ALKENYL SUCCINIMIDES AND THEIR USE AS NATURAL GAS HYDRATE INHIBITORS

Abstract

Succinimide-based compounds used in compositions and methods for inhibiting natural gas hydrate agglomerates are disclosed. These compounds are reaction products of an alkenylsuccinic anhydride and an amine or amine alcohol.

Description

ALKENYL SUCCINIMIDES AND THEIR USE AS NATURAL GAS HYDRATE INHIBITORS FIELD OF INVENTION The application is directed towards the inhibition or prevention of the formation of natural gas hydrate agglomerates. BACKGROUND OF THE INVENTION Natural gas hydrates is a term that refers to ice-like solids that form from dissolved gas and water molecules within liquid petroleum products (liquid hydrocarbons) when the liquid's temperature is decreased and / or the pressure on the liquid is increased. Under these conditions, water molecules can form cage-like structures around gas molecules such as carbon dioxide, hydrogen sulfide, methane, ethane, propane, butane, and isobutane, creating crystalline clathrate structures, also called clathrate gas hydrates. The specific architecture of a cage structure can be one of several types (called type 1, type 2, type H), depending on the identity of the host molecule(s). Once formed, these crystalline cage structures tend to precipitate and settle out of the liquid, accumulating into large solid masses. These masses form in petroleum liquids such as crude oil. Ref. 317335 obtained from an underground reservoir can travel in transport pipelines and potentially block or damage the pipelines, related equipment, or both. The resulting damage from a blockage can be costly because the equipment and pipelines need to be repaired, and crude oil production and the safety of field workers can be adversely affected. The recovery and production of petroleum liquids typically operate under high pumping rates and high pressures within processing and transport pipelines, conditions particularly favorable for the formation of natural gas hydrates. Additionally, climatic conditions in some field locations can cause a substantial drop in temperature during one or more production, transport, and storage operations carried out during and after the recovery of liquids from underground reservoirs. The industry uses a number of methods to prevent or reduce the formation of natural gas hydrates and their associated adverse effects. For example, natural gas hydrate inhibitors include thermodynamic gas hydrate inhibitors (THIs), anti-caking gas hydrate inhibitors (AAs), and gas hydrate inhibitors. Kinetic hydrocarbon inhibitors (KHIs) are substances that can lower the temperature at which gas hydrates form at a given pressure and water content. They are typically dosed at 50% based on the water content and as high as 100% of the water volume. Therefore, there is a substantial cost associated with transporting and storing large quantities of these inhibitors. A more cost-effective alternative is the use of low-dose gas hydrate inhibitors (LDHIs), which generally require a dose of less than approximately 2 percent by volume to inhibit gas hydrate nucleation or growth. The two general types of LDHIs, KHIs and anti-caking agents, are typically used at much lower concentrations. KHIs work by retarding the growth of gas hydrate crystals. They also act as antinuclear agents. In contrast, AAs allow natural gas hydrates to form but prevent them from agglomerating and subsequently accumulating into larger masses capable of causing blockages. AAs function to keep natural gas hydrate crystals and agglomerates dispersed as a thick suspension within the liquid hydrocarbon. While many inhibitors and dispersants have been developed to alleviate the effects of natural gas hydrates within liquid petroleum products, there remains a need for new and effective compositions and methods to prevent or reduce the formation of natural gas hydrate agglomerates. BRIEF DESCRIPTION OF THE INVENTION This document describes compositions and methods for inhibiting the formation of natural gas hydrate agglomerates in a fluid comprising water, gaseous molecules, and a liquid hydrocarbon. One aspect of the invention is a composition comprising at least one succinimide-based compound for inhibiting the formation of natural gas hydrate agglomerates, the at least one succinimide-based compound being formed by a reaction between an alkenylsuccinic anhydride and an amine or amine alcohol. Another aspect of the invention is a composition comprising: a fluid; and at least the succinimide-based compound is formed by a reaction between an alkenyl-succinic anhydride with an amine or amine alcohol. Yet another aspect of the invention is a method CZQtznn / l 7P7 / B / YILI for inhibiting the formation of natural gas hydrate agglomerates comprising: introducing into a fluid a composition comprising at least one succinimide-based compound to inhibit the formation of natural gas hydrate agglomerates, at least the succinimide-based compound being formed by a reaction between an alkenylsuccinic anhydride and an amine or amine alcohol. BRIEF DESCRIPTION OF THE FIGURES FIGURE 1 is a graphical representation of cell pressure as a function of run time for a formulation of an embodiment of the invention (whose title is: CELL 1: 55% WC: 3% DOSA-OBAPA of C12). FIGURE 2 is a graphical representation of cell pressure as a function of run time for a formulation of a modality of the invention (whose title is: CELL 4: 55% WC, 1% ASA OBAPA of C20). DETAILED DESCRIPTION OF THE INVENTION Although the present description provides references to several embodiments, persons skilled in the field will recognize that changes in form and detail can be made without departing from the spirit and scope of the invention. Several embodiments will be described in detail with reference to the figures. Reference to several embodiments does not limit the scope of the appended claims. czatznn / i ζπζ / β / υιλι Additionally, any example set forth in this specification is not intended to be limiting and merely sets forth some of the many possible embodiments of the appended claims. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by a person of ordinary experience in the field. In case of conflict, this document, including its definitions, shall prevail. Methods and materials are described below, although similar or equivalent methods and materials may be used in the practice or testing of the present invention. All publications, patent applications, patents, and other references mentioned herein are incorporated herein by reference in their entirety. As used in this document, the term alkyl refers to a monovalent group derived by the removal of a single hydrogen atom from a straight or branched chain or a cyclic saturated or unsaturated hydrocarbon containing from one to sixty carbon atoms. As used in this document, the term alkenyl refers to an unsaturated hydrocarbon containing at least one carbon-carbon double bond. CZQtznn / l 7Π7 / Β / YΙΛΙ As used in this document, the term anti-caking agent or AAI refers to a compound that inhibits the formation of natural gas hydrate agglomerates. The term shall be understood to refer to the AAI itself or to a composition which may include other AAIs or compounds or solvents, as determined by the context. As used in this document, the term fluid means liquid, gas molecules, or both in a crude oil or natural gas well production operation. As used in this document, the term inhibits, inhibits, or grammatical equivalents thereof refers to the prevention, delay, mitigation, reduction, control, and / or retardation of the formation of gas hydrates and / or gas hydrate agglomerates, and / or plugs in equipment / pipe formed from gas hydrate agglomerates. As used in this document, the terms natural gas hydrates or gas hydrates refer to a gaseous mixture in a water clathrate. As used in this document, the terms comprise, include, have, may, contain, and variants thereof are intended to be open-ended, transient phrases, terms, or words that do not preclude the possibility of additional acts or structures. The singular forms a, an, the, and the include plural references unless the context clearly dictates otherwise. CZQtznn / l 7Π7 / Β / YILI the contrary. The present description also contemplates other modalities that comprise, consist of and consist essentially of, the modalities or elements presented in this document, whether explicitly stated or not. As used in this document, the term optional or optionally means that the event or circumstance described below may, but does not necessarily, occur, and that the description includes cases where the event or circumstance occurs and cases where it does not occur. As used in this document, the term "approximately" that modifies, for example, the amount of an ingredient in a composition, concentration, volume, process temperature, process time, yield, flow rate, pressure, and similar values ​​and ranges thereof, as used in setting forth the modalities of the description, refers to a variation in numerical quantity that may occur, for example, through typical measurement and handling procedures used to make compounds, compositions, concentrates, or formulations for use; through an inadvertent error in those procedures; through differences in the manufacture, source, or purity of starting materials or ingredients used to carry out the methods; and similar proximate considerations. The term "approximately" also includes quantities that CZQtznn / l 7P7 / B / YILI differ due to the aging of a formulation with a particular initial concentration or mixture, and amounts that differ due to the mixing or processing of a formulation with a particular initial concentration or mixture. Where modified by the term approximately, the appended claims include equivalents of those amounts. Furthermore, where approximately is used to describe a range of values, for example approximately from 1 to 5, the statement means from 1 to 5 and from approximately 1 to approximately 5, and from 1 to approximately 5 and approximately from 1 to 5, unless specifically limited by the context. As used herein, the term substantially means consisting essentially of and includes consisting of. Consisting essentially of and consisting of are interpreted as in United States patent law. For example, a solution that is substantially free of a specified compound or material may be free of that compound or material, or it may have a minor amount of that compound or material present, such as from unintentional contamination, side reactions, or incomplete purification. A minor amount may be a trace, an immeasurable amount, an amount that does not interfere with a value or property, or some other amount as provided in the context.A composition having substantially only a provided list of components may consist of only those components, or have a trace amount of some other component present, or have one or more additional components that do not materially affect the properties of the composition. Additionally, "substantially" modifying, for example, the type or quantity of an ingredient in a composition, a property, a measurable quantity, a method, a value, or a range, as used in setting forth the modalities of the description, refers to a variation that does not affect the composition, property, quantity, method, value, or range as generally set forth in a manner that negates a specified composition, property, quantity, method, value, or range. Where modified by the term "substantially," the appended claims include equivalents in accordance with this definition. As used herein, any stated range of values ​​includes all values ​​within the range and should be construed as supporting claims that state any sub-range having endpoints that are actual numerical values ​​within the stated range. By way of example, a description in this specification of a range from 1 to 5 should be considered to support claims for any of the following ranges: 1-5; 1-4; 1-3; 1-2; 2-5; 2-4; 2-3; 3-5; 3-4; and 4-5. Compositions and methods are described for inhibiting the formation of natural gas hydrate agglomerates and / or plugs formed from natural gas hydrate agglomerates within liquefied hydrocarbon recovery, processing, transportation, and storage operations. The compositions can be applied to one or more liquefied hydrocarbon products to inhibit the plugging of annular spaces, such as pipes, transfer lines, valves, and similar components, including downhole equipment where conditions are conducive to gas hydrate formation. In certain embodiments, the compounds used in compositions and methods for inhibiting gas hydrate agglomerates are alkenyl-succinimidide-based compounds. These compounds are formed by the reaction of an alkene and unsaturated dicarboxylic acid anhydrides followed by a reaction with an amine or an alcohol. In one embodiment, the alkenyl-succinimidide is formed by the reaction of succinic acid or an alkenyl-substituted succinic anhydride with an amine or amine alcohol. The resulting alkenyl-succinimidide-based compound has the formula CZQtznn / l 7Π7 / Β / ΥΙΛΙ shown below as formula I, CZQtznn / l 7Π7 / Β / YΙΛΙ R3 Formula 1 Where, R1 = H or any saturated or unsaturated alkyl group of 1 to 10 carbon atoms, or a ring structure which would be attached to R2, for example, pyrrolidine or azepane; Where, R2 = H or any saturated or unsaturated alkyl group of 1 to 10 carbon atoms or a ring structure which would be attached to R1, e.g., pyrrolidine or azepane. In some forms, R1 and R2 are butyl, pentyl, isobutyl, or isopentyl groups. In some forms, R1 = R2. Where, R3= an alkyl or alkenyl chain or ring, saturated or unsaturated. In some embodiments, R3 is an alkyl or alkenyl chain of 5-30 carbon atoms. In other embodiments, R3 is 10 carbon atoms, 18-22 carbon atoms, 20-24 carbon atoms, or mixtures thereof. In certain embodiments, each of R1 and R2 includes one or more aminopropylamine chains such as dibutylaminopropylamine (DBAPA) or a DBAPA with additional aminopropylamine referred to herein as dibutylaminopropylaminediamine or an extended DBAPA. In certain embodiments, R1 = R2. In certain embodiments, each of R1 and R2 is derived from the following amines: Aminopropyl-pyrrolidine Aminopropyl-azepaneΗ2Ν\ / \χΝ J and An extended dibutylaminopropylenediamine In modalities, the succinimide-based compounds are shown below as formula II, with the various groups as previously described i—NBu2v τ y=o R3 Formula II The synthesis of alkenylsuccinimidide-based compounds is not limited by the processes described. Any suitable method can be used to synthesize alkenylsuccinimidide-based compounds. In embodiments, the first step is the generation of a portion of alkenylsuccinic anhydride via the Alder-ene reaction. In embodiments, the Alder-ene reaction is a thermal reaction in which an unsaturated dicarboxylic acid is reacted with primary alkenes. In embodiments, the unsaturated dicarboxylic acid is maleic acid. In embodiments, the reaction is as follows: czatznn / i znz / E / YiAi R In some versions, the alder-ene reaction is carried out at temperatures from 120°C to approximately 250°C for a period ranging from 1 to 48 hours. In other versions, the temperature ranges from approximately 120°C to approximately 160°C, approximately 150°C to approximately 250°C, approximately 150°C to approximately 225°C, or approximately 180°C to approximately 210°C. In some versions, the reaction takes place over approximately 1–48 hours, 5–10 hours, 4–6 hours, 23 hours, 12–36 hours, 24–36 hours, or 24–48 hours. In some versions, the reaction of the anhydride (e.g., maleic anhydride) and the primary alkene is in a 1:1 ratio. Various reaction modifiers, such as a catalyst to promote the reaction or suppress tar formation, and other materials and techniques to reduce the formation of byproducts known in the field, can be used in the present process. See, for example, United States Patents Nos. 3,412,111; 3,819,660; 4,255,340 and 4,396,774, 8,242,287, descriptions of which are incorporated herein by reference. In some embodiments, a second step is the reaction between the alkyl or alkenyl-1-succinic anhydride and an amine or alcohol. In some embodiments, the resulting succinimide-based compounds can be formed by reaction with an alkenyl-succinic anhydride and a dibutylaminopropylamine as shown below: czatznn / i ζπζ / β / υιλι The second stage is carried out at room temperature, followed by cooling, if desired. In some embodiments, the ratio of alkyl or alkenylsuccinic anhydride to amine ranges from 1:1 to approximately 3:1 or higher. Other embodiments include ratios of 10:1, 8:1, 6:1, or 3:1, with the most suitable ratios being those where the alkyl or alkenylsuccinic anhydride is greater than the amine. In general, an alkene consists of 2 to 30 carbon atoms with at least one carbon-carbon double bond. Some alkenes have a carbon-carbon double bond (mono-enes). Alkenes can be linear or branched, and mixtures thereof. Examples of mono-enes include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene, 1-tricocene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacocene, and similar compounds. In terms of forms, the alkene is 1-alkene, 20-24 carbon atoms or mixtures thereof. Any suitable amine can be used for the reaction with alkenylsuccinic anhydride to yield the described succinimide-based compound. The amine may be characterized by the presence of at least one primary, secondary, or tertiary amino group. In terms of specific compounds, an amine can be a monoamine, diamine, polyamine, or a combination thereof. Examples of monoamines include ethylamine, dimethylamine, diethylamine, n-butylamine, dibutylamine, allylamine, isobutylamine, cocoamine, stearylamine, laurylamine, methylurylamine, oleylamine, n-methyloctylamine, dodecylamine, diethanolamine, morpholine, and octadecylamine. In terms of modalities, amines are diamines, which can include aliphatic diamines, branched aliphatic diamines, and cyclic diamines. czatznn / i ζπζ / β / υιλι In terms of modalities, polyamines have the formula [R5-NH-R6] , where R5 and R6 are H or an alkyl group. In terms of modalities, the amine is a dibutylaminopropylenediamine: czatznn / i ζπζ / β / υιλι In some forms, the amine is a dibutylaminopropylenediamine with an additional aminopropylamine: In some forms, the amine is an aminopropylpyrrolidine: In terms of modalities, the amine is an aminopropyl-azepane: In some forms, polyalkylene polyamines have approximately 2 to 60, 2 to 40, 3 to 20 total carbon atoms and approximately 1 to 12, 3 to 12, 5 to 9 nitrogen atoms in the molecule. In some forms, amines are hydrocarbylamines or hydrocarbylamines that include other groups, for example, hydroxy groups, alkoxy groups, amide groups, nitriles, imidazoline groups, and the like. Hydroxyamines with 1 to 6 hydroxy groups or 1 to 3 hydroxy groups are useful. In terms of modalities, amines are aliphatic saturated amines, which include those with the general formulas: R—N—R', and R—N—(CHjh-fN—(CH2hf N—RIIIR' RR' R' wherein R, R', R and R' are independently selected from a hydrogen group; straight-chain or branched alkyl radicals of 1 to 25 carbon atoms; alkoxy radicals of 1 to 12 carbon atoms, alkylene radicals of 2 to 6 carbon atoms; hydroxyamino-alkylene radicals of 2 to 12 carbon atoms; and alkylamino radicals of 1 to 12 carbon atoms, alkylene radicals of 2 to 6 carbon atoms; and wherein R' may further comprise a portion of the formula: ±(€H2)?-N^H R' where R' is as defined above, and where sys' can be the same or a different number from 2 to 6, from 2 to 4; ytyt' can be the same or different and are numbers from 0 to 0, from 2 to 7, or approximately from 3 to 7, with the condition that the sum of tyt! is not greater than 15. Examples of amine compounds include: 1,2-diaminoethane; 1,3-diaminopropane; 1,4-diaminobutane; 1,6-diaminohexane; and polyethyleneamines such as diethylenetriamine; triethylenetetramine; and tetraethylenepentamine. CZQtznn / l 7Π7 / Β / ΥΙΛΙ polypropyleneamines such as 1,2-propylene-diamine; di-(1,2propylene)triamine; di-(1,3-propylene)triamine; N,N-dimethyl1,3-diaminopropane; N,N-di-(2-aminoethyl)ethylenediamine; N,N-di(2hydroxyethyl)-1,3-propylene-diamine; 3-dodecyloxypropylamine; Ndodecyl-1,3-propanediamine; tris-hydroxymethylaminomethane (ΤΗΆΜ); diisopropanolamine; diethanolamine; triethanolamine; mono-, di- and tri-sebo-amines; aminomorpholines such as N(3-aminopropyl)morpholine; and mixtures thereof. Any suitable alcohol can be used for the reaction with alkenyl-succinic anhydride to yield a succinate ester compound. In some forms, the alkenyl-succinic anhydride can react with a related amine alcohol for ring opening of the anhydride: NBu? Where, R3= alkyl or alkenyl chain or ring, saturated or unsaturated. In some embodiments, R3 is an alkyl or alkenyl chain of 5-30 carbon atoms. In other embodiments, R3 is 10 carbon atoms, 18-22 carbon atoms, 20-24 carbon atoms, or mixtures thereof. In some forms, alcohols with the formula OH-R4 are used, where R4 is an alkyl, aryl, or alkaryl-hydrocarbyl group having from one to twenty carbon atoms, and where R4 can be an unsubstituted or substituted alkyl group with 1 to 20 carbon atoms, an unsubstituted or substituted alkenyl group with 2 to 20 carbon atoms, an unsubstituted or substituted alkynyl group with 2 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group with 3 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group with 3 to 20 carbon atoms containing at least one heteroatom, an unsubstituted or substituted aryl group with 6 to 20 carbon atoms, an unsubstituted or substituted aryl group with 6 to 20 carbon atoms containing at least one heteroatom, or an unsubstituted or substituted alkaryl group with 7 to 20 carbon atoms. of unsubstituted or substituted carbon or alkaryl of 7 to 20 carbon atoms containing at least one heteroatom. In some forms, alcohols include methanol, ethanol, propanol, i-propanol, n-butanol, i-butanol, t-butanol, n-octanol, hexanol, cyclohexanol, and benzyl alcohol, or combinations thereof. In some forms, an alcohol is an amino alcohol. Amino alcohols include 2,2-disubstituted 2-amino-l-alkanols, which have two to three hydroxyl groups and contain a total of 4 to 8 carbon atoms. This amino alcohol can be represented by the formula: XI HZN—C—CH2OH X where X is an alkyl or hydroxyalkyl group in CZQtznn / l 7P7 / B / YILI where the alkyl groups have 1 to 3 carbon atoms where at least one, and preferably both, of the substituents X is a hydroxyalkyl group of the structure — (CH2)nOH, n is from 1 to 3. In some forms, alcohols are amino alcohols. Examples of amino alcohols include 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, and 2-amino-2-(hydroxymethyl)-1,3-propanediol (TEAM or tris(hydroxymethyl)aminomethane). Other forms of the alcohol include dibutylaminoethanol, diethylaminoethanol, dipropylaminoethanol, diisopropyl, diisobutyl, diisopentyl, dipentyl, and diisohexyl / dihexyl. In some forms, succinic acid anhydrides substituted with carbon-free chains terminated with an allyl or primary alkene are also used as anti-caking agents: CZQtznn / l 7Π7 / Β / YΙΛΙ In terms of modalities, the chains that do not contain carbon are polyethylene glycol, polypropylene glycol, polyesters, polycarbonates or polyamines. In some embodiments, an acidification step of secondary or tertiary amines is generally achieved through the addition of an organic acid. Exemplary organic acids include acetic acid or acrylic acid. In other embodiments, acrylic acid reacts with any residual primary or secondary amine (reversibly with tertiary amines) to produce a carboxybetaine structure. Other organic acids may be used for this acidification, including pivalic acid, malic acid, maleic acid, succinic acid, and any carboxylic acid with 1 to 12+ carbon atoms. Inorganic acids, such as common mineral acids (hydrochloric acid, phosphoric acid, nitric acid, carbonic acid) or related acids, as well as Lewis acids (tetrafluoroborate, aluminum trichloride, or similar), may also be used. The compositions and methods described herein are used to inhibit the formation of gas hydrate agglomerates and plugging during the production and transportation of liquid hydrocarbons. In some embodiments, the compositions comprise, consist of, or essentially consist of at least one of the succinimide-based compounds described. In some embodiments, the composition may further comprise one or more thermodynamic gas hydrate inhibitors, one or more kinetic gas hydrate inhibitors, one or more other additives, or any combination thereof. In some embodiments, the composition may include other additives such as one or more asphaltene inhibitors, paraffin inhibitors, corrosion inhibitors, scale inhibitors, demulsifiers, water clarifiers, dispersants, demulsifying agents, or any combination thereof. The composition comprising succinimide-based compounds is prepared or formulated in one or more solvents, depending on the application and requirements. In some embodiments, suitable solvents for formulating compositions with succinimide-based compounds include water, brine, seawater, alcohols such as methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol, t-butanol, or higher alcohols such as benzyl alcohol; ethanol such as acetone or methyl ethyl ketone (2-butanone); acetonitrile; esters such as ethyl acetate, propyl acetate, and butyl acetate; ethers such as diethyl ether or higher, for example, methyl-t-butyl ether, glime, diglyme, ethylene glycol monobutyl ether, ethylene-diglycol ethyl ether, 1,4-dioxane and related glycols;aromatic compounds such as toluene, xylene(s), diethylbenzene, naphthalene and related aromatic compounds or refinery cuts (heavy aromatic naphtha, heavy aromatic distillates, and related products); aliphatic compounds such as pentane, hexane, heptane, octane, or refined gasoline; or various green solvents such as 2-methyltetrahydrofuran, furfural alcohol, and cyclopentyl methyl ether. czatznn / i ζπζ / β / υιλι In some forms, other suitable solvents for formulation with the succinimide-based compound include aliphatic compounds such as pentane, hexane, cyclohexane, methylcyclohexane, heptane, decane, dodecane, diesel and the like, and aromatic compounds such as toluene, xylene, heavy aromatic naphtha, fatty acid derivatives (acids, esters, amides) and the like. In some formulations, the succinimide-based compound is formulated in a composition with an amount of approximately 1-80% w / v. In some formulations, the succinimide-based compound is added in an amount of approximately 1-10% w / v, 10-20% w / v, 20-60% w / v, 45-60% w / v, 60-80% w / v, or 1-60% w / v. In certain embodiments, the composition comprising the succinimide-based compound is used in a method for inhibiting the formation of natural gas hydrate agglomerates. The method comprises adding to a fluid a quantity of a composition comprising one or more succinimide-based compounds. In certain embodiments, the fluid comprises water, gas molecules, and liquid hydrocarbon. An exemplary application point for petroleum liquids production operations is near the surface-controlled subsea safety valve. In some cases, the succinimide-based compound is applied or introduced into a well. This ensures that, during a shutdown, the compound can be dispersed throughout the area where natural gas hydrates will form. Succinimide-based compounds can also be applied in other areas along the flow line, taking into account the density of the injected fluid. If the injection point is well above the depth of gas hydrate formation, the succinimide-based compound can be formulated with a solvent of sufficiently high density so that it will flow down the flow line and collect in the oil / water interfacial zone.In some applications, the application is also used in pipes or anywhere in the system where there is a possibility of gas hydrate agglomeration formation. In some embodiments, various dosage amounts of the succinimide-based compound, or compositions containing it, are introduced into the fluid to inhibit the formation of gas hydrate agglomerates. A person of ordinary experience in the field is able to calculate the amount of a composition comprising the succinimide-based compound for a given situation without undue experimentation. Factors that would be considered important in these calculations include, for example, fluid content, water cut percentage, and API hydrocarbon gravity. In some embodiments, the succinimide-based compound, either alone or in a composition, is introduced into a fluid to be treated at approximately 1,000 ppm to approximately 50,000 ppm, approximately 2,000 ppm to approximately 15,000 ppm, or 3,000 ppm to 20,000 ppm. The composition and methods are useful for inhibiting the formation of gas hydrate agglomerates for many hydrocarbons and hydrocarbon mixtures. The compositions are particularly useful for hydrocarbon gases or gas mixtures containing 1–5 carbon atoms lighter or with low boiling points under ambient conditions. In some forms, the gases are methane, ethane, propane, n-butane, isobutane, isopentane, and mixtures thereof. In other forms, natural gas mixtures are present in many gas and / or crude oil and natural gas liquid formations. The hydrocarbons may also comprise other compounds including, but not limited to, carbon dioxide, hydrogen sulfide, and other compounds commonly found in gas / crude oil formations or processing plants, whether naturally occurring and / or used in hydrocarbon recovery / processing from the formation, and mixtures thereof. In certain embodiments, the compositions and methods are useful for inhibiting gas hydrate formation in a variety of black crude oils, heavy black crude oils to condensates, from API 20-50. In certain embodiments, the compositions and methods are useful for inhibiting gas hydrate formation in paraffinic or asphaltenic crude oils. In these embodiments, paraffin or asphaltene inhibitors are used in conjunction with succinimide-based compounds. In some embodiments, the composition comprising the succinimide-based compound is applied to fluids containing varying levels of crude oil, brine, or both, with varying salinity levels. In one embodiment, the fluid has a salinity of approximately 0.1% to approximately 25% or approximately 10% to approximately 25% by weight / weight (w / w). In some formulations, the succinimide-based compound is applied to a fluid containing varying levels of water cut. A person with ordinary experience in the field understands that water cut refers to the percentage of water in a composition containing a mixture of crude oil and water. czatznn / i ζπζ / β / υιλι In one scenario, the water cut-off is approximately 1% approximately 80% w / w with respect to the hydrocarbon phase. In other modalities, the water cut is approximately 1% to approximately 30% w / w, approximately 5% to approximately 40% w / w, approximately 10% to approximately 60% w / w, of approximately 15% to approximately 80% w / w with respect to the hydrocarbon phase. The methods can be used at any pressure that results in hydrocarbon gas hydrates. When the hydrocarbons in the mixture are hydrocarbons or hydrocarbon gases with lower boiling points under ambient conditions, the pressure is usually greater than atmospheric pressure (e.g., approximately 101 kPa), greater than approximately 1 MPa, or greater than approximately 5 MPa. The pressure in certain formation or processing units or plants could be much higher, such as greater than approximately 20 MPa. There is no specific upper pressure limit. The composition comprising the succinimide-based compound can be introduced by any method suitable for ensuring its dispersion throughout the liquid being treated. In some embodiments, the succinimide-based compound can be injected before substantial gas hydrate formation. In some embodiments, the succinimide-based compound is introduced into a fluid contained within a crude oil and gas pipeline. In other embodiments, the succinimide-based compound is added to a fluid contained within refineries, such as separation vessels, dehydration units, gas lines, and pipelines. In these embodiments, the succinimide-based compounds are introduced into a fluid by means of various well-known methods and can be introduced at numerous different locations throughout a given system. In other embodiments, the composition comprising one or more succinimide-based compounds is injected by means of mechanical equipment such as chemical injection pumps, T-tubes, injection fittings, and the like. Succinimide-based compounds are blended or combined using mechanical mixing equipment or devices, stationary mixing facilities or equipment, magnetic mixing, or other suitable methods to provide adequate contact and / or dispersion of the composition in the mixture. The introduction of the succinimide-based compound may be done online and / or offline. The various components of the composition may be mixed before and / or during introduction. A person of experience will understand that the methods disclosed herein are not limited in any way by the timing or location of introduction. EXAMPLES The following examples serve to illustrate different aspects and embodiments of the invention and should not be considered as limiting its scope. CZQtznn / l 7Π7 / Β / YILI will acknowledge that various modifications and changes can be made without following the experimental modalities described in this document, and without departing from the scope of the claims. Example 1 - Synthesis of 12-carbon alkenyl-succinic anhydride and dibutylaminopropylamine 50.0 g of dodecenyl-succinimid (0.188 mol, 1.0 eq) were weighed into a 250 mL three-necked round-bottom flask. To this, 34.98 g of dibutylaminopropylamine (0.188 mol, 1.0 eq) were added in a qota-by-qota manner. Once the addition was complete, the flask was fitted with a Dean-Stark trap and a condenser. The contents were then heated to 120°C (248°F). Water was then removed over a period of 6 hours. After the reaction, the contents were cooled to room temperature. The resulting product was acidified with acetic acid (11.27 g, 0.188 mol, 1.0 eq) and diluted to 50% by weight with 96.3 g of methanol. Example 2 - Synthesis of alkenyl-succinic anhydride of 20 to 24 carbon atoms and dibutylaminopropylamine 50.0 g of 20-carbon / 24-carbon alkenyl succinimide (0.188 mol, 1.0 eq) were weighed into a 250 mL three-necked round-bottom flask. To this, 34.98 g of dibutylaminopropylamine (0.188 mol, 1.0 eq) were added in a qota-qota manner. Once the addition was complete, the flask was fitted with a Deanczatznn / i znz / E / YiAi trap Stark and a condenser. The contents were then heated to 120°C (248°F). Water was removed over a period of 6 hours. After the reaction, the contents were cooled to room temperature. The resulting product was acidified with acetic acid (7.94 g, 0.188 mol, 1.0 eq) and diluted to 50% by weight with 82.5 g of methanol. Example 3 The oscillating cell test was used to determine if succinimide-based compounds are able to minimize gas hydrate agglomerate particles and disperse those particles in a hydrocarbon phase. The oscillating cell includes a rack on which individual cells are placed. Each individual cell includes a sapphire tube containing a stainless steel ball. The stainless steel ball induces turbulence and mixes the liquids during the oscillation process. The sapphire tube can also withstand pressures up to approximately 351.53 kg / cm² (5,000 psi). Once the cells are mounted on the rack, the rack slowly oscillates up and down at a rate of approximately one complete cycle (up and down) per minute. The rack is further contained within a temperature-controlled bath attached to a refrigerator. The compositions included a hydrocarbon, an aqueous phase, a gas, and the succinimide-based compound to be tested. The aqueous phase used was a brine with approximately 4% salinity and a water content of 55%. Several crude oils, such as black crude oil, heavy black crude oil, and condensate, were tested. A synthetic gas (a synthetic blend of approximately 85% methane, which is a combination of Type II gas hydrate-forming gas) was used to pressurize the cells to the appropriate pressure: 175.77 kg / cm² (2500 psi) for black crude oil and heavy black crude oil, and 140.61 kg / cm² (2000 psi) for condensate. First, brine and gas were injected into each cell. The succinimide-based compound was then dosed according to the amount of brine in the test cell. The crude oil was heated to 60°C for a minimum of 2 hours beforehand, then introduced into the cell containing the brine, gas, and succinimide-based compound. The cells with the test compositions were then equilibrated at a temperature of approximately 29°C, while oscillating for 30 minutes. The test is a constant pressure test where the cells are left open to a propellant that forces additional gas into the cells as the gas dissolves in the liquids and / or gas hydrates formed. CZQtznn / l 7Π7 / Β / YΙΛΙ The cells were rocked for approximately 30 minutes to equilibrate and mix before being stopped in a horizontal position (shutdown). During the shutdown phase, the cells were cooled to approximately 4.4°C for approximately four hours, and once they reached 4.4°C, they were rocked for an additional eight hours at that temperature. After a shutdown period of approximately eight hours, the cell rocking was restarted for two hours. After two hours, the cells were visually inspected and classified as pass / fail. The pass / fail criteria were based on the ability of the ball in the oscillating cell to move within the sapphire tube. For example, a succinimide-based compound under test was considered effective and passed the oscillating cell test if, at the time of classification, the ball moved freely when the cell was swung, indicating that few agglomerates formed. In contrast, the succinimide-based compound failed if the ball's movement was obstructed or completely stopped by the formation of gas hydrate agglomerates. Anti-agglomeration performance was considered borderline when gas hydrate agglomerates were observable and at least some of the agglomerates became stuck to the walls of the sapphire tube; when these agglomerates were present and the ball's movement was not CZQtznn / l 7P7 / B / YILI restricted, the classification of the succinimide-based compound was considered to be at the limit of what is approved. Figure 1 shows the results for a succinimide-based compound (reaction between 12-carbon alkyl-succinic anhydride and dibutylaminopropylamine) that passed the oscillating cell dosed at 3% with a water cut of 55% and salinity of 4% in black crude oil. Figure 2 shows the results that passed the oscillating cell test when the succinimide-based compound was tested (reaction between 20-24 carbon atom alkyl-succinic anhydride and dibutylaminopropylamine) dosed at 1% with a water cut of 55% and salinity of 4% in black crude oil. It is hereby stated that, as of this date, the best method known to the applicant for putting the aforementioned invention into practice is the one that is clear from the present description of the invention.

Claims

1. A method for inhibiting the formation of natural gas hydrate agglomerates, characterized in that it comprises: introducing into a fluid a composition comprising at least one succinimide-based compound to inhibit the formation of natural gas hydrate agglomerates, wherein at least the succinimide-based compound is formed by a reaction between an alkenylsuccinic anhydride and an amine or amine alcohol.

2. The method according to claim 1, characterized in that the introduction is by means of injection or pumping.

3. The method in accordance with any of claims 1-2, characterized in that the introduction is into a well.

4. The method according to any of claims 1-3, characterized in that the fluid is contained in a crude oil or natural gas production operation or pipeline.

5. The method in accordance with any of the CZQtznn / l 7P7 / B / YILI 36 claims 1-4, characterized in that the fluid comprises water, natural gas and liquid hydrocarbon.

6. The method according to any of claims 1-5, characterized in that the fluid comprises water from approximately 1% to approximately 80% by weight / weight with respect to a hydrocarbon phase.

7. The method according to any of claims 1-6, characterized in that the composition further comprises one or more thermodynamic gas hydrate inhibitors, kinetic gas hydrate inhibitors, anti-caking agents, asphaltene inhibitors, paraffin inhibitors, scale inhibitors, emulsifiers, water clarifiers, dispersants, demulsifying agents, or any combination thereof.

8. The method according to any of claims 1-7, characterized in that the amine comprises primary, secondary or tertiary amine.

9. The method according to any of claims 1-8, characterized in that the amine comprises a dibutylaminopropylenediamine, a dibutylaminopropylenediamine with an additional aminopropylamino portion, or a combination thereof.

10. The method according to any of claims 1-9, characterized in that the succinimide-based compounds have the general formula: czatznn / i ζπζ / β / υιλι czatznn / i ζπζ / β / υιλι R3 wherein, R1 = H or any saturated or unsaturated alkyl group of 1 to 10 carbon atoms, or a ring structure which would be attached to R2, for example, pyrrolidine or azepane; wherein, R2 = H or any saturated or unsaturated alkyl group of 1 to 10 carbon atoms or a ring structure which would be attached to R1, for example, pyrrolidine or azepane; wherein R3 = a saturated or unsaturated alkyl or alkenyl chain or ring.

11. A composition, characterized in that it comprises at least one succinimide-based compound for inhibiting the formation of natural gas hydrate agglomerates, wherein at least the succinimide-based compound is formed by a reaction between an alkenylsuccinic anhydride and an amine or amine alcohol.

12. The composition according to claim 11, characterized in that the amine comprises primary, secondary or tertiary amine.

13. The composition according to any of claims 11-12, characterized in that the amine is a dibutylaminopropylenediamine, a dibutylaminopropylenediamine with an additional aminopropylamino portion, or a combination thereof.

14. The composition according to any of claims 11-13, characterized in that the succinimide-based compounds are approximately 1% w / v to approximately 80% w / v based on the composition.

15. The composition according to any of claims 11-14, characterized in that it further comprises one or more thermodynamic gas hydrate inhibitors, kinetic gas hydrate inhibitors, anti-caking agents, asphaltene inhibitors, paraffin inhibitors, scale inhibitors, emulsifiers, water clarifiers, dispersants, demulsifying agents, or any combination thereof.

16. A composition, characterized in that it comprises: a fluid; and at least the succinimide-based compounds according to any of claims 11-15.

17. The composition according to any of claims 11-16, characterized in that the succinimide-based compounds are from approximately 1,000 ppm to 50,000 ppm.

18. The composition according to any of claims 16-17, characterized in that the fluid comprises water, natural gas and liquid hydrocarbon.

19. A composition, characterized in that it comprises succinimide-based compounds having the general formula: czatznn / i znz / E / YiAi wherein, R1 = H or any saturated or unsaturated alkyl group of 1 to 10 carbon atoms, or a ring structure which would be attached to R2, for example, pyrrolidine or azepane; wherein, R2 = H or any saturated or unsaturated alkyl group of 1 to 10 carbon atoms or a ring structure which would be attached to R1, for example, pyrrolidine or azepane; wherein, R3 = a saturated or unsaturated alkyl or alkenyl chain or ring.

20. Use of the succinimide-based compound according to any of claims 1-19 for inhibiting natural gas hydrate agglomerates.