OA16452A

OA16452A - Composition and method for reducing hydrate agglomeration.

Info

Publication number: OA16452A
Application number: OA1201300242
Authority: OA
Inventors: Peter A. Webber
Original assignee: Nalco Company
Priority date: 2010-12-16
Filing date: 2011-12-14
Publication date: 2015-10-15

Abstract

Disclosed and claimed is a composition and method of inhibiting the formation of hydrate agglomerates in a fluid comprising water, gas, and optionally liquid hydrocarbon comprising adding to the fluid an effective anti-agglomerant amount of the following formula and optionally salts thereof formula (I) : wherein each R1 is independently absent, C1-C10 alkyl, benzyl, or H; wherein R2 is C1-C10 alkyl; wherein R3 C1-C10 alkyl; and wherein R4 is C4-C22 alkyl or alkenyl. Formula (I)

Description

COMPOSITION AND METHOD FOR REDUCING HYDRATE AGGLOMERATION

TECHNICAL FIELD OF THE INVENTION

This invention relates generally to reducing or inhibiting the formation and growth of hydrate particles in fluids containing hydrocarbon gas and water. More specifically, the invention relates to reducing or inhibiting such formation in the production and transport of natural gas, petroleum gas, or other gases. The invention has particular relevance to treating such Systems with beta-amino ester surfactants as anti-agglomérates to reduce or inhibit the formation of gas hydrates.

BACKGROUND OF THE INVENTION

Since Hammerschmidt discovered in 1934 that gas hydrates would block gas pipelines, research for the prévention of hydrate formation and agglomération has become an important matter. Gas hydrates can be easily formed during the transportation of oil and gas in pipelines when the appropriate conditions are présent. Water content, low températures, and elevated pressure are required for the formation of gas hydrates. The formation of gas hydrates often resuit on lost oil production, pipeline damage, and safety hazards to field workers. Modem oil and gas technologies commonly operate under severc conditions during the course of oil recovery and production; for instance, high pumping speed, high pressure in the pipelines, extendcd Iength of pipelines, and low température of the oil and gas flowing through the pipelines. These conditions are particularly favorable for the formation of gas hydrates, which can be particularly hazardous for oil productions offshore or for locations with cold climates.

Gas hydrates are ice-like solids that are formed from small nonpolar molécules and water at lower températures and at increased pressures, Under these conditions, the water molécules can form cage-like structures around these small nonpolar molécules (typically dissolved gases such as carbon dioxide, hydrogen sulfide, méthane, ethane, propane, butane and iso-butane), crcating a type of host-guest interaction also known as a clathrate or clathrate hydrate. The spécifie architecture of this cage structure can be one of several types (called type 1, type 2, type H), depending on the idenlity of the guest molécules. However, once formed, these crystalline cage structures tend to settle oui from the solution and accumulate into large solid masses that can travel by oil and gas transporting pipelines, and potentielly block or damage the pipelines and/or related equipment. The damage resulting from a blockage can be very costly from an

I equipment repair stand point, as well as from the loss of production, and finally the résultant environmental impact.

The industry uses a number of methods to prevent such blockuges such as thermodynamic hydrate inhibitors (TfC), anti-agglomerates (AA), and kinctic hydrate inhibitors (KHI). The amount of chemical needed to prevent blockages varies widely depending upon the type of inhibitor that is employed. Thermodynamic hydrate inhibitors are substances that can reduce the température at which the hydrates form at a given pressure and water content and are typically used at very high concentrations (regularly doscd as high as 50% based on water content - glycol is often used in amounts as high as 100% of the weight of the produced water), Therefore, there is a substantiai cost associated with the transportation and storage of large quantitics of these solvents.

A more cost-effective alternative is the use of LDHIs. as they generally require less that 2% dose to inhibit the nucléation or growth of gas hydrates. There are two general types of LDHIs, kinetic hydrate inhibitors (KHis) and anti-agglomerates (AAs), which are both typically used at much lower concentrations (0.3-0.5 % active concentration). KHIs work by delaying the growth of gas hydrate crystals and as anti-nucleators. AAs allow the hydrates to form but they prevent them from agglomerating and subséquent accumulation into larger masses capable of causing plugs. An AA enables gas hydrates to form but in the shape of fluid slurry dispersed in the liquid hydrocarbon phase. In general, the water eut should be below 50% otherwise the slurry become too viscous to transport.

There is therefore an ongoing need for new and effective methods of inhibiting the formation of hydrate agglomérâtes, particularly those that are capable of operating under higher water-cuts.

BRIEF SUMMARY OF THE INVENTION

Accordingly, this invention pertains to anti-agglomerant compositions as well as methods for inhibiting the formation of hydrate agglomérâtes in an aqueous medium comprising water, gas, and optionally liquid hydrocarbon.

In one aspect, the présent invention relates to the synthesis and use of beta-amino ester surfactants as anti-agglomerates. These surfactants comprise 3-(dialky]amino)-l-propylamine as the hydrophilic portion ofthe molécule and a fatty alkyl group as the hydrophobie portion of the »

molécule. Such antî-agglomérâtes providc for a composition comprising the following formula and optionally salis thereof.

Each Rj is independently Cj-Ciq alkyl, benzyl, or H, In an embodiment, at least one R> is absent. Ri and Rj are independently C|-Cio alkyl. R4 is C4-C22 alkyl or alkenyl.

In an embodiment, a counterion is présent when R| is présent on a quaternary or cationic nitrogen.

In another aspect, the présent invention provides for a method of inhibiting the formation of hydrate agglomérâtes in an aqueous medium comprising water, gas, and optionally liquid hydrocurbon comprising adding to the aqueous medium un effective anli-agglomerating amount of a composition comprising the above formula and optionally salts thereof.

It is an advantage of the invention to providc anti-agglomcrate compositions useful for the prévention of hydrate plugs in oil production pipes.

It is another advantage of the invention to providc anti-agglomerate compositions that do not negatively affect the overboard water quality.

It is a further advantage of the invention to provide anti-agglomerate compositions that are capable to be delivered in subsea umbilical Unes.

The foregoing has outlined radier broadly the features and technical advantages of the présent invention in order that the detailed description of the invention that follows may be better understood. Additional features and advantages of the invention will be described hereinafter that form the subject of the daims of the invention. It should be appreciated by those skilled in the art that the conception and the spécifie embodiments disdosed may be readily utilized as a basis for modifying or designing other embodiments for carrying out the same purposes of the présent invention. ît should also be realized by those skilled in the art that such équivalent embodiments do not départ from the spirit and scope of the invention as set forth in the appended daims.

DETAILED DESCRIPTION

The compositions of the invention comprise a generîc formula and optionally salts thereof as givcn below.

_n<^A_O'^r<

In one embodiment, at least one R| is absent. In another embodiment, each Ri is

I0 independently Ci-Cio alkyl, benzyl, or H. R2 and Rj are independently Cj-Cio alkyl. R4 is C^-Ck alkyl or alkenyl. In an embodiment, a counterion is présent when R| is présent on a quaternary or cationic nitrogen. The presence of R|, although not required, generally improves the properties of the composition in terms of anti-agglomération and water quality. Moreover, it is thought that the presence of the ester group in the generic structure may allow for improved biodégradation 15 profiles.

“Alkenyl” means a monovalent group derived from a straight, branched, or cyclic hydrocarbon containing at least one carbon-carbon double bond by the removal of a single hydrogen atom from each of two adjacent carbon atoms of an alkyl group. Représentative alkenyl groups include, for example, ethenyl, propenyl, butenyl, l-methyl-2-buten-l-yl, and the like.

Alkyl” refers to a monovalent group derived by the removal of a single hydrogen atom from a straight or branched chain or cyclic saturated or unsaturated hydrocarbon. Représentative alkyl groups include methyl, ethyl, propyl, butyl, pcntyl, hexyl, heptyl, octyl, nonyl, and decyl.

“Countcrion” refers to a halide selected from fluoride, chloride, bromide, iodide, or carboxylate selected from reaction with minera) acid, acrylic acid, acetic acid, methacrylic acid, 25 glycolic acid, thioglycolic acid, propionic acid, butyrîc acid, the like, and any combination thereof.

In one embodiment, the composition comprises the following formula and optionally salts thereof:

o

i ïn another embodiment, the composition comprises the following formula and optionally salts thereof:

Cl

Θ

O

In another embodiment, the composition comprises the following formula and optionally salts thereof:

Various synthesis méthodologies, which can be appreciated by one of ordinary skill in the urt, can be utilized to make the claimed compositions.

The compositions of this invention can contain one or more additional chemistries. Various formulations can be appreciated by one of ordinary skill in the art and can be made without undue expérimentation.

In one embodiment, the composition further comprises at least one additional hydrate inhibitor. Exemplary hydrate inhibitors are disclosed in U.S. Patent Application Serial Nos. 12/253,504, “Method of Controlling Gas Hydrates in Fluid Systems,” filed October 17, 2008, 12/253,529, “Method of Controlling Gas Hydrates in Fluid Systems,” filed October 17, 2008, 12/400,428, “Compositions and Methods for Inhibiting the Agglomération of Hydrates in a Process, filed March 9, 2009, ail currently pending.

In another embodiment, the composition further comprises one or more thermodynamic hydrate inhibitors, one or more kinctic hydrate inhibitors, one or more anti-agglomerants, or a combination thereof.

In another embodiment, the composition further comprises one or more asphaitene inhibitors, paraffin inhibitors, corrosion inhibitors, scale inhibitors, emulsifiers, water clarifiers, dispersants, émulsion breakers, or a combination thereof.

In another embodiment, the composition further comprises one or more polar or nonpolar solvents or a mixture thereof.

Tri another embodiment, the composition further comprises one or more solvents selected from isopropanol, methanol, éthanol, 2-cthylhexanol, heavy aromatic naptha, toluene, ethylene glycol, ethylene glycol monobutyl ether (EGMBE), dielhylenc glycol monoethyl ether, xylene, or a combination thereof,

The composition is introduced into the fluid by any means suitable for ensuring dispersai of the inhibitor through the fluid being treated. Typically the inhibitor is injected using mcchanical equipment such as chemical injection pumps, piping tees, injection fjttings, and the like. The inhibitor mixture can be injected as prepared or formulated in one or more additional polar or non-polar solvents depending upon the application and rcquirements.

Représentative polar solvents suitable for formulation with the inhibitor composition include water, brine, seawater, alcohois (including straight chain or branched aliphatic such as methanol, éthanol, propanol, isopropanol, butanol, 2-ethylhexanol, hexanol, octanol, decanol, 2butoxyethanol, etc.), glycols and dérivatives (ethylene glycol, 1,2-propylene glycol, 1,3propylene glycol, ethylene glycol monobutyl ether, etc.), ketones (cyclohexanonc, diisobutylketone), N-methylpyrrolidinone (NMP), Ν,Ν-diinethylformamide and the like.

Représentative of non-polar solvents suitable for formulation with the inhibitor composition include aliphatics such as penlane, hexane, cyclohexane, methylcyclohexane, heptane, decane, dodecane, diesel, and the like; aromatics such as toluene, xylene, heavy aromatic naptha, fatty acid dérivatives (acids, esters, amides), and the like.

In embodiments of the invention, the disclosed composition is used in a method of inhibiting the formation of hydrate agglomérâtes in an aqueous medium comprising water, gus, and optionally liquid hydrocarbon. The method comprises adding to the aqueous medium an effective anti-agglomerant amount of the disclosed composition.

I

The composition and method of this invention is effective to control gas hydrate formation and pluggïng in hydrocarbon production and transportation Systems. To ensure effective inhibition of hydrates, the inhibitor composition should be injected prior to substantial formation of hydrates. A preferred injection point for petroleum production operations is downhole near the near the surface controlled sub-sea safety valve. This ensures that during a shut-in, the product is able to disperse throughout the area where hydrates will occur. Treatment can also occur at other areas in the flowline, taking into account the density of the injected fluid. If the injection point is well above the hydrate formation depth, then the hydrate inhibitor should be formulated with a solvent with a density high enough that the inhibitor will sink in the flowline to collect at the water/oil interface. Moreover, the treatment can also be used for pipelines or anywhere in the system where there is a potential for hydrate formation.

In embodiments, the composition is applied to an aqueous medium that eontains various levels of salînity. In one embodiment, the fluid has a salinity of l % to 25% weight/weight (w/w) total dissolved solids (TDS). The aqueous medium in which the disclosed compositions and/or formulations are applied can be contained in many different types of apparatuses, especially those that transport an aqueous medium from one point to another point.

In embodiments, the aqueous medium is contained in an oil and gas pipeline, in other embodiments, the aqueous medium is contained in refineries, such as séparation vcssels, déhydration units, gas lines, and pipelines.

In embodiments, the composition is applied to an aqueous medium that eontains various levels of water eut. One of ordinary skill in the art would interpret water eut to mean the % of water in a composition containing an oil and water mixture. In one embodiment, the water eut is from I to 80% w/w total dissolved solids.

The compositions of the présent disclosure and/or formulations thereof can be applied to an aqueous medium in various ways that would be appreciated by of ordinary skill in the art. One of ordinary skill in the art would appreciate these techniques and the various locations to which the compositions or chemistries can be applied.

In one embodiment, the compositions and/or formulations are pumped into the oil/gas pipeline by using an umbîlical line. In a further embodiment, capillary string injection Systems can be utilized to dellver the compositions and/or formulations of the invention, in this case antiagglomerants. U.S. Patent No. 7,311,144 provides a description of an apparatus and methods relating to capillary injection.

t

Various dosage amounts of a composition and/or formulation can be applied to the aqueous medium to inhibit the formation of hydrate agglomérâtes. One of ordinary skill in the art would be able to calculate the amount of anti-agglomcrant for a given situation without undue expérimentation. Factors that would be considered of importance in such calculations include, for example, content of aqueous medium, percentage water eut, API gravity of hydrocarbon, and test gas composition.

In onc embodiment, the dose range for the hydrate înhibitor that is applied to an aqueous medium is between about 0.1% volume to about 3% volume based on water eut. In another embodiment, the dose range is from about 0.25% volume to about 1.5% volume based on water eut.

The méthodologies described in the présent invention may be utilized with other compositions that are commensurate in scope with this disclosure. Other chemistries used for inhibiting the formation of agglomérants in fluids, which are outside the spécifie generic formula described above, but are commensurate in scope with the claimed compositions generic formula, may be utilized if the system conditions permit lhe compositions to inhibit the formation of agglomérants (hydrate agglomérâtes). This protocol can be achieved without undue expérimentation, specifically, for example, the rocking test described below can be utilized in determining whether a chemistry works or not

The foregoing may be better understood by reference to the following examples, which are inlended for illustrative purposcs and are not intended to limit the scope of the invention.

Example 1

This example illustrâtes an embodiment of the composition of invention. A représentative synthetic procedure for 2-ethylhcxyI 3-(3-(dimethylamino)propylamino) propanoate is described.

To a 500-mL, 3-neck round bottom flask was added 50.0 g (0.49 .mol) 3(dimelhylamïno)-l-propylamtne and a magnetic stirbar. The flask was filted with a thermocouple, reflux condenser, and addition funnel containing 90.2 g (0.49 mol) 2cthylhexylacrylate. The acrylate was added to tire stirring amine in three equal volume shots. Once the addition was complété, the réaction mixture was heated to 100 °C for 5 hours. The final product was a light yellow liquid at ambient température. Complète conversion is apparent by the disappearance of the diaminc starting material by TLC (1/5 CHCL/McOH with 0.5% v/v NH4OH).

Example 2

This example illustrâtes an embodiment of the composition of invention. A représentative synthetic procedure for N-(3-(butyl(3-(2-ethylhexyloxy)-3oxopropyl)amino)propyl)-N,N-dimethylbutan-l-amïnium chloride is described.

Cl

To a 220 mL volume capacity sealed tube was added 25.0 g (87.3 mmol) 2-ethylhexyl 3(3-(dimethylamino)propylamÎno)propanoate, 16.2 g (174.6 mmol) 1-chlorobutane, 8.27 g 2prcpanol, and a magnetic stir bar. The tube was sealed tightly and heated in a silicone oil bath for 21 hours at 130 °C. Complète conversion was apparent by the disappearance of the diamine starting material by TLC (1/5 CHCIj/McOH with 0.5% v/v NH4OH).

Exemple 3

This example illustrâtes an embodiment of the composition of invention. A représentative synthetic procedure for 2-ethylhexyl 3-(3-(dibutylamino)propylamino)propanoate is described.

To a 500-mL, 3-ncck round bottom flask was added 50.0 g (0.27 .mol) 3-(dibutylamino)1-propylamine and a magnetic stîrbar. The flask was fitted with a thermocouple, reflux condenser, and addition funnel containing 49.4 g (0.27 mol) 2-cthylhexylacrylatc. The acryiatc was added to the stirring amine in three equal volume shots. Once the addition was complété, the reaction mixture was heated to 100 °C for 5 hours. The final product was a light yellow liquid at ambient température. Complété conversion is apparent by the disappearance of the diamine starting material by TLC (1/5 CHCIj/MeOH with 0.5% v/v NH4OH).

»

ΙΟ

Example 4

This example illustrâtes an embodiment of the composition of invention. A représentative synthetic procedure tor N-butyl-N-(3-(3-(2-c!hylliexyloxy)-3oxopropylamino)propyl)butan-]-aminium acetate is described.

Bu' 'Bu ^H

To a 500-mL 3-ncck round bottom flask was added 99.4 g 2-ethylhexyl 3-(3(dibutylamino)propylamino)propanoate and a magnetic stirbar. The flask was fitted with a thermocouple, reflux condenser, and addition tunnel containing 16.1 g (0.27 mol) acetic acid. The acetic acid was added at ambient température to the slowly over 10 minutes. Once the addition was complété, the reaction mixture was stirred for 2 hours at ambient température. The final product was a thick orange liquid at ambient température.

Structures of Table l are, for example, the quaternization products of the reaction of 1bromobutane with the ad duel formed from the addition of 2-ethylhexylacrylate to (3dime(hylamino)-l-propylamine or the quaternization products of the reaction of 1-chlorobutane with the adduct formed from the addition of commercially available 2-ethylhexylacrylate to (3dimethylamino)-l-propylamine. Ail of the quaternary ammonium species are soluble in 2propanol (IPA), methanol, ethylene glycol (MEG), ethylene giycol monobutyl ether (EGMBE), and combinations thereof. Variable in Structures 1 to 18 of Table ! refer to the general formula below.

u

Ο

°2

N

I R

Table 1

Structure	Ri	Rj	r₃	R4	X	Solvent
1	c₄h₉	CH₃	ch₃	CgHj?	Cl	IPA/MeOH
2	c₄h₉	ch₃	ch₃	c₈h_i7	Cl	IPA/MEG
3	C<H₉	CHj	CHj	CsHp	Cl	EGMBE/MEG
4	C4H9	CHj	ch₃	CgHp	Br	EPA/MeOH
5	C4H9	CHj	ch₃	CbH17	Br	IPA/MEG
6	C4H9	CHî	ch₃	c₈h_i7	Br	EGMBE/MEG
7	c₆h₁₃	~ch₃	ch₃	C₈H_i7	Dr	IPA/MeOH
8	C₆H,3	ch₃	CHj	C_SH\|7	Br	IPA/MEG
9	CôHu	ch₃	CHj	c₈h₁₇	Br	EGMBE/MEG
10	C₄H₉	ch₃	ch₃	CiîHîj	Cl	IPA/MeOH
11	c₄h₉	ch₃	CHj	CtîHîs	Cl	IPA/MEG
12	C4II9	CHj	CHj	C12H23	Cl	EGMBE/MEG
13	H	C4H9	C4II9	C₈H\|7	acetate	MeOH
14	H	C4H9	C₄H₉“	C₈H\|7	acctatc	IPA
15	H	C4H9	C₄H9	CrH\|7	‘acetate	EGMBE/MEG
16	H	C4H9	C4H9	’ C42H25	acetate	MeOH
17	H	C4H9	C4H9	CnHjs	acetate	IPA
18	H	C4H9	c₄h₉	C12H25	acetate	EGMBE/MEG

«

Example 4

Certain of structures I to 18 were dissolved to 40% w/w for the anti-agglomcration test (Table 2). The rocking cell test is the primary test for assessing the performance of an antiaggloméra te chemistry. Chemistries were evaluated based on their ability to efleclively minimize the size of hydrate agglomerate particles and then disperse those particles into the hydrocarbon phase. Chemical performance was evaluated by delermining the maximum treatable water eut (water to oil ratio) and the minimum chemical dosage to register a pass in the rocking cell test.

The rocking cell had two parts, a manifold and a cell body. The manifold was made of stainless steel fittings welded together and had three stems. Inlet stem was used to charge gas into the cell. Outlet stem was used to release the gas out of cell. Third stem was connected to a transducer, which measured the pressure inside of the cell. The cell body had three layers. The outer layer was a polycarbonate tube, the thickness of which was 0.7 cm. The middlc layer was made of stainless steel and was connected to the manifold. The inner layer was high-pressurc sapphire tube with an outer diameter of 2.8 cm, inner diameter of 1.85 cm, and length of 5 cm, This sapphire tube was rated up 3,000 psi. A stainless steel bail of 1.6 cm of diameter was located inside the sapphire tube to inducc turbulence and tnix fluids during the rocking process.

Test fluids contained three components. For this anti-agglomerate test, a correct amount of warm Magnolia crude oil was injected into the cell. Next, a solution of 7% by weight of NaCI and DI water was injected with the accurate amount according to the percent of aqueous phase. The tested anti-agglomerate of the invention was the final component injected into the cell. The dosage of chemical was based on the volume of aqueous phase. Test was set at 21 °C as initial condition. Each cell was charged by Green Canyon gas and pressurized up to 2,100 psi. Ail cells were rocked for at least l .5 to 2 hours until fluid was saturated and pressure stabilized. The température was reduced to a set point of 4°C. The cells were rocked for 16 hours, held static for 6 hours, and rocked back for 2 hours. Pressure data was recordcd during this time. Observations were taken every two to three hours, before rocking was stopped and also immediately aller the restait. The comparative examples are described in U.S. Patent Application Serial No. 12/396,076, “Compositions Containing Amide Surfactants and Methods for Inhibiting the Formation of Hydrate Agglomérâtes,” filed March 2, 2009, currently pending. Results are shown in Table 2.

I3

Table 2

Structure	Maximum Water Cut
Blank	None
Comparative Exemple A	50%
Comparative Examplc B	50%
I	55%
4	55%
7	55%
10	55%
13	60%
16	60%

It can be seen in Table 2, that the compositions of the invention provide not only an increase in chemical performance in the rocking ccll test, but a significant increase in overboard water qualily. The compositions of the invention (which are surfactants) hâve a tendency to 10 stabilise the émulsion at the oil/water interface. These compositions hâve also been shown in laboratory bottle test experiments to resuit in enhanced water qualily and rapid destabilization of émulsions in comparison to Comparative Examples A and B (Table 2).

Ail of the compositions and methods disclosed and claimed herein can be made and executed without undue expérimentation in light of the présent disclosure. While this invention 15 may be embodied in many different forms, tJiere are described in detail herein spécifie preferred embodiments ofthe invention. The présent disclosure is an exemplification ofthe principlcsof the invention and is not intended to limit the invention to the particular embodiments illustrated. In addition, unless expressly stated to the contrary, use of the term “a” is intended to include “at least one” or “one or more. For example, “a device is intended to include at least one device” 20 or “one or more devices.”

Any ranges given either in absolute terms or in approximate terms are intended to encompass both, and any définitions used herein arc intended to bc clarifying and not lîmiting. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the spécifie cxamples are reported 25 as prccisely as possible. Any numerical value, however, irtherently contains certain errors necessarily resulting from the standard déviation found in their respective testing measurements,

I4

Moreover, ail ranges disclosed herein are to be understood to encompass any and ail subranges (încluding ail fractional and whole values) subsumed therein.

Furthermore, the invention encompasses any and ail possible combinations of some or ail of the various embodiments described herein. Any and ail patents, patent applications, scientific papers, and other référencés cited in this application, as well as any référencés cited therein, are 10 hereby incorporated by reference in their entirety. It should also bç understood that various changes and modifications to the presently preferred embodiments described herein will bc apparent to those skilled in the art. Such changes and modifications can be made without departing from the spirit and scope of the invention and without diminishing ils intendcd advantages. It is therefore intended that such changes and modifications be coverçd by the 15 appended daims.

Claims

The claimed invention is:

1. A composition comprising the following formula and optionally salts thereof:

wherein each R| is independently absent, Ci-Cio alkyl, benzyl, or H;

wherein R2 is Cj-C|o alkyl;

wherein R3 C1-C10 alkyl; and wherein R4 is C4-C22 alkyl or alkenyl;

optionally further comprising at least one polar or nonpolar solvent or a mixture thereof.
2. The composition of Claim 1, wherein each alkyl is independently selected from tlic group consisting of: u straight chain alkyl, a branched chain alkyl, a cyclic alkyl, a saturated version of the foregoing, an unsaturated version of tho foregoing, and combinations thereof.
3. The composition of Claim 1, wherein tlie alkyl for each of Ri, R2, and R3 is independently selected from the group consisting of: methyl; ethyl; propyl; butyl; pentyl; hexyl; heptyl; octyl; nonyl; decyl; and combinations thereof.
4. The composition of Claim 1, wherein the alkyl for R4 is selected from the group consisting of: butyl; pentyl; hexyl; heptyl; octyl; nonyl; decyl; and combinations thereof.
5. The composition of Claim 1, wherein R2 and R3 are independently selected from: methyl, butyl, or n-butyl.

I
6

5 6. The composition of Claim 1, further comprising counterion X- as shown in the general formula below.
7. The composition of Claim 6, wherein the counterion is a halide.
8. The composition of Claim 6, wherein die counterion is a carboxylate selected

10 from: reaction with minerai acid; acrylic acid; acetic acid; methacrylic acid; glycolic acid; thioglycolic acid; propionic acid; butyric acid; and combinations thereof.
9. The composition of Claim 1, comprising at least one or any combination of the following formulas (1) to (8) and optionally salts thereof.

(?)

Me ό (3) ^nBü'N-— ^Bu O 0 Ct® 0’ *<A 0. Me Me _N -^xA₀<.Ç,₂H 25 Bu (4) Bu' Bu

(8>

4 f
10. The composition of Claim 1, further comprising at least one component selected from: thermodynamic hydrate inhibitors, one or more kinetic hydrate inhibitors, one or more additional anti-agglomerants, asphaltene inhibitors, paraffin inhibitors, corrosion inhibitors, scale inhibitors, emulsifiers, water clarifiers, dispersants, émulsion breakers, and combinations thereof,
11. The composition of Claim 1, further comprising at least one solvent selected from the group consisting of: isopropanol, methanol, éthanol, 2-ethylhexanol, heavy aromatic naptha, toluene, ethylene glycoi, ethylcnc glycol monobutyl ether (EGMBE), diethylcnc glycol monoethyl ether, xylene, and combinations thereof.
12. A method of inhibiting the formation of hydrate agglomérâtes in a fluid comprising water, gas, and optionally liquid hydrocarbon comprising addïng to the fluid an effective anti-agglomerant amount of the composition of Claim 1.
13. The method of Claim 12, wherein said fluid has a salinity of 1% to 25% w/w percent TDS.
14. The method of Claim 12, wherein said fluid has a water eut from 1 to 80% v/v total dissolved solids.
15. The method of Claim 12, wherein the fluid is contained in an oil or gas pipeline or refïnery.