GB2385324A

GB2385324A - Corrosion inhibiting compositions

Info

Publication number: GB2385324A
Application number: GB0311582A
Authority: GB
Inventors: George Richard Meyer
Original assignee: Nalco Exxon Energy Chemicals LP
Current assignee: Nalco Exxon Energy Chemicals LP
Priority date: 1999-03-15
Filing date: 1999-12-14
Publication date: 2003-08-20
Anticipated expiration: 2019-12-14
Also published as: GB2385324B; GB0311582D0

Abstract

A process for making and a method for using a corrosion inhibitor composition to reduce the corrosion rate of a metal by a fluid containing a corrosion agent. The corrosion inhibitor composition comprises at least a quaternized compound having a substituted diethylamino moiety; having the general formula: <EMI ID=1.1 HE=29 WI=141 LX=457 LY=914 TI=CF> <PC>wherein R1 is a <SL> <LI>(i) substituted or unsubstituted, saturated or unsaturated alkyl group having from about 5 to about 29 carbon atoms; <LI>(ii) substituted or unsubstituted, saturated or unsaturated alkyl group having from about 5 to about 29 carbon atoms which is at least oxygenized, sulfurized or phosphorylized; or <LI>(iii) a mixture thereof; </SL> ```each R ý is independently a -CO2H, -SO3H, -PO3H2 -CO2R7, - CONH2, -CONHR7 and -CON(R7)2 group or mixture thereof; each R7 is independently hydrogen or linear or a branched alkyl, aryl, ```alkylaryl, cycloalkyl or heteroaromatic group having from 1 to about 10 carbon atoms, or mixtures thereof; ```R8 is hydrogen or a linear alkyl group having from 1 to about 10 carbon atoms; and ```n =0 to about 8, p = 1 to about 5 and q = 2 to about 10.

Description

CORROSION INHIBITING COMPOSITIONS AND METHODS

The invention relates to a process for producing and a method for using a corrosion inhibitor composition for reducing the corrosion rate of a metal by a fluid having at least one corrosion agent. More specifically, the invention relates 10 to synthesis of one or more quaternized compounds having a substituted diethylamino moiety, for example quaternized imidazoline(s) having a substituted diethylamino moiety, and their use in such a corrosion inhibitor composition for oil and gas-field applications.

In order to reduce the rate of corrosion of metals, and particularly metals containing iron, from one or more i Unction agents present in a field (i.e. in a

gas, liquid, slurry or a mixture thereof a corrosion inhibitor is frequently introduced into the fluid to reduce the rate of corrosion of the metal vessel, 20 pipeline and/or equipment used to store and transport the fluid. In oil and gas field applications, for example, corrosion inhibitors are added to a wide array of

systems, including without limitation, cooling systems, refinery units, pipelines, .. steam generators and oil or gas producing units in efforts to combat a variety of types of corrosion.

25 One example of corrosion, among others, typically encountered in the transport of a fluid containing one or more corrosion agents (hereinafter simply referred to as Ufluidn) is flow-induced corrosion. In the case of flow-induced corrosion, the degree of corrosion that occurs is presently believed to depend on a variety of factors, including the corrosiveness of the fluid itself, the metallurgy of 30 the pipeline and the shear rate, temperature, and pressure of the fluid.

Also, to the extent that a corrosion inhibitor is used, the inhibitor's ability to reduce the rate of corrosion of a metal from flow-induced corrosion, among other types of corrosion, is presently believed to depend on at least two factors. One - 1 ,,

factor is the inhibitor's chemical affinity for the metal surface. A second factor is the inhibitor's resistance to breakdown under high shear conditions. Therefore. it is currently believed that the rate of corrosion. especially flow-induced corrosion.

of a metal more likely will be reduced where the inhibitor has good chemical affinity for the metal surface and can resist breakdown under high shear conditions. Many inhibitors have been developed to reduce corrosion. However, their activity is sufficiently low that high concentrations are often required to effectively treat a pipeline, most particularly where flow-induced corrosion is a problem, thereby increasing operating costs.

10 The presence of a free amine moiety in inhibitors, such as that described in U.S. Patent No. 5,322,640, enhances the reactivity of the pendant alkyl amine group versus the unsubstituted nitrogen atom in the imidazoline ring. Various imidazoline derivatives are produced typically by reacting the imidazoline intermediate with stoichiometric amounts (i.e. 1:1 mole ratio) of an organic 15 carboxylic acid, such as, for example, acrylic acid (CH2CH2COOH), which preferably reacts with the imidazoline's pendant alkyl amine group, to enhance its corrosion inhibition activity by increasing its partitioning into water.

Conventionally, the 1:1 intermediate: carboxylic acid mole ratio has been considered desirable because the pendant alkyl amine group would still have at 20 least one free amine (e.g., a NH2 group) available for interaction with a metal surface; Accordingly, until the disclosure of thepresent invention, those skilled in

the art of synthesizing corrosion inhibitors refrained from reacting higher mole ratios of an organic carboxylic acid and/or producing imidazoline derivatives where the group pendant to the imidazoline ring contains a substituted 25 diethylamino moiety, wherein the previously freely available pair of nonbonding electrons on the heteroatom of the pendant group would be less available for steric reasons. In turn, it was thought this would reduce the compound's ability to interact with a metal surface, and thereby reduce its overall inhibition activity.

A corrosion inhibitor is desired that has improved inhibition performance 30 as compared with inhibitors presently used for treating systems experiencing flow-induced corrosion, among other corrosion problems.

- 2

According to one aspect of the present invention, there is provided a method of reducing the corrosion rate of a metal by a fluid having at least one corrosion agent, said method comprising contacting the metal with an inhibitor composition having at least one compound which is a 5 quaternized substituted diethylamino compound having the general formula A: R. 10 R3-(CR7)n-tHCH2-N/N-(CH2)q NtCH2C I-(CR7)n-R3) R8 C2 - (CH2)p R8 2 wherein R' is (i) a substituted or unsubstituted, saturated or unsaturated 15 alkyl group having from about 5 to about 29 carbon atoms; (ii) a substituted or unsubstituted, saturated or unsaturated alkyl group having from about 5 to about 29 carbon atoms which is at least oxygenized, sulfurized or phosphorylized; and (iii) mixtures thereof; each R3 id independently a -C O2H, -S O3H, -PO3Hz, -CQ2R7, -C O N H2, -C O NH R7 and 20 CON(R7)2 group or mixture thereof; each R7 is independently hydrogen or linear or a branched alkyl, aryl, aikylaryl, cycloalkyl or heteroaromatic group having from 1 to about 10 carbon atoms, or mixtures thereof; R8 is hydrogen or a linear alkyl group having from 1 to about 10 carbon atoms; and n = 0 to about 8, p = 1 to about 5 and q = 2 to about 10.

25 According to another aspect of the present invention, there is provided a process for producing a composition comprising at least a quarternized compound having a substituted diethylamino moiety, from (a) a first organic compound which is (i) a substituted or unsubstituted, saturated or unsaturated fatty acid having from about 6 to about 30 30 carbon atoms; isubstituted or unsubstituted, saturated or unsaturated - 3

fatty acid having from about 6 to about 30 carbon atoms, wherein said fatty acid is at least oxygenized, sulfurizr phosphorylized; or (iii) a mixture thereof; (b) an alkyl polyamide having the general formula: 5 H2NCH2(CH2)pNH(CHz)qNH2 wherein p = 1 to about and q = 2 to about 10; and (c) a second organic compound which is (i) a substituted or unsubstituted a,,B-unsaturated carboxylic fatty acid, or amide or ester derivative thereof, having from about 3 10 to about 11 carbon atoms; (ii) substituted or unsubstituted a,,B-unsaturated sulfonic or phosphoric fatty acids having from about 2 to about 11 carbon atoms; and (iii) mixtures thereof; the method including (d) mixing said first organic compound (a) and said alkyl polyamine (b) in a mole ratio in a range of from about 0.6:1 to about 1.2:1 to produce at least one intermediate 15 compound, wherein said mole ratio is the total moles of said first organic compound to the total moles of said alkyl polyamine; and (e) mixing said at least one intermediate compound with said second organic compound (e) to produce said composition.

It is to be understood that the range of carbon atoms specified for each . ........

20 group described herein refers to the main chain of the alkyl groups, and does not include carbon atoms that may be contributed by substituents.

Many quaternary ammonium compounds are acyclic, having the general formula R4N+X, and are a type of ionic organic compound with at least one nitrogen atom. However, heterocyclic compounds with at least one nitrogen 25 atom also can be quaterna ammonium compounds.

In the case of acyclic quaternary ammonium compounds, a nitrogen is covalently bonded to four organic groups and bears a localized positive charge that is balanced by a negative counterion. The negative counterion may be either attached to or unattached to, but still associated with, the rest of the - 3Q compound. _ In the case of heterocyclic ammonium compounds, at least one nitrogen has four bonds, which are either (a) each single bonds or (b) two single bonds

NCC-002US

and a double bond. The present invention produces heterocyclic quaternized ammonium compounds. which, for convenience, are depicted as having two single bonds and a double bond with the double bond shown as a resonance type structure, indicating that it is delocalized between two nitrogen atoms of the same heterocyclic ring. However, it will be understood by those skilled in the art that the specified groups pendant to each nitrogen, could also, in whole or in part, be pendant to a single nitrogen.

The quaternized compounds A may be used alone or in combination with other corrosion inhibitors and/or corrosion inhibitor formulation substances, 10 including, without limitation, solvents, surfactants, and quaternized salts, which are more fully described below.

All compounds A have a heterocyclic ring containing two nitrogen atoms. The heterocyclic ring of compound A preferably has from about 3 to 7 carbon atoms, more preferably from about 3 to 5 carbon atoms and most 15 preferably 3 carbon atoms. Compound A is a quaternized imidazoline when there are 3 carbon atoms, a quaternized tetrahydropyrimidine when there are 4 carbon atoms, and so on.

As specified above, compound A may have one group pendant to the first nitrogen atom of the heterocyclic ring containing a -CO2H, 20 SO3H, PO3H2, -CO2R7, -CONH2, -CONHR7 and -CON(R7)2 group and a second ..... group pendant to the second nitrogen atom of the heterocyctic ring containing a substituted diethylamino group.

Also, compound A may have a group pendant to the apex carbon bridging the first and second nitrogen of the heterocyclic ring that is (i) a 25 substituted or unsubstituted, saturated or unsaturated alkyl group having from about 5 to about 29 carbon atoms; (ii) a substituted or unsubstituted, saturated or unsaturated, oxygenized, sulfurized or phosphorylized alkyl group having from about 5 to about 29 carbon atoms; or (iii) a combination thereof. Generally, preferred R' moieties include (a) unsubstituted, unsaturated alkyl groups having 30 from about 7 to about 23 carbon atoms, (b) substituted, unsaturated alkyl groups having from about 7 to about 23 carbon atoms, and (c) sulfurized unsubstituted, . .........................

5 - -. .,

it; saturated or unsaturated alkyl groups having from about 7 to about 23 carbon atoms. More preferred R' moieties include (a) unsubstituted, unsaturated alkyl groups having from about 11 to about 23 carbon atoms. and (b) substituted.

unsaturated alkyl groups having from about 11 to about 23 carbon atoms. Most 5 preferred R. moieties include unsubstituted, unsaturated alkyl groups having from about 17 to about 21 carbon atoms.

Examples of suitable substituents include, without limitation, OH, SH' halogen atoms, alkyl, aryl, alkylaryl and heteroaromatic groups and, combinations thereof.

10 The group pendant to the first nitrogen atom of the heterocyclic ring has at least 2 carbon atoms, one of which may be substituted with a linear alkyl group having from 1 to about 10 carbon atoms. The pendant group may or may not have a conjugated portion with up to 8 carbon atoms which may or may not be substituted with a linear or branched alkyl, aryl, alkylaryl, cycloalkyl or 15 heteroaromatic group having from 1 to about 10 carbon atoms, or a combination thereof. The group pendant to the first nitrogen atom of the heterocyclic ring preferably contains a -CO2H, -SO3H, -PO3H2, -CO2R7, -CONH2, -CONHR7 or -CON(R7)2 moiety. Preferably, the group pendant to the first nitrogen atom of the 20 heterocyclic ring contains a carboxylate, sulfonate or phosphonate moiety, more preferably contains a carboxylate or sulfonate moiety and most preferably contains a carboxylate moiety.

Preferably, the group pendant to the second nitrogen atom of the heterocyclic ring contains a linear or branched alkyl group having from about 2 to 25 about 10 carbon atoms, more preferably contains a linear or branched alkyl group having from about 2 to about 6 carbon atoms and most preferably contains a linear alkyl group having from about 2 to about 4 carbon atoms.

The group pendant to the second nitrogen atom of the heterocyclic ring pferably contains a substituted diethylamino moiety. Preferably, the groups pendant 30 to the nitrogen atom of the substituted diethylamino moiety contain a carboxylate, -6-

:.: rim sulfonate or phosphonate moiety, more preferably contain a carboxylate or sullfonate moiety and most preferably contain a carboxylate moiety.

For example, one of the preferred compounds A is a quaternized substituted diethylamino imidazoline having the following formula, 5 hereinafter referred to as compound A': I 47H33 CO2H

CON>N -CO2H

By' where R. is C,7H33, R3 is COO, R8 is hydrogen and n = 0, p =1 and q = 2 in 10 formula A. The synthesis of compound A derivatives, and more specifically, of the illustrative compound, A', described above is discussed more fully below.

However, it should be understood that commercial manufacture of compound A - will typically lead to a mixture of final-products-resulting from an incomplete 15 cyclization step and competing reaction pathways that can yield compound A. Accordingly, a mixture of compounds includes at least a compound A in combination with other compounds, including, without limitation, some unreacted starting material, some intermediate mono-, diand/or polyamides arising from the reaction pathway for compound A, and possibly others 20 derivatives produced by competing reaction pathways.

The quaternized compounds having a substituted diethylamino moiety can be made using a wide array of organic acids and acid derivatives and alkyl polyamides. Generally, two different types of organic compounds can be used to practice the invention.

25 The first type of organic compound is- generally selected from the class of-

fatty acids. More specifically, the taffy acids useful for practicing the invention can be selected from the group consisting of substituted and unsubstituted,

saturated and unsaturated fatty acids having from about 6 to about 30 carbon atoms: substituted and unsubstituted saturated and unsaturated fatty acids having from about 6 to about 30 carbon atoms, wherein the fatty acid is at least oxygenized, sulfurized or phosphorylized; and combinations thereof. It is to be understood that the range of carbon atoms specified for each group described herein refers to the main chain of the acid, and does not include carbon atoms that may be contributed by substituents.

Generally, preferred fatty acids of the first type include (a) unsubstituted, unsaturated fatty acids having from about 8 to about 24 carbon atoms, (b) 10 substituted, unsaturated fatty acids having from about 8 to about 24 carbon atoms and (c) sulfurized unsubstituted, saturated or unsaturated fatty acids having from about 8 to about 24 carbon atoms. More preferred fatty acids of the first type include (a) unsubstituted, unsaturated fatty acids having from about 12 to about 24 carbon atoms and (b) substituted, unsaturated fatty acids having 15 from about 12 to about 24 carbon atoms. Most preferred fatty acids of the first type include unsubstituted, unsaturated fatty acids having from about 18 to about 22 carbon atoms.

The second type of organic compound is generally selected from the class of ar,-unsaturated fatty carboxylic acids and amide and ester derivatives thereof, 20 a,-unsaturated fatty sulfonic or phosphoric acids, and combinations thereof.

...........DTD: More specifically, the second type of organic material useful for practicing the invention can be selected from the group consisting of (i) substituted and unsubstituted,,-unsaturated carboxylic fatty acids, and amide and ester derivatives thereof, having from about 3 to about 11 carbon atoms; (ii) substituted 25 or unsubstituted, or,-unsaturated sulfonic and phosphoric fatty acids having from about 2 to about 11 carbon atoms; and (iii) combinations thereof. It is to be understood that the range of carbon atoms specified for each group described herein refers to the main chain of the acid or acid derivative, and does not include carbon atoms that may be contributed by substituents.

30 Generally, preferred a,0-unsaturated carboxylic fatty acids and amide and ester derivatives thereof, and a,-unsaturated sulfonic and phosphoric fatty _e _ A\ i it.

acids are (a) unsubstituted and have from about 2 to about 9 carbon atoms, and (b) substituted and have from about 2 to about 9 carbon atoms. More preferred a,-unsaturated carboxylic fatty acids and amide and ester derivatives thereof.

and or,,B-unsaturated sulfonic and phosphoric fatty acids are (a) unsubstituted 5 and have from about 2 to about 7 carbon atoms, and (b) substituted and have from about 2 to about 7 carbon atoms. Most preferred a,0-unsaturated carboxylic fatty acids and amide and ester derivatives thereof, and a,0 unsaturated sulfonic and phosphoric fatty acids are unsubstituted and have from about 2 to about 5 carbon atoms.

10 Examples of suitable substituents include, without limitation, alkyl, aryl, alkylaryl, cycloalkyl and heteroaromatic groups, and combinations thereof.

Generally, preferred types of acid groups for selecting a,-unsaturated fatty acids are carboxylic and sulfonic acids, while the most preferred acid group is carboxylic acid.

15 The alkyl polyamine(s) that can be used to practice the invention can be selected from the group having the following general formula: H2N-CH2 (CH2)p-NH-tCH2)qNH2 wherein p = 1 to about 5 and q = 2 to about 10.

Generally, preferred alkylpolyamines include those where p - 1 to 2 and q 20 = 2 to 3. More preferred alkyl polyamines include p = 1 and q = 2 to 3. Most preferred alkyl polyamines include those where p = 1 and q = 2.

To produce a composition comprising an amine intermediate for a quatemized compound having a substituted diethylamino moiety, the mole ratio of the first organic compound to the alkyl polyamine may be selected from the 25 range of from about 0.6:1 to about 1.2:1, hereinafter referred to as the substituted diethylamino mole ratio range. As used herein, substituted diethylamino mole ratio means the ratio of the total number of moles of the first organic compound to the total number of moles of alkyl polyamine used in a process for making an amine intermediate for a quaternized compound having a substituted _9_ ..

diethylamino moiety. Generally, the preferred substituted diethylamino mole ratio range of the first organic compound to the alkyl polyamine is selected from the range of from about 0.65:1 to about 1:1. The more preferred substituted diethylamino mole ratio range of the first organic compound to the alkyl 5 polyamine is selected from the range of from about 0.7:1 to about 0.9:1. The most preferred substituted diethylamino mole ratio range of the first organic compound to the alkyl polyamine is selected from the range of from about 0.75:1 to about 0.8:1.

It should be understood that the terms "mix", "mixed" or "mixing" as used 10 herein are intended to embrace all synthesis procedures, including, without limitation, batch, continuous, in-situ, interracial and/or solution type processes and combinations thereof. Moreover, such terms and reference to any intermediates produced are used for convenience and for clarifying the scope of the Applicant's invention. Accordingly, such terms should not be construed to 15 limit the claimed invention to: (a) any particular sequence of reaction steps suggested herein, or (b) the production and/or separation of any specified amount of intermediate(s) for any specified length of time as a prerequisite to a subsequent process step.

To produce a quaternized compound having a moiety containing a 20 hydrocarbon and carbonyl, sulfonyl or phosphonyl group, the amine intermediate ........

mixture is mixed with one or more of the X,-unsaturated fatty acids or acid derivatives, described above as the second organic compound. Preferably, the relative amounts of the amine imidazoline mixture and the second organic acid or acid derivative are determined on a mole ratio basis. As mentioned above, the 25 intermediate mixtures produced in the process of this invention can comprise other compounds in addition to the target intermediate species (e.g., amine imidazoline intermediate species) specified for a particular process.

Thus, a composite molecular weight can be used to calculate the number of moles of a particular intemmediate mixture. Theoretically, such a composite 30 molecular weight determination could represent the molecular weights of all chemical species of the mixture and their respective mole percent contributions -10-

to the mixture composition. However, making such a determination requires time-consuming and tedious analysis of the mixture composition. Consequently.

for convenience, the composite molecular weight for an intermediate mixture.

produced by the processes of the present invention, was determined herein by 5 presuming the mixture is primarily comprised of the target species. So, for example, the composite molecular weight assigned to the amine imidazoline mixture of the Example below is 349 grams/mole (i.e., the molecular weight of the target imidazoline). Accordingly, such composite molecular weights can be used to calculate the number of moles of the mixture, and thereby determine the 10 preferred amount of the second organic compound to be used in view of the mole ratio ranges specified below.

To produce a quaternized compound having a substituted diethylamino.

moiety from the amine intermediate mixture, the mole ratio of the target amine intermediate mixture to the second organic acid or acid derivative is preferably 15 selected from the range of from about 1:3 to about 1:6. More preferably, the mole ratio of the target amine intemmediate mixture to the second organic acid or acid derivative is selected from the range of from about 1:3 to about 1:4. Most preferably, the mole ratio of the target amine intermediate mixture to the second organic acid or acid derivative is about 1:3.

? The corrosion inhibitors of the present invention can be used in any system exposed to fluids (i.e., liquid, gas, slurry or mixture thereof) containing a metal corrosion agent where improved corrosion inhibition is desired. However, the corrosion inhibitors of the present invention are particularly well-suited for use in oil and gas field applications and refinery operations.

25 With respect to such oil and gas field applications, the corrosion inhibitors

of the present invention may be added to oil and/or gas fluids in the form of a solution or dispersion in water or an organic solvent. Examples of suitable solvents are alcohols such as methanol, ethanol, isopropanol, isobutanol, secondary butanol, glycols, and aliphatic and aromatic hydrocarbons.

30 The amount of active ingredient in a corrosion inhibitor formulation required to sufficiently reduce the rate of corrosion varies with the system in which it is . -.

At' used. Methods for monitoring the severity of corrosion in different systems are well-known to those skilled in the art. and may be used to decide the effective amount of active ingredient required in a particular situation. The compounds may be used to impart the property of corrosion inhibition to a composition for 5 use in an oil or gas field application and may have one or more functions other

than corrosion inhibition, e.g. scale inhibition.

The inhibitors of the type described herein have proven to be particularly effective for inhibiting corrosion of mild steel in hydrocarbon, oil/brine mixtures and aqueous systems under a variety of conditions. The inhibitor compositions 10 claimed herein are preferably used in sweet systems, i.e. systems having a relatively high CO2 concentration. However, use of such compositions in systems having sour conditions (i.e., systems having a relatively high H2S concentration) is also acceptable. Although fluid content of flow lines may vary, the inhibitor may be used in a variety of environments. Oil cuts in the field can

15 range from less than 1% (oil field) to 100% (refinery) oil, while the nature of the

water can range from 0 to 300,000 ppm TDS (total dissolved solids) In addition, the inhibitor compositions of the present invention would also be useful in large diameter flow lines of from about 1 inch to about 4 feet in diameter, small gathering lines, small flow lines and headers In a preferred method, the inhibitor 20 composition is added at a point in the flow line upstream from the point at which corrosion prevention is desired.

In practice, the inhibitor compositions of the present invention are preferably added to the flow line continuously to maintain a corrosion inhibiting dose of from about 0.01 to about 5000 ppm. More preferably, the corrosion 25 inhibiting dose is from about 0.1 to about 500 ppm. In a most preferred embodiment of the present invention, the corrosion inhibiting dose is from about 1 to about 250 ppm. Although a most preferred use of the corrosion inhibitor compositions of the present invention is for mild steel flow lines, it is believed that the inhibitor compositions are also effective in inhibiting corrosion in other types 30 of metallurgy. In certain cases, batch treatments are the method of choice for application of the inhibitor compositions of the present invention. However, the -12,. ,, ;,. \,......

invention can also be practiced using a continuous process. Dosage rates for batch treatments range from about 0.1 to about 50,000 ppm. In a preferred embodiment of the present invention, the flow rate of the flow line in which the inhibitor composition is used is between 0 and 100 feet per second. A more 5 preferred flow rate is between 0.1 and 50 feet per second. In some cases, the inhibitors of the present invention may be formulated with water in order to facilitate addition to the flow line.

The inhibitors of the present invention may be used alone or in combination with other compounds. Typical formulations include pour point depressants 10 and/or surfactants. Examples of suitable.pour point depressants are C, to C3 linear or branched alcohols, ethylene and propylene glycol. Examples of suitable surfactants are ethoxylated nonylphenols and/or ethoxylated amines as wetting agents or additives for dispersing the inhibitor into the fluid stream to which they are added. The surfactant is advantageously water soluble to allow the product 15 to better wet the surface of the flow line where corrosion may take place. Water soluble surfactants utilized may be non-ionic, cationic or anionic and will generally have a hydrophilic-lipophilic (HLB) value of about 1. Oil soluble surfactants may be utilized if it is desired to disperse the inhibitor composition into a hydrocarbon fluid. Oil soluble surfactants may be non-ionic, cationic or 20 anionic. These surfactants typically have an. HLB value less than 7.

Other compounds which may also be blended with the inhibitor compositions claimed herein are quaternary amines, such as fatty, cyclic or aromatic amines quaternized with lower alkyl halides or benzyl chloride and certain amides. In addition, formulations including the inhibitors of the present 25 invention may include filming agents such as p-toluenesulfonic acid and dodecylbenzenesulfonic acid. The corrosion inhibitor may also contain components which are typically included in corrosion inhibiting compositions, such as scale inhibitors and/or surfactants. In some instances, it may be desirable to include a biocide in the composition.

30 An example of a formulation which has been generally found to give superior performance is presented in Table I.

Table I

Component % by weight Water i 10-60 : Methanol 5-30 i Isopropanol j 5-30 D-Toluenesulfonic acid O-S Ethoxylated alkyl amine 2-15 surfactant Quaternized compound of 5-50 the present invention Quaternary salt | 0-15 An example of a quaternary salt is an alkyl pyridine benzyl chloride 5 quaternary salt. In the alkyl pyridine benzyl chloride quaternary salt,the alkyl group is preferably a methyl, ethyl or disubstituted alkyl group. The ethoxylated alkyl amine surfactant preferably has a carbon chain length of from about C1O to about Can and preferably has about 20 moles of ethylene oxide per mole of amine. 10 The formulation is preferably produced by blending several ingredients into a homogeneous mixture. Though not critical to practicing the invention, the preferred order of addition is as follows: i) quaternized compound, ii) methanol and/or isopropanol, iii) quaternary salt, iv) ethoxylated alkyl amine surfactant, v) ............ ..

water and vi) p-toluenesulfonic acid.

15 The resultant inhibitor formulation may be used in a variety of petroleum operations in the oil and gas industry. It can be used to treat systems used in primary, secondary and tertiary oil and gas recovery. The inhibitor formulation may be introduced to such systems in accordance with techniques well-known to those skilled in the art. For example, one technique in which the inhibitor 20 formulation can be used is the squeeze treating technique, whereby the inhibitor formulation is injected under pressure into a producing formation, adsorbed onto the strata and absorbed as the fluids are produced. The inhibitor formulation can further be added in water flooding operations of secondary oil recovery, as well as be added to pipelines, transmission lines and refinery units. The inhibitor 25 formulation may also be used to inhibit acid solution in well-acidizing operations.

-14-

f The following non-limiting example of a preferred compound that may be made and used as claimed herein are provided for illustrative purposes only Also, it will be apparent to those skilled in the art, that the reaction schematics specifying particular intermediates and final products illustrate only 5 those compounds which the Applicant presumes are significant compounds formed based on current principles of organic reaction chemistry and qualitative infrared analysis of the final reaction product. Illustration of a specified intermediate does not exclude the presence of other significant intermediate(s) important to the formation of the final product. Also, illustration of a final 10 compound does not exclude the presence of other compounds in the final composition, including, without limitation, the unreacted starting reactants, intermediates and other final compound(s), if any, produced by competing reaction pathways.

1 5 Example

Synthesis of a Quaternized Substituted Diethylamino Imidazoline i,tH33 CO2H CON No CO2H Prenaration of Amine Imidazoline Mixture 175 9 (0.62 mol) of TOFA was placed in a 500 mL round bottom four-neck 20 flask equipped with an overhead stirrer, addition funnel, thermocouple and Dean Stark trap. The acid was heated to 60 C and a sweep of nitrogen gas was maintained over the surface of the liquid throughout the reaction. When the temperature reached 60 C, 82 9 (0.8 mol) of DETA was added dropwise rapidly.

An exotherm of about 40 C was observed. The mixture was heated to 1 75 C 25 with stirring until the theoretical amount of water for amide formation (11 9) was collected. The _f area spectrum of the mixture at this point indicated the -15-

f presence of amide (absorption at about 1630 and 1550 emu) and free N-H (absorption at about 3315 cm-). The temperature was increased to 225 C and maintained there for 2 hours (84% of the theoretical amount of water for 100% Imidazoline formation was collected). The infrared spectrum exhibited the same 5 two broad bands noted above and a sharper, intense band between them around 1610 cm', indicative of imidazoline. Without being bound by theory, the presumed predominant intermediate and product are illustrated schematically below: C,7HaaCOOH H2NH NH2 TOFA 0.62 mol DETA 0.8 mol 1 1 75 C

O + H2O

C,7H33C-NH NH2

225C C1 7H33

N;\N + H2O

Amine Imidazoline - - 10 Reactiori ofAmine Imidazoline Mixture witliAcrviic Acid 69.8 9 (0.2 mol. presuming the composite molecular weight of the amine Imidazoline is 349 g/mole) of the resultant amine Imidazoline mixture was weighed into a 250 mL round bottom four-neck flask equipped with an overhead stirrer, addition funnel and thermocouple. To this was added 43.2 g (0.6 mol) 15 - acrylic acid via the addition funnel. The exotherm was noted and the mixture heated at 120 C for 2 hours. Without being bound by theory, the presumed predominant intermediate and product are illustrated schematically below: -16- _i

C,7H3,

N;\N 3 /\CO2H

Amine Imidazoline | A CO2H

C.7H33 / \/

CO NAN CO2H

Inhibitor Performance The performance of the inhibitor produced in the Example was evaluated 5 by Wheelbox and Stirred Kettle Tests. Each of the tests is described below and the results of the two tests are presented in tabular form.

Wheelbox Test The Wheelbox Tests were conducted at 80 C in a rotary oven. The 10 coupons used were flat rectangular carbon steel coupons which had been water quenched and hardened. To prepare the coupons, metal surfaces were sand blasted, washed in an alcohol/toluene mixture and dried. The prepared coupons were weighed and piaced individually in sarnpie bottles.

The test medium was 90% by volume of a seawater brine and 10% by 15 volume of kerosene. The fluid was sparged with CO2. Each bottle was dosed with a measured amount of the inhibitor to be tested (2, 5 or 10 ppm in Wheelbox Test A and 5, 7.5 and 10 ppm in Wheelbox Tests B. C and D) . Finally, the coupons were placed in the bottles which were then capped and shaken.

The oven was heated to 80 C and loaded with the coupon-containing 20 bottles. The bottles were rotated in the oven for a period of 24 hours. After cleaning and drying, the coupons were reweighed and the percent corrosion inhibition was calculated using the formula: -17- i.

average blank weight loss - weight loss of treated coupon average blank weight loss Each coupon was also visually inspected and the appearance was recorded.

The inhibitors were tested in four Wheelbox Tests A - D. Wheelbox Test A was an "actives only" test. Wheelbox Tests B. C and D were tests of the 5 inhibitors at 8, 30 and 38 wt%, respectively, in formulations typically used in commercial applications.

The results presented in Table II are for Wheelbox Test A ("actives only") .

The term "actives only" means that the test was conducted with the final product of the Example only. The product was not mixed into a formulation, such as 10 described above, typically used in commercial applications. The "actives only" test was used as a preliminary indicator of the effectiveness of the inhibitor. The control used in the "actives only" Wheelbox Test A was the product of Example I of U.S Patent No. 5,322,640.

15 Table II

Wheelbox Test A - Actives Oniv % Protection __ Inhibitor2 ppm 5 ppm 10 ppm Blank 0 0 0 Control71 86 90 Example67 93 98 Wheelbox Test A demonstrates that the inhibitor produced in the Example produced better results than the Control inhibitor.

- Moreover, the improved performance results of the Example versus the 20 Control are surprising and unexpected. The results are surprising and unexpected because the primary compound of the Example does not contain a free amine or a freely available lone pair of electrons on a heteroatom in the group pendant to the second nitrogen of the imidazoline ring. The lone pair of electrons is localized on a tertiary nitrogen. Accordingly, it was surprising and 25 unexpected that this type of compound (a) would have any significant positive -18-

effect on inhibitor performance whatsoever and (b) would perform better than the Control. The inhibitor of the Example was then tested in a corrosion inhibition formulation, as an example of a commercial application. The Control I inhibitor 5 formulation used in Wheelbox Tests B. C and D was a proprietary corrosion inhibition formulation produced by Nalco/Exxon Energy Chemicals, L.P.. Sugar Land, Texas. The Control I inhibitor formulation includes up to 38% of a proprietary corrosion inhibitor active.

In Wheelbox Test B. 8 wt% of the corrosion inhibitor active of the Control I 10 inhibitor formulation was substituted with 8 wt% of the product of the Example to produce the Example formulation. Likewise, 8 wt% of the corrosion inhibitor active of the Control I inhibitor formulation was substituted with 8 wt% of the product of Example I of U.S. Patent No. 5,322,640 to produce the Control 11 inhibitor formulation for Wheelbox Test B. The amounts and type of the 15 remaining components of the Control I inhibitor formulation were constant in ail formulations. The results are shown in Table 111.

Table 111

Wheelbox Test B- 8 wt% formulation % Protection Inhibitor 5-ppm--- 7-. 5ppm 10ppm Blank O O O Control I 63 66 73 Control 11 78 88 86 Example 81 82 89 20 The formulation containing the inhibitor produced in the Example gave better corrosion protection results as compared with the Control I and Control 11 inhibitor formulations. Again, for the reasons discussed above, these results are both surprising and unexpected.

In Wheelbox Test C, 30 wt% of the corrosion inhibitor active of the Control I 25 inhibitor formulation was substituted with 30 wt% of the product of the Example to produce the Example formulation. Likewise, 30 wt% of the corrosion inhibitor .,.......... .. ... .....

active of the Control I formulation was substituted with 30 wt% of the product of _] 9_ \

Example i of U.S. Patent No. 5 322.640 to produce the Control II inhibitor formulation for Wheelbox Test C. The amounts and type of the remaining components of the Control I formulation were constant in all formulations The results are shown in Table IV.

Table IV

Wheelbox Test C - 30 wt% formulation /0 Protection Inhibitor 5 ppm 7.5 ppm 10 ppm Blank O OO Control I 63 66 _78 Control II 89 9397 _.._ Example 95 9595 The formulation containing the inhibitor produced in the Example gave better corrosion protection results as compared with the Control I inhibitor 10 formulation and comparable or better corrosion protection results as compared with the Control II inhibitor formulation.

In Wheelbox Test D, 38 wt% of the corrosion inhibitor active of the Control I inhibitor formulation was substituted with 38 wt% of the product of the Example to produce the Example formulation. Likewise, 38 wt% of the corrosion inhibitor 15 active of the Control I inhibitor formulation was substituted with 38 wt% of the product of Example I of U. S. Patent No. 5,322 640 to produce the Control II inhibitor formulation for Wheelbox Test D. The amounts and type of the remaining components of the Control I inhibitor formulation were constant in all formulations. The results are shown in Table V. Table V

Wheelbox Test D- 38 wt% formulation % Protection @ Inhibitor 5 pprn;7.5 ppm.10 ppm Blank O: O O Control I 63 66. 78 Control 11 92 _96 _ 96 Example 95 95 97 -20- -

The formulation containing the inhibitor produced in the Example gave better corrosion protection results as compared with the Control I inhibitor formulation and comparable or better corrosion protection results as compared with the Control II inhibitor formulation. Therefore, for the reasons stated above 5 these results are surprising and unexpected.

Stirred Kettle Test A "stirred kettle" apparatus was used to measure the corrosion inhibition capabilities of the corrosion inhibitors of the present invention.

10 The stirred kettle apparatus was a 1 L resin kettle with a four-neck removable top. A magnetic stirrer was used to agitate the fluids and a sparge tube was used to purge the fluids with N2 to remove any O2. A thermocouple and temperature controller were used to monitor/maintain the temperature of the system. The fluid used for the tests consisted of 700 mL brine and 300 mL 15 kerosene. The fluid was stirred for 14 hours at 80 C.

A baseline corrosion rate was measured and the system was then dosed with the corrosion inhibitor. Corrosion rates were measured using a probe with two electrodes (reference and working). The probes were connected to a CORRATER (Rohrbach Instruments, Santa Fe Springs, California), which 20 recorded corrosion rates at periodic intervals-.- The CORRATER used the method of linear polarization resistance (LPR, ASTM procedure G59-91) to determine corrosion rates. The data was then downloaded to a spreadsheet software program which allowed graphical interpretation of the results.

The Control I inhibitor formulation was as described above with reference to 25 Wheelbox Tests B. C and D. 8 wt%, 30 wt% and 38 wt% of the corrosion inhibitor active of the Control I inhibitor formulation was substituted with the inhibitor of the Example to produce the Example formulation (indicated by 8 wt%, 30 wt% or 38 wt% active, respectively). The inhibitor formulation was used at a concentration of 2.5 ppm. Table Vl illustrates the results of the Stirred Kettle 30 Test. -21-

Table Vl

Stirred Kettle Test Inhibitor (% Active Substituted)/ % Protection (% Total Active in after 14 hours Control I) Blank 0/0 0 Control I 0/38 _ 85 Example 8/38 85 Example 30/38 89 Example 38/38 83 The results of the Stirred Kettle Test show comparable or better corrosion inhibition by formulations containing the inhibitor produced in the Example, as 5 compared with the Control I inhibitor formulation. Again, these results are surprising and unexpected for the reasons discussed above.

Preferred compositions and applications for practicing the invention, as well as preferred processes for making such compositions, have been described. It 10 will be understood that the foregoing is illustrative only and that other compositions, processes for making such compositions, and applications for such compositions can be employed without departing from the true scope of the invention defined in the following claims.

-22-

Claims

CLAIMS: 1. A method of reducing the corrosion rate of a metal by a fluid having at 5 least one corrosion agent, said method comprising contacting the metal with an inhibitor composition having at least one quaternized substituted diethylamino compound having the general formula: R. 10 R3 (CR7)n-fHCH2-NiN-(CH2)q N<CH2CH-(CR7)n-R3) RB CH2 - (CH2)p wherein R' is a 15 (i) substituted or unsubstituted, saturated or unsaturated alkyl group having from about 5 to about 29 carbon atoms; (ii) substituted or unsubstituted, saturated or unsaturated alkyl group having from about 5 to about 29 carbon atoms which is at least oxygenized, sulfurized or phosphorylized; or ..... .... 20 (iii) a mixture thereof; each R3 is independently a -CO2H, -SO3H, PO3H2, -C O2R7, -CO NH2, -CON H R7 and -CON(R7)2 group or mixture thereof; each R7 is independently hydrogen or linear or a branched alkyl, aryl, alkylaryl, cycloalkyl or heteroaromatic group having from 1 to about 10 carbon 25 atoms, or mixtures thereof; R is hydrogen or a linear alkyl group having from 1 to about 10 carbon atoms; and n = 0 to about 8, p = 1 to about 5 and q = 2 to about 10. 30 2. A method according to claim 1 wherein R. is (a) unsubstituted, -23- unsaturated alkyl groups having from about 7 to about 23 carbon atoms. (b) substituted, unsaturated alkyl groups having from about 7 to about 23 carbon atoms, or (c) sulfurized unsubstituted, saturated and unsaturated alkyl groups having from about 7 to about 23 carbon atoms. 3. A method according to claim 1 or claim 2 wherein R3 is a carboxylate moiety. 4 A process for producing a composition comprising at least a quaternized 10 compound having a substituted diethylamino moiety from (a) a first organic compound which is (i) a substituted or unsubstituted, saturated or unsaturated fatty acid having from about 6 to about 30 carbon atoms; (ii) a substituted or unsubstituted, saturated or unsaturated fatty acid 15 having from about 6 to about 30 carbon atoms which is at least oxygenized, sulfurized or phosphorylized; or (iii) a mixture thereof; (b) an alkyl polyamine of the general formula: 20 H2NCH2(CH2)pNH(CH2)qNH2 wherein p = 1 to about 5 and q = 2 to about 10: (c) a second organic compound which is (i) a substituted or unsubstituted a,0-unsaturated carboxylic fatty 25 acid, or amide or ester derivative thereof, having from about 3 to about 11 carbon atoms; (ii) a substituted or unsubstituted a,0-unsaturated sulfonic and phosphoric fatty acid having from about 2 to about 11 carbon atoms; or - 30 - -- - - (iii3 - a mixture thereof; -24 comprising the steps of (d) mixing said first organic compound (a) and said alkyl polyamine (b) in a mole ratio in a range of from about 0.6:1 to about 1.2:1 to produce at least one intermediate compound, wherein said mole ratio is the total 5 moles of said first organic compound to the total moles of said alkyl polyamine; and (e) mixing said at least one intermediate compound with said second organic compound (c) to produce said composition. 10 5. The process of claim 4 wherein said quaternized compound having a substituted diethylamino moiety has the general formula: R1 R3 (CR,)n iCHCHz-N\/N-(CH2)q-NtCH2CH-(CR7)n-R3) given and defined in claim 1. 6. A process according to claim 4 or claim 5 wherein said at least one intermediate compound has the general formula: Rue 25 NON-(cH2)q-NH2 CH2(CH2)p wherein R' is 30 (i) a substituted or unsubstituted, saturated or unsaturated alkyl group -25- having from about 5 to about 29 carbon atoms; (ii) a substituted or unsubstituted, saturated or unsaturated alkyl group having from about 5 to about 29 carbon atoms which is at least oxygenized, sulfurized or phosphorylized; and 5 (iii) a mixture "hereof; p = 1 to about 5 and q = 2 to about 10. 7. A process according to claim 5 or claim 6 wherein R' of said quaterized compound is (a) an unsubstituted, unsaturated alkyl group having from about 7 10 to about 23 carbon atoms, (b) a substituted, unsaturated alkyl group having from about 7 to about 23 carbon atoms, or (c) a sulfurized unsubstituted, saturated and unsaturated alkyl group having from about 7 to about 23 carbon atoms. 15 8. A process according to claim 5, claim 6 or claim 7 wherein R3 is a carboxylate moiety. 9. A composition produced by the process according to any one of claims 4 to 8. 10. Use of the composition according to claim 9 for reducing the corrosion rate of a metal by a fluid having at least one corrosion agent. 11. Methods of reducing corrosion rate substantially as herein described 25 and exemplified. 12. Processes for the production of a corrosion inhibitor composition substantially as herein described and exemplified. -26 f Amendments to the claims have been filed as follows CLAIMS:

1. A method of reducing the corrosion rate of a metal by a fluid having at least one corrosion agent, said method comprising contacting the metal 5 with an inhibitor composition having at least one quaternized substituted diethylamino compound having the general formula: R1 R3 (CR7) n-CHCH2-NO N-(Ch2)q tCH2C -(CR,)n-R3) R8 CH2-(CH2)p 10 wherein R' is a (i) substituted or unsubstituted, saturated or unsaturated alkyl group having from about 5 to about 29 carbon atoms; (ii) substituted or unsubstituted, saturated or unsaturated alkyl group having from about 5 to about 29 carbon atoms which is at least _-15 =- =--==oger.-ized, sul. furizecl or-phosphorylized=.or (iii) a mixture thereof; each R3 is independently a -CO2H, -SO3H, -PO3H2, -CO2R7, -CONH2, CONHR7 and -CON(R7)

2 group or mixture thereof; each R7 is independently hydrogen or linear or a branched alkyl, 20 aryl, alkylaryl, cycloalkyl or heteroaromatic group having from 1 to about 10 carbon atoms, or mixtures thereof; R8 is hydrogen or a linear alkyl group having from 1 to about 10 carbon atoms; and n = 0 to about 8, p = 1 to about 5 and q = 2 to about 10.

..,.... ,.....,,,.,,,.,,,.,,..,. _,...CLME: 2. A method according to claim 1 wherein R' is (a) unsubstituted,

- if., I- r fig unsaturated aikyl groups having from about 7 to about 23 carbon atoms.

(b) substituted, unsaturated alkyl groups having from about 7 to about 23 carbon atoms, or (c) sulfurized unsubstituted, saturated and unsaturated alkyl groups having from about 7 to about 23 carbon atoms.

3. A method according to claim 1 or claim 2 wherein R3 is a carboxylate moiety.

4. Methods of reducing corrosion rate substantially as herein 10 described and exemplified.