AMINO ACID DERIVATIVES AND SULFUR DERIVATIVES AS BIODEGRADABLE CORROSION INHIBITORS

Abstract

Environmentally friendly corrosion-inhibiting compositions and methods of use thereof for corrosion inhibition of metal surfaces used in oil and gas operations are disclosed. Corrosion-inhibiting compositions include derivatized succinate corrosion inhibitors that beneficially avert bioaccumulation according to certain regulations and provides suitable biodegradability.

Claims

1. A method of reducing corrosion on a surface comprising: contacting a corrosive inhibiting effective amount of a corrosion inhibition composition comprising a derivatized succinate corrosion inhibitor with a metal surface in a system, wherein the contacting is added in a batch or continuous application, and reducing corrosion on the surface, wherein the derivatized succinate corrosion inhibitor has the following general structure or salts thereof: ##STR00029## wherein R.sup.1 and R.sup.2 are independently H or a carbon-containing group, and Z is a nitrogen or sulfur-containing group.

2. The method of claim 1, wherein one of R.sup.1 or R.sup.2 is H and the other R group is a carbon-containing group, or wherein both of R.sup.1 or R.sup.2 are H and Z is NHR.sup.3, SR.sup.3, or SO.sub.3H, wherein R.sup.3 is a carbon containing group.

3. (canceled)

4. The method of claim 1, wherein Z is selected from the group consisting of NHR.sup.3, N(R.sup.3).sub.2, SC(O)R.sup.3, SH, SO.sub.3H, and SR.sup.3, wherein R.sup.3 is a carbon-containing group.

5. (canceled)

6. The method of claim 1, wherein the derivatized succinate corrosion inhibitor makes up from about 0.1 wt-% to about 80 wt-% of the composition.

7. The method of claim 1, wherein the corrosion inhibition composition further comprise a solvent and/or at least one additional functional ingredient.

8. The method of claim 7, wherein the solvent comprises water, alcohols, hydrocarbon solvents, and/or wherein the at least one additional functional ingredient is selected from the group consisting of synergist, additional corrosion inhibitors, surfactants, polymers, pH modifiers, asphaltene inhibitors, paraffin inhibitors, scale inhibitors, metal complexing agents (chelants), emulsifiers, water clarifiers, dispersants, emulsion breakers and combinations thereof.

9. The method of claim 1, wherein the corrosive inhibiting effective amount of the derivatized succinate corrosion inhibitor is from about 0.1 ppm to about 5000 ppm based on the total volume of the system.

10. The method of claim 1, wherein the surface is a containment used in the production, transportation, storage and/or separation of crude oil, natural gas or a biofuel process, downstream chemical application, water treatment application, or geothermal application.

11. The method of claim 1, wherein the system comprises a hydrocarbon fluid or gas, produced water, or combination thereof.

12. A treated metal containment or water source comprising: a metal containment comprising a metal surface a water source comprising one or more corrodents; and a corrosive inhibiting effective amount a derivatized succinate corrosion inhibitor having the following general structure or salts thereof: ##STR00030## wherein R.sup.1 and R.sup.2 are independently H or a carbon-containing group, and Z is a nitrogen or sulfur-containing group, wherein the metal containment comprising the metal surface has a barrier or film substantially coating the metal surface with the derivatized succinate corrosion inhibitor.

13. The treated metal containment or water source of claim 12, wherein the corrosive inhibiting effective amount of the derivatized succinate corrosion inhibitor is from about 0.1 ppm to about 5000 ppm based on the total volume of the containment or water source.

14. (canceled)

15. The treated or water source water source of claim 12, wherein the corrosive inhibiting effective amount of the derivatized succinate corrosion inhibitor is from about 1 ppm to about 1000 ppm, based on the total volume of the containment or water source.

16. A method of making a derivatized succinate corrosion inhibitor comprising: reacting maleic anhydride with an alcohol to form a maleic ester acid intermediate, and thereafter reacting the maleic ester acid intermediate or maleic acid with an amine or a sulfur containing compound by addition to form the derivatized succinate corrosion inhibitor having the general structure (or salt thereof) ##STR00031## wherein one of R.sup.1 or R.sup.2 is H and the other R group is a carbon-containing group, or wherein both of R.sup.1 or R.sup.2 are H and Z is NHR.sup.3, N(R.sup.3).sub.2, or SR.sup.3, wherein R.sup.3 is a carbon containing group, and Z is a nitrogen or sulfur-containing group.

17. The method of claim 16, wherein the molar ratio of the maleic anhydride to the alcohol is from about 0.1:1 to about 1:0.1.

18. The method of claim 16, wherein the amine is a primary or secondary amine or wherein the sulfur-containing compound is a thiol or a thioacid.

19. The method of claim 16, wherein the derivatized succinate corrosion inhibitor is an isomeric mixture with the general structures ##STR00032## wherein Z is selected from the group consisting of NHR.sup.3, N(R.sup.3).sub.2, SC(O)R.sup.3, SH, SO.sub.3H, and SR.sup.3, wherein R.sup.3 is a carbon-containing group.

20-25. (canceled)

26. The method of claim 16, wherein the molar ratio of the maleic anhydride to the alcohol is about 1:1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0017] FIGS. 1A-1B show reaction schemes for the synthesis of the derivatized succinate corrosion inhibitors of structure 1, wherein FIG. 1A shows synthesis of the derivatized succinate corrosion inhibitors of structure 1 (4a, 4b) or salts thereof, and FIG. 1B shows synthesis of the derivatized succinate corrosion inhibitors of structure 1 (4c) or salts thereof.

[0018] FIG. 2 shows an undesirable reaction scheme distinct from FIG. 1 synthesis of the derivatized succinate corrosion inhibitors of structure 1 or salts thereof.

[0019] FIG. 3 shows a reaction scheme for the synthesis of the derivatized succinate corrosion inhibitors of structure 6 or salts thereof.

[0020] FIG. 4 shows a reaction scheme for the synthesis of the derivatized succinate corrosion inhibitors of structure 8 or salts thereof.

[0021] FIG. 5 shows a reaction scheme for the synthesis of the derivatized succinate corrosion inhibitors of structure 10 or salts thereof.

[0022] FIG. 6 shows a reaction scheme for the synthesis of the derivatized succinate corrosion inhibitors of structure 1 or salts thereof shown as thioethers 11a and 11b.

[0023] FIG. 7 shows a reaction scheme for the synthesis of the derivatized succinate corrosion inhibitors of structure 1 or salts thereof shown as thioesters 12a and 12b along with further reaction to thiols 13a and 13b.

[0024] FIG. 8 shows a reaction scheme for the synthesis of the derivatized succinate corrosion inhibitors of structure 1 with sulfite salts used to form sulfonate isomers 14a and 14b.

[0025] Various embodiments of the present disclosure will be described in detail with reference to the drawings, wherein like reference numerals represent like parts throughout the several views. Reference to various embodiments does not limit the scope of the disclosure. Figures represented herein are not limitations to the various embodiments according to the disclosure and are presented for exemplary illustration of the invention. An artisan of ordinary skill in the art need not view, within isolated figure(s), the near infinite number of distinct permutations of features described in the following detailed description to facilitate an understanding of the present invention.

DETAILED DESCRIPTION

[0026] It is further to be understood that all terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting in any manner or scope. For example, as used in this specification and the appended claims, the singular forms a, an and the can include plural referents unless the content clearly indicates otherwise. Further, all units, prefixes, and symbols may be denoted in its SI accepted form.

[0027] Numeric ranges recited within the specification are inclusive of the numbers defining the range and include each integer within the defined range. Throughout this disclosure, various aspects of this disclosure are presented in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosure. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges, fractions, and individual numerical values within that range. This applies regardless of the breadth of the range.

[0028] As used herein, the term and/or, e.g., X and/or Y shall be understood to mean either X and Y or X or Y and shall be taken to provide explicit support for both meanings or for either meaning, e.g. A and/or B includes the options i) A, ii) B or iii) A and B.

[0029] It is to be appreciated that certain features that are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any sub-combination.

[0030] The terms comprise(s), include(s), having, has, can, contain(s), and variants thereof, as used herein, are intended to be open-ended transitional phrases, terms, or words that do not preclude the possibility of additional acts or structures. The singular forms a, and, and the include plural references unless the context clearly dictates otherwise. The present disclosure also contemplates other embodiments comprising, consisting of and consisting essentially of, the embodiments or elements presented herein, whether explicitly set forth or not.

[0031] The methods and compositions of the present disclosure may comprise, consist essentially of, or consist of the components and ingredients of the present disclosure as well as other ingredients described herein. As used herein, consisting essentially of means that the methods and compositions may include additional steps, components or ingredients, but only if the additional steps, components or ingredients do not materially alter the basic and novel characteristics of the claimed methods and compositions.

[0032] Unless defined otherwise, all technical and scientific terms used above have the same meaning as commonly understood by one of ordinary skill in the art to which embodiments of the present disclosure pertain.

[0033] The term about, as used herein, refers to variation in the numerical quantity that can occur, for example, through typical measuring techniques and equipment, with respect to any quantifiable variable, including, but not limited to, concentration, mass, volume, time, molecular weight, molecular size, temperature, pH, molar ratios, and the like. Further, given solid and liquid handling procedures used in the real world, there is certain inadvertent error and variation that is likely through differences in the manufacture, source, or purity of the ingredients used to make the compositions or carry out the methods and the like. The term about also encompasses these variations. Whether or not modified by the term about, the claims include equivalents to the quantities.

[0034] The term actives or percent actives or percent by weight actives or actives concentration are used interchangeably herein and refers to the concentration of those ingredients involved in cleaning expressed as a percentage minus inert ingredients such as water or salts. It is also sometimes indicated by a percentage in parentheses, for example, chemical (10%).

[0035] As used herein, the term alkyl or alkyl groups refers to linear or branched 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). Alkyls can include straight-chain alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.), cyclic alkyl groups (or cycloalkyl or alicyclic or carbocyclic groups) (e.g., cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched-chain alkyl groups (e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc.), and alkyl-substituted alkyl groups (e.g., alkyl-substituted cycloalkyl groups and cycloalkyl-substituted alkyl groups). Commonly used alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, secondary-butyl, and tertiary-butyl.

[0036] Unless otherwise specified, the term alkyl includes both unsubstituted alkyls and substituted alkyls. As used herein, the term substituted alkyls refers to alkyl groups having substituents replacing one or more hydrogens on one or more carbons of the hydrocarbon backbone. Such substituents may include, for example, alkenyl, alkynyl, halogeno, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonato, phosphinato, cyano, amino (including alkyl amino, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfates, alkylsulfinyl, sulfonates, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclic, alkylaryl, or aromatic (including heteroaromatic) groups. In some embodiments, substituted alkyls can include a heterocyclic group. As used herein, the term heterocyclic group includes closed ring structures analogous to carbocyclic groups in which one or more of the carbon atoms in the ring is an element other than carbon, for example, nitrogen, sulfur or oxygen. Heterocyclic groups may be saturated or unsaturated. Exemplary heterocyclic groups include, but are not limited to, aziridine, ethylene oxide (epoxides, oxiranes), thiirane (episulfides), dioxirane, azetidine, oxetane, thietane, dioxetane, dithietane, dithiete, azolidine, pyrrolidine, pyrroline, oxolane, dihydrofuran, and furan.

[0037] The terms aryl or ar as used herein alone or as part of another group (e.g., aralkyl) denote optionally substituted homocyclic aromatic groups, preferably monocyclic or bicyclic groups containing from 6 to 12 carbons in the ring portion, such as phenyl, biphenyl, naphthyl, substituted phenyl, substituted biphenyl or substituted naphthyl. Phenyl and substituted phenyl are commonly used aryls. The term aryl also includes heteroaryl.

[0038] Arylalkyl means an aryl group attached to the parent molecule through an alkylene group. In some embodiments the number of carbon atoms in the aryl group and the alkylene group is selected such that there is a total of about 6 to about 18 carbon atoms in the arylalkyl group. A commonly used arylalkyl group is benzyl.

[0039] As used herein, the term containment or metal containment includes any metal surface or portion thereof that is in contact with a gas or liquid phase from an oil-field system containing corrodents. In embodiments the containment is in fluid communication with one or more devices or apparatuses, including other containments. In embodiments the containment is a pipe. In embodiments the containment is a tank. In embodiments, the metal is steel. In embodiments, the steel is carbon steel. In embodiments, the carbon steel is stainless steel.

[0040] As used herein, the term corrodent refers to one or more salts and/or other dissolved solids, liquids, or gases that cause, accelerate, or promote corrosion of metals. Exemplary corrodents common in oil and gas applications include, water electrolytes, such as sodium chloride, calcium chloride, oxygen, hydrogen sulfide, carbon dioxide, sulfur dioxide, and the like.

[0041] The term -ene as used as a suffix as part of another group denotes a bivalent substituent in which a hydrogen atom is removed from each of two terminal carbons of the group, or if the group is cyclic, from each of two different carbon atoms in the ring. For example, alkylene denotes a bivalent alkyl group such as methylene (CH.sub.2) or ethylene (CH.sub.2CH.sub.2), and arylene denotes a bivalent aryl group such as o-phenylene, m-phenylene, or p-phenylene.

[0042] As used herein, the term exemplary refers to an example, an instance, or an illustration, and does not indicate a most preferred embodiment unless otherwise stated.

[0043] As used herein, the term fluid source means any fluid used in oil or gas well production operations that contain one or more corrodents.

[0044] The term generally encompasses both about and substantially.

[0045] The term inhibiting as referred to herein includes inhibiting, preventing, retarding, mitigating, reducing, controlling and/or delaying corrosion on a surface or within a system, namely an oil-field system.

[0046] As used herein, the term injectate means water plus any solids or liquids dispersed therein that is injected into a subterranean formation for the purpose of inducing hydrocarbon recovery therefrom. Injectates optionally include salts, polymers, surfactants, scale inhibitors, stabilizers, metal chelating agents, corrosion inhibitors, paraffin inhibitors, and other additives as determined by the operator in a subterranean hydrocarbon recovery process.

[0047] As used herein, the term optional or optionally means that the subsequently described component, event or circumstance may but need not be present or occur. The description therefore discloses and includes instances in which the event or circumstance occurs and instances in which it does not, or instances in which the described component is present and instances in which it is not.

[0048] As used herein, the term produced water means water that flows back from a subterranean reservoir and is collected during a hydrocarbon recovery process including, but not limited to hydraulic fracturing and tertiary oil recovery. Produced water includes residual hydrocarbon products entrained therein and one or more of injectate, connate (native water present in the subterranean formation along with the hydrocarbon), brackish water, and sea water. Produced water ranges in temperature from about 30 C. to about 200 C., depending on the subterranean reservoir and the terranean environment and infrastructure proximal to the subterranean reservoir.

[0049] The scope of the present disclosure is defined by the appended claims, along with the full scope of equivalents to which such claims are entitled. The scope of the disclosure is further qualified as including any possible modification to any of the aspects and/or embodiments disclosed herein which would result in other embodiments, combinations, subcombinations, or the like that would be obvious to those skilled in the art.

[0050] The term substantially refers to a great or significant extent. Substantially can thus refer to a plurality, majority, and/or a supermajority of said quantifiable variable, given proper context.

[0051] The term substituted as in substituted aryl, substituted alkyl, and the like, means that in the group in question (i.e., the alkyl, aryl or other group that follows the term), at least one hydrogen atom bound to a carbon atom is replaced with one or more substituent groups such as hydroxy (OH), alkylthio, phosphino, amido (CON(R.sub.A)(R.sub.B), wherein R.sub.A and R.sub.B are independently hydrogen, alkyl, or aryl), amino(-N(R.sub.A)(R.sub.B), wherein R.sub.A and R.sub.B are independently hydrogen, alkyl, or aryl), halo (fluoro, chloro, bromo, or iodo), silyl, nitro (NO.sub.2), an ether (OR.sub.A wherein R.sub.A is alkyl or aryl), an ester (OC(O)R.sub.A wherein R.sub.A is alkyl or aryl), keto (C(O)R.sub.A wherein R.sub.A is alkyl or aryl), heterocyclo, and the like. Further, an alkylene group in the chain can be replaced with an ether, an amine, an amide, a carbonyl, an ester, a cycloalkyl, or a heterocyclo functional group. When the term substituted introduces a list of possible substituted groups, it is intended that the term apply to every member of that group. That is, the phrase optionally substituted alkyl or aryl is to be interpreted as optionally substituted alkyl or optionally substituted aryl.

[0052] As used herein, the term substantially free refers to compositions completely lacking the component or having such a small amount of the component that the component does not affect the performance of the composition. The component may be present as an impurity or as a contaminant and shall be less than 0.5 wt-%. In another embodiment, the amount of the component is less than 0.1 wt-% and in yet another embodiment, the amount of component is less than 0.01 wt-%.

[0053] The term weight percent, wt-%, percent by weight, % by weight, and variations thereof, as used herein, refer to the concentration of a substance as the weight of that substance divided by the total weight of the composition and multiplied by 100. It is understood that, as used here, percent, %, and the like are intended to be synonymous with weight percent, wt-%, etc.

Corrosion-Inhibiting Compositions

[0054] According to embodiments, the corrosion-inhibiting compositions include from about 0.1 wt-% to about 90 wt-% of a derivatized succinate corrosion inhibitor. In embodiments the corrosion-inhibiting compositions can further comprise a solvent and/or at least one additional functional ingredient.

[0055] In embodiments the corrosion-inhibiting compositions are described in weight percentages of the compositions. While the components may have a percent active of 100%, it is noted that the percent actives of the components is not defined, but rather, total weight percentage of the raw materials (i.e. active concentration plus inert ingredients) are disclosed. In an exemplary embodiment the derivatized succinate corrosion inhibitor comprises from about 0.1 wt-% to about 90 wt-% of the composition, and the solvent(s) and/or additional functional ingredient(s) comprises from about 10 wt-% to about 99.9 wt-% of the composition.

Succinate-Derived Corrosion Inhibitors

[0056] The corrosion-inhibiting composition comprise a derivatized succinate corrosion inhibitor which one skilled in the art will understand can include an amino acid-based or derivatized sulfur-based corrosion inhibitor, ultimately obtained from the addition of amines or sulfur compounds to derivatives of maleic acid. The term corrosion inhibitor (or referred to as CI) refers to a compound or mixture of compounds that prevents, retards, mitigates, reduces, controls and/or delays corrosion. Beneficially the derivatized succinate corrosion inhibitors contain ester functional groups that more readily biodegrade compared to amide or imidazoline derivatives as are commonly employed as corrosion inhibitors.

[0057] The derivatized succinate corrosion inhibitor or a corrosion inhibiting composition comprising a derivatized succinate corrosion inhibitor has the following general structures or salts thereof:

##STR00007##

wherein R.sup.1 and R.sup.2 are independently H or a carbon-containing group, and Z is a nitrogen or sulfur-containing group; or

##STR00008##

wherein R.sup.1 and R.sup.2 are independently H or a carbon-containing group; or

##STR00009##

wherein R.sup.1 is H or a carbon-containing group, and L.sup.1 is a diamine linker; or

##STR00010##

wherein Z is a nitrogen or sulfur-containing group, and L.sup.2 is a diamine, polyether or polyol linker.

[0058] In further embodiments the derivatized succinate corrosion inhibitors have the general structures or salts thereof:

##STR00011##

wherein R.sup.1 and R.sup.2 are independently H or a carbon-containing group, Z is a nitrogen or sulfur-containing group, L.sup.1 is a diamine linker, and L.sup.2 is a diamine, polyether or polyol linker.

[0059] In preferred embodiments R.sup.1 and R.sup.2 as carbon-containing groups can have an alkyl chain of varying lengths. In some embodiments R.sup.1 is at least 4 carbons.

[0060] In further preferred embodiments Z is selected from the group consisting of NHR.sup.3, N(R.sup.3).sub.2, SC(O)R.sup.3, SH, SO.sub.3H, and SR.sup.3, wherein R.sup.3 is a carbon-containing group. Exemplary carbon-containing groups can include additional nitrogen, oxygen and/or sulfur, such as for example NH(CH.sub.2).sub.nOH or SH(CH.sub.2).sup.nOH.

[0061] In further preferred embodiments L.sup.1 or L.sup.2 is a diamine having the general structure HN-L.sup.3-NH wherein L.sup.3 is a bifunctional carbon-containing group such that L.sup.1 or L.sup.2 can be a diamine having structures such as NH(CH.sub.2).sub.nNH or NH((CH.sub.2).sub.xO).sub.y(CH.sub.2).sub.xNH wherein x is an integer from 1 to 6 and y is an integer from 1 to 30. In still further embodiments L.sup.2 is a polyether or polyol having the structure O((CH.sub.2).sub.xO).sub.y wherein x is an integer from 1 to 6 and y is an integer from 1 to 30.

[0062] In further embodiments the derivatized succinate corrosion inhibitors have the general structure or salts thereof:

##STR00012##

or wherein R.sup.1 or R.sup.2 is H and the other R group is a carbon-containing group, or wherein both of R.sup.1 or R.sup.2 are H and Z is NHR.sup.3 or SR.sup.3, wherein R.sup.3 is a carbon containing group.

[0063] In embodiments the derivatized succinate corrosion inhibitors have the structures or salts thereof:

##STR00013## [0064] wherein R.sup.1 is H or a carbon-containing group, and Z is a nitrogen or sulfur-containing group.

[0065] In addition to the derivatized succinate corrosion inhibitors described herein and the corrosion inhibiting compositions comprising a derivatized succinate corrosion inhibitor are methods of synthesizing or making the derivatized succinate corrosion inhibitors.

[0066] In further embodiments the derivatized succinate corrosion inhibitors have the general structure or salts thereof:

##STR00014##

wherein R.sup.1 and R.sup.2 are independently H and a carbon-containing group. In further embodiments the derivatized succinate corrosion inhibitor of structure 6 occurs in the presence of an alcohol having the general structure R.sup.1OH, wherein R.sup.1 is an alkyl group. In some embodiments the alkyl chain length of R.sup.1 of the alcohol is the same as R.sup.1 in structure 6.

[0067] The derivatized succinate corrosion inhibitors are synthesized via the sequential reactivity of maleic anhydride in the synthesis of the derivatized succinate corrosion inhibitors at a good yield, cost effectively and with high purity. This is another distinction from conventional amide or imidazoline derivatives that are commonly employed as corrosion inhibitors that produce numerous side products. Such side products can present additional toxicity and/or biodegradability challenges. As a result, the methods of synthesis for the derivatized succinate corrosion inhibitors provide numerous advantages.

[0068] In embodiments the derivatized succinate corrosion inhibitors are efficiently synthesized following a sequential synthetic pathway wherein an alcohol first reacts with maleic anhydride to afford maleate ester acids containing a reactive carbon-carbon double bond capable of further derivatization. Thereafter amines or sulfur compounds react in this position with maleate ester acids by a 1,4-conjugate addition to give succinate-based products that are surface active and anionic or zwitterionic under neutral or weakly acidic conditions, favorable film-forming properties for the passivation of a metal surface against corrosion.

[0069] In embodiments the derivatized succinate corrosion inhibitors of structure 1 are synthesized according to a process comprising first reacting maleic anhydride with an alcohol to form a maleic ester acid intermediate, in some embodiments preferably at a temperature above about 60 C., and thereafter reacting the maleic ester acid intermediate with an amine or a sulfur-containing compound by addition to form the derivatized succinate corrosion inhibitor having the general structure or salts thereof

##STR00015##

wherein one of R.sup.1 or R.sup.2 is H and the other R group is a carbon-containing group, as shown in FIG. 1A.

[0070] In further embodiments the derivatized succinate corrosion inhibitors of structure 1 are synthesized according to a process comprising reacting maleic acid or a salt thereof with an amine or a sulfur-containing compound by addition to form the derivatized succinate corrosion inhibitor having the general structure or salts thereof

##STR00016##

wherein both of R.sup.1 or R.sup.2 are H and Z is NHR.sup.3 or SR.sup.3, wherein R.sup.3 is a carbon containing group, and Z is a nitrogen or sulfur-containing group. Beneficially the synthesis is a one-step reaction, as shown in FIG. 1B.

[0071] In embodiments where Z is nitrogen-containing the product is a substituted amino acid (i.e. aspartic acid derivative). Beneficially, the combination of a nitrogen-containing group in the Z position and the free carboxylic acid group imparts zwitterionic character in weakly acidic or neutral environments, giving the corrosion inhibitor absorptive capability on a metal surface, while the free carboxylic acid reduces toxicity and improves biodegradability. In embodiments where Z is a sulfur group there is a potential ligating effect on metal surfaces as the Z group provides hydrophobicity or hydrophilicity to the corrosion inhibitor.

[0072] In embodiments methods of making the derivatized succinate corrosion inhibitors of structure 1 are depicted in FIG. 1. The derivatized succinate corrosion inhibitors are prepared by first reacting maleic anhydride with alcohols, followed by the subsequent reaction with amines (depicted in FIG. 1A) or sulfur compounds. In some embodiments the reaction adds one equivalent of alcohol to maleic anhydride to cleanly afford the unsaturated maleic ester acid 2 in high yield. Thereafter the maleic ester acid 2 is reacted with an amine by 1,4-addition (aza-Michael addition for amines) to give an amino acid derivative as a mixture of isomers 4a and 4b, corresponding respectively to reaction at the 2- or 3-position relative to the acid group.

[0073] Notably, as shown in FIG. 1A the formation of diester 3 requires more vigorous conditions, including acid catalysis, water removal, and higher temperatures, and therefore does not occur appreciably in the absence of catalyst if temperature is kept below 120 C.

[0074] This selective reactivity makes maleic anhydride unique compared to other multifunctional compounds, which typically show a statistical product distribution due to inability to distinguish reactive sites, therefore being key aspects of the methods of synthesis for the derivatized succinate corrosion inhibitors.

[0075] In embodiments, the addition reaction is run at temperatures above about 60 C. (approximate melting point of maleic anhydride). Solvents are not required. In some embodiments organic solvents may be used to ensure adequate mixing. In some embodiments the alcohol can function as the solvent.

[0076] In embodiments the molar ratio of the maleic anhydride to the alcohol is from about 0.1:1 to about 1:0.1, and preferably about 1:1.

[0077] In embodiments the amine is a primary or secondary amine or the sulfur-containing compound is a thiol, thioacid, or sulfite salt. In some embodiments, primary amines are preferred as they do not lead to the formation of tertiary amines, which tend to be less biodegradable. Furthermore, primary amines react under milder conditions, whereas the higher temperatures needed to promote reaction with secondary amines can lead to side product formation.

[0078] FIG. 2 shows a reaction scheme with a 1,2-diamine reacting with the monoester to form lactams 5a and 5b spontaneously due to cyclization reactions. This is further not desirable as there is potential aminolysis of an ester group, leading to loss of surface activity and corrosion inhibitor performance. Still further there is a more complex mixture of resultant structures presenting challenges for characterization, commercialization, and regulatory approval.

[0079] The methods described provide an isomeric mixture of the derivatized succinate corrosion inhibitors with the general structures or salts thereof:

##STR00017##

wherein Z is selected from the group consisting of NHR.sup.3, N(R.sup.3).sub.2, SC(O)R.sup.3, SH, SO.sub.3H, and SR.sup.3, wherein R.sup.3 is a carbon-containing group.

[0080] In embodiments the derivatized succinate corrosion inhibitors of structure 6 are synthesized according to a process comprising reacting maleic anhydride with an alcohol to form a maleate diester intermediate 3, and thereafter reacting the maleate diester intermediate with a 1,2-diamine by an aza-Michael addition to form 1:1 mixtures of a lactam corrosion inhibitor having the general structure or salts thereof

##STR00018##

and an alcohol having the general structure R.sup.1OH, wherein R.sup.1 is an carbon-containing group, and wherein R.sup.2 is independently H or a carbon-containing group.

[0081] In embodiments methods of making the derivatized succinate corrosion inhibitors of structure 6 are depicted in FIG. 3 where the reaction of maleate diester 3 with a 1,2-diamine generates the lactam 6 along with one equivalent of alcohol 7. The fatty alcohols are surface active and potential corrosion inhibitors themselves, and often biodegradable, making this synthesis of lactams according to structure 6 in combination with a fatty alcohol desirable.

[0082] In embodiments the molar ratio of the maleic diester intermediate to the diamine is about 1:1. In embodiments the diamine has the general structure H.sub.2N(CH.sub.2).sub.2NHR.sup.2 wherein R.sup.2 is H or a carbon containing group. In embodiments the derivatized succinate corrosion inhibitors of structure 8 are synthesized according to a process comprising reacting maleic anhydride with an alcohol to form a maleic ester acid intermediate, and thereafter reacting the maleic ester acid intermediate with a diamine by an aza-Michael addition to form the derivatized succinate corrosion inhibitor having the general structure or salts thereof

##STR00019##

wherein R.sup.1 is independently H or a carbon-containing group, and L.sup.1 is a diamine linker having the general structure HN-L.sup.3-NH wherein L.sup.3 is a bifunctional carbon-containing group. In embodiments L.sup.1 is a diamine linker having the general structure HN(CH.sub.2).sub.xNR.sup.2 wherein x is an integer of 3 or greater. In other embodiments L.sup.1 is a diamine linker having the general structure HN((CH.sub.2).sub.x)O).sub.y)(CH.sub.2).sub.2NH wherein x is an integer from 1 to 6 and y is an integer from 1 to 30.

[0083] In embodiments methods of making the derivatized succinate corrosion inhibitors of structure 8 are depicted in FIG. 4, which shows the reaction of a diamine with greater than two atoms distance between nitrogen atoms react with maleate esters 2 and 3 to give bridged amino acids without cyclized product formation, as a result of the instability of larger ring sizes. As shown in FIG. 4, 1,6-hexamethylenediamine reacts with two equivalents of maleate 2 to give the bis-(amino acid) 8 with a hexamethylene linker wherein one of four possible regioisomers is depicted. Beneficially these larger corrosion inhibitor structures derived from multi-functional polyamines can have high molecular weight, preferably a molecular weight above 700 Da so as to be deemed to not bioaccumulate and have relaxed biodegradability requirements compared to smaller molecules.

[0084] In embodiments the molar ratio of the maleic ester acid intermediate and/or the maleate diester intermediate to the diamine is from about 5:1 to about 1:2, and preferably about 2:1.

[0085] As an alternative strategy to large molecule synthesis, FIG. 5 shows maleic anhydride reacted with polyols to form polyesters, such as 9 formed from ethylene glycol. Reaction with two equivalents of amine then affords poly-(amino acids) such as 10 with the linkage being at the ester group.

[0086] In embodiments the derivatized succinate corrosion inhibitors of structure 10 or salts thereof are synthesized according to a process comprising reacting maleic anhydride with a polyol to form a polyester intermediate, and thereafter reacting the polyester intermediate with an amine, thiol, thioester, or sulfite salt by addition to form the derivatized succinate corrosion inhibitor or salt thereof having the general structure or salts thereof

##STR00020##

wherein Z is a nitrogen or sulfur-containing group and L.sup.2 is a diamine, a polyether or polyol linker. In embodiments Z is selected from the group consisting of NHR.sup.3, N(R.sup.3).sub.2, SC(O)R.sup.3, SH, SO.sub.3H, and SR.sup.3, wherein R.sup.3 is a carbon-containing group. In further embodiments the diamine linker L.sup.2 has the general structure HN-L.sup.3-NH wherein L.sup.3 is a bifunctional carbon containing group. In further embodiments the diamine linker L.sup.2 has the general structure H.sub.2N(CH.sub.2).sub.xNHR.sup.2 wherein x is an integer of 3 or greater, or the general structure HN((CH.sub.2).sub.xO).sub.y(CH.sub.2).sub.xNH wherein x is an integer from 1 to 6 and y is an integer from 1 to 30, or wherein the polyol linker has the structure O((CH.sub.2).sub.xO).sub.y wherein x is an integer from 1 to 6 and y is an integer from 1 to 30.

[0087] FIG. 6 further shows reactions of maleates with thiols to synthesize additional corrosion inhibitors of structure 1 (shown as 11a and 11b). The reaction of the maleates with thiols instead of amines produces derivatives of 1 where Z contains a sulfur atom. The thioethers 11a and 11b are formed from the addition of thiol to maleate 2.

[0088] FIG. 7 further shows reactions with thiocarboxylic acids, where maleates react to provide thioesters. For example, maleate 2 reacts with thioacetic acid in the presence of catalytic base to give thioesters 12a and 12b, which are readily hydrolyzed when applied to produced water to give free thiols 13a and 13b, capable of strong interaction with metal surfaces.

[0089] In additional embodiments for methods of making derivatized succinate corrosion inhibitors, methods of making sulfonated succinates of general structure 14 are depicted in FIG. 8, which shows the reaction of maleate ester 2 with sulfite salts to form sulfonate isomers 14a and 14b. Suitable sulfite salts include sodium sulfite, sodium bisulfite, sodium metabisulfite and the corresponding potassium salts. The sulfites can also be prepared in situ by the addition of sulfur dioxide to aqueous conditions.

[0090] In embodiments carboxylic acid, amino acid, and sulfonic acid succinate derivatives of 1, 8, and 10 can be converted into salts with various cations by reaction with a corresponding base, such as the hydroxide, carbonate, or phosphate salt of the cation. Exemplary cations include sodium, potassium, lithium, ammonium, magnesium, calcium, strontium, barium, aluminum, tetramethylammonium, tetrabutylammonium, and combinations thereof.

[0091] In embodiments carboxylic acid, amino acid, and sulfonic acid succinate derivatives of 1, 8, and 10 can be converted into ammonium salts by reaction with various amines. Exemplary amines include ammonia, methylamine, ethylamine, butylamine, monoethanolamine, diethanolamine, triethanolamine, pyridine, piperidine, pyrrolidine, morpholine, quinoline, and combinations thereof.

[0092] In embodiments amino acid succinate derivatives of 1, 6, 8, and 10 can be converted into salts with various anions by reaction with the corresponding acid. Exemplary anions include chloride, bromide, iodide, acetate, lactate, formate, citrate, sulfate, bisulfate, perchlorate, phosphate, hydrogen phosphate, dihydrogen phosphate, and combinations thereof.

[0093] The aforementioned salts of succinate derivatives beneficially exhibit enhanced water solubility than the neutral compounds from which they are derived, enhancing their partition behavior in multi-phase fluids and improving their ability to inhibit corrosion.

Solvent

[0094] The corrosion-inhibiting compositions can include a solvent. Exemplary solvents include organic solvents, including aromatic solvents, and/or water.

[0095] Exemplary organic solvents include alcohols, hydrocarbons, ketones, ethers, alkylene glycols, glycol ethers, amides, nitriles, sulfoxides, esters, or a combination thereof. Examples of suitable organic solvents include, but are not limited to, methanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexanol, hexanol, octanol, decanol, 2-butoxyethanol, glycols and derivatives (ethylene glycol, methylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethyleneglycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, etc.), pentane, hexane, cyclohexane, methylcyclohexane, heptane, decane, dodecane, diesel, toluene, xylene, heavy aromatic naphtha, cyclohexanone, diisobutylketone, diethyl ether, propylene carbonate, N-methylpyrrolidinone, N,N-dimethylformamide, or a combination thereof. In preferred embodiments a solvent comprises isopropanol, ethylene glycol, methanol, and/or water.

[0096] Exemplary additional solvents include aromatic solvents including aromatic hydrocarbons such as toluene, xylene, heavy aromatic naphtha, or a combination thereof. Environmentally friendly aromatic solvents can include limonene. Preferably, the aromatic solvent comprises heavy aromatic naphtha or xylene.

[0097] In embodiments the solvent is one or more of water, alcohol and/or hydrocarbon solvent. Preferred hydrocarbon solvents can include, for example, paraffins and aromatic distillates, carboxylic acids, glycols, glycol ethers, and combinations thereof.

[0098] In some embodiments, the solvent is included in the composition at an amount of at least about 10 wt-% to about 99.9 wt-%, about 10 wt-% to about 99 wt-%, about 20 wt-% to about 99 wt-%, about 30 wt-% to about 99 wt-%, about 40 wt-% to about 99 wt-%, about 50 wt-% to about 99 wt-%, about 50 wt-% to about 90 wt-%, about 50 wt-% to about 85 wt-%, about 50 wt-% to about 80 wt-%, or about 50 wt-% to about 75 wt-%. In addition, without being limited according to the disclosure, all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.

Additional Functional Ingredients

[0099] The corrosion-inhibiting compositions can further be combined with various additional functional components suitable for uses disclosed herein. In some embodiments, the compositions including the derivatized succinate corrosion inhibitor and solvent make up a large amount, or even substantially all of the total weight of the compositions. For example, in some embodiments few or no additional functional ingredients are disposed therein. In some embodiments, the composition comprises, consists essentially of, or consists of the derivatized succinate corrosion inhibitor and solvent.

[0100] In some embodiments the compositions and methods of using the compositions do not include corrosion inhibitors having a molecular weight <700 Da or those that bioaccumulate according to regulatory agencies to present environmental concerns.

[0101] In other embodiments, additional functional ingredients may be included in the compositions. The functional ingredients provide desired properties and functionalities to the compositions. For the purpose of this application, the term functional ingredient includes a material that when dispersed or dissolved in the use and/or concentrate compositions described herein provides a beneficial property in a particular use.

[0102] In some embodiments, the compositions may include additional corrosion inhibitors, surfactants, corrosion inhibitor intensifiers (i.e. synergists), polymers, pH modifiers, scale inhibitors, metal complexing agents (i.e. chelants), emulsifiers, water clarifiers, demulsifiers, friction reducers, drag reducing agents, flow improvers, viscosity reducers, sulfur compounds, the like, or combinations thereof.

[0103] In further embodiments, the composition may include at least one additional functional ingredient is selected from the group consisting of synergist, additional corrosion inhibitor, surfactant, polymer, pH modifier, asphaltene inhibitors, paraffin inhibitors, scale inhibitor, metal complexing agent, emulsifier, water clarifier, dispersant, emulsion breaker, and combinations thereof.

[0104] Exemplary types of the various additional functional ingredients is included in U.S. Pat. No. 11,242,480, which is incorporated by reference in its disclosure of the various listings of additional functional ingredients.

[0105] According to embodiments of the disclosure, the various additional functional ingredients may be provided in a composition in the amount from about 0 wt-% and about 40 wt-%, from about 0 wt-% and about 30 wt-%, from about 0 wt-% and about 20 wt-%, from about 0.01 wt-% and about 40 wt-%, from about 0.1 wt-% and about 40 wt-%, from about 0.1 wt-% and about 30 wt-%, from about 0.1 wt-% and about 20 wt-%, or from about 1 wt-% and about 20 wt-%, from about 0.1 wt-% and about 10 wt-%, or from about 1 wt-% and about 10 wt-%. In addition, without being limited according to the disclosure, all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range. Additional examples of additional functional ingredients are listed herein as exemplary wt-% ranges based on the total weight of the compositions, in addition these weight percentage ranges.

[0106] The compositions can optionally include corrosion inhibitor intensifiers (i.e. synergists), also referred to as an additive that enhances the performance of corrosion inhibition. Suitable intensifiers may include, but are not limited to, carboxylic acid compounds having 1 to 12 carbon atoms or an ester (including protected carboxylic acid derivatives) or salt thereof, quaternary ammonium compounds, thiol chemistries and others when used in combination with a corrosion inhibitor.

[0107] The compositions can optionally include additional corrosion inhibitors. An exemplary additional corrosion inhibitor includes for example carboxylic acids. Carboxylic acids include organic acids having carboxyl group attached to an R-group (RCOOH). In some embodiments, the carboxylic acid is a fatty acid, such as monomeric or oligomeric fatty acid. Exemplary monomeric or oligomeric fatty acids can include saturated and unsaturated fatty acids as well as dimer, trimer and oligomer products obtained by polymerizing one or more of such fatty acids. Additional optional corrosion inhibitors include alkanolamines or salts thereof. Exemplary alkanolamines or salts thereof can include for example, fatty acid alkanolamines, fatty acid ethanolamines, fatty acid diethanolamines or triethanolamines, such as dicarboxylic acid diethanolamines, and salts thereof. Additional optional corrosion inhibitors include phosphate esters. Exemplary phosphate esters include for example, monoalkylphosphates, dialkylphosphates, trialkylphosphates, and salts thereof.

[0108] The compositions can optionally include a surfactant. Suitable surfactants include, but are not limited to, anionic surfactants, cationic 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, and alkyl and ethoxylated alkyl phosphate esters, and mono and dialkyl sulfosuccinates and sulfosuccinamates. Cationic surfactants include quaternary ammonium or phosphonium salts, including salts of tetraalkylammonium, benzyltrialkylammonium, and imidazolium ions. Nonionic surfactants include alcohol alkoxylates, alkylphenol alkoxylates, block copolymers of ethylene, propylene and butylene oxides, alkyl dimethyl amine oxides, alkyl-bis(2-hydroxyethyl) amine oxides, alkyl amidopropyl dimethyl amine oxides, alkylamidopropyl-bis(2-hydroxyethyl) amine oxides, alkyl polyglucosides, polyalkoxylated glycerides, sorbitan esters and polyalkoxylated sorbitan esters, and alkoyl polyethylene glycol esters and diesters. Also included are betaines and sultanes, amphoteric surfactants such as alkyl amphoacetates and amphodiacetates, alkyl amphopropionates and amphodipropionates, and alkyliminodipropionate.

[0109] The compositions can optionally include pH modifiers. Suitable pH control additives include, but are not limited to, alkali hydroxides, alkali carbonates, alkali bicarbonates, alkaline earth metal hydroxides, alkaline earth metal carbonates, alkaline earth metal bicarbonates and mixtures or combinations thereof. Exemplary pH modifiers include sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, magnesium oxide, and magnesium hydroxide.

[0110] The compositions can optionally include a demulsifier. An exemplary demulsifier comprises an oxyalkylate polymer, such as a polyalkylene glycol. The demulsifier can be included in the compositions from about 0.5 to about 5 wt-% of the composition, based on total weight of the composition.

[0111] The compositions can optionally include a dispersant. Suitable dispersants include, but are not limited to, aliphatic phosphonic acids with 2-50 carbons, such as hydroxyethyl diphosphonic acid, and aminoalkyl phosphonic acids, e.g. polyaminomethylene phosphonates with 2-10 N atoms e.g. each bearing at least one methylene phosphonic acid group; examples of the latter are ethylenediamine tetra(methylene phosphonate), diethylenetriamine penta(methylene phosphonate), and the triamine- and tetramine-polymethylene phosphonates with 2-4 methylene groups between each N atom, at least 2 of the numbers of methylene groups in each phosphonate being different. Other suitable dispersion agents include lignin, or derivatives of lignin such as lignosulfonate and naphthalene sulfonic acid and derivatives. The dispersant can be included in the compositions from about 0.1 to about 10 wt-% of the composition, based on total weight of the composition.

Methods of Use

[0112] In addition to the derivatized succinate corrosion inhibitors described herein and the corrosion inhibiting compositions comprising a derivatized succinate corrosion inhibitor are methods of use for controlling corrosion. Methods for controlling corrosion on a surface comprise contacting a corrosive inhibiting effective amount of a corrosion inhibition composition comprising a derivatized succinate corrosion inhibitor as described herein with a metal surface in a system, wherein the contacting is added in a batch or continuous application, and reducing corrosion on the surface.

[0113] In embodiments the derivatized succinate corrosion inhibitors or the corrosion-inhibiting compositions are provided to a system in need of effective corrosion control in the presence of corrodents. The methods of using the derivatized succinate corrosion inhibitors or the corrosion-inhibiting compositions provide environmentally friendly solutions for corrosion inhibition performance and persistency, thereby beneficially increasing the lifespan of the corrosion-inhibiting composition. In some embodiments the presence of a film on a treated surface can beneficially provide lubrication and improve wear and friction with the addition of the film to reduce the wear and friction between moving surfaces, e.g. case tubing and casing, in contact with each other. In other embodiments the corrosion-inhibiting compositions can treat a water system.

[0114] The derivatized succinate corrosion inhibitor or the corrosion-inhibiting compositions can be provided in a single composition to a system. In referring to compositions, the scope of the methods of using disclosure also includes combining more than one input (i.e. composition) for the treatment of the system in need of corrosion inhibition. In preferred embodiments a single composition provides the derivatized succinate corrosion inhibitor or the corrosion-inhibiting compositions.

[0115] The methods apply the compositions to a fluid or to a surface to prevent, reduce or mitigate corrosion. The mils penetration per year or milli-inch (one thousandth of an inch) (mpy) is used as an estimated general corrosion rate as it refers to the metal thickness lost in the corrosion process per year. 1 mm y.sup.1 equates to about 40 mpy. The MPY is calculated from the following equation:

[00001]$\mathrm{MPY}=\left(M\left[g\right].Math.C\right)/\left(\left[\frac{g}{{\mathrm{cm}}^2}\right].Math.A\left[{\mathrm{in}}^2\right].Math.t\left[\mathrm{hr}\right]\right)$

where M is the mass loss of the coupon at the end of the test in grams, C is a constant equal to 534000, is the density of the coupon in g/cm.sup.2, A is the surface area of the coupon in cm.sup.2, and t is the exposure time in hours. In an embodiment, the corrosion inhibiting compositions provide a reduction in corrosion measured by a milli-inches per year (mpy).

[0116] The methods may be applied to fluid systems or onto a surface, such as a containment in contact with fluid systems (also can be referred to as a water source comprising one or more corrodents), including those fluid systems moving through conduits, pipelines, tubulars, transfer lines, valves, and other places or equipment where hydrocarbon fluids are subject to corrosion. In embodiments, the surface can be a containment used in the production, transportation, storage and/or separation of crude oil, natural gas or a biofuel process, downstream chemical, water treatment, geothermal, and other fields.

[0117] In some embodiments, a treated metal containment can include the metal containment and a barrier or film substantially coating the metal surface with a corrosive inhibiting effective amount of the compositions or the derivatized succinate corrosion inhibitors described herein. In embodiments, the corrosive inhibiting effective amount of the derivatized succinate corrosion inhibitor is from about 0.1 ppm to about 5,000 ppm, or from about 1 ppm to about 1,000 ppm, based on the total volume of the containment.

[0118] In embodiments a water source or the fluid system can include an industrial water source, such as a produced water. In embodiments, the water source is a wastewater from an industrial process. The water source comprises one or more corrodents. In some embodiments, the water source comprises water and one or more corrodents, wherein the one or more corrodents comprises, consists essentially of, or consists of metal cations, metal complexes such as aqueous metal cations, metal chelates and/or organometallic complexes, aluminum ions, ammonium ions, barium ions, chromium ions, cobalt ions, cuprous ions, cupric ions, calcium ions, ferrous ions, ferric ions, hydrogen ions, magnesium ions, manganese ions, molybdenum ions, nickel ions, potassium ions, sodium ions, strontium ions, titanium ions, uranium ions, vanadium ions, zinc ions, bromide ions, carbonate ions, chlorate ions, chloride ions, chlorite ions, dithionate ions, fluoride ions, hypochlorite ions, iodide ions, nitrate ions, nitrite ions, oxide ions, perchlorate ions, peroxide ions, phosphate ions, phosphite ions, sulfate ions, sulfide ions, sulfite ions, hydrogen carbonate ions, hydrogen phosphate ions, hydrogen phosphite ions, hydrogen sulfate ions, hydrogen sulfite ions, carbonic acid, hydrochloric acid, nitric acid, sulfuric acid, nitrous acid, sulfurous acid, peroxy acids, phosphoric acid, ammonia, bromine, carbon dioxide, chlorine, chlorine dioxide, fluorine, hydrogen chloride, hydrogen sulfide, iodine, nitrogen dioxide, nitrogen monoxide, oxygen, ozone, sulfur dioxide, hydrogen peroxide, polysaccharide, or combinations thereof.

[0119] In some embodiments, the one or more corrodents comprises, consists of, or consists essentially of insoluble particulates such as metal oxides, sands, clays, silicon dioxide, titanium dioxide, muds, and other insoluble inorganic and/or organic particulates, which in some embodiments act as abrasives when entrained in a water flow contacting a metal.

[0120] In embodiments, a metal surface is in contact with the water source, such as a carbon steel metal surface. In embodiments the carbon steel is stainless steel. In embodiments, the water source is a continuously flowing water source, such as produced water flowing from a subterranean reservoir and into or through a pipe or tank, or wastewater isolated from a continuous manufacturing process flowing into a wastewater treatment apparatus. In other embodiments, the water source is a batch, or plug, substantially disposed in a batchwise or static state within the metal containment.

[0121] The derivatized succinate corrosion inhibitors or the compositions can be applied to a fluid system at various pH ranges, such as between about 2 to about 10, and temperatures, such as from about 0 C. to about 250 C., as well as various levels of water cut and/or various levels of salinity. The derivatized succinate corrosion inhibitors or the compositions can also be applied to a fluid system at various water cuts and salinity.

[0122] In embodiments, the fluid system comprises a hydrocarbon fluid, produced water, waste water from a manufacturing process, or combination thereof. As referred to herein, hydrocarbon fluid comprises crude oil, heavy oil, processed residual oil, bituminous oil, coker oils, coker gas oils, fluid catalytic cracker feeds, gas oil, naphtha, fluid catalytic cracking slurry, diesel fuel, fuel oil, jet fuel, gasoline, kerosene, or combinations thereof. In many embodiments, hydrocarbon fluids comprise refined hydrocarbon product.

[0123] In embodiments the fluid system is contained in an oil or gas pipeline or refinery, including both offshore wells and on-shore wells. In embodiments the surface treated with the derivatized succinate corrosion inhibitors or the corrosion-inhibiting compositions are metal surfaces in contact with fluid systems moving there through, including for example, conduits, pipelines, tubulars, transfer lines, valves, and other places or equipment where hydrocarbon fluids are subject to corrosion. In an embodiment, the metal surface is used in recovery of a hydrocarbon fluid is an offshore well or an onshore well. In an embodiment, the metal surface is used in recovery of a hydrocarbon fluid and is a downhole pumping rod.

[0124] A fluid to which the derivatized succinate corrosion inhibitors or the compositions can be introduced can be a liquid hydrocarbon. The liquid hydrocarbon can be any type of liquid hydrocarbon. The fluid can be a refined hydrocarbon product.

[0125] The fluid can be contained in and/or exposed to many different types of apparatuses. In embodiments, the fluid is contained in a containment, such as an oil and gas pipeline. Additionally, the fluid can be contained in refineries, such as surfaces used in the recovery, transportation, refining and/or storage of hydrocarbon fluids or gases. Exemplary surfaces can include separation vessels, dehydration units, gas lines, oil and/or gas pipelines, or other part of an oil and/or gas refinery. Similarly, the fluid can be contained in and/or exposed to an apparatus used in oil extraction and/or production, such as a wellhead. The apparatus can be part of a coal-fired power plant. The apparatus can be a cargo vessel, a storage vessel, a holding tank, or a pipeline connecting the tanks, vessels, or processing units.

[0126] The system to be treated has at least one surface susceptible to corrosion, namely the surface comprises a metal surface subject to corrosion. In embodiments the surfaces can include a variety of metal surfaces that are subject to corrosion. The metals can comprise a component selected from the group consisting of mild steel, galvanized steel, carbon steel, aluminum, aluminum alloys, copper, copper nickel alloys, copper zinc alloys, brass, chrome steels, ferritic alloy steels, austenitic stainless steels, precipitation-hardened stainless steels, high nickel content steels, and any combination thereof.

[0127] The derivatized succinate corrosion inhibitors or the compositions can be applied by any appropriate method for ensuring dispersal through the fluid or onto a surface, including for example injecting, pumping, pouring, spraying, dripping, or otherwise adding. The derivatized succinate corrosion inhibitors or the compositions can be applied to a fluid using various well-known methods and they can be applied at numerous different locations throughout a given system. For example, the derivatized succinate corrosion inhibitors or the compositions can be injected using mechanical equipment such as chemical injection pumps, piping tees, injection fittings, atomizers, quills, and the like. The derivatized succinate corrosion inhibitors or the compositions can be pumped into an oil and/or gas pipeline using an umbilical line, including capillary string injection systems. U.S. Pat. No. 7,311,144 provides a description of an apparatus and methods relating to capillary injection, the disclosure of which is incorporated into the present application in its entirety.

[0128] The method comprises adding a corrosion inhibiting effective amount of the derivatized succinate corrosion inhibitors or the composition to the fluid system or onto a surface as a batch dosing to provide a film-like coating on a treated surface, such as a containment. Batch dosing is intended to substantially or preferably fully coat the surface, such as a containment. In embodiments the derivatized succinate corrosion inhibitors or the composition is applied as a direct batch application to fully coat the metal surface at a desired concentration, such as from about 0.1 ppm to about 1,000,000 ppm, from about 0.1 ppm to about 5,000 ppm, or from about 1 ppm to about 1,000 ppm based on the total volume of the fluid system or the system to be treated.

[0129] The dosage amounts of the derivatized succinate corrosion inhibitors or the compositions described herein to be added to the fluid system or onto a surface within an oil-and-gas system, can be tailored by one skilled in the art based on factors for each fluid system in need of treatment, including, for example, content of fluid, volume of the fluid, surface area of the system, CO.sub.2 content, temperatures, pH, and CO.sub.2 content. In embodiments, an effective amount of the derivatized succinate corrosion inhibitors or the corrosion-inhibiting composition is from about 0.1 ppm to about 1,000,000 ppm, about 0.1 ppm to about 5,000 ppm, or from about 1 ppm to about 5,000 ppm based on the total volume of the system (i.e. the volume of the fluid treated or the volume of the system to be treated according to the methods described herein).

[0130] In embodiments where the derivatized succinate corrosion inhibitors or the composition is added to the fluid system in a batch dosing in-line or offline. In embodiments, offline dosing provides a slug dosing suitable to coat the surfaces (e.g. containment) to provide barrier to the corrodents when the system is back in-line. The embodiments of batch dosing can be done when with or without fluid in the system. In embodiments, batch treatments can use up to 100% of the corrosion-inhibiting compositions applied between two spheres (e.g. pigs, as referred to in the industry) to fully coat the surface. In embodiments, the batch treatments can be applied with a diluent (e.g. diesel, hydrocarbon, etc.) between about 20-80%, often about 50%, dependent upon operator preference.

[0131] In embodiments the batch derivatized succinate corrosion inhibitors or the composition can be applied at varying frequencies dependent upon the severity of the operating environment and conditions. In an embodiment, the derivatized succinate corrosion inhibitors or the corrosion-inhibiting compositions can be applied weekly, every other week, monthly, or quarterly. The methods described herein beneficially reduce the frequency of batch corrosion inhibitor application as a result of the derivatized succinate corrosion inhibitors or the corrosion-inhibiting compositions enhancing the film persistency of the compositions to improve the lifespan of the applied film while also decreasing the frequency of the chemical applications. This reduction in the frequency of chemical applications beneficially reduces costs while also decreasing chemical usage to streamline logistics, reduce chemical handling and any potential associated health and safety risks, reduces the operator's carbon footprint and thereby increasing sustainability of operations. The reduction in the frequency of chemical applications also reduces the need to employ more expensive coatings on infrastructure surfaces.

[0132] In embodiments the derivatized succinate corrosion inhibitors or the composition is added at a flow rate of a flow line in which the composition is used that can be between 0 and 100 feet per second, or between 0.1 and 50 feet per second. The bridged imidazoline corrosion inhibitors or the compositions can be formulated with water in order to facilitate addition to the flow line.

[0133] In embodiments where the derivatized succinate corrosion inhibitors or the composition is added to the fluid system in a batch dosing application, the derivatized succinate corrosion inhibitors or the corrosion-inhibiting compositions provide improved corrosion inhibition in a system or on the treated surface as measured by reduced milli-inches per year (mpy). The dosing of the derivatized succinate corrosion inhibitors or the corrosion-inhibiting compositions as batch inhibitors allows the chemistry to be applied directly onto the surface and form a film on the surface to act as a barrier to corrosion, including a barrier to the water electrolytes causing corrosion.

EMBODIMENTS

[0134] The present disclosure is further defined by the following numbered embodiments:

[0135] 1. A method of reducing corrosion on a surface comprising: contacting a corrosive inhibiting effective amount of a corrosion inhibition composition comprising a derivatized succinate corrosion inhibitor with a metal surface in a system, wherein the contacting is added in a batch or continuous application, and reducing corrosion on the surface, wherein the derivatized succinate corrosion inhibitor has at least one of the following general structures or salts thereof:

##STR00021##

wherein R.sup.1 and R.sup.2 are independently H or a carbon-containing group, Z is a nitrogen or sulfur-containing group, L.sup.1 is a diamine linker, and L.sup.2 is a diamine, polyether or polyol linker.

[0136] 2. The method of embodiment 1, wherein for the derivatized succinate corrosion inhibitor has the general structure 1 wherein one of R.sup.1 or R.sup.2 is H and the other R group is a carbon-containing group, or wherein both of R.sup.1 or R.sup.2 are H and Z is NHR.sup.3, SR.sup.3, or SO.sub.3H, wherein R.sup.3 is a carbon containing group.

[0137] 3. The method of embodiment 1, wherein the derivatized succinate corrosion inhibitor has the general structure 6 wherein no more than one of R.sup.1 or R.sup.2 is H and the other R group or groups are carbon-containing groups, and optionally is the presence of an alcohol having the general structure ROH, wherein R is a carbon-containing group.

[0138] 4. The method of embodiment 1, wherein Z is selected from the group consisting of NHR.sup.3, N(R.sup.3).sub.2, SC(O)R.sup.3, SH, SO.sub.3H, and SR.sup.3, wherein R.sup.3 is a carbon-containing group.

[0139] 5. The method of embodiments 1 or 4, wherein L.sup.1 or L.sup.2 is a diamine linker having the general structure HN-L.sup.3-NH wherein L.sup.3 is a bifunctional carbon containing group, or L.sup.2 is a polyether linker having the structure O((CH.sub.2).sub.xO).sub.y wherein x is an integer from 1 to 6 and y is an integer from 1 to 30.

[0140] 6. The method of any one of embodiments 1-5, wherein the derivatized amino acid-based or derivatized sulfur-based corrosion inhibitor makes up from about 0.1 wt-% to about 80 wt-% of the composition.

[0141] 7. The method of any one of embodiments 1-6, further comprising a solvent and/or at least one additional functional ingredient.

[0142] 8. The method of embodiment 7, wherein the solvent comprises water, alcohols, hydrocarbon solvents, and/or wherein the at least one additional functional ingredient is selected from the group consisting of synergist, additional corrosion inhibitors, surfactants, polymers, pH modifiers, asphaltene inhibitors, paraffin inhibitors, scale inhibitors, metal complexing agents (chelants), emulsifiers, water clarifiers, dispersants, emulsion breakers and combinations thereof.

[0143] 9. The method of any one of embodiments 1-8, wherein the corrosive inhibiting effective amount of the derivatized succinate corrosion inhibitor is from about 0.1 ppm to about 5000 ppm, or from about 1 ppm to about 1000 ppm, based on the total volume of the system.

[0144] 10. The method of any one of embodiments 1-9, wherein the surface is a containment used in the production, transportation, storage and/or separation of crude oil, natural gas or a biofuel process, downstream chemical application, water treatment application, or geothermal application.

[0145] 11. The method of any one of embodiments 1-10, wherein the system comprises a hydrocarbon fluid or gas, produced water, or combination thereof.

[0146] 12. A treated metal containment comprising: a metal containment comprising a metal surface; and a barrier or film substantially coating the metal surface with a corrosive inhibiting effective amount a derivatized succinate corrosion inhibitor having at least one of the following general structures or salts thereof:

##STR00022##

wherein R.sup.1 and R.sup.2 are independently H or a carbon-containing group, Z is a nitrogen or sulfur-containing group, I is a diamine linker, and L.sup.2 is a diamine, polyether or polyol linker.

[0147] 13. The treated metal containment of embodiment 12, wherein the corrosive inhibiting effective amount of the derivatized succinate corrosion inhibitor is from about 0.1 ppm to about 5000 ppm, or from about 1 ppm to about 1000 ppm, based on the total volume of the containment.

[0148] 14. A treated water source comprising: a water source comprising one or more corrodents; and a corrosive inhibiting effective amount a derivatized succinate corrosion inhibitor having at least one of the following general structures or salts thereof:

##STR00023##

wherein R.sup.1 and R.sup.2 are independently H or a carbon-containing group, Z is a nitrogen or sulfur-containing group, I is a diamine linker, and L.sup.2 is a diamine or polyether linker.

[0149] 15. The treated water source of embodiment 14, wherein the corrosive inhibiting effective amount of the derivatized succinate corrosion inhibitor is from about 0.1 ppm to about 5000 ppm, or from about 1 ppm to about 1000 ppm, based on the total volume of the containment.

[0150] 16. A method of making a derivatized succinate corrosion inhibitor comprising: reacting maleic anhydride with an alcohol to form a maleic ester acid intermediate, and thereafter reacting the maleic ester acid intermediate or maleic acid with an amine or a sulfur containing compound by addition to form the derivatized succinate corrosion inhibitor having the general structure

##STR00024##

or salts thereof, wherein one of R.sup.1 or R.sup.2 is H and the other R group is a carbon-containing group, or wherein both of R.sup.1 or R.sup.2 are H and Z is NHR.sup.3, N(R.sup.3).sub.2, or SR.sup.3, wherein R.sup.3 is a carbon containing group, and Z is a nitrogen or sulfur-containing group.

[0151] 17. The method of embodiment 16, wherein the molar ratio of the maleic anhydride to the alcohol is from about 0.1:1 to about 1:0.1, and preferably about 1:1.

[0152] 18. The method of any one of embodiments 16-17, wherein the amine is a primary or secondary amine or wherein the sulfur-containing compound is a thiol or a thioacid.

[0153] 19. The method of any one of embodiments 16-18, wherein the derivatized succinate corrosion inhibitor is an isomeric mixture with the general structures

##STR00025##

wherein Z is selected from the group consisting of NHR.sup.3, N(R.sup.3).sub.2, SC(O)R.sup.3, SH, SO.sub.3H, and SR.sup.3, wherein R.sup.3 is a carbon-containing group.

[0154] 20. A method of making a derivatized succinate corrosion inhibitor comprising: reacting maleic anhydride with an alcohol to form a maleate diester intermediate, and thereafter reacting the maleate diester intermediate with a 1,2-diamine by an aza-Michael addition to form mixtures of a lactam corrosion inhibitor having the general structure

##STR00026##

and an alcohol having the general structure R.sup.1OH, wherein R.sup.1 is a carbon-containing group, and wherein R.sup.2 is independently H or a carbon-containing group.

[0155] 21. The method of embodiment 20, wherein the molar ratio of the maleic diester intermediate to the diamine is about 1:1.

[0156] 22. The method of any one of embodiments 20-21, wherein the 1,2-diamine has the general structure H.sub.2N(CH.sub.2).sub.2NHR.sup.2 wherein R.sup.2 is H or a carbon-containing group.

[0157] 23. A method of making a derivatized succinate corrosion inhibitor comprising: reacting maleic anhydride with an alcohol to form a maleic ester acid intermediate, and thereafter reacting the maleic ester acid intermediate with a diamine by an aza-Michael addition to form the derivatized succinate corrosion inhibitor having the general structure or salts thereof

##STR00027##

wherein R.sup.1 is independently H or a carbon-containing group, and L.sup.1 is a diamine linker.

[0158] 24. The method of embodiment 23, wherein the molar ratio of the maleic ester acid intermediate and/or the maleate diester intermediate to the diamine is from about 5:1 to about 1:2, and preferably about 2:1.

[0159] 25. The method of any one of embodiments 23-24, wherein the diamine linker has the general structure HN-L.sup.3-NH wherein L.sup.3 is a bifunctional carbon-containing group.

[0160] 26. A method of making a derivatized succinate corrosion inhibitor comprising: reacting maleic anhydride with a polyol to form a polyester intermediate, and thereafter reacting the polyester intermediate with an amine, thiol, thioester, or sulfite salt by addition to form the derivatized succinate corrosion inhibitor having the general structure or salt thereof

##STR00028##

wherein Z is a nitrogen or sulfur-containing group and L.sup.2 is a diamine or a polyether linker.

[0161] 27. The method of embodiment 26, wherein Z is selected from the group consisting of NHR.sup.3, N(R.sup.3).sub.2, SC(O)R.sup.3, SH, SO.sub.3H, and SR.sup.3, wherein R.sup.3 is a carbon-containing group.

[0162] 28. The method of any one of embodiments 26-27, wherein the diamine linker has the general structure HN-L.sup.3-NH wherein L.sup.3 is a bifunctional carbon containing group, or wherein the polyol linker has the structure O((CH.sub.2).sub.xO).sub.y wherein x is an integer from 1 to 6 and y is an integer from 1 to 30.

Examples

[0163] Embodiments of the present disclosure are further defined in the following non-limiting Examples. It should be understood that these Examples, while indicating certain embodiments of the disclosure, are given by way of illustration only. From the above discussion and these Examples, one skilled in the art can ascertain the essential characteristics of this disclosure, and without departing from the spirit and scope thereof, can make various changes and modifications of the embodiments of the disclosure to adapt it to various usages and conditions. Thus, various modifications of the embodiments of the disclosure, in addition to those shown and described herein, will be apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims.

Example 1

Synthesis of N-(2-ethylhexyl)aspartic acid, C12-15-alkyl ester (General Structure 1)

[0164] A mixture of 65.50 grams of maleic anhydride and 133.80 grams of C12-15 alcohol (i.e. Shell Neodol 25) was mixed in a one-liter two-piece reactor equipped with a mechanical stirrer and thermocouple at 65 C. under slow agitation. After all the solid had melted, the stir rate was increased to 300 rotations per minute (rpm) and the reaction was allowed to exotherm to 90 C. This temperature and mixing were maintained for two hours before cooling to room temperature. In a 2-ounce jar was warmed 8.00 g of this reaction product to melting and 3.45 g of 2-ethylhexylamine was added. The lid was sealed, the contents were shaken, and then heated to 85 C. for 18 hours. Upon cooling to room temperature, the product was a yellow waxy solid.

Example 2

Synthesis of N-oleylaspartic acid, iso-C11-14-alkyl ester (General Structure 1)

[0165] A mixture of 68.01 g of maleic anhydride and 139.25 g of iso-C11-14 alcohol (Exxal 13, Exxon-Mobil) was mixed in a one-liter two-piece reactor equipped with a mechanical stirrer and thermocouple at 65 C. under slow agitation. Once all the solid had melted, the stir rate was increased to 300 rpm and the reaction was allowed to exotherm to 90 C. This temperature was maintained for one hour, then increased to 100 C. for three hours before cooling to room temperature. To a 2-ounce jar was added 11.84 g of this ester intermediate and 10.58 g of oleylamine. The lid was sealed, the contents were shaken, and then heated to 85 C. for 18 hours. Upon cooling to room temperature, the product was a yellow semisolid.

Example 3

Synthesis of N-(2-ethylhexyl)aspartic acid, 2-ethylhexyl ester (General Structure 1)

[0166] A mixture of 197.49 g of maleic anhydride and 263.40 g of 2-ethylhexanol were mixed in a one-liter two-piece reactor equipped with a mechanical stirrer and thermocouple at 65 C. under slow agitation. After all the solid had melted, the stir rate was increased to 300 rotations per minute (rpm) and the reaction was allowed to exotherm to 80 C. This temperature and mixing were maintained for two hours before cooling to room temperature. In a two-piece reactor equipped with a mechanical stirrer and thermocouple was added 58.62 g of this ester reaction product and 33.30 g of 2-ethylhexylamine. The mixture was heated to 85 C. for 6 hours. Upon cooling to room temperature, the product was a pale-yellow semisolid.

Example 4

Synthesis of N-(oleyl)aspartic acid, 2-ethylhexyl ester (General Structure 1)

[0167] A mixture of 197.49 g of maleic anhydride and 263.40 g of 2-ethylhexanol were mixed in a one-liter two-piece reactor equipped with a mechanical stirrer and thermocouple at 65 C. under slow agitation. After all the solid had melted, the stir rate was increased to 300 rotations per minute (rpm) and the reaction was allowed to exotherm to 80 C. This temperature and mixing were maintained for two hours before cooling to room temperature. To a 2-ounce jar was added 9.50 g of this ester reaction product and 11.14 g of oleylamine. The lid was sealed, the contents were shaken, and then heated to 85 C. for 18 hours. Upon cooling to room temperature, the product was a pale yellow waxy solid.

Example 5

Synthesis of N-(oleyl)aspartic acid, monopotassium salt (General Structure 1)

[0168] To a slurry of 32.62 g of maleic anhydride in 27.82 g of water, stirred at 300 rpm by means of an overhead mixer, was added 41.51 g of 45% potassium hydroxide solution in water dropwise over 10 minutes. Addition was done over a water bath to maintain the reaction temperature below 60 C. To this slurry was added 26.06 g of water then 26.56 g of ethylene glycol monobutyl ether (EGMBE). To this slurry was added 88.86 g of oleylamine at once and the reaction was heated to 80 C. for one hour. An additional 20.09 g of EGMBE was added and the reaction mixture heated to 100 C. for three hours. An additional 24.94 g of EGMBE was added and the reaction was continued for three hours. To the reaction mixture was added 28.81 g of monoethylene glycol and the mixture was transferred to a container while hot to afford 304.11 g of a viscous orange liquid which was 44% N-oleylaspartic acid, monopotassium salt by weight.

Example 6

Synthesis of 2-sulfosuccinic acid, iso-C11-14-alkyl ester, disodium salt (General Structure 1)

[0169] To a solution of 0.73 g of sodium metabisulfite in 1.91 g of water was added 3.07 g of isopropanol and 2.26 g of the ester intermediate of Example 2. To this mixture was added 0.61 g of a 50% solution of sodium hydroxide and the mixture was heated to 60 C. for three hours to afford the product as a 35.5% by weight hazy colorless solution.

Example 7

Synthesis of 2-(carboxymethylthio)succinic acid, iso-C11-14-alkyl ester, monosodium salt (General Structure 1)

[0170] To a solution of 2.71 g of the ester intermediate of Example 2 in 3.07 g of isopropanol was added 0.84 g of thioglycolic acid and 0.76 g of a 50% solution of sodium hydroxide. The mixture was heated to 60 C. for three hours to afford the product as a 49.0% by weight mixture in the form of a white pasty substance.

Example 8

Synthesis of 2-(dodecylthio)succinic acid, monosodium salt (General Structure 1)

[0171] To a mixture of 6.293 g of dimethyl maleate and 8.82 g of dodecanethiol was added 0.067 g (one drop) of a 50% solution of sodium hydroxide. The mixture was heated to 80 C. for 18 hours. To 3.56 g of this semi-solid material was added 4.56 g of methanol and 0.84 g of 50% sodium hydroxide solution and this mixture was heated to 60 C. for 20 hours to afford the product as a 37.9% by weight mixture in the form of a white pasty substance.

Example 9

Synthesis of (4-(2-aminoethyl)-3-oxo-2-piperazinyl)acetic acid, dodecyl ester (General Structure 6)

[0172] A mixture of 39.79 g of maleic anhydride, 151.11 g of 1-dodecanol, and one drop of sulfuric acid was mixed in a one-liter two-piece reactor equipped with a mechanical stirrer, Dean-Stark trap, and thermocouple at 100 C. for one hour. The mixture was heated to 160 C., at which water began collecting in the trap. After 4 hours of heating, the mixture was cooled and 181.42 g of the diester intermediate was recovered as a pale-yellow liquid that solidified upon cooling. A mixture of 60.11 g of diester and 12.60 g of diethylenetriamine was heated to 60 C. in a one-liter two-piece reactor equipped with a mechanical stirrer and thermocouple for one hour to afford 71.06 g of a yellow liquid consisting of an equimolar mixture of the product and 1-dodecanol.

Example 10

Synthesis of 6,9-dioxa-3,12-diazatetradecane-1,2,13,14-tetracarboxylic acid, dioleyl ester (General Structure 8)

[0173] A mixture of 138.85 g of oleyl alcohol and 50.60 g of maleic anhydride were mixed in a one-liter two-piece reactor equipped with a mechanical stirrer and thermocouple at 65 C. under slow agitation. After all the solid had melted, the stir rate was increased to 300 rotations per minute (rpm) and the reaction was allowed to exotherm to 80 C. This temperature and mixing was maintained for three hours before cooling to room temperature. To a two-ounce jar was added 9.90 g of this ester intermediate and 2.00 g of 2-(2-(2-aminoethoxy)ethoxy)ethanamine (Jeffamine EDR-148, Huntsman). The lid was closed, the contents were shaken, and the mixture was heated at 80 C. for 24 hours. Upon cooling, the product was a yellow waxy solid.

Example 11

[0174] The derivatized succinate corrosion inhibitors made according to Examples 1-5 were evaluated using bubble cell tests to assess corrosion performance using linear polarization resistance testing. The derivatized succinate corrosion inhibitors were combined with the sulfur synergist 2-mercaptoethanol in a solution so that the concentrations of corrosion inhibitor and 2-mercaptoethanol were 10% and 1% by weight, respectively. Methanol, isopropanol, water, and combinations thereof were used as solvents. Acids or bases were sometimes added either to form or neutralize salts of the inhibitors to influence their solubility. This solution was then dosed into the bubble cell at a concentration of 50 ppm, ultimately providing 5 ppm of corrosion inhibitor and 0.5 ppm of 2-mercaptoethanol. The bubble test simulates low flow areas where little or no mixing of water and oil occurs. The test was conducted using a mixed fluid composed of 80% by volume of synthetic brine composed of 3% sodium chloride and 20% of hydrocarbon oil.

[0175] The brine without inhibitor was first placed into kettles and purged with carbon dioxide for one hour resulting in carbon dioxide saturated brine. The brine was heated to 65 C., and electrodes were introduced into the de-aerated brine, followed by de-aerated oil, all of which was continually purged with carbon dioxide at 1 bar CO.sub.2 to saturate the brine for a 2 hour pre-corrode. The kettles were magnetically stirred at 100 revolutions per minute (rpm) for the duration of the test. The CO.sub.2 purge was switched to a blanket, the corrosion inhibitor solution was added, and the test timer started. Data were collected overnight for 15-hour test duration.

[0176] The corrosion rate was measured by Linear Polarization Resistance (LPR) techniques. The working electrode used was carbon steel (C1018 grade). The counter and reference electrodes were both Hastelloy. The electrodes were all cleaned and polished prior to testing. Corrosion rates were given in milli-inches per year (mpy), calculated from the current measured by LPR. The results are summarized in Table 1. Corrosion inhibition is compared to two known corrosion inhibitors: a cationic surfactant (alkylbenzyldimethylammonium chloride) and a Tall oil fatty acid (TOFA)-diethylenetriamine (DETA) imidazoline.

TABLE-US-00001 TABLE 1 Acid or base 2-Mercapto- additive CI ethanol Initial Final (molar Dosage dosage corrosion corrosion % CI Active eq.) (ppm) (ppm) rate (mpy) rate (mpy) Protection Cationic N/A 5.0 0.5 233.4 63.0 73.0 surfactant control Imidazoline Acetic 5.0 0.5 153.4 71.7 53.3 control acid (1 eq) Example 1 KOH (1 5.0 0.5 245.7 62.2 74.8 eq.) Example 2 KOH (1 5.0 0.5 252.4 42.9 83.0 eq) Example 3 Quinoline 5.0 0.5 248.8 20.9 91.6 (1 eq) Example 4 KOH (1 5.0 0.5 213.0 51.6 75.9 eq) Example 5 N/A 5.0 0.5 103.3 0.3 99.7 Example 6 H.sub.2SO.sub.4 5.0 0.5 186.9 75.9 59.4 (0.5 eq) Example 7 N/A 5.0 0.5 160.1 55.7 65.2 Example 8 N/A 5.0 0.5 137.2 32.4 76.4 Example 9 N/A 5.0 0.5 204.3 65.6 67.9 Example 10 KOH (1 5.0 0.5 157.2 20.1 87.2 eq)

[0177] The bubble cell results provide a low shear screening designed for continuous application. The performance is measured as percent protection by comparing the initial corrosion rate during pre-corrode, prior to the addition of a corrosion inhibitor, to the final corrosion rate, measured 15 hours after corrosion inhibitor dosing. The results show that the use of derivatized succinate corrosion inhibitors made according to Examples 1-10 provide similar or improved corrosion inhibition in comparison to the controls.

Example 12

[0178] The corrosion inhibitors were tested using wheel box testing which is a screening method for measuring corrosion inhibition persistence for batch applications. Metal coupons are dip-coated in a solution of the inhibitor in neutral form (non-salt), then placed onto a wheel and immersed in corrosive solution. The wheel is rotated in the solution under desired conditions. At regular time intervals, the solution without inhibitor is replenished. At the conclusion of the test, corrosion rates are measured as a function of the mass loss of the metal coupons.

[0179] Wheelbox Batch Testing Conditions: 1% corrosion inhibitor active in 3% NaCl, ran at 60 C., saturated CO.sub.2 at 1 atm CO.sub.2, for 96 hour average of 2 runs.

[0180] The results of the wheel box testing are shown in Table 2.

TABLE-US-00002 TABLE 2 Corrosion inhibitor Wheel-Box, % Inhibition Imidazoline control 43 Example 3 56 Example 4 64 Example 10 42

Example 13

[0181] Predictions of biodegradability were provided by two software packages for the examples described herein. This software included Epi Suite v 4.1 available from the US EPA, specifically the BIOWIN 3 ultimate biodegradation calculation, and an additional predictive software model program that provides biodegradability estimations. For the calculations the best-approximation chemical structures were converted into SMILES notation as inputs. The estimated biodegradability results are summarized in Table 3, with favorable comparisons to an imidazoline control in many cases.

TABLE-US-00003 TABLE 3 Corrosion Inhibitor Epi Suite (BIOWIN 3) Additional Program Imidazoline control 2.88 25% Example 1 3.35 51% Example 2 2.78 55% Example 3 3.54 51% Example 4 3.23 53% Example 5 3.40 67% Example 6 3.05 29% Example 7 3.21 42% Example 8 3.52 56% Example 9 2.82 20% Example 10 2.89 51%

[0182] It is to be understood that while the invention has been described in conjunction with the detailed description thereof, the foregoing description is intended to illustrate, and not limit the scope of the invention, which is defined by the scope of the appended claims. Other embodiments, advantages, and modifications are within the scope of the following claims. Any reference to accompanying drawings which form a part hereof, are shown, by way of illustration only. It is understood that other embodiments may be utilized and structural changes may be made without departing from the scope of the present disclosure. All publications discussed and/or referenced herein are incorporated herein in their entirety.

[0183] The features disclosed in the foregoing description, or the following claims, or the accompanying drawings, expressed in their specific forms or in terms of a means for performing the disclosed function, or a method or process for attaining the disclosed result, as appropriate, may, separately, or in any combination of such features, be utilized for realizing the invention in diverse forms thereof.