension at that bottom hole temperature and pressure of the gas well.
In some embodiments, a microemulsion suitable for treating a gas well is provided. The microemulsion comprises an aqueous phase, a surfactant, and a non-aqueous phase comprising a solvent or combination of solvents. The solvent or combination of solvents comprises one or more C6-C10 linear or branched alkane solvents, one or more methylated cyclic alkane solvents, and/or one or more methyl siloxane solvents of less than or equal to 800 g/mol molecular weight.
In some embodiments, a microemulsion suitable for treating a gas well and comprising an aqueous phase, a surfactant, and a non-aqueous phase comprising a solvent or combination of solvents has a surface tension of less than or equal to 24 mN/m and greater than or equal to 15 mN/m as measured by a capillary rise technique or a rising bubble technique.
Other advantages and novel features of the present invention will become apparent from the following detailed description of various non-limiting embodiments of the invention when considered in conjunction with the accompanying figures.
Non-limiting embodiments of the present invention will be described by way of example with reference to the accompanying figures, which are schematic and are not intended to be drawn to scale. In the figures, each identical or nearly identical component illustrated is typically represented by a single numeral. For purposes of clarity, not every component is labeled in every figure, nor is every component of each embodiment of the invention shown where illustration is not necessary to allow those of ordinary skill in the art to understand the invention. In the figures:
Wilhelmy plate technique for a variety of pure solvents, according to some embodiments;
Methods related to making, manufacturing, and/or formulating microemulsions and/or diluted microemulsions with especially low surface tensions in gas wells and methods for treating gas wells with such diluted microemulsions are generally provided. During well completion or well stimulation for gas wells, water may be injected into the gas-bearing rock formation. In addition, water or brine is typically present in the rock formation prior to drilling a well into the rock formation. Such water may form a water block, which may prevent flow of hydrocarbon gas out of the porous rock formation into the well.
Capillary pressure is defined as:
P
cap=(2γcosθ)/r
where γ is the surface tension, θ is the contact angle and r is the pore radius or capillary radius. For water in a rock formation, the relevant surface tension is that of water, the relevant contact angle is that of water on the rock formation, and the relevant pore or capillary radius is the pore or capillary radius of the pores in the rock formation. In a rock formation, capillary pressure is equivalent to the pressure required for a gas to force water out of the pores of the rock formation. Water that remains in the pores near the wellbore forms a water block that may prevent the flow of hydrocarbon gas into the well. Surfactants having lower surface tension than water may lower the surface tension of the water in the pores of a rock formation if added thereto. This may lower the capillary pressure of the water in the pores of the rock formation, which may in turn decrease the formation of undesirable water blocks therein. It is believed that larger reductions in the surface tension of water result in the formation of fewer water blocks, which it is believed allows more hydrocarbon gas to flow freely out of the rock formation and into the gas well, which may then be produced and recovered.
It is believed that the surface activity of surfactants is caused by their molecular structure, which is typically an amphiphilic structure including separated hydrophilic and hydrophobic portions. It is believed that this amphiphilic structure results in a propensity for the surfactant to adsorb at interfaces and lower surface tension (or surface energy). When a surfactant is adsorbed at the gas/water interface, it is believed that both the hydrophilic and the hydrophobic portions thereof are energetically satisfied. It is believed that hydrocarbon and silicone solvents include only one or more hydrophobic portion(s)—there are no separated hydrophilic and hydrophobic portions, and that therefore such molecules are not surface active and would not be expected to adsorb at the gas/water interface and lower surface tension.
The inventors have unexpectedly found that microemulsions comprising certain solvents result in even lower surface tension than surfactants alone. This is unexpected because such solvents were not known to be surface active agents—they are not known to be surfactants. As would be known to one of ordinary skill in the art, surfactants are surface active agents—they spontaneously go to or accumulate at interfaces and lower surface tension. However, solvents are not known to spontaneously go to interfaces and lower surface tension. The inventors have also found that this effect can be used to lower capillary pressure and increase flow back in the gas well, which may result in an increase in gas production and recovery from the gas well.
Surface tension may be measured in many different ways. One common measurement is the Wilhelmy plate technique, in which a thin rectangular piece of material, often platinum, is immersed in the gas-water interface and the force exerted on the plate is measured. Another method, called the capillary rise technique, measures the height of rise of the liquid phase in a small diameter capillary. A 100 micron diameter capillary is suitable for measurements on surfactant solutions. Another technique to measure surface tension is called the pendant drop technique, which involves forming a pendant drop of the liquid on the tip of a small diameter (e.g., 1-5 mm) tube immersed in the gas phase and determining the surface tension from the shape of the drop. Another technique, called the rising bubble technique, involves forming a bubble of gas phase on the tip of a small diameter (e.g., 1-5 mm) tube immersed in the liquid and determining the surface tension from the shape of the bubble.
When the surface tension of a microemulsion containing a volatile solvent is measured in an open container using the Wilhelmy plate technique, it is believed that the influence of the solvent on the surface tension is not detected because the solvent rapidly evaporates from the surface. When the surface tension is measured using the pendant drop technique, it is believed that the influence of the solvent on the surface tension is not detected because there is a large ratio of the volume of the gas phase to the volume of the pendant drop which allows the solvent to rapidly evaporate from the surface. It is believed that this effect may be partially offset by pre-saturating the volume of the gas phase with the volatile solvent. When the surface tension of a microemulsion containing a volatile solvent is measured using a 50-250 micron diameter capillary, the inventors have found that the influence of the solvent on the surface tension is detected. It is believed that this is because the rate of evaporation of the solvent from the surface is limited by the small vapor space of the capillary. When the surface tension of a microemulsion containing a volatile solvent is measured using the rising bubble technique, the inventors have found that influence of the solvent on the surface tension is detected. It is believed that this is because evaporation of the solvent from the surface is limited by the small volume of the bubble.
All liquids, including liquid hydrocarbon solvents and silicone solvents, possess a surface tension. It is believed that the surface tension of small molecule hydrocarbon solvents depends strongly on molecular weight, with pentane having a surface tension of 15.8 mN/m at 20° C. and ambient pressure of 1 atm, and tetradecane having a surface tension of 26.6 mN/m at 20° C. and ambient pressure of 1 atm. Hexamethyl disiloxane has a surface tension of 15.9 mN/m at 20° C. and ambient pressure of 1 atm. Some of these liquid hydrocarbon solvents and silicone solvents possess surface tension values significantly lower than most common surfactants. For example, a solution of the nonionic alcohol ethoxylate surfactant C12-C15 E7, when well above its Critical Micelle Concentration or CMC, has a surface tension of 29 mN/m at ambient temperature and pressure. As used herein, the letter “E” followed by an integer represents the number of moles of ethoxylation (i.e., number of ethylene oxide units) contained within a given surfactant.
A microemulsion is a single phase comprising water, solvent (e.g. oil), and surfactant. The inventors have unexpectedly found that even though hydrocarbon solvents and silicone solvents are not known to be surface active agents (they are not known to be surfactants) in aqueous solutions and would not be expected to lower aqueous surface tension, when certain such solvents are incorporated into a microemulsion, the surface tension of the microemulsion is lowered significantly below the value of the microemulsion in the absence of the solvent(s). Since many of the most useful hydrocarbon solvents and silicone solvents, giving the lowest surface tension values, are highly volatile, it may be beneficial to measure the surface tension of the microemulsion using a technique, such as capillary rise technique or the rising bubble technique, that limit evaporation of the solvent from the surface of the microemulsion. This is particularly relevant to the situation in porous rock formations containing recoverable hydrocarbon gas, in which the space containing the gas is present in the form of small pores, usually having diameters much smaller than 100 microns.
The hydrocarbon solvents and silicone solvents described herein have not previously been disclosed, and their use in microemulsions for gas and oil well treatment would not have been obvious because one of ordinary skill in the art would have believed that they would not have been useful solvents for some species commonly found in petroleum, such as asphaltenes and paraffins. In fact, some of these solvents (e.g., heptane) are known for their ability to precipitate asphaltenes from crude oil.
Bottom hole temperatures and pressures in gas wells are usually much higher than ambient conditions at the surface. In addition to disclosing solvents giving large surface tension reductions, the inventors have also discovered a method for selecting solvents that enhance the amount of surface tension lowering at the bottom hole temperature and pressure in a particular gas containing rock formation or reservoir.
Diluted microemulsions with low surface tensions in gas wells may be capable of penetrating into small pores in rock formations present in gas wells, enhancing the recovery of gas present in these pores. In some embodiments, the diluted microemulsion has a relatively low surface tension in the gas well, and the microemulsion comprises a non-aqueous phase comprising a solvent or combination of solvents with a relatively low surface tension in the gas well. In some embodiments, a solvent or combination of solvents may be selected based on the bottom hole temperature and pressure of the gas well. For example, the solvent or combination of solvents may be selected to have a low surface tension at the bottom hole temperature and pressure of the gas well, such as a surface tension lower than that of a surfactant present in the diluted microemulsion. The solvent or combination of solvents may adsorb into a layer of surfactant present on the surface of the diluted microemulsion, and, if it has or they have a lower surface tension than the surfactant, may lower the surface tension of the layer of surfactant and the surface tension of the diluted microemulsion as a whole.
In some embodiments, a solvent or combination of solvents (e.g., for use in a well treatment microemulsion) may be selected to have both a low surface tension at the bottom hole temperature and pressure of the gas well and a vapor pressure at the bottom hole temperature and pressure of the gas well such that there is not appreciable evaporation of the solvent or solvents from the diluted microemulsion. In such embodiments, the solvent or solvents may remain at the surface of the diluted microemulsion throughout its use in the gas well, reducing the surface tension of the diluted microemulsion throughout its use therein.
The diluted microemulsions described herein are generally formulated to have advantageous properties in gas wells (e.g., in gas wells in which the diluted microemulsions are used). Some diluted microemulsion components (e.g., solvents, combinations of solvents) may be selected based on gas well conditions, such as the bottom hole temperature of the gas well, the bottom hole pressure of the gas well, the type of gas present in the gas well, the hydrocarbon bearing rock formation in the gas well, the depth of the hydrocarbon bearing rock formation in the gas well, and the like. As an example, a solvent or combination of solvents may be selected to have a relatively low surface tension at the bottom hole temperature and pressure of the gas well. The solvent or combination of solvents may also be selected to have a relatively low vapor pressure at the bottom hole temperature and pressure of the gas well. In some embodiments, the values of certain properties (e.g., surface tension, vapor pressure) of diluted microemulsions and/or solvents therein may be particularly advantageous under conditions similar to those of gas wells in which the diluted microemulsions are used. These values of these properties may be different than the values of these properties under other conditions (e.g., in laboratory environments, at 20° C. and atmospheric pressure, at 60° C. and atmospheric pressure). Some diluted microemulsions described herein have beneficial properties both in gas wells and in other environments.
Unless otherwise specified, references to conditions of a gas well (e.g., gas well temperature, gas well pressure, and/or both gas well temperature and pressure) should be understood to refer to the bottom hole temperature and pressure of the gas well or the conditions of the gas well at the depth of the hydrocarbon bearing rock formation therein.
Gas wells typically have temperatures and pressures that are elevated in comparison to room temperature and pressure. In some embodiments, a gas well has a temperature of greater than or equal to 60° C., greater than or equal to 75° C., greater than or equal to 100° C., greater than or equal to 125° C., greater than or equal to 150° C., greater than or equal to 175° C., greater than or equal to 200° C., greater than or equal to 225° C., greater than or equal to 250° C., greater than or equal to 275° C., greater than or equal to 300° C., greater than or equal to 325° C., greater than or equal to 350° C., greater than or equal to 375° C., or greater than or equal to 400° C. The gas well may have a temperature of less than or equal to 400° C., less than or equal to 375° C., less than or equal to 350° C., less than or equal to 325° C., less than or equal to 300° C., less than or equal to 275° C., less than or equal to 250° C., less than or equal to 225° C., less than or equal to 200° C., less than or equal to 175° C., less than or equal to 150° C., less than or equal to 125° C., less than or equal to 100° C., less than or equal to 75° C., or less than or equal to 60° C. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 60° C. and less than or equal to 400° C., greater than or equal to 100° C. and less than or equal to 350° C., or greater than or equal to 300° C. and less than or equal to 400° C.). Other ranges are also possible.
A gas well may have a pressure of greater than or equal to 1,000 psi, greater than or equal to 2,000 psi, greater than or equal to 5,000 psi, greater than or equal to 8,000 psi, or greater than or equal to 10,000 psi. The gas well may have a pressure of less than or equal to 10,000 psi, less than or equal to 8,000 psi, less than or equal to 5,000 psi, less than or equal to 2,000 psi, or less than or equal to 1,000 psi. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 1,000 psi and less than or equal to 10,000 psi). Other ranges are also possible.
In some embodiments, one or more components of a microemulsion (e.g., a microemulsion to be diluted) may be selected based on a measurement technique that provides information about the properties of that component (and/or of the resultant diluted microemulsion as a whole) in a gas well. The measurement technique may be a measurement technique that closely approximates one or more conditions of a gas well, and/or may be a measurement technique that provides information from which the expected properties of the component and/or the diluted microemulsion in the gas well can be calculated. For instance, a property may be measured at 20° C. and atmospheric pressure, and a known relationship between the value of the property at 20° C. and atmospheric pressure and the value of that property (and/or another related property) at the gas well temperature and pressure may be employed to determine the value of that property (and/or another related property) at the gas well temperature and pressure. By way of example, the following procedure may be employed to determine a predicted surface tension of a diluted microemulsion at a temperature and pressure of a gas well: (1) the predicted vapor pressure of the solvents in the non-aqueous phase at the temperature and pressure of the gas well may be determined based upon a vapor pressure of the solvents at 20° C. and the Clausius-Clapeyron equation; (2) the predicted surface tension of the solvents in the non-aqueous phase at the temperature and pressure of the gas well may be determined based upon a surface tension of the solvents at 20° C. and the relationship described in Grigoryev, B. A., Nemzer, B. V., Kurumov, D. S. & Sengers, J. V. Surface tension of normal pentane, hexane, heptane, and octane. Int. J. Thermophys. (1992); and (3) an empirical relationship for the difference between the surface tension of a diluted microemulsion and the surface tension of the solvent(s) in a non-aqueous phase therein as a function of the vapor pressure of the solvent(s) in the non-aqueous phase therein may be employed to predict the diluted microemulsion surface tension (see Example 11).
As an example, in some embodiments, a surface tension of a diluted microemulsion described herein may refer to surface tension that is measured by a capillary rise technique. Without wishing to be bound by any particular theory, and as described in more detail below, it is believed that the value of surface tension measured for a diluted microemulsion may depend on the measurement technique employed to determine that value, and that the capillary rise technique is particularly accurate for measuring a value of surface tension that provides relevant information about the behavior that the diluted microemulsion would exhibit in a gas well.
When a diluted microemulsion comprises a volatile solvent (e.g., in a non-aqueous phase), its surface tension may change as the volatile solvent evaporates therefrom. Accordingly, it is believed that measurement techniques performed in environments where evaporation of volatile solvents from the diluted microemulsion is substantially different than evaporation of volatile solvents from diluted microemulsions in gas wells may yield values of surface tension that differ from the actual surface tension of the diluted microemulsion in the gas well. Gas wells typically include rock formations comprising interconnected pores that have small diameters (e.g., in the range of 1-5 microns or less). Together, the interconnected pores occupy a relatively large volume. For diluted microemulsions in these rock formations, there is typically a relatively limited interface between the diluted microemulsion and air through which volatile solvents may evaporate. After evaporation, the evaporated volatile solvents may diffuse away from this limited interface through the large volume of the interconnected pores. Therefore, measurement techniques performed in environments in which the interface between the diluted microemulsion and the air has a relatively small area but is fluidically connected to a relatively large volume of air through which evaporated volatile solvents can diffuse are believed to be particularly accurate at measuring microemulsion properties in gas well conditions.
It is believed that the capillary rise technique is one example of a measurement technique that occurs in an environment mimicking that of a gas well. The capillary rise technique is performed by: (1) positioning a capillary with a diameter of 150 microns in the fluid to be measured (e.g., a diluted microemulsion); (2) positioning a capillary with a diameter of 200 microns in the fluid to be measured; (3) allowing the fluid to be measured to rise along the two capillaries until it reaches a stable height in each capillary; and (4) solving Jurin's law for both capillaries determine the surface tension of the fluid. The capillary rise equation is the following:
where h is the height of the microemulsion in the capillary, γ is the surface tension of the microemulsion, θ is the angle between the microemulsion and the capillary at the air-capillary-microemulsion interface, ρ is the density of the microemulsion, g is the gravitational constant, and r is the radius of the capillary or the radius of the pore. It is believed that the diluted microemulsions in capillaries fluidically connected to an open ambient environment experience volatile organic solvent evaporation at similar rates to diluted microemulsions in rock formations in gas wells. For this reason, it is believed that employing the capillary rise technique to measure the surface tension of a diluted microemulsion yields a value of the surface tension of the diluted microemulsion that closely approximates its surface tension in a gas well. It is also believed that employing the capillary rise technique to measure the surface tension of a diluted microemulsion provides relevant information about the behavior of the microemulsion in the gas well (e.g., its tendency to penetrate a network of narrow-diameter interconnected pores therein).
Certain diluted microemulsions described herein may have beneficial properties at the bottom hole temperature and pressure in a gas well. As described in fuller detail elsewhere herein, microemulsions typically comprise one phase dispersed in another phase. One of the phases may be an aqueous phase, and/or one of the phases may be a non-aqueous phase. In some embodiments, emulsions or microemulsion are provided. The terms should be understood to include emulsions or microemulsions that have a water continuous phase, or that have an oil continuous phase, or microemulsions that are bicontinuous. The microemulsion may further comprise a surfactant. Diluted microemulsions are microemulsions that have been added to a dilution phase. The microemulsion may be added to the dilution phase prior to and/or during injection into a wellbore. In some embodiments, the dilution phase is an aqueous phase. For instance, it may comprise an aqueous fluid (e.g., an aqueous carrier fluid), such as water, water comprising one or more dissolved salts (e.g., KCl), brine, sea water, fresh water, and/or a well-treatment fluid. Non-limiting examples of suitable well-treatment fluids include acids, fracturing fluids comprising polymers, produced water, sand or proppant, and slick water. In some embodiments, a composition for injecting into a wellbore is provided comprising a microemulsion as described herein and a dilution phase.
In some embodiments, a diluted microemulsion comprises a dilution phase that comprises water and KCl. The KCl may be present in the dilution phase in an amount of greater than or equal to 0.5 wt %/vol, greater than or equal to 1 wt %/vol, greater than or equal to 2 wt %/vol, or greater than or equal to 5 wt %/vol. The KCl may be present in the dilution phase in an amount of less than or equal to 10 wt %/vol, less than or equal to 5 wt %/vol, or less than or equal to 1 wt %/vol. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0.5 wt %/vol and less than or equal to 10 wt %/vol). Other ranges are also possible. In some embodiments, the KCl is present in the dilution phase in an amount of 2 wt %/vol.
A diluted microemulsion may comprise a microemulsion in a variety of suitable amounts. The diluted microemulsion may comprise the microemulsion in an amount of less than or equal to 100 gpt, less than or equal to 50 gpt, less than or equal to 20 gpt, less than or equal to 10 gpt, less than or equal to 5 gpt, less than or equal to 2 gpt, less than or equal to 1 gpt, less than or equal to 0.5 gpt, less than or equal to 0.2 gpt, or less than or equal to 0.1 gpt. The diluted microemulsion may comprise the microemulsion in an amount of greater than or equal to 0.1 gpt, greater than or equal to 0.2 gpt, greater than or equal to 0.5 gpt, greater than or equal to 1 gpt, greater than or equal to 2 gpt, greater than or equal to 5 gpt, greater than or equal to 10 gpt, greater than or equal to 20 gpt, greater than or equal to 50 gpt, or greater than or equal to 100 gpt. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0.1 gpt and less than or equal to 100 gpt, greater than or equal to 0.2 gpt and less than or equal to 5 gpt, or greater than or equal to 0.2 gpt and less than or equal to 2 gpt). Other ranges are also possible. As would be known to one of ordinary skill in the art, the unit gpt refers to gallons per thousand and is equivalent to one tenth of a volume percent.
In some embodiments, a diluted microemulsion has an advantageously low surface tension. The surface tension of the diluted microemulsion may be less than or equal to 34 nM/m, less than or equal to 28 mN/m, less than or equal to 25 mN/m, less than or equal to 24 mN/m, less than or equal to 23 mN/m, less than or equal to 21 mN/m, less than or equal to 20 mN/m, less than or equal to 19 mN/m, less than or equal to 18 mN/m, less than or equal to 17 mN/m, or less than or equal to 15 mN/m. The surface tension of the diluted microemulsion may be greater than or equal to 15 mN/m, greater than or equal to 17 mN/m, greater than or equal to 18 mN/m, greater than or equal to 19 mN/m, greater than or equal to 20 mN/m, greater than or equal to 21 mN/m, greater than or equal to 23 mN/m, greater than or equal to 24 nM/m, greater than or equal to 25 mN/m, greater than or equal to 28 mN/m, or greater than or equal to 34 mN/m. Combinations of the above-referenced ranges are also possible (e.g., less than or equal to 23 mN/m and greater than or equal to 15 mN/m; less than or equal to 24 mN/m and greater than or equal to 15 mN/m; less than or equal to 21 mN/m and greater than or equal to 15 mN/m; less than or equal to 19 mN/m and greater than or equal to 15 mN/m; less than or equal to 17 mN/m and greater than or equal to 15 mN/m). Other ranges are also possible. The surface tension of the diluted microemulsion may be determined by the capillary rise technique or the rising bubble technique. It should be understood that the ranges above may refer to a range of surface tensions at a variety of suitable temperatures and pressures. In some embodiments, the diluted microemulsion may have a surface tension in one or more of the ranges listed above at a gas well temperature and pressure. In some embodiments, the diluted microemulsion may have a surface tension in one or more of the ranges listed above at 60° C. and atmospheric pressure. In some embodiments, the diluted microemulsion may have a surface tension in one or more of the ranges listed above at 20° C. and atmospheric pressure.
In some embodiments, a diluted microemulsion has a surface tension that is lower than it would be if it lacked one or more of its components. For instance, some diluted microemulsions described herein may have a surface tension that is lower than an otherwise equivalent composition lacking one or more solvents present in a non-aqueous phase therein. The diluted microemulsion may have a surface tension that is greater than or equal to 5% lower, greater than or equal to 10% lower, greater than or equal to 15% lower, greater than or equal to 20% lower, or greater than or equal to 25% lower, or greater than or equal to 30% lower than a surface tension of an otherwise equivalent composition lacking a solvent or combination of solvents included in an aqueous phase of the diluted microemulsion. The diluted microemulsion may have a surface tension that is less than or equal to 30% lower, less than or equal to 25% lower, less than or equal to 20% lower, less than or equal to 15% lower, less than or equal to 10% lower, or less than or equal to 5% lower than a surface tension of an otherwise equivalent composition lacking a solvent or combination of solvents included in an aqueous phase of the diluted microemulsion. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 5% lower and less than or equal to 30% lower, greater than or equal to 10% lower and less than or equal to 30% lower). Other ranges are also possible. The surface tension of the diluted microemulsion may be determined by the capillary rise technique. It should be understood that the ranges above may refer to a range of surface tensions at a variety of suitable temperatures and pressures. In some embodiments, the diluted microemulsion may have a surface tension in one or more of the ranges listed above at a gas well temperature and pressure. In some embodiments, the diluted microemulsion may have a surface tension in one or more of the ranges listed above at 60° C. and atmospheric pressure. In some embodiments, the diluted microemulsion may have a surface tension in one or more of the ranges listed above at 20° C. and atmospheric pressure.
In some embodiments, a diluted microemulsion has a surface tension that is relatively close to a surface tension of one or more of its components. The component may be one with a lower surface tension than some or all of the other components of the diluted microemulsion. For example, in some embodiments, a diluted microemulsion comprises an aqueous phase comprising a solvent or combination of solvents, and the diluted microemulsion has a surface tension that is relatively close to a surface tension of the solvent or combination of solvents. The surface tension of the diluted microemulsion may be greater than or equal to 10% lower than the surface tension of the solvent or combination of solvents, greater than or equal to 5% lower than the surface tension of the solvent or combination of solvents, greater than or equal to 2% lower than the surface tension of the solvent or combination of solvents, greater than or equal to the surface tension of the solvent or combination of solvents, greater than or equal to 2% higher than the surface tension of the solvent or combination of solvents, greater than or equal to 5% higher than the surface tension of the solvent or combination of solvents, greater than or equal to 10% higher than the surface tension of the solvent or combination of solvents, greater than or equal to 15% higher than the surface tension of the solvent or combination of solvents, greater than or equal to 20% higher than the surface tension of the solvent or combination of solvents, or greater than or equal to 25% higher than the surface tension of the solvent or combination of solvents.
The surface tension of the diluted microemulsion may be less than or equal to 30% higher than the surface tension of the solvent or combination of solvents, less than or equal to 25% higher than the surface tension of the solvent or combination of solvents, less than or equal to 20% higher than the surface tension of the solvent or combination of solvents, less than or equal to 15% higher than the surface tension of the solvent or combination of solvents, less than or equal to 10% higher than the surface tension of the solvent or combination of solvents, less than or equal to 5% higher than the surface tension of the solvent or combination of solvents, less than or equal to 2% higher than the surface tension of the solvent or combination of solvents, less than or equal to the surface tension of the solvent or combination of solvents, less than or equal to 2% lower than the surface tension of the solvent or combination of solvents, or less than or equal to 5% lower than the surface tension of the solvent or combination of solvents of an otherwise equivalent composition lacking a solvent or combination of solvents included in an aqueous phase of the diluted microemulsion. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 10% lower than the surface tension of the solvent or combination of solvents and less than or equal to 30% higher than the surface tension of the solvent or combination of solvents). Other ranges are also possible. The surface tension of the diluted microemulsion may be determined by the capillary rise technique. It should be understood that the ranges above may refer to a range of surface tensions at a variety of suitable temperatures and pressures. In some embodiments, the diluted microemulsion may have a surface tension in one or more of the ranges listed above at a gas well temperature and pressure. In some embodiments, the diluted microemulsion may have a surface tension in one or more of the ranges listed above at 60° C. and atmospheric pressure. In some embodiments, the diluted microemulsion may have a surface tension in one or more of the ranges listed above at 20° C. and atmospheric pressure.
As described herein, some microemulsions may comprise a non-aqueous phase, and some diluted microemulsions may comprise a non-aqueous phase. The non-aqueous phase may comprise a solvent and/or a combination of solvents (e.g., in the form of a solvent blend), examples of which are provided in further detail below. The non-aqueous phase may make up any suitable amount of the microemulsion (e.g., of the components of the diluted microemulsion other than the dilution phase). The non-aqueous phase may make up greater than or equal to 1 wt %, greater than or equal to 2 wt %, greater than or equal to 5 wt %, greater than or equal to 10 wt %, greater than or equal to 15 wt %, greater than or equal to 20 wt %, greater than or equal to 25 wt %, or greater than or equal to 30 wt % of the microemulsion. The non-aqueous phase may make up less than or equal to 30 wt % of the microemulsion, less than or equal to 25 wt % of the microemulsion, less than or equal to 20 wt % of the microemulsion, less than or equal to 15 wt % of the microemulsion, less than or equal to 10 wt % of the microemulsion, less than or equal to 5 wt % of the microemulsion, less than or equal to 2 wt %, or less than or equal to 1 wt % of the microemulsion. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 1 wt % and less than or equal to 30 wt % of the microemulsion, greater than or equal to 15 wt % and less than or equal to 30 wt % of the microemulsion, or greater than or equal to 20 wt % and less than or equal to 25 wt % of the microemulsion). Other ranges are also possible.
A solvent in a non-aqueous phase of a microemulsion and/or diluted microemulsion, a combination of solvents in a non-aqueous phase of a microemulsion and/or diluted microemulsion, and/or a non-aqueous phase as a whole in a microemulsion and/or diluted microemulsion may have one or more advantageous properties. For example, the solvent, combination of solvents (e.g. solvent blend), and/or non-aqueous phase as a whole may have a relatively low surface tension (e.g., at a gas well temperature and pressure, at 60° C. and atmospheric pressure, at 20° C. and atmospheric pressure). In some embodiments, a solvent, combination of solvents (e.g. solvent blend), and/or non-aqueous phase has a lower surface tension than a surfactant also present in the microemulsion and/or diluted microemulsion. In some embodiments, the non-aqueous phase comprises a solvent or a combination of solvents (e.g. solvent blend) with a relatively low surface tension (e.g., a surface tension lower than a surface tension of a surfactant also present in the microemulsion and/or diluted microemulsion) and also comprises a solvent or a combination of solvents (e.g. solvent blend) with a surface tension that is not relatively low (e.g., a surface tension higher than a surface tension of a surfactant also present in the diluted microemulsion).
The surface tension of any solvent in the non-aqueous phase, a combination of solvents (e.g. solvent blend) in the non-aqueous phase, and/or the non-aqueous phase as a whole may each independently be less than or equal to 34 mN/m, less than or equal to 30 mN/m, less than or equal to 28 mN/m, less than or equal to 25 mN/m, less than or equal to 24 mN/m, less than or equal to 23 mN/m, less than or equal to 20 mN/m, less than or equal to 18 mN/m, or less than or equal to 15 mN/m. The surface tension of any solvent in the non-aqueous phase, a combination of solvents in the non-aqueous phase, and/or the non-aqueous phase as a whole may each independently be greater than or equal to 15 mN/m, greater than or equal to 18 mN/m, greater than or equal to 20 mN/m, greater than or equal to 23 mN/m, greater than or equal to 24 mN/m, greater than or equal to 25 mN/m, greater than or equal to 28 mN/m, greater than or equal to 30 mN/m, or greater than or equal to 34 mN/m. Combinations of the above-referenced ranges are also possible (e.g., less than or equal to 34 mN/m and greater than or equal to 15 mN/m; less than or equal to 24 mN/m and greater than or equal to 15 mN/m). Other ranges are also possible.
The surface tension of the solvent, combination of solvents, and/or non-aqueous phase as a whole may be determined by the capillary rise technique. It should be understood that the ranges above may refer to a range of surface tensions at a variety of suitable temperatures and pressures. In some embodiments, the solvent, combination of solvents, and/or non-aqueous phase may have a surface tension in one or more of the ranges listed above at a gas well temperature and pressure. In some embodiments, the solvent, combination of solvents, and/or non-aqueous phase may have a surface tension in one or more of the ranges listed above at 60° C. and atmospheric pressure. In some embodiments, the solvent, combination of solvents, and/or non-aqueous phase may have a surface tension in one or more of the ranges listed above at 20° C. and atmospheric pressure.
In some embodiments, a non-aqueous phase comprises a solvent with an advantageous vapor pressure and/or moderate volatility. As used herein, a solvent with moderate volatility has a vapor pressure in the range from 1 mm Hg to 150 mm Hg. As represented here, a solvent may have moderate volatility at ambient temperature and pressure, and/or at gas well temperature and pressure. The vapor pressure of any solvent in the non-aqueous phase may be less than or equal to 150 mm Hg, less than or equal to 130 mm Hg, less than or equal to 100 mm Hg, less than or equal to 75 mm Hg, less than or equal to 60 g, less than or equal to 50 mm Hg, less than or equal to 40 mm Hg, less than or equal to 30 mm Hg, or less than or equal to 20 mm Hg, or less than or equal to 10 mm Hg, or less than or equal to 5 mm Hg, or less than or equal to 2 mm Hg, or less than or equal to 1 mm Hg. The vapor pressure of any solvent in the non-aqueous phase may be greater than or equal to 1 mm Hg, greater than or equal to 2 mm Hg, greater than or equal to 5 mm Hg, greater than or equal to 10 mm Hg, greater than or equal to 20 mm Hg, greater than or equal to 30 mm Hg, greater than or equal to 40 mm Hg, greater than or equal to 50 mm Hg, greater than or equal to 60 mm Hg, greater than or equal to 75 mm Hg, greater than or equal to 100 mm Hg, or greater than or equal to 130 mm Hg. Combinations of the above-referenced ranges are also possible (e.g., less than or equal to 150 mm Hg and greater than or equal to 1 mm Hg). Other ranges are also possible. In some embodiments, the solvent may have a vapor pressure in one or more of the ranges described above and have an advantageous surface tension (e.g., a surface tension lower than a surface tension of a surfactant also present in the diluted microemulsion; a surface tension in one or more of the ranges described above, such as less than or equal to 34 mN/m and greater than or equal to 15 mN/m). It should be understood that the ranges above may refer to a range of vapor pressures at a variety of suitable temperatures and pressures. In some embodiments, the solvent may have a vapor pressure in one or more of the ranges listed above at a gas well temperature and pressure. In some embodiments, the diluted microemulsion may have a surface tension in one or more of the ranges listed above at 60° C. and atmospheric pressure. In some embodiments, the solvent may have a vapor pressure in one or more of the ranges listed above at 20° C. and atmospheric pressure.
In some embodiments, a non-aqueous phase comprises a solvent with a moderate volatility at a gas well temperature and pressure (e.g., a solvent with a volatility in one or more of the ranges described above) and comprises a solvent that is essentially nonvolatile at a gas well temperature and pressure (e.g., a solvent with a vapor pressure of less than or equal to 10 mm Hg, less than or equal to 5 mm Hg, less than or equal to 2 mm Hg, less than or equal to 1 mm Hg, less than or equal to 0.5 mm Hg, less than or equal to 0.2 mm Hg, less than or equal to 0.1 mm Hg, or less than or equal to 0.05 mm Hg).
Below, non-limiting examples of different solvents that may be present in a non-aqueous phase of a microemulsion and/or a non-aqueous phase of a diluted microemulsion are provided.
In some embodiments, a combination of two or more of the solvents (e.g. a solvent blend) listed below may be present in a non-aqueous phase of a microemulsion and/or a non-aqueous phase of a diluted microemulsion (e.g., a blend of d-limonene and octamethylcyclotetrasiloxane, a blend of d-limonene and heptane). It should be understood that, unless otherwise indicated, the solvents listed below may or may not: (1) have a surface tension in one or more of the ranges described herein, (3) be a solvent in a combination of solvents having a surface tension in one or more of the ranges described herein, (3) have a surface tension lower than a surface tension of a surfactant also present in the microemulsion and/or diluted microemulsion, (4) be a solvent in a combination of solvents having a surface tension lower than a surface tension of a surfactant also present in the microemulsion and/or diluted microemulsion, and/or (5) have a vapor pressure in one or more of the ranges described herein.
In some embodiments, a non-aqueous phase of a microemulsion and/or a diluted microemulsion comprises at least one terpene solvent. In some embodiments, the non-aqueous phase comprises a terpene and another solvent (e.g., an alcohol, a siloxane solvent). In some embodiments, the non-aqueous phase comprises a first terpene and a second, different terpene.
Terpenes are generally derived biosynthetically from units of isoprene. Terpenes may be generally classified as monoterpenes (e.g., having two isoprene units), sesquiterpenes (e.g., having three isoprene units), diterpenes, or the like. The term “terpenoid” includes natural degradation products, such as ionones, and natural and synthetic derivatives, e.g., terpene alcohols, ethers, aldehydes, ketones, acids, esters, epoxides, and hydrogenation products (e.g., see Ullmann's Encyclopedia of Industrial Chemistry, 2012, pages 29-45, herein incorporated by reference). In some embodiments, the terpene is a naturally occurring terpene. In some embodiments, the terpene is a non-naturally occurring terpene and/or a chemically modified terpene (e.g., saturated terpene, terpene amine, fluorinated terpene, or silylated terpene). Terpenes that are modified chemically, such as by oxidation or rearrangement of the carbon skeleton, may be referred to as terpenoids. Many references use “terpene” and “terpenoid” interchangeably, and this disclosure will adhere to that usage.
In some embodiments, the terpene is a non-oxygenated terpene. In some embodiments, the terpene is a citrus terpene. In some embodiments, the terpene is d-limonene. In some embodiments, the terpene is dipentene. In some embodiments, the terpene is selected from the group consisting of d-limonene, nopol, alpha terpineol, eucalyptol, dipentene, linalool, alpha-pinene, beta-pinene, alpha-terpinene, geraniol, alpha-terpinyl acetate, menthol, menthone, cineole, citranellol, and combinations thereof. As used herein, “ terpene” refers to a single terpene compound or a blend of terpene compounds.
In some embodiments, the terpene is an oxygenated terpene. Non-limiting examples of oxygenated terpenes include terpenes containing alcohol, aldehyde, ether, or ketone groups. In some embodiments, the terpene comprises an ether-oxygen, for example, eucalyptol, or a carbonyl oxygen, for example, menthone. In some embodiments the terpene is a terpene alcohol. Non-limiting examples of terpene alcohols include linalool, geraniol, nopol, a-terpineol, and menthol. Non-limiting examples of oxygenated terpenes include eucalyptol, 1,8-cineol, menthone, and carvone.
In some embodiments, the non-aqueous phase (e.g., the solvent) of the microemulsion and/or the diluted microemulsion does not comprise a terpene. It is believed that terpene solvents generally have surface tension values, and provide surface tension values when incorporated into microemulsions and/or diluted microemulsions, that are comparable to conventional hydrocarbon surfactants, and are therefore not especially useful for their surface tension lowering ability when incorporated into a microemulsion or a diluted microemulsion.
In some embodiments, a non-aqueous phase of a microemulsion and/or a non-aqueous phase of a diluted microemulsion comprises an alkyl aliphatic carboxylic acid ester solvent. As used herein “alkyl aliphatic carboxylic acid ester” refers to a compound or a blend of compounds having the general formula:
wherein R1 is a C6 to C16 optionally substituted aliphatic group, including those bearing heteroatom-containing substituent groups, and R2 is a C1 to C6 alkyl group. In some embodiments, R1 is C6 to C16 alkyl. In some embodiments, R1 is substituted with at least one heteroatom-containing substituent group. For example, wherein a blend of compounds is provided and each R2 is —CH3 and each R1 is independently a C6 to C16 aliphatic group, the blend of compounds is referred to as methyl aliphatic carboxylic acid esters, or methyl esters. In some embodiments, such alkyl aliphatic carboxylic acid esters may be derived from a fully synthetic process or from natural products, and thus comprise a blend of more than one ester. In some embodiments, the alkyl aliphatic carboxylic acid ester comprises butyl 3-hydroxybutyrate, isopropyl 3-hydroxybutyrate, hexyl 3-hydroxylbutyrate, and combinations thereof. Non-limiting examples of alkyl aliphatic carboxylic acid esters include methyl octanoate, methyl decanoate, a blend of methyl octanoate and methyl decanoate, and butyl 3-hydroxybutyrate.
In some embodiments, a non-aqueous phase of a microemulsion and/or a non-aqueous phase of a diluted microemulsion comprises an unsubstituted cyclic or acyclic, branched or unbranched alkane solvent. In some embodiments, the cyclic or acyclic, branched or unbranched alkane has from 6 to 12 carbon atoms (e.g., from 6 to 10 carbon atoms). When the cyclic or acyclic alkane solvent is branched, the branches may include 1 carbon atom (e.g., in the case of methylated cyclic or acyclic alkane solvents), 2 carbon atoms (e.g., in the case of ethylated cyclic or acyclic alkane solvents), 3 carbon atoms (e.g., in the case of propylated cyclic or acyclic alkane solvents), or more carbon atoms. Non-limiting examples of unsubstituted, acyclic, unbranched alkanes include hexane, heptane, octane, nonane, decane, undecane, dodecane, and combinations thereof. Non-limiting examples of unsubstituted, acyclic, branched alkanes include isomers of methylpentane (e.g., 2-methylpentane, 3-methylpentane), isomers of dimethylbutane (e.g., 2,2-dimethylbutane, 2,3-dimethylbutane), isomers of methylhexane (e.g., 2-methylhexane, 3-methylhexane), isomers of ethylpentane (e.g., 3-ethylpentane), isomers of dimethylpentane (e.g., 2,2,-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane), isomers of trimethylbutane (e.g., 2,2,3-trimethylbutane), isomers of methylheptane (e.g., 2-methylheptane, 3-methylheptane, 4-methylheptane), isomers of dimethylhexane (e.g., 2,2-dimethylhexane, 2,3-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3,3-dimethylhexane, 3,4-dimethylhexane), isomers of ethylhexane (e.g., 3-ethylhexane), isomers of trimethylpentane (e.g., 2,2,3-trimethylpentane, 2,2,4-trimethylpentane, 2,3,3-trimethylpentane, 2,3,4-trimethylpentane), isomers of ethylmethylpentane (e.g., 3-ethyl-2-methylpentane, 3-ethyl-3-methylpentane), and combinations thereof. Non-limiting examples of unsubstituted cyclic branched or unbranched alkanes include cyclohexane, methylcyclopentane, ethylcyclobutane, propylcyclopropane, isopropylcyclopropane, dimethylcyclobutane, cycloheptane, methylcyclohexane, dimethylcyclopentane, ethylcyclopentane, trimethylcyclobutane, cyclooctane, methylcycloheptane, dimethylcyclohexane, ethylcyclohexane, isopropylcyclohexane, cyclononane, methylcyclooctane, dimethylcycloheptane, ethylcycloheptane, trimethylcyclohexane, ethylmethylcyclohexane, propylcyclohexane, cyclodecane, and combinations thereof. In some embodiments, the unsubstituted cyclic or acyclic, branched or unbranched alkane having from 6 to 12 carbon atoms is selected from the group consisting of heptane, octane, nonane, decane, 2,2,4-trimethylpentane (isooctane), and propylcyclohexane, and combinations thereof.
In some embodiments, a non-aqueous phase of a microemulsion and/or a non-aqueous phase of a diluted microemulsion comprises a solvent that is an unsubstituted acyclic branched alkene or unsubstituted acyclic unbranched alkene having one or two double bonds and from 6 to 12 carbon atoms. In some embodiments, the non-aqueous phase comprises an unsubstituted acyclic branched alkene or unsubstituted acyclic unbranched alkene having one or two double bonds and from 6 to 10 carbon atoms. Non-limiting examples of unsubstituted acyclic unbranched alkenes having one or two double bonds and from 6 to 12 carbon atoms include isomers of hexene (e.g., 1-hexene, 2-hexene), isomers of hexadiene (e.g., 1,3-hexadiene, 1,4-hexadiene), isomers of heptene (e.g., 1-heptene, 2-heptene, 3-heptene), isomers of heptadiene (e.g., 1,5-heptadiene, 1-6, heptadiene), isomers of octene (e.g., 1-octene, 2-octene, 3-octene), isomers of octadiene (e.g., 1,7-octadiene), isomers of nonene, isomers of nonadiene, isomers of decene, isomers of decadiene, isomers of undecene, isomers of undecadiene, isomers of dodecene, isomers of dodecadiene, and combinations thereof. In some embodiments, the acyclic, unbranched alkene having one or two double bonds and from 6 to 12 carbon atoms is an alpha-olefin (e.g., 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene). Non-limiting examples of unsubstituted, acyclic, branched alkenes include isomers of methylpentene, isomers of dimethylpentene, isomers of ethylpentene, isomers of methylethylpentene, isomers of propylpentene, isomers of methylhexene, isomers of ethylhexene, isomers of dimethylhexene, isomers of methylethylhexene, isomers of methylheptene, isomers of ethylheptene, isomers of dimethylhexptene, isomers of methylethylheptene, and combinations thereof. In a particular embodiment, the unsubstituted, acyclic, unbranched alkene having one or two double bonds and from 6 to 12 carbon atoms is 1-octene, 1,7-octadiene, or a combination thereof.
In some embodiments, a non-aqueous phase of a microemulsion and/or a non-aqueous phase of a diluted microemulsion comprises an aromatic solvent having a boiling point from 300 to 400° F. Non-limiting examples of aromatic solvents having a boiling point from 300 to 400° F. include butylbenzene, hexylbenzene, mesitylene, light aromatic naphtha, heavy aromatic naphtha, and combinations thereof.
In some embodiments, a non-aqueous phase of a microemulsion and/or a non-aqueous phase of a diluted microemulsion comprises an aromatic solvent having a boiling point from 175 to 300° F. Non-limiting examples of aromatic liquid solvents having a boiling point from 175 to 300° F. include benzene, xylenes, and toluene. In a particular embodiment, the non-aqueous phase does not comprise toluene or benzene.
In some embodiments, a non-aqueous phase of a microemulsion and/or a non-aqueous phase of a diluted microemulsion comprises a solvent that is a branched or unbranched dialkylether having the formula CnH2n+1OCmH2m+1 wherein n+m is from 6 to 16. In some embodiments, n+m is from 6 to 12, or from 6 to 10, or from 6 to 8. Non-limiting examples of branched or unbranched dialkylether compounds having the formula CnH2n+1OCmH2m+1 include isomers of C3H7OC3H7, isomers of C4H9OC3H7, isomers of C5H11OC3H7, isomers of C6H13OC3H7, isomers of C4H9OC4H9, isomers of C4H9OC5H11, isomers of C4H9OC6H13, isomers of C5H11OC6H13, and isomers of C6H13OC6H13. In a particular embodiment, the branched or unbranched dialkylether is an isomer of C6H13OC6H13 (e.g., dihexylether).
In some embodiments, a non-aqueous phase of a microemulsion and/or a non-aqueous phase of a diluted microemulsion comprises a bicyclic hydrocarbon solvent with varying degrees of unsaturation including fused, bridgehead, and spirocyclic compounds. Non-limiting examples of bicyclic solvents include isomers of decalin, tetrahydronaphthalene, norbornane, norbornene, bicyclo[4.2.0]octane, bicyclo[3.2.1]octane, spiro[5.5]dodecane, and combinations thereof.
In some embodiments, a non-aqueous phase of a microemulsion and/or a non-aqueous phase of a diluted microemulsion comprises a solvent that is a cyclic or acyclic, branched or unbranched alkane having from 6 to 12 carbon atoms or from 5 to 10 carbon atoms, and substituted with a hydroxyl group. Non-limiting examples of cyclic or acyclic, branched or unbranched alkanes having from 6 to 12 carbon atoms or from 5 to 10 carbon atoms, and substituted with a hydroxyl group include isomers of nonanol, isomers of decanol, isomers of undecanol, isomers of dodecanol, and combinations thereof. In a particular embodiment, the cyclic or acyclic, branched or unbranched alkane having from 9 to 12 carbon atoms and substituted with a hydroxyl group is 1-nonanol, 1-decanol, or a combination thereof.
Non-limiting examples of cyclic or acyclic, branched or unbranched alkanes having from 5 to 10 carbon atoms, and substituted with a hydroxyl group include isomers of pentanol, isomers of hexanol, and isomers of heptanol.
Non-limiting examples of cyclic or acyclic, branched or unbranched alkanes having 8 carbon atoms and substituted with a hydroxyl group include isomers of octanol (e.g., 1-octanol, 2-octanol, 3-octanol, 4-octanol), isomers of methyl heptanol, isomers of ethylhexanol (e.g., 2-ethyl-1-hexanol, 3-ethyl-1-hexanol, 4-ethyl-1-hexanol), isomers of dimethylhexanol, isomers of propylpentanol, isomers of methylethylpentanol, isomers of trimethylpentanol, and combinations thereof. In a particular embodiment, the cyclic or acyclic, branched or unbranched alkane having 8 carbon atoms and substituted with a hydroxyl group is 1-octanol, 2-ethyl-1-hexanol, or a combination thereof.
In some embodiments, a non-aqueous phase of a microemulsion and/or a non-aqueous phase of a diluted microemulsion comprises a solvent that is an amine of the formula NR1R2R3, wherein R1, R2, and R3 are the same or different and are C1-16 alkyl groups that are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments any two of R1, R2, and R3 are joined together to form a ring. In some embodiments, each of R1, R2, and R3 are the same or different and are hydrogen or alkyl groups that are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments, any two of R1, R2, and R3 are joined together to form a ring, provided at least one of R1, R2, and R3 is a methyl or an ethyl group. In some embodiments, R1 is C1-C6 alkyl group that is (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted and R2 and R3 are hydrogen or a C8-16 alkyl group that is (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments, R2 and R3 may be joined together to form a ring. In some embodiments, R1 is a methyl or an ethyl group and R2 and R3 are the same or different and are C8-16 alkyl groups that are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments R2 and R3 may be joined together to form a ring. In some embodiments, R1 is a methyl group and R2 and R3 are the same or different and are hydrogen or C8-16 alkyl groups that are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments R2 and R3 may be joined together to form a ring. In some embodiments, R1 and R2 are the same or different and are hydrogen or C1-C6 alkyl groups that are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted and R3 is a C8-16 alkyl group that is (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments, R1 and R2 are the same or different and are a methyl or an ethyl group and R3 is hydrogen or a C8-16 alkyl group that is (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments, R1 and R2 are methyl groups and R3 is hydrogen or a C8-16 alkyl group that is (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted.
In some embodiments, the amine is of the formula NR1R2R3, wherein R1 is methyl and R2 and R3 are C8-16 alkyl groups that are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments R2 and R3 are joined together to form a ring. Non-limiting examples of amines include isomers of N-methyl-octylamine, isomers of N-methyl-nonylamine, isomers of N-methyl-decylamine, isomers of N-methylundecylamine, isomers of N-methyldodecylamine, isomers of N-methyl teradecylamine, isomers of N-methyl-hexadecylamine, and combinations thereof. In some embodiments, the amine is N-methyl-decylamine, N-methyl-hexadecylamine, or a combination thereof.
In some embodiments, the amine is of the formula NR1R2R3, wherein R1 is a methyl group and R2 and R3 are the same or different and are C8-16 alkyl groups that are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments R2 and R3 are joined together to form a ring. Non-limiting examples of amines include isomers of N-methyl-N-octyloctylamine, isomers of N-methyl-N-nonylnonylamine, isomers of N-methyl-N-decyldecylamine, isomers of N-methyl-N-undecylundecylamine, isomers of N-methyl-N-dodecyldodecylamine, isomers of N-methyl-N-tetradecylteradecylamine, isomers of N-methyl-N-hexadecylhexadecylamine, isomers of N-methyl-N-octylnonylamine, isomers of N-methyl-N-octyldecylamine, isomers of N-methyl-N-octyldodecylamine, isomers of N-methyl-N-octylundecylamine, isomers of N-methyl-N-octyltetradecylamine, isomers of N-methyl-N-octylhexadecylamine, N-methyl-N-nonyldecylamine, isomers of N-methyl-N-nonyldodecylamine, isomers of N-methyl-N-nonyltetradecylamine, isomers of N-methyl-N-nonylhexadecylamine, isomers of N-methyl-N-decylundecylamine, isomers of N-methyl-N-decyldodecylamine, isomers of N-methyl-N-decyltetradecylamine, isomers of N-methyl-N-decylhexadecylamine, isomers of N-methyl-N-dodecylundecylamine, isomers of N-methyl-N-dodecyltetradecylamine, isomers of N-methyl-N-dodecylhexadecylamine, isomers of N-methyl-N-tetradecylhexadecylamine, and combinations thereof. In some embodiments, the amine is selected from the group consisting of N-methyl-N-octyloctylamine, isomers of N-methyl-N-nonylnonylamine, isomers of N-methyl N-decyldecylamine, isomers of N-methyl-N-undecylundecylamine, isomers of N-methyl-N-dodecyldodecylamine, isomers of N-methyl-N-tetradecylteradecylamine, and isomers of N-methyl-N-hexadecylhexadecylamine, and combinations thereof. In some embodiments, the amine is N-methyl-N-dodecyldodecylamine, one or more isomers of N-methyl-N-hexadecylhexadecylamine, or combinations thereof. In some embodiments, the amine is selected from the group consisting of isomers of N-methyl-N-octylnonylamine, isomers of N-methyl-N-octyldecylamine, isomers of N-methyl-N-octyldodecylamine, isomers of N-methyl-N-octylundecylamine, isomers of N-methyl-N-octyltetradecylamine, isomers of N-methyl-N-octylhexadecylamine, N-methyl-N-nonyldecylamine, isomers of N-methyl-N-nonyldodecylamine, isomers of N-methyl-N-nonyltetradecylamine, isomers of N-methyl-N-nonylhexadecylamine, isomers of N-methyl-N-decyldodecylamine, isomers of N-methyl-N-decylundecylamine, isomers of N-methyl-N-decyldodecylamine, isomers of N-methyl-N-decyltetradecylamine, isomers of N-methyl-N-decylhexadecylamine, isomers of N-methyl-N-dodecylundecylamine, isomers of N-methyl-N-dodecyltetradecylamine, isomers of N-methyl-N-dodecylhexadecylamine, isomers of N-methyl-N-tetradecylhexadecylamine, and combinations thereof. In some embodiments, the cyclic or acyclic, branched or unbranched tri-substituted amine is selected from the group consisting of N-methyl-N-octyldodecylamine, N-methyl-N-octylhexadecylamine, and N-methyl-N-dodecylhexadecylamine, and combinations thereof.
In some embodiments, the amine is of the formula NR1R2R3, wherein R1 and R2 are methyl and R3 is a C8-16 alkyl that is (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. Non-limiting examples of amines include isomers of N,N-dimethylnonylamine, isomers of N,N-dimethyldecylamine, isomers of N,N-dimethylundecylamine, isomers of N,N-dimethyldodecylamine, isomers of N,N-dimethyltetradecylamine, and isomers of N,N-dimethylhexadecylamine. In some embodiments, the amine is selected from the group consisting of N,N-dimethyldecylamine, isomers of N,N-dodecylamine, and isomers of N,N-dimethylhexadecylamine.
In some embodiments, a non-aqueous phase of a microemulsion and/or a non-aqueous phase of a diluted microemulsion comprises an amide solvent. In some embodiments, the amide is of the formula N(C═OR4)R5R6, wherein R4, R5, and R6 are the same or different and are hydrogen or C4-6 alkyl groups wherein the alkyl groups are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments R5 and R6 are joined together to form a ring. In some embodiments, each of R4, R5, and R6 are the same or different and are hydrogen or C4-6 alkyl groups wherein the alkyl groups are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted, provided at least one of R4, R5, and R6 is a methyl or an ethyl group. In some embodiments R5 and R6 are joined together to form a ring. In some embodiments, R4 is hydrogen, C1-C6 alkyl, wherein the alkyl group is (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted, and R5 and R6 are the same or different and are hydrogen or C8-16 alkyl groups wherein the alkyl groups are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments, R5 and R6 are joined together to form a ring. In some embodiments, R4 is hydrogen, methyl, or ethyl and R5 and R6 are C8-16 alkyl groups wherein the alkyl groups are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments, R5 and R6 are joined together to form a ring. In some embodiments, R4 is hydrogen and R5 and R6 are the same or different and are C8-16 alkyl groups wherein the alkyl groups are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments R5 and R6 are joined together to form a ring. In some embodiments, R4 and R5 are the same or different and are hydrogen or C1-C6 alkyl groups wherein the alkyl groups are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted and R6 is a C8-16 alkyl group that is (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments, R4 and R5 are the same or different and are independently hydrogen, methyl, or ethyl and R6 is a C8-16 alkyl group that is (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments, R4 and R5 are hydrogen and R6 is a C8-16 alkyl group that is (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments, R6 is hydrogen or R6 is a C1-6 alkyl group that is (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted and R4 and R5 are the same or different and are C8-16 alkyl groups wherein the alkyl groups are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments, R6 is hydrogen, methyl, or ethyl and R4 and R5 are the same or different and are C8-16 alkyl groups wherein the alkyl groups are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments, R6 is hydrogen and R4 and R5 are the same or different and are C8-16 alkyl groups wherein the alkyl groups are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments, R5 and R6 are the same or different and are hydrogen or C1-6 alkyl groups wherein the alkyl groups are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted, and R4 is a C8-16 alkyl group that is (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments, R5 and R6 are the same or different and are independently hydrogen, methyl, or ethyl and R4 is a C8-16 alkyl group that is (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments, R5 and R6 are hydrogen and R4 is a C8-16 alkyl group that is (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted.
In some embodiments, the amide is of the formula N(C═OR4)R5R6, wherein each of R4, R5, and R6 are the same or different and are C4-16 alkyl groups wherein the alkyl groups are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments R5 and R6 are joined together to form a ring. In some embodiments, the amide is of the formula N(C═O R4)R5R6, wherein each of R4, R5, and R6 are the same or different and are C8-16 alkyl groups wherein the alkyl groups are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments R5 and R6 are joined together to form a ring. Non-limiting examples of amides include N,N-dioctyloctamide, N,N-dinonylnonamide, N,N-didecyldecamide, N,N-didodecyldodecamide, N,N-diundecylundecamide, N,N-ditetradecyltetradecamide, N,N-dihexadecylhexadecamide, N,N-didecyloctamide, N,N-didodecyloctamide, N,N-dioctyldodecamide, N,N-didecyldodecamide, N,N-dioctylhexadecamide, N,N-didecylhexadecamide, N,N-didodecylhexadecamide, and combinations thereof. In some embodiments, the amide is N,N-dioctyldodecamide, N,N-didodecyloctamide, or a combination thereof.
In some embodiments, the amide is of the formula N(C═OR4)R5R6, wherein R6 is selected from the group consisting of hydrogen, methyl, ethyl, propyl and isopropyl, and R4 and R5 are the same or different and are C4-16 alkyl groups wherein the alkyl groups are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments, R6 is selected from the group consisting of hydrogen, methyl, ethyl, propyl and isopropyl, and R4 and R5 are the same or different and are C4-8 alkyl groups wherein the alkyl groups are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments, at least one of R4 and R5 is substituted with a hydroxyl group. In some embodiments, at least one of R4 and R5 is C1-16 alkyl substituted with a hydroxyl group.
In some embodiments, the amide is of the formula N(C═OR4)R5R6, wherein R6is C1-C3 alkyl and R4 and R5 are the same or different and are C4-16 alkyl groups that are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments, R6 is selected from the group consisting of methyl, ethyl, propyl, and isopropyl, and R4 and R5 are the same or different and are C4-16 alkyl groups that are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments, R6 is selected from the group consisting of methyl, ethyl, propyl, and isopropyl, and R4 and R5 are the same or different and are C8-16 alkyl groups that are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments, at least one of R4 and R5 is substituted with a hydroxyl group. In some embodiments, R6 is selected from the group consisting of methyl, ethyl, propyl, and isopropyl, and R4 and R5 are the same or different and are C4-16 alkyl groups that are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments at least one of R4 and R5 is C1-16 alkyl substituted with a hydroxyl group.
Non-limiting examples of amides include N,N-di-tert-butylformamide, N,N-dipentylformamide, N,N-dihexylformamide, N,N-diheptylformamide, N,N-dioctylformamide, N,N-dinonylformamide, N,N-didecylformamide, N,N-diundecylformamide, N,N-didodecylformamide, N,N-dihydroxymethylformamide, N,N-di-tert-butylacetamide, N,N-dipentylacetamide, N,N-dihexylacetamide, N,N-diheptylacetamide, N,N-dioctylacetamide, N,N-dinonylacetamide, N,N-didecylacetamide, N,N-diundecylacetamide, N,N-didodecylacetamide, N,N-dihydroxymethylacetamide, N,N-dimethylpropionamide, N,N-diethylpropionamide, N,N-dipropylpropionamide, N,N-di-n-propylpropionamide N,N-diisopropylpropionamide, N,N-dibutylpropionamide, N,N-di-n-butylpropionamide, N,N-di-sec-butylpropionamide, N,N-diisobutylpropionamide or N,N-di-tert-butylpropionamide, N,N-dipentylpropionamide, N,N-dihexylpropionamide, N,N-diheptylpropionamide, N,N-dioctylpropionamide, N,N-dinonylpropionamide, N,N-didecylpropionamide, N,N-diundecylpropionamide, N,N-didodecylpropionamide, N,N-dimethyl-n-butyramide, N,N-diethyl-n-butyramide, N,N-dipropyl-n-butyramide, N,N-di-n-propyl-n-butyramide or N,N-diisopropyl-n-butyramide, N,N-dibutyl-n-butyramide, N,N-di-n-butyl-n-butyramide, N,N-di-sec-butyl-n-butyramide, N,N-diisobutyl-n-butyramide, N,N-di-tert-butyl-n-butyramide, N,N-dipentyl-n-butyramide, N,N-dihexyl-n-butyramide, N,N-diheptyl-n-butyramide, N,N-dioctyl-n-butyramide, N,N-dinonyl-n-butyramide, N,N-didecyl-n-butyramide, N,N-diundecyl-n-butyramide, N,N-didodecyl-n-butyramide, N,N-dipentylisobutyramide, N,N-dihexylisobutyramide, N,N-diheptylisobutyramide, N,N-dioctylisobutyramide, N,N-dinonylisobutyramide, N,N-didecylisobutyramide, N,N-diundecylisobutyramide, N,N-didodecylisobutyramide, N,N-pentylhexylformamide, N,N-pentylhexylacetamide, N,N-pentylhexylpropionamide, N,N-pentylhexyl-n-butyramide, N,N-pentylhexylisobutyramide, N,N-methylethylpropionamide, N,N-methyl-n-propylpropionamide, N,N-methylisopropylpropionamide, N,N-methyl-n-butylpropionamide, N,N-methylethyl-n-butyramide, N,N-methyl-n-butyramide, N,N-methylisopropyl-n-butyramide, N,N-methyl-n-butyl-n-butyramide, N,N-methylethylisobutyramide, N,N-methyl-n-propylisobutyramide, N,N-methylisopropylisobutyramide, and N,N-methyl-n-butylisobutyramide. In some embodiments, the amide is selected from the group consisting of N,N-dioctyldodecacetamide, N,N-methyl-N-octylhexadecyldidodecylacetamide, N-methyl-N-hexadecyldodecylhexadecacetamide, and combinations thereof.
In some embodiments, the amide is of the formula N(C═OR4)R5R6, wherein R6 is hydrogen or a methyl group and R4 and R5 are C8-16 alkyl groups that are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. Non-limiting amides include isomers of N-methyloctamide, isomers of N-methylnonamide, isomers of N-methyldecamide, isomers of N-methylundecamide, isomers of N methyldodecamide, isomers of
N methylteradecamide, and isomers of N-methyl-hexadecamide. In some embodiments, the amides are selected from the group consisting of N-methyloctamide, N-methyldodecamide, N-methylhexadecamide, and combinations thereof.
Non-limiting amides include isomers of N-methyl-N-octyloctamide, isomers of N-methyl-N-nonylnonamide, isomers of N-methyl-N-decyldecamide, isomers of N methyl-N undecylundecamide, isomers of N methyl-N-dodecyldodecamide, isomers of N methyl N-tetradecylteradecamide, isomers of N-methyl-N-hexadecylhdexadecamide, isomers of N-methyl-N-octylnonamide, isomers of N-methyl-N-octyldecamide, isomers of N-methyl-N-octyldodecamide, isomers of N-methyl-N-octylundecamide, isomers of N-methyl-N-octyltetradecamide, isomers of N-methyl-N-octylhexadecamide, N-methyl-N-nonyldecamide, isomers of N-methyl-N-nonyldodecamide, isomers of N-methyl-N-nonyltetradecamide, isomers of N-methyl-N-nonylhexadecamide, isomers of N-methyl-N-decyldodecamide, isomers of N methyl-N-decylundecamide, isomers of N-methyl-N-decyldodecamide, isomers of N-methyl-N-decyltetradecamide, isomers of N-methyl-N-decylhexadecamide, isomers of N methyl-N-dodecylundecamide, isomers of N methyl-N-dodecyltetradecamide, isomers of N-methyl-N-dodecylhexadecamide, isomers of N methyl-N-tetradecylhexadecamide, and combinations thereof. In some embodiments, the amide is selected from the group consisting of isomers of N-methyl-N-octyloctamide, isomers of N-methyl-N-nonylnonamide, isomers of N-methyl-N-decyldecamide, isomers of N methyl-N undecylundecamide, isomers of N methyl-N-dodecyldodecamide, isomers of N methyl N-tetradecylteradecamide, isomers of N-methyl-N-hexadecylhdexadecamide, and combinations thereof. In some embodiments, amide is selected from the group consisting of N-methyl-N-octyloctamide, N methyl-N-dodecyldodecamide, and N-methyl-N-hexadecylhexadecamide. In some embodiments, the amide is selected from the group consisting of isomers of N-methyl-N-octylnonamide, isomers of N-methyl-N-octyldecamide, isomers of N-methyl-N-octyldodecamide, isomers of N-methyl-N-octylundecamide, isomers of N-methyl-N-octyltetradecamide, isomers of N-methyl-N-octylhexadecamide, N-methyl-N-nonyldecamide, isomers of N-methyl-N-nonyldodecamide, isomers of N-methyl-N-nonyltetradecamide, isomers of N-methyl-N-nonylhexadecamide, isomers of N-methyl-N-decyldodecamide, isomers of N methyl-N-decylundecamide, isomers of N-methyl-N-decyldodecamide, isomers of N-methyl-N-decyltetradecamide, isomers of N-methyl-N-decylhexadecamide, isomers of N methyl-N-dodecylundecamide, isomers of N methyl-N-dodecyltetradecamide, isomers of N-methyl-N-dodecylhexadecamide, and isomers of N methyl-N-tetradecylhexadecamide. In some embodiments, the amide is selected from the group consisting of N-methyl-N-octyldodecamide, N-methyl-N-octylhexadecamide, and N-methyl-N-dodecylhexadecamide. In some embodiments, the amide is of the formula N(C═OR4)R5R6, wherein R5 and R6 are the same or different and are hydrogen or C1-C3 alkyl groups and R4 is a C4-16 alkyl group that is (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments, R5 and R6 are the same or different and are selected from the group consisting of hydrogen, methyl, ethyl, propyl and isopropyl, and R4 is a C4-16 alkyl group that is (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments, R5 and R6 are the same or different and are selected from the group consisting of hydrogen, methyl, ethyl, propyl and isopropyl and R4 is a C8-16 alkyl group that is (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. In some embodiments, R4 is substituted with a hydroxyl group. In some embodiments, R5 and R6 are the same or different and are selected from the group consisting of hydrogen, methyl, ethyl, propyl, and isopropyl, and R4 is selected from the group consisting of tert-butyl and C5-16 alkyl groups that are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted, and C1-16 alkyl groups that are (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted with a hydroxyl group.
In some embodiments, the amide is of the formula N(C═OR4)R5R6, wherein R5 and R6 are methyl groups and R4 is a C8-16 alkyl group that is (i) branched or unbranched; (ii) cyclic or acyclic; and (iii) substituted or unsubstituted. Non-limiting examples of amides include isomers of N,N-dimethyloctamide, isomers of N,N-dimethylnonamide, isomers of N,N-dimethyldecamide, isomers of N,N-dimethylundecamide, isomers of N,N-dimethyldodecamide, isomers of N,N-dimethyltetradecamide, isomers of N,N-dimethylhexadecamide, and combinations thereof. In some embodiments, the cyclic or acyclic, branched or unbranched tri-substituted amines is selected from the group consisting of N,N-dimethyloctamide, N,N-dodecamide, and N,N-dimethylhexadecamide.
In some embodiments, a non-aqueous phase of a microemulsion and/or a non-aqueous phase of a diluted microemulsion comprises a methyl siloxane solvent, also known as a silicone solvent. The microemulsion and/or diluted microemulsion may comprise a single methyl siloxane solvent or a combination of two or more methyl siloxane solvents. Methyl siloxane solvents may be classified as linear, cyclic, or branched. Methyl siloxane solvents are a class of oligomeric liquid silicones that possess the characteristics of low viscosity and high volatility. Non-limiting examples of linear siloxane solvents include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, and dodecamethylpentasiloxane. Non-limiting examples of cyclic siloxane solvents include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane.
In some embodiments a non-aqueous phase of a microemulsion and/or a non-aqueous phase of a diluted microemulsion comprises a first type of siloxane solvent and a second type of siloxane solvent.
The siloxanes used in this embodiment can be linear methyl siloxanes, cyclic methyl siloxanes, branched methyl siloxanes, and combinations thereof. The linear methyl siloxanes have the formula
(CH3)3SiO{(CH3)2SiO}kSi(CH3)3
wherein the value of k is 0-5. The cyclic methyl siloxanes have the formula
{(CH3)2SiO}t
wherein the value of t is 3-6. Preferably, these methyl siloxanes have a boiling point less than 250° C. and viscosity of 0.65 to 5.0 cSt.
In some embodiments, the silicone solvent is 0.65 cSt polydimethylsiloxane, trimethylsiloxy terminated. In some embodiments, the silicone solvent is 1.0 cSt polydimethylsiloxane, trimethylsiloxy terminated. In some embodiments, the silicone solvent is 1.5 cSt polydimethylsiloxane, trimethylsiloxy terminated. In some embodiments, the silicone solvent is 2 cSt polydimethylsiloxane, trimethylsiloxy terminated. In some embodiments, the silicone solvent is 3 cSt polydimethylsiloxane, trimethylsiloxy terminated.
In some embodiments, the silicone solvent has a low molecular weight. In certain embodiments, the molecular weight of the silicone solvent ranges between 150 g/mol and 800 g/mol. In some embodiments, the molecular weight of the silicone solvent is greater than or equal to 150 g/mol, greater than or equal to 200 g/mol, greater than or equal to 300 g/mol, greater than or equal to 370 g/mol, greater than or equal to 500 g/mol, greater than or equal to 550 g/mol, or greater than or equal to 770 g/mol. In certain embodiments, the molecular weight of the silicone solvent is less than or equal to 800 g/mol, less than or equal to 770 g/mol, less than or equal to 550 g/mol, less than or equal to 500 g/mol, less than or equal to 370 g/mol, less than or equal to 300 g/mol, or less than or equal to 200 g/mol. Combinations of the above-referenced ranges are also possible (e.g., between 162 g/mol and 770 g/mol; between 162 g/mol and 550 g/mol; between 162 g/mol and 370 g/mol). Other ranges and molecular weights are also possible.
Some representative linear methyl siloxanes are hexamethyldisiloxane with a boiling point of 100° C., viscosity of 0.65 cSt, and structure
octamethyltrisiloxane with a boiling point of 152° C., viscosity of 1.04 cSt, and structure
decamethyltetrasiloxane with a boiling point of 194° C., viscosity of 1.53 cSt, and structure
dodecamethylpentasiloxane with a boiling point of 229° C., viscosity of 2.06 cSt, and structure
tetradecamethylhexasiloxane with a boiling point of 245° C., viscosity of 2.63 cSt, and structure
and hexadecamethylheptasiloxane with a boiling point of 270° C., viscosity of 3.24 cSt, and structure
Some representative cyclic methyl siloxanes are hexamethylcyclotrisiloxane with a boiling point of 134° C. and structure
octamethylcyclotetrasiloxane with a boiling point of 176° C., viscosity of 2.3 cSt, and structure
decamethylcyclopentasiloxane with a boiling point of 210° C., viscosity of 3.87 cSt, and structure
and dodecamethylcyclohexasiloxane with a boiling point of 245° C., viscosity of 6.62 cSt, and structure
In some embodiments, a solvent (e.g., a terpene) may be extracted from a natural source (e.g., citrus, pine), and may comprise one or more impurities present from the extraction process. In some embodiments, the solvent comprises a crude cut (e.g., uncut crude oil, e.g., made by settling, separation, heating, etc.). In some embodiments, the solvent is a crude oil (e.g., naturally occurring crude oil, uncut crude oil, crude oil extracted from the wellbore, synthetic crude oil, crude citrus oil, crude pine oil, eucalyptus, etc.). In some embodiments, the solvent comprises a citrus extract (e.g., crude orange oil, orange oil, etc.). In some embodiments, the solvent is a citrus extract (e.g., crude orange oil, orange oil, etc.).
In some embodiments, a non-aqueous phase of a microemulsion and/or a non-aqueous phase of a diluted microemulsion may comprise a plant-based methyl ester (e.g. soy methyl ester, canola methyl ester). In some embodiments, the non-aqueous phase of a diluted microemulsion may comprise an alkyl aliphatic ester solvent. In some embodiments, the alkyl aliphatic ester solvent is a methyl ester. In some embodiments, the non-aqueous phase of a diluted microemulsion may comprise a solvent selected from the group consisting of soy methyl ester, canola methyl ester, octanoic acid methyl ester, decanoic acid methyl ester, dodecanoic acid methyl ester, palm methyl ester, coconut methyl ester, undecanoic acid methyl ester, tridecanoic acid methyl ester, tetradecanoic acid methyl ester, pentadecanoic acid methyl ester, hexadecanoic acid methyl ester, 9-decenoic acid methyl ester, 10-undecenoic acid methyl ester, 11-dodecenoic acid methyl ester, 12-tridecenoic acid methyl ester, 13-tetradecenoic acid methyl ester, 14-pentadecenoic acid methyl ester, 15-hexadecenoic acid methyl ester, or combinations thereof. In some embodiments, the third type of solvent is butyl 3-hydroxybutanoate. In some embodiments, a non-aqueous phase of a microemulsion and/or a non-aqueous phase of a diluted microemulsion may comprise an alcohol. In some embodiments, the alcohol is selected from the group consisting of primary, secondary, and tertiary alcohols having from 1 to 20 carbon atoms. Non-limiting examples of alcohols include methanol, ethanol, isopropanol, n-propanol, n-butanol, i-butanol, sec-butanol, iso-butanol, t-butanol, ethylene glycol, propylene glycol, dipropylene glycol monomethyl ether, triethylene glycol, and ethylene glycol monobutyl ether.
In some embodiments, a non-aqueous phase of a microemulsion and/or a non-aqueous phase of a diluted microemulsion comprises a solvent that serves as a coupling agent between the other components of the non-aqueous phase (e.g., a solvent or combination of solvents therein) and the one or more surfactant. Without wishing to be bound by any theory, it is believed that alkyl aliphatic ester solvents may have this property.
A wide variety of suitable surfactants may be employed in the microemulsions and diluted microemulsions described herein, examples of which are provided in further detail below. The surfactant may make up any suitable amount of the microemulsion (e.g., of the components of the diluted microemulsion other than the dilution phase). The surfactant may make up greater than or equal to 0.1 wt %, greater than or equal to 0.2 wt %, greater than or equal to 0.5 wt %, greater than or equal to 1 wt %, greater than or equal to 2 wt %, greater than or equal to 5 wt %, greater than or equal to 10 wt %, greater than or equal to 20 wt %, greater than or equal to 30 wt %, greater than or equal to 40 wt %, greater than or equal to 50 wt %, greater than or equal to 60 wt % of the microemulsion, or greater than or equal to 65 wt % of the micromeulsion. The surfactant may make up less than or equal to 65 wt %, less than or equal to 60 wt %, less than or equal to 50 wt %, less than or equal to 40 wt %, less than or equal to 30 wt %, less than or equal to 20 wt %, less than or equal to 10 wt %, less than or equal to 5 wt %, less than or equal to 2 wt %, less than or equal to 1 wt %, less than or equal to 0.5 wt %, less than or equal to 0.2 wt %, or less than or equal to 0.1 wt % of the microemulsion. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0.1 wt % and less than or equal to 65 wt % of the microemulsion, greater than or equal to 10 wt % and less than or equal to 30 wt % of the microemulsion, or greater than or equal to 20 wt % and less than or equal to 30 wt % of the microemulsion). Other ranges are also possible.
Non-limiting examples of suitable surfactants include nonionic surfactants with linear or branched structure, including, but not limited to, alkoxylated alcohols, alkoxylated fatty alcohols, alkoxylated castor oils, alkoxylated fatty acids, and alkoxylated fatty amides with a hydrocarbon chain of at least 8 carbon atoms and 5 units or more of alkoxylation. The term alkoxylation includes ethoxylation and propoxylation. Other nonionic surfactants include alkyl glycosides and alkyl glucamides.
Surfactants described herein may have a variety of surface tensions. A microemulsion and/or a diluted microemulsion may comprise a surfactant with a surface tension of less than or equal to 45 mN/m, less than or equal to 43 mN/m, less than or equal to 40 mN/m, less than or equal to 38 mN/m, less than or equal to 35 mN/m, less than or equal to 33 mN/m, less than or equal to 30 mN/m, less than or equal to 28 mN/m, less than or equal to 25 mN/m, less than or equal to 23 mN/m, or less than or equal to 20 mN/m. A microemulsion and/or a diluted microemulsion may comprise a surfactant with a surface tension of greater than or equal to 20 mN/m, greater than or equal to 23 mN/m, greater than or equal to 25 mN/m, greater than or equal to 28 mN/m, greater than or equal to 30 mN/m, greater than or equal to 33 mN/m, greater than or equal to 35 mN/m, greater than or equal to 38 mN/m, greater than or equal to 40 mN/m, greater than or equal to 43 mN/m, or greater than or equal to 45 mN/m. Combinations of the above-referenced ranges are also possible (e.g., less than or equal to 45 mN/m and greater than or equal to 20 mN/m). Other ranges are also possible. It should be understood that the ranges above may refer to a range of surface tensions at a variety of suitable temperatures and pressures. In some embodiments, the surfactant may have a surface tension in one or more of the ranges listed above at a gas well temperature and pressure. In some embodiments, the surfactant may have a surface tension in one or more of the ranges listed above at 60° C. and atmospheric pressure. In some embodiments, the surfactant may have a surface tension in one or more of the ranges listed above at 20° C. and atmospheric pressure.
Below, non-limiting examples of different surfactants that may be present in a microemulsion and/or a diluted microemulsion are provided.
It should be understood that a microemulsion or diluted microemulsion may comprise one surfactant, or may comprise two or more surfactants. In some embodiments, a microemulsion or diluted microemulsion may comprise a co-surfactant in addition to one or more surfactants. The term surfactant is given its ordinary meaning in the art and generally refers to compounds having an amphiphilic structure which gives them a specific affinity for oil/water-type and water/oil-type interfaces. In some embodiments, the affinity helps the surfactants to reduce the free energy of these interfaces and to stabilize the dispersed phase of a microemulsion.
The term surfactant includes but is not limited to nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, switchable surfactants, cleavable surfactants, dimeric or gemini surfactants, glucamide surfactants, alkyl polyglycoside surfactants, extended surfactants containing a nonionic spacer arm central extension and an ionic or nonionic polar group, and combinations thereof. Nonionic surfactants generally do not contain any charges. Anionic surfactants generally possess a net negative charge. Cationic surfactants generally possess a net positive charge. Amphoteric surfactants generally have both positive and negative charges, however, the net charge of the surfactant can be positive, negative, or neutral, depending on the pH of the solution. Zwitterionic surfactants are generally not pH dependent. A zwitterion is a neutral molecule with a positive and a negative electrical charge, though multiple positive and negative charges can be present.
“Extended surfactants” are defined herein to be surfactants having propoxylated/ethoxylated spacer arms. The extended chain surfactants are intramolecular mixtures having at least one hydrophilic portion and at least one lipophilic portion with an intermediate polarity portion in between the hydrophilic portion and the lipophilic portion; the intermediate polarity portion may be referred to as a spacer. They attain high solubilization in the single phase emulsion or microemulsion, and are in some instances, insensitive to temperature and are useful for a wide variety of oil types, such as natural or synthetic polar oil types in a non-limiting embodiment. More information related to extended chain surfactants may be found in U.S. Pat. No. 8,235,120, which is incorporated herein by reference in its entirety.
The term co-surfactant as used herein is given its ordinary meaning in the art and refers to compounds (e.g., pentanol) that act in conjunction with surfactants to form an emulsion or microemulsion.
In some embodiments, the one or more surfactants is a surfactant described in U.S. patent application Ser. No. 14/212,731, filed Mar. 14, 2014, entitled “METHODS AND COMPOSITIONS FOR USE IN OIL AND/OR GAS WELLS,” now published as US/2014/0284053 on Sep. 25, 2014, herein incorporated by reference. In some embodiments, the surfactant is a surfactant described in U.S. patent application Ser. No. 14/212,763, filed Mar. 14, 2014, entitled “METHODS AND COMPOSITIONS FOR USE IN OIL AND/OR GAS WELLS,” now published as US/2014/0338911 on Nov. 20, 2014 and issued as U.S. Pat. No. 9,884,988 on Feb. 6, 2018, herein incorporated by reference.
In some embodiments, the surfactants described herein in conjunction with solvents, generally form emulsions or microemulsions that may be diluted to a use concentration to form an oil-in-water nanodroplet dispersion and/or a diluted microemulsion. In some embodiments, the surfactants generally have hydrophile-lipophile balance (HLB) values from 8 to 18, or from 8 to 14.
Suitable surfactants for use with the compositions and methods are generally described herein. In some embodiments, a microemulsion and/or a diluted microemulsion comprises a hydrophilic hydrocarbon surfactant. The hydrophilic hydrocarbon surfactant may comprise an alcohol ethoxylate, wherein the alcohol ethoxylate contains a hydrocarbon group of 10 to 18 carbon atoms (e.g., from 12 to 15 carbon atoms) and contains an ethoxylate group of 5 to 12 ethylene oxide units (e.g., 7 ethylene oxide units, 10 ethylene oxide units). Non-limiting examples of suitable alcohol ethoxylates include C12-C15 E7, C12-C15 E9, C12-C15 E12, C12-C18 E10, and C12 E7.
In some embodiments, a microemulsion and/or a diluted microemulsion comprises a nonionic surfactant. In some embodiments, the surfactant is an alkoxylated aliphatic alcohol having from 3 to 40 ethylene oxide (EO) units and from 0 to 20 propylene oxide (PO) units. The term aliphatic alcohol generally refers to a branched or linear, saturated or unsaturated aliphatic moiety having from 6 to 18 carbon atoms.
In some embodiments, a microemulsion and/or a diluted microemulsion comprises a surfactant is selected from the group consisting of ethoxylated fatty acids, ethoxylated fatty amines, and ethoxylated fatty amides wherein the fatty portion is a branched or linear, saturated or unsaturated aliphatic hydrocarbon moiety having from 6 to 18 carbon atoms.
In some embodiments, a microemulsion and/or a diluted microemulsion comprises a surfactant that is an alkoxylated castor oil. In some embodiments, the surfactant is a sorbitan ester derivative. In some embodiments the surfactant is an ethylene oxide—propylene oxide copolymer wherein the total number of ethylene oxide (EO) and propylene oxide (PO) units is from 8 to 40 units. In some embodiments, the surfactant is an alkoxylated tristyryl phenol containing from 6 to 100 total ethylene oxide (EO) and propylene oxide (PO) units (e.g., tristyrylphenol E16).
In some embodiments, the surfactant has a structure as in Formula I:
wherein each of R7, R8, R9, R10, and R11 are the same or different and are selected from the group consisting of hydrogen, optionally substituted alkyl, and —CH═CHAr, wherein Ar is an aryl group, provided at least one of R7, R8, R9, R10, and R11 is —CH═CHAr, R12 is hydrogen or alkyl, n is 1-100, and each m is independently 1 or 2. In some embodiments, Ar is phenyl. In some embodiments, for a compound of Formula (I), R12 is hydrogen or C1-6 alkyl. In some embodiments, for a compound of Formula (I), R12 is H, methyl, or ethyl. In some embodiments, for a compound of Formula (I), R12 is H.
In some embodiments the surfactant of Formula I is a nonionic tristyryl phenol ethoxylate surfactant. In some embodiments, the nonionic tristyryl phenol surfactant comprises a tristyryl phenol ethoxylate containing 10 to 30 ethylene oxide (EO) units. In some embodiments, the nonionic tristyryl phenol surfactant comprises a tristyryl phenol ethoxylate containing 16 ethylene oxide (EO) units.
In some embodiments, a microemulsion and/or a diluted microemulsion comprises an amine-based surfactant selected from the group consisting of ethoxylated alkylene amines, ethoxylated alkyl amines, propoxylated alkylene amines, propoxylated alkyl amines, ethoxylated-propoxylated alkylene amines and ethoxylated propoxylated alkyl amines. The ethoxylated/propoxylated alkylene or alkyl amine surfactant component preferably includes more than one nitrogen atom per molecule. Suitable amines include ethylenediaminealkoxylate and diethylenetriaminealkoxylate.
In some embodiments a microemulsion and/or a diluted microemulsion comprises a surfactant that is an alkoxylated polyimine with a relative solubility number (RSN) in the range of 5-20. As will be known to those of ordinary skill in the art, RSN values are generally determined by titrating water into a solution of surfactant in 1,4 dioxane. The RSN values is generally defined as the amount of distilled water necessary to be added to produce persistent turbidity. In some embodiments the surfactant is an alkoxylated novolac resin (also known as a phenolic resin) with a relative solubility number in the range of 5-20. In some embodiments the surfactant is a block copolymer surfactant with a total molecular weight greater than 5000 g/mol.
The block copolymer may have a hydrophobic block that is comprised of a polymer chain that is linear, branched, hyperbranched, dendritic or cyclic.
In some embodiments, microemulsion and/or a diluted microemulsion comprises a surfactant that is an aliphatic polyglycoside having the following formula:
wherein R3 is an aliphatic group having from 6 to 18 carbon atoms; each R4 is independently selected from H, —CH3, or —CH2CH3; Y is an average number of from 0 to 5; and X is an average degree of polymerization (DP) of from 1 to 4; G is the residue of a reducing saccharide, for example, a glucose residue. In some embodiments, Y is zero.
In some embodiments, a microemulsion and/or a diluted microemulsion comprises a surfactant that is an aliphatic glycamide having the following formula:
wherein R6 is an aliphatic group having from 6 to 18 carbon atoms; R5 is an alkyl group having from 1 to 6 carbon atoms; and Z is —CH2(CH2OH)bCH2OH, wherein b is from 3 to 5. In some embodiments, R5 is -CH3. In some embodiments, R6 is an alkyl group having from 6 to 18 carbon atoms. In some embodiments, b is 3. In some embodiments, b is 4. In some embodiments, b is 5.
Suitable anionic surfactants include, but are not necessarily limited to, alkali metal alkyl sulfates, alkyl or alkylaryl sulfonates, linear or branched alkyl ether sulfates and sulfonates, alcohol polypropoxylated and/or polyethoxylated sulfates, alkyl or alkylaryl disulfonates, alkyl disulfates, alkyl sulphosuccinates, alkyl ether sulfates, linear and branched ether sulfates, fatty carboxylates, alkyl sarcosinates, alkyl phosphates and combinations thereof.
In some embodiments, a microemulsion and/or a diluted microemulsion comprises a surfactant that is an aliphatic sulfate wherein the aliphatic moiety is a branched or linear, saturated or unsaturated aliphatic hydrocarbon moiety having from 6 to 18 carbon atoms. In some embodiments, the surfactant is an aliphatic sulfonate wherein the aliphatic moiety is a branched or linear, saturated or unsaturated aliphatic hydrocarbon moiety having from 6 to 18 carbon atoms.
In some embodiments, a microemulsion and/or a diluted microemulsion comprises a surfactant that is an aliphatic alkoxy sulfate wherein the aliphatic moiety is a branched or linear, saturated or unsaturated aliphatic hydrocarbon moiety having from 6 to 18 carbon atoms and from 4 to 40 total ethylene oxide (EO) and propylene oxide (PO) units.
In some embodiments, a microemulsion and/or a diluted microemulsion comprises a surfactant that is an aliphatic-aromatic sulfate wherein the aliphatic moiety is a branched or linear, saturated or unsaturated aliphatic hydrocarbon moiety having from 6 to 18 carbon atoms. In some embodiments, the surfactant is an aliphatic-aromatic sulfonate wherein the aliphatic moiety is a branched or linear, saturated or unsaturated aliphatic hydrocarbon moiety having from 6 to 18 carbon atoms.
In some embodiments, a microemulsion and/or a diluted microemulsion comprises a surfactant that is an ester or half ester of sulfosuccinic acid with monohydric alcohols.
In some embodiments, the surfactant has a structure as in Formula II:
wherein each of R7, R8, R9, R10, and R11 are the same or different and are selected from the group consisting of hydrogen, optionally substituted alkyl, and —CH═CHAr, wherein Ar is an aryl group, provided at least one of R7, R8, R9, R10, and R11 is —CH═CHAr, Y− is an anionic group, X+ is a cationic group, n is 1-100, and each m is independently 1 or 2. In some embodiments, Ar is phenyl. In some embodiments, for a compound of Formula (II), X+ is a metal cation or N(R13)4, wherein each R13 is independently selected from the group consisting of hydrogen, optionally substituted alkyl, or optionally substituted aryl. In some embodiments, X+ is NH4. Non-limiting examples of metal cations are Na+, K+, Mg+2, and Ca+2. In some embodiments, for a compound of Formula (II), Y− is —O—, —SO2O—, or —OSO2O−.
In some embodiments, a microemulsion and/or a diluted microemulsion comprises a cationic surfactant. In some embodiments, a microemulsion and/or a diluted microemulsion comprises a cationic surfactant that is a quaternary alkylammonium salt or a quaternary alkylbenzylammonium salt, whose alkyl groups have 1 to 24 carbon atoms (e.g., a halide, sulfate, phosphate, acetate, or hydroxide salt). In some embodiments, the surfactant is a quaternary alkylbenzylammonium salt, whose alkyl groups have 1-24 carbon atoms (e.g., a halide, sulfate, phosphate, acetate, or hydroxide salt). In In some embodiments, the surfactant is an alkylpyridinium, an alkylimidazolinium, or an alkyloxazolinium salt whose alkyl chain has up to 18 carbons atoms (e.g., a halide, sulfate, phosphate, acetate, or hydroxide salt).
In some embodiments, a microemulsion and/or a diluted microemulsion comprises a surfactant that is a cationic surfactant such as, monoalkyl quaternary amines, such as cocotrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, soyatrimethylammonium chloride, behentrimethylammonium chloride, and the like and mixtures thereof. Other suitable cationic surfactants that may be useful include, but are not necessarily limited to, dialkylquaternary amines such as dicetyldimethylammonium chloride, dicocodimethylammonium chloride, distearyldimethylammonium chloride, and the like and mixtures thereof.
In some embodiments, the surfactant has a structure as in Formula III:
wherein each of R7, R8, R9, R10, and R11 are the same or different and are selected from the group consisting of hydrogen, optionally substituted alkyl, and —CH═CHAr, wherein Ar is an aryl group, provided at least one of R7, R8, R9, R10, and R11 is —CH═CHAr, Z+ is a cationic group, n is 1-100, and each m is independently 1 or 2. In some embodiments, Ar is phenyl. In some embodiments, for a compound of Formula (III), Z+ is N(R13)3, wherein each R13 is independent selected from the group consisting of hydrogen, optionally substituted alkyl, or optionally substituted aryl.
In some embodiments, for a compound of Formula (I), (II), or (III), two of R7, R8, R9, R10, and R11 are —CH═CHAr. In some embodiments, for a compound of Formula (I), (II), or (III), one of R7, R8, R9, R10, and R11 is —CH═CHAr and each of the other groups is hydrogen. In some embodiments, for a compound of Formula (I), (II), or (III), two of R7, R8, R9, R10, and R11 are —CH═CHAr and each of the other groups is hydrogen. In some embodiments, for a compound of Formula (I), (II), or (III), R7 and R8 are —CH═CHAr and R9, R10, and R11 are each hydrogen. In some embodiments, for a compound of Formula (I), (II), or (III), three of R7, R8, R9, R10, and R11 are —CH═CHAr and each of the other groups is hydrogen. In some embodiments, for a compound of Formula (I), (II), or (III), R7, R8, and R9 are —CH═CHAr and R1° and R11 are each hydrogen. In embodiments, for a compound of Formula (I), (II), or (III), Ar is phenyl. In some embodiments, for a compound of Formula (I), (II), or (III), each m is 1. In some embodiments, for a compound of Formula (I), (II), or (III), each m is 2. In some embodiments, for a compound of Formula (I), (II), or (III), n is 6-100, or 1-50, or 6-50, or 6-25, or 1-25, or 5-50, or 5-25, or 5-20.
In some embodiments, a microemulsion and/or a diluted microemulsion comprises a zwitterionic or amphoteric surfactant. In some embodiments, a microemulsion and/or a diluted microemulsion comprises a surfactant that is an amine oxide (e.g., dodecyldimethylamine oxide). In some embodiments, the surfactant is amphoteric or zwitterionic, including sultaines (e.g., cocamidopropyl hydroxysultaine), betaines (e.g., cocamidopropyl betaine), or phosphates (e.g., lecithin).
In some embodiments, a microemulsion and/or a diluted microemulsion comprises an organosilicone surfactant. In some embodiments a microemulsion and/or a diluted microemulsion comprises a mixture of a hydrophilic hydrocarbon surfactant and a hydrophilic organosilicone surfactant. Although the hydrophilic-lipophilic balance (HLB) system cannot strictly be applied to organosilicone surfactants, approximate HLB values for a hydrophilic organosilicone surfactant are from 8 to 18. In some embodiments, the hydrophilic organosilicone surfactant comprises one or more polyalkylene oxide groups containing from 4 to 40 total ethylene oxide (EO) and propylene oxide (PO) units. In some embodiments, the hydrophilic organosilicone surfactant comprises one or more polyethylene oxide groups containing from 4 to 12 ethylene oxide (EO) groups.
In some embodiments, a microemulsion and/or a diluted microemulsion may comprise a single hydrophilic organosilicone surfactant or a combination of two or more hydrophilic organosilicone surfactants. For example, in some embodiments the hydrophilic organosilicone surfactant comprises a first type of hydrophilic organosilicone surfactant and a second type of hydrophilic organosilicone surfactant.
Non-limiting examples of hydrophilic organosilicone surfactants include polyalkyleneoxide-modified pentamethyldisiloxane, polyalkyleneoxide-modified heptamethyltrisiloxane, polyalkyleneoxide-modified nonamethyltetrasiloxane, polyalkyleneoxide-modified undecamethylpentasiloxane, polyalkyleneoxide-modified tridecamethylhexasiloxane and combinations thereof. The polyalkyleneoxide moiety may be end capped with —H, —CH3, an acetoxy group, or an ethoxy group. The polyalkylene oxide group comprises polyethylene oxide, polypropyleneoxide, polybutyleneoxide, and combinations thereof.
In some embodiments, a microemulsion and/or a diluted microemulsion comprise an ethoxylated nonionic organosilicone surfactant. For example, the ethoxylated nonionic organosilicone surfactant may be a trisiloxane with an ethoxylate group having 4 to 12 ethylene oxide (EO) units. Non-limiting examples of such surfactants include trisiloxane surfactants having from 7 to 8 EO units, Momentive® Silwet L-77®, Momentive Silwet 408®, Dow Corning® Q2-5211 superwetting agent, and Dow Corning® Q2-5212 wetting agent.
In some embodiments, a microemulsion and/or a diluted microemulsion comprises a hydrophilic organosilicone surfactant. The microemulsion and/or diluted microemulsion may comprise a single hydrophilic organosilicone surfactant or a combination of two or more hydrophilic organosilicone surfactants. For example, in some embodiments the hydrophilic organosilicone surfactant comprises a first type of hydrophilic organosilicone surfactant and a second type of hydrophilic organosilicone surfactant. Non-limiting examples of hydrophilic organosilicone surfactants include but are not limited to polyalkyleneoxide-modified pentamethyldisiloxane, polyalkyleneoxide-modified heptamethyltrisiloxane, polyalkyleneoxide-modified nonamethyltetrasiloxane, polyalkyleneoxide-modified undecamethylpentasiloxane, polyalkyleneoxide-modified tridecamethylhexasiloxane, polyalkyleneoxide-modified polydimethylsiloxane and combinations thereof.
In some embodiments, the hydrophilic organosilicone surfactant comprises methoxy-modified polyalkylene pentamethyldisiloxane, methoxy-modified polyalkylene heptamethyltrisiloxane, methoxy-modified polyalkylene nonamethyltetrasiloxane, methoxy-modified polyalkylene undecamethylpentasiloxane, polyalkylene methoxy-modified tridecamethylhexasiloxane, methoxy-modified polyalkyleneoxide-modified polydimethylsiloxane, ethoxy-modified polyalkylene pentamethyldisiloxane, ethoxy-modified polyalkylene heptamethyltrisiloxane, ethoxy-modified polyalkylene nonamethyltetrasiloxane, ethoxy-modified polyalkylene undecamethylpentasiloxane, ethoxy-modified polyalkylene tridecamethylhexasiloxane, ethoxy-modified polyalkyleneoxide-modified polydimethylsiloxane and combinations thereof.
The polyalkyleneoxide moiety may be end capped with —H, —CH3, an acetoxy group, or an ethoxy group. The polyalkylene oxide group comprises polyethylene oxide, polypropyleneoxide, polybutyleneoxide, and combinations thereof.
In some embodiments, the hydrophilic organosilicone surfactant comprises an ethoxylated nonionic organosilicone surfactant. In some embodiments, the ethoxylated nonionic organosilicone surfactant is a trisiloxane with an ethoxylate group having 4 to 12 ethylene oxide units.
Additional surfactants are described herein. Other non-limiting examples of surfactants include adsorption modifiers, foamers, surface tension lowering enhancers, and emulsion breaking additives. Specific examples of such surfactants include cationic surfactants with a medium chain length, linear or branched anionic surfactants, alkyl benzene anionic surfactants, amine oxides, amphoteric surfactants, silicone based surfactants, alkoxylated novolac resins (e.g. alkoxylated phenolic resins), alkoxylated polyimines, alkoxylated polyamines, and fluorosurfactants. In some embodiments, a microemulsion and/or a diluted microemulsion comprises a nonionic surfactant. In certain embodiments, the nonionic surfactant may be one or more of an ethoxylated castor oil (e.g., castor oil E30), an ethoxylated alcohol, an ethoxylated tristyrylphenol, or an ethoxylated sorbitan ester, or combinations thereof.
As described above, microemulsions and/or diluted microemulsions may comprise an aqueous phase. The aqueous phase may make up any suitable amount of the microemulsion and/or diluted micromeulsion (e.g., of the components of the diluted microemulsion other than the dilution phase). The aqueous phase may make up greater than or equal to 1 wt %, greater than or equal to 2 wt %, greater than or equal to 5 wt %, greater than or equal to 10 wt %, greater than or equal to 15 wt %, greater than or equal to 20 wt %, greater than or equal to 25 wt %, greater than or equal to 30 wt %, greater than or equal to 35 wt %, greater than or equal to 40 wt %, greater than or equal to 45 wt %, greater than or equal to 50 wt %, greater than or equal to 55 wt % of the microemulsion, or greater than or equal to 60 wt %. The aqueous phase may make up less than or equal to 60 wt %, less than or equal to 55 wt %, less than or equal to 50 wt %, less than or equal to 45 wt %, less than or equal to 40 wt %, less than or equal to 35 wt %, less than or equal to 30 wt %, less than or equal to 25 wt %, less than or equal to 20 wt %, less than or equal to 15 wt %, less than or equal to 10 wt %, less than or equal to 5 wt %, less than or equal to 2 wt %, or less than or equal to 1 wt % of the microemulsion. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 1 wt % and less than or equal to 60 wt % of the microemulsion, greater than or equal to 15 wt % and less than or equal to 30 wt % of the microemulsion, or greater than or equal to 20 wt % and less than or equal to 25 wt % of the microemulsion). Other ranges are also possible.
When present, the aqueous phase generally comprises water or is water. The water may be provided from any suitable source (e.g., sea water, fresh water, deionized water, reverse osmosis water, water from field production). The aqueous phase may also comprise dissolved salts. Non-limiting examples of dissolved salts include salts comprising K, Na, Br, Cr, Cs, or Bi, for example, halides of these metals, including NaCl, KCl, CaCl2, and MgCl and combinations thereof.
In some embodiments, a microemulsion and/or a diluted microemulsion further comprises a co-solvent. In some embodiments, the co-solvent is an alcohol. The co-solvent (e.g., alcohol) may serve as a coupling agent between the solvent and the surfactant and/or may aid in the stabilization of the emulsion or microemulsion. The alcohol may also be a freezing point depression agent for the emulsion or microemulsion. That is, the alcohol may lower the freezing point of the emulsion or microemulsion. In some embodiments, the alcohol is selected from primary, secondary, and tertiary alcohols having from 1 to 20 carbon atoms.
In some embodiments, the alcohol is selected from primary, secondary, and tertiary alcohols having from 1 to 5 carbon atoms. In some embodiments, the co-solvent is selected from the group consisting of methanol, ethanol, isopropanol, n-propanol, n-butanol, i-butanol, sec-butanol, iso-butanol, t-butanol, ethylene glycol, propylene glycol, dipropylene glycol monomethyl ether, triethylene glycol, and ethylene glycol monobutyl ether.
In some embodiments, a microemulsion and/or a diluted microemulsion comprises from 1 wt % to 50 wt %, or from 1 wt % to 40 wt %, from 1 wt % to 35 wt %, or from 1 wt % to 30 wt %. In some embodiments, a micromeulsion and/or a diluted microemulsion comprises from 5 wt % to 40 wt %, from 5 wt % to 35 wt %, or from 10 wt % to 30 wt % of the co-solvent (e.g., alcohol), versus the total weight of the microemulsion and/or diluted microemulsion composition.
In some embodiments, a microemulsion and/or a diluted microemulsion may comprise one or more additives in addition to the components discussed elsewhere herein. In some embodiments, the one or more additional additives are present in an amount from 0 wt % to 70 wt %, from 1 wt % to 40 wt %, from 0 wt % to 30 wt %, from 0.5 wt % to 30 wt %, from 1 wt % to 30 wt %, from 0 wt % to 25 wt %, from 1 wt % to 25 wt %, from 0 wt % to 20 wt %, from 1 wt % to 20 wt %, from 3 wt % to 20 wt %, or from 8 wt % to 16 wt % versus the total weight of the microemulsion and/or diluted microemulsion composition.
Non-limiting examples of additives include a demulsifier, a freezing point depression agent, a proppant, a scale inhibitor, a friction reducer, a biocide, a corrosion inhibitor, a buffer, a viscosifier, an oxygen scavenger, a clay control additive, a paraffin control additive, an asphaltene control additive, an acid, an acid precursor, or a salt.
In some embodiments, the additive is a demulsifier. The demulsifier may aid in preventing the formulation of an emulsion between a treatment fluid and crude oil. Non-limiting examples of demulsifiers include polyoxyethylene (50) sorbitol hexaoleate. In some embodiments, the demulsifier is present in the microemulsion in an amount from 4 wt % to 8 wt % versus the total weight of the microemulsion composition.
In some embodiments, a microemulsion and/or a diluted microemulsion comprises a freezing point depression agent (e.g., propylene glycol). The microemulsion and/or diluted microemulsion may comprise a single freezing point depression agent or a combination of two or more freezing point depression agents. The term “freezing point depression agent” is given its ordinary meaning in the art and refers to a compound which is added to a solution to reduce the freezing point of the solution. That is, in some embodiments, a solution comprising the freezing point depression agent has a lower freezing point as compared to an essentially identical solution not comprising the freezing point depression agent. Those of ordinary skill in the art will be aware of suitable freezing point depression agents for use in the emulsions or the microemulsions described herein. Non-limiting examples of freezing point depression agents include primary, secondary, and tertiary alcohols with from 1 to 20 carbon atoms and alkylene glycols. In some embodiments, the alcohol comprises at least 2 carbon atoms. Non-limiting examples of alcohols include methanol, ethanol, i-propanol, n-propanol, t-butanol, n-butanol, n-pentanol, n-hexanol, and 2-ethyl hexanol. In some embodiments, the freezing point depression agent is not methanol (e.g., due to toxicity). Non-limiting examples of alkylene glycols include ethylene glycol (EG), polyethylene glycol (PEG), propylene glycol (PG), and triethylene glycol (TEG). In some embodiments, the freezing point depression agent is not ethylene oxide (e.g., due to toxicity). In some embodiments, the freezing point depression agent comprises an alcohol and an alkylene glycol. In some embodiments, the freezing point depression agent comprises a carboxycyclic acid salt and/or a di-carboxycyclic acid salt. Another non-limiting example of a freezing point depression agent is a combination of choline chloride and urea. In some embodiments, the emulsion or microemulsion comprising the freezing point depression agent is stable over a wide range of temperatures, e.g., from 50° F. to 200° F. In some embodiments a freezing point depression agent is present in the microemulsion in an amount from 10 wt % to 15 wt %.
In some embodiments, a microemulsion and/or a diluted microemulsion comprises a proppant. In some embodiments, the proppant acts to hold induced hydraulic fractures open in an oil and/or gas well. Non-limiting examples of proppants (e.g., propping agents) include grains of sand, glass beads, crystalline silica (e.g., quartz), hexamethylenetetramine, ceramic proppants (e.g., calcined clays), resin coated sands, and resin coated ceramic proppants. Other proppants are also possible and will be known to those skilled in the art.
In some embodiments, a microemulsion and/or a diluted microemulsion comprises a scale inhibitor. The scale inhibitor may slow scaling in, e.g., the treatment of an oil and/or gas well, wherein scaling involves the unwanted deposition of solids (e.g., along a pipeline) that hinders fluid flow. Non-limiting examples of scale inhibitors include one or more of methyl alcohol, organic phosphonic acid salts (e.g., phosphonate salt, aminopolycarboxlic acid salts), polyacrylate, ethane-1,2-diol, calcium chloride, and sodium hydroxide. Other scale inhibitors are also possible and will be known to those skilled in the art.
In some embodiments, a microemulsion and/or a diluted microemulsion comprises a friction reducer. The friction reducer may reduce drag, which reduces energy input required in the context of e.g. delivering the diluted microemulsion and/or microemulsion into a wellbore. Non-limiting examples of friction reducers include oil-external emulsions of polymers with oil-based solvents and an emulsion-stabilizing surfactant. The emulsions may include natural-based polymers like guar, cellulose, xanthan, proteins, polypeptides or derivatives of same or synthetic polymers like polyacrylamide-co-acrylic acid (PAM-AA), polyethylene oxide, polyacrylic acid, and other copolymers of acrylamide and other vinyl monomers. For a list of non-limiting examples, see U.S. Pat. No. 8,865,632, filed Nov. 10, 2008, entitled “DRAG-REDUCING COPOLYMER COMPOSITION,” herein incorporated by reference. Other common drag-reducing additives include dispersions of natural or synthetic polymers and copolymers in saline solution and dry natural or synthetic polymers and copolymers. These polymers or copolymers may be nonionic, zwitterionic, anionic, or cationic depending on the composition of polymer and pH of solution. Other non-limiting examples of friction reducers include petroleum distillates, ammonium salts, polyethoxylated alcohol surfactants, and anionic polyacrylamide copolymers. Other friction reducers are also possible and will be known to those skilled in the art.
In some embodiments, a microemulsion and/or a diluted microemulsion comprises a biocide. The biocide may kill unwanted organisms (e.g., microorganisms) that come into contact with the emulsion or microemulsion. Non-limiting examples of biocides include didecyl dimethyl ammonium chloride, glutaral, Dazomet, bronopol, tributyl tetradecyl phosphonium chloride, tetrakis (hydroxymethyl) phosphonium sulfate, AQUCAR®, UCARCIDE®, glutaraldehyde, sodium hypochlorite, and sodium hydroxide. Other biocides are also possible and will be known to those skilled in the art.
In some embodiments, a microemulsion and/or a diluted microemulsion comprises a corrosion inhibitor. The corrosion inhibitor may reduce corrosion during e.g. treatment of an oil and/or gas well (e.g., in a metal pipeline). Non-limiting examples of corrosion inhibitors include isopropanol, quaternary ammonium compounds, thiourea/formaldehyde copolymers, propargyl alcohol, and methanol. Other corrosion inhibitors are also possible and will be known to those skilled in the art.
In some embodiments, a microemulsion and/or a diluted microemulsion comprises a buffer. The buffer may maintain the pH and/or reduce changes in the pH of the aqueous phase of the microemulsion and/or the diluted microemulsion. Non-limiting examples of buffers include acetic acid, acetic anhydride, potassium hydroxide, sodium hydroxide, and sodium acetate. Other buffers are also possible and will be known to those skilled in the art.
In some embodiments, a microemulsion and/or a diluted microemulsion comprises a viscosifier. The viscosifier may increase the viscosity of the microemulsion and/or the diluted microemulsion. Non-limiting examples of viscosifiers include polymers, e.g., guar, cellulose, xanthan, proteins, polypeptides or derivatives of same or synthetic polymers like polyacrylamide-co-acrylic acid (PAM-AA), polyethylene oxide, polyacrylic acid, and other copolymers of acrylamide and other vinyl monomers. Other viscosifiers are also possible and will be known to those skilled in the art.
In some embodiments, a microemulsion and/or a diluted microemulsion comprises an oxygen scavenger. The oxygen scavenger may decrease the level of oxygen in the emulsion or the microemulsion. Non-limiting examples of oxygen scavengers include sulfites and bisulfites. Other oxygen scavengers are also possible and will be known to those skilled in the art.
In some embodiments, a microemulsion and/or a diluted microemulsion comprises a clay control additive. The clay control additive may minimize damaging effects of clay (e.g., swelling, migration), e.g., during treatment of oil and/or gas wells. Non-limiting examples of clay control additives include quaternary ammonium chloride, tetramethylammonium chloride, polymers (e.g., polyanionic cellulose (PAC), partially hydrolyzed polyacrylamide (PHPA), etc.), glycols, sulfonated asphalt, lignite, sodium silicate, and choline chloride. Other clay control additives are also possible and will be known to those skilled in the art.
In some embodiments, a microemulsion and/or a diluted microemulsion comprises a paraffin control additive and/or an asphaltene control additive. The paraffin control additive or the asphaltene control additive may minimize paraffin deposition or asphaltene precipitation respectively in crude oil, e.g., during treatment of oil and/or gas wells. Non-limiting examples of paraffin control additives and asphaltene control additives include active acidic copolymers, active alkylated polyester, active alkylated polyester amides, active alkylated polyester imides, aromatic naphthas, and active amine sulfonates. Other paraffin control additives and asphaltene control additives are also possible and will be known to those skilled in the art.
In some embodiments, a microemulsion and/or a diluted microemulsion comprises an acid and/or an acid precursor (e.g., an ester). For example, the microemulsion and/or the diluted microemulsion may comprise an acid when used during acidizing operations. In some embodiments, the surfactant is alkaline and an acid (e.g., hydrochloric acid) may be used to adjust the pH of the emulsion or the microemulsion towards neutral. Non-limiting examples of acids or di-acids include hydrochloric acid, acetic acid, formic acid, succinic acid, maleic acid, malic acid, lactic acid, and hydrochloric-hydrofluoric acids. In some embodiments, the microemulsion and/or the diluted microemulsion comprises an organic acid or organic di-acid in the ester (or di-ester) form, whereby the ester (or diester) is hydrolyzed in the wellbore and/or reservoir to form the parent organic acid and an alcohol in the wellbore and/or reservoir. Non-limiting examples of esters or di-esters include isomers of methyl formate, ethyl formate, ethylene glycol diformate, alpha,alpha-4-trimethyl-3-cyclohexene-1-methylformate, methyl lactate, ethyl lactate, alpha,alpha-4-trimethyl 3-cyclohexene-1-methyllactate, ethylene glycol dilactate, ethylene glycol diacetate, methyl acetate, ethyl acetate, alpha,alpha,-4-trimethyl-3-cyclohexene-1-methylacetate, dimethyl succinate, dimethyl maleate, di(alpha,alpha-4-trimethyl-3-cyclohexene-1-methyl)-succinate, 1-methyl-4-(1-methylethenyl)-cyclohexylformate, 1-methyl-4-(1-ethylethenyl)-cyclohexylacetate, 1-methyl-4-(1-methylethenyl)-cyclohexylacetate, and di(1-methy-4-(1-methylethenyl)cyclohexyl)-succinate. Other acids are also possible and will be known to those skilled in the art.
In some embodiments, a microemulsion and/or a diluted microemulsion comprises a salt. The salt may reduce the amount of water needed as a carrier fluid and/or may lower the freezing point of the microemulsion and/or diluted micromeulsion. Non limiting examples of salts include salts comprising K, Na, Br, Cr, Cs, or Li, e.g., halides of these metals, including but not limited to NaCl, KCl, CaCl2, and MgCl2. Other salts are also possible and will be known to those skilled in the art.
In some embodiments, a microemulsion and/or a diluted microemulsion comprises an additive as described in U.S. patent application Ser. No. 15/457,792, filed Mar. 13, 2017, entitled “METHODS AND COMPOSITIONS INCORPORATING ALKYL POLYGLYCOSIDE SURFACTANT FOR USE IN OIL AND/OR GAS WELLS,” now published as US/2017/0275518 on Sep. 28, 2017, herein incorporated by reference.
The microemulsions and/or diluted microemulsions described herein may be formed using methods known to those of ordinary skill in the art. In some embodiments, the aqueous and non-aqueous phases may be combined (e.g., the water and the solvent(s)), followed by addition of a surfactant(s) and optionally a co-solvent(s) (e.g., alcohol(s)) and agitation). The strength, type, and length of the agitation may be varied as known in the art depending on various factors including the components of the microemulsion and/or diluted microemulsion, the quantity of the microemulsion and/or diluted microemulsion, and the resulting type of microemulsion and/or diluted microemulsion formed. For example, for small samples, a few seconds of gentle mixing can yield a microemulsion and/or diluted micromeulsion, whereas for larger samples, longer agitation times and/or stronger agitation may be required. Agitation may be provided by any suitable source, e.g., a vortex mixer, a stirrer (e.g., magnetic stirrer), etc.
Any suitable method for injecting the microemulsion and/or diluted microemulsion into a wellbore may be employed. For example, in some embodiments, the microemulsion and/or diluted microemulsion may be injected into a subterranean formation by injecting it into a well or wellbore in the zone of interest of the formation and thereafter pressurizing it into the formation for the selected distance in the well or wellbore. Methods for achieving the placement of a selected quantity of a mixture in a subterranean formation are known in the art. The well may be treated with the microemulsion and/or diluted microemulsion for a suitable period of time. The microemulsion, diluted microemulsion, and/or other fluids may be removed from the well using known techniques, including producing the well.
It should be understood, that in embodiments where a microemulsion is said to be injected into a wellbore, that the microemulsion may be diluted and/or combined with other liquid component(s) prior to and/or during injection (e.g., via straight tubing, via coiled tubing, etc.). In some embodiments, a composition for injecting into a wellbore is provided comprising a microemulsion as described herein and a dilution phase (e.g., an aqueous carrier fluid).
The microemulsions and/or diluted microemulsions described herein may be used in various aspects (e.g. steps) of the life cycle of a gas well, including, but not limited to, drilling, mud displacement, casing, cementing, perforating, stimulation, kill fluids, enhanced gas recovery, improved gas recovery, stored fluid, and offshore applications. Inclusion of a microemulsion and/or a diluted microemulsion into the fluids typically employed in these processes, e.g., drilling fluids, mud displacement fluids, casing fluids, cementing fluids, perforating fluid, stimulation fluids, kill fluids, etc., may result in many advantages as compared to use of the fluid alone.
Various aspects of the well life cycle are described in detail in U.S. patent application Ser. No. 14/212,731, filed Mar. 14, 2014, entitled “METHODS AND COMPOSITIONS FOR USE IN OIL AND/OR GAS WELLS,” now published as US/2014/0284053 on Sep. 25, 2014 and in U.S. patent application Ser. No. 14/212,763, filed Mar. 14, 2014, entitled “METHODS AND COMPOSITIONS FOR USE IN OIL AND/OR GAS WELLS,” now published as US/2014/0338911 on Nov. 20, 2014, and issued as U.S. Pat. No. 9,884,988 on Feb. 6, 2018, each herein incorporated by reference.
As will be understood by those of ordinary skill in the art, the steps of the life cycle of an oil and/or gas well may be carried out in a variety of orders. In addition, in some embodiments, each step may occur more than once in the life cycle of the well.
As used herein, the term emulsion is given its ordinary meaning in the art and refers to dispersions of one immiscible liquid in another, in the form of droplets, with diameters approximately in the range from 100 to 1,000 nanometers (nm). Emulsions may be thermodynamically unstable and/or require high shear forces to induce their formation.
As used herein, the term microemulsion is given its ordinary meaning in the art and refers to dispersions of one immiscible liquid in another, in the form of droplets, with diameters approximately in the range from 1 nm to 1000 nm, from 10 nm to 1000 nm, from 10 nm to 500 nm, from 10 nm to 300 nm, or from 10 nm to 100 nm.
In some embodiments, microemulsions are clear or transparent because they contain particles smaller than the wavelength of visible light. In addition, microemulsions are homogeneous thermodynamically stable single phases, and form spontaneously, and thus, differ markedly from thermodynamically unstable emulsions, which generally depend upon intense mixing energy for their formation. Microemulsions may be characterized by a variety of advantageous properties including, by not limited to, (i) clarity, (ii) very small particle size, (iii) ultra-low interfacial tensions, (iv) the ability to combine properties of water and oil in a single homogeneous fluid, (v) shelf life stability, and (vi) ease of preparation.
In some embodiments, the microemulsions described herein are formed by the combination of a solvent-surfactant blend with an appropriate oil-based or water-based carrier fluid. Generally, the microemulsion forms upon simple mixing of the components without the need for high shearing generally required in the formation of ordinary emulsions. In some embodiments, the microemulsion is a thermodynamically stable system, and the droplets remain finely dispersed over time. In some embodiments, the average droplet size ranges from 10 nm to 300 nm.
It should be understood that the description herein which focuses on microemulsions and/or diluted microemulsion is by no means limiting, and emulsions and/or diluted emulsions may be employed where appropriate.
The conventional terms water-in-oil and oil-in-water, whether referring to macroemulsions, emulsions, or microemulsions, simply describe systems that are water-discontinuous and water-continuous, respectively. They do not denote any additional restrictions on the range of substances denoted as “oil”.
The terms “clear” or “transparent” as applied to a microemulsion are given its ordinary meaning in the art and generally refers to the microemulsion appearing as a single phase without any particulate or colloidal material or a second phase being present when viewed by the naked eye.
The terms “substantially insoluble” or “insoluble” is given its ordinary meaning in the art and generally refers to embodiments wherein the solubility of the compound in a liquid is zero or negligible. In connection with the compositions described herein, the solubility of the compound may be insufficient to make the compound practicably usable in an agricultural end use without some modification either to increase its solubility or dispersability in the liquid (e.g., water), so as to increase the compound's bioavailability or avoid the use of excessively large volumes of solvent.
Definitions of specific functional groups and chemical terms are described in more detail below. For purposes of this invention, the chemical elements are identified in accordance with the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75th Ed., inside cover, and specific functional groups are generally defined as described therein. Additionally, general principles of organic chemistry, as well as specific functional moieties and reactivity, are described in Organic Chemistry, Thomas Sorrell, University Science Books, Sausalito: 1999, the entire contents of which are incorporated herein by reference.
Certain compounds of the present invention may exist in particular geometric or stereoisomeric forms. The present invention contemplates all such compounds, including cis-and trans-isomers, R- and S-enantiomers, diastereomers, (d)-isomers, (1)-isomers, the racemic mixtures thereof, and other mixtures thereof, as falling within the scope of the invention. Additional asymmetric carbon atoms may be present in a substituent such as an alkyl group. All such isomers, as well as mixtures thereof, are intended to be included in this invention.
Isomeric mixtures containing any of a variety of isomer ratios may be utilized in accordance with the present invention. For example, where only two isomers are combined, mixtures containing 50:50, 60:40, 70:30, 80:20, 90:10, 95:5, 96:4, 97:3, 98:2, 99:1, or 100:0 isomer ratios are all contemplated by the present invention. Those of ordinary skill in the art will readily appreciate that analogous ratios are contemplated for more complex isomer mixtures.
The term “aliphatic,” as used herein, includes both saturated and unsaturated, nonaromatic, straight chain (i.e., unbranched), branched, acyclic, and cyclic (i.e., carbocyclic) hydrocarbons, which are optionally substituted with one or more functional groups. As will be appreciated by one of ordinary skill in the art, “aliphatic” is intended herein to include, but is not limited to, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, and cycloalkynyl moieties. Thus, as used herein, the term “alkyl” includes straight, branched and cyclic alkyl groups. An analogous convention applies to other generic terms such as “alkenyl”, “alkynyl”, and the like.
Furthermore, as used herein, the terms “alkyl”, “alkenyl”, “alkynyl”, and the like encompass both substituted and unsubstituted groups. In certain embodiments, as used herein, “aliphatic” is used to indicate those aliphatic groups (cyclic, acyclic, substituted, unsubstituted, branched or unbranched) having 1 to 20 carbon atoms. Aliphatic group substituents include, but are not limited to, any of the substituents described herein, that result in the formation of a stable moiety (e.g., aliphatic, alkyl, alkenyl, alkynyl, heteroaliphatic, heterocyclic, aryl, heteroaryl, acyl, oxo, imino, thiooxo, cyano, isocyano, amino, azido, nitro, hydroxyl, thiol, halo, aliphaticamino, heteroaliphaticamino, alkylamino, heteroalkylamino, arylamino, heteroarylamino, alkylaryl, arylalkyl, aliphaticoxy, heteroaliphaticoxy, alkyloxy, heteroalkyloxy, aryloxy, heteroaryloxy, aliphaticthioxy, heteroaliphaticthioxy, alkylthioxy, heteroalkylthioxy, arylthioxy, heteroarylthioxy, acyloxy, and the like, each of which may or may not be further substituted).
As used herein, the term “alkyl” is given its ordinary meaning in the art and refers to the radical of saturated aliphatic groups, including straight chain alkyl groups, branched-chain alkyl groups, cycloalkyl (alicyclic) groups, alkyl substituted cycloalkyl groups, and cycloalkyl substituted alkyl groups. In some embodiments, the alkyl group may be a lower alkyl group, e.g., an alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl). In some embodiments, a straight chain or branched chain alkyl may have 30 or fewer carbon atoms in its backbone, and, in some embodiments, 20 or fewer. In some embodiments, a straight chain or branched chain alkyl may have 12 or fewer carbon atoms in its backbone (e.g., C1-C12 for straight chain, C3-C12 for branched chain), 6 or fewer, or 4 or fewer. Likewise, cycloalkyls may have from 3 to 10 carbon atoms in their ring structure, or 5, 6 or 7 carbon atoms in their ring structure. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, t-butyl, cyclobutyl, hexyl, and cyclochexyl.
The term “heteroalkyl” is given its ordinary meaning in the art and refers to an alkyl group as described herein in which one or more carbon atoms is replaced by a heteroatom. Suitable heteroatoms include oxygen, sulfur, nitrogen, phosphorus, and the like. Examples of heteroalkyl groups include, but are not limited to, alkoxy, alkoxyalkyl, amino, thioester, poly(ethylene glycol), and alkyl-substituted amino.
The terms “alkenyl” and “alkynyl” are given their ordinary meaning in the art and refer to unsaturated aliphatic groups analogous in length and possible substitution to the alkyls described above, but that contain at least one double or triple bond respectively.
In certain embodiments, the alkyl, alkenyl and alkynyl groups employed in the invention contain 1 to 20 aliphatic carbon atoms. In certain other embodiments, the alkyl, alkenyl, and alkynyl groups employed in the invention contain 1 to 10 aliphatic carbon atoms. In yet other embodiments, the alkyl, alkenyl, and alkynyl groups employed in the invention contain 1 to 8 aliphatic carbon atoms. In still other embodiments, the alkyl, alkenyl, and alkynyl groups employed in the invention contain 1 to 6 aliphatic carbon atoms. In yet other embodiments, the alkyl, alkenyl, and alkynyl groups employed in the invention contain 1 to 4 carbon atoms.
Illustrative aliphatic groups thus include, but are not limited to, for example, methyl, ethyl, n-propyl, isopropyl, allyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-pentyl, sec-pentyl, isopentyl, t-pentyl, n-hexyl, sec-hexyl, moieties and the like, which again, may bear one or more substituents. Alkenyl groups include, but are not limited to, for example, ethenyl, propenyl, butenyl, 1-methyl-2-buten-1-yl, and the like. Representative alkynyl groups include, but are not limited to, ethynyl, 2-propynyl (propargyl), 1-propynyl and the like.
The term “cycloalkyl,” as used herein, refers specifically to groups having three to ten, preferably three to seven carbon atoms. Suitable cycloalkyls include, but are not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and the like, which, as in the case of other aliphatic, heteroaliphatic, or hetercyclic moieties, may optionally be substituted with substituents including, but not limited to aliphatic; heteroaliphatic; aryl; heteroaryl; arylalkyl;
heteroarylalkyl; alkoxy; aryloxy; heteroalkoxy; heteroaryloxy; alkylthio; arylthio; heteroalkylthio; heteroarylthio; —F; —Cl; —Br; —I; —OH; —NO2; —CN; —CF3; —CH2CF3; —CHCl2; —CH2OH; —CH2CH2OH; —CH2NH2; —CH2SO2CH3; —C(O)Rx; —CO2(Rx); —CON(Rx)2; —OC(O)Rx; —OCO2Rx; —OCON(Rx)2; —N(Rx)2; —S(O)2Rx; —NRx(CO)Rx, wherein each occurrence of Rx independently includes, but is not limited to, aliphatic, heteroaliphatic, aryl, heteroaryl, arylalkyl, or heteroarylalkyl, wherein any of the aliphatic, heteroaliphatic, arylalkyl, or heteroarylalkyl substituents described above and herein may be substituted or unsubstituted, branched or unbranched, cyclic or acyclic, and wherein any of the aryl or heteroaryl substituents described above and herein may be substituted or unsubstituted. Additional examples of generally applicable substituents are illustrated by the specific embodiments shown in the examples that are described herein.
The term “heteroaliphatic,” as used herein, refers to an aliphatic moiety, as defined herein, which includes both saturated and unsaturated, nonaromatic, straight chain (i.e., unbranched), branched, acyclic, cyclic (i.e., heterocyclic), or polycyclic hydrocarbons, which are optionally substituted with one or more functional groups, and that contain one or more oxygen, sulfur, nitrogen, phosphorus, or silicon atoms, e.g., in place of carbon atoms. In certain embodiments, heteroaliphatic moieties are substituted by independent replacement of one or more of the hydrogen atoms thereon with one or more substituents. As will be appreciated by one of ordinary skill in the art, “heteroaliphatic” is intended herein to include, but is not limited to, heteroalkyl, heteroalkenyl, heteroalkynyl, heterocycloalkyl, heterocycloalkenyl, and heterocycloalkynyl moieties. Thus, the term “heteroaliphatic” includes the terms “heteroalkyl,” “heteroalkenyl”, “heteroalkynyl”, and the like. Furthermore, as used herein, the terms “heteroalkyl”, “heteroalkenyl”, “heteroalkynyl”, and the like encompass both substituted and unsubstituted groups. In certain embodiments, as used herein, “heteroaliphatic” is used to indicate those heteroaliphatic groups (cyclic, acyclic, substituted, unsubstituted, branched or unbranched) having 1 to 20 carbon atoms. Heteroaliphatic group substituents include, but are not limited to, any of the substituents described herein, that result in the formation of a stable moiety (e.g., aliphatic, alkyl, alkenyl, alkynyl, heteroaliphatic, heterocyclic, aryl, heteroaryl, acyl, sulfinyl, sulfonyl, oxo, imino, thiooxo, cyano, isocyano, amino, azido, nitro, hydroxyl, thiol, halo, aliphaticamino, heteroaliphaticamino, alkylamino, heteroalkylamino, arylamino, heteroarylamino, alkylaryl, arylalkyl, aliphaticoxy, heteroaliphaticoxy, alkyloxy, heteroalkyloxy, aryloxy, heteroaryloxy, aliphaticthioxy, heteroaliphaticthioxy, alkylthioxy, heteroalkylthioxy, arylthioxy, heteroarylthioxy, acyloxy, and the like, each of which may or may not be further substituted).
The terms “heteroalkenyl” and “heteroalkynyl” are given their ordinary meaning in the art and refer to unsaturated aliphatic groups analogous in length and possible substitution to the heteroalkyls described above, but that contain at least one double or triple bond respectively.
Some examples of substituents of the above-described aliphatic (and other) moieties of compounds of the invention include, but are not limited to aliphatic; heteroaliphatic; aryl; heteroaryl; alkylaryl; alkylheteroaryl; alkoxy; aryloxy; heteroalkoxy; heteroaryloxy; alkylthio; arylthio; heteroalkylthio; heteroarylthio; F; Cl; Br; I; —OH; —NO2; —CN; —CF3; —CHF2; —CH2F; —CH2CF3; —CHCl2; —CH2OH; —CH2CH2OH; —CH2NH2; —CH2SO2CH3; —C(O)Rx; —CO2(Rx); —CON(Rx)2; —OC(O)Rx; —OCO2Rx; —OCON(Rx)2; —N(Rx)2; —S(O)2Rx; —NRx(CO)Rx wherein each occurrence of Rx independently includes, but is not limited to, aliphatic, alycyclic, heteroaliphatic, heterocyclic, aryl, heteroaryl, alkylaryl, or alkylheteroaryl, wherein any of the aliphatic, heteroaliphatic, alkylaryl, or alkylheteroaryl substituents described above and herein may be substituted or unsubstituted, branched or unbranched, cyclic or acyclic, and wherein any of the aryl or heteroaryl substituents described above and herein may be substituted or unsubstituted. Additional examples of generally applicable substituents are illustrated by the specific embodiments shown in the Examples that are described herein.
As used herein, the term “aromatic” is given its ordinary meaning in the art and refers to aromatic carbocyclic groups, having a single ring (e.g., phenyl), multiple rings (e.g., biphenyl), or multiple fused rings in which at least one is aromatic (e.g., 1,2,3,4-tetrahydronaphthyl, naphthyl, anthryl, or phenanthryl). That is, at least one ring may have a conjugated pi electron system, while other, adjoining rings can be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls and/or heterocyclyls.
As used herein, the term “aryl” is given its ordinary meaning in the art and refers to aromatic carbocyclic groups, optionally substituted, having a single ring (e.g., phenyl), multiple rings (e.g., biphenyl), or multiple fused rings in which at least one is aromatic (e.g., 1,2,3,4-tetrahydronaphthyl, naphthyl, anthryl, or phenanthryl). That is, at least one ring may have a conjugated pi electron system, while other, adjoining rings can be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls and/or heterocyclyls. The aryl group may be optionally substituted, as described herein. Substituents include, but are not limited to, any of the previously mentioned substituents, e.g., the substituents recited for aliphatic moieties, or for other moieties as disclosed herein, resulting in the formation of a stable compound. In some embodiments, an aryl group is a stable monocyclic or polycyclic unsaturated moiety having preferably 3 to 14 carbon atoms, each of which may be substituted or unsubstituted.
The term “heterocycle” is given its ordinary meaning in the art and refers to cyclic groups containing at least one heteroatom as a ring atom, in some embodiments, 1 to 3 heteroatoms as ring atoms, with the remainder of the ring atoms being carbon atoms. Suitable heteroatoms include oxygen, sulfur, nitrogen, phosphorus, and the like. In some embodiments, the heterocycle may be 3-membered to 10-membered ring structures or 3-membered to 7-membered rings, whose ring structures include one to four heteroatoms.
The term “heterocycle” may include heteroaryl groups, saturated heterocycles (e.g., cycloheteroalkyl) groups, or combinations thereof. The heterocycle may be a saturated molecule, or may comprise one or more double bonds. In some embodiments, the heterocycle is a nitrogen heterocycle, wherein at least one ring comprises at least one nitrogen ring atom. The heterocycles may be fused to other rings to form a polycylic heterocycle. The heterocycle may also be fused to a spirocyclic group. In some embodiments, the heterocycle may be attached to a compound via a nitrogen or a carbon atom in the ring.
Heterocycles include, e.g., thiophene, benzothiophene, thianthrene, furan, tetrahydrofuran, pyran, isobenzofuran, chromene, xanthene, phenoxathiin, pyrrole, dihydropyrrole, pyrrolidine, imidazole, pyrazole, pyrazine, isothiazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, isoindole, indole, indazole, purine, quinolizine, isoquinoline, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, carbazole, carboline, triazole, tetrazole, oxazole, isoxazole, thiazole, isothiazole, phenanthridine, acridine, pyrimidine, phenanthroline, phenazine, phenarsazine, phenothiazine, furazan, phenoxazine, pyrrolidine, oxolane, thiolane, oxazole, oxazine, piperidine, homopiperidine (hexamethyleneimine), piperazine (e.g., N-methyl piperazine), morpholine, lactones, lactams such as azetidinones and pyrrolidinones, sultams, sultones, other saturated and/or unsaturated derivatives thereof, and the like. The heterocyclic ring can be optionally substituted at one or more positions with such substituents as described herein. In some embodiments, the heterocycle may be bonded to a compound via a heteroatom ring atom (e.g., nitrogen). In some embodiments, the heterocycle may be bonded to a compound via a carbon ring atom. In some embodiments, the heterocycle is pyridine, imidazole, pyrazine, pyrimidine, pyridazine, acridine, acridin-9-amine, bipyridine, naphthyridine, quinoline, benzoquinoline, benzoisoquinoline, phenanthridine-1,9-diamine, or the like.
The term “heteroaryl” is given its ordinary meaning in the art and refers to aryl groups comprising at least one heteroatom as a ring atom. A “heteroaryl” is a stable heterocyclic or polyheterocyclic unsaturated moiety having preferably 3 to 14 carbon atoms, each of which may be substituted or unsubstituted. Substituents include, but are not limited to, any of the previously mentioned substituents, e.g., the substituents recited for aliphatic moieties, or for other moieties as disclosed herein, resulting in the formation of a stable compound. In some embodiments, a heteroaryl is a cyclic aromatic radical having from five to ten ring atoms of which one ring atom is selected from S, 0, and N; zero, one, or two ring atoms are additional heteroatoms independently selected from S, 0, and N; and the remaining ring atoms are carbon, the radical being joined to the rest of the molecule via any of the ring atoms, such as, e.g., pyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, isooxazolyl, thiadiazolyl, oxadiazolyl, thiophenyl, furanyl, quinolinyl, isoquinolinyl, and the like.
It will be appreciated that the above groups and/or compounds, as described herein, may be optionally substituted with any number of substituents or functional moieties. That is, any of the above groups may be optionally substituted. As used herein, the term “substituted” is contemplated to include all permissible substituents of organic compounds, “permissible” being in the context of the chemical rules of valence known to those of ordinary skill in the art. In general, the term “substituted” whether preceded by the term “optionally” or not, and substituents contained in formulas of this invention, refer to the replacement of hydrogen radicals in a given structure with the radical of a specified substituent. When more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituent may be either the same or different at every position. It will be understood that “substituted” also includes that the substitution results in a stable compound, e.g., which does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, etc. In some embodiments, “substituted” may generally refer to replacement of a hydrogen with a substituent as described herein. However, “substituted,” as used herein, does not encompass replacement and/or alteration of a key functional group by which a molecule is identified, e.g., such that the “substituted” functional group becomes, through substitution, a different functional group. For example, a “substituted phenyl group” must still comprise the phenyl moiety and cannot be modified by substitution, in this definition, to become, e.g., a pyridine ring. In a broad aspect, the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, for example, those described herein. The permissible substituents can be one or more and the same or different for appropriate organic compounds. For purposes of this invention, the heteroatoms such as nitrogen may have hydrogen substituents and/or any permissible substituents of organic compounds described herein which satisfy the valencies of the heteroatoms. Furthermore, this invention is not intended to be limited in any manner by the permissible substituents of organic compounds. Combinations of substituents and variables envisioned by this invention are preferably those that result in the formation of stable compounds useful for the formation of an imaging agent or an imaging agent precursor.
The term “stable,” as used herein, preferably refers to compounds which possess stability sufficient to allow manufacture and which maintain the integrity of the compound for a sufficient period of time to be detected and preferably for a sufficient period of time to be useful for the purposes detailed herein.
Examples of optional substituents include, but are not limited to, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxyl, amino, nitro, sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio, sulfonyl, sulfonamido, ketone, aldehyde, ester, heterocyclyl, aromatic or heteroaromatic moieties, —CF3, —CN, aryl, aryloxy, perhaloalkoxy, aralkoxy, heteroaryl, heteroaryloxy, heteroarylalkyl, heteroaralkoxy, azido, amino, halide, alkylthio, oxo, acylalkyl, carboxy esters, carboxamido, acyloxy, aminoalkyl, alkylaminoaryl, alkylaryl, alkylaminoalkyl, alkoxyaryl, arylamino, aralkylamino, alkylsulfonyl, carboxamidoalkylaryl, carboxamidoaryl, hydroxyalkyl, haloalkyl, alkylaminoalkylcarboxy , aminocarboxamidoalkyl , cyano, alkoxyalkyl, perhaloalkyl, arylalkyloxyalkyl, and the like.
This Example compares the surface tensions of diluted microemulsions comprising d-limonene to those of otherwise identical compositions lacking d-limonene, and compares surface tension measurements made using the capillary rise technique to surface tension measurements made using the Wilhelmy plate technique.
Microemulsions comprising d-limonene, various surfactants, water, and isopropanol were prepared. For each microemulsion, d-limonene, one of the various surfactants, water, and isopropanol were combined to form a microemulsion comprising 25 wt % d-limonene, 25 wt % water, 25 wt % isopropanol, and 25 wt % of the surfactant. The microemulsion was then added to water comprising 2 wt %/vol KCl to form a diluted microemulsion comprising the microemulsion in an amount of 2 gallons per thousand (gpt). The water comprising the 2 wt %/vol KCl was stirred with a stir bar as the microemulsion was added. Otherwise equivalent compositions lacking the d-limonene and including 50 wt % water (diluted surfactant solutions) were also prepared. The surface tensions of each diluted microemulsion and each diluted surfactant solution at 20° C. were measured using the capillary rise technique and using the Wilhelmy plate technique. Table 1, below, shows the surface tension for each diluted microemulsion and each diluted surfactant solution measured using each technique.
The results summarized in Table 1 demonstrate that even though d-limonene is not a surface active agent (it is not a surfactant), and would therefore, not be expected to lower the surface tension of an aqueous solution, a microemulsion incorporating d-limonene has a somewhat lower surface tension than the otherwise equivalent compositions lacking the d-limonene. Table 1 also shows that the magnitude of surface tension lowering for a microemulsion containing d-limonene is most useful for relatively inefficient surfactants, such as castor oil E30. As used herein, “E” followed by an integer represents the number of ethoxylate groups (i.e., ethylene oxide units) contained within the surfactant. In this example, castor oil E30 represents a castor oil surfactant with 30 ethylene oxide units, which may not be very useful by itself for gas well treatment. For more efficient surfactants, such as C12-C15 E7, that may be more useful than castor oil E30 in gas well treatments, d-limonene has a much smaller effect on the surface tension than other solvents. For instance, for C12-C15 E7 in particular, the magnitude of the effect, from 29 mN/m for the surfactant alone to 26 mN/m for the microemulsion, is much smaller than the effects obtained for other solvents shown in further examples below.
The results summarized in Table 1 also show that surface tension values measured using the Wilhelmy plate technique do not reveal the surface tension lowering effect of the solvent while values measured using the capillary rise technique reveal the effect. Surface tension values for the surfactant alone are essentially equal using the two techniques while values for the microemulsions are lower using the capillary rise technique which limits evaporation of the solvent from the aqueous surface. Stated another way, as can be seen from Table 1, surface tensions measured using the capillary rise technique showed a reduction upon addition of d-limonene to the surfactant solutions, while those measured using the Wilhelmy plate technique did not. The values of surface tension measured for the surfactant solutions were substantially similar for both the capillary rise technique and the Wilhelmy plate technique.
This Example compares the surface tensions of diluted microemulsions comprising hexane diluted to varying degrees.
Microemulsions comprising 25 wt % hexane, 25 wt % C12-C15 E7, 25 wt % water, and 25 wt % isopropanol were prepared as described in Example 1. These microemulsions were diluted to varying degrees following the dilution procedure described in Example 1. The surface tension of each diluted microemulsion at 20° C. was measured using the capillary rise technique.
This Example compares the surface tensions of diluted microemulsions comprising alkane solvents to the surface tensions of these solvents, and compares surface tension measurements made using the capillary rise technique to surface tension measurements made using the Wilhelmy plate technique for microemulsions comprising alkane solvents.
Microemulsions comprising 25 wt % of an n-alkane, 25 wt % C12-C15 E7, 25 wt % water, and 25 wt % isopropanol were prepared and diluted to 2 gpt concentration, as described in Example 1. The surface tensions of the diluted microemulsions at 20° C. were measured using the pendant drop technique (both with and without saturation of the vapor space by vapor of the n-alkane), the Wilhelmy plate technique, and the capillary rise technique. Table 2, below, shows the minimum surface tension for three diluted microemulsions measured using each technique.
Thus, the results summarized in Table 2 demonstrate that hexane, octane, and decane, which are not known to be surface active agents (they are not known to be surfactants), unexpectedly lower the surface tension of a diluted aqueous microemulsion to values of 21-24 mN/m compared to 29 mN/m for the surfactant alone. It is believed that these values indicate that diluted microemulsions containing hexane, octane, and decane would lower capillary pressure in a gas well substantially below values achievable using surfactant alone and that this would lead to reduced water blocks and increased hydrocarbon gas production.
Column 5 of Table 2, which shows the surface tension measured using the Wilhelmy plate technique, represents the surface tension for the surfactant alone since the effect of the solvent for volatile solvents such as hexane, octane and decane is not observed using this measurement technique. Column 2 of Table 2, which shows the surface tension measured using the capillary rise technique, and Column 4 of Table 2, which shows the surface tension measured using the pendant drop technique with vapor saturation. The values measured using the capillary rise technique and the pendant drop technique with vapor saturation most accurately characterize the effect of the solvent on the microemulsion surface tension. Because of the extreme volatility of hexane, in this Example, the pendant drop technique with vapor saturation resulted in the most accurate (and lowest) value for a microemulsion comprising hexane.
This Example compares the surface tensions of diluted microemulsions comprising linear n-alkane solvents, cyclic alkane solvents (also known as cycloalkane solvents), and methylated cyclic alkane solvents (also known as methylated cycloalkane solvents).
Microemulsions comprising 25 wt % of an alkane solvent, 25 wt % C12-C15 E7, 25 wt % water, and 25 wt % isopropanol were prepared and diluted to 2 gpt concentration as described in Example 1. The surface tensions at 20° C. of each diluted microemulsion were measured using the capillary rise technique.
This Example compares the surface tensions of diluted microemulsions comprising siloxane solvent blends to the surface tensions of the pure siloxane solvents and to the surface tensions of the siloxane solvent blends.
Microemulsions comprising a 1:1 blend of siloxane solvent and d-limonene (specifically 12.5 wt % of a siloxane solvent and 12.5 wt % d-limonene), 25 wt % C12-C15 E7, 25 wt % water, and 25 wt % isopropanol were prepared and diluted as described in Example 1. The surface tensions of these diluted microemulsions at 20° C. were measured using the capillary rise technique, and the surface tensions of the pure siloxane solvents at 20° C. were measured using the Wilhelmy plate technique.
Further diluted microemulsions comprising blends of octamethylcyclotetrasiloxane (D4) and d-limonene in different relative amounts (together totaling 10 wt %) were also prepared and diluted as described in Example 1.
This Example compares the surface tensions of diluted microemulsions comprising heptane and d-limonene solvent blends to the surface tensions of the heptane and d-limonene solvent blends.
Microemulsions comprising 25 wt % of blends of heptane and d-limonene in various relative amounts, 25 wt % C12-C15 E7, 25 wt % water, and 25 wt % isopropanol were prepared and diluted as described in Example 1.
This Example compares the surface tensions of diluted microemulsions comprising various solvents and surfactants to the surface tension of otherwise identical compositions lacking the solvents.
Microemulsions comprising various solvents, various surfactants, water, and isopropanol were prepared. For each microemulsion, one of the various solvents, one of the various surfactants, water, and isopropanol were combined to form a microemulsion comprising 20 wt % of the solvent, 20 wt % water, 30 wt % isopropanol, and 30 wt % of the surfactant. The microemulsion was then added to water comprising 2 wt %/vol KCl to form a diluted microemulsion comprising the microemulsion in an amount of 2 gpt. The water comprising the 2 wt %/vol KCl was stirred with a stir bar as the microemulsion was added. Otherwise equivalent compositions lacking the solvents and including 40 wt % water (diluted surfactant solutions) were also prepared by this procedure. The various solvents included in the diluted microemulsions were alpha-terpineol, alpha-pinene, d-limonene, methyl laurate, and o-xylene. The various surfactants included in the diluted microemulsions were C12-C15 E7 and C12-C18 E10. The surface tension of each diluted microemulsion at 20° C. and each diluted surfactant solution at 20° C. was measured using the capillary rise technique.
This Example compares the surface tensions of diluted microemulsions comprising various solvents and surfactants to the surface tension of the pure solvents.
Microemulsions comprising 20 wt % of various solvents, 30 wt % of various surfactants, 20 wt % water, and 30 wt % isopropanol were prepared and diluted to 2 gpt concentration as described in Example 7. The various solvents included in the diluted microemulsions were alpha-terpineol, alpha-pinene, d-limonene (d-L), methyl laurate, and o-xylene. The various surfactants included in the diluted microemulsions were C12-C15 E7, C12-C18 E10, and an alcohol ethoxylate surfactant with a hydrocarbon group of 12 carbon atoms and an ethoxylate group of 7 ethylene oxide units (C12 E7). The surface tension of each diluted microemulsion at 20° C. was measured using the capillary rise technique. The surface tension of each of the pure solvents at 20° C. was measured using the Wilhelmy plate technique.
This Example compares the surface tensions of diluted microemulsions comprising various solvents at varying levels of dilution.
Microemulsions comprising 20 wt % of either o-xylene or d-limonene, 30 wt % C12-C18 E10, 20 wt % water, and 30 wt % isopropanol were prepared as described in Example 7. Each microemulsion was diluted to form diluted microemulsions comprising the microemulsion in varying amounts. An otherwise equivalent composition lacking o-xylene and d-limonene and including 40 wt % water was also prepared as described in Example 7. This composition was also diluted in varying amounts to form diluted surfactant solutions. The surface tension of each diluted microemulsion at 20° C. and the surface tension of the diluted surfactant solution at 20° C. was measured using the capillary rise technique.
This Example compares the surface tensions of diluted microemulsions comprising various solvents in various amounts.
Microemulsions comprising 25 wt % C12-C15 E7, 25 wt % isopropanol, and a combination of water and solvents totaling 50 wt % were prepared and diluted as described in Example 7. The surface tension of each diluted microemulsion at 20° C. was measured using the capillary rise technique. Table 3, below, shows the various diluted microemulsions and their measured surface tensions. As shown in Table 3, varying the amount of solvent in the microemulsion does not have a strong effect on the measured surface tension of the diluted microemulsion for amounts of solvent in excess of 5 wt % of the microemulsion. Diluted microemulsions comprising 5-25 wt % d-limonene and blends of d-limonene with alpha-terpineol do not lower the surface tension below 25-26 mN/m. The d-limonene and blends comprising d-limonene with alpha-terpineol do not result in diluted microemulsions with sufficiently low surface tension to be expected to substantially lower capillary pressure and reduce water blocks in a gas well treatment compared with an efficient conventional surfactant.
This Example describes the prediction of the surface tensions of diluted microemulsions at higher temperatures and pressures such as might be encountered in the producing formation of a gas well (the bottom hole temperature and pressure). The calculation illustrates how to predict the surface tension of a diluted microemulsion at 60° C. based on measurements of surface tension at 20° C. and vapor pressure at 20° C. of a solvent therein, and compares the predicted values for surface tension to values of surface tension measured at 60° C. using the capillary rise technique.
Microemulsions comprising a solvent, a surfactant, and water were prepared and then diluted into aqueous phases to form diluted microemulsions. The surface tensions of the diluted microemulsions at 20° C. were measured using the capillary rise technique, and the surface tensions of the pure solvents at 20° C. were measured using the Wilhelmy plate technique. The difference between the measured surface tension of each diluted microemulsion and the measured surface tension of the solvent therein are shown in
The Clausius-Clapeyron equation was used to predict the vapor pressures of the solvents at 60° C. based on their vapor pressures at 20° C. The surface tensions of the solvents at 60° C. were predicted based on their surface tensions at 20° C. and the relationship between surface tension and temperature described in Grigoryev, B. A., Nemzer, B. V., Kurumov, D. S. & Sengers, J. V. Surface tension of normal pentane, hexane, heptane, and octane. Int. J. Thermophys. (1992), in which the surface tension of the solvent is predicted to decrease by approximately 1 mN/m for every 18-19° F. increase in temperature. The model fit shown in
This Example shows that the lowering of surface tensions that are disclosed for certain solvents incorporated into diluted microemulsions would also occur at the higher temperatures and pressures in the hydrocarbon gas producing formation (e.g., at the bottom hole temperature and pressure of the gas well).
Diluted microemulsions comprising linear C6-C10 solvents are able to substantially lower the surface tension relative to a pure surfactant solution, which it is believed enables them to lower the capillary pressure and reduce water blocks in a gas well treatment, which leads to increased gas production from the gas well. The diluted microemulsions comprising C6-C10 solvents have an even greater effect on surface tension at the higher temperature. At 60° C., which is representative of the bottom hole temperature within certain gas wells, the diluted microemulsions have surface tensions of 18-25 mN/m, providing strong evidence that the diluted microemulsions comprising C6-C10 solvents will substantially lower the capillary pressure and reduce water blocks in a gas well treatment, which leads to increased gas production from the gas well.
This Example compares the surface tensions of diluted microemulsions comprising various solvents.
Microemulsions comprising 3.4 wt % siloxane solvent, 16.2 wt % C12-C15 E7 surfactant, 16.2 wt % isopropanol, and a combination of water and isooctanol totaling 64.2 wt % were prepared and diluted as described in Example 1. The surface tension of each diluted microemulsion at 20° C. was measured using the rising bubble technique. Table 4, below, shows the various diluted microemulsions and their measured surface tensions. As shown in Table 4, diluted microemulsions comprising siloxane solvents had substantially lower surface tensions than an otherwise equivalent surfactant solution lacking the siloxane solvents. The surfactant solution of alcohol ethoxylate C12-C15 E7 and isooctanol had a surface tension of 26 mN/m, while the surface tensions of the diluted microemulsions comprising siloxane solvent were 17-25 mN/m. It is thus believed that the diluted microemulsions comprising siloxane solvents would significantly lower capillary pressure and reduce water blocks within a gas well treatment, which leads to increased gas production from the gas well.
While several embodiments of the present invention have been described and illustrated herein, those of ordinary skill in the art will readily envision a variety of other means and/or structures for performing the functions and/or obtaining the results and/or one or more of the advantages described herein, and each of such variations and/or modifications is deemed to be within the scope of the present invention. More generally, those skilled in the art will readily appreciate that all parameters, dimensions, materials, and configurations described herein are meant to be exemplary and that the actual parameters, dimensions, materials, and/or configurations will depend upon the specific application or applications for which the teachings of the present invention is/are used. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. It is, therefore, to be understood that the foregoing embodiments are presented by way of example only and that, within the scope of the appended claims and equivalents thereto, the invention may be practiced otherwise than as specifically described and claimed. The present invention is directed to each individual feature, system, article, material, kit, and/or method described herein. In addition, any combination of two or more such features, systems, articles, materials, kits, and/or methods, if such features, systems, articles, materials, kits, and/or methods are not mutually inconsistent, is included within the scope of the present invention.
The indefinite articles “a” and “an,” as used herein in the specification and in the claims, unless clearly indicated to the contrary, should be understood to mean “at least one.”
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, e.g. elements that are conjunctively present in some cases and disjunctively present in other cases. 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 unless clearly indicated to the contrary. 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 without B (optionally including elements other than B); in another embodiment, to B without A (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, e.g. 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 or a list of elements. In general, the term “or” as used herein shall only be interpreted as indicating exclusive alternatives (e.g. “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.” “Consisting essentially of,” when used in the claims, shall have its ordinary meaning as used in the field of patent law.
As used herein in the specification and in the claims, the phrase “between” in reference to a range of elements or a range of units should be understood to include the lower and upper range of the elements or the lower and upper range of the units, respectively. For example, the phrase describing a molecule having “between 6 to 12 carbon atoms” should mean a molecule that may have, e.g., from 6 carbon atoms to 12 carbon atoms, inclusively. For example, the phrase describing a composition comprising “between about 5 wt % and about 40 wt % surfactant” should mean the composition may have, e.g., from about 5 wt % to about 40 wt % surfactant, inclusively.
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 any one 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 non-limiting 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.
In the claims, as well as in the specification above, all transitional phrases such as “comprising,” “including,” “carrying,” “having,” “containing,” “involving,” “holding,” and the like are to be understood to be open-ended, e.g. 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.
This application claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Application No. 62/680,457, filed Jun. 4, 2018, and entitled “Diluted Microemulsions with Low Surface Tensions”, which is incorporated herein by reference in its entirety. This application is also a continuation-in-part of U.S. patent application Ser. No. 16/267,032, filed Feb. 4, 2019, and entitled “Methods and Compositions for Stimulating the Production of Hydrocarbons from Subterranean Formations”, which is a continuation of U.S. patent application Ser. No. 15/071,332 (now U.S. Pat. No. 10,196,557), filed Mar. 16, 2016, and entitled “Methods and Compositions for Stimulating the Production of Hydrocarbons from Subterranean Formations”, which is a continuation of U.S. patent application Ser. No. 13/918,155 (now U.S. Pat. No. 9,321,955), filed Jun. 14, 2013, and entitled “Methods and Compositions for Stimulating the Production of Hydrocarbons from Subterranean Formations”, each of which is incorporated by herein by reference in its entirety for all purposes. This application is also a continuation-in-part of U.S. patent application Ser. No. 15/869,406, filed Jan. 12, 2018, and entitled “Methods and Compositions for Use in Oil and/or Gas Wells”, which is a continuation of U.S. patent application Ser. No. 14/644,351 (now U.S. Pat. No. 9,868,893), filed Mar. 11, 2015, and entitled “Methods and Compositions for Use in Oil and/or Gas Wells”, which is a continuation-in-part of U.S. patent application Ser. No. 14/489,437 (now U.S. Pat. No. 10,000,693), filed Sep. 17, 2014, which claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Application No. 61/946,176 filed Feb. 28, 2014, and entitled “Methods and Compositions for Use in Oil and/or Gas Wells”, each of which is incorporated herein by reference in its entirety for all purposes. U.S. patent application Ser. No. 14/644,351 is also a continuation-in-part of U.S. patent application Ser. No. 14/212,763 (now U.S. Pat. No. 9,884,988), filed Mar. 14, 2014, and entitled “Methods and Compositions for Use in Oil and/or Gas Wells”, which also claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Application No. 61/946,176, each of which is incorporated herein by reference in its entirety for all purposes. U.S. patent application Ser. No. 14/489,437 is also a continuation-in-part of U.S. patent application Ser. No. 14/212,763. U.S. patent application Ser. No. 14/212,763 is also a continuation-in-part of U.S. application Ser. No. 13/918,155. U.S. patent application Ser. No. 14/212,763 is also a continuation-in-part of U.S. patent application Ser. No. 13/918,166, filed Mar. 14, 2014, and entitled “Methods and Compositions for Use in Oil and/or Gas Wells”, which is incorporated by reference herein in its entirety. U.S. patent application Ser. No. 14/212,763 is also a continuation-in-part of U.S. application Ser. No. 13/829,495 (now U.S. Pat. No. 9,428,683), filed Mar. 14, 2013, and entitled “Methods and Compositions for Stimulating the Production of Hydrocarbons from Subterranean Formations”, which is incorporated by reference herein in its entirety. U.S. patent application Ser. No. 14/212,763 is also a continuation-in-part of U.S. application Ser. No. 13/829,434 (now U.S. Pat. No. 9,068,108), filed Mar. 14, 2013, and entitled “Methods and Compositions for Stimulating the Production of Hydrocarbons from Subterranean Formations”, which is incorporated by reference herein in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| 62680457 | Jun 2018 | US | |
| 61946176 | Feb 2014 | US | |
| 61946176 | Feb 2014 | US |
| Number | Date | Country | |
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| Parent | 15071332 | Mar 2016 | US |
| Child | 16267032 | US | |
| Parent | 13918155 | Jun 2013 | US |
| Child | 15071332 | US | |
| Parent | 14644351 | Mar 2015 | US |
| Child | 15869406 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 16267032 | Feb 2019 | US |
| Child | 16430898 | US | |
| Parent | 15869406 | Jan 2018 | US |
| Child | 13918155 | US | |
| Parent | 14489437 | Sep 2014 | US |
| Child | 14644351 | US | |
| Parent | 14212763 | Mar 2014 | US |
| Child | 14489437 | US | |
| Parent | 13918155 | Jun 2013 | US |
| Child | 14212763 | US | |
| Parent | 13918166 | Jun 2013 | US |
| Child | 13918155 | US | |
| Parent | 13829495 | Mar 2013 | US |
| Child | 13918166 | US | |
| Parent | 13829434 | Mar 2013 | US |
| Child | 13829495 | US | |
| Parent | 14212763 | Mar 2014 | US |
| Child | 14644351 | US |
