WO2005116399A1 - Enhancement modifiers for gas hydrate inhibitors - Google Patents
Enhancement modifiers for gas hydrate inhibitors Download PDFInfo
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- WO2005116399A1 WO2005116399A1 PCT/US2005/017251 US2005017251W WO2005116399A1 WO 2005116399 A1 WO2005116399 A1 WO 2005116399A1 US 2005017251 W US2005017251 W US 2005017251W WO 2005116399 A1 WO2005116399 A1 WO 2005116399A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/20—Use of additives, e.g. for stabilisation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/107—Limiting or prohibiting hydrate formation
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- the invention relates to methods and compositions for inhibiting the formation of hydrocarbon hydrates, and most particularly relates, in one non- limiting embodiment, to methods and compositions for inhibiting the formation of hydrocarbon hydrates during the production of oil and gas.
- a number of hydrocarbons, especially lower-boiling light hydrocarbons, in formation fluids or natural gas are known to form hydrates in conjunction with the water present in the system under a variety of conditions - particularly at a combination of lower temperature and higher pressure.
- the hydrates usually exist in solid forms that are essentially insoluble in the fluid itself. As a result, any solids in a formation or natural gas fluid are at least a nuisance for production, handling and transport of these fluids.
- hydrocarbon hydrates have been of substantial interest as well as concern to many industries, particularly the petroleum and natural gas industries.
- Hydrocarbon hydrates are clathrates, and are also referred to as inclusion compounds. Clathrates are cage structures formed between a host molecule and a guest molecule.
- a hydrocarbon hydrate generally is composed of crystals formed by water host molecules surrounding the hydrocarbon guest molecules.
- ethane it is possible for ethane to form hydrates at as high as 4°C at a pressure of about 1 MPa. If the pressure is about 3 MPa, ethane hydrates can form at as high a temperature as 14°C.
- Even certain non-hydrocarbons such as carbon dioxide, nitrogen and hydrogen sulfide are known to form hydrates under the proper conditions.
- thermody- namic approach there are a number of reported or attempted methods, including water removal, increasing temperature, decreasing pressure, addition of "antifreeze” to the fluid and/or a combination of these.
- the kinetic approach generally attempts (a) to prevent the smaller hydrocarbon hydrate crystals from agglomerating into larger ones (known in the industry as an anti- agglomerate and abbreviated AA) and/or; (b) to inhibit and/or retard initial hydrocarbon hydrate crystal nucleation; and/or crystal growth (known in the industry as a kinetic hydrate inhibitor and abbreviated KHI).
- Thermodynamic and kinetic hydrate control methods may be used in conjunction. Kinetic efforts to control hydrates have included use of different materials as inhibitors.
- onium compounds with at least four carbon substituents are used to inhibit the plugging of conduits by gas hydrates.
- Additives such as polymers with lactam rings have also been employed to control clathrate hydrates in fluid systems.
- These kinetic inhibitors are commonly labeled Low Dosage Hydrate Inhibitors (LDHI) in the art. KHIs and even LDHIs are relatively expensive materials, and it is always advantageous to determine ways of lowering the usage levels of these hydrate inhibitors while maintaining effective hydrate inhibition. Thus, it is desirable if new gas hydrate inhibitors or modifiers for existing hydrate inhibitors were discovered which would yield comparable or improved results over known gas hydrate inhibitors.
- LDHI Low Dosage Hydrate Inhibitors
- An object of the invention is to provide a method for inhibiting gas hydrate formation in mixtures of hydrate-forming guest molecules and water where hydrates would otherwise form to a greater extent in absence of the method.
- Another object of the invention is to provide gas hydrate inhibitor compositions and/or hydrate inhibitor synergists that are readily produced. These compositions may be blended with other oil field chemistries such as, but not limited to, corrosion, paraffin, scale and/or asphaltene inhibitors.
- Still another object of the invention is to reduce the dosage levels of the more expensive components of the gas hydrate inhibitors.
- the method involves contacting the mixture with an amount of an ion pair effective to inhibit formation of hydrocarbon hydrates.
- the ion pair includes a first component that can be a cationic low dosage hydrate inhibitor (LDHI), an anionic LDHI, an amphoteric LDHI or a non-ionic LDHI.
- the ion pair also includes a second counter-ion component. If the first component is a cationic LDHI, the second counter-ion component is either an anionic compound, a non-ionic compound or an amphoteric compound. If the first component is an anionic LDHI, then the second counter-ion component is either a non-ionic compound, an amphoteric compound or a cationic compound.
- the second counter-ion component can be either an anionic compound, a cationic compound, a non-ionic compound or an amphoteric compound.
- a method for inhibiting formation of hydrocarbon hydrates in a mixture containing water and hydrate-forming guest molecules involves contacting the mixture with an amount of an ion pair effective to inhibit formation of hydrocarbon hydrates.
- the ion pair includes a cationic quaternary onium compound, and a non-cationic counter-ion component that is either an anionic compound, a non-ionic compound or an amphoteric compound.
- the invention includes hydrocarbon mixtures inhibited against hydrate formation formed by the methods described above.
- methods and compositions used therein for inhibiting, retarding, mitigating, reducing, controlling and/or delaying formation of hydrocarbon hydrates or agglomerates of hydrates The method may be applied to prevent or reduce or mitigate plugging of conduits, pipes, transfer lines, valves, and other places or equipment where hydrocarbon hydrate solids may form under conditions conducive to their formation or agglomeration.
- the ion pairs of this invention may be active as an anti-agglomerate (AA) and/or as a kinetic inhibitor (KHI), and the invention should be understood as not restricted to one particular mechanism or the other.
- inhibitor is used herein in a broad and general sense to mean any improvement in preventing, controlling, delaying, reducing or mitigating the formation, growth and/or agglomeration of hydrocarbon hydrates, particularly light hydrocarbon gas hydrates in any manner, including, but not limited to kinetically, thermodynamically, by dissolution, by breaking up, by anti-agglomeration other mechanisms, or any combination thereof.
- inhibiting is not intended to be restricted to the complete cessation of gas hydrate formation, it may include the possibility that formation of any gas hydrate is entirely prevented.
- formation or “forming” relating to hydrates are used herein in a broad and general manner to include, but are not limited to, any formation of hydrate solids from water and hydrocarbon(s) or hydrocarbon and non-hydrocarbon gas(es), growth of hydrate solids, agglomeration of hydrates, accumulation of hydrates on surfaces, any deterioration of hydrate solids plugging or other problems in a system and combinations thereof.
- the present method is useful for inhibiting hydrate formation for many hydrocarbons and hydrocarbon and/or non-hydrocarbon mixtures.
- the method is particularly useful for lighter or low-boiling, C 1 -C 5 , hydrocarbon gases, non-hydrocarbon gases or gas mixtures at ambient conditions.
- gases include, but are not necessarily limited to, methane, ethane, ethylene, acetylene, propane, propylene, methylacetylene, n-butane, isobutane, 1-butene, trans-2-butene, cis-2-butene, isobutene, butene mixtures, isopentane, pentenes, natural gas, carbon dioxide, hydrogen sulfide, nitrogen, oxygen, argon, krypton, xenon, and mixtures thereof. These molecules are also termed hydrate-forming guest molecules herein.
- Other examples include various natural gas mixtures that are present in many gas and/or oil formations and natural gas liquids (NGL).
- the hydrates of all of these low-boiling hydrocarbons are also referred to as gas hydrates.
- the hydrocarbons may also comprise other compounds including, but not limited to CO, CO 2 , COS, hydrogen, hydrogen sulfide (H 2 S), and other compounds commonly found in gas/oil formations or processing plants, either naturally occurring or used in recovering/processing hydrocarbons from the formation or both, and mixtures thereof.
- Suitable LDHIs for use in the methods of this invention include, but are not necessarily limited to, ammonium or onium compounds with at least four carbon substituents, including but not necessarily limited to, lactam rings, amides having at least 3 carbon atoms, imides having at least 3 carbon atoms, and halide quaternary amines; and combinations thereof.
- substances useful for improving, modifying, extending and/or enhancing the performance of gas hydrate inhibitors are made by adding the appropriate counter-ion. The resulting ion pair is as effective as, if not more effective than, the original gas hydrate inhibitor.
- the amount of original gas hydrate inhibitor used can be reduced by almost half, yet give the same hydrate-inhibiting effect together with the counter-ion.
- This pairing of ions has sufficient impact on the cost of the gas hydrate inhibitor product and may prove to increase the environmental friendliness of the inhibitor.
- having relatively large low dosage hydrate inhibitor (LDHI) and relatively large counter-ions paired therewith give pairs with increased steric bulk that aids in hydrate inhibition.
- LDHI low dosage hydrate inhibitor
- counter ion impacts the partitioning (presumably at the liquid interface) of the active molecule between the brine and liquid hydrocarbon phase, when such a liquid hydrocarbon phase is present.
- the counter-ion component is also called a modifier herein, and may also be properly termed an inhibitor synergist when an effect is achieved that is over and above a simple additive effect of the two components.
- the scope of the invention includes any appropriate counter-ion to the active LDHI. More specifically, the invention includes anionic, non-ionic and amphoteric counter-ions for a cationic LDHI; a non-ionic, amphoteric and cationic counter-ion for an anionic LDHI, and an anionic non-ionic, cationic or amphoteric counter ion for an amphoteric or non-ionic LDHI.
- a suitable ion pair is one where the LDHI is a cationic component that is a quaternary ammonium compound or an onium compound.
- the non-cationic counter-ion component for this LDHI may be an anionic compound, a non- ionic compound and/or an amphoteric compound.
- Suitable onium compounds for use in the composition for the present invention are defined to have a general structure of the following formula A having a cation with a center atom X and an anion Y " :
- R 1 and R 2 each are independently selected from normal or branched alkyls containing a chain of at least 4 carbon atoms, with or without one or more substituents, or one or more heteroatoms;
- R 3 is an organic moiety containing a chain of at least 4 carbon atoms, with or without one or more substituents, or one or more heteroatoms;
- X is S, N— R 4 or P— R 4 ;
- R 4 if present, is selected from H or an alkyl, aryl, alkylaryl, alkenylaryl or alkenyl group, preferably those having from about 1 to about 20 carbon atoms, with or without one or more substituents, or one or more heteroatoms;
- Heteroatoms are defined herein as oxygen, nitrogen, sulfur and phosphorus.
- suitable substituents or moieties include, but are not necessarily limited to, hydroxyl, ether, carboxylic ester, ketone, amine, amide, nitro, mercaptan, thiol. thioether, sulfide, sulfoxide, sulfone, sulfonic acid, or ether sulfate groups.
- R 1 , R 2 , R 3 and R 4 may contain these groups in a linear or branched manner. When a group is on R x in a branched manner, the group may be referred to as a substituent on R x .
- R x When a group is in R x in a linear manner, the group may be referred to as a moiety of R x .
- suitable substituents or moieties include, but are not necessarily limited to, phosphonic acid, a phosphonic acid ester or a phosphoric acid ester.
- Ammonium and phosphonium compounds of the above formula may also be bound through R 4 to become pendant groups of a number of oxygen- containing polymers.
- Suitable oxygen-containing polymers include, but are not limited to polyacrylic acid, polymethacrylic acid, copolymers of acrylic and methacrylic acids, and polymers or co-polymers of poly-N-vinyl-2-pyrrolidone.
- Alkyl ammonium and alkyl phosphonium compounds are preferred onium compounds for the composition of the present invention when R 4 is H or any alkyl or alkenyl group.
- R 3 can be optionally selected from the group consisting of -(CH 2 CHR 5 -O-) n H and -(CH 2 CH 2 NH-) m H, wherein R 5 is H or methyl; n is an integer from about 5 to about 50; and m is an integer from 1 to about 5.
- Ammonium and phosphonium compounds are quaternary onium compounds.
- Examples of preferred cation moiety for the onium compounds include, but are not limited to, tetrapentylammonium, tripentylbutylammonium, triisopentylbutylammonium, tripentyldecylammonium, triisopentylammonium, tributyloctadecylammonium, tetrabutylphosphonium, tributyl(9-octadecenyl) phosphonium ions and mixtures thereof.
- examples of onium compounds include, but are not limited to, tributyldecylammonium, tributylundecylammonium, tributyldodecylammonium, tributyltridecylammonium, tributyltetradecylammonium, tributyl- pentadecylammonium, tributylhexadecylammonium, tributylheptade- cylammonium, tributyloctadecylammonium, tributylnonadecylammonium, tripentyldecylammonium, tripentylundecylammonium, tripentyldodecylammonium, tripentyltridecylammonium, tripentyltetradecylammonium, tripentylpentadecylammonium, trip
- Additional preferred “onium” compounds include the phosphonium compounds corresponding to above ammonium compounds. These "onium” compounds include, but are not limited to tributyldecylphosphonium, tributylundecylphosphonium, tributyldodecylphosphonium, tributyltridecylphosphonium, tributyltetradecylphosphonium, tributylpentadecylphosphonium, tributylhexadecylphosphonium, tributylheptadecylphosphonium, tributyloctadecylphosphonium, tribu- tylnonadecylphosphonium, tripentyldecylphosphonium, tripentylundecylphos- phonium, tripentyldodecylphosphonium, tripentyltridecylphosphonium, tripentyltetradecylphospho
- the onium compound may contain methyl groups, hydroxyl groups, ether groups or linkages, ester groups or linkages, and/or ketone groups.
- One advantage of such materials is that oxygen atoms in the chains, when present, can improve the biodegradability of the onium compounds.
- the "onium” compounds are named after the parent hydrocarbon and the replacement group(s) in the longest chain are then stated.
- tributyldodecylammonium where C5 is replaced with O.
- Suitable anionic compounds for use with these cationic LDHIs include, but are not necessarily limited to, alcohol sulfates that contain at least 4 carbon atoms; alcohol ether sulfates where the alcohol group contains at least 1 carbon atom and an ether linkage derived from at least one group consisting of ethylene oxide, propylene oxide, butylene oxide and styrene oxide; mono- or di-phosphate esters where the alcohol contains at least one carbon atom or contains an ether linkage derived from at least one group consisting of ethylene oxide, propylene oxide, butylene oxide and styrene oxide; sulfonic acids having at least 4 carbon atoms; phosphonic acids having at least 4 carbon atoms; carboxylic acids having at least 4 carbon atoms; taurates derived from a carboxylic acid having at least 1 carbon atom; and sarcosinates derived from carboxylic acids that contain at least 1 carbon atom; and forms of the anionic compounds as inorganic salts
- Non-ionic compounds suitable for use with these cationic LDHIs take in, but are not necessarily limited to, ethoxylated, propoxylated, and/or butoxylated alcohols, phenols, carboxylic acids and amines; sorbitan esters and ethoxylated, propoxylated, and/or butoxylated sorbitan esters; alkanolamine esters and/or amides.
- Acceptable amphoteric compounds betaines derived from amines that contain at least 3 carbon atoms; alkyldimethyl-3-sulfopropylammonium inner salts; and alkyldimethyl-2-hydroxy-3-sulfopropylammonium inner salts.
- Suitable amphoteric compounds contain both cationic and anionic components of course; in this case the cationic component may be contributed from a source such as a strong acid.
- the anion may be Cl ⁇ , Br ⁇ , in essence any of the anions useful for the onium compounds discussed supra at formula A.
- sodium dodecyl sulfate and ammonium alkyl ether sulfates are two more specific counter-ions found to be effective when used with cationic LDHIs.
- the operational active molar ratio range of first hydrate inhibitor component to second counter-ion component for this invention may be from about 100 to 1 to about 1 to 100. In another non-limiting embodiment, the range may be from about 100 to 10 to about 10 to 100. In an alternate non- restrictive embodiment, the range of the gas hydrate inhibiting ion to the counter ion may range from about 100 to 30 to about 30 to 100. In the context of this invention, molar ratios are close to weight ratios.
- the contacting of the ion pair with the mixture of hydrocarbon, water and hydrate-forming guest molecules may be achieved by a number of ways or techniques, including, but not necessarily limited to, mixing, blending with mechanical mixing equipment or devices, stationary mixing setup or equipment, magnetic mixing or other suitable methods, other equipment and means known to one skilled in the art and combinations thereof to provide adequate contact and/or dispersion of the composition in the mixture.
- the contacting can be made in-line or offline or both.
- the various components of the composition may be mixed prior to or during contact, or both. As discussed, if needed or desired, the composition or some of its components may be optionally removed or separated mechanically, chemically, or by other methods known to one skilled in the art, or by a combination of these methods after the hydrate formation conditions are no longer present.
- the pressure of the condition is usually at or greater than atmospheric pressure (i.e. greater than or equal to about 101 kPa), preferably greater than about 1 MPa, and more preferably greater than about 5 MPa.
- the pressure in certain formations or processing plants or units could be much higher, say greater than about 20 MPa.
- the present method can be used at any pressure that allows formation of hydrocarbon gas hydrates.
- the temperature of the condition for contacting is usually below, the same as, or not much higher than the ambient or room temperature. Lower temperatures tend to favor hydrate formation, thus requiring the treatment with the compositions of the present invention.
- the amount of the ion pair is less than 5 wt%, alternatively less than 2 wt%, and in another non-limiting embodiment is less than 1 wt%, but is limited only by what is economically feasible.
- the lower limit is about 0.005 wt%, and alternatively is about 0.01 wt% and possibly is about 0.02 wt%.
- the amount of ion pair may range from less than 5 wt% to 0.005 wt%, and in an alternate non-limiting embodiment may range from less than 2 wt% to about 0.02 wt%.
- the hydrocarbon inhibitor composition may further comprise other additional components, including, but not limited to, different controlling chemistries such as corrosion inhibitors, wax inhibitors, scale inhibitors, asphaltene inhibitors and other hydrate inhibitors and/or solvents.
- different controlling chemistries such as corrosion inhibitors, wax inhibitors, scale inhibitors, asphaltene inhibitors and other hydrate inhibitors and/or solvents.
- Suitable solvents include, but are not limited to water; at least one oxygenated compound selected from C C ⁇ alcohols, C 2 - C 6 glycols, C ⁇ -C 6 mono-aliphatic, preferably mono-alkyl, ethers of C 2 -C 6 glycol, glycerin, C C 6 mono-aliphatic, particularly mono-alkyl, ethers of glycerin, di-aliphatic, particularly dialkyl, ethers of glycerin, glycerin esters of d-C 6 carboxylate; tetrahydrofuran; N-methylpyrrolidone; sulfolane; C 3 -C 10 ketones, and mixtures thereof.
- oxygenated compound selected from C C ⁇ alcohols, C 2 - C 6 glycols, C ⁇ -C 6 mono-aliphatic, preferably mono-alkyl, ethers of C 2 -C 6 glycol, glycerin, C C 6 mono-aliphatic, particularly mono-alkyl
- acceptable solvents in one non-limiting embodiment of the invention include water and liquid oxygenated materials such as methanol, ethanol, propanol, glycols like ethylene glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol, glycerin, esters and ethers of glycerin, CELLOSOLVE ® (2-ethoxyethanol), CELLOSOLVE derivatives, 2- methoxyethanol, ethoxylated propylene glycols, ketones such as cyclohexanone and diisobutylketone, and mixtures thereof.
- water and liquid oxygenated materials such as methanol, ethanol, propanol, glycols like ethylene glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol, glycerin, esters and ethers of glycerin, CELLOSOLVE ® (2-ethoxyethanol), CELLOSOLVE derivatives, 2- methoxyethanol, ethoxylated
- the solvent is present in the total hydrocarbon hydrate inhibiting composition in the range of from 0 wt% to about 85 wt%, preferably from about 0 wt% to about 65 wt%, of the total composition, based on volume.
- CELLOSOLVE is a registered trademark of Union Carbide Corporation. Because some of the ion pairs disclosed herein will be solids under ambient conditions, it is often preferred to use a suitable solvent as described above in the composition. This allows the formation of a homogeneous or uni- form solution, suspension, emulsion or a combination of these, of all the components for easier mixing or distributing or dispersing the composition in the hydrocarbon/water fluid or system to be treated.
- the present invention also may be used in combination with other methods or processes, which have been known to one skilled in the art as discussed in the background to help inhibit formation of hydrates.
- Experimental Set-up All testing is isochoric. This results in the cell pressure dropping as the cell temperature is ramped or dropped from 72°F to 40°F (22°C to 4°C). The starting pressure is about 1500 psig (10.3 MPa), the final cell pressure at 40°F (4°C), before hydrate formation, varies, and is dependent on the test fluids (composition, liquid hydrocarbon ratio, etc.) employed.
- the cell pressure drops to the 1200 to 1300 psig range (8.3 to 9.0 MPa) before hydrate formation.
- Testing is performed with a bank of modified sight flow indicators, which serve as pressure vessel reactors. Each reactor or cell is isolated from its companions, and is independently pressurized and contains its own, independent pressure transducer. Up to six reactors constitute a bank of test cells. A test is performed by immersing a bank of test cells in a common temperature controlled water bath. Depending upon the experimental protocol, the water bath (and therefore the cells within) is gently rocked and/or held stationary at time intervals. Stationary intervals are designed to mimic pipeline shut-ins. Other important procedural features include:
- the bath water temperature and each pressure transducer are independently monitored and the data preserved by a computerized data acquisition system.
- Each cell contains stainless steel ball(s) that provide agitation of the cell's contents when the water bath is rocked.
- test bank 3. Often, one cell in every test bank is a control, containing either a reference inhibitor or none at all.
- Tests employ either the shock cool method wherein the cells are placed in pre-chilled water or are ramp cooled from near room temperature to some target low temperature.
- Each cell has a window for visual observations.
- sodium dodecylsulfate is combined with the quaternary amine HI-M-PACT TM 4394 LDHI,_having at least one appendage containing less than six carbon atoms and at least one appendage having more than six carbon atoms.
- the resulting ion pair has been shown to perform at active (dosage) levels equal to, if not less than the active (dosage) level of HI-M-PACT 4394 LDHI by itself.
- active (dosage) levels equal to, if not less than the active (dosage) level of HI-M-PACT 4394 LDHI by itself.
- the effective quaternary amine dosage is reduced from 0.59 wt% to 0.30 wt% active with the addition of as little as 0.04 wt% SDS, as tested with a Gulf of Mexico (GOM) condensate.
- the dosage level can be reduced to nearly half that normally or usually employed. This result reduces the amount of the quaternary amine required to control hydrates in the target matrix.
- an alcohol ether sulfate is added to HI-M-PACT 4394 LDHI with results parallel to those with SDS.
- the effective quaternary amine dosage is reduced from 0.75 wt% to 0.15 wt% with the addition of 0.12 wt% of the AES as tested with a GOM condensate.
- Both the AES and SDS are known to have little or no independent hydrate inhibiting ability.
- DBSA dodecylbenzenesulfonic acid
- RE 4907 contains a small quaternary amine with appendages containing less than six carbon atoms.
- the resulting quaternary amine-DDBSA ion pair is shown to perform as an AA.
- RE 4907 nor DDBSA demonstrate any applicable AA activity individually.
- LDHI and counter-ions may be different from those explicitly mentioned herein.
- Various combinations of ion pairs other than those described here are also expected to find use in providing improved hydrate inhibitors. Further, combinations of ion pairs with mixtures of water, hydrocarbons and hydrate-forming guest molecules different from those exemplified herein would be expected to be successful within the context of this invention.
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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CA002565880A CA2565880A1 (en) | 2004-05-18 | 2005-05-18 | Enhancement modifiers for gas hydrate inhibitors |
BRPI0510589-7A BRPI0510589A (en) | 2004-05-18 | 2005-05-18 | method for inhibiting hydrocarbon formation in a mixture comprising water and hydrate formation host molecules and inhibited hydrocarbon mixture against hydrocarbon formation in the presence of water |
EP05749566A EP1766183A1 (en) | 2004-05-18 | 2005-05-18 | Enhancement modifiers for gas hydrate inhibitors |
AU2005248369A AU2005248369A1 (en) | 2004-05-18 | 2005-05-18 | Enhancement modifiers for gas hydrate inhibitors |
NO20065358A NO20065358L (en) | 2004-05-18 | 2006-11-22 | Methods and Modifiers for Gas Hydrate Inhibitors |
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US57202204P | 2004-05-18 | 2004-05-18 | |
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US11/129,799 | 2005-05-16 | ||
US11/129,799 US20050261529A1 (en) | 2004-05-18 | 2005-05-16 | Enhancement modifiers for gas hydrate inhibitors |
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EP (1) | EP1766183A1 (en) |
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CA (1) | CA2565880A1 (en) |
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US11332657B2 (en) * | 2019-05-23 | 2022-05-17 | Halliburton Energy Services, Inc. | Dual cation hydrate inhibitors |
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- 2005-05-18 WO PCT/US2005/017251 patent/WO2005116399A1/en active Application Filing
- 2005-05-18 BR BRPI0510589-7A patent/BRPI0510589A/en not_active IP Right Cessation
- 2005-05-18 AU AU2005248369A patent/AU2005248369A1/en not_active Abandoned
- 2005-05-18 EP EP05749566A patent/EP1766183A1/en not_active Withdrawn
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Also Published As
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US20050261529A1 (en) | 2005-11-24 |
EP1766183A1 (en) | 2007-03-28 |
NO20065358L (en) | 2006-12-08 |
CA2565880A1 (en) | 2005-12-08 |
BRPI0510589A (en) | 2007-11-20 |
AU2005248369A1 (en) | 2005-12-08 |
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