OA22162A - Combination products containing antiagglomerant low dose hydrate inhibitors and corrosion inhibitors with improved corrosion resistance. - Google Patents

Abstract

Hydrate inhibitor and corrosion inhibitor composition are disclosed and include from about 10 wt-% to about 99.9 wt-% of an antiagglomerant low dose hydrate inhibitor (AALDHI), wherein the AA-LDHI is a zwitterionic compound or a cationic ammonium compound; from about 0.01 wt-% to about 50 wt-% of a corrosion inbibitor, and at least one additional functional ingredient, solvent, or a combination thereof. Methods for inbibiting corrosion and formation of gas hydrate agglomerants in a fluid are disclosed and include contacting the fluid with a hydrate inhibitor and corrosion inhibitor composition or contacting the fluid with an AA-LDHI, wherein the AA-LDHI is a zwitterionic compound or a cationic ammonium compound, and a corrosion inhibitor, wherein the AA-LDHI and corrosion inbibitor are provided at a weight ratio of about 1:0.001 to about 1:1, and wherein the composition inhibits general and localized corrosion and formation of gas hydrate agglomerants in the fluid.

Description

T1TLE: COMBINATION PRODUCTS CONTAINING ANTI-AGGLOMERANT

LOW DOSE HYDRATE INHIBITORS AND CORROSION INHIBITORS WITH 1MPROVED CORROSION RESISTANCE

CROSS-REFERENCE TO RELATED APPLICATION |0001| This application daims priority under 35 U.S.C. § U9to Provisional Application U.S. Serial No. 63/374,685, filed on September 6, 2022, which is herein incorporated by reference in its entirety including without limitation, the spécification, daims, and abstract, as wdl as any figures, tables, or examples thereof.

FIELD |0002] The disclosure relates generally to compositions and methods for reducing or inhibiting the growth, formation, and/or agglomération of hydrate particles in fluids while also inhibiting corrosion. More speciflcally, the disclosure relates to combinational use of anti-agglomerate low 15 dose hydrate inhibitors and corrosion inhibitors providing corrosion inhibition and reducing or inhibiting hydrate agglomération in the production and transport of petroleum fluids, including mixtures of varying amounts of water/brine, crude oil/condensate, and natural gas.

BACKGROUND |0003J A significant risk to oil and gas production infrastructure is accelerated internai pipeline corrosion. The production of oil and gas réservoirs présent corrosive environments that place the internai metallurgy of process equipment (e.g., transport pipelines, flow fines, séparation equipment), ofïen constructed of mild carbon Steel, at risk for failure. The rate of corrosion détérioration in oil and gas field equipment metallurgy is dépendent upon production parameters such as oil/water ratio, fluid brine composition, température. pH. and the concentration of corrosive gases typically présent in the réservoir formation, such as CO₂, H₂S, or combinations thereof.

[0004] In order to preserve the integrity of oil and gas infrastructure, corrosion inhibitors are added into production fluids upstream of piping infrastructure intended to be protected. !n 30 general, corrosion inhibitors of this type protect the métal through formation of a passivation film on the métal surface. This passivation layer oil wets the métal surface, which in turn prevents contact of the métal from the corrosive nature of the produced réservoir fluids. Typically, corrosion inhibitor formulations of this type contain a variety of aliphatic organic surfactant molécules ranging from, but not limited to, amines, quaternary amines, imidazolines, 35 phosphate esters, amides, carboxylic acids, or combinations thereof.

|0005| In addition to corrosion, another challenge are gas hydrates known to block gas pipelines and therefore the prévention of hydrate formation and agglomération has become a requirement in the oil and gas industry. Naturel gas hydrates are crystalline solids composed of water and gas. Gas hydrates can easily form during the transportation of oil and gas in pipelines when the 5 appropriale conditions are présent, such as water content, low températures, and elevated pressure, causing the ice-like gas hydrate solids to form from the small, nonpolar molécules and water. Under these conditions, the water molécules can form cage-like structures around these small nonpolar molécules (typically dissolved gases such as carbon dioxide, hydrogen sulfide, methane, ethane, propane, butane and iso-butane), creating a type of host-guest interaction also 10 known as a clathrate or clathrate hydrate. The spécifie architecture of these structures can vary.

However, once formed, they tend to settle out from the solution and accumulate into large solid masses that can travel by oil and gas transporting pipelines, and potentially block or damage the pipelines and/or reiated equipment. The formation of gas hydrates can cause damage, including resulting from a blockage, that can be very costly from an equipment repair standpoint, as well as from the loss of production, and finally the résultant environmental impact. As a resuit, the formation of gas hydrates often results in lost oil production and pipeline damage.

[0006] Modem oil and gas technologies commonly operate under severe conditions during the course of oil recovery and production, such as high pumping speed, high pressure in the pipelines, extended length of pipelines, and low température of the oil and gas flowing through 20 the pipelines. These conditions are particularly favorable for the formation of gas hydrates, which is an undesirable outcome. Various classes of hydrate inhibitors are used to prevent blockages, such as thermodynamic hydrate inhibitors (THI), anti-agglomerant hydrate inhibitors (AAs), and kinetic hydrate inhibitors (KHis). The amount of Chemical needed to prevent blockages varies widely depending upon the type of inhibitor employed. Thermodynamic hydrate inhibitors are substances that can reduce the température at which the hydrates form at a given pressure and water content, and are typically used at very high concentrations. Therefore, there is a substantial cost associated with the transportation and storage of large quantifies of these solvents. A more cost-effective alternative is the use of low dosage hydrate inhibitors (LDHls), as they generally require a dose of less than about 2% to inhibit the nucléation or growth of gas hydrates. There are two general types of LDHls, kinetic hydrate inhibitors and anti-agglomerants which are both typically used at much lower concentrations. KHis work by delaying the growth of gas hydrate crystals. They also function as anti-nucleators. In contrast, AAs aliow hydrates to form but they prevent them from agglomerating and subsequently accumulating into larger masses capable of causing plugs. The function of an AA is to keep hydrate particles dispersed as a fluid slurry within the hydrocarbon phase.

[0007] Thus, there exists a need in the art for enhanced treatment compositions for combined corrosion inhibition and hydrate inhibition.

[0008] It is therefore an object of this disclosure to provide a hydrate inhibitor and corrosion inhibitor composition that simultaneously provides effective hydrate inhibition and iocalized corrosion inhibition.

[0009] It is a further object of the disclosure to provide methods for inhibiting corrosion and formation of gas hydrate agglomérants in a fluid superiorto conventional treatments.

[0010] Other objects, embodiments and advantages of this disclosure wil 1 be apparent to one skiiled in the art in view of the following disclosure, the drawings. and the appended daims.

BRIEF SUMMARY

[0011 ] The following objects, features, advantages, aspects, and/or embodiments, are not exhaustive and do not limit the overall disclosure. No single embodiment need provide each and every object, feature, or advantage. Any of the objects, features, advantages, aspects, and/or embodiments disclosed herein can be integrated with one another, either in full or in part. It is a primary object, feature, and advantage of the présent disclosure to provide a hydrate inhibitor and corrosion inhibitor composition that simultaneously provides effective hydrate inhibition and Iocalized corrosion inhibition.

[0012] According to some aspects of the présent disclosure, a hydrate inhibitor and corrosion inhibitor composition comprises: from about 10 wt-% to about 99.9 wt-% of an antiagglomerant low dose hydrate inhibitor (AA-LDHI), wherein the AA-LDHI is a zwitterionic compound or a cationic ammonium compound; from about 0.01 wt-% to about 50 wt-% of a corrosion inhibitor; and at least one additional functional ingrédient, solvent, or a combination thereof.

[0013] According to an additional aspect of the présent disclosure, method for inhibiting corrosion and formation of gas hydrate agglomérants in a fluid comprises: contacting the fluid with a hydrate inhibitor and corrosion inhibitor composition as described herein, or contacting the fluid with an anti-agglomerant low dose hydrate inhibitor (AA-LDHI), wherein the AALDHI is a zwitterionic compound or a cationic ammonium compound, and a corrosion inhibitor, wherein the AA-LDHI and corrosion inhibitor are provided at a weight ratio of about 1:0.001 to about 1:1, wherein the composition inhibits general and Iocalized corrosion and formation of gas hydrate agglomérants in the fluid.

[0014] These and/or other objects, features, advantages, aspects, and/or embodiments will become apparent to those skiiled in the art after reviewing the following brief and detailed descriptions of the drawings. Furthermore, the présent disclosure encompasses aspects and/or

embodiments not expressly disclosed but which can be understood from a reading of the présent disclosure, including at least: (a) combinations of disclosed aspects and/or embodiments and/or (b) reasonable modifications not shown or described.

[0015] While multiple embodiments are disclosed, still other embodiments will become apparent to those skilled in the art from the following detailed description, which shows and describes illustrative embodiments. Accordingly, the drawings and detailed description are to be regarded as illustrative in nature and not restrictive.

DETAILED DESCRIPTION

[0016] The présent disclosure is not to be limited to that described herein, which can vary and are understood by skilled artisans. No features shown or described are essential to permit basic operation of the présent disclosure unless otherwise indicated. It is further to be understood that ail terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting in any manner or scope. For example, as used in this spécification and the appended daims, the singular forms a, an and the can include plural referents unless the content clearly indicates otherwise. Further, ail units, préfixés, and symbols may be denoted in its SI accepted form.

[0017] Numeric ranges recited within the spécification are inclusive of the numbers defining the range and include each integer within the defined range. Throughout this disclosure, various aspects of this disclosure are presented in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosure. Accordingly, the description of a range should be considered to hâve specificaliy disclosed ail the possible sub-ranges, fractions, and individual numerical values within that range. For example, description of a range such as from

1 to 6 should be considered to hâve specificaliy disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1,2, 3, 4, 5, and 6, and décimais and fractions, for example, 1.2, 3.8, 1Ά, and 4%. This applies regardless of the breadth of the range.

[0018] As used herein, the term “and/or”, e.g., “X and/or Y” shall be understood to mean either

X and Y or X or Y and shall be taken to provide explicit support for both meanings or for either meaning, e.g. A and/or B includes the options i) A, ii) B or iii) A and B.

[0019| It is to be appreciated that certain features that are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any sub-combination.

(0020] The methods and compositions of the présent disclosure may comprise, consist essentially of, or consist of the components and ingrédients of the présent disclosure as well as other ingrédients described herein. As used herein, “consisting essentially of’ means that the methods, Systems, apparatuses and compositions may include additional steps, components or 5 ingrédients, but only if the additional steps, components or ingrédients do not materially alter the basic and novel characteristics of the claimed methods, Systems, apparatuses, and compositions. (0021) Unless defined otherwise, ail technical and scientific ternis used above hâve the same meaning as commonly understood by one of ordinary skill in the art to which embodiments of the présent disclosure pertain.

| (1022 J The tenus “invention” or “présent invention” are not intended to refer to any single embodiment of the particular invention but encompass ail possible embodiments as described in the spécification and the daims.

|0023| The term “about,” as used herein, refers to variation in the numerical quantity that can occur, for example, through typical measuring techniques and equipment, with respect to any 15 quantifiable variable, including, but not limited to, mass, volume, time, température, pH, and log count of bacteria or viruses. Further, given solid and liquid handling procedures used in the real world, there is certain inadvertent error and variation that is likely through différences in the manufacture, source, or purity of the ingrédients used to make the compositions or carry out the methods and the like. The term “about” also encompasses these variations. Whether or not 20 modified by the term “about,” the daims include équivalents to the quantities.

[0024] The term actives or percent actives or percent by weight actives or actives concentration are used interchangeably herein and refers to the concentration of fhose ingrédients involved in cleaning expressed as a percentage minus inert ingrédients such as water or salts. It is also sometimes indicated by a percentage in parenthèses, for example, “Chemical 25 (10%).”

[0025] As used herein, the term “alkyl” or “alky 1 groups” refers to saturated hydrocarbons having one or more carbon atoms, including straight-chain alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.), cyclic alkyl groups (or “cycloalkyl” or “alicydic” or “carbocyclic” groups) (e.g., cyclopropyl, cyclopentyl, cyclohexyl, 30 cycloheptyl, cydooctyl, etc.), branched-chain alkyl groups (e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc.), and alkyl-substituted alkyl groups (e.g., alkyl-substituted cycloalkyl groups and cycloalkyl-substituted alkyl groups).

|0026] Unless otherwise specifïed, the term “alkyl” includes both “unsubstituted alky 1s” and “substituted alkyls.” As used herein, the term “substituted alkyls” refers to alkyl groups having 35 substituents replacing one or more hydrogens on one or more carbons of the hydrocarbon

backbone. Such substituents may include, for example, alkenyl, alkynyl, halogeno, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkyiaminocarbonyi, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonate, phosphinato, cyano, 5 amino (including alkyl amino, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino (including alkylcarbonyl ami no, arylcarbonylamino, carbamoyl and ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfates, alkyIsulfinyl, sulfonates, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclic, alkylaryl, or aromatic (including heteroaromatic) groups,

[0027] In some embodiments, substituted alkyls can include a heterocyclic group. As used herein, the term “heterocyclic group” includes closed ring structures analogous to carbocyclic groups in which one or more of the carbon atoms in the ring is an element other than carbon, for example, nitrogen, sulfur or oxygen. Heterocyclic groups may be saturated or unsaturated.

Exemplary heterocyclic groups include, but are not l imited to, aziridine, ethylene oxide 15 (epoxides, oxiranes), thiirane (episulfides), dioxirane, azetidine, oxetane, thietane, dioxetane, dithietane, dithiete, azolidine, pyrrolidine, pyrroline, oxolane, dihydrofuran, and furan.

[0028] The tenus aryl or ar as used herein alone or as part of another group (e,g„ aralkyl) dénoté optionally substituted homocyclic aromatic groups, preferably monocyclic or bicyclic groups containing from 6 to 12 carbons in the ring portion, such as phenyl, biphenyl, naphthyl, 20 substituted phenyl, substituted biphenyl or substituted naphthyl. Phenyl and substituted phenyl are the more preferred aryl. The term ary l also includes heteroaryl.

[0029| Arylalkyl means an aryl group attached to the parent molécule through an alkylene group. In some embodiments the number of carbon atoms in the aryl group and the alkylene group is selected such that there is a total of about 6 to about 18 carbon atoms in the arylalkyl 25 group. A preferred arylalkyl group is benzyl.

[0030] The term “configured” describes structure capable of performing a task or adopting a particular configuration. The term “configured” can be used interchangeably with other similar phrases, such as constructed, arranged, adapted, manufactured, and the like. Terms characterizing sequential order, a position, and/or an orientation are not limiting and are only 30 referenced according to the views presented.

[0031J The term -ene as used as a suffix as part of another group dénotés a bivalent substituent in which a hydrogen atom is removed from each of two terminal carbons of the group, or if the group is cyclic, from each of two different carbon atoms in the ring. For example, alkylene dénotés a bivalent alkyl group such as methylene (-CH2-) or ethylene (-CH2CH2-), and arylene 35 dénotés a bivalent aryl group such as o-phenylene, m-phenylene, or p-phenylene.

[0032] As used herein, the term “exemplary” refers to an example, an instance, or an illustration, and does not indicate a most preferred embodiment unless otherwise stated.

[0033] As used herein, the term free refers to compositions completely lacking the component or having such a small amount of the component that the component does not affect the performance of the composition. The component may be présent as an impurity or as a contaminant and shall be less than 0.5 wt-%, less than 0.1 wt-% and in yet another embodiment, the amount of component is less than 0.01 wt-% or 0 wt-%.

[0034] The term “generally” encotnpasses both “about” and “substantially.”

[0035] The term inhibiting as referred to herein includes both inhibiting and preventing, such 10 as in reference to corrosion and the formation and agglomération of hydrate crystals.

[0036] As used herein the term polymer refers to a molecular complex comprised of a more than ten monomeric units and generally includes, but is not limited to, homopolymers, copolymers, such as for example, block, graft, random and alternating copolymers, terpolymers, and higher xmers, further including their analogs, dérivatives, combinations, and blends thereof. Furthermore, unless otherwise specifically limited, the term polymer shall include ail possible isomeric configurations of the molécule, including, but are not limited to isotactic, syndiotactic and random symmetries, and combinations thereof. Furthermore, unless otherwise specifically limited. the term polymer shall include ail possible geometrical configurations of the molécule.

[0037] The “scope” of the présent disclosure is defined by the appended daims, along with the full scope of équivalents to which such daims are entitled. The scope of the disclosure is further qualified as including any possible modification to any of the aspects and/or embodiments disclosed herein which would resuit in other embodiments, combinations, subcombinations, or the like that would be obvious to those skiiled in the art.

[0038] The term “substantially” refers to a great or significant extent. “Substantially” can thus refer to a plurality, majority, and/or a supermajority of said quantifiable variable, given proper context.

[0039] As used herein, the term “substantially free” refers to compositions completely lacking the component or having such a small amount of the component that the component does not affect the performance of the composition. The component may be présent as an impurity or as a contaminant and shall be less than 0.5 wt-%.

[00401 The term substituted as in substituted aryl, substituted alkyl, and the like, means that in the group in question (i.e., the alkyl, aryl or other group that follows the term), at least one hydrogen atom bound to a carbon atom is replaced with one or more substituent groups such 35 as hydroxy (-OH), alkylthio, phosphino, amido (-CON(Ra)(Rb), wherein Ra and Rb are independently hydrogen, alkyl, or aryl), amino(-N(RA)(RB), wherein Ra and Rb are independently hydrogen, alkyl, or aryl), halo (fluoro, chloro, bromo, or iodo), silyl, nitro (NO;), an ether (-ORa wherein Ra is alkyl or aryl), an ester (-OC(O)Ra wherein Ra is alkyl or aryl), keto (-C(O)Ra wherein Ra is alkyl or aryl), heterocyclo, and the like. Further, an alkylene 5 group in the chain can be replaced with an ether, an amine, an amide, a carbonyl, an ester, a cycloalkyl, or a heterocyclo functional group. When the term substituted introduces a list of possible substituted groups, it is intended that the term apply to every member of that group. That is, the phrase optionally substituted alkyl or aryl is to be interpreted as optionally substituted alkyl or optionally substituted aryl.

IO [00411 The term surfactant or surface active agent refers to an organic Chemical that when added to a liquid changes the properties of that liquid at a surface.

[0042] The term weight percent, wt-%, percent by weight, % by weight, and variations thereof, as used herein, refer to the concentration of a substance as the weight of that substance divided by the total weight of the composition and multiplied by 100. It is understood that, as 15 used here, percent, %, and the like are intended to be synonymous with weight percent, wt-%, etc.

COMPOSITIONS

[0043] According to embodiments, the compositions for inhibiting corrosion and gas hydrate agglomération to effectively control corrosion and gas hydrate formation and plugging in hydrocarbon production and transportation Systems are disclosed herein. The compositions include an anti-agglomerant low dose hydrate inhibitor (AA-LDHI), a corrosion inhibitor, and a solvent. The compositions can include additional functional ingrédients and can be provided as concentrate or use compositions. Exemplary compositions are shown in Table 1 in weight percentage.

[0044] While the components may hâve a percent actives of 100%, it is noted that Table 1 does not recite the percent actives of the components, but rather, recites the total weight percentage of the raw materials (i.e. active concentration plus inert ingrédients) if provided in a single composition.

[0045] TABLE 1

Material	First Exemplary Range wt.-%	Second Exemplary Range wt.-%	Third Exemplary Range wt.-%
AA-LDHI	10-99.9	20-99.9	50-99.9
Corrosion Inhibitor	0.001-50	0.005-20	0.01-10

Solvent	0-10	0-8	0-5
Additional Functional Ingrédients	0.0001-20	0.001-10	0.001-5

[0046| The composition (and methods employing the AA-LDHI and Cls) are preferably free of kinetic hydrate inhibitors, including for example those disclosed in U.S. Patent No. 8,821,754 and WO93/25798. The compositions (and methods employing the AA-LDHI and Cls) are further preferably free of fluoroalkyl compounds. In still further embodiments, the composition (and methods employing the AA-LDHI and Cls) are preferably free of kinetic hydrate inhibitors and fluoroalkyl compounds.

Anti-Agglomérant Low Dose Hydrate Inhibitors |0047] The composition comprises at least one anti-agglomerant low dose hydrate inhibitor (AA-LDHI). AA-LDHI in the compositions can include zwitterionic compounds and cationic ammonium compound.

(0048] The zwitterionic AA-LDHI included in the hydrate inhibitor and corrosion inhibitor compositions can include a compound of Formula (I), or an acid, a free base, a zwitterion, or a sait thereof:

R] O

Rs N

Rs (I), wherein Ri is hydrogen, a Ci to C20 substituted or unsubstituted alkyl group, or a Ci to C20 substituted or unsubstituted alkenyl group; R₂ is hydrogen, a Ci to C20 substituted or unsubstituted alkyl group, or a C, to C20 substituted or unsubstituted alkenyl group, an alkylcarboxyl, or an alkylamido group; R4 and R5 are independently hydrogen, a Ci to C20 substituted or unsubstituted alkyl group, a C, to C20 substituted or unsubstituted alkenyl group, or wherein the nitrogen atom and the R4 and R5 groups form a substituted or unsubstituted heterocyclo group; and Rs is a C2 to Cio substituted or unsubstituted alkylene group.

[0049] The substituted alkyl group of Ri, R₂, R4, and Rs can hâve at least one of the -CH₂groups in the chain replaced with an ether, an amine, an amide, a carbonyl, or an ester functional group or can hâve at least one of the hydrogen atoms attached to a carbon atom of the chain be replaced with a hydroxy, a halo, or an amine group, The substituted alkyl group of Ri, R₂, R4, and R5 can also hâve at least one of the -CH?- groups in the chain replaced with an amine. The compound of Formula (I) can hâve Rs be -C₂H4- Additionally, the compound of Formula (I) can hâve Ri be Cio to C₂o alkyl or-Rio-NRoR?, wherein Rio is Ci to C5 alkylene, and Ro and R7

ΙΟ are independently substituted or unsubstituted C, to C& alkyl. Further, the compound of Formula (I), can be —R20-C(O)O', wherein R20 is Ci to C4 alkylene. For the compound of Formula (I), R.i can be hydrogen. For the compound of Formula (I), R5 can be Cioto C20 alkyl or-RsoNRôR?, R50 can Ci to Cs alkylene, and Rô and R7 can independently be Ci to Cô alkyl.

Additionally, the compounds of Formula (I) can hâve R₂o can be -C2H4-, and Rsocan be -C3H66[0050| Exemplary AA-LDHI of Formula (1) can hâve the following structures:

(la), or

(Ib), wherein Ri 1 is Cs to C20 alkyl, and Ri₂ and R13 are independently C1 to Cô alkyI. In an embodiment, Ru is C12 to C20 unsubstituted alkyl, and R12 and R13 are independently Ci to C4 unsubstituted alkyl.

[00511 Further exemplary AA-LDHI of Formula (1) can be:

|0052| When the compound of Formula (I) is in sait form, the counterion can be selected from the group consisting of a halide, a carboxylate, hydrogen sulfate, dihydrogen phosphate, nitrate, and a combination thereof. In an exemplary embodiment, the counterion can be an acetate, an acrylate, or a combination thereof.

|00531 The cationic ammonium AA-LDHI included in the hydrate inhibitor and corrosion inhibitor compositions can include a compound of Formulae (lia) or (Hb):

(lia) or (Ilb), wherein Ri is an alkyl group or alkenyl group that can contain one or more heteroatoms or ionizable heteroatoms, R; is présent or not as hydrogen, depending on the ionization of the 10 attached nitrogen atom, R3 comprises a group selected from the generic formula CnHimi, wherein n is a number from 0 to 10, R4 is an alkyl group or alkenyl group that can contain one or more heteroatoms or ionizable heteroatoms, R5 is selected from the group consisting of hydrogen, an alkyl group that can contain one or more heteroatoms or ionizable heteroatoms, an alkenyl group that can contain one or more heteroatoms or ionizable heteroatoms, and any combination thereof, 15 B is a group selected from the generic formula (CH;)_n, wherein n is a number from 1 to 4, A is a substituent selected from the group consisting of CH;, NR5, oxygen (O), and any combination thereof, and X is a counterion, such as a halide, any carboxylate, hydrogen sulfate, dihydrogen phosphate, or nitrate. Non-limiting examples include acetate and acrylate.

[0054] For the cationic ammonium compound AA-LDHI compounds of Formula (lia) or (Ilb), 20 Ri can be any alkyl or alkenyl group that can contain one or more heteroatoms or ionizable heteroatoms. Rt can comprise any group having from about 8 carbons atoms to about 20 carbon atoms, e.g. a Cs to C20 group. For example, Ri can comprise a Cg to C12 group, a Cg to C12 group, a C12 to Ci6 group, a Ciô to C20 group, or a Cis to C;o group.

[0055| Forthese cationic ammonium compound AA-LDHI compounds, 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 the removal of a single hydrogen atom from each of two adjacent carbon atoms of an alkyl group. Représentative alkenyl groups include, for example, ethenyi, propenyl, oleyl, butenyl, 1-methyl-2-buten-l-yl, and the like. For these cationic AA-LDHI compounds, the term alkyl refers to a monovalent group derived by the removal of a single hydrogen atom from a straight or branched chain or cyclic saturated or unsaturated hydrocarbon. Représentative alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, lauryl, and the like.

[0056] Further to the cationic ammonium compound AA-LDHI compounds described herein, Table 2 shows additional compounds that hâve been synthesized and intended to be included in the AA-LDHI of the présent disclosure:

(0057] TABLE 2

Example	Ri	R2	R4	R,	Bi		X
1	oleyl	H	—	—	c2Hj	ch2	acetate
2	oleyl	H	—	—	C-Hj	ch2	sulfate
3	COCO	H	—	—	C2H4	CH2	acrylate
4	coco	H	CA(N(CAC(CH3hh)	H	—	—	2x acetate
5	coco	—	CAfNfC.IWCH^h)	H	—	—	acetate
6	oleyl	H		H	—	—	2x acetate
7	oleyl	H	CA(N(CA)2))	H	—	—	2x acetate
8	COCO	—	CA(N(CA)2»	H	—	—	acrylate
9	oleyl	H	—	—	C;H*	¢3¾	acetate
10	oleyl	H	—	—	C2H4	C'A	acrylate
11	COCO	H	—	—	CîH*	CA	sulfate
12	coco	H	CA	CA	—	—	acrylate
13	CA(N(CAC(CH3)2)2)	H	oleyl	H	—	—	2x acetate
14	CîHitNtC.^CtCHshh)	—	COCO	H	—	—	acrylate
15	CA(N(CA)î))	H	oleyl	H	—	—	2x acetate
16	CsHitNfCjHçlj))	H	COCO	H			2x acetate

[0058] In connection with the spécifie compounds Iisted in Table 2 and the generic structures depicted above, R a was selected to be hydrogen and A was selected to be Chb. Although the generic structure above only lists B as two of the substituents and Table 2 lists ΒΓ and B2, the generic structure is intended to cover wherein the Bl substituent is located at either of the B group positions and the B2 substituent is located at either of the B group positions.

[0059] Further exemplary cationic ammonium compound AA-LDHI of Formula (lia) include the following general structure:

, wherein Rfatty is any alkyl group having from about 8 carbon atoms to about 20 carbon atoms, e.g. a Cs to C₂o group. For example, Rf_at!y can comprise a Cs to C12 group, a C12 to C16 group, or a Ci6 to C₂o group. For this structure, Rf_a«_y comprises a Cs group, a Ciogroup, a Cj₂ group, a Cie group, or a C20 group.

[0060| With respect to the term hydrate-philie used in the présent disclosure when describing a certain portion of the hydrate inhibitor molécule, the portion of the molécule being referred to as the hydrate-philic portion is, with respect to the spécifie composition shown above, the portion opposite the Rfam group. That is, in the above example, the portion including the tertiary N atom and the two butyl groups.

[0061 ] Further exemplary cationic ammonium compound AA-LDHI of Formula (Ilb) include the following general structure:

[0062[ Additional cationic ammonium compound AA-LDHI included in the hydrate inhibitor and corrosion inhibitor compositions can include a compound of Formula (Ilia) or(lllb):

(Hla)

(Illb), wherein A is an optionally substituted pyrrole, pyrrolidine, piperidine, pyrazole, imidazole, triazole, isoxazole, oxazole, thiazole, isothiazole, oxadiazole, oxatriazole, dioxazole, oxathiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxazine, isoxazine, oxadiazine, morpholine, azepane, azepine, caprolactam, or quinoline; Ri is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aryl; R₂ is hydrogen, optionally substituted alkyl, alkenyl, or alkynyl; Z is -NR₃-C(O)-, -C(O)-NRi-, -O-C(O)-, -C(O)-O-, -S-C(O)-, -C(O)S-, -O-C(O)-NR3-, -NR3-C(O)-O-, —NR3—C(O)—NR₃—, or absent; R₃ is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aryl; n is an integer from 0 to 25; X is an anion; and when A is oxazolidine and R₂ is

I5 alkyl, Z is -NR₃-C(O)-, -C(O)-NR₃-, -O-C(O)-, -C(O)-O-, -S-C(O)-, -C(O)-S-, -OC(O)-NR₃-, -NR₃-C(O)-O-, or -NR₃-C(O)-NR₃-.

[0063] The compound of Formula (Ilia) or (lUb) can also hâve A as an optionally substituted nitrogen-containing heterocycle; Ri is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aryl; R 2 is hydrogen, optionally substituted alkyl, alkenyl, or alkynyl; Z as -NR₃-C(O)-,-O-C(O)-, -S-C(O)-, C(O)-S-, —O—C(O)—NR₃—, -NR₃-C(O)-O-, —NR3-C(O)-NR₃- or absent; R₃ is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aryl; n is an integer from 0 to 25; X is an anion; and when A is oxazolidine, Z is —NR₃—C(O)—, —C(O)—NR₃—, —O—C(O)—, —C(O)—O—, —S—C(O)—, —C(O)—S—, — O-C(O)-NR₃-, -NR₃-C(O)-O~, or -NR₃-C(O)-NR₃-.

[0064] The optionally substituted nitrogen-containing heterocycle A ofthe compound of Formula (Ilia) or (Illb) can be an optionally substituted pyrroie, pyrroline, pyrrolidine, piperidine, pyrazole, pyrazoline, pyrazolidine, imidazole, imidazoline, imidazolidine, triazole, isoxazole, isoxazoline, isoxazolidine, oxazole, oxazoline, oxazolidine, thiazole, isothiazole, oxadiazole, oxatriazole, dioxazole, oxathiazole, pyridine, pyridazine, pyrimidine, pyrazine, piperazine, triazine, oxazine, oxathiazine, oxazine, isoxazine, oxadiazine, morpholine, azepane, azepine, caprolactam, or quinoline.

[0065| Further, the optionally substituted nitrogen-containing heterocycle A of the compound of Formula (Ilia) or (lllb) can be an optionally substituted five-membered nitrogen-containing heterocycle. For example, the five-membered nitrogen-containing heterocycle can be pyrroie, pyrroline, pyrrolidine, pyrazole, pyrazoline, pyrazolidine, imidazole, imidazoline, imidazolidine, isoxazole, isoxazoline, isoxazolidine, oxazole, oxazoline, or oxazolidine.

[0066] The compound of Formula < H la) or (lllb) can hâve A as an optionally substituted pyrroie, pyrrolidine, piperidine, pyrazole, imidazole, pyridine, pyrimidine, piperazine, or morpholine.

[0067] The compound of Formula (lllb) can comprise the compound of Formula (IIIb?), (Hlbs), (lllbé), (lllb?), (lllbe), (lllbo), or (Illbio):

(Hlb₂)

R₂;

R»;

(Illbs) (lllb?) (IIIb₈) (lUbç) or

(Illbio), wherein η, Z, Ri, R;, and X are as defined in connection with Formula (11Ib) and R₂o, R21, R22, R23, R24, R25, R26, R27, R28, and R29 are each independently hydrogen, alkyl, alkoxy, aminoaikyl, carboxyl, carboxyalkyl, alkenyl, alkenoxy; carboxyalkenyl, aryl, aryloxy, or carboxyaryl; R30 is hydrogen, alkyl, or aryl; and R31, R32, R33,

R34, R35, R36, and R37 are each independently hydrogen, alkyl, alkoxy, aminoaikyl, carboxyl, carboxyalkyl, alkenyl, alkenoxy; carboxyalkenyl, aryl, aryloxy, or carboxyaryl.

[0068] Further exemplary cationic ammonium compound AA-LDHI of Formula (IHb₂) include the following general structure:

(Illbî), wherein R20, R21, R22, R23, R24, R25, R26, and Rjyare

IO hydrogen. Alternatively, R20, R21, R22, R23, R24, R25, and R₂6, are hydrogen and R₂7is carboxyl. In additional embodiments as described herein R, is hydrogen, Z is -NR3-C(O)-and Ra is hydrogen.

[0069] Further exemplary cationic ammonium compound AA-LDHI of Formula (Illbs) include the following general structure:

(IHbs), wherein R20, Ru, Ru, R23, R24, Ris, Ris, R27, R28, and R₂9 are hydrogen, Z is -NR₃-C(O)- or -C(O)-NR3-, R3 is hydrogen, R₂ is C10-C20 alkyl or alkenyl, and n is 2 or 3.

[0070] The compound of Formula (IHa) can comprise the compound of Formula (Ilia?), (llla₃), 5 (llla^), (lilas), (Illb₆), (Illb₇), (IIIb₈), (Hlbo), or (IIIbn):

(nia₃) (Hlar)

(lilas)

^-22

^R^⁷ *²⁸ (HIbô)

(Hlbu), wherein η, Z, Rj, and R: are as defined in connection with Formula (Ilia) and R20, R21, R22, R23, R24, R25, R26, R27, R28, and R29 are each independently hydrogen, alkyl, alkoxy, aminoalkyl, carboxyl, carboxyalkyl, alkenyl, alkenoxy; carboxyalkenyl, aryl, aryloxy, or carboxyaryl; R30 is hydrogen, alkyl, or aryl; and R31, R32, R33, R34, R35, and R36 are each independently hydrogen, alkyl, aikoxy, aminoalkyl, carboxyl, carboxyalkyl, alkenyl, alkenoxy; carboxyalkenyl, aryl, aryloxy, or carboxyaryl.

[0071 | Further exemplary cationic AA-LDH1 of Formula (Ilia) as described above can hâve R2 as C10-C24 alkyl or alkenyl; Z as -NR3-C(O)-or-C(O)-NR3-; n as an integer from 0 to 12; and X’ as an organic anion.

|0072| Further exemplary cationic ammonium compound AA-LDHI of Formula (lilas) include the following general structure:

Formula (IIlaj) can hâve R31, R32, R33, and R34 are hydrogen, Z is -NRs-C(O)- or-C(O)-NR3-, Rs is hydrogen, Ri is C10-C20 alkyl or alkenyl, and n is 2 or 3. [0073| Further exemplary cationic ammonium compound AA-LDHI of Formula (Ilia) or (IIIb) wherein: Z is -C(O)-NR3— and R3 is hydrogen; R2 is Cio-C^o alkyl or alkenyl, and n is 2 or 3; and/or wherein the anion is a halide, a carbonate, or a carboxylate anion.

|0074| As referred to herein, the AA-LDHIs when referring to a hydrate inhibitor in the présent disclosure, it is to be understood that the reference can refer to a single AA-LDHI, or a combination of two or more AA-LDHI. In embodiments, the compositions include a single AALDHI. However in additional embodiments, the compositions include an AA-LDHI in combination with an additional hydrate inhibitor, such as an additional AA-LDHI. Additional disclosure of suitable AA-LDHIs is described in U.S. Patent Nos. 9,410,073, 9,765,254, 10,281,086, and 10,435,616, each of which are herein incorporated by reference in their entirety. [0075] In soine embodiments the composition does not include any quaternary ammonium compound AA-LDHIs. In further embodiments the composition does not include any or halidecontaining AA-LDHIs. In still further embodiments the composition does not include any quaternary ammonium compound AA-LDHIs or halide-containing AA-LDHIs.

|0076| In some embodiments, the AA-LDHI is included in the composition at an amount of at least about 10 wt-% to about 99.9 wt-%, 20 wt-% to about 99.9 wt-%, 30 wt-% to about 99.9 wt%, 40 wt-% to about 99.9 wt-%, 50 wt-% to about 99.9 wt-%, about 60 wt-% to about 99.9 wt%, about 70 wt-% to about 99.9 wt-%, about 75 wt-% to about 99.9 wt-%, about 80 wt-% to about 99.9 wt-%, or about 85 wt-% to about 99.9 wt-%. In addition, without being limited according to the disclosure, ail ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.

[0077] In some embodiments, the AA-LDHI is dosed with or combined with a composition compnsing the corrosion inhibitor and other additional functional ingrédients (î.e. corrosion inhibitor composition) at a weight ratio of up to about 1 part AA-LDHI to about 1 part corrosion inhibitor composition, or about 1:0.001 to about 1:1, about 1:0.005 to about 1:1, about 1:0.005 to about 1:0.01, or about 1:0.01 to about 1:1. In addition, without being limited according to the disclosure, ail ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.

Corrosion Inhibitors

[0078] The composition comprises at least one corrosion inhibitor (CI). Cls include amines, including for example aromatic amines, aliphatic amines, heterocyclic amines or alkoxylated amines, amidoamines, quatemary amines or quaternary ammonium compounds, amides, imidazolines and imido imidazolines (referred to as fatty acid amine condensâtes and imido fatty acid amine condensâtes, respectively), imidazolinium compounds, pyridines, quinolines, phosphate esters, carboxylic acids or monomeric or oligomeric fatty acids, or combinations thereof. Generally preferred Cls include an imidazoline, imidazoline compound, a quaternary ammonium compound, a pyridinium compound, or a combination thereof.

(0079] Exemplary imidazolines can include an imidazoline derived from a diamine, such as ethylene diamine (EDA), diethylene triamine (DETA), triethylene tetraamine (TETA) etc. and a long chain fatty acid such as tall oil fatty acid (TOFA). The imidazoline can be an imidazoline of Formula (1) below or an imidazoline dérivative. Représentative imidazoline dérivatives include an imidazolinium compound of Formula (II) below or a bis-quaternized compound of Formula (III) below.

|0080] The imidazoline of Formula (I) is as follows:

wherein R¹⁰ is a C1-C20 alkyl or a C1-C20 alkoxyalkyl group; R¹¹ is hydrogen, Ci-Cô alkyl, C|-Cô hydroxyalkyl, or Ci-Ch arylalky 1; and R¹² and R¹³ are independently hydrogen or a Ci-Cô alkyl group. Preferably, the imidazoline includes an R¹⁰ which is the alkyl mixture typical in tall oil fatty acid (TOFA), and R¹¹, R¹² and R¹³ are each hydrogen.

[0081 ] The imidazolinium CI can include an imidazolimum compound of Formula (II):

' wherein R¹⁰ is a C1-C20 alkyl or a Ci-C₂o alkoxyalkyi group; R¹¹ and

R¹⁴ are independently hydrogen, C i-Cô alkyl, C i-Cô hydroxyalkyl, or C j-Cs arylalkyl; R¹² and R¹³ are independently hydrogen or a Ci-Cô alkyl group; and X is a halide (such as chloride, bromide, or iodide), carbonate, sulfonate. phosphate, or the anion of an organic carboxylic acid (such as acetate). Preferably, the imidazolinium compound includes I-benzyl-1 -(2hydroxyethyl)-2-tall-oil-2-imidazolinium chloride.

[0082] The Cls can comprise a bis-quatemized compound having the formula (III):

independently unsubstituted branched, chain or ring alkyl or alkenyl having from 1 to about 29 carbon atoms; partially or fully oxygenized, sulfurized, and/or phosphorylized branched, chain, or ring alkyl or alkenyl having from 1 to about 29 carbon atoms; or a combination thereof; R3 and R4 are each independently unsubstituted branched, chain or ring alkylene or alkenylene having from 1 to about 29 carbon atoms; partially or fully oxygenized, sulfurized, and/or phosphorylized branched, chain, or ring alkylene or alkenylene having from 1 to about 29 carbon atoms; or a combination thereof; Li and L₂ are each independently absent. H, -COOH, SO3H, -POsHi, -COOR5, -CONH?, -CONHR5, or —CON(Rs)₂; Rî is each independently a branched or unbranched alkyl, aryl, alkylaryl, alkylheteroaryl, cycloalkyl, or heteroaryl group having from 1 to about 10 carbon atoms; n is 0 or 1, and when n is 0, L₂ is absent or H; x is from to about 10; and y is from I to about 5.

[0083] Preferably, Ri and R₂ are each independently C&-C₂₂ alkyl, Cs-C₂o alkyl, C12-C18 alkyl, Cιό-Cis alkyl, or a combination thereof; R 3 and R4 are C1-C10 alkylene, C₂-Cs alkylene, C2-C6 alkylene, or C2-C3 alkylene; n is 0 or 1; x is 2; y is I; R3 and R4 are -C₂H₂-; L, is-COOH, SO3H, or -PO3H2; and L₂ is absent, H, —COOH, -SO3H, or -PO3H2. For example, R, and R₂ can be denved from a mixture of tall oil fatty acids and are predominantly a mixture of C17H33 and C17H31 or can be Ciô-Cis alkyl; R3 and Rj can be C2-C3 alkylene such as -C2H2-; n is 1 and L2 is -COOH or n is 0 and L? is absent or H; x is 2; y is 1 ; R3 and Rj are -C2H2-; and Li is -COOH. {0084] It should be appreciated that the number of carbon atoms specified for each group of formula (111) refers to the main chain of carbon atoms and does not include carbon atoms that may be contributed by substituents.

[0085] The imidazoline Cis can comprise a bis-quaternized imidazoline compound having the formula (111) wherein Ri and R? are each independently Cô-C₂2 alkyl, C8-C20 alkyl, C12-C18 alkyl, or Ci6-Cig alkyl or a combination thereof; R4 is C1-C10 alkylene, Ci-Ce alkylene, C2-C6 alkylene, or C2-C3 alkylene; x is 2; y is 1 ; n is 0; L1 is-COOH, -SO3H, or -PO3H2; and L2 is absent or H. Preferably, a bis-quaternized compound has the formula (111) wherein Ri and R? are each independently Ciô-Cie alkyl; R4 is -C2H2-; x is 2; y is 1 ; n is 0; Li is-COOH, -SO3H, or -PO3H2 and L2 is absent or H.

[0086] The Cis can be a quatemary ammonium compound of Formula (IV):

R₂ X^e

I φ _Rl----N----r₃ p

⁴ (IV) wherein Ri, R2, and R3 are independently Ci to C20 alkyl, R4 is methyl or benzyl, and X' is a halide or methosulfate.

[0087| Suitable alkyl, hydroxyalkyl, alkylaryl, arylalkyl or aryl amine quaternaty salts include those alkylaryl, arylalkyl and aryl amine quatemary salts of the formula [N'R^îaR^6aR^7aR^8a][X“] wherein R^5a, R^6a, R^7a, and R^8a contain one to 18 carbon atoms, and X is Cl, Br or 1. For the quatemary salts, R^5a, R^6a, R^7a, and R^8a can each be independently alkyl (e.g., C1-C18 alkyl), hydroxyalkyl (e.g., Ci-Ci8 hydroxyalkyl), and arylalkyl (e.g., benzyl). The mono or polycyclic aromatic amine sait with an alkyl or alkylaryl halide include salts of the formula [N*R^5aR^6aR^7aR^8a][X^-] wherein R^îa, R^6a, R^7a, and R^Sa contain one to 18 carbon atoms and at least one aryl group, and X is Cl, Br or 1.

[0088] Suitable quatemary ammonium salts include, but are not limited to, atetramethyl ammonium sait, a tetraethyl ammonium sait, a tetrapropyl ammonium sait, a tetrabutyl ammonium sait, a tetrahexyl ammonium sait, a tetraoctyl ammonium sait, a benzyltrimethyl ammonium sait, a benzyltriethyl ammonium sait, a phenyltrimethyl ammonium sait, a phenyltriethyl ammonium sait, a cetyl benzyldîmethyl ammonium sait, a hexadecyl trimethyl ammonium sait, adimethyl alkyl benzyl quatemary ammonium sait, amonomethyl dialkyl benzyl quatemary ammonium sait, or a trialkyl benzyl quatemary ammonium sait, wherein the alkyl group has about 6 to about 24 carbon atoms, about 10 and about 18 carbon atoms, or about to about 16 carbon atoms. The quaternary ammonium sait can be a benzyl tnalkyl quatemary ammonium sait, a benzyl triethanolamine quaternary ammonium sait, or a benzyl dimethyiaminoethanolamine quaternary ammonium sait.

[0089] The quatemary ammonium Cls can comprise a pyridinium sait such as those represented by Formula (V):

R⁹ (V) wherein R⁹ is an alkyl group, an aryl group, or an arylalkyl group, wherein said alkyl groups hâve from l to about 18 carbon atoms and X is a halide such as chloride, bromide, or iodide. Among these compounds are alkyl pyridinium salts and alkyl pyridinium benzyl quats. Exemplary compounds include methyl pyridinium chloride, ethyl pyridinium chloride, propyi pyridinium chloride, butyl pyridinium chloride, octyl pyridinium chloride, decyl pyridinium chloride, lauryl pyridinium chloride, cetyl pyridinium chloride, benzyl pyridinium chloride and an alkyl benzyl pyridinium chloride, preferably wherein the alkyl is a Ci-Cô hydrocarbyl group. Preferably, the pyridinium compound includes benzyl pyridinium chloride. [0090] Exemplary phosphate esters include, for example mono-, di- and tri-alkyl as well as alkylaryI phosphate esters and phosphate esters of mono, di, and triethanolamine typically contain between from I to about I8 carbon atoms. Preferred mono-, di-and trialkyl phosphate esters, alkylaryl or arylalkyl phosphate esters are those prepared by reacting a C3-C18 aliphatic alcohol with phosphorous pentoxide. The phosphate intermediate interchanges its ester groups with triethylphosphate producing a broader distribution of alkyl phosphate esters.

[0091] Altematively, the phosphate ester can be made by admixing with an alkyl diester, a mixture of low molecular weight alkyl alcohols or diols. The low molecular weight alkyl alcohols or diols preferably include Ce to Cio alcohols or diols. Further, phosphate esters of polyols and their salts containing one or more 2-hydroxyethyl groups, and hydroxylamine phosphate esters obtained by reacting polyphosphoric acid or phosphorus pentoxide with hydroxylamines such as diethanolamine or triethanolamine are preferred.

[0092] Exemplary monomeric or oligomeric fatty acid Cl include, for example, C14-C22 saturated and unsaturated fatty acids as well as dimer, trimer and oligomer products obtained by polymerizing one or more of such fatty acids.

[0093] Exemplary alkoxylated amine Cl include, for example, ethoxylated alkyl amine. The alkoxylated amine can be ethoxylated tallow amine.

[0094| Additional CI can include an organic sulfur compound, such as a mercaptoalkyl alcohol, mercaptoacetic acid, thioglycolic acid, 3,3'-dithiodipropionic acid, sodium thiosulfate, thiourea, L-cysteine, tert-butyl mercaptan, sodium thiosulfate, ammonium thiosulfate, sodium thiocyanate, ammonium thiocyanate, sodium metabisulfite, or a combination thereof.

Preferably, the mercaptoalkyl alcohol comprises 2-mercaptoethanol.

[0095] In some embodiments the composition can be substantially free of or free of any organic sulfur compound other than the compound of formula ( l ). A composition is substantially free of any organic sulfur compound if it contains an amount of organic sulfur compound less than 0.50 wt.% preferably less than 0.10 wt.%, and more preferably less than 0.01 wt.%.

[0096] Additional exemplaty amines can include thiol-amines as disclosed in U.S. Patent No.

11,242,480, which is incorporated herein by référencé in its entirety. These thiol-amines include a class of anti-corrosion compounds having the formula:

(1) wherein: each R, is independently —CH₂OH and -C(O)OH;

R₂ is ⁿ or ^z^· ;

each Ri is independently hydrogen or R5, or both R₃ together form a ring via a iinker

1 R5 » each R4 is independently hydrogen or R5; Rs is-CH2SC2H4Ri; and n is an integer from 0 to 3. R3 Γ r4 „ 1 1 A r3 [0097] Preferably, when R2 is n CH2OH.

, n is 0 and R3 is hydrogen. Ri is -

[0098] The compound of formula (l) can hâve Ri be-CH₂OH or-C(O)OH and R? be

[0099] The compound of formula ( l ) can hâve R i be — CH2OH or -C(O)OH; R? be

R3 R₄

; both R? together form a ring via linker

R₄ be hydrogen; R5 be-CH₂SC2H₄Ri; and n be l.

[0100] The compound of formula (1) can hâve R, bc-CH₂OH or-C(O)OH;R₂ be

R₄

; R₃ and R₄ be Rs; and R5 be-CHaSCaHrRi.

(01011 The compound of formula ( 1 ) can hâve R1 be - CH₂OH or -C(O)OH; R₂ be

; R 3 be hydrogen or R5; R5 is -CH2SC2H4R1; and n be 0 or 1.

Preferably, R3 is hydrogen and n is 0, or R3 is R5; R5 is-CH2SC2H4R1; and n is I.

[0102] Représentative compounds of formula (1) derived from the reaction of hexamethylenetetramine (HMTA) and 2-mercaptoethanol (2-ME) include:

ΙΟ

[0103] Représentative compounds of formula ( l) derived from the reaction of hexamethylenetetramine and thiolglycolic acid (TGA) include:

COOH

[0104] In preferred embodiments, more than one Cl is included in the composition include a quaternary ammonium compound (e.g. benzyl alkyl quats, amine quats), an imidazoline, and at least one organic sulfur compound. In further embodiments the organic sulfur compound includes at least one of mercaptoalkyl alcohol, mercaptoacetic acid, and/or thioglycolic acid. [0105] In preferred embodiments, more than one Cl is included in the composition include a quaternary ammonium compound, an imidazoline, a phosphate ester and at least one organic sulfur compound. In further embodiments the organic sulfur compound includes at least one of mercaptoalkyl alcohol, mercaptoacetic acid, and/or thioglycolic acid.

[0106] In embodiments, the CI does not include any boron-hydroxylalkyl(amine) compounds. In further embodiments, the CI does not include any urea corrosion inhibitors. In further embodiments, the Cl does not include any calcium nitrate corrosion inhibitors. In still further embodiments, the CI does not include any boron-hydroxylalkyl(amine) compounds, urea corrosion inhibitors and calcium nitrate corrosion inhibitors.

[0107] In some embodiments, the CI(s) is included in the composition at an amount of at least about 0.001 wt-% to about 50 wt-%, about 0.005 wt-% to about 50 wt-%, about 0.01 wt-% to about 50 wt-%, about 0.01 wt-% to about 40 wt-%, about 0.01 wt-% to about 20 wt-%, about 0.1 wt-% to about 10 wt-%. or about 0.I wt-% to about 10 wt-%. In addition, without being limited according to the disclosure, ail ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.

[0108] In some embodiinents, the Cl(s) or a composition comprising the Cl(s) with additional functional ingrédients (i.e. corrosion inhibitor composition) can be dose with the AA-LDHI at a weight ratio of up to about I part AA-LDHI to about 1 part corrosion inhibitor composition, or about 1:0.001 to about 1:1, about 1:0.005 to about 1:1, about 1:0.005 to about 1:0.01, or about 1:0.01 to about 1:1. In addition, without being !imited according to the disclosure, ail ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.

Solvents

[0109] In some embodiments, the composition comprises at least one solvent. The solvents can include one or more polar or nonpolar solvents or a mixture thereof. Représentative polar solvents suitable for compositions include water, brine, seawater, alcohols (including straight chain or branched aliphatic such as methanol, éthanol, propanol, isopropanol, butanol, 2ethylhexanol, hexanol, octanol, decanol, 2-butoxyethanol, etc.), glycols and dérivatives (ethylene glycol, methylene giycol, 1,2-propylene glycol, 1,3-propylene glycol, diethyleneglycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, etc.), ketones (cyclohexanone, diisobutylketone), N-methylpyrrolidinone (NMP), N,N-dimethylformamide, and the like. Représentative 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 as toluene, xylene, heavy aromatic naphtha, cyclohexanone, diisobutylketone, diethyl ether, propylene carbonate, N-methylpyrrolidinone, Ν,Ν-dimethylformamide, fatty acid dérivatives (acids, esters, amides), and the like.

[0110] Preferably, the composition further comprises one or more solvents selected from the group consisting of water, isopropanol, methanol, éthanol, 2-ethylhexanol, heavy aromatic naphtha, toluene, ethylene glycol, ethylene glycol monobutyl ether (EGMBE), diethylene glycol monoethyl ether, xylene, or any combination thereof.

[OUI] In embodiments the composition includes water an additional solvent.

[0112] In some embodiments, where a solvent(s) is încluded in the composition it is included at an amount of at least about 0.0001 wt-% to about 10 wt-%, about 0.001 wt-% to about 10 wt-%, about 0.01 wt-% to about 5 wt-%, or about 0.1 wt-% to about 1 wt-%. In addition, without being limited according to the disclosure, ail ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.

[0113] In other embodiments, the solvent(s) can be included in a composition with the CI(s) and other additional functional ingrédients that is combined at a point of use with the AA-LDHI. In such embodiments where the AA-LDHI is not included in the same composition, the solvent is included at an amount of at least about 1 wt-% to about 40 wt-%, about 5 wt-% to about 40 wt5 %, about 10 wt-% to about 40 wt-%, or about 20 wt-% to about 40 wt-%. In addition, without being limited according to the disclosure, ail ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.

Additional Functional Ingrédients

[0114] The components of the composition can further be combined with various functional components suitable for uses disclosed herein. In some embodiments, the compositions including the anti-agglomerant low dose hydrate inhibitor, corrosion inhibitor(s) and solvent make up a large amount, or even substantially ail of the total weight of the compositions. For example, in some embodiments few or no additional functional ingrédients are disposed therein. ]0115] In other embodiments, additional functional ingrédients may be included in the compositions to combine with the anti-agglomerant low dose hydrate inhibitor, corrosion inhibitor(s) and solvent. The functional ingrédients provide desired properties and functionalities to the compositions. For the purpose of this application, the term functional ingrédient includes a material that when dispersed or dissolved in a use and/or concentrate solution, such as an aqueous solution, provides a bénéficiai property in a particular use. Some particular examples of functional materials are discussed in more detail below, although the particular materials discussed are given by way of example only, and that a broad variety of other functional ingrédients may be used.

[0116] In some embodiments, the compositions may include asphaltene inhibitors, paraffin inhibitors, additional corrosion inhibitors, scale inhibitors, emulsifiers, water clarifiers, dispersants, émulsion breakers, biocides, pH modifiers, surfactants, or any combination thereof and the like.

[0117] These additional ingrédients can be pre-formulated with the compositions (either the composition with the anti-agglomerant low dose hydrate inhibitor, corrosion inhibitor(s) and solvent, or a separate composition with the corrosion inhibitor(s) and solvent, wherein the anti30 agglomérant low dose hydrate inhibitor is added separately) or added to the use solution before, after, or substantially simultaneously with the addition of the compositions.

[0118| According to embodiments of the disclosure, the various additional functional ingrédients may be provided in a composition in the amount from about 0 wt-% and about 30 wt-%, from about 0 wt-% and about 25 wt-%, from about 0 wt-% and about 20 wt-%, from about 0.01 wt-% and about 20 wt-%, from about 0.1 wt-% and about 10 wt-%, from about 1 wt22162 % and about 10 wt-%, from about 0.01 wt-% and about 8 wt-%, or from about 0.1 wt-% and about 8 wt. In addition, without being limited according to the disclosure, ail ranges recited are inclusive of the numbers defining the range and include each integer within the defïned range. Emulsion Breakers

[0119] In some embodiments the compositions may include an émulsion breakers. Suitable émulsion breakers include, but are not limited to, dodecylbenzylsulfonic acid (DDBSA), the sodium sait of xylenesulfonic acid (NAXSA), epoxylated and propoxylated compounds, anionic, cationic and nonionic surfactants, including for example nonylphenols and nonylphenol ethoxylates, and resins, such as phenolic and epoxide resins.

[0120] In an exemplary embodiment the additional functional ingrédient comprises an émulsion breaker in an amount from about 0.01 wt-% and about 10 wt-%, from about 0.1 wt-% and about 10 wt-%, from about 1 wt-% and about 10 wt-%, or from about 1 wt-% and about 8 wt-% when included in a composition with the Cl (wherein the AA-LDHI is provided separately). In an exemplary embodiment where the components are provided in a single composition the émulsion breaker is in an amount from about 0.0001 wt-% and about 5 wt-%, from about 0.001 wt-% and about 2 wt-%, or from about 0.01 wt-% and about 2 wt-% of the composition.

METHODS OF USE |0121 ] According to embodiments, the compositions for inhibiting corrosion and gas hydrate agglomération to effectively control corrosion, including both general and Iocalized corrosion, and gas hydrate formation and plugging in hydrocarbon production and transportation Systems are disclosed herein. As referred to herein, compositions comprising the AA-LDHI and CI(s) can be provided in a single composition to contact a fluid in need of treatment for inhibiting corrosion and formation of gas hydrate agglomérants. In referring to compositions, the scope of the disclosure also includes combining more than one input (i.e. composition) for the treatment ofa fluid to inhibit corrosion and formation of gas hydrate agglomérants. For example, in some embodiments the AA-LDHI can be separately dosed or combined with a composition comprising the Cl(s), solvent and/or additional functional ingrédients. Similarly the AA-LDHI can be combined with Cl(s), solvents and/or additional functional ingrédients.

[0122] In embodiments where the AA-LDHI contacts a fluid in need of treatment to inhibit corrosion and formation of gas hydrate agglomérants from a separate composition from the Cl(s), the AA-LDHI and corrosion inhibitor are provided at a weight ratio of up to about I part AA-LDHI to about 1 part corrosion inhibitor composition, or about 1:0.001 to about 1:1, about 1:0.005 to about 1:1, about 1:0.005 to about 1:0.01, or about 1:0.01 to about 1:1. In addition, without being limited according to the disclosure, ail ranges recited are inclusive of the numbers defining the range and include each integer within the defïned range.

[0123] The methods may be applied to a fluid to prevent, reduce or mitigate corrosion (as referred to herein including both localized and general) and the plugging of conduits, pipes, transfer fines, valves, and other places or equipment where hydrate agglomérâtes may form. Beneficially, for the corrosion inhibition both localized and generalized corrosion are reduced, 5 including a general corrosion rate (GCR) of < 4 mpy, and more preferably < 3 mpy, and minimal or reduced pitting. In some embodiments, reduced pitting resulting from reduced localized corrosion can include réduction in quantity and depth of pitting compared to use of conventional Cls. In some embodiments, the methods reduce pitting at depths above about 20 mm.

[0124] The mils pénétration per year (MPY) is used as an estimated general corrosion rate. The

MPY is calculated from the following équation:

MPY = (ΔΜ[tf] C)/ (p MU · A [ï n²] · ^cm where ΔΜ is the mass loss of the coupon at the end of the test in grams, C is a constant equal to 534000, p is the density of the coupon in g/cm², A is the surface area of the coupon in cm², and t is the exposure time in hours.

[0125] The methods may be applied to fluids moved through conduits, pipes, transfer fines, valves, and other places or equipment where hydrocarbon hydrate solids can form and corrosion can occur.

[0126] The methods including contacting the compositions to a fluid. Fluids include aqueous medium comprising water, gas, and/or optionally liquid hydrocarbons. The method comprises 20 adding to the fluid an effective amount of the composition comprising the anti-agglomerant low dose hydrate inhibitor (AA-LDHI), wherein the AA-LDHI is a zwitterionic compound or a cationic ammonium compound, and corrosion inhibitor(s). In embodiments the fluids are contained in an oil or gas pipeline or refinery, including offshore applications.

[0127] In embodiments, the compositions and methods are effective to control corrosion and gas 25 hydrate formation and plugging during hydrocarbon production and transportation. Specifically, the compositions can be injected prior to substantial formation of hydrates. An exemplary injection point for petroleum production operations is downhole near the surface controlled subsea safety valve. This ensures that during a shut-in, the product is able to disperse throughout the area where hydrates wil! occur. Treatment can also occur at other areas in the flowline, taking 30 into account the density of the injected fluid. If the injection point is well above the hydrate formation depth, then the hydrate inhibitor can be formulated with a solvent having a density high enough that the inhibitor will sink in the flowline to collect at the water/oil interface. Moreover, the treatment can also be used in pipelines or anywhere in the System where the potential for corrosion and hydrate formation exists.

[0128) In embodiments, the fluid is contained m an oïl and gas pipeline. Additionally, the fluid can be contained in refineries, such as séparation vessels, déhydration units, gas lines, and pipelines.

[0129] Further, the compositions can be applied to a fluid that contains various levels of salinity. The fluid can hâve a salinity of about 0% to about 25%, or about 10% to about 25% weight/weîght (w/w) total dissol ved solids (TDS). The fluid in which the compositions are applied can be contained in many different types of apparatuses, especially those that transport an aqueous medium from one location to another.

[0130] The composition can be applied to a fluid that contains various levels of water eut. One of ordinary skill in the art understands that water eut refers to the % of water in a composition containing an oil and water mixture. In particular, the water eut of the fluid can be from about 1% to about 90% w/w, or from about 1% to about 80% w/w based on the total weight of the fluid comprising water, gas, and/or optîonally liquid hydrocarbon.

[0131| The compositions are applied at an effective amount to inhibit general and localized corrosion and formation of gas hydrate agglomérants in the fluid. The dosage amounts of the compositions described herein to be added to the fluid can be tailored by one skilled in the art based on factors for each fluid in need of treatment, including, for example, content of fluid, percentage water eut, API gravity of hydrocarbon, and test gas compositions. In embodiments, an effective amount is from about 0.1% to about 10 % v/v (volume percentage) based on an amount of the total composition described herein and the amount of fluid that is treated. In further embodiments, an effective amount is from about 0.1 % to about 5% v/v, from about 0.5% to about 5% v/v, or from about 0.75% to about 2% v/v, based on an amount of the total composition described herein and the amount of fluid that is treated.

[0132] The compositions can be applied to a fluid using various well-known methods and they can be applied at numerous different locations throughout a given System. The composition can be pumped into an oil/gas pipeline using an umbilical line. Further, capillary string injection Systems can be utilized to deliver the composition. U.S. Pat. No. 7.311,144 provides a description of an apparatus and methods relating to capillary injection, the disclosure of which is incorporated into the présent application in its entirety.

EXAMPLES

[0133] Embodiments of the présent disclosure are further defined in the following non-limiting Examples. It shouid be understood that these Examples, while indicating certain embodiments of the disclosure, are given by way of illustration only. From the above discussion and these Examples, one skilled in the art can ascertain the essential characteristics of this disclosure, and without departing from the spirit and scope thereof, can make various changes and modifications of the embodiments of the disclosure to adapt it to various usages and conditions. Thus, varions modifications of the embodiments of the disclosure, in addition to those shown and described herein, will be apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended daims.

EX AMPLE 1

Rocking Cell Hydrate Performance Testing

[0134] The combinations of AA-LDHI and Cls shown in Table 3 were evaluated in this Example. The AA-LDHI and Cl ratios were fixed across ail combination products trialed using higher (95-99.5) vol% of the AA-LDHI and low (0.5-5%) vol% of a mixture of varying corrosion inhibitor components. The variation in Cls in the evaluated products were controlled by including in the testing a total CI ppm concentration of 10,000 ppm.

|0135] TABLE 3

Product	Additives Included
AA-LDHI/CI Combo Product 1	Fatty acid amine condensate, quaternary ammonium compound, methanol, nonylphenol surfactant, sulfur compound
AA-LDHI/CI Combo Product 2	Imido fatty acid amine condensate, fatty pyridine dérivative, nonylphenol surfactant, sulfur compound
AA-LDHI/CI Combo Product 3	Quaternary ammonium compound, imido fatty acid amine condensate, sulfur compound
AA-LDHI/CI Combo Product 4	Fatty pyridine dérivative, fatty acid amine condensate, methanol, sulfur compound
AA-LDHI/CI Combo Product 5	Quaternary ammonium compound, Imido fatty acid amine condensate, nonylphenol surfactant, sulfur compound
AA-LDHI/CI Combo Product 6	Fatty acid amine condensate, quaternary ammonium compound, sulfur compound

[0136] Testing parameters are summarized in Table 4 and the composition of the synthetic gas 15 (or Green Canyon gas) shows in Table 5.

[0137] TABLE 4

Parameter	Value
Oil	Field Crude
API	30@60°F
Gas	Synthetic Green Canyon Gas Blend (see Table 5)
Brine	5.0 wt.% NaCI
AA-LDHI	AA-LDHI/CI Combo Products 1-6 (see Table 3)
Water Cut(s)	30%

Test Equipment	Low Shear Automated Visual Rocking Cell
Pressure(s)	2,000 psig

|0138[ TABLE 5

Component	mol%
Methane	87.2
Ethanc	7.60
Propane	3,08
n~Butane	0.79
/-Butane	0.50
n-Pentane	0.20
/-Pentane	0.20
Nîtrogen	0.39

[0139] The low shear automated visual rocking cell apparatus used for évaluation of low dosage hydrate inhîbitors contains pressure cells made of sapphire tubes, each of which contains a stainless-steel bail. The cells are placed on a rack, and the rack is gently rocked up and then down using a cornputer-controlied stepper motor. The cells are charged with appropriate sample liquids prier to being placed in the rack and then immersed in the water bath. Once the cells are immersed in the bath, they can then be charged with gas to the desired pressure, and the experiment may begin. Sensors are used to monitor bail movement within the cells, with a sensor placed near each end of the cell: a top sensor, and a bottom sensor. The time it takes for the bail to travel from the top sensor to the bottom sensor in each cell, (i.e., bail travel time) is recorded.

|Û140] The following parameters are recorded during low shear rocking cell tests:

1. Bath température

2. Individual cell pressure

3. Bail travel time (in seconds) as monitored by the sensors 1 (green) and 2 (red)

4. Visual observations

[0141] Hydrate formation or blockage is indicated by:

1. Increase in bail travel time

2. Pressure drop in constant volume test

3. Visual observation of hydrate particles m the cells |01421 When evaluating the data, the results can indicate the following:

|01431 Fluid viscosity increase - Increase of bail falling time in both sensors indicates a fluid viscosity increase, which could be due to an increase of hydrate slurry concentration, or a viscosity increase of the liquid phase itself.

[0144] A partial plug - This is indicated by one sensor continuing to see bail movement while the other does not. A lack of bail movement is indicated by a sensor constantly seeing the bail (bail falling times are zéro seconds) or by never seeing the bail (bail falling times are greater than or equal to 30 seconds).

[0145| A complété plug - This is indicated by a lack of bail movement from both sensors, constantly seeing the bail (bail falling times are zéro seconds) or by never seeing the bail (bail falling times are greater than or equal to 30 seconds).

Low Shear Automated Visual Rocking Cell Protocol

[0146J The rocking cell test protocol for a shut-in/restart simulation is outlined here:

1. Condition the οί 1 at 176 °F (80 °C) for 2 h.

2. Charge the cell to 10 mL total volume with brine and crude oil.

3. Dose AA-LDHI into each cell. Displace the residual air in each cell by flushing with synthetic gas and venting three times.

4. Pressurize the cells to 2,000 psi at 80 °F.

5. Cool the cells to 40 °F over a period of 4 hours while rocking.

6. Rock the cells for additional 6 hours at 40 °F.

7. Simulate a shut-in by stopping the cells for a minimum of 16 h.

8. Simulate a restart by rocking the cells for a minimum of 2 h. Record visual observations.

9. End test.

|0147[ Testing was performed using low shear hydrate rocking cells per standard shut in/restart protocol of an established field crude System. The results are summarized in Table 6. A passing dose rate is indicated by hydrate formation with no blockage occurring in the cell for the duration of the test. As per industry standard, replicate passes of any given dose rate were required to fully qualify as passing. Failure mechanisms vary, from blockage of the bail at any point during the test, to bail falls greater than 30 seconds, to the formation of endcap hydrates on the left and/or right side of the cell (confirmed by visual observation).

[0148] TABLE 6

Water Cut (%)	AA-LDHI/CI Combo Product	AA-LDHI Dose Rate (vol%)	Resuit	Pass Rate
30	Noue	Blank	Fail	0/1
AA-LDHI, no CI	1.0	Fail	0/1
AA-LDHI, no Cl	1.5	Pas s	2/2
AA-LDHI/CI Combo 1	1.0	Fail	0/1
AA-LDHl/CI Combo 1	1.5	Pas s	2/2
AA-LDHl/CI Combo 2	1.0	Fail	0/1
AA-LDHI/CI Combo 2	1.5	Pas s	2/2
AA-LDHI/CI Combo 3	1.0	Fail	0/1
AA-LDHI/CI Combo 3	1.5	Pas s	2/2
AA-LDHI/CI Combo 4	Not tested	N/A	N/A
AA-LDHl/CI Combo 5	1.0	Fail	1/2
AA-LDHI/CI Combo 5	1.5	Pass	2/2
AA-LDHI/CI Combo 6	1.0	Fail	0/1
AA-LDHI/CI Combo 6	1.5	Pass	2/2

|0149] AA-LDHl/CI Combo 4 was not tested since it failed one of the product stability tests of the umbilical certification protocol. The data confîrms that there is no interférence in the hydrate inhibition of the AA-LDHI when combined with the various Cls.

EXAMPLE 2

Cold Stress Testing - Corrosion Performance

[0150] The AA-LDHl/CI combination products in Table 3 were further evaluated for corrosion performance using 7-day rotating cage autoclave (RCA) testing. The corrosion performance was analyzed using RCA with the following testing methodology. Two pre-weighed and six additional Hastelloy coupons were mounted on a holder. The coupon holder was attached to the shaft and placed in a 2-liter autoclave that was previously de-aerated in three cycles using nitrogen. After closing the autoclave, the desired ratio of synthetic brine and hydrocarbon was introduced into the autoclave using vacuum. Chemical-free crude oii was utilized as the hydrocarbon phase. After heating the autoclave to the testing température, it was charged with the required amount of CO₂. The coupons were rotated for seven days at the speed corresponding to the target shear stress. After cooling down and depressurizing the autoclave, the coupons were removed, cleaned in inhibited acid solution, dried, and weighed to obtain mass loss for general corrosion rate calculation.

Vertical Scanning Interferometry (VSI)

[0151] The post-test coupons were further evaluated for localized/pitting corrosion performance using VSI. A Bruker optical three-dimensional surface profilometer NPFlex-LA was used for characterizing corrosion coupon surface features. The VSI was applied to capture ail features developed on the métal surface during the test. VSI provides noncontact, quantitative measurements with nanometer resolution on the vertical (Z) axis. The NPFlex-LA détermines the size and shape of the surface features over the whole scan area. The corrosion coupons used in the study hâve a rectangular shape with 1 x 2 x 1/8” dimensions. Ail surface features with a depth of 10 microns and deeper were captured in the scans. The depth is used as the metric for the surface analysis. Industry standard pitting corrosion performance pass/fail criteria allows one 10 feature with a depth greater than 20 microns within the scan area of each coupon. Bruker optical three-dimensional surface profilometer NPFlex-LA was used to obtain VSI images, while the test parameters used for the corrosion testing are shown in Table 7. The water analysis of the brine composition had approximately a TDS of 90,000 and approximately 50,000 mg/L of chloride.

|0152] TABLE 7

Parameters	Value
Water eut, %	99
Oil Type	Field Crude Oil
O 0 Température, F ( C)	160 (71)
CO2 Pressure, psig	(Contents purged with the gas in the autoclave before closing and no additional gas added)
Dosage, ppm	10,000 ppm of combination product (Chemical added on top of oil layer)
Time, hr	168
Shear Stress, Pa (rpm)	40 (680 rpm)
Coupon Metallurgy and # of fiat coupons per test	X-65, 2

[0153] The variation in Cls in the evaluated products were controlled by including in the testing a total Cl ppm concentration of 10,000 ppm in combination with the AA-LDHI. The results are summarized in Table 8 These show that combination products 1-6 (except 4, not tested) generated < 4 mpy general corrosion rates. The coupons were then scanned for localized/pitting corrosion and VSI data indicates that both AA-LDH1/CI-3 and AA-LDHI/CI-1 did not pass localized criteria (pit depths of <10 pm). Products 2, 5 and 6 were able to meet both general corrosion rate and localized criteria showing solid pitting prévention performance at the optimal dosages of l% AA-LDHI/CI combination products.

|0154] TABLE 8

Test	Chemical	CR (mpy) each coupon	Average CR (mpy)	Depth of Five deepest Features (pm)
1	Blank	105.89	103.1	Not performed
100.31
2	Control AA-LDH1	26.97	26.5	Not performed
26.03
3	AA-LDHI/CI-1	0.95	0.98	No features > 10 pm
1	33.1,29.8, 29.0, 28.1,24.2
4	AA-LDHI/CI-2	1.01	1.03	No features > 10 pm
1.05
5	AA-LDH1/CI-3	0.89	0.87	18.5, 17.2, 15.0, 14.5, 14.1
0.84	39, 25.3,24.5, 24.3,23.4
6	AA-LDHI/CI-4	Not tested	Not tested	Not tested
7	AA-LDHI/CI-5	0.9	0.84	No features > 10 pm
0.78
8	AA-LDHI/CI- 6	1.19	1.11	No features > 10 pm
1.04

[0155] Synergies were noted in AA-LDHI/CI combo products AA-LDHI/CI 2, AA-LDHI/CI 5, and AA-LDHI/CI 6.

[0156] It is to be understood that while the invention has been described in conjunction with the detailed description thereof, the foregoing description is intended to illustrate, and not limit the scope of the invention, which is defined by the scope of the appended daims. Other embodiments, advantages, and modifications are within the scope of the following daims. Any reference to accompanying drawings which form a part hereof, are shown, by way of illustration only. It is understood that other embodiments may be utilized and structural changes may be made without departing from the scope of the présent disclosure. Ail publications discussed and/or referenced herein are incorporated herein in their entirety.

[0157] The features disclosed in the foregoing description, or the following daims, or the accompanying drawings, expressed in their spécifie forms or in terms of a means for performing the disclosed fonction, or a method or process for attaining the disclosed resuit, as appropriate, may, separately, or in any combination of such features, be utilized for realizing the invention in diverse fonns thereof.

Claims (21)

1. l. A hydrate inhibitor and corrosion inhibitor composition comprising:

   from about 10 wt-% to about 99.9 wt-% of an anti-agglomerant low dose hydrate inhibitor (AA-LDHI), wherein the AA-LDHI is a zwitterionic compound or a cationic ammonium compound;

   from about 0.01 wt-% to about 50 wt-% of a corrosion inhibitor, and at least one additional functional ingrédient, solvent, or a combination thereof.
2. 2. The composition of claim l, wherein the AA-LDHI is a zwitterionic compound having the structure of Formula (I), or an acid, a free base, a zwitterion, or a sait thereof:

   R₂ Rs

   Rs (D, wherein:

   Ri is hydrogen, C1-C20 substituted or unsubstituted alkyl or alkenyl group;

   R₂ is hydrogen, C1-C20 substituted or unsubstituted alkyl or alkenyl group, an alkylcarboxyl, or an alkylamido group;

   Ra and R; are independently hydrogen, C1-C20 substituted or unsubstituted alkyl or alkenyl group, or wherein the nitrogen atom and the R4 and R5 groups form a substituted or unsubstituted heterocyclo group; and

   Rs is a C2-C10 substituted or unsubstituted alkylene group.
3. 3. The composition of claim 1, wherein the AA-LDHI is a cationic ammonium compound having the structure of Formulae (lia) or (Ilb):

   (lia) or

   AMENDED SHEET

   (Ilb), wherein:

   Ri is an alkyl group or alkenyl group, optionally having one or more heteroatoms or ionizable heteroatoms;

   Ri îs absent or hydrogen;

   Ri is CnHzn+i, wherein n is a number from 0 to 10;

   R4 is an alkyl group or alkenyl group, optionally having one or more heteroatoms or ionizable heteroatoms;

   R5 is hydrogen, or an alkyl or alkenyl group, optionally having one or more heteroatoms or ionizable heteroatoms;

   B is a group selected from the generic formula (CH2)n, wherein n is a number from 1 to 4;

   A is a substituent selected from the group consisting of CH2, NR5, oxygen (O), and any combination thereof, and

   X is a counterion.
4. 4. The composition of claim 1, wherein the AA-LDHI is a cationic ammonium compound having the structure of Formulae (Ilia) or (Illb):

   Ri; or (nia)

   (IHb), wherein:

   A is an optionally substituted pyrrole, pyrrolidine, piperidine, pyrazole, imidazole, triazole, isoxazole, oxazole, thiazole, isothiazole, oxadiazole, oxatriazole, dioxazole, oxathiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxazine, isoxazine, oxadiazine, morpholine, azepane, azepine, caprolactam, or quinoline;

   AMENDED SHEET

   Ri is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aryl;

   R; is hydrogen, optionally substituted alkyl, alkenyl, or alkynyl; Z is -NR3-C(0H -QOHMRj-, -O-C(O)-, -C(O)-O-, -S-C(O)-, -C(O)-S~, -O-C(O)-NR₃-NR,-C(O)-O-, -NRj-C(O)-NRî-, or absent;

   R; is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aryl;

   n is an integer from 0 to 25;

   X is an anion; and when A is oxazolidine and R; is alkyl, Z is -NR₃-C(O)-, -C(O)-NR₃-, -O-C(O)-, -C(O)-O-, -S-C(O)-, -C(O)-S- -O -C(0)-NR3- -NR₃-C(O)-O-, or -NR₃-C(O)-NR₃-.
5. 5. A hydrate inhibitor and corrosion inhibitor composition comprising:

   from about 10 wt-% to about 99.9 wt-% of an anti-agglomerant low dose hydrate inhibitor (AA-LDHI);

   from about 0.01 wt-% to about 50 wt-% of a corrosion inhibitor, and at least one additional functional ingrédient, solvent, or a combination thereof, wherein the AA-LDHI is one of (a), (b), or (c):

   (a) a zwitterionic compound having the structure of Formula (I), or an acid, a free base, a zwitterion, or a sait thereof:

   Ri O

   *5 wherein:

   Ri is hydrogen, Ct-C2o substituted or unsubstituted alkyl or alkenyl group;

   R? is hydrogen, C1-C20 substituted or unsubstituted alkyl or alkenyl group, an alkylcarboxyl, or an alkylamido group;

   R₃ and Rî are independently hydrogen, C1-C20 substituted or unsubstituted alkyl or alkenyl group, or wherein the nitrogen atom and the R4 and R5 groups form a substituted or unsubstituted heterocyclo group; and

   Ru is a C2-C1Ü substituted or unsubstituted alkylene group, or (b) a cationic ammonium compound having the structure of Fonnulae (Ha) or (Ilb):

   AMENDED SHEET

   (lia) or

   Glb), wherein:

   Ri is an alkyl group or alkenyl group, optionally having one or more heteroatoms or ionizable heteroatoms;

   R2 is absent or hydrogen;

   R3 is C_nH2n-i, wherein n is a number from 0 to IO;

   Rj is an alkyl group or alkenyl group, optionally having one or more heteroatoms or ionizable heteroatoms;

   Rs is hydrogen, or an alkyl or alkenyl group, optionally having one or more heteroatoms or ionizable heteroatoms;

   B is a group selected from the generic formula (CHi)_n, wherein n is a number from l to 4;

   A is a substituent selected from the group consisting of CH2, NR5, oxygen (O), and any combination thereof, and

   X is a counterion, or (c) a cationic ammonium compound having the structure of Formulae (111a) or (Illb):

   wherein:

   A is an optionally substituted pyrrole, pyrrolidine, piperidine, pyrazole, imidazole, triazole,

   AMENDED SHEET isoxazole, oxazole, thiazole, isothiazole, oxadiazole, oxatriazole, dioxazole, oxathîazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxazine, isoxazine, oxadiazine, morpholine, azepane, azepine, caprolactam, orquinoline;

   Ri is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aryl;

   R; is hydrogen, optionally substituted alkyl, alkenyl, or alkynyl; Z is -NRj-C(O)-, -C(O}-NR3- -O-C(O)-, -C(O)-O-, -S-C(O)-, -C(O)-S- -O-C(O)-NRj-NRj-C(O)-O-, -NR₃-C(O)-NR₃-, or absent;

   R₃ is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aryl;

   n is an integer from 0 to 25;

   X is an anion; and when A is oxazolidine and R₂ is alkyl, Z is -NR₃^C(O)-, -C(O) NR₃-, -O-C(O)-C(O)-O-, -S-C(O)-, -C(O)-S-, -O-C(O)-NR₃-, -NR₃H2(O)-O- or -NR₃-C(O)-NR₃-.
6. 6. The composition of any one of daims l-5, wherein the corrosion inhibitor is an aromatic amine, aliphatic amine, heterocyclic amine, alkoxylated amine, amidoamine, quaternary ammonium compound, amide, imidazoline, imidazolinium compound, pyridine, quinoiine, phosphate ester, monomeric or oligomeric fatty acid, or any combination thereof.
7. 7. The composition of any one of daims 1-6, wherein the composition comprises more than one corrosion inhibitor, and/or does not include any boron-hydroxylalkyl(amine) compounds, urea or calcium nitrate corrosion inhibitors.
8. 8. The composition of daim 7, wherein the corrosion inhibitors comprise (a) a quaternary ammonium compound, fatty acid amine condensate, and at least one sulfur compound; (b) a quaternary ammonium compound, fatty acid amine condensate, a phosphate ester, and at least one sulfur compound; (c) a quaternary ammonium compound, imido fatty acid amine condensate, nonylphenol/nonionic surfactant, and at least one sulfur compound; or (d) imido imidazoline, alkyl pyridine dérivative, nonylphenol/ nonionic surfactant, and at least one sulfur compound, and wherein the sulfur compound is an organic sulfur compound comprising at least one of mercaptoalkyl alcohol, mercaptoacetic acid, and/or thioglycolic acid.

   AMENDED SHEET
9. 9. The composition of any one of daims l-8, wherein the composition includes a single AA-LDHI.
10. 10. The composition of any one of daims l-9, wherein the composition does not include any quatemary ammonium compound AA-LDHIs or halide-containing AA-LDHIs.
11. 11. The composition of any one of daims l-10, wherein the solvent comprises a polar and/or nonpolar solvent.
12. 12. The composition of any one of daims l-l l, wherein the additional functional ingrédient comprising one or more asphaltene inhibitors, paraffm inhibitors, scale inhibitors, emulsifiers, water clarifiers, dispersants, émulsion breakers, biocides, pH modifiées, surfactants, or any combination thereof.
13. 13. The composition of any one of daims l-12, wherein the composition is free of kinetic hydrate inhibitors and fluoroalkyl compounds.
14. 14. The composition of any one of daims 1-13, wherein the composition is a two-part composition wherein the first part comprises the AA-LDHI and the second part comprises the corrosion inhibitor and the additional functional ingrédient, solvent or combination thereof.
15. 15. A method for inhibiting corrosion and formation of gas hydrate agglomérants in a fluid comprising:

    contacting the fluid with a hydrate inhibitor and corrosion inhibitor composition of any one of daims 1- 14, or contacting the fluid with an anti-agglomerant low dose hydrate inhibitor (AA-LDHI), wherein the AA-LDHI is a zwitterionic compound or a cationic ammonium compound, and a corrosion inhibitor, w herein the AA-LDHI and corrosion inhibitor are provided at a weight ratio of about 1:0.001 to about 1:1, wherein the composition inhibits general and localized corrosion and formation of gas hydrate agglomérants in the fluid.
16. 16. The method of claim 15, wherein the fluid comprises water, gas, and/or a hydrocarbon.

    AMENDED SHEET
17. 17. The method of any one of daims 15-16, wherein the fluid is contained in an oil or gas pipeline or refinery.
18. 18. The method of claim 17, wherein the oil or gas pipeline or refinery is an offshore application.
19. 19. The method of any one of daims 15-18, wherein the effective amount is from about 0.1 to about 5 volume %, based on an amount of fluid that is treated.
20. 20. The method of any one of daims 15-19, wherein the fluid has a water eut from about 1 to about 90 v/v percent.
21. 21. The method of any one of daims 15-20, wherein the inhibition of localized corrosion reduces pitting on surfaces and provides general corrosion rate of < 4 mpy.