Patent Grant
11319634
The present disclosure is generally related to chemical compositions, and more particularly related to corrosion inhibitor compositions.
In the oil and gas industry, corrosion can be a reoccurring issue in refinery equipment, piping, and pipelines that are exposed to hydrocarbons feeds and other corrosive fluids. Among various types of corrosion, naphthenic acid corrosion is common in refinery processes that occur at high temperatures (e.g., 200° C. to 400° C.) and in refinery processes that process crude oil and its various fractions. For instance, naphthenic acid corrosion can be induced during distillation of an acidic crude oil. In some circumstances, this type of corrosion can be predicted in a given refinery apparatus based on the total acid number (TAN) of the fluid that is exposed to the apparatus.
Conventionally, corrosion inhibitors and corrosion-resistant alloys (CRAs) are used to mitigate naphthenic acid corrosion in refineries. For instance, phosphate-based corrosion inhibitors are known to have some effectiveness in controlling naphthenic acid corrosion. However, phosphate-based corrosion inhibitors can have negative effects on downstream refinery units, as these types of inhibitors can result in catalyst poisoning (partial or complete deactivation of the catalyst), for example.
The present application addresses these and other challenges related to mitigating and preventing corrosion in refinery equipment.
In a first aspect, a corrosion inhibitor composition is provided. The composition can include 2-aminoterephthalic acid, dimethyl sulfoxide and heavy aromatic naphtha (HAN). In another aspect, the composition includes approximately: 10-30 weight % of 2-aminoterephthalic acid, 60-80 weight % of dimethyl sulfoxide, and 10-30 weight % heavy aromatic naphtha.
In another aspect, the composition includes approximately: 20 weight % of 2-aminoterephthalic acid, 70 weight % of dimethyl sulfoxide, and 10 weight % heavy aromatic naphtha. In another aspect, the corrosion inhibitor composition inhibits corrosion caused by naphthenic acid. In another aspect, the corrosion inhibitor composition is free of phosphate.
In a second aspect, a corrosion inhibitor composition is provided, where the composition includes a corrosion inhibitor. The corrosion inhibitor is 4-methylamino benzoic acid or 4-methylsulfonyl benzoic acid. The corrosion inhibition composition further includes N-methyl pyrrolidone and heavy aromatic naphtha.
In another aspect, the composition comprises approximately: 10-30 weight % of the corrosion inhibitor, 60-80 weight % of N-methyl pyrrolidone, and 10-30 weight % heavy aromatic naphtha (HAN). In a further aspect, the corrosion inhibitor is 4-methylamino benzoic acid. In another aspect, the corrosion inhibitor is 4-methylsulfonyl benzoic acid.
In another aspect, the composition comprises approximately: 20 weight % of the corrosion inhibitor, 70 weight % of N-methyl pyrrolidone, and 10 weight % heavy aromatic naphtha (HAN). In a further aspect, the corrosion inhibitor is 4-methylamino benzoic acid. In a further aspect, the corrosion inhibitor is 4-methylsulfonyl benzoic acid. In another aspect, the corrosion inhibitor composition inhibits corrosion caused by naphthenic acid. In another aspect, the corrosion inhibitor composition is free of phosphate.
In a third aspect, a method for inhibiting corrosion on a metal surface exposed to a hydrocarbon fluid is provided. In the method, a corrosion inhibitor composition is added to the hydrocarbon fluid exposed to the metal surface, where the corrosion inhibitor composition includes 2-aminoterephthalic acid, 4-methylamino benzoic acid, or 4-methylsulfonyl benzoic acid.
In another aspect, the corrosion inhibitor composition is added to the hydrocarbon fluid in a concentration of approximately 100 ppm to approximately 1000 ppm. In another aspect, the corrosion inhibitor composition includes 2-aminoterephthalic acid, and further comprises dimethyl sulfoxide, and heavy aromatic naphtha (HAN). In another aspect, the corrosion inhibitor composition includes approximately: 20 weight % of 2-aminoterephthalic acid, 70 weight % of dimethyl sulfoxide, and 10 weight % heavy aromatic naphtha, and the corrosion inhibitor composition is added to the hydrocarbon fluid in a concentration of approximately 250 ppm.
In another aspect, the corrosion inhibitor composition includes 4-methylamino benzoic acid, and further includes N-methyl pyrrolidone, and heavy aromatic naphtha. In a further aspect, the corrosion inhibitor composition includes approximately: 20 weight % of, 4-methylamino benzoic acid, 70 weight % of N-methyl pyrrolidone, and 10 weight % heavy aromatic naphtha (HAN), and the corrosion inhibitor composition is added to the hydrocarbon fluid in a concentration of approximately 500 ppm.
In another aspect, the corrosion inhibitor composition comprises 4-methylsulfonyl benzoic acid, and further comprises N-methyl pyrrolidone, and heavy aromatic naphtha. In another aspect, the corrosion inhibitor composition comprises approximately: 20 weight % of 4-methylsulfonyl benzoic acid, 70 weight % of N-methyl pyrrolidone, and 10 weight % heavy aromatic naphtha (HAN), and the corrosion inhibitor composition is added to the hydrocarbon fluid in a concentration of approximately 1000 ppm.
In another aspect, the corrosion inhibitor composition is added to the hydrocarbon fluid in a refinery process, the refinery process is performed at a temperature of approximately 200° C. to approximately 400° C., and the corrosion inhibitor composition inhibits naphthenic acid corrosion on the metal surface.
By way of overview and introduction, the present application discloses compositions and methods for inhibiting corrosion on metal surfaces exposed to hydrocarbon fluids. The corrosion inhibitor compositions of the present application are phosphate-free and can comprise a corrosion inhibitor, such as 2-aminoterephthalic acid, 4-methylamino benzoic acid, or 4-methylsulfonyl benzoic acid. Specifically, in one or more embodiments, the corrosion inhibitor composition comprises (i) 2-aminoterephthalic acid, (ii) dimethyl sulfoxide, and (iii) heavy aromatic naphtha. In one or more embodiments, the corrosion inhibitor composition comprises (i) 4-methylamino benzoic acid or 4-methylsulfonyl benzoic acid, (ii) N-methyl pyrrolidone, and (iii) heavy aromatic naphtha.
In one or more embodiments of the present methods, a corrosion inhibitor composition of the present application can be added to a hydrocarbon fluid in a refinery process in which the hydrocarbon fluid is exposed to one or more metal surfaces. The addition of the corrosion inhibitor composition to the hydrocarbon fluid can mitigate or prevent corrosion on the metal surfaces typically caused by the hydrocarbon fluid. For example, the present compositions and methods can be used to mitigate or prevent naphthenic acid corrosion that is induced during high-temperature (e.g., 200° C. to 400° C.) refinery processes, such as distillation of an acidic crude oil. In such an embodiment, at least one of the present corrosion inhibitor compositions is added to the acidic crude oil, thereby reducing the amount of naphthenic acid corrosion that occurs on the metal surfaces exposed to the acidic crude oil.
As such, the present compositions and methods can be used to reduce corrosion—and in particular, naphthenic acid corrosion—in various refinery units, such as crude distillation units, vacuum distillations units, and furnaces, that are exposed to hydrocarbon fluids.
These and other aspects of the present compositions and methods are described in further detail below with reference to the accompany drawing figures, in which one or more illustrated embodiments and/or arrangements of the corrosion inhibitors are shown. The compositions and methods of the present application are not limited in any way to the illustrated embodiments and/or arrangements. It should be understood that the compositions and methods as shown in the accompanying figures are merely exemplary of the compositions and methods of the present application, which can be embodied in various forms as appreciated by one skilled in the art. Therefore, it is to be understood that any structural and functional details disclosed herein are not to be interpreted as limiting the present compositions and methods, but rather are provided as a representative embodiment and/or arrangement for teaching one skilled in the art one or more ways to implement the present compositions and methods.
The corrosion inhibitor compositions of the present application generally comprise at least one corrosion inhibitor.
In one or more embodiments, the corrosion inhibitor compositions can comprise one or more additional compounds in addition to the at least one corrosion inhibitor. For instance, in at least one embodiment, the corrosion inhibitor composition can comprise 2-aminoterephthalic acid, dimethyl sulfoxide, and heavy aromatic naphtha. In one or more implementations, the heavy aromatic naphtha as mentioned herein is the compound identified by CAS #64742-94-5.
In one or more embodiments, the corrosion inhibitor composition can comprise approximately 10-30 weight % of 2-aminoterephthalic acid, approximately 60-80 weight % of dimethyl sulfoxide, and approximately 10-30 weight % heavy aromatic naphtha. In at least one embodiment, the composition can comprise approximately 20 weight % of 2-aminoterephthalic acid, approximately 70 weight % of dimethyl sulfoxide, and approximately 10 weight % heavy aromatic naphtha. It should be understood that, as used in the present application, the term “approximately” when used in conjunction with a number refers to any number within 5% of the referenced number, including the referenced number.
In one or more embodiments, the corrosion inhibitor composition can comprise: (i) 4-methylamino benzoic acid or 4-methylsulfonyl benzoic acid; (ii) N-methyl pyrrolidone; and (iii) heavy aromatic naphtha. In at least one embodiment, the composition comprises approximately 10-30 weight % of either 4-methylamino benzoic acid or 4-methylsulfonyl benzoic acid, approximately 60-80 weight % of N-methyl pyrrolidone, and approximately 10-30 weight % heavy aromatic naphtha (HAN).
In at least one embodiment, the corrosion inhibitor composition can comprise approximately 20 weight % of either 4-methylamino benzoic acid or 4-methylsulfonyl benzoic acid, approximately 70 weight % of N-methyl pyrrolidone, and approximately 10 weight % heavy aromatic naphtha (HAN).
In accordance with one or more embodiments, the present application also discloses methods for inhibiting corrosion on a metal surface that is exposed to a hydrocarbon fluid. The present methods utilize one or more of the corrosion inhibitor compositions discussed above. In one or more embodiments, the method can comprise adding at least one of the corrosion inhibitor compositions of the present application to a hydrocarbon fluid exposed to the metal surface. The hydrocarbon fluid can be in-use in a metal refinery unit, such as a crude distillation unit, vacuum distillation unit, or furnace. The addition of the at least one corrosion inhibitor composition to the hydrocarbon fluid can reduce corrosion on the metal surfaces typically caused by the hydrocarbon fluid.
In one or more embodiments using the present methods, the corrosion inhibitor compositions can mitigate or prevent naphthenic acid corrosion that is induced during high-temperature (e.g., 200° C. to 400° C.) refinery processes, such as distillation of an acidic crude oil. For example, in one or more embodiments, at least one of the present corrosion inhibitor compositions can be added to an acidic crude oil that is used in a high-temperature refinery unit, such as a crude distillation unit. Acidic crude oil typical causes naphthenic acid corrosion on the metal surfaces of a crude distillation unit over time. However, the addition of the at least one corrosion inhibitor composition to the acidic crude oil mitigates the occurrence naphthenic acid corrosion or, in certain implementations, prevents naphthenic acid corrosion from occurring on the metal surfaces exposed to the acidic crude oil. In one or more embodiments, the at least one corrosion inhibitor composition is added to the hydrocarbon fluid (e.g., acidic crude oil) after it enters the refinery unit. As such, the corrosion inhibitor composition(s) of the present application can be continuously added in the hydrocarbon fluid at a selected parts per million (ppm) amount to protect the refinery equipment from naphthenic acid corrosion.
In one or more embodiments of the present methods, the corrosion inhibitor composition can be added to the hydrocarbon fluid in a concentration of approximately 100 ppm to approximately 1000 ppm. For example, in at least one embodiment, a corrosion inhibitor composition comprising approximately 20 weight % of 2-aminoterephthalic acid, approximately 70 weight % of dimethyl sulfoxide, and approximately 10 weight % heavy aromatic naphtha can be added to a hydrocarbon fluid in a concentration of approximately 250 ppm.
In one or more embodiments, a corrosion inhibitor composition comprising approximately 20 weight % of 4-methylamino benzoic acid, approximately 70 weight % of N-methyl pyrrolidone, and approximately 10 weight % heavy aromatic naphtha can be added to the hydrocarbon fluid in a concentration of approximately 500 ppm.
In at least one embodiment, a corrosion inhibitor composition comprising approximately 20 weight % of 4-methylsulfonyl benzoic acid, approximately 70 weight % of N-methyl pyrrolidone, and approximately 10 weight % heavy aromatic naphtha (HAN). It can be added to the hydrocarbon fluid in a concentration of approximately 1000 ppm. Additional aspects and advantages of the present compositions and methods are further described in the Example Section below, in which one or more illustrated embodiments and/or arrangements of the compositions and methods are shown and discussed.
In the present example, three formulations of the present corrosion inhibitor compositions were tested to show their ability to inhibit naphthenic acid corrosion on metal coupons exposed to a hydrocarbon stream in accordance with one or more embodiments herein.
Specifically, a rotating cage autoclave corrosion test was performed to measure the corrosion inhibition efficiency of the various formulations. The test was performed in accordance with ASTM standard G170. A hydrocarbon fluid comprising 310 gm (about 350 mL) of mineral oil heavy (CAS #8042-47-5) was provided to the rotating cage autoclave cell and 4.2 gm (about 4.56 mL) of naphthenic acid (CAS #1338-24-5; commercial grade with acid value of 230 mg KOH/g) was added to the fluid to make a test solution having a TAN value of 3 mg KOH/g.
Three formulations (formulations 1, 2, and 3) of corrosion inhibitor compositions were tested. The respective compositions of the three formulations are shown in Table 1 below:
The three formulations of corrosion inhibitor compositions were added separately in the test solution in separate runs and in varying concentrations as shown in results of Table 2, below. The mixture of the test solution and the respective formulations were exposed metal coupons in the test cell. A control run was also done in which no corrosion inhibitor composition was added to the test solution. Nitrogen gas purging was done to remove the oxygen content in the test solution as well as in the test cell. The experimental conditions were as follows:
These conditions were maintained for three hours. After the procedure, the metal coupons (corrosion specimens) were removed, excess oil was rinsed away, and the excess corrosion product was removed from the surface of the metal coupons using Clarke's solution. Each metal coupon was then weighed, and the corrosion rate was calculated in mils per year. The detailed steps of the rotating cage autoclave corrosion test are shown below:
The corrosion inhibition efficiency was calculated using the below equations. In this calculation, corrosion inhibition efficiency for each of the test formulations was calculated by comparing weight loss of the metal coupon due to the respective test formulations with weight loss of metal coupon in the test run without a corrosion inhibitor formulation.
Corrosion inhibition efficiency={(weight loss for coupon without corrosion inhibitor)−(weight loss for coupon with corrosion inhibitor)/(weight loss for coupon without corrosion inhibitor)}×100.
The corrosion rate in MPY (mils per year) was calculated by the following formula:
MPY={534×Weight loss in mg}/(Density in gm/cc)×(Area in inch2)×(Test duration in hours).
The results obtained from the rotating cage experiments with and without a corrosion inhibitor are presented in Table 2.
The corrosion inhibition efficiencies of the various formulations are presented in Table 2. The corrosion rate of the control experiment (i.e., run 1, without a corrosion inhibitor) was 221 mpy. The results of Table 2 also showed that each of formulations 1-3 at the varying concentrations exhibited substantial decreases in corrosion rate relative to control (run 1). Notably, formulation 1 exhibited 98% corrosion inhibition efficiency at 250 ppm concentration (run 3). Formulation 2 exhibited 70% corrosion inhibition efficiency at 500 ppm concentration (run 4), and formulation 3 exhibited 20% corrosion inhibition efficiency at 1000 ppm concentration (run 5). Formulation 1 also exhibited a 58% corrosion inhibition efficiency at 100 ppm concentration (run 2).
Accordingly, based on the experimental results, corrosion inhibitor formulations 1, 2 and 3 each showed corrosion inhibition efficiency in high-temperature naphthenic acid conditions (i.e., 300° C. and 3 TAN mineral oil solution). Formulations 1 and 2 were particularly effective at forming a protective barrier layer on the metal surfaces of the coupons in contact with the corrosive fluids. As such, the present experiments exemplify that the metal surfaces in refinery piping (e.g., furnaces, pump arounds) and equipment (e.g., crude distillation unit, vacuum distillation unit) can be protected from naphthenic acid corrosion by adding the corrosion inhibitor compositions of the present application to the corrosive fluids (e.g., 3 TAN mineral oil heavy).
Although much of the foregoing description has been directed to compositions and methods for inhibiting corrosion on metal surfaces in refineries or pipelines, the compositions and methods disclosed herein can be similarly deployed and/or implemented in scenarios, situations, and settings far beyond the referenced scenarios. It should be further understood that any such implementation and/or deployment is within the scope of the composition and methods described herein.
It is to be further understood that like numerals in the drawings represent like elements through the several figures, and that not all components and/or steps described and illustrated with reference to the figures are required for all embodiments or arrangements. Further, the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms “including,” “comprising,” or “having,” “containing,” “involving,” and variations thereof herein, when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It should be noted that use of ordinal terms such as “first,” “second,” “third,” etc., in the claims to modify a claim element does not by itself connote any priority, precedence, or order of one claim element over another or the temporal order in which acts of a method are performed, but are used merely as labels to distinguish one claim element having a certain name from another element having a same name (but for use of the ordinal term) to distinguish the claim elements.
Notably, the figures and examples above are not meant to limit the scope of the present disclosure to a single implementation, as other implementations are possible by way of interchange of some or all of the described or illustrated elements. Moreover, where certain elements of the present disclosure can be partially or fully implemented using known components, only those portions of such known components that are necessary for an understanding of the present disclosure are described, and detailed descriptions of other portions of such known components are omitted so as not to obscure the disclosure. In the present specification, an implementation showing a singular component should not necessarily be limited to other implementations including a plurality of the same component, and vice-versa, unless explicitly stated otherwise herein. Moreover, applicants do not intend for any term in the specification or claims to be ascribed an uncommon or special meaning unless explicitly set forth as such. Further, the present disclosure encompasses present and future known equivalents to the known components referred to herein by way of illustration.
The foregoing description of the specific implementations will so fully reveal the general nature of the disclosure that others can, by applying knowledge within the skill of the relevant art(s), readily modify and/or adapt for various applications such specific implementations, without undue experimentation, without departing from the general concept of the present disclosure. Such adaptations and modifications are therefore intended to be within the meaning and range of equivalents of the disclosed implementations, based on the teaching and guidance presented herein. It is to be understood that the phraseology or terminology herein is for the purpose of description and not of limitation, such that the terminology or phraseology of the present specification is to be interpreted by the skilled artisan in light of the teachings and guidance presented herein, in combination with the knowledge of one skilled in the relevant art(s). It is to be understood that dimensions discussed or shown are drawings are shown accordingly to one example and other dimensions can be used without departing from the disclosure.
The subject matter described above is provided by way of illustration only and should not be construed as limiting. Various modifications and changes can be made to the subject matter described herein without following the example embodiments and applications illustrated and described, and without departing from the true spirit and scope of the invention encompassed by the present disclosure, which is defined by the set of recitations in the following claims and by structures and functions or steps which are equivalent to these recitations.
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