OA16465A

OA16465A - Composition and method for reducing hydrate agglomeration.

Info

Publication number: OA16465A
Application number: OA1201300266
Authority: OA
Inventors: Peter A. Webber; Peter G. Conrad; Austen K. Flatt
Original assignee: Nalco Company
Priority date: 2011-12-15
Filing date: 2011-12-22
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 any of the formulas described above and optionally salts thereof.

Description

REDUCING HYDRATE AGGLOMERATION

CROSS REFERNCE TORELATED APPLICATION

This application claims the benefit ofU.S. provisiona) patent application no. 61/426,029, “Composition and Method for Reducing Hydrate Agglomération, tiled on December 22, 2010, 10 which is incorporated herein in its entirety by reference.

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 und transport of 15 natural gas, petroleum gas, or other gases. The invention has particular relcvance to treating such Systems with beta-amino amide surfactants as anli-agglomerants to reduce or înhiblt the formation of gas hydrates.

BACKGROUND O F THE INVENTION

Since Hammerschmidt discovered in 1934 that gas hydrates would block gas pipelines, 20 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 oflen resuit on lost oil production, pipeline damage, and safety hazards to field workers. Modem oil 25 and gas technologies commonly operatc under severe conditions during the course of oil recovery and production; for instance, high pumping speed, high pressure in the pipelines, extended length of' pipelines, and low température of the oil and gas flowing through the pipelines. These conditions are particularly favorable for ihe formation of gas hydrates, which can be particularly bazardons for oil productions offshore or for locations with cold climates.

Gas hydrates are Îce-like solids that are formed from small nonpolar molécules and water at lower températures and et increased pressures. Under these conditions, the water molécules can form cagc-likc structures around these small nonpolar molécules (typically dissolved gases

r such as carbon dioxide, hydrogen sulfide, methane, ethane, propane, butane and iso-buiane), creating a type of host-guest interaction also known as a clathrate or clathratc hydrate. The spécifie architecture of this cage structure can be one of several types (called type l, type 2, type H), depending on lhe identity of the guest molécules. However, once formed, these crystalline cage structures tend to settle out from the solution and accumulate into large solid masses that 10 can travel by oil and gas transporting pipelines, and potentially block or damage the pipelines and/or related equipment. The damage resulting from a blockage can be very costly from an equipment repair standpo^ as well as from the loss of production, and finally the résultant environmental impact.

The industry uses a number of methods toprevent such blockages such as thermodynamic hydrate inhibitors (TI1J), anti-agglomcrants (AA), and kinetic 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 dosed 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 substantial cost associated with the transportation and storage of large quantifies of these solvents.

A more cost-efTective alternative is the use of LDHIs, as they generally rcquîrc less that 2% dose to inhibit the nucléation or growth of gas hydrates. There are two general types of 25 LDHIs, kinetic hydrate inhibitors (KHIs) and anti-agglomerants (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 erystals and as anti-nucleators. AAs allow the hydrates to form but they prevent them from agglomcratîng and subséquent accumulation into larger masses capable of causing plugs. An AA enables gas hydrates to form but in the shapc of fluid slurry dispersed in 30 the liquid hydrocarbon phase. In general, lhe water eut should be below 50% otherwise the slurry bccome 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.

f

BRIEF SUMMARY OF THE INVENTION

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

X® o

R₂R₃ ^H ln the above formula, Ri, R₂, and R_: are each independently C_t)H_2n+i or benzyl. R₄ is C₄C20 alkyl or alkenyl. n is an integer from 0 to 10. X‘ is a counterion.

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 hydrocarbon comprising adding to the aqueous medium an effective anti-agglomerating amount of a composition comprising the above formula and optionally salts thereof.

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

It is another advantage of the invention to provide anti-agglomerant compositions thaï do not ncgatively affect the overboard water quality.

It is a further advantage of the invention to provide anti-agglomerant compositions that are capable to be delivered in subsea umbîlical lines.

The foregoing has outlined rather 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 appredated by those skilled in the ait that the conception and the spécifie embodiments disclosed may be readily utilized as a basis for modifying or designing other embodiments for carrying out the saine purposes of the présent invention. It 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 appendcd daims.

DETAILED DESCRIPTION

The compositions of the invention comprise a generic formula and optionally salts thereof as given below.

R's R₃ ^R

In the above formula, Rj, R₂, and Rj are each independently C_nH2_n+i or benzyl. R.| is C<iC₂o alkyl or alkenyl. n is an integer from 0 to I0. X‘ is a counterton, “Alkenyl” means a monovalent group derived from a straight, branched, or cyclic hydrocarbon containing at least one carbon-carbon double bond by the rcmoval of o single hydrogen atom from each of two adjacent carbon atoms of an alkyl group. Représentative alkenyl groups include, for example, ethenyl, propcnyl, butcnyl, l-mcthyl-2-buten-l-yJ, 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, pentyl, hexyl, heptyl, octyl, nonyl, and decyl.

“Counterion” refers to a halide selected from fluoride, chloride, bromide, iodide, or carboxylate selected from réaction with minerai acid, acrylic acid, acetic acid, methacrylic acid, glycolic acid, thioglycolic acid, propîonic acid, butyric acid, the like, and any combination thereof.

In an embodiment, the composition comprises the following formula and optionally salts thereof, R is at least one or a mixture of saturated or unsaturated C«, Cio, Ci₂, Cm, Cie, and Cm. In embodiments, R is derived from cocoamine.

BU uu

t

In an embodiment, the composition comprises the following formula and optionally salts thereof. R is at least one or a mixture of saturated or unsaturated Cg, Cio, Cn, Cu, Ciî, and Cig. In embodiments, R is derived from cocoamine (“coco”).

o θ

«.g^A r

Bu Bu ^H

In an embodiment, the composition comprises the following formula and optionally salts thereof.

H.®^A _ / ‘ Bu Bu fi

ln an embodiment, the composition comprises the following formula and optionally salts thereof.

x® O

Hex,®.^A aoco

Bu Bu

^Br® 0

Bu Bu ^H

Bu Bu ln an embodiment, the composition comprises the following formula and optionally salts thereof.

Bu Bu ^H

Various synthesis méthodologies, which can bc appreciated by one of ordinary skill in the art, can be utîlized to make the claimed compositions. Detailed représentative synthctic schcmes are provided in the examples.

The compositions of this inventiou 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.

ln one embodiment, the composition further comprises at least one additional hydrate inhibitor. Exemplury hydrate inhibitors are disclosed in U.S. Patent Application Serial Nos. 12/253,504, “Method of Controliing Gas Hydrates in Fluid Syslcms,” filed October 17, 2008, 12/253,529, “Method of Controliing 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, 12/967,811, Composition and Method for Reducing Hydrate Agglomération,” filed December 16, 2008, ail currently pending and incorporated herein by reference.

In an embodiment, the invention comprises the following formula and optionally salts thereof (including at least monobutyl amine reactions with 2 équivalents of acrylic acid):

.10 In another embodiment, the composition further comprises one or more thermodynantie hydrate inhibitors, one or more kinetic hydrate inhibitors, one or more anti-agglomeranls, or a combination thereof.

Γη another embodiment, the composition further comprises one or more asphaltene inhibitors, paraffin inhibitors, corrosion inhibitors, scale inhibitors, emulsifiers, water clariflers, 15 dispersants, émulsion breakers, or a combination thereof.

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

In another embodiment, the composition further comprises one or more solvents selected from isopropanol, methanol, éthanol, 2-ethylhexanol, heavy aromatic naphtha, toluene, ethylene 20 glycol, ethylene glycol monobutyl ether (EGMBE), diethylene 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 mechanical equipment such as chemical injection pumps, piping tees, injection fittings, and the 25 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 requjrements.

Représentative polar solvents suitable for formulation with the inhibitor composition include water, brine, seawater, alcohols (including straight chain or branched aliphatic such as methanol, éthanol, propanol, isopropanol, butanol, 2-ethylhexanol, hexanol, octanol, decanol, 230 butoxyethanol, etc.), glycols and dérivatives (ethylene glycol, 1,2-propylene glycol, 1,3propylene glycol, ethylene glycol monobutyl ether, etc.), ketones (cyclohexttnone, diisobutylketone), N-niethylpyrroIidînone (NMP), Ν,Ν-diinethylformainide and the like.

Représentative of non-polar solvents suitable for formulation with the inhibitor composition include aliphatics such as pentane, hexane, cyclohexane, mcthylcyclohexane, heptane, decane, dodecane, diesel, and the like; aromatics such as toluene, xylene, heavy aromatîc naphtha, 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, gas, and optionally liquid hydrocarbon. The method comprises adding to the aqueous medium an 10 effective anti-agglomerant amount of the disclosed composition.

The composition and method of this invention is effective to control gas hydrate formation and plugging in hydrocarbon production and transportation Systems. To ensure effective inhibition of hydrates, the inhibitor composition should be injected prior to substanlial formation of hydrates. A preferred injection point for petroleum production operations is 15 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 20 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 lo an aqueous medium that eontains various levels of salinity. In one embodiment, the fluid has a salinity of 0% to 25%, about 1% to 24%, or about 10% to 25% weight/weight (w/w) total dissolved solids (TDS). The aqueous medium in 25 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 refînerics, such as séparation vesscls, 30 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 1 to 80% w/w total dissolved solids.

The compositions ofthe 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 apprcciate these techniques and the various locations to which the compositions or chemïstries can be applied,

In one embodiment, the compositions and/or formulations are pumped into the oil/gas pipeline by using an ombilical line. In a further embodiment, capillary string injection Systems can be utilized to deliver the compositions and/or formulations o F the invention, in this case antiagglomerants. U.S. Patent No. 7,31 l,l44 provides a description of an apparatus and methods relating to capillary injection.

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-agglomerant for a given situation without undue expérimentation. Factors that would be considered of importance in such calculations include, for exumple, content of aqueous medium, percentage water eut, ΛΡ1 gravity of hydrocarbon, and test gas composition.

In one embodiment, the dose range for the hydrate inhibitor that is applied to an aqueous medium is between about 0.l% volume to about 3% volume bascd on water eut. In anotheT 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 commensuratc in scope with this disclosure. Other chemïstries used for inhibiting the formation of agglomérants ïn lluids, which are oulside the spécifie gcneric formula described above, but are commensurate in scope with the claimed compositions generic formula, may be utilized if the System conditions permit the 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 determîning the effectiveness of a given chcmîstry.

The foregoing may be better underslood by reference to the following cxamples, which are intended for illustrative purposes and are not inlended to limit the scope ofthe invention.

ίο

Example 1

A représentative synthetic scheme is given below for the synthesis of N-butyl-bl-(3 (cocoamino)-3-oxopropyl)butan-1 -aminium acetate.

cocoamfne

-H₂O

•aceiicacitf

O

,coco

To a 250-mL, 3-neck round bottom flask was added 40.00 g (0.31 mol) dibutylamine and a magnetic stirbar. The tlask was fitted with a thermocouple, reflux condenser, and addition funnel containing 22.30 g (0.31 mol) acrylic acid. The acrylate was added to the stirring amine slowly. Once the addition was complété, the addition funnel was replaced with a glass stopper and the reaction mixture wus heated al 120 °C for 2 hours. Upon cooling to ambient température, an orange solid was formed. Complété conversion was confîrmed by the disappearance of the dibutylamine starting material by TLC (1/5 CHCIj/MeOH with 0.5% v/v bIHeOH). To the orange solid was added 60.58 g (0.31 mol) cocoamine. An insulated Dean-Stark trap was attached to the apparatus between the flask and reflux condenser for water removal. The réaction mixture was heated at 165 °C for 6 hours at which time TLC analysis (8/1 CHCIj/MeOH with 0.5% v/v 20 NH4OH) confîrmed the disappearance of the intermediate carboxylic acid. Upon cooling to ambient température a light orange liquid was formed. To Lhe resulting amide at ambient température was slowly added 18.59 g (0.31 mmol) acetic acid and the reaction mixture was stirred at ambient température for 2 hours.'

Example 2

A représentative synthetic scheme is given below for the synthesis of N.’N-dibutyl-N-iS (cocoamino)-3-oxopropyl)hexan-l-aminium bromide.

OH

OH cocoamlne

-HjO

1-bromohexane

To a 250-mL, 3-neck round bottom flask was added 40.00 g (0.31 mol) dibutylamine and a magnetic stirbar. The flask was fitted with a thermocouple, reflux condenser, and addition funnel containing 22.30 g (0.31 mol) acrylic acid. The acrylate was added to the stirring amine slowly. Once the addition was complété, the addition funnel was replaced with a glass stopper and the reaction mixture was heated at 120 °C for 2 hours. Upon cooling to ambient température, an orange solid was formed. Complété conversion was confirmed by the disappearance of the dibutylamîne starting material by TLC (1/5 CtlClj/MeOH with 0.5% v/v NH4OH). To the orange solid was added 60.58 g (0.31 mol) cocoainine. An insulated Dean-Stark trap was attached to the apparatus between the flask and reflux condenser for water reinoval. The réaction mixture was heated at 165 °C for 6 hours at which time TLC analysis (8/1 CIlClj/MeOH with 0,5% v/v NH4OH) confirmed the disappearance of the intermediate carboxylic acid. Upon cooling to ambient température a light orange liquid was formed. To the resulting amide at ambient température was added 51.09 g (0.31 mol) 1-bromohcxanc and 42.07 g 2-propanol. The réaction mixture was heated at 97.5 °C for 6 hours.

Example 3

Samples I to 4 of Table 1 are the cationic ammonium products of the reaction of acrylic or acetic acid with the adduct formed from the addition of commercially available acrylic acid to dibutylamine followed by amidation with cocoaminc. Samples 5 to 10 arc the quaternization products of the réaction of 1-chlorobutane, 1-bromobutane, or 1-bromohexane with the adduct 10 formed From the addition of commercially available acrylic acid to dibutylamine followed by amidation with cocoaminc, Ali of the ammonium species are soluble in 2-propanol (IPA), methanol, ethylene glycol (MEG), ethylene glycol monobutyl ether (EGMBE), glycerol, heavy aromatic naphtha (HAN) and combinations thereof. Samples 1 to 10 were dissolved to 40% w/w for the anti-agglomération test.

X®

Table 1. New anti-agglomeranl chemistries

Sample	RI	R2	R3	R4	X	Solvent
1	C4.H9	C₄H₉	H	coco	acrylate	MeOH
2	C₄II₉	c₄h₉	H	coco	acetate	MeOH
3	C4H9	c₄h₉	H	coco	acrylate	[PA
4	C₄H₉	c₄h₉	H	coco	acetate	IPA
5	c₄h₉	c₄h₉	C4H9	coco	Cl	IPA/MeOH
6	C₄H₉	c₄h₉	c₄h₉	coco	Br	IPA/MeOH
7	c₄h₉	c₄h₉	c₆h₁₃	coco	Br	IPA/MeOH
8	C₄11₉	c₄h₉	c₄h₉	coco	Cl	IPA/MEC
9	C4I-I9	c₄h₉	c₄h₉	coco	Br	IPA/MEG
10	C4H9	c₄i-i₉	CéHn	coco	Br	IPA/MEG

Tlie rocking cell lest is the primary test for assessing the performance of an antiagglomerant chemistry. Chemistries are evaluated based on their ability to effectivcly minimize the size of hydrate agglomerate particles and then disperse those particles into the hydrocarbon phase. Chemîcal performance is evaluated by determining the maximum treatable water eut (walcr to oil ratio) and the minimum chemîcal dosage to register a pass in the rocking cell test,

A rocking cell has two parts, manifoid and cell body. The manifoid is made of stainless steel flttîngs weld together. It has three stems. Inlet stem is used to charge gas into the cell. Outlet stem is used to release the gas out of cell. Third steam is connecting to transducer, which measures the pressure inside of the cell. Cell body has Ihree layers. The outer layer is a polycarbonate tube, which thickness is 0.7 cm. The middle loyer is made of stainless steel métal, 15 and been connected to the manifoid. The ïnner layer is high-pressure sapphire tube, which outer diameter is 2.8 cm, inner diameter is 1.85 cm, and length is 5 cm. This sapphire tube can handle up 3000 psi. A stainless steel bail of 1.6 cm of diameter is located inside sapphire tube to induce turbulence and mix fluids during the rocking process.

Test fluids usually contain three components. For this anti-agglomerant test, a correct 20 amount of warm Mngnolia crude oil is injected into the cell first. 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. Chemîcal, low dosage hydrate inhibitor, is the final component injected into the cell. The dosage of chemîcal is based on the volume of aqueous phase. Test was set at 21 °C as initial condition. Each cell is charged by Green Canyon gas and pressurtzed up to 2,100 psi. Ail 25 cells rock for at least 1.5 to 2 hours until fluid is saturated and pressure stabilizes. Next, température is reduced to the set point of 4°C. Cells rocked for 16 hours, held static for 6 hours, and rocked back for 2 hours. Pressure data is recorded during this time. Observations are taken every two to three hours, before stopped rocking and also immediately after the restart.

Table 2. Rocking cell experiment results for new anti*agglomerant chemîstries

Sample	Maximum Water Cut
Blank	None
Comparative Sample A	50%
Comparative Sample B	55%
1	65%
2	65%
3	65%
4	65%
5	55%
6	55%
7	55%
8	55%
9	55%
10	55%

The new chemîstries provide not only an increase in chemical performance in the rocking cell lest, but a significant increase jn ovcrboard water quality. Surfactant has a lendency to stabilize émulsion at the oil/water interface. This chemistry has shown in laboratory bottle test 1Q experiments to resuit in enhanced water quality and found to be more reactive with a number of water elarifiers.

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 may be embodied in many different forms, there are described in detail herein spécifie preferred 15 embodiments of the invention. The présent disclosure is an exemplification of the principles of the invention and is not întended to limit the invention to the particular embodiments illustrated. In addition, unless expressly stated to the contrary, use of the term “a” is întended to include “at least one” or “one or more.” For exemple, “a device is întended to include “at least one device” or “one or more devices.

Any ranges given either in absolute tenus or in approximate terms are întended to crtcompass both, and any définitions used herein are întended to be clarifying and not limîting. Notwithstanding that the numcrical ranges and parameters setting forth the broad scope of the invention are approximations, the numcrical values set forth in the spécifie examples arc reported as precisely as possible. Any numerical value, however, inherently contains certain errors 25 necessarily resulting from the standard déviation found in their respective lesting measurements.

Moreover, ail ranges disclosed herein are to be understood to encompass any and ail subranges (including ail fractional and whole values) subswticd 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 references cited in this application, as well as any référencés cited therein, are hereby incorporated by reference in their entirety. It should also be understood that varions changes and modifications to the presently preferred embodiments described herein will be 10 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 its inlended advantages. It is therefore intended that such changes and modifications be covered by the uppended daims.

t

CLAÏMS

Claims

CLAÏMS

The claimed invention is:

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

X® o

M— wherein R₍₁ R₂, and R₃ are each independently C_nH_2n+i or benzyl;

wherein R4 is Cj-Cîo alkyl or alkenyl;

n is an integer from 0 to 10; and

X‘ is a counterion;

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 the group consisting of: a straight chain alkyl, a branched chain alkyl, a cyclic alkyl, a saturated version of the foregoing, an unsaturated version οΓthe foregoing, and combinations thereof.
3. The composition of claim 1, wherein the alkyl for each of R>, R₂, and R3 is independently selected front the group consisting of: methyl; ethyl; propyl; butyl; pentyl; hexyl; heptyl; octyl; nonyl; decyi; and combinations thereof.
4. The composition of claim I, wherein the alkyl for R4 is selected front the group consisting of: butyl; pentyl; hexyl; heptyl; octyl; nonyl; decyi; and combinations thereof.
5. The composition of claim 1, wherein R₂ and R 3 are methyl.
6. The composition of claim 1, wherein R₂ and Rj are butyl or n-butyl.
7. The composition of claim 1, wherein the counterion comprises at least one halide,
8. The composition of claim 1, wherein the counterion is at least one carboxylate.
9. The composition of claim 8, wherein the at least one carboxylate is selected from at least 011c of the following; réaction with minerai acid; acrylic acid; acetic acid; methacrylic acid; glycolic acid; thioglycolic acid; propionic acid; butyric acid; and combinations thereof.

I7

5
10. The composition of claim 1, comprising at least one or any combination of the following formulas (1) to (V) and optionally salts thereof:

coco

III

X® Q

Hex XijHjs

8u Bu'

IV V wherein R is at least one or a mixture of saturated. or unsaturated Cg, Cio, C|₂, Ci4, Cu, 10 andC|g,
11. The composition of claim 10, wherein R is derived from cocoamine.
12. The composition of claim 1, further comprising at least one component selected from: thermodynamie hydrate inhibitors, one or more kinetic hydrate inhibitors, one or more additional anti-agglomerants, asphaltene inhibitors, paraffin inhibitors, corrosion inhibitors, scale

15 inhibitors, emulsifiers, water clarî fiers, dispersants, émulsion breakers, and combinations thereof.
13. The composition of claim I, further comprising at least one solvent selected from the group consisting of: isopropanol, methanol, éthanol, 2-ethylhexanol, heavy aromatic naphtha, toluene, ethylene glycol, ethylene glycol monobutyl ether (EGMBE), diethylene glycol monoethyl ether, xylene, and combinations thereof.

20
14. A method of inhibiting the formation of hydrate agglomérâtes in a fluid comprising water, gas, and optionally. liquid hydrocarbon comprising adding to the fluid an effective antiagglomerant amount of the composition of claim 1, wherein the fluid is optionally conlaîned in an oil or gas pipeline or refinery.
15. The method of claim 15, wherein said fluid has a salinity of 0% to 25% w/w percent

25 TDS and/or wherein said fluid has a water eut from I to 80% v/v total dissolved solids.