Compositions and methods for dissolving iron sulfide and inhibiting corrosion

Abstract

The present disclosure provides methods and compositions for inhibiting corrosion of metal surfaces and dissolving iron sulfide deposits in aqueous systems. The method may include adding the composition to an aqueous medium. The composition may comprise malic acid or a salt thereof. The composition may optionally include an organic solvent and / or a resist.

Description

Technical Field

[0001] The present disclosure provides compositions and methods for cleaning, dissolving and / or inhibiting corrosion. More specifically, the present disclosure provides compositions and methods for removing oilfield hydrocarbons and iron sulfide-based deposits from equipment and optionally for protecting the equipment from corrosion by corrosive fluids and gases. Background Art

[0002] As oil fields age, oil production decreases and the amount of water produced with the oil increases. Water is usually disposed of or injected into the formation to maintain reservoir pressure. The separation process is effective, but not perfect, and a small portion of oil and other debris may exist after the fluid passes through the separation equipment. As oil fields age, the remaining portion of the oil carried in the water can cause serious problems. Oil fields can produce up to 1,000,000 barrels of water per day. Residual oil and other particles such as paraffin, asphaltene, iron sulfide and biomass can accumulate in separation equipment and pipelines. If not treated, this form of deposits can plug pipelines, which can lead to loss of revenue and / or equipment failure. Since pipelines cannot be cleaned mechanically, chemical solutions that can be injected into the system are required to maintain control of deposits in the pipelines.

[0003] Fluids produced in the oil and gas industry can be quite corrosive to the infrastructure that produces them. Such internal corrosion of pipelines and production equipment is often treated using chemical corrosion inhibitors. Corrosion inhibitors work primarily by forming a protective film on the surface of the infrastructure. This forms a protective barrier that prevents the corrosive fluid from eroding. If deposits, such as those containing iron sulfide, are present on the internal surfaces, the equipment cannot be effectively coated and protected with the dosed corrosion inhibitor.

[0004] Such unwanted deposits can be a complex mixture of inorganic compounds (such as sand and iron sulfide) and organic compounds (such as asphaltenes and crude oil). The deposits are sticky and difficult to clean. Currently, commercially available detergents for removing deposits from equipment used in oil and gas applications help remove organic deposits, but are less effective for inorganic deposits, especially iron sulfide. Conventional detergents can disperse iron sulfide, but are relatively ineffective in inhibiting or dissolving iron sulfide, providing only limited cleaning capabilities. Conventional detergents can also be acidic and therefore incompatible with the metallurgy of the system they are designed to treat. Summary of the invention

[0005] In certain aspects, the present disclosure provides methods for inhibiting corrosion of metal surfaces in aqueous systems. In addition, the present disclosure provides methods for dissolving iron sulfide deposits in aqueous systems. In addition, the present disclosure provides methods for dissolving iron sulfide deposits and inhibiting corrosion of metal surfaces in aqueous systems.

[0006] The method comprises adding a composition to an aqueous medium, wherein the composition comprises malic acid or a salt thereof.

[0007] In some embodiments, the composition comprises an organic solvent. The organic solvent may include, for example, an alcohol, a hydrocarbon, a ketone, an ether, an alkylene glycol, a glycol ether, an amide, a nitrile, a sulfoxide, an ester, a polyol, or any combination thereof.

[0008] The organic solvent may include methanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexanol, hexanol, octanol, decanol, 2-butoxyethanol, methanediol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, pentane, hexane, cyclohexane, methylcyclohexane, heptane, decane, dodecane, diesel, toluene, xylene, heavy aromatic naphtha, cyclohexanone, diisobutyl ketone, ethyl ether, propylene carbonate, N-methylpyrrolidone, N,N-dimethylformamide, glycerol, or any combination thereof.

[0009] In some embodiments, the composition comprises a resist selected from the group consisting of an imidazoline compound, a quaternary ammonium compound, a pyridinium compound, and any combination thereof.

[0010] In certain embodiments, the resist includes one or more of the following imidazoline compounds: (A) an imidazoline of formula (I):

[0011]

[0012] Where R 10 C 1 -C 20 Alkyl or C 1 -C 20 Alkoxyalkyl groups;

[0013] R 12 and R 13 are independently hydrogen or C 1 -C 6 an alkyl group; and

[0014] R 11 are independently hydrogen, C 1 -C 6 Alkyl, C 1 -C 6 Hydroxyalkyl, aminoalkyl, aminoaryl, aminoarylalkyl, aminoalkylaryl or C 1 -C 6 Arylalkyl;

[0015] (B) Imidazolinium salt of formula (II):

[0016]

[0017] Where R 10 C 1 -C 20 Alkyl or C 1 -C 20 Alkoxyalkyl groups;

[0018] R 12 and R 13 are independently hydrogen or C 1 -C 6 Alkyl groups;

[0019] R 11 and R 14 are independently hydrogen, C 1 -C 6 Alkyl, C 1 -C 6 Hydroxyalkyl or C 1 -C 6 arylalkyl; and

[0020] X is a halide, carbonate, sulfonate, phosphate or an anion of an organic carboxylic acid;

[0021] (C) a diquaternized imidazoline compound of formula (III):

[0022]

[0023] Where R 1 and R 2 Each is independently an unsubstituted branched, chain or cyclic alkyl or alkenyl group having 1 to about 29 carbon atoms; a partially or fully oxidized, sulfurized and / or phosphorylated branched, chain or cyclic alkyl or alkenyl group having 1 to about 29 carbon atoms; or a combination thereof;

[0024] R 3 and R 4 Each is independently an unsubstituted branched, chain or cyclic alkylene or alkenylene group having 1 to about 29 carbon atoms; a partially or fully oxidized, sulfurized and / or phosphorylated branched, chain or cyclic alkylene or alkenylene group having 1 to about 29 carbon atoms; or a combination thereof;

[0025] L 1 and L 2 Each independently is absent, H, -COOH, -SO 3 H, -PO 3 H 2 、-COOR 5 、-CONH 2 ,-CONHR 5 or-CON(R 5 )2 ;

[0026] R 5 each independently is a branched or unbranched alkyl, aryl, alkylaryl, alkylheteroaryl, cycloalkyl or heteroaryl group having 1 to about 10 carbon atoms;

[0027] n is 0 or 1, and when n is 0, L 2 Not present or H;

[0028] x is from 1 to about 10; and

[0029] y is from 1 to about 5; or

[0030] (D)A combination thereof.

[0031] In some embodiments, the resist comprises an imidazoline of formula (I) or an imidazolinium salt of formula (II), R 10 It is an alkyl mixture of tall oil fatty acid (TOFA), R 11 is benzyl, R 12 and R 13 Each is hydrogen, R 14 is hydroxyethyl, and X - For chloride ion.

[0032] In some embodiments, the resist comprises a diquaternized imidazoline compound of formula (III), R 1 and R 2 Derived from a mixture of tall oil fatty acids and mainly C 17 H 33 and C 17 H 31 A mixture of x=2, y=1, R 3 and R 4 For -C 2 H 2 -, and L 1 and L 2 For -CO 2 H, -SO 3 H or -PO 3 H 2 .

[0033] In certain embodiments, the resist comprises a diquaternized imidazoline compound of formula (III), R 1 and R 2 Independently for C 16 -C 18 Alkyl; R 4 For -C 2 H 2 -; x is 2; y is 1; n is 0; L 1 -COOH, -SO3 H or -PO 3 H 2 , and L 2 Not present or H.

[0034] In some embodiments, the resist includes a quaternary ammonium compound and a diquaternized imidazoline compound of formula (III).

[0035] In some embodiments, the resist includes a pyridinium compound of formula (V):

[0036]

[0037] Where R 9 is an alkyl group, an aryl group or an arylalkyl group,

[0038] wherein the alkyl group has 1 to about 18 carbon atoms; and

[0039] X - In certain embodiments, R 9 is a benzyl group, and X is a chloride ion.

[0040] In some embodiments, the resist further comprises a member selected from the group consisting of alkoxylated amines, phosphate esters, monomeric fatty acids, oligomeric fatty acids, and any combination thereof.

[0041] In some embodiments, the composition comprises from about 5% to about 95% by weight malic acid.

[0042] In certain embodiments, the composition comprises from about 5% to about 95% by weight of an organic solvent.

[0043] In some embodiments, the composition comprises from about 5 wt % to about 95 wt % resist.

[0044] In some embodiments, the composition comprises about 15 wt % to about 30 wt % of malic acid, about 20 wt % to about 40 wt % of an organic solvent, and about 15 wt % to about 30 wt % of a resist.

[0045] In certain embodiments, the composition further comprises a compound of the formula HS-(CH 2 ) n A compound of OH wherein n is 2 to 6.

[0046] In some embodiments, the composition further comprises thioglycolic acid, 3,3'-dithiodipropionic acid, thiourea, 2-mercaptoethanol, L-cysteine, tert-butyl mercaptan, sodium thiosulfate, ammonium thiosulfate, sodium thiocyanate, ammonium thiocyanate, sodium metabisulfite, or any combination thereof.

[0047] In some embodiments, the composition further comprises an asphaltene inhibitor, a paraffin inhibitor, a scale inhibitor, an emulsifier, a water clarifier, a dispersant, a demulsifier, a hydrogen sulfide scavenger, a gas hydrate inhibitor, a biocide, a pH adjuster, a surfactant, or any combination thereof.

[0048] In some embodiments, surfaces in aqueous systems comprise iron sulfide deposits.

[0049] In any of the preceding embodiments, the composition may include a pH adjuster.

[0050] The above has been a fairly broad overview of the features and technical advantages of the present disclosure so that the following specific description may be better understood. Other features and advantages of the present disclosure will be described below, which constitute the subject matter of the claims of this application. It should be understood by those skilled in the art that the disclosed concepts and specific embodiments may be easily utilized as a basis for modifying or designing other embodiments in order to perform the same purpose of the present disclosure. It should also be appreciated by those skilled in the art that such equivalent embodiments do not depart from the spirit and scope of the present disclosure as set forth in the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] The following describes specific embodiments of the present invention with reference to the accompanying drawings, in which:

[0052] Figure 1 The results of the bubble cell test are shown;

[0053] Figure 2 The results of the bubble cell test are shown;

[0054] Figure 3 shows the results of the iron sulfide dissolution test;

[0055] Figure 4 shows the results of an iron sulfide dissolution test; and

[0056] Figure 5 The results of the iron sulfide dissolution test are shown. DETAILED DESCRIPTION

[0057] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those of ordinary skill in the art. In the event of a conflict, this document (including definitions) shall prevail. Examples of methods and materials are described below, but methods and materials similar or equivalent to those described herein can be used to practice or test the present disclosure. All publications, patent applications, patents and other reference materials mentioned herein are incorporated by reference in their entirety. The materials, methods and examples disclosed herein are illustrative only and are not intended to be limiting.

[0058] Unless otherwise specified, an alkyl group described herein, alone or as part of another group, is an optionally substituted straight or branched chain saturated monovalent hydrocarbon substituent containing, for example, 1 to about 60 carbon atoms, such as 1 to about 30 carbon atoms in the backbone chain. Examples of unsubstituted alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, and the like.

[0059] The term "aryl" or "ar" as used herein alone or as part of another group (e.g., arylene) means an optionally substituted carbocyclic aromatic group, such as a monocyclic or bicyclic group containing about 6 to about 12 carbons in the ring portion, such as phenyl, biphenyl, naphthyl, substituted phenyl, substituted biphenyl or substituted naphthyl. The term "aryl" also includes heteroaryl functional groups. It should be understood that the term "aryl" applies to cyclic substituents that are planar and include 4n+2n electrons according to Huckel's Rule.

[0060] "Cycloalkyl" refers to a cyclic alkyl substituent containing, for example, about 3 to about 8 carbon atoms, preferably about 4 to about 7 carbon atoms, and more preferably about 4 to about 6 carbon atoms. Examples of such substituents include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. The cyclic alkyl group may be unsubstituted or may be further substituted with an alkyl group such as a methyl group, an ethyl group, and the like.

[0061] "Halogen" or "halo" refers to F, Cl, Br and I.

[0062] "Heteroaryl" refers to a monocyclic or bicyclic 5- or 6-membered ring system in which the heteroaryl group is unsaturated and satisfies Huckel's rule. Non-limiting examples of heteroaryl groups include furanyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, 1,3,4-oxadiazol-2-yl, 1,2,4-oxadiazol-2-yl, 5-methyl-1,3,4-oxadiazole, 3-methyl-1,2,4-oxadiazole, pyridinyl, pyrimidinyl, pyrazinyl, triazinyl, benzofuranyl, benzothienyl, indolyl, quinolyl, isoquinolyl, benzimidazolyl, benzimidazolinyl, benzothiazolinyl, quinazolinyl, and the like.

[0063] "Oxo" refers to an oxygen atom double bonded to a carbon atom.

[0064] The compounds of the present disclosure can be substituted with suitable substituents. As used herein, the term "suitable substituents" means a chemically acceptable functional group, preferably a part that does not invalidate the activity of the compound. Such suitable substituents include, but are not limited to, halo groups, perfluoroalkyl groups, perfluoroalkoxy groups, alkyl groups, alkenyl groups, alkynyl groups, hydroxyl groups, oxo groups, sulfhydryl groups, alkylthio groups, alkoxy groups, aryl or heteroaryl groups, aryloxy or heteroaryloxy groups, aralkyl or heteroaralkyl groups, aralkyloxy or heteroaralkyloxy groups, HO-(C=O)-groups, heterocyclyl groups, cycloalkyl groups, amino groups, alkyl and dialkylamino groups, carbamoyl groups, alkylcarbonyl groups, alkoxycarbonyl groups, alkylaminocarbonyl groups, dialkylaminocarbonyl groups, arylcarbonyl groups, aryloxycarbonyl groups, alkylsulfonyl groups, and arylsulfonyl groups. In some embodiments, suitable substituents may include halogen, unsubstituted C 1 -C 12 Alkyl groups, unsubstituted C 4 -C 6 Aryl group or unsubstituted C 1 -C 10 Alkoxy groups. Those skilled in the art will appreciate that many substituents may be substituted with other substituents.

[0065] The term "substituted" as in "substituted alkyl" means that in the group in question (i.e., alkyl), at least one hydrogen atom bonded to a carbon atom is replaced by one or more of the following substituents: hydroxy (-OH), alkylthio, phosphino, amido (-CON(R) A )(R B ), where R A and R B are independently hydrogen, alkyl or aryl), amino (-N(R A )(R B ), where R A and R B independently hydrogen, alkyl or aryl), halo (fluorine, chlorine, bromine or iodine), silane, nitro (-NO 2 ), ether (-OR A , where R A is alkyl or aryl), ester (-OC(O)R A , where R A is an alkyl or aryl group), a keto group (-C(O)R A , where R A is an alkyl or aryl group), a heterocyclic group, and the like.

[0066] When the term "substituted" introduces a list of possible substituted groups, it is intended that the term applies to every member of that group. That is, the phrase "optionally substituted alkyl or aryl" should be interpreted as "optionally substituted alkyl or optionally substituted aryl".

[0067] The terms "polymer", "copolymer", "polymerization", "copolymerization" and the like include not only polymers comprising two monomer residues and polymerizing two different monomers together, but also (co)polymers comprising more than two monomer residues and polymerizing more than two other monomers together. For example, the polymers disclosed herein include terpolymers, tetrapolymers, polymers comprising more than four different monomers, and polymers comprising, consisting of, or consisting essentially of two different monomer residues. In addition, "polymers" as disclosed herein may also include homopolymers, which are polymers comprising a single type of monomer unit.

[0068] Unless otherwise specified, the polymers of the present disclosure may be linear, branched, cross-linked, structured, synthetic, semi-synthetic, natural and / or functionally modified. The polymers of the present disclosure may be in the form of, for example, a solution, dry powder, liquid or dispersion.

[0069] The present disclosure provides a composition for inhibiting corrosion and / or removing iron sulfide deposits in oil and gas processes. In some embodiments, the composition comprises an iron sulfide dissolving agent, such as malic acid and / or its salt, which can be used to dissolve iron sulfide. The composition disclosed herein may optionally include other components, such as a solvent (e.g., an organic solvent) and an anti-corrosion agent, which may include, for example, a functionalized imidazoline compound, a quaternary ammonium compound, a pyridinium compound, a quaternary iminium compound, a zwitterionic betaine compound, an amidoamine compound, or any combination thereof. In some embodiments, the composition disclosed herein does not include a solvent, an anti-corrosion agent, and / or phosphorus.

[0070] The composition disclosed herein can be used for products, processes and refinery streams based on crude oil and natural gas. The composition effectively inhibits corrosion of low carbon steel in hydrocarbons, oil / brine mixtures and aqueous systems. The composition can also be used to remove hydrocarbon-containing deposits on metal and / or mineral surfaces in contact with fluids in oil and gas applications, including removing iron sulfide, to reduce the risk of corrosion failure caused by corrosion of deposits. The composition can be used in sweet systems (i.e., systems with relatively high carbon dioxide concentrations) or systems with acidic conditions (i.e., relatively high hydrogen sulfide concentrations). The composition can be used in a wide range of climates and a wide range of processing conditions, such as from about 0°C to about 200°C, under which other available cleaning agents / corrosion resist compositions fail.

[0071] The iron sulfide dissolving agent comprises malic acid. The iron sulfide dissolving agent may optionally comprise a polyfunctional hydroxycarboxylic acid and / or additional components, such as allaric acid, altaric acid, altraric acid, altersonic acid, arabinonic acid, arabinuronic acid, citric acid, dihomocitric acid, fructic acid, alginic acid, fumaric acid, galactaric acid, galacturonic acid, galacturonic acid, glucaric acid, glucoheptonic acid, gluconic acid, glucuronic acid, gulonic acid, homocitric acid, homoisocitric acid, itaconic acid, idonic acid, iduronic acid, isocitric acid, mannonic acid, mannonic acid, octulonic acid, rhamnosonic acid, ribonic acid, tagaturonic acid, xylonic acid, xyluronic acid, tartaric acid, trienoic acid, glyceric acid, malonic acid and pantoic acid, salts of any of these acids, or any combination thereof. Suitable salts of the iron sulfide dissolving agent include alkali metal and alkaline earth metal salts, such as sodium, potassium, lithium, magnesium, calcium and cesium salts.The iron sulfide dissolving agent inhibits the formation of iron sulfide and / or dissolves iron sulfide.

[0072] The iron sulfide solubilizing agent can be present in the composition in an amount ranging from about 1 wt % to about 100 wt %, such as from about 1 wt % to about 90 wt %, from about 1 wt % to about 80 wt %, from about 1 wt % to about 70 wt %, from about 1 wt % to about 60 wt %, from about 1 wt % to about 50 wt %, from about 1 wt % to about 40 wt %, from about 1 wt % to about 30 wt %, from about 1 wt % to about 20 wt %, from about 1 wt % to about 10 wt %, from about 5 wt % to about 100 wt %, from about 10 wt % to about 100 wt %, from about 20 wt % to about 100 wt %, from about 30 wt % to about 100 wt %, from about 40 wt % to about 100 wt %, from about 50 wt % to about 100 wt %, from about 60 wt % to about 100 wt %, from about 70 wt % to about 100 wt %, from about 80 wt % to about 100 wt %, or from about 90 wt % to about 100 wt %, based on the total weight of the composition.

[0073] The compositions disclosed herein may include additional components, such as resists. Based on the total weight of the composition, the resist can be present in an amount of about 0 wt % to about 95 wt %, such as about 1 wt % to about 75 wt %, about 5 wt % to about 50 wt %, or about 10 wt % to about 25 wt %.

[0074] Suitable resists include, but are not limited to, quaternary salts of alkyl, hydroxyalkyl, alkylaryl, arylalkyl or aryl amines, salts of monocyclic or polycyclic aromatic amines, imidazoline derivatives, monoalkyl, dialkyl or trialkyl or alkylaryl phosphates, phosphate esters of hydroxylamines, phosphate esters of polyols, esters of alcoholamines and / or monomeric and / or oligomeric fatty acids.

[0075] In some embodiments, the resist includes an imidazoline. The imidazoline can be, for example, an imidazoline derived from a diamine such as ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), etc. and a long chain fatty acid such as TOFA.

[0076] The imidazoline may be an imidazoline of formula (I) and / or a derivative thereof. Representative imidazoline derivatives include, but are not limited to, an imidazolinium compound of formula (II) or a diquaternary ammonium compound of formula (III).

[0077] Suitable imidazolines include those of formula (I):

[0078]

[0079] Where R 10 C 1 -C 20 Alkyl or C 1 -C 20 Alkoxyalkyl group; R 11 are independently hydrogen, C 1 -C 6 Alkyl, C 1 -C 6 Hydroxyalkyl, aminoalkyl, aminoaryl, aminoarylalkyl, aminoalkylaryl or C 1 -C 6 Arylalkyl; and R 12 and R 13 are independently hydrogen or C 1 -C 6 In some embodiments, the imidazoline comprises R 10 , which is a typical alkyl mixture in TOFA, and R 11 , R 12 and R 13 Each is hydrogen.

[0080] The resist composition may include an imidazolinium compound of formula (II):

[0081]

[0082] Where R 10 C 1 -C 20 Alkyl or C 1 -C 20 Alkoxyalkyl group; R 11 and R 14 are independently hydrogen, C 1 -C 6 Alkyl, C 1 -C 6 Hydroxyalkyl or C 1 -C6 Arylalkyl; R 12 and R 13 are independently hydrogen or C 1 -C 6 an alkyl group; and X - is a halide (such as chloride, bromide or iodide), carbonate, sulfonate, phosphate or an anion of an organic carboxylic acid (such as acetate). In some embodiments, the imidazolinium compound includes 1-benzyl-1-(2-hydroxyethyl)-2-tall oil-2-imidazolinium chloride.

[0083] The resist may include a diquaternized compound having formula (III):

[0084]

[0085] Where R 1 and R 2 Each is independently a substituted or unsubstituted branched, annular or cyclic alkyl or alkenyl group having 1 to about 29 carbon atoms, a partially or fully oxidized, sulfurized and / or phosphorylated branched, annular or cyclic alkyl or alkenyl group having 1 to about 29 carbon atoms, or a combination thereof; R 3 and R 4 Each is independently an unsubstituted branched, chain or cyclic alkylene or alkenylene group having 1 to about 29 carbon atoms, a partially or fully oxidized, sulfurized and / or phosphorylated branched, chain or cyclic alkylene or alkenylene group having 1 to about 29 carbon atoms, or a combination thereof; L 1 and L 2 Each independently is absent, H, -COOH, -SO 3 H, -PO 3 H 2 、-COOR 5 、-CONH 2 ,-CONHR 5 or-CON(R 5 ) 2 ; R 5 Each is independently a branched or unbranched alkyl, aryl, alkylaryl, alkylheteroaryl, cycloalkyl or heteroaryl group having 1 to about 10 carbon atoms; n is 0 or 1, and when n is 0, L 2 is absent or is H; x is from 1 to about 10; and y is from 1 to about 5.

[0086] In some embodiments, R 1 and R 2 Each independently is C 6 -C 22 Alkyl, C 8 -C 20 Alkyl, C 12 -C18 Alkyl, C 16 -C 18 Alkyl or a combination thereof; R 3 and R 4 C 1 -C 10 Alkylene, C 2 -C 8 Alkylene, C 2 -C 6 Alkylene or C 2 -C 3 Alkylene; n is 0 or 1; x is 2; y is 1; R 3 and R 4 For -C 2 H 2 -;L 1 -COOH, -SO 3 H or -PO 3 H 2 ; and L 2 Does not exist, H, -COOH, -SO 3 H or -PO 3 H 2 For example, R 1 and R 2 Can be derived from a mixture of tall oil fatty acids and is primarily C 17 H 33 and C 17 H 31 A mixture of, or may be C 16 -C 18 Alkyl; R 3 and R 4 Can be C 2 -C 3 Alkylene, such as -C 2 H 2 -; n is 1 and L 2 is -COOH, or n is 0 and L 2 Does not exist or is H; x is 2; y is 1; R 3 and R 4 For -C 2 H 2 -; and L 1 It is -COOH.

[0087] In certain embodiments, the number of carbon atoms specified for each group of formula (III) refers to the backbone chain of carbon atoms and does not include carbon atoms that may be contributed by substituents.

[0088] The resist may include a diquaternized imidazoline compound having formula (III), wherein R 1 and R 2Each independently is C 6 -C 22 Alkyl, C 8 -C 20 Alkyl, C 12 -C 18 Alkyl or C 16 -C 18 Alkyl or a combination thereof; R 4 C 1 -C 10 Alkylene, C 2 -C 8 Alkylene, C 2 -C 6 Alkylene or C 2 -C 3 Alkylene; x is 2; y is 1; n is 0; L 1 -COOH, -SO 3 H or -PO 3 H 2 ; and L 2 is absent or is H. In some embodiments, the diquaternized compound has formula (III), wherein R 1 and R 2 Each independently is C 16 -C 18 Alkyl; R 4 For -C 2 H 2 -; x is 2; y is 1; n is 0; L 1 -COOH, -SO 3 H or -PO 3 H 2 , and L 2 Not present or H.

[0089] Based on the total weight of the resist component, the imidazoline and / or imidazolinium compound may account for about 0 wt % to about 100 wt %, about 10 wt % to 60 wt %, or about 30 wt % to 45 wt % of the resist component. For example, based on the total weight of the resist component, the imidazoline and / or imidazolinium compound may account for about 10 wt % to about 70 wt %, about 20 wt % to about 60 wt %, or about 30 wt % to 40 wt % of the resist component.

[0090] The resist may be a quaternary ammonium compound of formula (IV):

[0091]

[0092] Where R 1 , R 2 and R 3 Independently for C 1 -C 20Alkyl, R 4 is methyl or benzyl, and X - It is a halide ion or methylsulfate.

[0093] Suitable alkyl, hydroxyalkyl, alkaryl, aralkyl or aryl quaternary ammonium salts include those of the formula [N + R 5a R 6a R 7a R 8a ][X - ] those alkylaryl, aralkyl and aryl quaternary ammonium salts, wherein R 5a , R 6a , R 7a and R 8a Contains 1 to 18 carbon atoms, and X is Cl, Br or I. For quaternary ammonium salts, R 5a , R 6a , R 7a and R 8a can be independently selected from alkyl groups (e.g., C 1 -C 18 alkyl), hydroxyalkyl (e.g., C 1 -C 18 The monocyclic or polycyclic aromatic amine salts with alkyl or alkaryl halides include the formula [N + R 5a R 6a R 7a R 8a ][X - ], wherein R 5a , R 6a , R 7a and R 8a Contains 1 to 18 carbon atoms and at least one aryl group, and X is Cl, Br or I.

[0094] Suitable quaternary ammonium salts include, but are not limited to, tetramethylammonium salts, tetraethylammonium salts, tetrapropylammonium salts, tetrabutylammonium salts, tetrahexylammonium salts, tetraoctylammonium salts, benzyltrimethylammonium salts, benzyltriethylammonium salts, phenyltrimethylammonium salts, phenyltriethylammonium salts, cetylbenzyldimethylammonium salts, hexadecyltrimethylammonium salts, dimethylalkylbenzylquaternary ammonium salts, monomethyldialkylbenzylquaternary ammonium salts, or trialkylbenzylquaternary ammonium salts, wherein the alkyl group has from about 6 to about 24 carbon atoms, from about 10 to about 18 carbon atoms, or from about 12 to about 16 carbon atoms.

[0095] In some embodiments, the quaternary ammonium salt can be a benzyltrialkyl quaternary ammonium salt, a benzyltriethanolamine quaternary ammonium salt, or a benzyldimethylaminoethanolamine quaternary ammonium salt.

[0096] Based on the total weight of the resist component, the quaternary ammonium salt may comprise from about 0 wt % to about 100 wt %, from about 20 wt % to 80 wt %, or from about 50 wt % to 65 wt % of the resist component. For example, based on the total weight of the resist component, the quaternary ammonium salt may comprise from about 10 wt % to about 90 wt %, from about 30 wt % to about 70 wt %, or from about 50 wt % to about 60 wt % of the resist component.

[0097] The resist composition may comprise a pyridinium salt, such as those represented by formula (V):

[0098]

[0099] Where R 9 X- is an alkyl group, an aryl group or an aralkyl group, wherein the alkyl group has 1 to about 18 carbon atoms and X- is a halide ion such as chloride, bromide or iodide. Among these compounds are alkyl pyridinium salts and alkyl pyridinium benzyl quaternary ammonium compounds. Examples of compounds include, but are not limited to, methyl pyridinium chloride, ethyl pyridinium chloride, propyl pyridinium chloride, butyl pyridinium chloride, octyl pyridinium chloride, decyl pyridinium chloride, lauryl pyridinium chloride, cetyl pyridinium chloride, benzyl pyridinium chloride and alkyl benzyl pyridinium chloride. In some embodiments, alkyl is C 1 -C 6 In certain embodiments, the pyridinium compound comprises benzylpyridinium chloride.

[0100] The pyridinium salt may comprise from about 0 wt % to about 100 wt %, from about 10 wt % to about 60 wt %, or from about 30 wt % to about 40 wt % of the resist component, based on the total weight of the resist component.

[0101] The resist component may include additional resists such as phosphate esters, monomeric or oligomeric fatty acids, and / or alkoxylated amines.

[0102] In some embodiments, the resist component comprises a phosphate ester. Suitable monoalkyl, dialkyl and trialkyl phosphates and alkyl aryl phosphates and phosphate esters of monoethanolamine, diethanolamine and triethanolamine generally contain from about 1 to about 18 carbon atoms. Examples of monoalkyl, dialkyl and trialkyl phosphates, alkyl aryl or aralkyl phosphates are obtained by using C 3 -C 18 Those prepared by reacting fatty alcohols with phosphorus pentoxide. The phosphate intermediate interchanges its ester group with triethyl phosphate, resulting in a wider distribution of alkyl phosphates. Alternatively, the phosphate esters can be prepared by mixing with alkyl diesters or mixtures of low molecular weight alkyl alcohols and / or diols. The low molecular weight alkyl alcohols and / or diols may include C 6 to C 10Alcohols and / or diols. Additional examples include phosphoric acid esters of polyols containing one or more 2-hydroxyethyl groups and their salts, and hydroxylamine phosphates obtained by reacting polyphosphoric acid or phosphorus pentoxide with a hydroxylamine such as diethanolamine or triethanolamine.

[0103] In some embodiments, the resist component may include monomeric and / or oligomeric fatty acids. Examples of monomeric and / or oligomeric fatty acids include C 14 -C 22 Saturated and unsaturated fatty acids and dimer, trimer and oligomer products obtained by polymerizing one or more of such fatty acids.

[0104] The resist component may include an alkoxylated amine. For example, the alkoxylated amine may be an ethoxylated alkylamine. In some embodiments, the alkoxylated amine includes an ethoxylated tallow amine. Based on the total weight of the resist component, the alkoxylated amine may comprise from about 0 wt % to about 100 wt %, from about 10 wt % to about 60 wt %, or from about 20 wt % to about 30 wt % of the resist component.

[0105] In some embodiments, compositions disclosed herein may include solvents. Based on the gross weight of the composition, the solvent can be present in an amount of about 0 wt % to about 99 wt %, about 5 wt % to about 95 wt %, about 20 wt % to about 80 wt % or about 40 wt % to about 60 wt %. In some embodiments, the solvent accounts for about 5 wt %, about 10 wt %, about 15 wt %, about 20 wt %, about 25 wt %, about 30 wt %, about 35 wt %, about 40 wt %, about 45 wt %, about 50 wt %, about 55 wt %, about 60 wt %, about 65 wt %, about 70 wt %, about 75 wt %, about 80 wt %, about 85 wt %, about 90 wt % or about 95 wt % of the composition.

[0106] Suitable solvents include, but are not limited to, alcohols, hydrocarbons, ketones, ethers, alkylene glycols, glycol ethers, amides, nitriles, sulfoxides, esters, and water. The solvent may include water, isopropanol, methanol, ethanol, 2-ethylhexanol, heavy aromatic naphtha, toluene, ethylene glycol, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, and / or xylene.

[0107] The solvent can be a polar solvent such as water, brine, seawater, alcohol (including straight-chain or branched aliphatic alcohols such as methanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexanol, hexanol, octanol, decanol, 2-butoxyethanol, etc.), alkylene glycols (such as methylene glycol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, etc.), glycol ethers (such as diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, etc.), ketones (such as cyclohexanone or diisobutyl ketone), ethers (such as ethyl ether), alkylene carbonates (such as propylene carbonate), N-methylpyrrolidone (NMP), N,N-dimethylformamide, polyols (such as glycerol), etc.

[0108] Illustrative, non-limiting examples of non-polar solvents suitable for formulation with the composition include, but are not limited to, aliphatic hydrocarbons such as pentane, hexane, cyclohexane, methylcyclohexane, heptane, decane, dodecane, diesel, and the like; aromatic hydrocarbons such as toluene, xylene, heavy aromatic oils; and fatty acid derivatives such as acids, esters, and amides.

[0109] The solvent may be compatible with the arctic environment. For example, methanol, ethanol, ethylene glycol or glycerol may improve the antifreeze properties of the composition. Such solvents are typically present in an amount of about 5 wt % to about 15 wt %, such as about 10 wt %, based on the total weight of the composition, to have an antifreeze effect.

[0110] In some embodiments, composition disclosed herein may include sulfur-containing compound.If present, based on the gross weight of composition, the content of sulfur-containing compound may be about 0.1 wt % to about 25 wt %, about 0.5 wt % to about 20 wt %, about 1 wt % to about 10 wt % or about 1 wt % to about 5 wt %.Based on the gross weight of composition, sulfur-containing compound may account for about 0.1 wt %, about 0.5 wt %, about 1 wt %, about 2 wt %, about 3 wt %, about 4 wt %, about 5 wt %, about 6 wt %, about 7 wt %, about 8 wt %, about 9 wt %, about 10 wt %, about 11 wt %, about 12 wt %, about 13 wt %, about 14 wt %, about 15 wt %, about 16 wt %, about 17 wt %, about 18 wt %, about 19 wt % or about 20 wt % of composition.

[0111] Suitable sulfur-containing compounds include, but are not limited to, compounds that enhance the corrosion inhibition and / or cleaning performance of the composition. The sulfur-containing compound may include, for example, thioglycolic acid, 3,3'-dithiodipropionic acid, thiourea, 2-mercaptoethanol, L-cysteine, tert-butyl mercaptan, sodium thiosulfate, ammonium thiosulfate, sodium thiocyanate, ammonium thiocyanate, sodium pyrosulfite, or any combination thereof. In some embodiments, the sulfur-containing compound is 2-mercaptoethanol.

[0112] The composition may optionally include additives. Suitable additives include, but are not limited to, asphaltene inhibitors, paraffin inhibitors, scale inhibitors, emulsifiers, water clarifiers, dispersants, demulsifiers, hydrogen sulfide scavengers, gas hydrate inhibitors, biocides, defoamers, pH regulators, and / or surfactants. The composition disclosed herein may include about 0.1 wt % to about 10 wt %, about 0.1 wt % to about 5 wt %, or about 0.5 wt % to about 3 wt % of an additive or a combination of additives.

[0113] Suitable asphaltene inhibitors include, but are not limited to, aliphatic sulfonic acids, alkylaryl sulfonic acids, aryl sulfonates, lignin sulfonates, alkylphenol / aldehyde resins and / or similar sulfonated resins, polyolefin esters, polyolefin imides, polyolefin esters having alkyl, alkylene phenyl or alkylene pyridyl functional groups, polyolefin amides, polyolefin amides having alkyl, alkylene phenyl or alkylene pyridyl functional groups, polyolefin imides having alkyl, alkylene phenyl or alkylene pyridyl functional groups, alkenyl / vinyl pyrrolidone copolymers, graft polymers of polyolefins with maleic anhydride or vinylimidazole, hyperbranched polyester amides, polyalkoxylated asphaltenes, amphoteric fatty acids, salts of alkyl succinates, sorbitan monooleate, and polyisobutylene succinic anhydride.

[0114] Suitable paraffin inhibitors include, but are not limited to, paraffin crystal modifiers and dispersant / crystal modifier combinations. Suitable paraffin crystal modifiers include, but are not limited to, alkyl acrylate copolymers, alkyl acrylate vinyl pyridine copolymers, ethylene vinyl acetate copolymers, maleic anhydride ester copolymers, branched polyethylene, naphthalene, anthracene, microcrystalline wax and / or asphaltenes.

[0115] Suitable antiscalants include, but are not limited to, phosphates, phosphate esters, phosphoric acid, phosphonates, phosphonic acid, polyacrylamide, salts of acrylamidomethylpropanesulfonic acid / acrylic acid copolymer (AMPS / AA), phosphinate maleic acid copolymer (PHOS / MA), and salts of polymaleic acid / acrylic acid / acrylamidomethylpropanesulfonic acid terpolymer (PMA / AA / AMPS).

[0116] Suitable emulsifiers include, but are not limited to, carboxylates, acylation reaction products between carboxylic acids or carboxylic anhydrides and amines, and alkyl, acyl, and amide derivatives of sugars (alkyl-saccharide emulsifiers).

[0117] Suitable water clarifying agents include, but are not limited to, inorganic metal salts such as alum, aluminum chloride, and aluminum chlorohydrate, or organic polymers such as acrylic acid-based polymers, acrylamide-based polymers, polymeric amines, alkanolamines, thiocarbamates, and cationic polymers such as diallyldimethylammonium chloride (DADMAC).

[0118] Suitable dispersants include, but are not limited to, aliphatic phosphonic acids with 2 to 50 carbons, such as hydroxyethyl diphosphonic acid, and aminoalkylphosphonic acids, such as polyaminomethylenephosphonates with 2 to 10 N atoms, each with at least one methylenephosphonic acid group; examples of the latter include ethylenediaminetetrakis (methylenephosphonates), diethylenetriaminepenta (methylenephosphonates), and triaminepolymethylenephosphonates and tetraaminepolymethylenephosphonates with 2 to 4 methylene groups between each N atom, at least 2 of the methylene numbers in each phosphonate being different. Other suitable dispersants include lignin or lignin derivatives, such as lignin sulfonates and naphthalenesulfonic acid and derivatives. In some embodiments, the dispersant is selected from dodecylbenzenesulfonate, alkoxylated alkylphenol and / or alkoxylated alkylphenol-formaldehyde resin.

[0119] Suitable demulsifiers include, but are not limited to, dodecylbenzenesulfonic acid (DDBSA), sodium salt of xylenesulfonic acid (NAXSA), epoxidized and propoxylated compounds, cationic, anionic and nonionic surfactants and resins, such as phenolic resins and epoxy resins.

[0120] Suitable hydrogen sulfide scavengers include, but are not limited to, oxidants (e.g., inorganic peroxides such as sodium peroxide or chlorine dioxide); aldehydes (e.g., aldehydes of 1 to 10 carbons such as formaldehyde, glyoxal, glutaraldehyde, acrolein, or methacrolein); and triazines (e.g., monoethanolamine triazine, monomethylamine triazine, and triazines from a variety of amines or mixtures thereof).

[0121] Suitable gas hydrate inhibitors include, but are not limited to, thermodynamic hydrate inhibitors, kinetic hydrate inhibitors, and anti-caking agents. Suitable thermodynamic hydrate inhibitors include, but are not limited to, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium bromide, formate brine (e.g., potassium formate), polyols (such as glucose, sucrose, fructose, maltose, lactose, gluconate, monoethylene glycol, diethylene glycol, triethylene glycol, monopropylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, monobutylene glycol, dibutylene glycol, tributylene glycol, glycerol, diglycerol, and triglycerol), sugar alcohols (e.g., sorbitol and mannitol), methanol, propanol, ethanol, glycol ethers (such as diethylene glycol monomethyl ether, ethylene glycol monobutyl ether), and alkyl or cyclic esters of alcohols (such as ethyl lactate, butyl lactate, methyl ethyl benzoate).

[0122] Suitable kinetic hydrate inhibitors and anti-caking agents include, but are not limited to, polymers and copolymers, polysaccharides (such as hydroxyethylcellulose, carboxymethylcellulose, starch, starch derivatives and xanthan gum), lactams (such as polyvinyl caprolactam, polyvinyl lactam), pyrrolidones (such as polyvinyl pyrrolidones of various molecular weights), surfactants (such as fatty acid salts, ethoxylated alcohols, propoxylated alcohols, sorbitan esters, ethoxylated sorbitan esters, polyglycerol esters of fatty acids, alkyl glucosides, alkyl polyglucosides, alkyl sulfates, alkyl sulfonates, alkyl ester sulfonates, alkyl aromatic sulfonates, alkyl betaines and alkylaminobetaines), hydrocarbon-based dispersants (such as lignin sulfonates, iminodisuccinates and polyaspartates), amino acids and proteins.

[0123] Suitable biocides include, but are not limited to, oxidizing biocides and non-oxidizing biocides. Suitable non-oxidizing biocides include, for example, aldehydes (e.g., formaldehyde, glutaraldehyde, and acrolein), amine compounds (e.g., quaternary ammonium compounds and coconut diamine), halogenated compounds (e.g., 2-bromo-2-nitropropane-3-diol and 2-2-dibromo-3-nitropropionamide (DBNPA)), sulfur compounds (e.g., isothiazolone, carbamate, and metronidazole), and quaternary phosphonium salts (e.g., tetrakis (hydroxymethyl) phosphonium sulfate (THPS)). Suitable oxidizing biocides include, for example, sodium hypochlorite, trichloroisocyanuric acid, dichloroisocyanuric acid, calcium hypochlorite, lithium hypochlorite, chlorinated hydantoin, stabilized sodium hypobromite, activated sodium bromide, brominated hydantoin, chlorine dioxide, ozone, and peroxide.

[0124] Suitable pH adjusting agents include, but are not limited to, alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, alkaline earth metal hydroxides, alkaline earth metal carbonates, alkaline earth metal bicarbonates, and mixtures or combinations thereof. For example, pH adjusting agents may include sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, magnesium oxide, and magnesium hydroxide. In some embodiments, pH adjusting agents may include hydrophilic or amphiphilic amines, such as methyldiethanolamine (MDEA).

[0125] Suitable surfactants include, but are not limited to, anionic surfactants and nonionic surfactants. Anionic surfactants include alkyl aryl sulfonates, olefin sulfonates, paraffin sulfonates, alcohol sulfates, alcohol ether sulfates, alkyl carboxylates and alkyl ether carboxylates, alkyl and ethoxylated alkyl phosphates, and monoalkyl and dialkyl sulfonated succinates and sulfonated succinamates. Nonionic surfactants include, but are not limited to, block copolymers of alcohol alkoxylates, alkylphenol alkoxylates, ethylene oxide, propylene oxide and butylene oxide, alkyl dimethyl amine oxides, alkyl-bis (2-hydroxyethyl) amine oxides, alkyl amide propyl dimethyl amine oxides, alkyl amide propyl-bis (2-hydroxyethyl) amine oxides, alkyl polyglucosides, polyalkoxylated glycerides, sorbitan esters and polyalkoxylated sorbitan esters and alkoxy polyethylene glycol esters and diesters. Also included are betaines and sulfobetaines, amphoteric surfactants such as alkyl amphoacetates and amphodiacetates, alkyl amphopropionates and propionic acid dipropionates, and alkyl imino dipropionates.

[0126] The surfactant may be a quaternary ammonium compound, an amine oxide, an ionic or nonionic surfactant, or any combination thereof. Suitable quaternary ammonium compounds include, but are not limited to, alkylbenzyl ammonium chloride, benzylcocoalkyl (C 12 -C 18 ) dimethyl ammonium chloride, dicocoalkyl (C 12 -C 18 ) dimethyl ammonium chloride, ditallow dimethyl ammonium chloride, di(hydrogenated tallow alkyl) dimethyl quaternary ammonium methyl chloride, methyl bis(2-hydroxyethyl coconut oil alkyl (C 12 -C 18 ) quaternary ammonium chloride, dimethyl (2-ethyl) tallow ammonium methyl sulfate, n-dodecylbenzyldimethylammonium chloride, n-octadecylbenzyldimethylammonium chloride, n-dodecyltrimethylammonium sulfate, soy alkyltrimethylammonium chloride and hydrogenated tallow alkyl (2-ethylhexyl) dimethyl quaternary ammonium methyl sulfate.

[0127] In some embodiments, the compositions disclosed herein comprise the following Formulation 1:

[0128]

[0129] In some embodiments, the compositions disclosed herein comprise the following Formulation 2:

[0130]

[0131] In some embodiments, the compositions disclosed herein comprise the following Formulation 3:

[0132]

[0133]

[0134] In some embodiments, the compositions disclosed herein comprise the following formulation 4:

[0135]

[0136] In some embodiments, the compositions disclosed herein comprise the following formulation 5:

[0137]

[0138] In some embodiments, the compositions disclosed herein comprise the following formulation 6:

[0139]

[0140] In some embodiments, the compositions disclosed herein comprise the following formulation 7:

[0141]

[0142] In some embodiments, the compositions disclosed herein comprise the following formulation 8:

[0143]

[0144] In some embodiments, the compositions disclosed herein consist of or consist essentially of any component (or combination of components) disclosed in Formulations 1-8.

[0145] In some embodiments, the compositions of the present disclosure can be prepared by combining an iron sulfide dissolving agent with a solvent to form a solution. If desired, additional components such as an anticorrosive agent, a sulfur-containing compound, a solvent, and / or an additive can be added to the solution.

[0146] The compositions of the present disclosure can be used to dissolve iron sulfide, inhibit corrosion and / or remove hydrocarbon-containing deposits in oil and gas applications. The compositions can be used in any industry where it is necessary to dissolve iron sulfide, inhibit corrosion and / or remove hydrocarbon-containing deposits from a surface.

[0147] In some embodiments, the present disclosure provides a method for dissolving iron sulfide deposits in an aqueous system. The method includes adding a composition to an aqueous medium, wherein the composition includes malic acid or a salt thereof. In some embodiments, the present disclosure provides a method for inhibiting corrosion of a metal surface in an aqueous system. The method includes adding a composition to an aqueous medium, wherein the composition includes malic acid or a salt thereof.

[0148] In some embodiments, the method of the present disclosure can be carried out by treating gas and / or liquid streams with an effective amount of a composition as described herein. The method can be carried out in an aqueous system, an oil system, and / or a gas system. For example, the composition and method can be used to dissolve iron sulfide deposits on the surface of a heat exchanger. Some methods may include applying the composition disclosed herein to the gas or liquid produced or used in the production, transportation, storage, and / or separation of crude oil or natural gas. In some embodiments, the composition can be applied to the gas stream used or produced in a coal-fired process (such as a coal-fired power plant). In certain embodiments, the composition can be applied to the gas or liquid produced or used in a wastewater process, a farm, a slaughterhouse, a landfill, a municipal wastewater plant, a coking coal process, and / or a biofuel process.

[0149] Compounds and compositions disclosed herein can be added to aqueous media. Aqueous media can include water, gas and / or liquid hydrocarbons. In some embodiments, compounds or compositions can be added to liquid hydrocarbons. Liquid hydrocarbons can be any type of liquid hydrocarbons, including but not limited to crude oil, heavy oil, process residue, asphalt oil, coker oil, coker gas oil, fluidized catalytic cracking feed, gas oil, naphtha, fluidized catalytic cracking slurry, diesel, fuel oil, jet fuel, gasoline, kerosene and any combination thereof. In some embodiments, fluid or gas can include refined hydrocarbon products.

[0150] The fluid or gas treated with the composition of the present disclosure may be at any selected temperature, such as ambient temperature or elevated temperature. Fluid (e.g., liquid hydrocarbon) or gas may be at a temperature of about 40°C to about 250°C. In some embodiments, fluid or gas may be at a temperature of about -50°C to about 300°C, about 0°C to about 200°C, about 10°C to about 100°C, or about 20°C to about 90°C. For example, fluid or gas may be at a temperature of about -20°C, about -15°C, about -10°C, about -5°C, or about 0°C. In certain embodiments, fluid or gas may be found in an arctic environment, and may have a temperature and salinity typical of such an environment.

[0151] Composition of the present disclosure can be added to fluid with various water content levels.For example, water content can be about 0% to about 100% volume / volume (v / v), about 1% to about 80%v / v, or about 1% to about 60%v / v. Fluid can be an aqueous medium containing different salinity levels.For example, fluid can have a salinity of about 0% to about 25%, about 1% to about 24%, or about 10% to about 25% weight / weight (w / w) total dissolved solids (TDS).

[0152] The fluid or gas introduced into the composition of the present disclosure can be contained in many different types of devices and / or exposed to the device. For example, the fluid or gas can be contained in the device or equipment that transports the fluid or gas from one point to another point, such as in an oil and / or gas pipeline. The device or equipment can be a part of an oil and / or gas refinery, such as a pipeline, a separation container, a dehydration unit or a gas pipeline. The composition can be introduced into a large diameter flow pipeline, a small collection pipeline, a small flow pipeline and a header having a diameter of about 1 inch to about 4 feet. The fluid can be contained in the equipment or device for oil recovery and / or production and / or exposed to the equipment or device, such as a wellhead. The device or equipment can be a part of a coal-fired power plant. The device or equipment can be a scrubber (for example a wet flue gas desulfurizer, a spray drying absorber, a dry adsorbent injector, a spray tower, a contact tower or a bubble tower, etc.). The device or equipment can be a cargo ship, a storage container, a storage tank or a pipeline connecting a tank, a container or a processing unit.

[0153] The composition can be introduced into the fluid or gas by any appropriate method to ensure dispersion through the fluid or gas. In some embodiments, the composition can be added to the hydrocarbon fluid before the hydrocarbon fluid contacts the surface in the system. The composition can be added at a point upstream of the point in the flow line where the iron sulfide is to be dissolved and / or corrosion is to be prevented. Mechanical equipment such as chemical injection pumps, pipeline tees, injection fittings, atomizers, sleeves, etc. can be used to inject / add the composition. In certain embodiments, an integrated pipeline can be used to pump the composition of the present disclosure into an oil and / or gas pipeline. In other embodiments, a capillary injection system can be used to deliver the composition to the selected fluid.

[0154] The composition can be injected into the stream as an aqueous or non-aqueous solution, mixture or slurry. The composition can be applied to a fluid or gas to provide a component of any selected concentration. For example, the composition can be added to a flow line to provide a desired component of an effective treatment dose of about 0.01ppm to about 5,000ppm, such as an iron sulfide dissolving agent, an anti-corrosion agent, etc. The composition can be applied to a fluid or gas to provide an iron sulfide dissolving agent, an anti-corrosion agent, etc., at a concentration of about 1ppm to about 1,000,000ppm, about 1ppm to about 100,000ppm, about 10ppm to about 75,000ppm, about 10ppm to about 50,000ppm, about 10ppm to about 25,000ppm, about 10ppm to about 10,000ppm, about 200ppm to about 8,000ppm, or about 500ppm to about 6,000ppm.

[0155] According to the methods disclosed herein, the composition can be applied continuously, in batches, or in a combination thereof. For example, the feed rate for continuous processing can be in the range of about 10 ppm to about 500 ppm, or about 10 ppm to about 200 ppm. For example, the feed rate for batch processing can be in the range of about 10 ppm to about 400,000 ppm, or about 10 ppm to about 20,000 ppm. The composition can also be applied as a pill in a pipeline, for example, to provide a high dose (e.g., about 20,000 ppm) of a composition component, such as an iron sulfide dissolving agent and / or an anticorrosive agent.

[0156] The foregoing may be better understood by reference to the following examples, which are intended for illustrative purposes and are not intended to limit the scope of the disclosure or its application in any way.

[0157] Example

[0158] The bubble cell test was used to study the effectiveness of the composition disclosed herein as a corrosion inhibitor. The test measures the corrosion rate of a steel electrode in an aqueous environment by linear polarization resistance (LPR). A carbon steel electrode (C1018) was placed in a synthetic brine solution degassed with carbon dioxide. The LPR measurement results determined the corrosion rate of a C1018 sample immersed in a synthetic brine dosed with about 50,000 ppm (about 5 wt%) of the composition. The pH of the brine was between about 5.5 and 6.0. Prior to starting the test, CO 2 The brine solution was purged for approximately 16 hours. Table 1 summarizes the test conditions.

[0159] Table 1: Summary of test conditions

[0160]

[0161]

[0162] The results of the bubble pool test are shown in Figure 1 and Figure 2 Where "mpy" is mils / year. The corrosion rate was obtained for about 4 hours in the absence of the test formulation to establish a baseline corrosion rate. After the introduction of the formulation, the corrosion rate dropped dramatically until a plateau was reached.

[0163] The corrosion inhibition of Formulations 1 and 2 (see paragraphs

[0092] and

[0093] ) was directly compared to Comparative Formulation A in an identically dosed synthetic brine solution. Both Formulations 1 and 2 exhibited similar performance to Comparative Formulation A, which contained 10 to 30 wt % of a quaternary ammonium compound, 5 to 10 wt % of a fatty acid-amine condensate, 5 to 10 wt % of methanol, 1 to 5 wt % of ethylene glycol, 1 to 5 wt % of 2-mercaptoethanol, and 1 to 5 wt % of isopropanol.

[0164] In another set of experiments, various acids were tested for their ability to dissolve iron sulfide. The parameters are shown in Table 2 and the results are shown in Table 3.

[0165] Table 2 :

[0166] Theoretical Fe 30ppm Dissolution agent dosage 50ppm Water Source DI water, 3.5% sea salt water, synthetic salt water Filter size 0.22μm

[0167] Table 3 :

[0168] Solvent (50ppm) Water Source Dissolved Fe% 0.22μm blank DI water 19％ Gluconic acid DI water 40％ Malic Acid DI water 73％ Disodium Maleate DI water 1％ Maleic acid DI water 58％ Galacturonic acid DI water 49％ Glucuronic acid DI water 46％ mucic acid DI water 38％ blank 3.5% sea salt 0％ Gluconic acid 3.5% sea salt 10％ Malic Acid 3.5% sea salt 48％ Disodium Maleate 3.5% sea salt 0％ Maleic acid 3.5% sea salt 36％ Galacturonic acid 3.5% sea salt 7％ Glucuronic acid 3.5% sea salt 8％ mucic acid 3.5% sea salt 13％ blank Synthetic brine 0％ Gluconic acid Synthetic brine 48％ Malic Acid Synthetic brine 101％ Disodium Maleate Synthetic brine 0％ Maleic acid Synthetic brine 69％ Galacturonic acid Synthetic brine 43％ Glucuronic acid Synthetic brine 37％ mucic acid Synthetic brine 56％

[0169] As can be seen in Table 3, the inventors have found that malic acid unexpectedly outperforms all other acids in all water sources.

[0170] The effectiveness of the inventive compositions disclosed herein as iron sulfide dissolving agents was determined according to the following procedure. First, two aqueous solutions were prepared. The first solution contained about 5.64 g of calcium chloride (CaCl 2 ), about 7.2 g magnesium chloride (MgCl 2 ), about 1.32g potassium chloride (KCl), about 0.96g sodium sulfate (Na 2 SO 4 ), about 16.8 g sodium bicarbonate (NaHCO 3 ), about 205.8 g sodium chloride (NaCl), about 1.08 g sodium bromide (NaBr), about 10.8 g acetic acid, and about 12 L of demineralized water. The second aqueous solution included about 3.5% (w / w) seawater in demineralized water. The solutions were incubated at about 65° C. Ferric chloride and sodium sulfide were added to each solution to provide an aqueous ferric sulfide composition of about 30 ppm. In addition to the synthetic brine and diluted seawater, deionized water was also used.

[0171] Each solution prepared was dosed with about 250 ppm of the candidate formulation. Similarly, another portion of the solution was treated with about 500 ppm of the candidate formulation. The treated solution was then incubated at about 65°C for another 30 minutes. The solution was then filtered using a 0.2 micron filter. The filtrate was collected and analyzed for iron concentration using inductively coupled plasma (ICP). The results for the compositions of the present invention and the comparative formulations are shown in Tables 4 to 5 and Figures 3 to 5 middle.

[0172] Table 4 :

[0173]

[0174] Table 5 :

[0175]

[0176]

[0177] It can be seen that the inventive formulations are significantly more effective in dissolving iron sulfide than Comparative Formulation A and Comparative Formulation B, which contains 10 wt % to 30 wt % methanol, 10 wt % to 30 wt % tetrakis(hydroxymethyl)phosphonium sulfate, 10 wt % to 30 wt % quaternary ammonium compound, 5 wt % to 10 wt % fatty acid-amine condensate, 1 wt % to 5 wt % 2-mercaptoethanol, and 1 wt % to 5 wt % isopropanol.

[0178] All compositions and methods disclosed and claimed herein can be prepared and performed according to the present disclosure without undue experimentation. Although the present invention can be embodied in many different forms, specific preferred embodiments of the present invention are described in detail herein. The present disclosure is an example of the principles of the present invention and is not intended to limit the present invention to the specific embodiments described. In addition, unless clearly stated to the contrary, the use of the term "one / kind" is intended to include "at least one / at least one" or "one or more / one or more". For example, "resist" is intended to include "at least one resist" or "one or more resists".

[0179] Any range given in absolute terms or in approximate terms is intended to cover both, and any definition used herein is intended to be clarifying and not restrictive. Although the numerical ranges and parameters describing the wide range of the present invention are approximate, the numerical values ​​described in the specific embodiments are reported as accurately as possible. However, any numerical value inherently contains certain errors caused by the standard deviation found in its corresponding experimental measurement. In addition, all ranges disclosed herein are understood to cover any and all subranges (including all fractional values ​​and overall values) contained therein.

[0180] Any composition disclosed herein may comprise, consist of, or consist essentially of any element, component, and / or ingredient disclosed herein, or any combination of two or more of the elements, components, or ingredients disclosed herein.

[0181] Any method disclosed herein may comprise, consist of, or consist essentially of any method step disclosed herein or any combination of two or more of the method steps disclosed herein.

[0182] The transitional phrase "comprising," which is synonymous with "including," "containing," or "characterized by," is inclusive or open-ended and does not exclude additional unrecited elements, components, ingredients, and / or method steps.

[0183] The transitional phrase "consisting of" excludes any element, component, ingredient and / or method step not specified in the claim.

[0184] The transition phrase "consisting essentially of" limits the scope of a claim to the specified elements, components, ingredients and / or steps, and those that do not materially affect the basic and novel characteristics of the claimed invention.

[0185] Unless otherwise specified, all molecular weights referred to herein are weight average molecular weight and all viscosities are measured at 25°C using neat (undiluted) polymer.

[0186] As used herein, the term "about" means that the recited value is within the error caused by the standard deviation found in their respective testing measurements, and if those errors are not determinable, then "about" may mean, for example, within 5%, 4%, 3%, 2% or 1% of the recited value.

[0187] In addition, the present invention encompasses any and all possible combinations of some or all of the various embodiments described herein. It should also be understood that the various changes and modifications made to the current preferred embodiments described herein will be apparent to those skilled in the art. Such changes and modifications may be made without departing from the spirit and scope of the present invention and without reducing its expected advantages. Therefore, the appended claims are intended to cover such changes and modifications.

Claims

1. A method for dissolving iron sulfide deposits in an aqueous system, the method comprising: A composition is added to an aqueous medium, wherein the composition comprises malic acid or a salt thereof.

2. The method of claim 1, wherein the composition comprises an organic solvent.

3. The method of claim 2, wherein the organic solvent comprises an alcohol, a hydrocarbon, a ketone, an ether, an alkylene glycol, a glycol ether, an amide, a nitrile, a sulfoxide, an ester, a polyol, or any combination thereof.

4. according to the composition described in claim 2 or claim 3, wherein the organic solvent comprises methanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexanol, hexanol, octanol, decanol, 2-butoxyethanol, methyl glycol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, pentane, hexane, cyclohexane, methylcyclohexane, heptane, decane, dodecane, diesel, toluene, xylene, heavy aromatic naphtha, cyclohexanone, diisobutyl ketone, ether, propylene carbonate, N-methyl pyrrolidone, N,N-dimethylformamide, glycerine or any combination thereof.

5. The method according to any one of the preceding claims, wherein the composition comprises a resist selected from the group consisting of imidazoline compounds, quaternary ammonium compounds, quaternary iminium compounds, zwitterionic betaine compounds, amidoamine compounds, pyridinium compounds, and any combination thereof.

6. The method of claim 5, wherein the resist comprises one or more of the following imidazoline compounds: (A) an imidazoline of formula (I): Where R 10 C1-C 20 Alkyl or C1-C 20 Alkoxyalkyl groups; R 12 and R 13 are independently hydrogen or a C1-C6 alkyl group; and R 11 are independently hydrogen, C1-C6 alkyl, C1-C6 hydroxyalkyl, aminoalkyl, aminoaryl, aminoarylalkyl, aminoalkylaryl or C1-C6 arylalkyl; (B) Imidazolinium salt of formula (II): Where R 10 C1-C 20 Alkyl or C1-C 20 Alkoxyalkyl groups; R 12 and R 13 are independently hydrogen or a C1-C6 alkyl group; R 11 and R 14 are independently hydrogen, C1-C6 alkyl, C1-C6 hydroxyalkyl or C1-C6 arylalkyl; and X - is a halide, carbonate, sulfonate, phosphate or an anion of an organic carboxylic acid; (C) a diquaternized imidazoline compound of formula (III): wherein R1 and R2 are each independently an unsubstituted branched, chain or cyclic alkyl or alkenyl group having 1 to about 29 carbon atoms; a partially or fully oxidized, sulfurized and / or phosphorylated branched, chain or cyclic alkyl or alkenyl group having 1 to about 29 carbon atoms; or a combination thereof; R3 and R4 are each independently an unsubstituted branched, chain or cyclic alkylene or alkenylene having 1 to about 29 carbon atoms; a partially or fully oxidized, sulfurized and / or phosphorylated branched, chain or cyclic alkylene or alkenylene having 1 to about 29 carbon atoms; or a combination thereof; L1 and L2 are each independently absent, H, -COOH, -SO3H, -PO3H2, -COOR5, -CONH2, -CONHR5 or -CON(R5)2; R5 is each independently a branched or unbranched alkyl, aryl, alkylaryl, alkylheteroaryl, cycloalkyl or heteroaryl group having 1 to about 10 carbon atoms; n is 0 or 1, and when n is 0, L2 is absent or H; x is from 1 to about 10; and y is from 1 to about 5; or (D)A combination thereof.

7. The method according to claim 6, wherein the resist comprises an imidazoline of formula (I) or an imidazolinium salt of formula (II), R 10 It is an alkyl mixture of tall oil fatty acid (TOFA), R 11 is benzyl, R 12 and R 13 Each is hydrogen, R 14 is hydroxyethyl, and X - For chloride ion.

8. The method according to claim 6, wherein the anti-corrosion agent comprises a diquaternized imidazoline compound of formula (III), R1 and R2 are derived from a mixture of tall oil fatty acids and are mainly C 17 H 33 and C 17 H 31 A mixture of, x is 2, y is 1, R3 and R4 are -C2H2-, and L1 and L2 are -CO2H, -SO3H or -PO3H2.

9. The method according to claim 6, wherein the resist comprises a diquaternized imidazoline compound of formula (III), R1 and R2 are independently C 16 -C 18 Alkyl; R4 is -C2H2-; x is 2; y is 1; n is 0; L1 is -COOH, -SO3H or -PO3H2, and L2 is absent or is H.

10. The method of claim 6, wherein the resist comprises the quaternary ammonium compound and a diquaternized imidazoline compound of formula (III).

11. The method of claim 5, wherein the resist comprises a pyridinium compound of formula (V): Where R 9 is an alkyl group, an aryl group or an arylalkyl group, wherein the alkyl group has 1 to about 18 carbon atoms; and X - It is a halide ion.

12. The method according to claim 11, wherein R 9 is benzyl, and X - For chloride ion.

13. The method according to any one of claims 5 to 12, wherein the resist further comprises a member selected from the group consisting of alkoxylated amines, phosphate esters, monomeric fatty acids, esters of alcohol amines, oligomeric fatty acids, and any combination thereof.

14. The method of any one of the preceding claims, wherein the composition comprises from about 5% to about 95% by weight of the malic acid.

15. The method of any one of claims 2 to 4, wherein the composition comprises from about 5% to about 95% by weight of the organic solvent.

16. The method of any one of claims 5 to 13, wherein the composition comprises from about 5 wt% to about 95 wt% of the resist.

17. The method of any one of claims 5 to 16, wherein the composition comprises about 15 wt % to about 30 wt % of the malic acid, about 20 wt % to about 40 wt % of the organic solvent, and about 15 wt % to about 30 wt % of the resist.

18. The method according to any one of the preceding claims, wherein the composition further comprises a compound of the formula HS-(CH2) n A compound of OH wherein n is 2 to 6.

19. The method of any one of the preceding claims, wherein the composition further comprises thioglycolic acid, 3,3'-dithiodipropionic acid, thiourea, 2-mercaptoethanol, L-cysteine, tert-butyl mercaptan, sodium thiosulfate, ammonium thiosulfate, sodium thiocyanate, ammonium thiocyanate, sodium metabisulfite, or any combination thereof.

20. The method of any one of the preceding claims, wherein the composition further comprises an asphaltene inhibitor, a paraffin inhibitor, a scale inhibitor, an emulsifier, a water clarifier, a dispersant, a demulsifier, a hydrogen sulfide scavenger, a gas hydrate inhibitor, a biocide, a pH adjuster, a defoamer, a surfactant, or any combination thereof.

21. The method of any one of the preceding claims, wherein a surface in the aqueous system comprises the iron sulfide deposit.

22. The method of any one of the preceding claims, wherein the method also inhibits corrosion of metal surfaces in the aqueous system.

23. A method for inhibiting corrosion of a metal surface in an aqueous system, the method comprising: adding a composition to an aqueous medium, wherein the composition comprises malic acid or a salt thereof, and A resist selected from the group consisting of an imidazoline compound, a quaternary ammonium compound, a quaternary iminium compound, a zwitterionic betaine compound, an amidoamine compound, a pyridinium compound, and any combination thereof.

24. The method of claim 23, wherein the composition comprises an organic solvent.

25. The method of claim 24, wherein the organic solvent comprises an alcohol, a hydrocarbon, a ketone, an ether, an alkylene glycol, a glycol ether, an amide, a nitrile, a sulfoxide, an ester, a polyol, or any combination thereof.

26. The method of any one of the preceding claims, wherein the composition comprises an additional component selected from the group consisting of allaric acid, alta dioic acid, tyrosaric acid, altersonic acid, arabinonic acid, arabinuronic acid, citric acid, dihomocitric acid, fructose acid, alginic acid, fumaric acid, galactaric acid, galacturonic acid, galacturonic acid, glucaric acid, glucoheptonic acid, gluconic acid, glucuronic acid, gulonic acid, homocitric acid, homoisocitric acid, itaconic acid, idonic acid, iduronic acid, isocitric acid, mannonic acid, mannonic acid, octulonic acid, rhamnonic acid, ribonic acid, tagaturonic acid, xylonic acid, xyluronic acid, tartaric acid, trienoic acid, glyceric acid, malonic acid and pantoic acid, salts of any of these acids, and any combination thereof.

27. The method of any one of the preceding claims, wherein the composition further comprises a pH adjuster.

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