MX2013009634A - Anti-agglomerate gas hydrate inhibitors for use in petroleum and natural gas systems. - Google Patents

Abstract

A method of inhibiting gas hydrate formation in petroleum and natural gas production systems through the use of low dosage hydrate inhibitors which include reaction products of non-halide-containing inorganic acids, organic acids, and organic amines. The use of these non-halide-containing reaction products rather than chloride containing acids or alkylating agents avoids corrosion and stress cracking caused by residual inorganic chloride and other inorganic, halide-containing acids. The anti-agglomerate compositions can be administered continuously to effectively inhibit gas hydrate formation. In preferred embodiments, the anti- agglomerate compositions are mixtures of reaction products of non-halide-containing organic acids and organic amines.

Description

INHIBITORS OF ANTI-AGGLOMERATING GASEOUS HYDRATES FOR USE IN OIL AND NATURAL GAS SYSTEMS FIELD OF THE INVENTION The systems and methods described herein pertain to the production of petroleum products and natural gas, and in particular to compositions effective as gaseous hydrate inhibitors of low dosage anti-caking agents ("LDHI") for the prevention of gaseous hydrate plugs.

BACKGROUND OF THE INVENTION Gaseous hydrates are solids that can be formed during the production of hydrocarbons, particularly in pipes and other equipment, which can impede or completely block the flow of hydrocarbons. These blockages not only decrease or stop production, potentially costing millions of dollars in lost production, but they are also very difficult and harmful to supply. Unless they are handled "properly, gaseous hydrates can explode, break pipes, damage equipment, endanger workers and put the ocean environment at risk.

Gaseous hydrates can be formed when Water molecules agglomerate after coming into contact with certain "metasomatic" gaseous molecules. The agglomeration of hydrogen causes water molecules to form a regular reticular structure that is stabilized by gaseous metasomatic molecules. The resulting crystalline structure is precipitated as a solid gaseous hydrate "". The metasomatic molecules can include any number of molecules, among which are included carbon dioxide, methane, butane, propane, hydrogen, helium, freons, halogens, and noble gases.

Thermodynamic, anti-binding, and kinetic inhibitors are three general classes of hydrate inhibitors. Thermodynamic inhibitors are the most commonly used. Thermodynamic inhibitors, such as methanol and ethylene glycol will typically be used at high concentrations to be effective, concentrations can present environmental problems. For example, methanol is used in concentrations of up to 50% ratio of methanol to water, with glycol 'as much as 30% glycol to water. Methanol presents other challenges, as it is flammable and can be corrosive. In this way, thermodynamic inhibitors are often not suitable for many of the drilling operations, particularly ambierially sensitive drilling operations.

Kinetic inhibitors and anti-caking inhibitors typically function at lower concentrations than thermodynamic inhibitors and are therefore called LDHI. Kinetic hydrate inhibitors are polymers that can prevent or delay the nucleation of hydrates. In this way, the inhibitors of. Kinetic hydrates limit the crystalline size of the hydrate and grow in such a way that the hydrate plugs are not allowed to form in the pipe and fittings. However, kinetic hydrate inhibitors are able to manipulate low to moderate subcooling - typically a subcooling of about -12.22 / -3.88 ° C (10-25 ° F) (subcooling is the difference between the operating temperature of the hydrocarbon system and the temperature at which the hydrates could be formed at the same operating pressure). In this way, kinetic hydrate inhibitors may not be suitable in deep and ultra-deep wells, where sub-cooling may be greater than -1.11 ° C (30 ° F).

Gaseous anti-caking inhibitors typically have a more cost-effective cost than thermodynamic inhibitors, since they can be used in much lower concentrations and are typically useful in environments with greater sub-cooling than could be suitable for kinetic inhibitors. However, many of the traditional LDHI anti-binders contain residual halides, such as HC1, HBr, and the like, and residual organic halides. It has been known that residual halides cause corrosion and cracking by thermal corrosion ("SCC") in metal pipes and production equipment. An example of a commonly used anti-binder LDHI is the quaternary anti-caking agent containing residual organic halides, such as Kelland, 2006. As an example, Milburn et al., U.S. Patent No. 6,444,852 entitled "Mines Useful in Inhibiting Gas Hydrate Formation, "which is incorporated herein by reference in its entirety, discloses amine compounds containing anti-agglomeration ether that are quaternized with a halide. Especially in the case of organic halides, they can be very toxic and harmful to the environment. This is particularly true when the inhibitors are applied continuously. In addition, traditional anti-binder LDHIs can decompose and become less effective when exposed to high temperatures above 121.11 ° C (250 ° F).

When an anti-binder LDHI is needed that does not contain residual halides in sufficient quantities to present an inadequate risk of corrosion or cracking mechano-chemical and that is less toxic and less harmful to the environment than the additional LDHI.

SUMMARY OF THE INVENTION The present description relates in general to the field of oil and gas production. By means of the same also, other uses can be made .. In particular, compositions and methods for inhibiting the formation of gaseous hydrate plugs are described.

Disclosed are compositions that are inhibitors of low-dosage anti-binding hydrates ("AA-LDHI") that are produced without the use of organic chlorides or halides to minimize residual organic halides, other resulting inorganic halides that are respectively toxic and corrosive. Examples of these halides include HF, HC1, HBr, HI, and the like. These novel AA-LDHIs can be injected continuously without the problem of high corrosion rates or thermal corrosion cracking of the injection equipment and metal fittings for production caused by residual halides, such as HC1, HBr, and the like. While the compositions are structurally similar to quaternary amines, they are reaction products of organic acids and organic amines that virtually eliminate or reduce inorganic halides. or residual organic (MX), and / or residual hydrogen halides (HC1, HBr, HI, and the like). Inorganic halides (MX), and / or residual HX are often created as byproducts when quaternary salts are produced using chlorinated or halogenated alkylating agents. These agents typically include chloride, bromide, benzyl iodide, or the like, of the R-X structure wherein R is any organic structure. This formation of by-products is due to their reaction with water, either during or after the reaction. In the present compositions, instead of a halide anion which is associated with the quaternary ammonium cation, an organic acid anion is present. This is a significant difference that distinguishes the described compositions from other anti-caking compounds. · In some preferred embodiments, inhibitors of low dosage anti-caking hydrates are mixtures of organic reaction products of organic acids and organic amines, including but not limited to those which include fatty acids and fatty amines.

The compositions described effectively inhibit the formation of gaseous hydrates in systems for the production of petroleum and natural gas without the negative effects associated with residual chlorides or other halides, such as 1 (high corrosion rates, mecha chemical cracking, high potential toxicity.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows a general structure of a quaternary ammonium salt having a chloride or other halide anion, wherein R1, R2, R3, and R4 are independently and independently H or C1-C40 alkyl, and X in general is F, Cl, Br, I, other halides, or similar suitable substituents.

Figures 2a, 2b show the general structures (a) and (b) of organic reaction products of organic acids and organic amines having an organic anion, wherein R1, R2, and R3 are independently H or Ci-C40 alkyl , including all the alkyl and aryl structures and isomers, and wherein R 4 is C 1 -C 40 including all the alkyl and aryl structures and isomers.

Figure 3 shows a preferred embodiment of a general structure of the reaction product of an amine based on coconut oil and a fatty acid based on coconut oil, where n is 8-12.

Figure 4 shows the results of a comparison of the effectiveness of four anti-caking compositions based on evaluation criteria.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES Current anti-agglomeration compositions include mixtures of inorganic acid reaction products which do not contain halide and / or organic acids with organic amines. The reaction products are structurally similar to other analogs of quaternary amine halides, although the reaction products lack acid halides, inorganic halides, and organic halides. Certain embodiments include mixtures of reaction products of organic acids and organic amines, including a low dosage anti-caking hydrate inhibitor that is free of acid halides, inorganic halides, and organic halides and that can be continuously injected with minimal corrosion problems , cracking by thermo-corrosion or reactive or reaction products quite toxic.

Figure 1 shows a traditional example of a quaternary ammonium salt that uses a halide as an anion. The quaternary ammonium cation is the portion of the molecule that has a positive charge, NRiR2R3R4 + - The term quaternary amine is often used to refer to a positively charged quaternary ammonium compound. In 'a quaternary ammonium cation, Ri, R2, R3, and R4 may be any number of suitable constituents, including hydrogen (H), methyl (CH3), ethyl (CH2CH3), acetyl (COCH3), other alkyl or aryl groups or varying lengths and structures, and others. Some of the constituents R may also be connected to each other. Those with experience in the art with the benefit of this description will understand the variable natures of the R. institutions.

In reaction or manufacturing processes to form quaternary ammonium halides for use as AA-LDHI, it is common to form hydrogen halides and organic alcohols due to the residual water present during and the remainder in the reaction mixtures. This is due to the reaction of R-X with HOH (H20) to form ROH and HX. This is generally because an excess of RX must be used to drive the reaction. In some cases, as much as 1% of RX (for example, benzyl chloride and the like) is in the final reaction mixture that is converted over time to HX (HC1 and the like), and ROH and mixtures of the same. In some cases it has been found that acid corrosion inhibitors are required to mitigate the acid corrosion caused by the residual HC1. In addition, residual RX may prove to have some acute and chronic severe toxicity.

In one embodiment of the present description, the LDHI anti-binder is the reaction products of organic acid and organic amines. The reaction products of organic acids and organic amines are formed when certain organic acids are partially neutralized, giving them at least a partial negative charge which allows them to serve as anions in a salt. Figures 2a, 2b show some general examples of reaction products or organic acids and organic amines having the structure RXR2R3HN + (R4C00 ~) or R1R2R3HN + (R4PhO ~), wherein R1, R2, and R3 are independently H or C1- C40 alkyl, wherein R4 is Ci-Cw, and wherein Ph is any phenyl group. The Ci-C40 alkyl substituents include all the alkyl and aryl structures and the isomers within these embodiments. In these examples, the negatively charged anions are anions created by the partial or complete neutralization of acids. Certain embodiments may include reactions or mixtures that include varying proportions of the organic acid, the organic amine, and the salt resulting from the reaction of the organic acid and the amine. In certain embodiments of the present disclosure, approximately stoichiometric amounts of the organic acid and the amine are used to create the resulting salt. In other embodiments of the present invention, the molar proportions of the reagents are adjusted to create a surplus of free organic amine in the resulting reaction product. Typically, the excess amine is less than about 1% (molar) of the reaction product.

The compounds that can be used as cations with the desired acid anions can be any amines that do not contain suitable Halide. As discussed with respect to Figure 1, R, Rz and R3, may be any suitable substituents' *, including hydrogen '(?), Methyl (CH3), ethyl (CH2CH3),' acetyl (COCH3), and other groups alkyl or aryl of varying lengths. Some of the R substituents may also be connected to each other, and may include oxygen, nitrogen, and the like. Those skilled in the art with the benefit of this disclosure will understand the variable natures of the R substituents within the cation. Examples of suitable cations include, but are not limited to, ammonia, methylamine, di-methylamine, tri-methylamine, ethylamine, di-ethylamine, tri-ethylamine, n-propylamine, di-n-propylamine, tri-n-propylamine, mono -ethanolamine, di-ethanolamine, di-ethylethanolamine, methylethanolamine, tri-ethanolamine, methyldiethanolamine, propylethanolamine, ethyldiethanolamine, di-methylaminopropylamine, di-propylethanolamine, di-n-butylamine, di-butylpropanolamine, di-butylethanolamine, morpholine , piperazine, octylamine, di-methyloctylamine, decylamine, di- Methyldzylamine, laurylamine, di-methylaurylamine, myristylamine, di-methylpalmitylamine, stearylamine, di-methylstearylamine, di-stearylamine, N, N-di-butylcocoamidopropylamine, cocoamine of N, N-di-methylcocoamidopropylamine, cocodiamine, dimethylcocoamine, ceboamine, bait di -amine, di-methyl-bait amine, soy amine, dimethyl soy, amine, di-dodecylmonomethylamine, fatty imidazolines, fatty amido-amines, fatty amines and mixtures thereof.

Compounds that can be used as cationless anions discussed above can also be acids that do not contain suitable halide. As discussed with respect to Figure 1, R4 can be any suitable constituents, including hydrogen (H), methyl (CH3), ethyl (CH2CH3), acetyl (COCH3), and other alkyl or aryl groups of varying lengths, and can Include oxygen, nitrogen, and the like. Examples of suitable anions include formic acid, acetic acid, lactic acid, cyanuric acid, angelic acid, propionic acid, butyric acid, aspartic acid, glycolic acid, adipic acid, maleic acid, citric acid,: italic acid, anthranilic acid, octanoic acid, lauric acid, benzoic acid, salicylic acid, fumaric acid, oxalic acid, succinic acid, acrylic acid, cinnamic acid, azelaic acid, acid Neodecanoic acid, benzyl acid, pelargonic acid, stearic acid, acid dimer, acid. trimer, various variations of dimer-trimers, mixtures of acids, methanesulfonic acid, dodecylbenzenesulfonic acid, para-toluenesulfonic acid, oleic acid, fatty acid of resin oil, linoleic acid, abietic acid, rosin acid, naphthenic acid, carboxylic acids and anhydrides thereof, phenols, sulfonic acids, sulfuric acid, phosphoric acid, nitric acid or mixtures thereof. Those skilled in the art with the benefit of this disclosure will understand the variable natures of the R constituents within the anion.

As those skilled in the art with the benefit of the present disclosure will appreciate, certain salts prepared in accordance with the present disclosure will have performance characteristics superior to other salts. As described in U.S. Patent No. 5, 460, 728 to Klomp et al., Which is incorporated herein by reference, compounds suitable for use as AA-LDHI will have at least some of the following characteristics: They inhibit the growth of hydrate crystals; emulsify in the hydrocarbon phase, thus maintaining the concentration of water available for the formation of hydrates in the thin wall of the canal; Concentrate close to the water-hydrocarbon interfaces, where the formation of hydrates is more pronounced, increasing with this the local concentration of ions to the level of depression of the freezing point; modifying the structure of the water near the hydrocarbon-water interface in such a way as to prevent the formation of hydrate crystals; preventing additional action of water molecules to the hydrated crystals after binding of the compound to the hydrate crystals; avoid agglomeration of hydrate crystals by making their surface hydrophobic; Adhere to the wall of the canal, thus avoiding the adhesion of hydrates to it.

Examples of salts that meet one or more of the above criteria include the reaction product of a 1: 1 molar ratio of benzoic acid and dimethylpalmitoylamine, a 2: 1 molar ratio of italic anhydride and cocodiamine, and a molar ratio of 2: 1 of salicylic acid and cocodiamine.

Certain reaction products of organic acids and organic amines derived from coconut oil have the structure [CH3 (CH2) "(CH3) 2HN +] [CH3 (CH2) nC00"]. shows a general representation of these possible reaction products and an amine and acid based on coconut oil in which n may vary from, for example, 8 to 12. This is an illustrative embodiment which in no way limits the scope of the invention. general anti-agglomeration composition.

The reaction products of organic acids and amines, organic are more advantageous than. Traditional AA-LDHI prepared, from alkyl or aryl halides in various aspects. In the processes of reaction or manufacture to form quaternary ammonium halides to be used as ÁA-LDHI it is common to form hydrogen halides and organic alcohols due to the residual water present during and the remainder in the reaction mixtures. The reactants and reaction products in the current AA-LDHI compositions are not as corrosive as the similar ones of HC1 or HX, do not cause mechanochemical cracking by halide, and are not as toxic. Because of these advantages, anti-caking compositions can be continuously injected into petroleum and natural gas systems. Methods for continuous injection include umbilical or capsule chain. Batch applications are also suitable. The anti-caking compositions can be applied at a concentration between about 0.05% to about 10%, and preferably between about 0.2% to approximately 1.5%.

Without wishing to be bound by theory, the anti-caking compositions consist of mixtures of reaction products of organic acids and organic amines which function to help emulsify the water in the oil. It is generally accepted that LDHI anti-caking molecules need hydrocarbons to function and tend to emulsify water as an internal emulsion phase. This limits the growth 'size of the hydrate crystals to a form and size that does not allow: that the hydrates formed obstruct the production equipment.

Current anti-caking compositions have distinct advantages over those commercially available anti-agglomerate compositions, since all of these compositions contain residual chlorides. One advantage is the difference in corrosion capacity, which is the result of basic differences in the corrosion capacity between inorganic acids such as HC1 or HX and that of organic acids. The pKa associated with HX is much smaller than that associated with COOH. The current AA-LDHIs potentially solve the long-term corrosion problems present with the chlorides or HC1 that are or are inherent in the quaternary type products typically used where a continuous injection of anti-oxidant is required. binders. Cracking by chloride corrosion or hydrogen penetration is accelerated by the trace HC1 formed in the reaction of R-Cl / RX in quaternary processing which has proved to be a problem in continuous use against AA-LDHI batch of quaternary basis. The test has shown that current anti-caking compositions are equal if not superior to the industrial standard in performance. further, current non-quaternary anti-caking compositions have higher oil solubility for the reduction of water quality problems. This leads to increased "greenness" or environmental compatibility when dividing more for the oil phase. Current compositions also lack certain inherent chronic or carcinogenic toxicity characteristics associated with RC1, residual RX, and other organic chloride or halide found in traditional AA-LDHIs, including vinyl chloride, benzyl chloride, alkyl bromides, and the similar.

In addition, AA-LDHI produced according to the present disclosure have better stability at higher temperatures than traditional AA-LDHI. In certain applications, it may be necessary for the AA-LDHI to be subjected to temperatures in excess of 121.11 ° C (250 ° F). Certain traditional AA-LDHIs, such as those prepared from Quaternary amines are known to be derated at higher temperatures, resulting in a reduction in efficiency to control hydrates. Those AA-LDHIs prepared in accordance with the present disclosure retain their effectiveness after exposure to temperatures in excess of 121.11 ° C (250 ° F).

In addition, unlike the traditional AA-LDHI, the AA7-LDH prepared according to the present description, function as corrosion inhibitors. Corrosion in oil and gas production is often the result of the presence of water in the production equipment, either produced from the formation, from the condensation, or from the water injected into the well, through example, to help lift. Hydrogen sulfide (H2S) and carbon dioxide (CO2) are often present in the fluids produced, which can, in the presence of water, form acids such as sulfuric and carbonic acids (respectively). When present, oxygen can also contribute to corrosivity and is sometimes a contaminant in the water used for injection.

The AA-LDHI of the present description can, in addition to serving as AA-LDHI, function as corrosion inhibitors by contacting them and coating the exposed metal of the equipment and pipeline for oil production and gas. The exposed metal, after being coated, by the corrosion inhibitor, prevents further corrosion of the surface by the corrosive agents in the hydrocarbon stream.

Corrosion inhibitors are normally supplied through an umbilical conduit to the equipment and pipeline for oil and gas production. The further use of the AA-LDHIs of the present disclosure as corrosion inhibitors has the benefit of both reducing costs for the driller by removing an additional chemical at the site, but also by eliminating the umbilical conduit used to deliver the inhibitor. of traditional corrosion.

Example 1 ·" Four AA-LDHIs prepared according to the present disclosure were tested and compared to determine their effectiveness in preventing the formation of hydrate crystals in gas production systems. The four AA-LDHI tested were benzoic acid / dimethylpalmitoylamine mixed in a 1: 1 molar ratio, maleic anhydride / dimethylpalmitoylamine mixed in a molar ratio of 1: 1, methanesulfonic acid / cocodiamine mixed in a molar ratio of '2: 1, anhydride' phthalic / cocodiamine mixed in a 2: 1 molar ratio, and salicylic acid / cocodiamine mixed in a 2: 1 molar ratio. A rocky cell test was performed in each of the four AA-LDHI.

The AA-LDHI were tested in a bank of high pressure rock cells. - Each cell was equipped with clear sapphire tubes, housed and sealed in a Hastelloy box.Sapphire tubes allow visual observation of pressurized, cooled fluids The cells were isolated from each other and equipped with pressure transducers and proximity sensors.A magnetic ball provided agitation as the cells were rotated back and forth at a predetermined angle and speed. The cells were submerged in a temperature controlled bath that consisted of glycol and water.

The < temperature and rolling was programmed and automated. Each cell was pressurized independently and the pressure was monitored and recorded, coupled with the temperature data and the signals from the proximity sensors.

The four AA-LDHIs were tested under conditions that simulated an offshore pipeline in the Gulf of Mexico (GOM). The processes of stable state, temporary closure and re-initiation were replicated. The test fluids (hydrocarbons and gas) were the representative GOMs shown in Table 1.

Table 1. Test fluids The composition of gas was similar to Canyon, a hydrate trainer with structure Table 2. Type II gas composition All tests were conducted at a constant volume. The concentration of the inhibitor varied from 1-5% by volume based on the total amount of water. The cells were initially pressurized at 20 ° C to 154.68 kg / cm2 (2200 psig). The rolling began at 15 rocks / min at an angle of ± 25 ° from the horizontal. At a constant temperature of 20 ° C, the cells were balanced for 2 hours to mix the fluids and allow the gas to saturate the fluids. The temperature was then continuously lowered to 4 ° C over a period of 2 hours while rolling continued.

After reaching 4 ° C, the cells were balanced for 12 hours, at which time they "temporarily closed". This phase consists in stopping the balancing with the cells in a horizontal position, simulating a closing of the pipes. At the end of the closing period, the balancing was restarted and the cells were balanced for 2 hours. This was followed by a temperature ramp of 4 ° C to 20 ° C for a period of 2 hours. Finally, the cells were rocked at 20 ° C for 2 hours. The final pressure was observed to ensure there was no leakage from the cells.

The performance of the chemicals is classified according to the following scale: 1. Ball of; blockage, low level of liquid, large agglomerations: or solid crystals, visible deposits in the tube. 2. The ball is free but resists rolling, moderate-to-little change in the liquid level, large solid crystals, agglomerations that separate with agitation, without visible deposits in the tube. 3. The ball is free, without change · in the level of liquid, viscous liquid, small agglomerations dispersible or crystals, without visible deposits on the tube. 4. The ball is free, without change in the level of liquid, low viscosity, fine crystals "easily dispersed, without large crystals. 5. The ball is free, with no change in fluid level, little or no change in viscosity,. no visible deposits in the tube or cylinder extremely fine crystals easily dispersible.

Figure 4 shows the results of the performance classification.

Although the invention has been described with reference to specific embodiments, this does not mean that the description will be construed in a limited sense. Various modifications of the described modalities, as well as the alternative modalities of the; invention, will become apparent to those skilled in the art with reference to the description of the invention. Therefore, it it is contemplated that the appended claims will cover these modifications that fall within the scope of the invention, or their equivalents.

References cited The following publication is incorporated herein by reference.

Kelland, Malcom A. "History of the Development of Low Dosage Hydrate Inhibitors." Energy & Fuels, An American Chemical Society Journal, vol. 20, May / June 2006.

Claims (13)

NOVELTY OF THE INVENTION Having described the present invention, it is considered as a novelty and, therefore, the content of the following is claimed as property CLAIMS:

1. "A composition of an inhibitor, anti-agglomerating hydrate, characterized in that it comprises: a product of. reaction of an organic amine and an acid selected from the group consisting of inorganic acids that do not contain halide, one of the organic acids, and mixtures thereof, wherein the reaction product is practically free of compounds containing halides.

2. The composition of the anti-caking hydrate inhibitor according to claim 1, characterized in that the inorganic acid is selected from the group consisting of a sulfonic acid, sulfuric acid, phosphoric acid, nitric acid, and mixtures thereof.

3. The composition of the anti-agglomeration hydrate inhibitor according to claim 1, characterized in that the organic acid is selected from the group consisting of formic acid, acetic acid, lactic acid, cyanuric acid, angelic acid, propionic acid, butyric acid, 'aspartic acid, glycolic acid, adipic acid acid, maleic acid, citric acid, italic acid, anthranilic acid, octanoic acid, lauric acid, benzoic acid, salicylic acid, fumaric acid, oxalic acid, succinic acid, acrylic acid, cinnamic acid, azelaic acid, neodecanoic acid, benzyl acid, pelargonic acid, stearic acid, a dimer acid, trimer acid, methanesulfonic acid, dodecylbenzenesulfonic acid, para-toluene acid, oleic acid, fatty acid of resin oil, linoleic acid, abietic acid, rosin acid, naphthenic acid, carboxylic acids and anhydrides or carboxylic acids, phenols, and mixtures thereof.

4. The composition of the anti-caking hydrate inhibitor according to claim 1, characterized in that the organic amine is selected from the group consisting of ammonia, methylamine, di-methylamine, tri-methylamin, ethylamine, di-ethylamine, tri-ethylamine, n- propylamine, di-n-propylamine, tri-n-propylamine, mono-ethanolamine, di-ethanolamine, di-ethylethanolamine, methylethanolamine, tri-ethanolamine, methyldiethanolamine, propylethanolamine, ethyldiethanolamine, di-methylaminopropylamine, di-propylethanolamine, di-n- butylamine, di-butylpropanolamine, di-butylethanolamine, morpholine, piperazine, octylamine, di-methyloctylamine, decylamine, di-methyldecylamine, laurylamine, 'di-methylaurylamine, myristylamine, di-methylpalmitylamine, stearylamine, di-methylstearylamine, di-stearylamine, N, N-di-butylcocoamidopropylamine, cocoamine of N, N-di-methylcocoamidopropylamine, cocodiamine, dimethylcocoamine, baboamine, di-amine bait, di-methyl-bait amine, soy amine, dimethyl soya amine, di-dodecylmonomethylamine, a fatty imidazoline, a fatty amine amine, a fatty amine and mixtures thereof.

5. The composition of the anti-caking inhibitor hydrate according to claim 1, characterized in that the reaction products comprise the structure R1R2R3HN + (R4C00-), wherein 'R1, R2, and R3 are independently H or C1-C40 alkyl, and wherein R 4 is Cl-C 40 alkyl.

6. The anti-caking hydrate inhibitor composition according to claim 1, characterized in that the reaction products have the structure R 1 R 2 R 3 HN + (R PhO-), wherein R 1, R 2, and R 3 are independently H or C 1 -C 40 alkyl, wherein R 4 is C1-C40 alkyl, and wherein Ph is any phenyl group.

7. The composition of the anti-caking hydrate inhibitor according to claim 3, characterized in that the reaction products have the structure [CH3 (CH2) n (CH3) 2HN +] [CH3 (CH2) nCOO-].

8. The composition of the anti-caking inhibitor d-hydrate according to claim 7, characterized in that n is from 8 to 12.

9. - A method for applying a composition of an anti-agglomeration hydrate inhibitor to a hydrocarbon stream comprising: mixing an organic amine and an acid selected from the group consisting of an inorganic acid that does not contain halide, an organic acids, and mixtures thereof, to form a reaction product, wherein the reaction product is practically free of compounds that contain halides; Y apply the reaction product to a stream of hydrocarbons.

10. The method according to claim 9, characterized in that the organic amine and the acid are mixed in an approximately stoichiometric ratio.

11. The method according to claim 9, characterized in that the anti-binder hydrate inhibitor composition is applied continuously or in batch applications to the petroleum or natural gas stream.

12. The method according to claim 9, characterized in that the composition of the inhibitor of The anti-caking hydrate is applied to the hydrocarbon stream in an amount sufficient to form a concentration between about 0.05% to about 10% by weight of the anti-caking hydrate inhibitor in the hydrocarbon stream.

13. The method according to claim 9, characterized in that the composition of the anti-caking hydrate inhibitor is applied to the hydrocarbon stream in an amount sufficient to form a concentration between about 0.2% to about 1.5% by weight of the anti-caking hydrate inhibitor. in the hydrocarbon stream.