Corrosion inhibitors for mitigating alkaline carbonate stress corrosion cracking.

Abstract

Compounds, compositions, and methods for reducing, inhibiting, or preventing corrosion of a surface using a corrosion-inhibiting composition comprising a dispersant having the structure of Formula 1 and a corrosion inhibitor having the structure of Formula 2, wherein X1 is hydroxyl or -OC(O)R1, X2 is hydroxyl or -OC(O)R2, X3 is hydroxyl or -OC(O)R3, and R1, R2, and R3 are independently selected from the group consisting of C 10 ~C 30 alkyl or alkenyl, m, n, and o are independently integers from 1 to 10, and R 20 , R 21 , R 22 , R 23 , and R 24 are independently hydrogen or -C(O)-R 31 and R 31 But, C 10 ~C 30 alkyl or alkenyl, p is an integer of 0 or 1, q is an integer of 1 to 4, r is an integer of 0 or 1, s is an integer of 0 or 1, t is an integer of 1 to 4, p1, q1, r1, r2, s1, and t1 are independently integers of 1 to 6, and when p, r, and s are 0, q+t is an integer of 4 to 8, and R 20 , R 21 , R 22 , R 23 , and R 24 At least one of the groups is -C(O)-R 31 Compounds, compositions and methods are provided, wherein JPEG2024530622000012.jpg82156

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) Not applicable.

[0002] (Statement Regarding Federally Sponsored Research or Development) Not applicable.

[0003] (Names of parties involved in the joint research agreement) Not applicable.

[0004] (Reference to a sequence listing, table, or computer program listing appendix submitted on a compact disc and incorporation by reference of the material on the compact disc) Not applicable.

[0005] FIELD OF THEINVENTION Compounds, compositions, and methods are provided for reducing, inhibiting, or preventing corrosion of a surface using a corrosion-inhibiting composition comprising a dispersant having the structure of Formula 1 and a corrosion inhibitor having the structure of Formula 2. [Background technology]

[0006] Intergranular cracking and failure of carbon steel piping and vessels occurs in various refinery overhead or other systems. These systems subject to stress corrosion cracking include hydrogen sulfide, ammonia, carbon dioxide, water, and / or hydrogen cyanide in contact with the carbon steel. The presence of these chemicals appears to contribute to carbonate stress corrosion cracking (hereafter carbonate SCC). The occurrence of this carbonate SCC can jeopardize the refining operation in which it is occurring and can cause dangerous and harmful conditions of operational instability.

[0007] A particular problem observed with intergranular carbonate SCC and failure of carbon steel in either piping or vessel construction is in steel piping and vessels contained in fluid cracking catalytic fractionator overhead systems where ammonia, hydrogen sulfide, carbon dioxide, hydrogen cyanide, and water are present. This type of carbonate SCC differs from hydrogen blistering or hydrogen induced cracking because microscopic examination of the cracks shows the presence of iron oxides that are not present when hydrogen blistering and / or hydrogen induced cracking are present. Summary of the Invention [Problem to be solved by the invention]

[0008] Although there are several potential approaches to control hydrogen induced cracking and hydrogen blistering, there is no known solution to carbonate SCC, and therefore there is a continuing need to provide agents to mitigate carbonate SCC. [Means for solving the problem]

[0009] A corrosion-inhibiting composition and method comprising a dispersant having the structure of Formula 1 and a corrosion inhibitor having the structure of Formula 2, [ka] wherein X1 is hydroxyl or -OC(O)R1, X2 is hydroxyl or -OC(O)R2, X3 is hydroxyl or -OC(O)R3, and R1, R2, and R3 are independently selected from the group consisting of C 10 ~C 30 alkyl or alkenyl, m, n, and o are independently integers from 1 to 10, and R 20 , R 21 , R 22 , R 23 , and R 24 are independently hydrogen or -C(O)-R 31 and R 31 But, C 10 ~C 30alkyl or alkenyl, p is an integer of 0 or 1, q is an integer of 1 to 4, r is an integer of 0 or 1, s is an integer of 0 or 1, t is an integer of 1 to 4, p1, q1, r1, r2, s1, and t1 are independently integers of 1 to 6, and when p, r, and s are 0, q+t is an integer of 4 to 8, and R 20 , R 21 , R 22 , R 23 , and R 24 At least one of the groups is -C(O)-R 31 Disclosed herein are corrosion-inhibiting compositions and methods, wherein

[0010] The composition has a dispersant of formula 1, wherein m, n, and o are independently integers from 1 to 8, preferably m, n, and o are independently integers from 1 to 6, more preferably m, n, and o are independently integers from 2 to 6, even more preferably m, n, and o are independently integers from 2 to 4, more preferably m, n, and o are independently integers from 2 or 3, and most preferably m, n, and o are 2.

[0011] The composition has a dispersant of Formula 1 having X1 of hydroxyl or -OC(O)R1, preferably X1 is hydroxyl or X1 is -OC(O)R1.

[0012] The compositions and methods described herein have a dispersant of Formula 1, which comprises 12 ~C 24 R1 is alkyl or alkenyl, preferably C 14 ~C 22 R1 is alkyl or alkenyl, more preferably C 16 ~C 20 It has R1 which is alkyl or alkenyl.

[0013] Additionally, the compositions and methods include a dispersant of Formula 1, wherein X2 is hydroxyl or -OC(O)R2, preferably X2 is hydroxyl or X2 is -OC(O)R2.

[0014] The compositions and methods include a dispersant of Formula 1, the dispersant comprising 12 ~C 24 R2 is alkyl or alkenyl, preferably C 14 ~C 22 R2 is alkyl or alkenyl, more preferably C 16 ~C 20 It has R2 which is alkyl or alkenyl.

[0015] Still further, the compositions and methods comprise a dispersant of Formula 1 having X3 of hydroxyl or -OC(O)R3, preferably having X3 of hydroxyl or having X3 of -OC(O)R3.

[0016] The dispersant of formula 1 is C 12 ~C 24 R3 is alkyl or alkenyl, preferably C 14 ~C 22 R3 is alkyl or alkenyl, more preferably C 16 ~C 20 It has R3 which is alkyl or alkenyl.

[0017] In particular, the dispersant of formula 1 has the formula 1A: [ka] It has the structure:

[0018] The corrosion inhibitor of formula 2 has the structure: wherein p1, q1, r1, r2, s1, and t1 are independently integers from 2 to 6, preferably, p1, q1, r1, r2, s1, and t1 are independently integers from 2 to 4, more preferably, p1, q1, r1, r2, s1, and t1 are independently integers from 2 or 3, and most preferably, p1, q1, r1, r2, s1, and t1 are independently integers of 2.

[0019] The corrosion inhibitor of Formula 2 is represented by Formula 2A: [ka] It has the structure:

[0020] The corrosion inhibitors of formulas 2 and 2A have the structure: 31 But, C 12 ~C 24 alkyl or alkenyl, preferably R 31 But, C 14 ~C 22 alkyl or alkenyl, more preferably R 31 But, C 16 ~C 20 It is alkyl or alkenyl.

[0021] The corrosion-inhibiting composition comprising the dispersant of Formula 1 and the corrosion inhibitor of Formula 2 can further comprise a solvent. Suitable solvents are water, salt water, seawater, alcohols (such as methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol, t-butanol, etc.) or higher alcohols (such as benzyl alcohol); ketones such as acetone or methyl ethyl ketone (2-butanone); acetonitrile; esters such as ethyl acetate, propyl acetate, butyl acetate; ethers (such as diethyl ether and above) (e.g., methyl t-butyl ether, glyme, diglyme, ethylene glycol monobutyl ether, ethylene diglycol ethyl ether, 1,4-dioxane, and related substances); aromatics (such as toluene, xylene, diethylbenzene, naphthalene, and related aromatics) or refined cuts (heavy aromatic naphtha, heavy aromatic distillate, and related substances); aliphatics (such as pentane, hexane, heptane, octane, refined gasoline, etc.); or some "green" solvents (such as 2-methyltetrahydrofuran, furfural alcohol, and cyclopentyl methyl ether).

[0022] Additionally, suitable solvents for blending are aliphatic, such as pentane, hexane, cyclohexane, methylcyclohexane, heptane, decane, dodecane, etc.; and aromatic, such as toluene, xylene, heavy aromatic naphtha diesel, fatty acid derivatives (acids, esters, amides), etc. Preferably, the solvent is a hydrocarbon solvent. More preferably, the hydrocarbon solvent can include heavy aromatic naphtha, toluene, xylene, diethylbenzene, and naphthalene, or a combination thereof.

[0023] The corrosion-inhibiting compositions described herein are capable of forming a film on a surface.

[0024] The corrosion-inhibiting composition can be used in a method of inhibiting corrosion by contacting the corrosion-inhibiting composition with a surface that is in contact with an aqueous medium containing hydrogen sulfide, ammonia, carbon dioxide, hydrogen cyanide, carbonates, bicarbonates, or combinations thereof.

[0025] Preferably, in the method of inhibiting corrosion, the aqueous medium comprises a carbonate, a bicarbonate, or a combination thereof.

[0026] Additionally, in the methods of inhibiting corrosion described herein, the surface is a metal surface. In particular, the metal surface comprises carbon steel.

[0027] In the methods of inhibiting corrosion described herein, the corrosion-inhibiting composition can protect the metal surface by forming a barrier between the metal and the corrosive medium.

[0028] Additionally, in the methods of inhibiting corrosion described herein, the surface is included in a fluid catalytic cracking unit (FCCU) or a sour water stripper (SWS).

[0029] In these corrosion inhibition methods, the corrosion-inhibiting composition is contacted with the surface at a concentration of 1 to 1000 ppm based on the process vapor stream, i.e., the FCC main fractionator overhead stream, and preferably the corrosion-inhibiting composition is contacted with the surface at a concentration of 1 to 1000 ppm.

[0030] Other objects and features will be in part apparent and in part pointed out hereinafter. [Brief description of the drawings]

[0031] [Figure 1] 1 is a bar graph of ductility ratios (total time to failure, plastic time to failure, total elongation at failure, plastic strain to failure, and reduction in area) calculated after testing of C1018 carbon steel coupons that were untreated ("Blank") and treated with various formulations (e.g., Comparative Formulation A - formulation containing only corrosion inhibitor (Formulation 1), Comparative Formulation B - formulation containing only dispersant (Formulation 2), and the proposed invention corrosion inhibitor (Formulation 1) and dispersant (Formulation 2)).

[0032] [Diagram 2] A-E are a series of optical micrographs of C1018 carbon steel coupons after SSR testing in the presence of inert atmosphere (A), carbonate solution (B), carbonate solution and comparative formulation A (formulation containing only corrosion inhibitor (formulation 1)) (C), carbonate solution and comparative formulation B (formulation containing only dispersant (formulation 2)) (D), and carbonate solution and the proposed invention (corrosion inhibitor (formulation 1) and dispersant (formulation 2)) (E). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0033] Described herein is a process for the purification of high carbonate (CO3 2-A corrosion-inhibiting composition for mitigating stress corrosion cracking (SCC) in environments having a Cr concentration of 0.1 to 0.5% by weight is disclosed, the blend comprising a dispersant and a film-forming corrosion inhibitor. The disclosed blend comprises a dispersant of Formula 1 and a corrosion inhibitor of Formula 2. The corrosion-inhibiting composition is capable of protecting metal surfaces from carbonate SCC and other corrosion mechanisms.

[0034] Compounds, compositions, and methods are provided for reducing, inhibiting, or preventing corrosion of a surface using a corrosion-inhibiting composition comprising a dispersant having the structure of Formula 1 and a corrosion inhibitor having the structure of Formula 2.

[0035] a dispersant having the structure of Formula 1 and a corrosion inhibitor having the structure of Formula 2: [ka] wherein X1 is hydroxyl or -OC(O)R1, X2 is hydroxyl or -OC(O)R2, X3 is hydroxyl or -OC(O)R3, and R1, R2, and R3 are independently selected from the group consisting of C 10 ~C 30 alkyl or alkenyl, m, n, and o are independently integers from 1 to 10, and R 20 , R 21 , R 22 , R 23 , and R 24 are independently hydrogen or -C(O)-R 31 and R 31 But, C 10 ~C 30 alkyl or alkenyl, p is an integer of 0 or 1, q is an integer of 1 to 4, r is an integer of 0 or 1, s is an integer of 0 or 1, t is an integer of 1 to 4, p1, q1, r1, r2, s1, and t1 are independently integers of 1 to 6, and when p, r, and s are 0, q+t is an integer of 4 to 8, and R 20 , R 21 , R 22 , R 23 , and R 24 At least one of the groups is -C(O)-R31 It is.

[0036] The composition has a dispersant of formula 1, wherein m, n, and o are independently integers from 1 to 8, preferably m, n, and o are independently integers from 1 to 6, more preferably m, n, and o are independently integers from 2 to 6, even more preferably m, n, and o are independently integers from 2 to 4, more preferably m, n, and o are independently integers from 2 or 3, and most preferably m, n, and o are 2.

[0037] The composition has a dispersant of Formula 1 having X1 of hydroxyl or -OC(O)R1, preferably X1 is hydroxyl or X1 is -OC(O)R1.

[0038] The compositions and methods described herein have a dispersant of Formula 1, which comprises 12 ~C 24 R1 is alkyl or alkenyl, preferably C 14 ~C 22 R1 is alkyl or alkenyl, more preferably C 16 ~C 20 It has R1 which is alkyl or alkenyl.

[0039] Additionally, the compositions and methods include a dispersant of Formula 1, wherein X2 is hydroxyl or -OC(O)R2, preferably X2 is hydroxyl or X2 is -OC(O)R2.

[0040] The compositions and methods include a dispersant of Formula 1, the dispersant comprising 12 ~C 24 R2 is alkyl or alkenyl, preferably C 14 ~C 22 R2 is alkyl or alkenyl, more preferably C 16 ~C 20 It has R2 which is alkyl or alkenyl.

[0041] Still further, the compositions and methods comprise a dispersant of Formula 1 having X3 of hydroxyl or -OC(O)R3, preferably having X3 of hydroxyl or having X3 of -OC(O)R3.

[0042] The dispersant of formula 1 is C 12 ~C 24 R3 is alkyl or alkenyl, preferably C 14 ~C 22 R3 is alkyl or alkenyl, more preferably C 16 ~C 20 It has R3 which is alkyl or alkenyl.

[0043] In particular, the dispersant of formula 1 has the formula 1A: [ka] It has the structure:

[0044] The corrosion inhibitor of formula 2 has the structure: wherein p1, q1, r1, r2, s1, and t1 are independently integers from 2 to 6, preferably, p1, q1, r1, r2, s1, and t1 are independently integers from 2 to 4, more preferably, p1, q1, r1, r2, s1, and t1 are independently integers from 2 or 3, and most preferably, p1, q1, r1, r2, s1, and t1 are independently integers of 2.

[0045] The corrosion inhibitor of Formula 2 is represented by Formula 2A: [ka] It has the structure:

[0046] The corrosion inhibitor of formula 2 or 2A has the structure: 31 But, C 12 ~C 24 alkyl or alkenyl, preferably R 31 But, C 14 ~C 22 alkyl or alkenyl, more preferably R 31 But, C 16 ~C20 It is alkyl or alkenyl.

[0047] The corrosion-inhibiting composition comprising the dispersant of Formula 1 and the corrosion inhibitor of Formula 2 can further comprise a solvent. Suitable solvents are water, salt water, seawater, alcohols (such as methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol, t-butanol, etc.) or higher alcohols (such as benzyl alcohol); ketones such as acetone or methyl ethyl ketone (2-butanone); acetonitrile; esters such as ethyl acetate, propyl acetate, butyl acetate; ethers (such as diethyl ether and above) (e.g., methyl t-butyl ether, glyme, diglyme, ethylene glycol monobutyl ether, ethylene diglycol ethyl ether, 1,4-dioxane, and related substances); aromatics (such as toluene, xylene, diethylbenzene, naphthalene, and related aromatics) or refined cuts (heavy aromatic naphtha, heavy aromatic distillate, and related substances); aliphatics (such as pentane, hexane, heptane, octane, refined gasoline, etc.); or some "green" solvents (such as 2-methyltetrahydrofuran, furfural alcohol, and cyclopentyl methyl ether).

[0048] Solvents suitable for blending are aliphatic, such as pentane, hexane, cyclohexane, methylcyclohexane, heptane, decane, dodecane, etc.; and aromatic, such as toluene, xylene, heavy aromatic naphtha diesel, fatty acid derivatives (acids, esters, amides), etc. Preferably, the solvent is a hydrocarbon solvent. More preferably, the hydrocarbon solvent can include heavy aromatic naphtha, xylene, or a combination thereof.

[0049] The corrosion-inhibiting composition comprises the dispersant of Formula 1 in a concentration of about 10% to about 70% by weight, the corrosion inhibitor of Formula 2 in a concentration of about 5% to about 40% by weight, based on the total weight of the dispersant of Formula 1, the corrosion inhibitor of Formula 2, and the solvent, with the remainder of the composition being the solvent.

[0050] The corrosion-inhibiting composition may be about 10% by weight to about 70% by weight, about 10% by weight to about 65% by weight, about 10% by weight to about 60% by weight, about 10% by weight to about 55% by weight, about 10% by weight to about 50% by weight, about 10% by weight to about 45% by weight, about 10% by weight to about 40% by weight, about 15% by weight to about 70% by weight, about 15% by weight to about 65% by weight, about 15% by weight to about 60% by weight, about 15% by weight to about 65% by weight, about 15% by weight to about 60% by weight, about 15% by weight to about 7 ...70% by weight, about 15% by weight to about 65% by weight, about 15% by weight to about 60% by weight, about 15% by weight to about 70% by weight, about 15% by weight to about 70% by weight, about 15% by weight to about 65% by weight, about 15% by weight to about 60% by weight, about 15% by weight to about 70% by weight, about 15% by weight to about 70% by weight, about 15% by %~about 55 weight%, about 15 weight%~about 50 weight%, about 15 weight%~about 45 weight%, about 15 weight%~about 40 weight%, about 20 weight%~about 70 weight%, about 20 weight%~about 65 weight% %, about 20% to about 60% by weight, about 20% to about 55% by weight, about 20% to about 50% by weight, about 20% to about 45% by weight, about 20% to about 40% by weight, about 25% by weight ~70% by weight, approximately 25% by weight ~ approximately 65% ​​by weight, approximately 25% by weight ~ approximately 60% by weight, approximately 25% by weight ~ approximately 55% by weight, approximately 25% by weight ~ approximately 50% by weight, approximately 25% by weight ~ approximately 45% by weight , about 25% to about 40% by weight, about 30% to about 70% by weight, about 30% to about 65% by weight, about 30% to about 60% by weight, about 30% to about 55% by weight, about 30% to about 55% by weight The dispersant of Formula 1 may be included in a concentration of about 50% by weight, about 30% to about 45% by weight, about 30% to about 40% by weight, about 35% to about 70% by weight, about 35% to about 65% by weight, about 35% to about 60% by weight, about 35% to about 55% by weight, about 35% to about 50% by weight, about 35% to about 45% by weight, or about 35% to about 40% by weight.

[0051] The corrosion-inhibiting composition may comprise a corrosion inhibitor of Formula 2 in a concentration of about 5% to about 40% by weight, about 5% to about 35% by weight, about 5% to about 30% by weight, about 5% to about 25% by weight, about 5% to about 20% by weight, about 10% to about 40% by weight, about 10% to about 35% by weight, about 10% to about 30% by weight, about 10% to about 25% by weight, about 10% to about 20% by weight, about 15% to about 40% by weight, about 15% to about 35% by weight, about 15% to about 30% by weight, about 15% to about 25% by weight, or about 15% to about 20% by weight.

[0052] The corrosion-inhibiting composition may contain the solvent at a concentration of about 5 wt% to about 40 wt%, about 5 wt% to about 35 wt%, about 5 wt% to about 30 wt%, about 5 wt% to about 25 wt%, about 5 wt% to about 20 wt%, about 10 wt% to about 40 wt%, about 10 wt% to about 35 wt%, about 10 wt% to about 30 wt%, about 10 wt% to about 25 wt%, about 10 wt% to about 20 wt%, about 15 wt% to about 40 wt%, about 15 wt% to about 35 wt%, about 15 wt% to about 30 wt%, about 15 wt% to about 25 wt%, or about 15 wt% to about 20 wt%.

[0053] Preferably, the corrosion-inhibiting composition comprises 40% by weight of the dispersant of Formula 1, 20% by weight of the corrosion inhibitor of Formula 2, and 20% by weight of the solvent.

[0054] The corrosion-inhibiting compositions described herein are capable of forming a film on a surface.

[0055] The corrosion-inhibiting composition can be used in a method of inhibiting corrosion by contacting the corrosion-inhibiting composition with a surface that is in contact with an aqueous medium containing hydrogen sulfide, ammonia, carbon dioxide, hydrogen cyanide, carbonates, bicarbonates, or combinations thereof.

[0056] Preferably, in the method of inhibiting corrosion, the aqueous medium comprises a carbonate, a bicarbonate, or a combination thereof.

[0057] Additionally, in the methods of inhibiting corrosion described herein, the surface is a metal surface. In particular, the metal surface comprises carbon steel.

[0058] In the methods of inhibiting corrosion described herein, the corrosion-inhibiting composition is capable of forming a protective layer between the metal surface and the corrosive medium.

[0059] Additionally, in the methods of inhibiting corrosion described herein, the surfaces are included in fluid catalytic cracking units (FCCUs) and sour water strippers (SWSs).

[0060] An effective amount of the corrosion-inhibiting compositions is preferably a dosage that provides from 1 ppm to about 1,000 ppm of active compound based on the total amount of refinery stream treated by these compositions. Preferably, the dosage ranges from about 2 to about 500 ppm active ingredient, and most preferably, the dosage ranges from about 5 to about 150 ppm, based on the refinery stream being treated.

[0061] For optimal results, it is preferred to initially add the above dosage at the upper limit, after which the maintenance dosage can be reduced to the lower concentration limit. As an example, a system would be expected to be optimized by treating with about 250-500 ppm of active compound in the corrosion-inhibiting composition based on the refinery stream being treated for the first 24-72 hours of operation. Thereafter, the dosage treatment rate would be effectively reduced over a period of 1 to about 10 days to a maintenance level ranging from about 1 ppm to about 100 ppm, preferably about 5 to about 50 ppm, of active material in the composition based on the refinery stream being treated.

[0062] Refinery processes or streams that are likely to promote carbonate stress cracking corrosion are those that may contain at least one or more of the following chemicals: ammonia, hydrogen cyanide, carbon dioxide, hydrogen sulfide, water, or similar compounds that are somewhat volatile. These process streams may include, but are not necessarily limited to, overhead vapor and condensate from a fluid catalytic cracking unit, or process streams that handle effluent acid water treated in a sour water stripper. In particular, it has been found that process streams of a fluid catalytic cracking unit (FCCU) include, but are not limited to, the FCCU fractionator, any overhead condenser, fractionator reflux condensate drum / vessel, overhead accumulator, knockout drum, interstage cooler and / or condenser, deethanizer, debutanizer, depropanizer, etc., as well as any pipelines, connectors, pumps, etc. that may be connected to this type of operation.

[0063] Carbonate stress corrosion cracking is apparently diagnosed primarily by the presence of iron oxide in the cracks, as compared to the reported absence of iron oxide in blisters or cracks caused by hydrogen gas intrusion or hydrogen induced cracking. Thus, carbonate stress corrosion cracking is not the same as hydrogen induced cracking or blistering, although hydrogen blistering may also be observed in these same systems, especially when hydrogen sulfide is present in the refinery stream.

[0064] For the dispersant compound of formula 1, a hydroxylated polyamine (e.g., triethanolamine) is reacted with a carboxylic acid RCOOH (where R can be an alkyl or alkenyl group having 1 to 30 carbon atoms) at a suitable temperature until the condensation reaction is complete. Completion of the reaction is determined when the consumption of the acid reaches a desired amount. The reaction product is then diluted with a suitable solvent.

[0065] For the corrosion inhibitor compounds of formula 2, a carboxylic acid RCOOH, where R can be an alkyl or alkenyl group having 1 to 30 carbon atoms, is reacted with a polyamine (e.g., diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.) in a suitable solvent at a suitable temperature until the reaction is complete, which is determined when the desired amount of acid has been consumed.

[0066] The corrosion-inhibiting composition may also further comprise one or more additional corrosion inhibitors, organic solvents, corrosion inhibitors, organic solvents, asphaltene inhibitors, paraffin inhibitors, scale inhibitors, emulsifiers, water clarifiers, dispersants, emulsion breakers, gas hydrate inhibitors, biocides, pH adjusters, surfactants, or combinations thereof.

[0067] The corrosion-inhibiting compositions described herein contain from about 0.1 to about 20 weight percent of one or more compounds of Formula 1 or 2 in a solvent system.

[0068] The organic solvent may include an alcohol, a hydrocarbon, a ketone, an ether, an alkylene glycol, a glycol ether, an amide, a nitrile, a sulfoxide, an ester, or any combination thereof, and the composition optionally includes water.

[0069] Preferably, the organic solvent comprises methanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexanol, hexanol, octanol, decanol, 2-butoxyethanol, methylene 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, diethyl ether, propylene carbonate, N-methylpyrrolidinone, N,N-dimethylformamide, or a combination thereof.

[0070] Compounds used to enhance the corrosion performance of the composition may also be included in the anticorrosive composition, such as thioglycolic acid, 3,3'-dithiopropioinic acid, thiosulfates, thiourea, 2-mercaptoethanol, L-cysteine, tert-butyl mercaptan, or combinations thereof.

[0071] The methods described herein can have a surface that is part of equipment used in an industrial system, which can be a water recirculation system, a cooling water system, a boiler water system, a pulp slurry, a paper making process, a ceramic slurry, a mixed solid / liquid system, or an oil field system.

[0072] The methods described herein may include fluids used in the operation of industrial systems.

[0073] The fluid may include seawater, produced water, fresh water, brackish water, drilling fluids, completion fluids, or combinations thereof.

[0074] The corrosion-inhibiting compositions can be used, for example, to inhibit corrosion in oil and gas applications by treating a gas or liquid stream with an effective amount of the compounds or compositions as described herein. The compounds and compositions can be used in any industry where it is desirable to inhibit corrosion at a surface.

[0075] The corrosion-inhibiting composition can be used in water systems, condensate / oil systems, gas systems, or any combination thereof. For example, the corrosion-inhibiting composition can be used to control scale on heat exchanger surfaces.

[0076] The corrosion inhibiting compositions may be applied to produced gases or liquids or may be used in the production, transportation, storage, and / or separation of crude oil or natural gas.

[0077] The fluid into which the corrosion-inhibiting composition may be introduced may be an aqueous medium, which may include water, gas, and optionally liquid hydrocarbons.

[0078] The fluid into which the corrosion-inhibiting composition may be introduced may be any type of liquid hydrocarbon, including, but not limited to, crude oil, heavy oil, processing residual oil, bituminous oil, coker oil, coker gas oil, fluid catalytic cracking feedstock, gas oil, naphtha, fluid catalytic cracking slurry, diesel fuel, fuel oil, jet fuel, gasoline, and kerosene.

[0079] The fluid or gas may be a refined hydrocarbon product.

[0080] The fluid or gas treated with the corrosion-inhibiting composition may be at any selected temperature, such as ambient temperature or elevated temperature. The fluid (e.g., liquid hydrocarbon) or gas may be at a temperature of about 40° C. to about 250° C. The fluid or gas may be at a temperature of −50° C. to 300° C., 0° C. to 200° C., 10° C. to 100° C., or 20° C. to 90° C. The fluid or gas may be at a temperature of 22° C., 23° C., 24° C., 25° C., 26° C., 27° C., 28° C., 29° C., 30° C., 31° C., 32° C., 33° C., 34° C., 35° C., 36° C., 37° C., 38° C., 39° C., or 40° C. The fluid or gas may be at a temperature of 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, 96°C, 97°C, 98°C, 99°C, or 100°C.

[0081] The corrosion-inhibiting composition can be added to the fluid at various levels of water content. For example, the water content can be 0% to 100% volume / volume (v / v), 1% to 80% v / v, or 1% to 60% v / v. The fluid can be an aqueous medium containing various levels of salinity. The fluid can have a salinity of 0% to 25%, about 1% to 24%, or about 10% to 25% weight / weight (w / w) total dissolved solids (TDS).

[0082] The fluid or gas into which the corrosion-inhibiting composition is introduced may be contained in and / or exposed to many different types of equipment. For example, the fluid or gas may be contained in equipment that transports the fluid or gas from one point to another, such as an oil and / or gas pipeline. The equipment may be part of an oil and / or gas refinery, such as a pipeline, a separation vessel, a dehydration unit, or a gas line. The equipment may be a scrubber (e.g., a wet flue gas desulfurization unit, a spray dryer absorber, a dry sorbent injection unit, a spray tower, a contact tower, or a bubble column, etc.). The equipment may be a cargo ship, a storage ship, a storage tank, or a pipeline connecting tanks, ships, or processing units.

[0083] The corrosion-inhibiting composition may be introduced into the fluid or gas by any suitable method to ensure its distribution throughout the fluid or gas.

[0084] The corrosion-inhibiting composition may be added to the hydrocarbon fluid before it contacts the surface.

[0085] The corrosion-inhibiting composition may be added at a point in the flowline upstream from the point where corrosion inhibition is desired.

[0086] For example, the corrosion-inhibiting composition can be injected using mechanical devices such as chemical injection pumps, piping tees, injection fixtures, atomizers, quills, and the like.

[0087] The corrosion-inhibiting composition may be applied with or without one or more additional polar or non-polar solvents, depending on the application and requirements.

[0088] The corrosion inhibiting composition can be pumped into the oil and / or gas pipeline using an umbilical line. A capillary injection system can be used to deliver the compound / composition to the selected fluid.

[0089] The corrosion-inhibiting composition may be introduced and mixed into the liquid.

[0090] The corrosion-inhibiting composition may be injected into the gas stream as an aqueous or non-aqueous solution, mixture, or slurry.

[0091] The fluid or gas may be passed through an absorber tower that contains the corrosion-inhibiting composition.

[0092] The corrosion-inhibiting composition can be applied continuously, in batches, or a combination thereof. The dosage of the corrosion-inhibiting composition can be continuous to prevent corrosion. The dosage of the corrosion-inhibiting composition can be intermittent (i.e., batch processing), or the dosage of the corrosion-inhibiting composition can be continuous / maintenance and / or intermittent to inhibit corrosion.

[0093] The flow velocity of the flowline in which the corrosion-inhibiting composition is used can be from 0 to 100 feet per second, or from 0.1 to 50 feet per second. The corrosion-inhibiting composition can also be formulated with water for ease of addition to the flowline.

[0094] The corrosion-inhibiting composition can be used to inhibit corrosion in other applications.

[0095] The corrosion inhibiting compositions may also be used on or in other industrial equipment and in other industrial process streams, such as heaters, cooling towers, boilers, retort water, rinse water, aseptic packaging wash water, and the like.

[0096] The corrosion-inhibiting composition can be dispensed by immersion in water, either intermittently or continuously. The composition can then be dissolved, for example, at a controlled or predetermined rate. This rate can be effective to maintain a concentration of the dissolving agent that is effective for use in accordance with the methods disclosed herein.

[0097] The term "alkyl" as used herein refers to a straight or branched chain hydrocarbon radical, preferably having 1 to 32 carbon atoms (i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39, 30, 31, or 32 carbons). Alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, and tertiary butyl. Alkyl groups can be unsubstituted or substituted with one or more suitable substituents as defined above.

[0098] The term "alkenyl" as used herein refers to a straight or branched chain hydrocarbon radical, preferably having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39, 30, 31, or 32 carbons, and having one or more carbon-carbon double bonds. Alkenyl groups include, but are not limited to, ethenyl, 1-propenyl, 2-propenyl (allyl), iso-propenyl, 2-methyl-1-propenyl, 1-butenyl, and 2-butenyl. Alkenyl groups can be unsubstituted or substituted by one or more suitable substituents, as defined above.

[0099] The term "alkoxy," as used herein, refers to an alkyl group, as defined herein, appended to the parent molecular moiety through an oxygen atom.

[0100] The term "aryl," as used herein, means a monocyclic, bicyclic, or tricyclic aromatic radical, such as phenyl, naphthyl, tetrahydronaphthyl, indanyl, and the like, optionally substituted by one or more suitable substituents, preferably 1 to 5 suitable substituents, as defined above.

[0101] The term "cycloalkyl" as used herein refers to a monocyclic, bicyclic or tricyclic carbocyclic radical (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclopentenyl, cyclohexenyl, bicyclo[2.2.1]heptanyl, bicyclo[3.2.1]octanyl, bicyclo[5.2.0]nonanyl, etc.), optionally containing one or two double bonds. Cycloalkyl groups can be unsubstituted or substituted with one or more suitable substituents, preferably 1 to 5 suitable substituents, as defined above.

[0102] The term "halo" or "halogen" as used herein refers to a fluoro, chloro, bromo, or iodo radical.

[0103] The term "heteroaryl" as used herein refers to a monocyclic, bicyclic, or tricyclic aromatic heterocyclic group containing one or more heteroatoms (e.g., 1 to 3 heteroatoms) selected from O, S, and N in the ring. Heteroaryl groups include, but are not limited to, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, thienyl, furyl, imidazolyl, pyrrolyl, oxazolyl (e.g., 1,3-oxazolyl, 1,2-oxazolyl), thiazolyl (e.g., 1,2-thiazolyl, 1,3-thiazolyl), pyrazolyl, tetrazolyl, triazolyl (e.g., 1,2,3-triazolyl, 1,2,4-triazolyl), oxadiazolyl (e.g., 1,2,3-oxadiazolyl), thiadiazolyl (e.g., 1,3,4-thiadiazolyl), quinolyl, isoquinolyl, benzothienyl, benzofuryl, and indolyl. A heteroaryl group can be unsubstituted or optionally substituted with one or more suitable substituents, preferably 1 to 5 suitable substituents, as defined above.

[0104] As used herein, the term "heterocycle" or "heterocyclyl" refers to any ring system including N, O, S(O), n , P(O) n , P.R. z , NH, or NR z wherein R zis a suitable substituent. Heterocyclic groups optionally contain one or two double bonds. Heterocyclic groups include, but are not limited to, azetidinyl, tetrahydrofuran, imidazolidinyl, pyrrolidinyl, piperidinyl, piperazinyl, oxazolidinyl, thiazolidinyl, pyrazolidinyl, thiomorpholinyl, tetrahydrothiazinyl, tetrahydro-thiadiazinyl, morpholinyl, oxetanyl, tetrahydrodiazinyl, oxazinyl, oxathiazinyl, indolinyl, isoindolinyl, quinuclidinyl, chromanyl, isochromanyl, and benzoxazinyl. Examples of monocyclic saturated or partially saturated ring systems include tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, imidazolidin-1-yl, imidazolidin-2-yl, imidazolidin-4-yl, pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, piperidin-1-yl, piperidin-2-yl, piperidin-3-yl, piperazin-1-yl, piperazin-2-yl, piperazin-3-yl, 1,3-oxazolidin-3-yl, isothiazolidine-1-yl, tetrahydrofuran-3-yl, imidazolidin-1-yl, imidazolidin-2-yl, imidazolidin-4-yl, pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, piperidin-1-yl, piperazin-2-yl, piperazin-3-yl, 1,3-oxazolidin-3-yl, isothiazolidine-1-yl, zolidine, 1,3-thiazolidin-3-yl, 1,2-pyrazolidin-2-yl, 1,3-pyrazolidin-1-yl, thiomorpholin-yl, 1,2-tetrahydrothiazin-2-yl, 1,3-tetrahydrothiazin-3-yl, tetrahydrothiadiazin-yl, morpholin-yl, 1,2-tetrahydrodiazin-2-yl, 1,3-tetrahydrodiazin-1-yl, 1,4-oxazin-2-yl, and 1,2,5-oxathiazin-4-yl. The heterocyclic groups may be unsubstituted or substituted by one or more suitable substituents, preferably 1 to 3 suitable substituents, as defined above.

[0105] As used herein, the term "hydroxy" refers to an --OH group.

[0106] The term "suitable substituent" as used herein is intended to mean a chemically acceptable functional group, preferably a moiety that does not negate the activity of the compound of the present invention.Such suitable substituents include, but are not limited to, halo group, perfluoroalkyl group, perfluoroalkoxy group, alkyl group, alkenyl group, alkynyl group, hydroxy group, oxo group, mercapto group, alkylthio group, alkoxy group, aryl or heteroaryl group, aryloxy or heteroaryloxy group, aralkyl or heteroaralkyl group, aralkoxy or heteroaralkoxy group, HO-(C=O)- group, heterocyclic group, cycloalkyl group, amino group, alkyl and dialkylamino group, carbamoyl group, alkylcarbonyl group, alkoxycarbonyl group, alkylaminocarbonyl group, dialkylaminocarbonyl group, arylcarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, and arylsulfonyl group.Those skilled in the art will understand that many substituents can be substituted with further substituents.

[0107] Having described the invention in detail, it will be apparent that modifications and variations are possible without departing from the scope of the invention as defined in the appended claims. EXAMPLES

[0108] The following non-limiting examples are provided to further illustrate the present invention.

[0109] Example 1: Synthesis of Compounds For the dispersant compound of formula 1, a hydroxylated polyamine (e.g., triethanolamine) is reacted with a carboxylic acid RCOOH (where R can be an alkyl or alkenyl group having 1 to 30 carbon atoms) at a suitable temperature until the condensation reaction is complete. Completion of the reaction is determined when the consumption of the acid reaches a desired amount. The reaction product is then diluted with a suitable solvent.

[0110] For the corrosion inhibitor compounds of formula 2, a carboxylic acid RCOOH, where R can be an alkyl or alkenyl group having 1 to 30 carbon atoms, is reacted with a polyamine (e.g., diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.) in a suitable solvent at a suitable temperature until the reaction is complete, which is determined when the desired amount of acid has been consumed.

[0111] Example 2: Corrosion Test The performance of the formulations was evaluated using slow strain rate (SSR) testing of C1018 carbon steel coupons. Sodium chloride (NaCl) was used in the test solution to inhibit the repassivation process at the crack tip, so that the propagation of intergranular SCC was accelerated sufficiently to occur within the time frame of the SSR test. Table 1 summarizes the experimental conditions used in the SSR tests. [Table 1]

[0112] Testing was generally performed in accordance with the methodology described in NACE TM0198-2016, “Slow Strain Rate Test Method for Screening Corrosion-Resistant Alloys for Stress Corrosion Cracking in Sour Oilfield Service.”

[0113] The corrosion-inhibiting composition includes 40% by weight of the dispersant of Formula 1, 20% by weight of the corrosion inhibitor of Formula 2, and 20% by weight of the heavy aromatic naphtha, based on the total weight of the dispersant of Formula 1, the corrosion inhibitor of Formula 2, and the heavy aromatic naphtha. The composition, with the aid of the dispersant, provides a passivation and protective layer on the target metal surface. This layer and the dispersant then inhibit stress corrosion cracking by preventing corrosive species (i.e., carbonate and bicarbonate ions) from initiating intergranular cracking. The performance of the composition is evaluated by slow strain rate (SSR) testing of metal coupons at high temperature and pressure in the presence of the formulation and the corrosive species. The ductility ratio of the samples and optical micrographs of the metal coupons are used to evaluate the effectiveness of the formulation in preventing alkaline stress corrosion cracking (ASCC).

[0114] Coupon preparation and passivation for SSR testing was performed as follows: AISI 1018 SSR test specimens (i.e., coupons) were machined, then longitudinally removed and prepared according to NACE TM0198-2016. The coupons were degreased in a detergent solvent, followed by a two-step solvent rinse in alcohol and then acetone, and air-dried at room temperature. Each specimen was then assembled into a 0.5 liter Alloy C276 test vessel and pressure tested for leaks. The electrical resistance between the specimen / pull rod assembly and the vessel body was checked to ensure that no electrical continuity was present. AISI 1018 SSR test specimens (except for the "inactive" coupons) were preconditioned (passivated) in degassed, deionized water at 248°F for 20 hours to create a magnetite layer.

[0115] The SSR test was performed as follows: OLI's Stream Analyzer simulation software was used to calculate the amount of each pure component required at standard conditions to achieve specific environmental conditions upon heating to the test temperature. - (as sodium chloride), 52,750 mg / L HCO2, and 12,058 mg / L CO3 -2A concentrated carbonate test medium (375 mL) was prepared consisting of: 100% CrN2O2, 100% CO2, ...

[0116] The ductility ratios shown in Figure 1 were calculated using stress-strain overlay plots for inert coupons, carbonate coupons, and coupons treated with the following formulations: Comparative Formulation A (only corrosion inhibitor of Formula 2), Comparative Formulation B (only dispersant of Formula 1), and the proposed invention (corrosion inhibitor of Formula 2 and dispersant of Formula 1). The ductility ratio of the C1018 carbon steel coupon increased in the presence of all formulations used compared to a "blank" coupon (no formulation used). The proposed invention has the highest ratio overall of all formulations used.

[0117] Optical micrographs of C1018 carbon steel specimens after SSR testing are shown in Figure 2, which depicts a magnified image of the area where failure occurred. Note that only the coupons tested with the proposed invention and in the presence of an inert environment show no evidence of SCC or other corrosion features (i.e., pits). All other formulations tested show evidence of cracking (b and c) and / or pitting (b and d).

[0118] As used herein, the terms "comprise," "include," "having," "has," "can," "contain," and variations thereof are intended to be open-ended transitional phrases, terms, or words that do not exclude the possibility of additional steps or components. The singular forms "a," "and," "the," and "said" include plural referents unless the context clearly dictates otherwise. The present disclosure also contemplates other embodiments that "comprise," "consist," and "consist essentially of" the embodiments or elements presented herein, whether or not expressly stated.

[0119] In view of the above, it will be seen that the several objects of the invention are achieved and other advantageous results attained.

[0120] It is intended that all matter contained in the above description be interpreted in an illustrative and not a limiting sense, as various modifications can be made to the above compounds and methods without departing from the scope of the invention.

Claims

1. 1. A corrosion-inhibiting composition comprising a dispersant having the structure of Formula 1 and a corrosion inhibitor having the structure of Formula 2: 【Chemical 1】 During the ceremony, X １ is hydroxyl or —OC(O)R １ and X ２ is hydroxyl or —OC(O)R ２ and X ３ is hydroxyl or —OC(O)R ３ and R １ , R ２ , and R ３ But independently, C １０ ~C ３０ alkyl or alkenyl, m, n, and o are independently integers from 1 to 10; R ２０ , R ２１ , R ２２ , R ２３ , and R ２４ are independently hydrogen or —C(O)—R ３１ and R ３１ But C １０ ~C ３０ alkyl or alkenyl, p is an integer of 0 or 1; q is an integer from 1 to 4, r is an integer of 0 or 1; s is an integer of 0 or 1; t is an integer from 1 to 4, p1, q1, r1, r2, s1, and t1 are independently integers from 1 to 6; When p, r, and s are 0, q+t is an integer from 4 to 8, and R ２０ , R ２１ , R ２２ , R ２３ , and R ２４ At least one of the groups is —C(O)—R ３１ The corrosion-inhibiting composition of claim 1,

2. 2. The corrosion-inhibiting composition of claim 1, wherein m, n, and o are independently integers from 1 to 6, preferably m, n, and o are independently integers from 2 to 4, and more preferably m, n, and o are independently integers of 2 or 3.

3. R １ But C １２ ~C ２４ alkyl or alkenyl, preferably R 1 is C 14 -C 22 alkyl or alkenyl, more preferably R 1 is C 16 -C 20 alkyl or alkenyl; and / or R 2 is a C 12 -C 24 alkyl or alkenyl, preferably R 2 is a C 14 -C 22 alkyl or alkenyl, more preferably R 2 is a C 16 -C 20 alkyl or alkenyl; and / or 3. The corrosion-inhibiting composition of claim 1 or 2, wherein R 3 is a C 12 to C 24 alkyl or alkenyl, preferably R 3 is a C 14 to C 22 alkyl or alkenyl, more preferably R 3 is a C 16 to C 20 alkyl or alkenyl.

4. The dispersant of Formula 1 is a compound of Formula 1A: 【Chemistry 2】 3. The corrosion-inhibiting composition of claim 1, having the structure:

5. 3. The corrosion-inhibiting composition of claim 1, wherein p1, q1, r1, r2, s1, and t1 are independently integers from 2 to 6, and preferably p1, q1, r1, r2, s1, and t1 are independently integers of 2 or 3.

6. The corrosion inhibitor of Formula 2 is a compound of Formula 2A: 【Chemistry 3】 3. The corrosion-inhibiting composition of claim 1, having the structure:

7. R ３１ But C １２ ~C ２４ The composition of claim 6, wherein R 31 is alkyl or alkenyl, preferably R 31 is C 14 to C 22 alkyl or alkenyl, more preferably R 31 is C 16 to C 20 alkyl or alkenyl.

8. 3. The corrosion-inhibiting composition of claim 1 or 2, further comprising a solvent, preferably the solvent is a hydrocarbon solvent, more preferably the solvent comprises a fluid comprising a gas, a liquid hydrocarbon, and optionally water, or a combination thereof.

9. 3. The corrosion-inhibiting composition of claim 1 or 2, wherein the corrosion inhibitor forms a film on the surface.

10. 10. A method of inhibiting corrosion by contacting the corrosion-inhibiting composition of claim 1 or 2 with a surface in contact with an aqueous medium containing hydrogen sulfide, ammonia, carbon dioxide, hydrogen cyanide, carbonates, bicarbonates, or combinations thereof.

11. 3. Use of the corrosion-inhibiting composition of claim 1 or 2 to inhibit corrosion on a surface in contact with an aqueous medium containing hydrogen sulfide, ammonia, carbon dioxide, hydrogen cyanide, carbonates, bicarbonates, or combinations thereof.

12. The method of claim 10 , wherein the aqueous medium comprises a carbonate, a bicarbonate, or a combination thereof.

13. The method of claim 10, wherein the surface is a metal surface, preferably the metal surface comprises carbon steel.

14. 11. The method of claim 10, wherein the surface is contained in a fluid catalytic cracking unit (FCCU) or a sour water stripper (SWS).

15. 11. The method of claim 10, wherein the corrosion-inhibiting composition is contacted with the surface at a concentration of 1 to 1000 ppm, based on the total weight of the aqueous medium, and preferably the corrosion-inhibiting composition is contacted with the surface at a concentration of 100 to 500 ppm.

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