Ethylene tar dispersants and charge gas compressor surface modifiers

Abstract

A method of preventing fouling in a quench system or charge gas compressor of an ethylene plant comprising adding to the system and / or compressor a dispersant chemistry comprising an effective amount of a reaction product formed by reaction of reactants (A), (B), and (C), wherein (A) comprises an alkyl substituted phenol of the structure Formula (I), (B) comprises a polyamine of the structure, Formula (II), and (C) comprising an aldehyde of the structure, Formula (III).

Description

PCT P2023_028-WO-PCT (40980-912) ETHYLENE TAR DISPERSANTS AND CHARGE GAS COMPRESSOR SURFACE MODIFIERS CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to United States Provisional Patent Application No. 63 / 507,635, filed on June 12, 2023, which is incorporated by reference herein in its entirety.FIELD

[0002] The disclosed technology relates generally to compositions and methods for preventing fouling, deposition, and / or emulsification in ethylene plant quench systems and charge gas compressors. More specifically, the disclosed technology relates to compositions and methods for preventing fouling, deposition, and / or emulsification in ethylene plant quench systems and charge gas compressors by adding a dispersant chemistry. BACKGROUND

[0003] During the thermal cracking of feedstock (naphtha, LPG, ethane, shale gas, etc.) to produce ethylene, several secondary substances are also generated, including a relatively heavy condensable material, referred to by varied names such as tar, pyrolysis tar, ethylene tar, py-tar, cracker tar, residue, ethylene cracker residue, etc., and can manifest itself as solids or viscous liquids. This heavy material / tar is condensable in the quench section of the ethylene production plant, and can lead to considerable fouling throughout the quench system and dilution steam system. This heavy material / tar may also migrate to the hydrocarbon-water interface in the quench water separator and cause emulsification issues. When the cracking feedstock is light, such as shale gas, ethane, or LPG, less of this heavy material / tar is generated in the cracker, but somewhat counterintuitively, the problems caused by this heavy material / tar can be worse when cracking light feedstock because there is also a reduction in other condensable hydrocarbons that can help solubilize and naturally disperse the heavy material / tar. Fouled quench system components and emulsification issues in the quench water separator canPCT P2023_028-WO-PCT (40980-912) lead to reduced production throughput, operational challenges, reduced run lengths, and expensive cleaning operations.

[0004] Additionally, Charge Gas Compressors (CGCs) of ethylene production plants can experience fouling with a similar type material that will lead to throughput reductions and plant shutdowns for cleaning.

[0005] Improved chemistries to prevent fouling of these systems are needed. SUMMARY

[0006] The disclosed technology provides for compositions and methods for preventing fouling, deposition, and / or emulsification in ethylene plant quench systems and charge gas compressors.

[0007] Various aspects of the disclosure relate to a method of preventing fouling, deposition, plugging and / or emulsification in a quench system of an ethylene plant comprising adding to the system a dispersant chemistry comprising an effective amount of a reaction product formed by reaction of reactants (A), (B), and (C), wherein (A) comprises an alkyl substituted phenol of the structure

[0008] wherein R and R1are the same or different and are independently selected from alkyl, aryl, alkaryl, or arylalkyl of from about 1 to 20 carbon atoms and x is 0 or 1; (B) comprises a polyamine of the structure

[0009] or different and are independently selected from H, alkyl, aryl, aralkyl, or alkaryl having from 1 to 20 carbon atoms, y being 0 or 1; and (C) comprising an aldehyde of the structurePCT P2023_028-WO-PCT (40980-912)

[0010] wherein R4comprises H or C1-C6alkyl.

[0011] Various aspects of the disclosure relate to a method of preventing fouling in a charge gas compressor (CGC) of an ethylene plant comprising adding to the compressor a dispersant chemistry comprising an effective amount of a reaction product formed by reaction of reactants (A), (B), and (C), wherein (A) comprises an alkyl substituted phenol of the structure

[0012] wherein R and R1are the same or different and are independently selected from alkyl, aryl, alkaryl, or arylalkyl of from about 1 to 20 carbon atoms and x is 0 or 1; (B) comprises a polyamine of the structure

[0013] or different and are independently selected from H, alkyl, aryl, aralkyl, or alkaryl having from 1 to 20 carbon atoms, y being 0 or 1; and (C) comprising an aldehyde of the structure

[0015] In various aspects, the fouling may be caused by solid or viscous liquids comprising ethylene tar or polymers formed through radical-induced polymerization reactions. BRIEF DESCRIPTION OF THE FIGURES

[0016] 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.PCT P2023_028-WO-PCT (40980-912)

[0017] FIGS. 1A-1H illustrate the treatment effectiveness of an embodiment of the dispersant chemistry of the disclosure on a tar sample in caustic water as compared to untreated and comparative chemistries at t=0 minutes after shaking (FIGS. 1A and 1B), t=4 minutes after shaking (FIGS. 1C and 1D), t=120 minutes after shaking (FIGS. 1E and 1F), and t=24 hours after shaking (FIGS.1G and 1H).

[0018] FIGS. 2A-2G illustrate the treatment effectiveness of an embodiment of the dispersant chemistry of the disclosure on a tar sample in A-150 as compared to untreated and comparative chemistries before shaking (FIG. 2A), at t=0 minutes after shaking (FIGS.2B and 2C), at t=15 minutes after shaking (FIGS. 2D and 2E), and at t=60 minutes after shaking (FIGS.2F and 2G).

[0019] FIGS. 3A-3D illustrate the treatment effectiveness of an embodiment of the dispersant chemistry of the disclosure on a tar sample in caustic water as compared to untreated and comparative chemistries at t=0 minutes after shaking (FIGS. 3A and 3B) and t=30 minutes after shaking (FIGS.3C and 3D).

[0020] FIGS. 4A-4E illustrate the treatment effectiveness of an embodiment of the dispersant chemistry of the disclosure on a tar sample in A-150 as compared to untreated and comparative chemistries at t=0 minutes after shaking (FIG. 4A), at t=10 minutes after shaking (FIG. 4B), at t=45 minutes after shaking (FIG. 4C and 4D), and at t=65 minutes after shaking (FIG.4E).

[0021] FIGS. 5A-5C illustrate the treatment effectiveness of an embodiment of the dispersant chemistry of the disclosure on a tar sample in caustic water as compared to untreated and comparative chemistries at t=0 minutes after shaking (FIG. 5A), and at t=120 minutes after shaking (FIG.5B and 5C).

[0022] FIGS.6A and 6B illustrate the treatment effectiveness of an embodiment of the dispersant chemistry of the disclosure on a tar sample in A-150 as compared to untreated and comparative chemistries at t=0 minutes after shaking (FIG. 6A), and at t=35 minutes after shaking (FIG.6B).

[0023] FIGS.7A and 7B illustrate the treatment effectiveness of an embodiment of the dispersant chemistry of the disclosure on a tar sample in A-150 as compared to untreated and comparative chemistries at t=0 minutes after shaking (FIG. 7A), and at t=35 minutes after shaking (FIG.7B).PCT P2023_028-WO-PCT (40980-912)

[0024] FIGS.8A and 8B illustrate the treatment effectiveness of an embodiment of the dispersant chemistry of the disclosure on a tar sample in caustic water as compared to untreated and comparative chemistries at t=0 minutes after shaking (FIG. 8A), and at t=3 minutes after shaking (FIG.8B). DETAILED DESCRIPTION

[0025] 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 otherwise indicated, 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”.

[0026] “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.

[0027] 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.

[0028] The singular forms “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise.

[0029] The disclosed technology provides for compositions and methods for preventing fouling, deposition, and / or emulsification in ethylene plant quench systems and charge gas compressors.PCT P2023_028-WO-PCT (40980-912)

[0030] The compositions and methods disclosed herein provide a solution for ethylene plant quench systems that experience fouling, deposition, plugging, or emulsification issues caused by solids or viscous liquids (often referred to by terms such as tar, ethylene tar, pyrolysis tar, py-tar, residue, cracker residue, and other terms) by providing a dispersant chemistry that dissolves or disperses the solids and / or viscous liquids into an aqueous or hydrocarbon continuous phase, preventing the deposition of the solids and / or viscous liquids within the quench system and / or preventing the migration of the solids and / or viscous liquids to the hydrocarbon-water interface of a quench water separator. Without being bound by theory, by dispersing the heavy material / tar into either the bulk hydrocarbon phase or the bulk caustic phase, the heavy material / tar is not allowed to deposit / foul the quench system or the charge gas compressor. By also keeping the material in the bulk phase, it cannot migrate to the oil-hydrocarbon interface of the quench water separator, and thus cannot contribute to emulsion issues.

[0031] As used herein, the term “an effective amount” refers to any amount of the disclosed dispersant chemistry that is effective in preventing fouling, deposition, and / or emulsification in ethylene plant quench systems and charge gas compressors caused by fouling substances such as ethylene tar and / or polymers formed through radical-induced polymerization reactions.

[0032] As used herein, the term “tar” or “ethylene tar” refers to the by-product of thermal cracking feedstock (ethane, natural gas, naphtha, heavy gas oil, etc.) to produce ethylene. It may be in the form of a heavy solid or viscous liquid that often has a high carbon content and is often highly aromatic. In some cases, tar may also include inorganic components that are entrained in the feedstock or are byproducts of corrosion within the feedstock processing equipment.

[0033] In various aspects of the disclosed technology, a method of preventing fouling, deposition, and / or emulsification in ethylene plant quench systems or charge gas compressors is disclosed. In various aspects, the method comprises adding to the system or compressor a dispersant chemistry comprising an effective amount of a reaction product formed by reaction of reactants (A), (B), and (C), wherein (A) comprises an alkyl substituted phenol of the structurePCT P2023_028-WO-PCT (40980-912)

[0034] wherein R selectedfrom alkyl, aryl, alkaryl, or and x is 0 or 1;

[0035] wherein (B) comprises a polyamine of the structure

[0036] wherein Z is a positive integer, R2and R3may be the same or different and are independently selected from H, alkyl, aryl, aralkyl, or alkaryl having from 1 to 20 carbon atoms, y may be 0 or 1; and wherein (C) comprises an aldehyde of the structure

[0037] wherein R4 may be selected from hydrogen and alkyl having 1 to 6 carbon atoms.

[0038] In various aspects, exemplary compounds that may fall within the scope of Formula I include p-cresol, 4-ethylphenol, 4-t-butylphenol, 4-t-amylphenol, 4-t- octylphenol, 4-dodecylphenol, 2,4-di-t-butylphenol, 2,4-di-t-amylphenol, and 4- nonylphenol.

[0039] In various aspects, exemplary polyamines which may be used in accordance with Formula II include ethylenediamine, propylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentaamine and the like.

[0040] In various aspects, the aldehyde component may comprise formaldehyde, acetaldehyde, propanaldehyde, butrylaldehyde, hexaldehyde, heptaldehyde, and the like. In some aspects, the formaldehyde may be used in its monomeric form, or its polymeric form, i.e., paraformaldehyde.

[0041] In various aspects, the reaction may proceed at temperatures from about 50°C to about 200°C, or between about 75°C to about 175°C. In various aspects, the timePCT P2023_028-WO-PCT (40980-912) required for completion of the reaction may vary from about 1 to about 8 hours, varying based on the specific reactants chosen and the reaction temperature.

[0042] In various aspects, the molar range of components (A):(B):(C) may fall within 0.5-5:1:0.5-5, or from about 1-2:1:1-2, or from about 2:1:2.

[0043] In various aspects, the dispersant chemistries of the disclosure may be added in an amount of about 0.05 to 50,000 ppm, or from about 0.5; 1; 50; 100; 200; 300; 400; 500; 600; 700; 800; 900; 1,000; 2,000; 3,000; 4,000; 5,000; 10,000; 20,000; 30,000; 40,000; or 50,000 ppm, or about 1 ppm to about 10,000 ppm, or about 5 ppm to about 500 ppm, or about 200 ppm, or any value between any of these amounts.

[0044] In various aspects, the methods may further comprise adding to the system or compressor, a wash oil.

[0045] In various aspects of the disclosed methods, the fouling, deposition, and / or emulsification may be caused by solid or viscous liquids comprising ethylene tar or polymers formed through radical-induced polymerization reactions.

[0046] In various aspects, the disclosed method may be used in quench systems of an ethylene plant, charge gas compressors, or any other system that would benefit from the disclosed methods. EXAMPLES

[0047] 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.

[0048] Examples

[0049] Preparation of Reaction Products

[0050] 15.9 gm of Paraform (92% active), 61 gm (technical grade) of nonylphenol, and 40 gm of solvent A-150 were placed in a flask. The mixture was stirred and 15.4 (99% active) gm of ethylenediamine (EDA) was added. The temperature was allowed to rise from 15°C to 70°C. The reaction mixture was heated to 125°C while distilling off an azeotropic mixture of water and A-150. After 9 gm of water and 3 gm of A-150 were removed, the reaction was kept at 140°C for two additional hours. The mixture was cooled to the desired temperature and loaded into a storage container.

[0051] General Testing MethodsPCT P2023_028-WO-PCT (40980-912)

[0052] Ethylene tar deposits were examined either in an aqueous phase or organic phase environment. A solution of caustic water with pH=10 represented the aqueous phase, while an A-150 solution represented the organic phase.

[0053] The tar was pre-heated at 80°C for 20 minutes and then shaken for 1 minute at a constant rate. After shaking, and under continued heating, the settling rate between the untreated sample and each treatment sample was compared. To better assist the observation, a LED light panel was placed behind the Combi instrument. The guideline below explains how the best treatment was selected.

[0054] Case A: Untreated Tar sample was settled immediately

[0055] 1) Any treatment vials that blocked the light were considered effective.

[0056] 2) The effective treatments were ranked by how long they blocked the light. The treatment vial that blocked the light the longest was considered the best.

[0057] Case B: Untreated Tar sample was slowly settled

[0058] 1) Ineffective treatment vials that allowed the light fully to pass through were eliminated.

[0059] 2) At specific periods, treatments were compared by the darkness of the solution and the volume of dark materials at the tip of the vials. The darkest solution with the least materials volume at the tip of a vial was considered the best treatment.

[0060] 3) Compared to the untreated sample vial, the best treatment was effective if it blocked the light longer than the untreated sample vial. The effective treatments were determined by the long blocking time and / or less amount of settling deposit.

[0061] Example 1

[0062] 0.2 g of tar was individually added into a set of 245 mL combi vials.4 mL of a pH=10 caustic water and various treatment chemistries, as listed in Table 1 below, were added to each vial. The vials were preheated to 80°C for 20 minutes. The vials were then shaken for 1 minute at the level 4 mark on the Combi instrument. Photos were taken and the effectiveness of the treatments were compared.

[0063] Table 1 Vial Number Product Dosage (ppmA)P2023_028-WO-PCT (40980-912) 6 Comparative Treatment 3 200 7 Comparative Treatment 4 200 f thed spersant c em stry o t e d sc osure, ex b ted super or g t b oc ng act v ty when compared to the untreated vials 1, 9 and 17 and the comparative vials 2-8, 10-16, 18-20 and 22-24.

[0065] Example 2

[0066] 0.2 g of tar was individually added into a set of 245 mL combi vials.4 mL of A-150 and various treatment chemistries, as listed in Table 2 below, were added to each vial. The vials were preheated to 80°C for 20 minutes. The vials were then shaken for 1 minute at the level 4 mark on the Combi instrument. After shaking, and under continued heating, photos were taken and the effectiveness of the treatments were compared.

[0067] Table 2 Vial Number Product Dosage (ppmA)P2023_028-WO-PCT (40980-912) 10 Comparative Treatment 6 200 11 Comparative Treatment 7 200 f thespe sa c e s y o e sc osu e, e e supe o g oc g ac v y over a period of time of up to 60 minutes when compared to the untreated vials 1, 9 and 17 and the comparative vials 2-8, 10-16, 18-20 and 22-24.

[0069] Example 3

[0070] 0.2 g of tar was individually added into a set of 11 5 mL combi vials numbered 12-22. 4 mL of caustic and various treatment chemistries, as listed in Table 3 below, were added to each vial. The vials were preheated to 80°C for 20 minutes. The vials were then shaken for 1 minute at the level 4 mark on the Combi instrument. After shaking, and under continued heating, photos were taken and the effectiveness of the treatments were compared.

[0071] Table 3 Vial Number Product Dosage (ppmA)P2023_028-WO-PCT (40980-912)

[0072] As shown in FIGS. 3A-3D, vial 13, which included an embodiment of the dispersant chemistry of the disclosure, exhibited superior light blocking activity over a period of time of up to 30 minutes when compared to the untreated vials 12 and 20 and the comparative vials 14-19, 21 and 22.

[0073] Example 4

[0074] 0.2 g of tar was individually added into a set of 115 mL combi vials.4 mL of A-150 and various treatment chemistries, as listed in Table 4 below, were added to each vial. The vials were preheated to 80°C for 20 minutes. The vials were then shaken for 1 minute at the level 4 mark on the Combi instrument. After shaking, and under continued heating, photos were taken and the effectiveness of the treatments were compared.

[0075] Table 4 Vial Number Product Dosage (ppmA) 1 Untreated thedispersant chemistry of the disclosure, exhibited superior light blocking activity over a period of time of up to 65 minutes when compared to the untreated vials 1 and 6 and the comparative vials 3-5 and 7-11.

[0077] Example 5

[0078] 0.2 g of tar was individually added into a set of 115 mL combi vials.4 mL of caustic water and various treatment chemistries, as listed in Table 5 below, were added to each vial. The vials were preheated to 80°C for 20 minutes. The vials were then shaken for 1 minute at the level 4 mark on the Combi instrument. After shaking, and under continued heating, photos were taken and the effectiveness of the treatments were compared.

[0079] Table 5P2023_028-WO-PCT (40980-912) Vial Number Product Dosage (ppmA) 1 Untreated f thep y , p g g y ver a period of time of up to 120 minutes when compared to the untreated vials 1 and 6 and the comparative vials 3-5 and 7-11.

[0081] Example 6

[0082] 0.2 g of tar was individually added into a set of 55 mL combi vials. 4 mL of A-150 and various treatment chemistries, as listed in Table 6 below, were added to each vial. The vials were preheated to 80°C for 20 minutes. The vials were then shaken for 1 minute at the level 4 mark on the Combi instrument. After shaking, and under continued heating, photos were taken and the effectiveness of the treatments were compared.

[0083] Table 6 Vial Number Product Dosage (ppmA) 1 U t t d f thedispersant chemistry of the disclosure, exhibited superior light blocking activity over a period of time of up to 35 minutes when compared to the untreated vial 1 and the comparative vials 3-5.

[0085] Example 7

[0086] 0.2 g of tar was individually added into a set of 55 mL combi vials. 4 mL of A-150 and various treatment chemistries, as listed in Table 7 below, were added to eachP2023_028-WO-PCT (40980-912) vial. The vials were preheated to 80°C for 20 minutes. The vials were then shaken for 1 minute at the level 4 mark on the Combi instrument. After shaking, and under continued heating, photos were taken and the effectiveness of the treatments were compared.

[0087] Table 7 Vial Number Product Dosage (ppmA) 1 Untreated f thep y , p g g y ver a period of time of up to 35 minutes when compared to the untreated vial 1 and the comparative vials 3-5.

[0089] Example 8

[0090] 0.2 g of tar was individually added into a set of 55 mL combi vials. 4 mL of caustic water and various treatment chemistries, as listed in Table 6 below, were added to each vial. The vials were preheated to 80°C for 20 minutes. The vials were then shaken for 1 minute at the level 4 mark on the Combi instrument. After shaking, and under continued heating, photos were taken and the effectiveness of the treatments were compared.

[0091] Table 8 Vial Number Product Dosage (ppmA) 1 U d f thedispersant chemistry of the disclosure, exhibited superior light blocking activity over a period of time of up to 3 minutes when compared to the untreated vial 1 and the comparative vials 3-5.

[0093] While embodiments of the disclosed technology have been described, it should be understood that the present disclosure is not so limited and modifications mayPCT P2023_028-WO-PCT (40980-912) 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

PCT P2023_028-WO-PCT (40980-912) CLAIMS 1. A method of preventing fouling, deposition, plugging and / or emulsification in a quench system of an ethylene plant comprising adding to the system a dispersant chemistry comprising an effective amount of a reaction product formed by reaction of reactants (A), (B), and (C), wherein (A) comprises an alkyl substituted phenol of the structure wherein R and R1are selected from alkyl, aryl,alkaryl, or arylalkyl of from about 1 to 20 carbon atoms and x is 0 or 1; (B) comprises a polyamine of the structure . wherein Z is a positive integer, R2 and R3 are the same or different and are independently selected from H, alkyl, aryl, aralkyl, or alkaryl having from 1 to 20 carbon atoms, y being 0 or 1; and (C) comprising an aldehyde of the structure wherein R4 comprises H or C1-C6 alkyl.

2. The method of claim 1, wherein the fouling, deposition, plugging and / or emulsification is caused by solid or viscous liquids comprising ethylene tar.

3. The method of claim 1, wherein the molar ratio of reactants (A):(B):(C) is 0.5- 5:1:0.5-5.PCT P2023_028-WO-PCT (40980-912) 4. The method of claim 1, wherein the reaction product is added to the quench system in an amount of from 0.5 to 50,000 ppm.

5. The method of claim 4, wherein the reaction product is added to the quench system in an amount of 1 to 10,000 ppm.

6. The method of claim 4, wherein the reaction product is added to the quench system in an amount of 5 to 500 ppm.

7. The method of claim 4, wherein the reaction product is added to the quench system in an amount of about 200 ppm.

8. The method of claim 1, wherein (A) comprises a member or members selected from the group consisting of p-cresol, 4-ethylphenol, 4-t-butylphenol, 4-t-amylphenol, 4-t- octylphenol, 4-dodecylphenol, 2,4-di-t-butylphenol, 2,4-di-t-amylphenol, and 4- nonylphenol.

9. The method of claim 1, wherein the polyamine (B) is selected from the group consisting of ethylenediamine and triethylenetetramine.

10. The method of claim 1, wherein the aldehyde (C) is selected from the group consisting of formaldehyde and paraformaldehyde.

11. A method of preventing fouling in a charge gas compressor (CGC) of an ethylene plant comprising adding to the compressor a dispersant chemistry comprising an effective amount of a reaction product formed by reaction of reactants (A), (B), and (C), wherein (A) comprises an alkyl substituted phenol of the structurePCT P2023_028-WO-PCT (40980-912) wherein R and R1are the same or different and are independently selected from alkyl, aryl, alkaryl, or arylalkyl of from about 1 to 20 carbon atoms and x is 0 or 1; (B) comprises a polyamine of the structure . are independentlyselected from H, alkyl, aryl, aralkyl, or alkaryl having from 1 to 20 carbon atoms, y being 0 or 1; and (C) comprising an aldehyde of the structure wherein R4 comprises H12. The method of claim 11, wherein the fouling is caused by solid or viscous liquids comprising ethylene tar or polymers formed through radical-induced polymerization reactions.

13. The method of claim 11, wherein the molar ratio of reactants (A):(B):(C) is 0.5- 5:1:0.5-5.

14. The method of claim 11, wherein the reaction product is added to the CGC in an amount of from 0.5 to 50,000 ppm.

15. The method of claim 14, wherein the reaction product is added to the CGC in an amount of 1 to 10,000 ppm.

16. The method of claim 14, wherein the reaction product is added to the CGC in an amount of 5 to 500 ppm.

17. The method of claim 14, wherein the reaction product is added to the CGC in an amount of about 200 ppm.PCT P2023_028-WO-PCT (40980-912) 18. The method of claim 11, wherein (A) comprises a member or members selected from the group consisting of p-cresol, 4-ethylphenol, 4-t-butylphenol, 4-t-amylphenol, 4-t- octylphenol, 4-dodecylphenol, 2,4-di-t-butylphenol, 2,4-di-t-amylphenol, and 4- nonylphenol.

19. The method of claim 11, wherein the polyamine (B) is selected from the group consisting of ethylenediamine and triethylenetetramine.

20. The method of claim 11, wherein the aldehyde (C) is selected from the group consisting of formaldehyde and paraformaldehyde.

21. The method of claim 11, wherein the method further comprises adding a wash oil.

Images