Method to prevent or clean organic fouling in steam generating systems

Abstract

A treatment composition comprising a carboxylate surfactant solution comprising alkyl or alkenyl (C6-C22) succinic acids, alkyl or alkenyl (C6-C22) dicarboxylic acids, or mixtures thereof; and methods of use thereof.

Description

METHOD TO PREVENT OR CLEAN ORGANIC FOULING IN STEAM GENERATING SYSTEMSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] The present application claims the benefit of United States Provisional Application Serial No. 63 / 608,910 filed December 12, 2023, the contents of which is incorporated herein by reference.FIELD

[0002] The disclosed technology relates to compositions and methods for preventing or reducing fouling in steam generating systems. More specifically, the disclosed technology relates to compositions for preventing or reducing fouling in steam generating systems comprising a carboxylate surfactant solution, and methods of use of such compositions.BACKGROUND

[0003] Organic fouling in steam generating systems can cause catastrophic boiler tube failures, which can hinder reliable operation of refineries and petrochemical plants. Oil contamination in boiler feed water (BFW), especially in refineries and petrochemical plants, is becoming more and more common due to either process leakage or deferred maintenance. This is undesirable because, once oil enters the system, it can agglomerate with metal or metal- oxides to form a deposit on heat transfer surfaces resulting in over-heating and related boiler tube failures. Conventional inorganic deposit control approaches, i.e., various polymer treatment programs, are ineffective in mitigating such an issue because of their inability to interact with or disperse hydrocarbons.

[0004] Surface active agents, also known as surfactants, are known for their ability to interact with both oil and water because of their water-loving hydrophilic head and oil-loving hydrophobic tail. These properties of surfactants make them suitable for dispersing and removing oil from boiler systems. However, because of the high temperature and pressure of boiler applications, many surfactant systems undergo severe thermal decomposition, making them ineffective. In certain instances, the decomposed by-products of surfactants, such as SO4, and low molecular organic acids, could be detrimental to the boiler system as they can corrode equipment involved in the steam-water cycle. More stable solutions are needed.SUMMARY

[0005] The disclosed technology provides for preventing or reducing fouling on metallic surfaces in steam generating systems by adding compositions including a carboxylate surfactant solution.

[0006] Various aspects of the disclosure relate to a treatment composition comprising a carboxylate surfactant solution comprising alkyl or alkenyl (C6-C22) succinic acids and anhydrides, alkyl or alkenyl (C6-C22) dicarboxylic acids, or mixtures thereof.

[0007] Various aspects of the disclosure additionally relate to a method of preventing or reducing fouling in steam generating systems comprising adding an effective amount of a treatment composition comprising a carboxylate surfactant solution comprising alkyl or alkenyl (C6-C22) succinic acids, alkyl or alkenyl (C6-C22) dicarboxylic acids, or mixtures thereof.BRIEF DESCRIPTION OF THE FIGURES

[0008] Those of skill in the art will understand that the figures, described below, are for illustrative purposes only. The figures are not intended to limit the scope of the present teachings in any way.

[0009] FIG. 1 illustrates ethylene tar dispersion after various treatments: A) blank; B) resin oxyalkylate; C) polyisobutylene succinimide (PIBSI) derivative; D) a first embodiment of the carboxylate surfactant solution of the disclosure; E) a second embodiment of the carboxylate surfactant solution of the disclosure.DETAILED DESCRIPTION

[0010] Approximating language, as used herein throughout the specification and claims, may be applied to modify any quantitative representation that could permissibly vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as “about”, is not limited to the precise value specified. In at least some instances, the approximating language may correspond to the precision of an instrument for measuring the value. Range limitations may be combined and / or interchanged, and such ranges are identified and include all the sub-ranges stated herein unless context or language indicates otherwise. Other than in the operating examples or where otherwiseindicated, all numbers or expressions referring to quantities of ingredients, reaction conditions and the like, used in the specification and the claims, are to be understood as modified in all instances by the term “about”.

[0011] “Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, or that the subsequently identified material may or may not be present, and that the description includes instances where the event or circumstance occurs or where the material is present, and instances where the event or circumstance does not occur or the material is not present.

[0012] As used herein, the terms “comprises”, “comprising”, “includes”, “including”, “has”, “having”, or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article or apparatus that comprises a list of elements is not necessarily limited to only those elements, but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

[0013] The singular forms “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise.

[0014] The disclosed technology provides for compositions and methods for use in preventing or reducing fouling in steam generating systems comprising a carboxylate surfactant solution comprising alkyl or alkenyl (C6-C22) succinic acids, alkyl or alkenyl (C6-C22) dicarboxylic acids, or mixtures thereof.

[0015] The compositions and methods disclosed herein exhibit excellent thermal stability under boiler conditions and may be used to mitigate organic fouling in boiler systems. Without being bound by theory, the compositions of the disclosure may prevent or reduce fouling by (1) solubilizing or dispersing oil into the water phase, preventing it from sticking to the pipe walls and heat transfer surfaces, and removing oil from the system via boiler blowdown; and / or (2) penetrating and loosening existing oil-metal / metal-oxide complexes and making them easier to be transported out of the system with the aid of a polymeric dispersant.

[0016] As used herein, the term “an effective amount” refers to any amount of the disclosed composition that is effective in preventing or reducing fouling in a steam generating system.

[0017] In various aspects of the disclosed technology, a treatment composition for use in preventing or reducing fouling in steam generating systems is disclosed. In various aspects, the treatment composition comprises a carboxylate surfactant solution. In some aspects, thetreatment composition comprises a carboxylate surfactant solution comprising alkyl or alkenyl (C6-C22) succinic acids. In some aspects, the treatment composition comprises a carboxylate surfactant solution comprising alkyl or alkenyl (C6-C22) dicarboxylic acids. In some aspects, the treatment composition comprises a carboxylate surfactant solution comprising a mixture of alkyl or alkenyl (C6-C22) succinic acids and alkyl or alkenyl (C6-C22) dicarboxylic acids.

[0018] In various aspects, suitable alkyl or alkenyl (C6-C22) succinic acids may include any alkyl or alkenyl (C6-C22) succinic acid that is effective in preventing or reducing fouling in high temperature heating and steam generating systems. In some aspects, suitable alkyl or alkenyl (C6-C22) succinic acids may include octenyl succinic acids, or the like. In various aspects, suitable alkyl or alkenyl (C6-C22) dicarboxylic acids may include any alkyl or alkenyl (C6-C22) dicarboxylic acid that is effective in preventing or reducing fouling in steam generating systems. In some aspects, suitable alkyl or alkenyl (C6-C22) dicarboxylic acids may include azelaic acid, sebacic acid, or the like, or combinations thereof

[0019] In various aspects, the treatment composition may further comprise a neutralizing agent. Suitable neutralizing agents may include any agent that is effective in neutralizing the succinic and dicarboxylic acids described herein. In some aspects, suitable neutralizing agents may include alkali metal hydroxides, such as sodium hydroxide, potassium hydroxide, or the like, or combinations thereof. In other aspects, suitable neutralizing agents may include neutralizing amines such as monoethanolamine, cyclohexylamine, morpholine, diethylaminoethanol, methoxypropylamine, or the like, or combinations thereof.

[0020] In various aspects, the treatment composition may further comprise a stabilizing agent. Suitable stabilizing agents may include any agent that is effective in stabilizing the treatment composition. In some aspects, suitable stabilizing agents may include non-ionic surfactants or polymers, or combinations thereof.

[0021] In various aspects, the treatment composition may include from 1 ppm to about 1000 ppm of the carboxylate surfactant solution, or from about 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, or 1000 ppm of the carboxylate surfactant solution, or from about 100 ppm to about 500 ppm, or about 200 ppm to 300 ppm, or any amount between any of these values.

[0022] In various aspects, the treatment compositions of the disclosed technology may be used in a method of preventing or reducing fouling in steam generating systems. In various aspects, the method may include adding an effective amount of a treatment compositioncomprising a carboxylate surfactant solution. In some aspects, the treatment composition comprises a carboxylate surfactant solution comprising alkyl or alkenyl (C6-C22) succinic acids. In some aspects, the treatment composition comprises a carboxylate surfactant solution comprising alkyl or alkenyl (C6-C22) dicarboxylic acids. In some aspects, the treatment composition comprises a carboxylate surfactant solution comprising a mixture of alkyl or alkenyl (C6-C22) succinic acids and alkyl or alkenyl (C6-C22) dicarboxylic acids.

[0023] In various aspects, suitable alkyl or alkenyl (C6-C22) succinic acids may include any alkyl or alkenyl (C6-C22) succinic acid that is effective in preventing or reducing fouling in steam generating systems. In some aspects, suitable alkyl or alkenyl (C6-C22) succinic acids may include octenyl succinic acids, or the like. In various aspects, suitable alkyl or alkenyl (C6-C22) dicarboxylic acids may include any alkyl or alkenyl (C6-C22) dicarboxylic acid that is effective in preventing or reducing fouling in steam generating systems. In some aspects, suitable alkyl or alkenyl (C6-C22) dicarboxylic acids may include azelaic acid, sebacic acid, or the like, or combinations thereof

[0024] In various aspects, the treatment composition may further comprise a neutralizing agent. Suitable neutralizing agents may include any agent that is effective in neutralizing the succinic and dicarboxylic acids described herein. In some aspects, suitable neutralizing agents may include alkali metal hydroxides, such as sodium hydroxide, potassium hydroxide, or the like, or combinations thereof. In other aspects, suitable neutralizing agents may include neutralizing amines such as monoethanolamine, cyclohexylamine, morpholine, diethylaminoethanol, methoxypropylamine, or the like, or combinations thereof.

[0025] In various aspects, the treatment composition may further comprise a stabilizing agent. Suitable stabilizing agents may include any agent that is effective in stabilizing the treatment composition. In some aspects, suitable stabilizing agents may include non-ionic surfactants or polymers, or combinations thereof.

[0026] In various aspects, the treatment composition may be added in an amount from 1 ppm to about 1000 ppm, or from about 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, or 1000 ppm, or from about 100 ppm to about 500 ppm, or about 200 ppm to 300 ppm, or any amount between any of these values.

[0027] In various aspects of the disclosed method, the steam generating systems may include boiler systems and heat transfer systems.EXAMPLES

[0028] The present technology will be further described in the following examples, which should be viewed as being illustrative and should not be construed to narrow the scope of the disclosed technology or limit the scope to any particular embodiments.

[0029] Example 1

[0030] Boiler organic deposit (ethylene tar) dispersions in the presence of various treatments were evaluated through simple closed bottle shaker tests. Samples were prepared by adding 0.2 g of organic deposit in solutions containing 200 ppm of the following treatments: Treatment A: blank; Treatment B: resin oxyalkylate; Treatment C: PIBSI derivative; Treatment D: surfactant solution comprising a mixture of octenyl succinic acids; Treatment E: octenyl succinic acid. The pH of each treatment solution was adjusted to around 8.5 with a dilute NaOH solution. The prepared samples were then transferred to shaker equipment, where they were gently stirred (50 rpm) for 19 days at 125°C. After 19 days, samples were removed from the shaker and the tar dispersant efficacy of treatments were qualitatively evaluated.

[0031] As can be seen in FIG. 1, with Treatments B and C, deposits were settled at the bottom of the sample vials, suggesting that these treatments were not effective ethylene / organic tar dispersants. However, with Treatments D and E, deposits were dispersed in the water phase, indicating that the treatments containing octenyl succinic acids were effective in dispersing the organic / ethylene tar.

[0032] While embodiments of the disclosed technology have been described, it should be understood that the present disclosure is not so limited and modifications may be made without departing from the disclosed technology. The scope of the disclosed technology is defined by the appended claims, and all devices, processes, and methods that come within the meaning of the claims, either literally or by equivalence, are intended to be embraced therein.

Claims

CLAIMS1. A treatment composition comprising a carboxylate surfactant solution comprising alkyl or alkenyl (C6-C22) succinic acids, alkyl or alkenyl (C6-C22) dicarboxylic acids, or mixtures thereof.

2. The treatment composition of claim 1, wherein the carboxylate surfactant solution comprises alkyl or alkenyl (C6-C22) succinic acids.

3. The treatment composition of claim 1, wherein the carboxylate surfactant solution comprises alkyl or alkenyl (C6-C22) dicarboxylic acids.

4. The treatment composition of claim 1, wherein the carboxylate surfactant solution comprises a mixture of alkyl or alkenyl (C6-C22) succinic acids and alkyl or alkenyl (C6-C22) dicarboxylic acids.

5. The treatment composition of claim 1, wherein the carboxylate surfactant solution comprises octenyl succinic acids.

6. The treatment composition of claim 1, wherein the carboxylate surfactant solution comprises azelaic acid, sebacic acid, or combinations thereof.

7. The treatment composition of any one of claims 1-6, further comprising a neutralizing agent.

8. The treatment composition of claim 7, wherein the neutralizing agent comprises sodium hydroxide or potassium hydroxide.

9. The treatment composition of claim 7, wherein the neutralizing agent comprises a neutralizing amine.

10. The treatment composition of claim 9, wherein the neutralizing amine is selected from monoethanolamine, cyclohexylamine, morpholine, diethylaminoethanol, methoxypropylamine, and combinations thereof.

11. The treatment composition of any one of claims 1-10, further comprising one or more stabilizing agents.

12. The treatment composition of claim 11, wherein the stabilizing agents are selected from one or more non-ionic surfactants, one or more polymers, or combinations thereof.

13. A method of preventing or reducing fouling in steam generating systems comprising adding an effective amount of a treatment composition comprising a carboxylate surfactant solution comprising alkyl or alkenyl (C6-C22) succinic acids, alkyl or alkenyl (C6-C22) dicarboxylic acids, or mixtures thereof.

14. The method of claim 13, wherein the carboxylate surfactant solution comprises alkyl or alkenyl (C6-C22) succinic acids.

15. The method of claim 13, wherein the carboxylate surfactant solution comprises alkyl or alkenyl (C6-C22) dicarboxylic acids.

16. The method of claim 13, wherein the carboxylate surfactant solution comprises a mixture of alkyl or alkenyl (C6-C22) succinic acids and alkyl or alkenyl (C6-C22) dicarboxylic acids.

17. The method of claim 13, wherein the carboxylate surfactant solution comprises octenyl succinic acids.

18. The method of claim 13, wherein the carboxylate surfactant solution comprises azelaic acid, sebacic acid, or combinations thereof.

19. The method of any one of claims 13-18, wherein the treatment composition further comprises a neutralizing agent.

20. The method of claim 19, wherein the neutralizing agent comprises sodium hydroxide or potassium hydroxide.

21. The method of claim 19, wherein the neutralizing agent comprises a neutralizing amine.

22. The method of claim 21, wherein the neutralizing amine is selected from monoethanolamine, cyclohexylamine, morpholine, diethylaminoethanol, methoxypropylamine, and combinations thereof.

23. The method of any one of claims 13-22, wherein the treatment composition further comprises one or more stabilizing agents.

24. The method of claim 23, wherein the one or more stabilizing agents comprises one or more non-ionic surfactants, one or more polymers, or combinations thereof.

25. The method of claim 13, wherein the treatment composition is added in an amount of about 1 ppm to about 1000 ppm.

26. The method of any one of claims 13-25, wherein the steam generating system is a boiler system or a heat transfer system.

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