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    • 专利摘要:
    This description refers to low-dose anti-caking hydrate inhibitors that can inhibit the formation of agglomerates and / or hydrate buffers. Anti-caking low-dose hydrate inhibitors can be surfactants. Hydrate inhibitors can be used to inhibit, delay, mitigate, reduce, control and / or delay the formation of hydrocarbon hydrates, hydrate binders and / or buffers. Hydrate inhibitors can be applied to prevent, reduce and or mitigate the obstruction of ducts, tubes, transfer lines, valves and other places or equipment where hydrocarbon solids can form. Hydrate inhibitors can be zwitterionic or cationic ammonia surfactants.
    公开号:BR112017008861B1
    申请号:R112017008861-4
    申请日:2015-10-30
    公开日:2021-01-26
    发明作者:Rebecca Michele Lucente-Schultz；Jeff Servesko
    申请人:Ecolab Usa Inc.；
    IPC主号:
    专利说明:

    CROSS REFERENCE WITH RELATED ORDER
    [01] This application claims the priority of U.S. Patent Application Series N ° 14 / 528,877 filed on October 30, 2014, the description of which is incorporated herein by reference in its entirety. FUNDAMENTALS 1. Field of the Invention
    [02] This description generally refers to compositions and methods for reducing or inhibiting the development, formation and / or agglomeration of hydrate particles in fluids. More specifically, the description refers to zwitterionic and cationic ammonium surfactants used to reduce or inhibit hydrate agglomeration in the production and transport of petroleum fluids, since a petroleum fluid is defined as a mixture of varying amounts of water / brine, crude / condensed oil and natural gas. 2. Description of the Related Art
    [03] Since Hammerschmidt discovered in 1934 that gaseous hydrates can block gas pipelines, research to prevent hydrate formation and agglomeration has become increasingly popular. Gas hydrates can be easily formed during the transportation of oil and gas in pipelines when appropriate conditions are present. Water content, low temperatures and high pressure are generally required for the formation of gas hydrates. The formation of gas hydrates often results in loss of oil production, pipeline damage and safety hazards for workers in the field. Modern oil and gas technologies commonly operate under severe conditions during the course of oil recovery and production, such as high pumping speed, high pipeline pressure, extended pipeline length and low oil and gas temperature flowing through the pipelines. These conditions are particularly favorable for the formation of gas hydrates, which can be particularly harmful for oil production on the high seas or for places with cold climates.
    [04] Gas hydrates are ice-solid that are formed of small non-polar molecules and water at low temperatures and increased pressures. Under these conditions, water molecules can form cage-like structures around these small non-polar molecules (typically dissolved gases, such as carbon dioxide, hydrogen sulfide, methane, ethane, propane, butane and isobutane), creating a type host-parasite interaction also known as clathrate or hydrate. The specific architecture of this cage structure can be one of several types (called type 1, type 2, type H), depending on the identity of the parasitic molecules. However, once formed, these crystalline cage structures tend to sediment from the solution and accumulate large solid masses that can travel through the oil and gas transport pipelines and potentially block or damage the pipelines and / or related equipment. The damage that results from a blockage can be very expensive from the point of view of repairing the equipment, as well as from the loss of production and, finally, the resulting environmental impact.
    [05] The industry uses several methods to avoid these blockages, such as thermodynamic hydrate inhibitors (THI), anti-caking hydrate inhibitors (AAs) and kinetic hydrate inhibitors (KHIs). The amount of chemical needed to prevent blockages varies widely depending on the type of inhibitor used. Thermodynamic hydrate inhibitors are substances that can reduce the temperature at which hydrates form at a given pressure and water content and are typically used in very high concentrations (regularly dosed as high as 50% based on water content - glycol is often used in amounts as high as 100% by weight of the water produced). Therefore, there is a substantial cost associated with transporting and storing large quantities of these solvents. A more cost-effective alternative is the use of low-dose hydrate inhibitors (LDHIs), when they generally require a dose less than about 2% to inhibit nucleation or the development of gas hydrates. There are two general types of LDHIs, kinetic hydrate inhibitors and anti-caking agents that are both used in much lower concentrations. KHIs work by delaying the development of gas hydrate crystals. These also function as anti-nucleators. In contrast, AAs allow hydrates to form but these prevent their accumulation and subsequent accumulation in large masses capable of causing clogging. The function of an AA is to keep the hydrate particles dispersed as a fluid slurry within the hydrocarbon phase. BRIEF SUMMARY
    [06] One aspect of the invention is a hydrate inhibitor composition that comprises an effective hydrate inhibitor amount of a compound of Formula (I) or an acid, a free base, a zwitterion or a salt thereof:
    wherein R1 is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C1 to C20 alkenyl group; R2 is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C1 to C20 alkenyl group, an alkylcarboxyl group or an alkyl starch; R4 and R5 are independently hydrogen, a substituted or unsubstituted alkyl group C1 to C20, a substituted or unsubstituted alkenyl group C1 to C20 or in which the nitrogen atom and groups R4 and R5 form a substituted or unsubstituted heterocycle group and R8 is a C2 to C10 substituted or unsubstituted alkylene group.
    [07] The present description also relates to anti-caking low-dose hydrate inhibitors that can inhibit the formation of pellets and / or hydrate buffers. In this way, a hydrate inhibitor composition can comprise at least one component selected from the group consisting of:

    [08] R1 is an alkyl group or an alkenyl group that can contain one or more ionizable heteroatoms or heteroatoms. R2 is present or not as hydrogen, depending on the ionization of the attached hydrogen atom. R3 comprises a group selected from the generic formula CnH2n + 1, where n is a number from 0 to 10. R4 is an alkyl group or an alkenyl group that may contain one or more ionizable heteroatoms or heteroatoms. R5 is selected from the group consisting of hydrogen, an alkyl group that can contain one or more ionizable heteroatoms or heteroatoms, an alkenyl group that can contain one or more ionizable heteroatoms or heteroatoms and any combination of these. B is a group selected from the generic formula (CH2) n, where n is a number from 1 to 4. A is a substituent selected from the group consisting of CH2, NR5, oxygen and any combination of these, and X is a counterion.
    [09] Another aspect is a method of inhibiting the formation of hydrate binders in a fluid comprising water, a gas and optionally liquid hydrocarbon is disclosed. The method may comprise the step of adding to the fluid an effective amount of a composition comprising hydrate inhibitor selected from the group consisting of:

    [10] R1 is an alkyl group or an alkenyl group that can contain one or more heteroatoms or ionizable heteroatoms. R2 is present or not as hydrogen, depending on the ionization of the attached hydrogen atom. R3 comprises a group selected from the generic formula CnH2n + 1, where n is a number from 0 to 10. R4 is an alkyl group or an alkenyl group that may contain one or more ionizable heteroatoms or heteroatoms. R5 is selected from the group consisting of hydrogen, an alkyl group that can contain one or more ionizable heteroatoms or heteroatoms, an alkenyl group that can contain one or more ionizable heteroatoms or heteroatoms and any combination of these. B is a group selected from the generic formula (CH2) n, where n is a number from 1 to 4. A is a substituent selected from the group consisting of CH2, NR5, oxygen and any combination of these, and X is a counterion.
    [11] The precedent summarized rather than expanded the technical features and advantages of the present description so that the detailed description that follows can be better understood. The additional features and advantages of the description will be described below forming the subject of the claims in this application. It should be appreciated by those skilled in the art that the specific design and modalities disclosed can easily be used as a basis for modifying or designing other modalities to accomplish the same purpose as the present description. It should also be realized by those skilled in the art that such equivalent modalities do not differ from the spirit and scope of the description as presented in the attached claims. DETAILED DESCRIPTION
    [12] The present description relates to anti-caking low-dose hydrate inhibitors that can inhibit the formation of pellets and / or hydrate buffers. Low-dose anti-caking hydrate inhibitors can be surfactants. In the following, these compounds (low-dose anti-caking / surfactant hydrate inhibitors) can be referred to as "hydrate inhibitors". In addition, when referring to a hydrate inhibitor in the present description, it is to be understood that the reference may refer to a hydrate inhibitor alone, a combination of two or more hydrate inhibitors or a composition comprising a or more of the inventive hydrate inhibitors disclosed herein. Also, when referring to a composition comprising a hydrate inhibitor, it is to be understood that the composition can comprise a simple hydrate inhibitor or a combination of two or more of the hydrate inhibitors presently disclosed.
    [13] Hydrate inhibitors can be used to inhibit, delay, mitigate, reduce, control and / or delay the formation of hydrocarbon hydrates, hydrate binders and / or buffers. Hydrate inhibitors can be applied to prevent, reduce and / or mitigate clogging of ducts, tubes, transfer lines, valves and other places or equipment where hydrocarbon solids can form.
    [14] Hydrate inhibitors can be zwitterionic compounds. These hydrate inhibitors can be used as low-dose hydrate inhibitors to inhibit the formation or agglomeration of natural gas hydrates.
    [15] Hydrate inhibitors can be cationic ammonium surfactants. These hydrate inhibitors can be used as low-dose hydrate inhibitors to inhibit the formation and / or agglomeration of natural gas hydrates, for example, which can lead to undesirable clogging in the oil industry if left untreated.
    [16] Hydrate inhibitors may also comprise a secondary ionizable amine, which is in contrast to known hydrate inhibitors, which may include tertiary, quaternary or non-ionized amines. A hydrate-phyl group may be in proximity to the amide bond, which is still described and represented below.
    [17] The currently disclosed hydrate inhibitors may be kinetic hydrate inhibitors because, in some aspects, they can act to delay hydrate formation in addition to controlling clumping.
    [18] Referring to the compounds of Formula 1, the compounds can generally be prepared according to Schemes 1A and 1B:
    wherein R2, R4, and R5 are as defined for the Formula 1 compound described herein. As known to a person of ordinary skill in the art, Schemes 1A and 1B can be altered to prepare compounds having a longer carbon chain linker between the amine group and the carbonyl carbon of the amide group. The salts of these compounds can be prepared by combining the product with an acid, such as a hydrogen halide, a carboxylic acid, sulfuric acid, phosphoric acid, nitric acid or a combination of these.
    [19] The synthesis of specific hydrate inhibitors is detailed below. As mentioned above, the synthesis can only be adapted so that the hydrophilic group of the inhibitor is in close proximity to the amide bond of the inhibitor. For example, oleylamine can be reacted with methyl acrylate. The reaction product can be mixed with pyrrolidine to form an amide, which can then be treated with methanol and acetic acid, for example, to form the hydrate inhibitor.
    [20] Hydrate inhibitors can be synthesized according to the following general procedures:
    Figure caption: oleyl - heat - acetic acid.
    [21] For example, the above synthesis can be performed using the following specific reagents as illustrative examples:

    [22] released can be synthesized according to the following procedure:

    [23] However, it should be noted that there may be other chemical reactions that can be used to synthesize the currently disclosed inhibitors and hydrates and, therefore, methods of making the presently disclosed hydrate inhibitors are not limited to the specific steps described above. All of the foregoing "R" groups are defined below in connection with the general debate regarding the basic structure of hydrate inhibitors.
    [24] One aspect of the invention is a hydrate inhibitor composition that comprises an effective hydrate inhibitor amount of a compound of Formula (I) or an acid, a free base, a zwitterion or a salt thereof:
    wherein R1 is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C1 to C20 alkenyl group; R2 is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C1 to C20 alkenyl group, an alkylcarboxyl group or an alkyl starch; R4 and R5 are independently hydrogen, a substituted or unsubstituted alkyl group C1 to C20, a substituted or unsubstituted alkenyl group C1 to C20 or in which the nitrogen atom and the groups R4 and R5 form a substituted or unsubstituted heterocycle group and R8 is a C2 to C10 substituted or unsubstituted alkylene group.
    [25] The substituted alkyl group of R1, R2, R4, and R5 may have at least one of the -CH2- groups in the chain substituted by an ether, an amine, an amide, a carbonyl or a functional ester group or may have at least one of the hydrogen atoms attached to a carbon atom of the chain to be replaced with a hydroxy group, a halo or an amine.
    [26] The substituted alkyl group of R1, R2, R4, and R5 may also have one of the -CH2- groups on the chain substituted by an amine.
    [27] The compound of Formula 1 can have R8 being -C2H4-.
    [28] In addition, the compound of Formula 1 can have R1 being C10 to C20 alkyl or -R10-NR6R7, where R10 is C1 to C5 alkylene and R6 and R7 are independently substituted or unsubstituted C1 to C6 alkyl.
    [29] In addition, the compound of Formula 1, R2 can be -R20-C (O) O-, where R20 is C1 to C4 alkylene.
    [30] For the Formula 1 compound, R4 can be hydrogen.
    [31] For the compound of Formula 1, R5 can be C10 to C20 alkyl or -R50-NR6R7, R50 can C1 to C5 alkylene and R6 and R7 can independently be C1 to C6 alkyl.
    [32] Additionally, the compounds of Formula 1 can have R20 being -C2H4-, and R50 being -C3H6-.
    [33] The Formula 1 compound can have the following structures:

    wherein R11 is C8 to C20 alkyl and R12 and R13 are independently C1 to C6 alkyl.
    [34] Preferably, R11 is C12 to C20 unsubstituted alkyl and R12 and R13 are independently C1 to C4 unsubstituted alkyl.
    [35] In addition, the Formula 1 compound can be:

    [36] When the Formula 1 compound is in its salt form, the counterion can be selected from the group consisting of a halide, a carboxylate, hydrogen sulfate, dihydrogen phosphate, nitrate and a combination of these. Preferably, a counterion can be an acetate, an acrylate or a combination of these.
    [37] The hydrate inhibitor can comprise one of the following generic cationic chemical structures:

    [38] R1 can be any alkyl or alkenyl group that can contain one or more ionizable heteroatoms or heteroatoms. R1 can comprise any group having from about 8 carbon atoms to about 20 carbon atoms, for example, a C8 to C20 group. For example, R1 can comprise a C8 to C12 group, a C12 to C16 group or a C16 to C20 group. Preferably, R1 can comprise a C8 group, a C10 group, a C18 group or a C20 group.
    [39] For these cationic structures, R2 can comprise hydrogen (H) or no atom or group at all, depending on the ionization of the attached hydrogen atom.
    [40] These cationic structures may have R3 comprising a group selected from the generic formula CnH2n + 1, where "n" is a number from 0 to 10. For these compounds, "n" can be 0 or 1.
    [41] Cationic structures can have R4 being any alkyl or alkenyl group that can contain one or more ionizable heteroatoms or heteroatoms and R5 can be H, any alkyl group that can contain one or more ionizable heteroatoms or heteroatoms or any alkenyl group that can contain one or more heteroatoms or ionizable heteroatoms. B comprises a group selected from the generic formula (CH2) n, where "n" is a number from 1 to 4. One comprises a substituent selected from CH2, NR5 or oxygen (O) and X can comprise any counterion, such as a halide, any carboxylate, hydrogen sulfate, dihydrogen phosphate or nitrate. Non-limiting examples include acetate and acrylate.
    [42] For these cationic structures, the term "alkenyl" refers to a monovalent group derived from a straight, branched or cyclic hydrocarbon containing at least one carbon-carbon double bond by removing a single hydrogen atom from each of the two adjacent carbon atoms of an alkyl group. Representative alkenyl groups include, for example, ethylene, propenyl, oleyl, butenyl, 1-methyl-2-buten-1-yl and the like.
    [43] For these cationic structures, the term "alkyl" refers to a monovalent group derived by the removal of a simple hydrogen atom from a straight or branched cyclic saturated or unsaturated hydrocarbon. Representative alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, lauryl and the like.
    [44] In addition to the generic cationic structures described in the preceding paragraph, the following are additional compositions that have been synthesized and are intended to be covered under the scope of the currently disclosed hydrate inhibitors: Table 1.

    [45] In connection with the specific compounds listed in Table 1 above and the generic structures described above, R3 was selected to be hydrogen and "A" was selected to be CH2. Although the generic structure above only lists “B” as two of the substituents and Table 1 lists “B1” and “B2”, the generic structure is intended to cover where the substituent “B1” is located in each of the positions of the group “B ”And the substitute“ B2 ”is located in each of the positions of group“ B ”.
    [46] Specifically, the hydrate inhibitor comprises the following general structure:
    where "Rgraxo" is any alkyl group having from about 8 carbon atoms to about 20 carbon atoms, for example, a C8 to C20 group. For example, Rgraxo may comprise a C8 to C12 group, a C12 to C16 group or a C16 to C20 group. For this structure, Rgraxo comprises a C8 group, a C10 group, a C12 group, a C18 group or a C20 group.
    [47] In addition, the hydrate inhibitor comprises the following general structure:
    where "Rgraxo" is any alkyl group having from about 8 carbon atoms to about 20 carbon atoms, for example, a C8 to C20 group. For example, Rgraxo may comprise a C8 to C12 group, a C12 to C16 group or a C16 to C20 group. In addition, Rgraxo comprises a C8 group, a C10 group, a C18 group or a C20 group.
    [48] With respect to the term "hydrate-phyllic" used in the present description when describing a certain portion of the hydrate inhibitor molecule, the portion of the molecule being referred to as the hydrate-phyllic portion is, with respect to the specific composition shown above, the portion opposite the Rgraxo group. That is, in the example above, the portion including the tertiary N atom and the two butyl groups.
    [49] In particular, the hydrate inhibitor comprises the following general structure:

    [50] With respect to prior art anti-caking inhibitors, the hydrophilic portion of the inhibitor molecule is also the portion of the molecule that comprises the charge and the amide comprised of the fatty end, which was considered necessary for anti-caking functionality. binder. However, the present inventors have discovered a highly functional hydrate inhibitor that comprises the fatty end on the non-traditional side of the molecule (the opposite side of the amide, where the amide does not comprise the fatty end) instead of forming a secondary amine that also serves as the place for salting. In the prior art, the positive charge has always been centered around a quaternary or tertiary amine but not a secondary amine as in the hydrate inhibitors presently disclosed.
    [51] The compositions disclosed here, which comprise one or more hydrate inhibitors, may still comprise one or more additional chemicals. The composition may further comprise at least one additional hydrate inhibitor. Exemplary additional hydrate inhibitors are disclosed in US Patent Application No. 12 / 253,504, filed on October 17, 2008, 12 / 253,529, filed on October 17, 2008, 12 / 400,428, filed on March 9, 2008 2009 and 12 / 967,811, filed on December 16, 2008, the disclosures of which are incorporated in this application in their entirety.
    [52] The composition comprising the hydrate inhibitor can further comprise one or more thermodynamic hydrate inhibitors, one or more kinetic hydrate inhibitors, one or more anti-caking agents or any combination thereof.
    [53] The composition may further comprise one or more asphaltene inhibitors, paraffin inhibitors, corrosion inhibitors, scale inhibitors, emulsifiers, water clarifiers, dispersants, emulsion breakers or any combination thereof.
    [54] Additionally, the composition further comprises one or more polar or non-polar solvents or a mixture of these. Preferably, the composition further comprises one or more solvents selected from the group consisting of isopropanol, methanol, ethanol, 2-ethylhexanol, heavy aromatic naphtha, toluene, ethylene glycol, ethylene glycol monobutyl ether (EGMBE), diethylene monoethyl ether glycol, xylene or any combination thereof.
    [55] The composition comprising the hydrate inhibitor can be introduced into the fluid by suitable means to ensure dispersion of the hydrate inhibitor through the fluid being treated. Typically, the composition comprising the hydrate inhibitor is injected using mechanical equipment, such as mechanical equipment, such as chemical injection pumps, T-pipes, injection settings and the like. The composition comprising the hydrate inhibitor can be injected as prepared or formulated in one or more additional polar or non-polar solvents, depending on the application and requirements.
    [56] Representative polar solvents suitable for formulation with the hydrate inhibitor composition include, brine, seawater, alcohols (including straight or branched aliphatic, such as methanol, ethanol, propanol, isopropanol, butanol, 2- ethylhexanol, hexanol, octanol, decanol, 2-butoxyethanol, etc.), glycols and derivatives (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, ethylene glycol monobutyl ether, etc.), ketones (cyclohexanone, diisobutyl ketone), N-methylpyrrolidinone (NMP), N, N-dimethylformamide and the like.
    [57] Representative non-polar solvents suitable for formulation with the hydrate inhibitor composition include aliphatics, such as, pentane, hexane, cyclohexane, methylcyclohexane, heptane, decane, dodecane, diesel and the like and aromatics, such such as toluene, xylene, heavy aromatic naphtha, fatty acid derivatives (acids, esters, amides) and the like.
    [58] The composition comprising the hydrate inhibitor can be used in a method of inhibiting the formation of hydrate binders in an aqueous medium comprising water, gas and optionally liquid hydrocarbon. The method comprises adding to the aqueous medium an effective amount of the composition comprising one or more hydrate inhibitors.
    [59] The compositions and methods of this description are effective in controlling the formation of gaseous hydrates and clogging during the production and transport of hydrocarbons. Specifically, the hydrate inhibitor can be injected before substantial hydrate formation. An exemplary injection point for oil production operations is a bore below the surface-controlled submerged safety valve. This ensures that during a closure, the product is able to disperse throughout the area where the hydrates will occur. Treatment can also take place in other areas or in the flow line, taking into account the density of the injected fluid. If the injection point is well above the depth of hydrate formation, then the hydrate inhibitor can be formulated with a solvent having a high enough high density that the inhibitor will sink into the flow line for collection at the water / oil interface. In addition, the treatment can also be used in pipelines or anywhere in the system where the potential for hydrate formation exists.
    [60] In addition, the composition comprising the hydrate inhibitor can be applied to an aqueous medium containing varying levels of salinity. The fluid can have a salinity of about 0% to about 25% or about 10% to about 25% total weight / weight (w / w) of dissolved solids (TDS). The aqueous medium in which the disclosed compositions are applied can be contained in many different types of mechanisms, especially those that transport an aqueous medium from one location to another.
    [61] The aqueous medium may be contained in an oil and gas pipeline. In addition, the aqueous medium can be contained in refineries, such as separation vessels, dewatering units, gas lines and pipelines.
    [62] In addition, the currently disclosed hydrate inhibitors may function as corrosion inhibitors useful for inhibiting corrosion of any surface that they may contact, such as surfaces found in refineries, such as separation vessels, dewatering units, lines gas and oil pipelines.
    [63] Hydrate inhibitors may also have antimicrobial properties in refineries, such as separation vessels, dewatering units, gas lines and pipelines.
    [64] The composition comprising the hydrate inhibitor can be applied to an aqueous medium that contains various levels of water cut. A person of ordinary skill in the art understands that "water cut" refers to the% water in a composition containing a mixture of oil and water. In particular, the water cut-off of the aqueous medium can be from about 1% to about 80% w / w based on the total weight of the aqueous medium comprising water, gas and optionally liquid hydrocarbon.
    [65] The compositions of the present description can be applied to an aqueous medium using several well-known methods and these can be applied in numerous different locations throughout a given system. The composition comprising the hydrate inhibitor can be pumped into an oil / gas pipeline using an umbilical line. In addition, capillary series injection systems can be used to release the composition. U.S. Patent No. 7,311,144 provides a description of a mechanism and methods with respect to capillary injection, the description of which is incorporated in the present application in its entirety.
    [66] Various dosage amounts of the composition and / or the hydrate inhibitor (s) can be applied to the aqueous medium to inhibit the formation of hydrate binders. A person skilled in the art will be able to calculate the amount of hydrate inhibitor or composition comprising a hydrate inhibitor for a given situation without undue experimentation. Factors that should be considered of importance in such calculations include, for example, the content of aqueous medium, percentage of water cut, gravity of hydrocarbon API and test gas composition. In addition, the hydrate inhibitor (s) is added in an amount of about 0.1 to about 5% by volume, based on the water cut.
    [67] A method of inhibiting the formulation of hydrate binders in a fluid comprising water, a gas and optionally a liquid hydrocarbon, which comprises contacting the fluid with an effective amount of a hydrate inhibitor composition as described herein.
    [68] The fluid can be contained in an oil pipeline, a gas pipeline or a refinery.
    [69] The composition can be added to the hole below near the surface controlled underwater safety valve.
    [70] When the nitrogen atom and R4 and R5 form a heterocycle group, the group can be considered a "nitrogen-containing heterocycle" which may indicate aromatic or non-aromatic monocyclic or bicyclic groups that are fully saturated or optionally substituted having at least one atom of nitrogen in at least one ring and preferably 5 or 6 atoms in each ring. The nitrogen-containing heterocycle can also contain 1 or 2 oxygen atoms or 1 or 2 sulfur atoms in the ring. Exemplary nitrogen-containing heterocycles include pyrrole, pyrroline, pyrrolidine, piperidine, pyrazole, pyrazoline, pyrazolidine, imidazole, imidazoline, imidazolidine, triazole, isoxazole, isoxazoline, isoxazolidine, oxazole, oxazoline, oxazolidine, oxazolidine, oxazolidine, oxazole, oxazole, oxazole, oxazol, oxatiazol, pyridine, pyridazine, pyrimidine, pyrazine, piperazine, triazine, oxazine, oxathiazine, oxazine, isoxazine, oxadiazine, morpholine, olive oil, azepine, caprolactam or quinoline. When the substituted exemplary substituents include one or more of the following groups: substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, keto, hydroxy, protected hydroxy, acyl, acyloxy, alkoxy, alkenoxy, alkoxy, aryloxy, halogen, starch, amino, nitro, cyano, thiol, ketals, acetals, esters and ethers.
    [71] Unless otherwise indicated, an alkyl group as described herein alone or as part of another group is an optionally substituted linear saturated monovalent hydrocarbon substituent containing from one to thirty carbon atoms in the main chain or a substituent of optionally substituted branched saturated monovalent hydrocarbon containing from three to sixty carbon atoms, and preferably from one to twenty carbon atoms in the main chain. Examples of unsubstituted alkyl include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, s-pentyl, t-pentyl and the like.
    [72] Unless otherwise indicated, the alkenyl groups described herein are preferably lower alkenyl containing two to thirty carbon atoms in the main chain and up to 60 carbon atoms. These can be straight or branched or cyclic and include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, hexenyl and the like.
    [73] The terms "aryl" or "air" as used here or as part of another clip (for example, aralkyl) indicate optionally substituted homocyclic aromatic groups, preferably monocyclic or bicyclic groups containing 6 to 12 carbons in the ring portion , such as phenyl, biphenyl, naphthyl, substituted phenyl, substituted biphenyl or substituted naphthyl. Phenyl and substituted phenyl are the most preferred aryl. The term "aryl" also includes heteroaryl.
    [74] The term "-eno" as used as a suffix as part of another group indicates a divalent substituent in which a hydrogen atom is removed from each of the two terminal carbons in the group or if the group is cyclic, from each one of the two different carbon atoms in the ring. For example, alkylene indicates a divalent alkyl group, such as methylene (-CH2-) or ethylene (-CH2CH2-) and arylene indicates a divalent aryl group, such as o-phenylene, m-phenylene or p-phenylene.
    [75] The term "substituted" as in "substituted aryl", "substituted alkyl" and others, means that in the group in question (that is, the alkyl, aryl or other group that follows the term), at least one atom of hydrogen attached to a carbon atom is replaced by one or more substituent groups, such as hydroxy (-OH), alkylthio, phosphine, starch (- CON (RA) (RB), where RA and RB are independently hydrogen, alkyl or aryl), amino (-N (RA) (RB), where RA and RB are independently hydrogen, alkyl or aryl), halo (fluorine, chlorine, bromine or iodine), silyl, nitro (-NO2), an ether (-ORA where RA is alkyl or aryl), an ester (-OC (O) RA where RA is alkyl or aryl), keto (-C (O) RA where RA is alkyl or aryl), heterocycle and the like . In addition, an alkylene group in the chain can be replaced by an ether, an amine, an amide, a carbonyl, an ester, a cycloalkyl or a heterocycle functional group. When the term "substituted" introduces a list of possible substituted groups, it is intended that the term applies to each member of that group. That is, the phrase "optionally substituted alkyl or aryl" should be interpreted as "optionally substituted alkyl or optionally substituted aryl".
    [76] "Arylalkyl" means an aryl group attached to the parent molecule through an alkylene group. The number of carbon atoms in the carbonyl group and the alkylene group is selected such that there is a total of about 6 to about 18 carbon atoms in the arylalkyl group. A preferred arylalkyl group is benzyl.
    [77] "Inhibit" includes both inhibiting and preventing the formation and agglomeration of hydrate crystals.
    [78] Unless otherwise indicated, "AA" means anti-caking agent; "IPA" means isopropanol (isopropyl alcohol); "KHI" means kinetic hydrate inhibitor; "LDHI" means low dose hydrate inhibitor; "MeOH" means methanol; "NaCl" means sodium chloride; "PE" means pentaerythritol and "THI" means thermodynamic hydrate inhibitor. EXAMPLES
    [79] To assess the performance of the currently disclosed hydrate inhibitors and show their superior properties as hydrate inhibitors, a shaking cell test was used. The shaking cell test is a test commonly used in the art to estimate the performance of anti-caking chemicals. Briefly, the chemicals are evaluated based on their availability to effectively minimize the particle size of hydrate binder and then disperse those particles in the hydrocarbon phase. Chemical performance is assessed by determining the minimum effective dose (MED) required to register as "approved" in the shaking cell test.
    [80] The cell in agitation generally includes individual cells and a shelf on which the cells are placed. The cells can comprise sapphire tubes containing a stainless steel sphere and can withstand pressures up to about 5,000 psi. Once the cells are mounted on the shelf, the shelf shakes up and down slowly, at a rate of about 1 full cycle (up and down) per minute. The shelf is still contained within a temperature-controlled bath connected to a cooler.
    [81] Anti-caking test cells generally contain three components: hydrocarbon, aqueous phase and gas. In these examples, the inventors injected a synthetic brine of about 10.3% salinity into each cell followed by a particular make the hydrate inhibitor. In the experiments, the hydrate inhibitor was dosed according to the amount of aqueous phase in the test cell. The last component added to each cell was heated crude oil. The initial temperature for the test was about 80 ° F (26.67 ° C) and at that temperature, the cells are charged with a mixture of synthetic natural gas (SNG) at about 2,500 psi. The test is a constant pressure where the cells are often opened to an intensifier that intensifies the additional gas in the cells when the gas is solubilized in the fluids and / or forms hydrates. The cells were shaken for about 0.5 hours to equilibrate and mix before stopping in a horizontal position and cooling to about 40 ° F (4.44 ° C) for an 8 hour period. After a closing time of about 48 hours at temperature, the cells were shaken again for one hour and visual observations were recorded. Table 2 below shows the results of some of the shaking cell tests. Table 2
    [82] Examples 1, 2, 16, 4 and 8 correspond to Examples 1, 2, 16, 4, and 8 in Table 1. The comparative examples were as follows:


    [83] The hydrate inhibitors presently disclosed can be synthesized according to any of the methods known in the art. As an illustrative example, hydrate inhibitors can be synthesized as follows:

    [84] To a 3-neck round-bottom flask, about 100.0 g (0.374 mol) of oleylamine and a magnetic stir bar were added. The flask was fitted with a thermo-connection, reflux condenser and addition funnel containing about 32.18 g (0.374 mol) of methyl acrylate. Acrylate was added to the amine while stirring slowly. Once the addition was complete, the mixture was stirred for about 1 hour. LC-MS and FT-IR confirmed the total conversion of the starting materials.
    [85] About 26.59 g (0.374 mol) of pyrrolidine and catalytic para-toluenesulfonic acid (about 0.79 g) were added to the resulting yellow liquid. An isolated Dean-Stark mechanism was connected between the round-bottom flask and the reflux condenser to remove methanol. The reaction mixture was heated to about 90 ° C for about 12 hours, at which time the FT-IR analysis confirmed the disappearance of the ester. Upon cooling to room temperature, a yellow-orange liquid was formed. To the resulting amide at room temperature, about 97.39 g of methanol and then about 19.36 g (0.322 mol) of acetic acid were added and the mixture was stirred at room temperature for about 2 hours to produce the hydrate inhibitor. .
    [86] As an illustrative example, zwitterionic hydrate inhibitors can be synthesized as follows:

    [87] To a 3-neck round-bottom flask, about 100.0 g (0.523 mol) cocoamine and a magnetic stir bar were added. The flask was fitted with a thermo-connection, reflux condenser and an addition funnel containing about 45.06 g (0.523 mol) of methyl acrylate. Acrylate was slowly added to the amine while stirring at room temperature. Once the addition was complete, the mixture was stirred for about 1 hour. LC-MS and FT-IR confirmed the total converted of the starting materials.
    [88] To the resulting yellow liquid, about 97.53 g (0.523 mol) of dibutylaminopropylamine was added. An isolated Dean-Stark mechanism was connected between the round-bottom flask and reflux condenser to remove methanol. The reaction mixture was heated at 165 ° C for about 6 hours, during which time the FT-IR analysis confirmed the disappearance of the ester. Upon cooling to room temperature, a yellowish white solid was formed. After melting the yellowish white amide solid at 40 ° C in a water bath, about 100.0 g (0.232 mol) was loaded into a 3-neck round bottom flask and equipped with an overhead stirrer with a stirring, thermolinking and an addition funnel containing about 16.72 g of acrylic acid. Acrylic acid was slowly added to the amide while stirring at room temperature and then heated to 90 ° C for about 6 hours to produce Michael's addition product, a syrupy orange liquid. After cooling to room temperature, about 25.0 g (0.050 mol) of the resulting betaine product was combined with about 23.87 g of methanol to form a homogeneous liquid solution.
    [89] To assess the performance of the currently disclosed hydrate inhibitors and their properties as hydrate inhibitors, a shaking cell test was used. The shaking cell test is a test commonly used in the art to estimate the performance of anti-caking chemicals. Briefly, the chemicals are evaluated based on their ability to effectively minimize the particle size of hydrate binder and then disperse those particles in the hydrocarbon phase. Chemical performance is assessed by determining the minimum effective dose (MED) required to register as an “approved” in the shaking cell test.
    [90] The shaking cell usually includes individual cells and a shelf on which the cells are placed. The cells can comprise sapphire tubes containing a stainless steel sphere and can withstand pressures up to about 5,000 psi. Once the cells are mounted on the shelf, the shelf shakes up and down slowly, at a rate of about 1 full cycle (up and down) per minute. the shelf is still contained within a temperature-controlled bath connected to a cooler.
    [91] Anti-caking test cells generally contain three components: hydrocarbon, aqueous phase and gas. In these examples, the inventors injected a synthetic brine of about 10.3% salinity into each cell followed by a particular make the hydrate inhibitor. In the experiments, the hydrate inhibitor was dosed according to the amount of aqueous phase in the test cell. The last component added to each cell was heated crude oil. The initial temperature for the test was about 80 ° F (26.67 ° C) and at that temperature, the cells are charged with a mixture of synthetic natural gas (SNG) at about 2,500 psi. The test is a constant pressure where the cells are often opened to an intensifier that intensifies the additional gas in the cells when the gas is solubilized in the fluids and / or forms hydrates. The cells were shaken for about 0.5 hours to equilibrate and mix before stopping in a horizontal position and cooling to about 40 ° F (4.44 ° C) for an 8 hour period. After a closing time of about 48 hours at temperature, the cells were shaken again for one hour and visual observations were recorded. The tests performed using Oil D were carried out in an autoclave.
    [92] The hydrate inhibitor of Example 17 has the structure of:

    [93] The hydrate inhibitor of Example 18 has the structure of:

    [94] The anti-caking agents traditionally used were used to compare the performance of the compounds described in this. The comparative anti-caking agents used were commercially designed as C, D, E and F.
    [95] Table 3 below shows the results of some of the shaking cell tests. Table 3.

    [96] All compositions and methods disclosed and claimed herein can be made and performed without undue experimentation in the light of the present description. While this invention can be embodied in a different form, they are described in detail in the specific preferred embodiments of the invention. The present description is an example of the principles of the invention and is not intended to limit the invention to the particular embodiments illustrated. In addition, unless expressly stated to the contrary, the use of the term "one" is intended to include "at least one" or "one or more". For example, "a device" is intended to include "at least one device" or "one or more devices"
    [97] Any ranges given in absolute or approximate terms are intended to cover both and any definitions used here are intended to be illuminating and not limiting. Despite the numerical ranges and parameters presented, in the broad scope of the invention are approximations, the numerical values presented in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors that necessarily result from the standard deviation and its respective test measures. In addition, all ranges disclosed herein must be understood to cover any and all sub-ranges (including all fractional and total values) included in this.
    [98] In addition, the invention encompasses any and all possible combinations of some or all of the various compositions and methods described herein. It should also be understood that several changes and modifications to the presently preferred modalities described herein will be evident 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 intended advantages. Therefore, it is intended that such changes and modifications may be covered by the appended claims.
    权利要求:
    Claims (11)
    [0001]
    1. Hydrate-inhibiting composition, characterized by the fact that it comprises an effective hydrate-inhibiting amount of a compound of Formula (I), or an acid, a free base, a zwitterion, or a salt thereof:
    [0002]
    Composition according to claim 1, characterized in that the substituted alkyl group of R1, R2, R4 and R5 have at least one of the -CH2- groups in the chain substituted by an ether, an amine, a starch, a carbonyl or an ester functional group or at least one of the hydrogen atoms attached to a carbon atom in the chain is replaced by a hydroxy group, a halo or an amine.
    [0003]
    Composition according to claim 2, characterized in that the substituted alkyl group of R1, R2, R4 and R5 has at least one of the -CH2- groups in the chain substituted with an amine.
    [0004]
    Composition according to any one of Claims 1 to 3, characterized in that R8 is -C2H4-.
    [0005]
    Composition according to any one of Claims 1 to 4, characterized in that the symbol RI represents a C1-C20 or -R50-NR6R7 alkyl, wherein the symbol R10 represents a C1 to C5 alkylene and R6 and R7 represent each C1 to C6 alkyl independently substituted or unsubstituted.
    [0006]
    Composition according to any one of Claims 1 to 5, characterized in that R2 represents a group of general formula -R20-C (O) O-, where R20 represents a C1 to C4 alkylene group.
    [0007]
    Composition according to any one of claims 1 to 6, characterized by the fact that R4 is hydrogen.
    [0008]
    8. Composition according to claim 6 or 7, characterized by the fact that R20 is C2H4 and R50 is C3H6.
    [0009]
    Composition according to any one of claims 1 to 8, characterized by the fact that the compound of Formula 1 is
    [0010]
    10. Composition according to any one of claims 1 to 9, characterized in that, when the compound is in its salt form, the counterion is selected from the group consisting of a halide, a carboxylate, sulfate of hydrogen, dihydrogen phosphate, nitrate and a combination thereof.
    [0011]
    11. Method for inhibiting the formation of hydrate binders in a fluid comprising water, a gas and, optionally, a liquid hydrocarbon, characterized by the fact that it comprises contacting the fluid with an effective amount of a hydrate inhibiting composition as defined in any of claims 1 to 10.
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    同族专利:
    公开号 | 公开日
    AU2015339100A1|2017-05-18|
    WO2016069987A1|2016-05-06|
    BR112017008861A2|2017-12-19|
    US20160122619A1|2016-05-05|
    US20170335169A1|2017-11-23|
    BR112017008861B8|2021-03-23|
    AU2015339100B2|2020-08-06|
    US10435616B2|2019-10-08|
    US9765254B2|2017-09-19|
    SA517381415B1|2020-12-07|
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    法律状态:
    2019-09-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-11-24| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-01-26| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 30/10/2015, OBSERVADAS AS CONDICOES LEGAIS. |
    2021-03-23| B16C| Correction of notification of the grant [chapter 16.3 patent gazette]|Free format text: REF. RPI 2612 DE 26/01/2021 QUANTO AO TITULO. |
    2022-01-11| B25A| Requested transfer of rights approved|Owner name: CHAMPIONX USA INC. (US) |
    优先权:
    申请号 | 申请日 | 专利标题
    US14/528,877|US9765254B2|2014-10-30|2014-10-30|Cationic ammonium surfactants as low dosage hydrate inhibitors|
    US14/528,877|2014-10-30|
    PCT/US2015/058216|WO2016069987A1|2014-10-30|2015-10-30|Cationic ammonium surfactants as low dosage hydrate inhibitors|
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