Antifouling compositions for use in crude oil production and processing - Patents.com

Abstract

An antifouling composition and method for inhibiting fouling of structural parts in an oil refinery system exposed to hydrocarbon fluids is provided. An antifouling composition has been developed that advantageously reduces fouling of structural parts of petroleum refinery systems, including reducing coking reactions and inhibiting solids build-up in equipment and lines used in the production and processing of crude oil. The antifouling composition contains a resin comprising an alkylphenol-aldehyde resin, a polyolefin comprising a polyalkylene ester, a polyolefinamide alkenamine, a polyethylene polyamine, a polyalkylene imine, or a combination thereof, and optionally a polyalkylene imide, an amine substituted polyalkylene imide, or a combination thereof, and optionally N,N'-disalicylidene-1,2-propane diamine.

Description

[Technical field]

[0001] Antifouling compositions have been developed that advantageously reduce fouling of structural parts of petroleum refinery systems, including reducing coking reactions and inhibiting solids buildup in equipment and lines used in the production and processing of crude oil. Antifoulants may also be used in oil production processes. The antifouling compositions contain a resin including an alkylphenol-aldehyde resin, a polyolefin including a polyalkylene ester, a polyolefinamide alkenamine, a polyethylene polyamine, a polyalkylene imine, or a combination thereof, and optionally a polyalkylene imide, an amine substituted polyalkylene imide, or a combination thereof, and optionally N,N'-disalicylidene-1,2-propane diamine. [Background technology]

[0002] Petrochemical products and their feedstocks are typically heated to temperatures between about 35° C. and about 550° C. during processing. Additionally, petroleum hydrocarbons used as heating fluids in heating and heat exchange systems are similarly heated to high temperatures. When heated to such high temperatures, contaminant deposits can form on the petroleum hydrocarbons, which can form deposits on the surfaces of processing and heating equipment, fouling these surfaces.

[0003] Fouling deposits can slow the rate of heat transfer to the crude oil or other hydrocarbon streams and, over time, can slow the throughput of a heat exchanger or furnace. If not addressed, equipment fouling can progress to impede the flow of crude oil through processing equipment and piping, or plug filter screens, valves, and traps. Surface fouling can thus result in increased energy costs, increased capital costs (e.g., equipment modifications or replacement), and increased maintenance costs (e.g., cleaning or replacement of screens, filters, pipes, valves, traps, etc.).

[0004] Although the exact mechanism of contamination is unclear, several different components of the crude oil or hydrocarbon stream may be responsible for contamination. For example, asphaltenes, polycyclic aromatic hydrocarbons, coke, organic polymers, organic reaction products, inorganic silicates, inorganic salts, metal oxides, metal sulfides, etc. are believed to contribute to the complex nature of contamination deposits in petroleum processing. Furthermore, metal oxides and metal sulfides are believed to contribute to contamination by promoting degenerate branching and accelerating the oxidation rate of petroleum hydrocarbons by forming free radicals. The formed free radicals can subsequently react by oxidizing and polymerizing components of the petroleum to form gums, polymeric materials, and deposits. Summary of the Invention [Problem to be solved by the invention]

[0005] Due to the constraints of relatively low viscosity (e.g., less than 500 centipoise) and high stability, there remains a need for effective coke inhibition and antifouling compositions that inhibit (i.e., reduce or prevent) the fouling of structural parts of petroleum refinery systems exposed to hydrocarbon fluids. [Means for solving the problem]

[0006] The present disclosure relates to an antifouling composition for inhibiting fouling of structural parts in a petroleum refinery system exposed to hydrocarbon fluids, the antifouling composition comprising an effective amount of a resin comprising an alkylphenol-aldehyde resin and an effective amount of a polyolefin comprising a polyalkylene ester, a polyolefin amide alkene amine, a polyethylene polyamine, a polyalkylene imine, or a combination thereof.

[0007] The antifouling composition may further comprise an effective amount of a polyalkyleneimide, an amine-substituted polyalkyleneimide, or a combination thereof.

[0008] Additionally, the antifouling compositions described herein can further comprise an effective amount of a chelating compound, including N,N'-disalicylidene-1,2-propanediamine.

[0009] The antifouling composition comprises an alkylphenol-aldehyde resin, including an alkylphenol-formaldehyde resin.

[0010] Furthermore, the alkylphenol-aldehyde resin is C1-C 20 Alkylphenol-aldehyde resins, preferably C1-C 16 Alkylphenol-aldehyde resins, more preferably C1-C 12 Alkylphenol-aldehyde resins, even more preferably C3-C 12 Alkylphenol-aldehyde resins, even more preferably C6-C 12 Alkylphenol-aldehyde resins, most preferably nonylphenol-formaldehyde resins.

[0011] Further, the antifouling composition comprises a polyalkylene ester of a polyalkylene succinic acid ester, a polyalkylene succinic anhydride, a polyalkylene succinic acid, or a combination thereof, preferably a polyalkylene ester of a polyethylene succinic acid ester, a polyethylene succinic anhydride, a polyethylene succinic acid, a polypropylene succinic acid ester, a polypropylene succinic anhydride, a polypropylene succinic acid, a polyisobutylene succinic acid ester, a polyisobutylene succinic anhydride, a polyisobutylene succinic acid, or a combination thereof, and more preferably the polyalkylene ester comprises a polyisobutylene succinic acid ester.

[0012] In the antifouling composition, the polyisobutylene succinate ester is derived from the reaction of polyisobutylene succinic anhydride with a polyol. The polyol may include pentaerythritol, triethanolamine, glycerol, glucose, sucrose, arabitol, erythritol, maltitol, mannitol, ribitol, sorbitol, xylitol, threitol, galactitol, isomalt, iditol, lactitol, or combinations thereof. Preferably, the polyol includes pentaerythritol.

[0013] The antifouling composition may comprise a polyalkyleneimide or an amine-substituted polyalkyleneimide, where the polyalkyleneimide is a polyalkylene succinimide, and the amine-substituted polyalkyleneimide is an amine-substituted polyalkylene succinimide, preferably the polyalkylene succinimide is a polyethylene succinimide, a polyisopropylene succinimide, a polyisobutylene succinimide, or a combination thereof, and the amine-substituted polyalkylene succinimide is an amine-substituted polyethylene succinimide, an amine-substituted polyisopropylene succinimide, an amine-substituted polyisobutylene succinimide, or a combination thereof.

[0014] The antifouling composition can also include a chelating compound that includes N,N'-disalicylidene-1,2-propanediamine.

[0015] The antifouling composition has a resin present in a concentration of about 1 to about 99% by weight, and a polyolefin present in a concentration of about 1 to about 99% by weight, based on the total weight of the resin and polyolefin; preferably, the resin is present in a concentration of about 20 to about 80% by weight, and the polyolefin is present in a concentration of about 20 to about 80% by weight, based on the total weight of the resin and polyolefin.

[0016] Further, the antifouling composition has a resin present in a concentration of about 10 to about 80% by weight, a polyolefin present in a concentration of about 10 to about 80% by weight, and a chelating agent present in a concentration of about 1 to about 25% by weight, based on the total weight of the resin, polyolefin, and chelating agent, and preferably, the resin is present in a concentration of about 20 to about 70% by weight, the polyolefin is present in a concentration of about 20 to about 70% by weight, and the chelating agent is present in a concentration of about 5 to about 15% by weight, based on the total weight of the resin, polyolefin, and chelating agent.

[0017] Also disclosed is a method for reducing or preventing fouling of a structural part in a petroleum refinery system exposed to a hydrocarbon fluid, the method comprising contacting the structural part with an effective amount of the antifouling composition described herein.

[0018] Also disclosed is a method for reducing or preventing fouling of a structural part in a refinery system exposed to a hydrocarbon fluid, the method comprising contacting the structural part with the antifouling composition described herein.

[0019] In a method for reducing or preventing contamination of structural parts of a refinery system exposed to a hydrocarbon fluid, the hydrocarbon fluid may be a petrochemical fluid.

[0020] In a method for reducing or preventing contamination of structural parts of a petroleum refinery system exposed to hydrocarbon fluids, the petrochemical fluids may include asphaltenes, paraffins, waxes, scales, naphthenates, coke, or combinations thereof.

[0021] The methods described herein contact the antifouling composition with the petrochemical fluid in an amount effective to disperse the contaminant precursors.

[0022] The methods described herein also include contacting the antifouling composition with the petrochemical fluid in an amount effective to prevent or reduce the deposition of contaminants.

[0023] In the disclosed method, the antifouling composition can be contacted with the petrochemical fluid in an amount effective to disperse asphaltenes.

[0024] In the disclosed method, the antifouling composition can be contacted with the petrochemical fluid in an amount effective to prevent or reduce coke deposition.

[0025] Further, in the disclosed method, the antifouling composition can be contacted with the petrochemical fluid in an amount effective to prevent or reduce the deposition of contaminants.

[0026] In the disclosed method, the structural portion of the oil refinery system may include a portion of a storage unit, a heat exchanger, a pipe, a pump, a flow meter, a valve, a desalter, a furnace, a coker, a distillation column, a fractionation column, an atmospheric column, a pipe still, a debutanizer, a reactor, a fluid catalytic cracker, a fluid catalytic cracking slurry settler, a hydrocracker, a steam cracker, a thermal cracker, a visbreaker, a reflux unit, a condenser, a scrubber, or a combination thereof. Preferably, the structural portion may include a portion of a heat exchanger, a crude oil processor, a fluid catalytic cracker, a fluid catalytic cracking slurry settler, a hydrocracker, a steam cracker, a thermal cracker, a visbreaker, or a combination thereof. More preferably, the structural portion may include a portion of a fluid catalytic cracker, a visbreaker, or a combination thereof.

[0027] In a method for reducing or preventing fouling of structural portions of a petroleum refinery system exposed to a hydrocarbon fluid, an effective amount of the antifouling composition is from about 1 ppm to about 50,000 ppm, or from about 1 ppm to about 500 ppm of the antifouling composition based on the total amount of the hydrocarbon fluid.

[0028] Other objects and features will be in part apparent and in part pointed out hereinafter. [Brief description of the drawings]

[0029] [Figure 1]1 shows a graph of temperature difference between inlet and outlet temperatures versus time in a hot liquid process simulator (HLPS) test using various reagents. [Diagram 2] 1 shows a graph of temperature difference between inlet and outlet temperatures versus time in a hot liquid process simulator (HLPS) test using various reagents.

[0030] [Diagram 3] Photographs of asphaltene dispersancy test (ADT) results using various reagents at 50 ppm dosage are shown. [Figure 4] Photographs of asphaltene dispersancy test (ADT) results using various reagents at 50 ppm dosage are shown. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0031] Disclosed is an antifouling composition that can be used in a method to inhibit (e.g., reduce or prevent) fouling of structural parts in an oil refinery system exposed to a hydrocarbon fluid. The antifouling composition reduces the deposition of fouling compounds on the surfaces of structural parts in the oil refinery system as well as in oil production. Without being bound to a particular theory, it is believed that the components of the antifouling composition provide two or more mechanisms of action, one component chelates metals in the hydrocarbons to render them chemically inert, while another component or components of the composition disperse components of the hydrocarbon fluid, in particular, another component disperses asphaltene / foulant precursors in the hydrocarbon fluid.

[0032] The antifouling compositions described herein can be used to inhibit fouling of structural parts in a refinery system exposed to hydrocarbon fluids. The present disclosure relates to an antifouling composition for inhibiting fouling of structural parts in a refinery system exposed to hydrocarbon fluids, the antifouling composition comprising an effective amount of a resin comprising an alkylphenol-aldehyde resin and an effective amount of a polyolefin comprising a polyalkylene ester, a polyolefin amide, an alkene amine, a polyethylene polyamine, a polyalkylene imine, or a combination thereof.

[0033] The antifouling composition may further comprise an effective amount of a polyalkyleneimide, an amine-substituted polyalkyleneimide, or a combination thereof.

[0034] Additionally, the antifouling compositions described herein can further comprise an effective amount of a chelating compound, including N,N'-disalicylidene-1,2-propanediamine.

[0035] The antifouling composition comprises an alkylphenol-aldehyde resin, including an alkylphenol-formaldehyde resin.

[0036] Furthermore, the alkylphenol-aldehyde resin is C1-C 20 Alkylphenol-aldehyde resins, preferably C1-C 16 Alkylphenol-aldehyde resins, more preferably C1-C 12 Alkylphenol-aldehyde resins, even more preferably C3-C 12 Alkylphenol-aldehyde resins, even more preferably C6-C 12 Contains alkylphenol-aldehyde resins.

[0037] The preferred nonylphenol-formaldehyde resin was prepared by polycondensation of a mixture of nonyl- and dinonylphenols (in a molar ratio of about 10:1) with formaldehyde in a heavy aromatic solvent. The preferred nonylphenol-formaldehyde resin has a weight average molecular weight of about 3200 Daltons as determined by gel permeation chromatography.

[0038] Alkylphenol-formaldehyde resins are represented by the formula 1 [ka] (Wherein, R1 is C1 to C 20 R2 is hydrogen, C1-C6 alkyl, or alkaryl, and n is an integer of 4 to 75.

[0039] Preferably, for the resin of formula 1, R1 is C1-C 16 Alkyl, C1-C 12 Alkyl, C3-C 12 Alkyl, C6-C 12 Alkyl, most preferably nonyl.

[0040] Additionally, the resin of Formula 1 preferably has R2 equal to hydrogen.

[0041] Moreover, the resin of formula 1 preferably has n as an integer of 10-20.

[0042] Further, the antifouling composition comprises a polyalkylene ester of a polyalkylene succinic acid ester, a polyalkylene succinic anhydride, a polyalkylene succinic acid, or a combination thereof, preferably a polyalkylene ester of a polyethylene succinic acid ester, a polyethylene succinic anhydride, a polyethylene succinic acid, a polypropylene succinic acid ester, a polypropylene succinic anhydride, a polypropylene succinic acid, a polyisobutylene succinic acid ester, a polyisobutylene succinic anhydride, a polyisobutylene succinic acid, or a combination thereof, and more preferably the polyalkylene ester comprises a polyisobutylene succinic acid ester.

[0043] In the antifouling composition, the polyisobutylene succinate ester is derived from the reaction of polyisobutylene succinic anhydride with a polyol. The polyol may include pentaerythritol, triethanolamine, glycerol, glucose, sucrose, arabitol, erythritol, maltitol, mannitol, ribitol, sorbitol, xylitol, threitol, galactitol, isomalt, iditol, lactitol, or combinations thereof. Preferably, the polyol includes pentaerythritol.

[0044] Polyisobutenylene (PIB) having a number average molecular weight of 500 to 4200 is reacted with pentaerythritol in the presence of a catalyst at about 160 to about 230° C. The PIB portion is modified based on the performance required for specific crude oil properties.

[0045] A preferred polyisobutenylene pentaerythritol ester has the following structure: [ka] (wherein n and m are integers from 2 to 16).

[0046] The antifouling composition may comprise a polyalkyleneimide or an amine-substituted polyalkyleneimide, where the polyalkyleneimide is a polyalkylene succinimide, and the amine-substituted polyalkyleneimide is an amine-substituted polyalkylene succinimide, preferably the polyalkylene succinimide is a polyethylene succinimide, a polyisopropylene succinimide, a polyisobutylene succinimide, or a combination thereof, and the amine-substituted polyalkylene succinimide is an amine-substituted polyethylene succinimide, an amine-substituted polyisopropylene succinimide, an amine-substituted polyisobutylene succinimide, or a combination thereof.

[0047] The antifouling composition can also include a chelating compound that includes N,N'-disalicylidene-1,2-propanediamine.

[0048] The antifouling composition having a resin and a polyolefin is preferably about 1 to about 99% by weight, about 1 to about 90% by weight, about 1 to about 80% by weight, about 1 to about 70% by weight, about 1 to about 65% by weight, about 1 to about 60% by weight, about 1 to about 55% by weight, about 1 to about 50% by weight, about 1 to about 45% by weight, about 10 to about 99% by weight, about 10 to about 90% by weight, about 10 to about 80% by weight, about 10 to about 70% by weight, about 10 to about 80% by weight, about 10 to about 9 ... About 65% by weight, about 10 to about 60% by weight, about 10 to about 55% by weight, about 10 to about 50% by weight, about 10 to about 45% by weight, about 20 to about 99% by weight, about 20 to about 90% by weight, about 20 to about 80% by weight, about 20 to about 70% by weight %, about 20 to about 65% by weight, about 20 to about 60% by weight, about 20 to about 55% by weight, about 20 to about 50% by weight, about 20 to about 45% by weight, about 25 to about 99% by weight, about 25 to about 90% by weight, about 25 to about 80% by weight, about 25 to about About 70% by weight, about 25 to about 65% by weight, about 25 to about 60% by weight, about 25 to about 55% by weight, about 25 to about 50% by weight, about 25 to about 45% by weight, about 30 to about 99% by weight, about 30 to about 90% by weight, about 30 to about 80% by weight , about 30 to about 70% by weight, about 30 to about 65% by weight, about 30 to about 60% by weight, about 30 to about 55% by weight, about 30 to about 50% by weight, about 30 to about 45% by weight, about 35 to about 99% by weight, about 35 to about 90% by weight, about 35 to about The composition has a resin present at a concentration of about 80% by weight, about 35 to about 70% by weight, about 35 to about 65% by weight, about 35 to about 60% by weight, about 35 to about 55% by weight, about 35 to about 50% by weight, about 35 to about 45% by weight, about 40 to about 99% by weight, about 40 to about 90% by weight, about 40 to about 80% by weight, about 40 to about 70% by weight, about 40 to about 65% by weight, about 40 to about 60% by weight, about 40 to about 55% by weight, about 40 to about 50% by weight, or about 40 to about 45% by weight.

[0049] The antifouling composition having a resin and a polyolefin may be, based on the total weight of the resin and the polyolefin, about 1 to about 99% by weight, about 1 to about 90% by weight, about 1 to about 80% by weight, about 1 to about 70% by weight, about 1 to about 65% by weight, about 1 to about 60% by weight, about 1 to about 55% by weight, about 1 to about 50% by weight, about 1 to about 45% by weight, about 10 to about 99% by weight, about 10 to about 90% by weight, about 10 to about 80% by weight, about 10 to about 70% by weight, or about 10 to about 65% by weight. , about 10 to about 60% by weight, about 10 to about 55% by weight, about 10 to about 50% by weight, about 10 to about 45% by weight, about 20 to about 99% by weight, about 20 to about 90% by weight, about 20 to about 80% by weight, about 20 to about 70% by weight, about 20 to about About 65% by weight, about 20 to about 60% by weight, about 20 to about 55% by weight, about 20 to about 50% by weight, about 20 to about 45% by weight, about 25 to about 99% by weight, about 25 to about 90% by weight, about 25 to about 80% by weight, about 25 to about 70% by weight , about 25 to about 65% by weight, about 25 to about 60% by weight, about 25 to about 55% by weight, about 25 to about 50% by weight, about 25 to about 45% by weight, about 30 to about 99% by weight, about 30 to about 90% by weight, about 30 to about 80% by weight, about 30 to about About 70% by weight, about 30 to about 65% by weight, about 30 to about 60% by weight, about 30 to about 55% by weight, about 30 to about 50% by weight, about 30 to about 45% by weight, about 35 to about 99% by weight, about 35 to about 90% by weight, about 35 to about 80% by weight , about 35 to about 70 weight%, about 35 to about 65 weight%, about 35 to about 60 weight%, about 35 to about 55 weight%, about 35 to about 50 weight%, about 35 to about 45 weight%, about 40 to about 99 weight%, about 40 to about 90 weight%, about 40 to about 80 weight%, about 40 to about 70 weight%, about 40 to about 65 weight%, about 40 to about 60 weight%, about 40 to about 55 weight%, about 40 to about 50 weight%, or about 40 to about 45 weight%.

[0050] Further, the antifouling composition having a resin, a polyolefin, and a chelating agent may have an average molecular weight of about 10 to about 80% by weight, about 10 to about 70% by weight, about 10 to about 65% by weight, about 10 to about 60% by weight, about 10 to about 55% by weight, about 10 to about 50% by weight, about 10 to about 45% by weight, about 20 to about 80% by weight, about 20 to about 70% by weight, about 20 to about 65% by weight, about 20 to about 60% by weight, about 20 to about 55% by weight, about 20 to about 50% by weight, about 20 to about 45% by weight, about 25 to about 80% by weight, about 25 to about 70% by weight, about 25 to about 65% by weight, about 25 to about 60% by weight, about 25 to about 55% by weight, The resin is present at a concentration of about 25 to about 50% by weight, about 25 to about 45% by weight, about 30 to about 80% by weight, about 30 to about 70% by weight, about 30 to about 65% by weight, about 30 to about 60% by weight, about 30 to about 55% by weight, about 30 to about 50% by weight, about 30 to about 45% by weight, about 35 to about 80% by weight, about 35 to about 70% by weight, about 35 to about 65% by weight, about 35 to about 60% by weight, about 35 to about 55% by weight, about 35 to about 50% by weight, about 35 to about 45% by weight, about 40 to about 80% by weight, about 40 to about 70% by weight, about 40 to about 65% by weight, about 40 to about 60% by weight, about 40 to about 55% by weight, about 40 to about 50% by weight, or about 40 to about 45% by weight.

[0051] The antifouling composition having a resin, a polyolefin, and a chelating agent may contain, based on the total weight of the resin, the polyolefin, and the chelating agent, about 10 to about 80% by weight, about 10 to about 70% by weight, about 10 to about 65% by weight, about 10 to about 60% by weight, about 10 to about 55% by weight, about 10 to about 50% by weight, about 10 to about 45% by weight, about 20 to about 80% by weight, about 20 to about 70% by weight, about 20 to about 65% by weight, about 20 to about 60% by weight, about 20 to about 55% by weight, about 20 to about 50% by weight, about 20 to about 45% by weight, about 25 to about 80% by weight, about 25 to about 70% by weight, about 25 to about 65% by weight, about 25 to about 60% by weight, about 25 to about 5 ...45% by weight, about 25 to about 80% by weight, about 25 to about 70% by The polyolefin is present in a concentration of about 50% by weight, about 25 to about 45% by weight, about 30 to about 80% by weight, about 30 to about 70% by weight, about 30 to about 65% by weight, about 30 to about 60% by weight, about 30 to about 55% by weight, about 30 to about 50% by weight, about 30 to about 45% by weight, about 35 to about 80% by weight, about 35 to about 70% by weight, about 35 to about 65% by weight, about 35 to about 60% by weight, about 35 to about 55% by weight, about 35 to about 50% by weight, about 35 to about 45% by weight, about 40 to about 80% by weight, about 40 to about 70% by weight, about 40 to about 65% by weight, about 40 to about 60% by weight, about 40 to about 55% by weight, about 40 to about 50% by weight, or about 40 to about 45% by weight.

[0052] The antifouling composition having a resin, a polyolefin, and a chelating agent has the chelating agent present in a concentration of about 1 to about 25 weight percent, about 1 to about 20 weight percent, about 1 to about 15 weight percent, about 5 to about 25 weight percent, about 5 to about 20 weight percent, about 5 to about 15 weight percent, about 10 to about 25 weight percent, about 10 to about 20 weight percent, or about 10 to about 15 weight percent, based on the total weight of the resin, the polyolefin, and the chelating agent.

[0053] Also disclosed is a method for reducing or preventing fouling of structural parts in petroleum refining and / or production systems exposed to hydrocarbon fluids, the method comprising contacting the structural parts with an effective amount of the antifouling composition described herein.

[0054] Also disclosed is a method for reducing or preventing fouling of structural parts in refinery and / or production systems exposed to hydrocarbon fluids, the method comprising contacting the structural parts with the antifouling compositions described herein.

[0055] In a method for reducing or preventing contamination of structural parts in a refinery and / or production system exposed to a hydrocarbon fluid, the hydrocarbon fluid may be a petrochemical fluid.

[0056] In a method for reducing or preventing contamination of structural parts in a petroleum refinery and / or production system exposed to hydrocarbon fluids, the petrochemical fluids may include asphaltenes, paraffins, waxes, scale, naphthenates, coke, or combinations thereof.

[0057] The methods described herein contact the antifouling composition with the petrochemical fluid in an amount effective to disperse the contaminant precursors.

[0058] The methods described herein also include contacting the antifouling composition with the petrochemical fluid in an amount effective to prevent or reduce the deposition of contaminants.

[0059] In the disclosed method, the antifouling composition can be contacted with the petrochemical fluid in an amount effective to disperse asphaltenes.

[0060] In the disclosed method, the antifouling composition can be contacted with the petrochemical fluid in an amount effective to prevent or reduce coke deposition.

[0061] Further, in the disclosed method, the antifouling composition can be contacted with the petrochemical fluid in an amount effective to prevent or reduce the deposition of contaminants.

[0062] In the disclosed method, the structural portion of the oil refinery system may include a portion of a production, storage unit, heat exchanger, pipe, pump, flow meter, valve, desalter, furnace, coker, distillation column, fractionator, atmospheric column, pipe still, debutanizer, reactor, fluid catalytic cracker, fluid catalytic cracking slurry settler, hydrocracker, steam cracker, thermal cracker, visbreaker, reflux unit, condenser, scrubber, or combination thereof. Preferably, the structural portion may include a portion of a fluid catalytic cracker, fluid catalytic cracking slurry settler, hydrocracker, steam cracker, thermal cracker, visbreaker, or combination thereof. More preferably, the structural portion may include a portion of a crude oil processor, visbreaker, or combination thereof.

[0063] The antifouling composition may further consist essentially of resins and polyolefins as described herein. Antifouling compositions consisting essentially of these components, when used in the methods described herein, have the novel property of acceptable reduction or prevention of deposition of contaminants in hydrocarbon fluids in contact with structural portions of a refinery system exposed to the hydrocarbon fluids.

[0064] The antifouling composition may further consist essentially of the resin, polyolefin, and chelating agent as described herein. Antifouling compositions consisting essentially of these components, when used in the methods described herein, have the novel property of acceptable reduction or prevention of deposition of contaminants in hydrocarbon fluids in contact with structural portions of a refinery system exposed to the hydrocarbon fluids.

[0065] In a method for reducing or preventing the deposition of components of crude oil, an effective amount of the antifouling composition is from about 1 ppm to about 50,000 ppm, from about 1 ppm to about 40,000 ppm, from about 1 ppm to about 30,000 ppm, from about 1 ppm to about 20,000 ppm, from about 1 ppm to about 10,000 ppm, from about 1 ppm to about 7,500 ppm, from about 1 ppm to about 5,000 ppm, from about 1 ppm to about 2,500 ppm, from about 1 ppm to about 2,000 ppm, from about 1 ppm to about 1,500 ppm, from about 1 ppm to about 1,000 ppm, from about 1 ppm to about The antifouling composition is about 500 ppm, about 1 ppm to about 100 ppm, about 5 ppm to about 50,000 ppm, about 5 ppm to about 40,000 ppm, about 5 ppm to about 30,000 ppm, about 5 ppm to about 20,000 ppm, about 5 ppm to about 10,000 ppm, about 5 ppm to about 7,500 ppm, about 5 ppm to about 5,000 ppm, about 5 ppm to about 2,500 ppm, about 5 ppm to about 2,000 ppm, about 5 ppm to about 1,500 ppm, about 5 ppm to about 1,000 ppm, about 5 ppm to about 500 ppm, or about 5 ppm to about 100 ppm.

[0066] definition The term "alkyl" as used herein refers to a straight or branched chain hydrocarbon radical, preferably having 1 to 32 carbon atoms (i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39, 30, 31, or 32 carbons). Alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, and tertiary butyl. Alkyl groups can be unsubstituted or substituted with one or more suitable substituents as defined above.

[0067] The term "alkenyl" as used herein refers to a straight or branched chain hydrocarbon radical, preferably having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39, 30, 31, or 32 carbons, and having one or more carbon-carbon double bonds. Alkenyl groups include, but are not limited to, ethenyl, 1-propenyl, 2-propenyl (allyl), iso-propenyl, 2-methyl-1-propenyl, 1-butenyl, and 2-butenyl. Alkenyl groups can be unsubstituted or substituted by one or more suitable substituents as defined above.

[0068] The term "alkynyl" as used herein refers to a straight or branched chain hydrocarbon radical, preferably having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39, 30, 31, or 32 carbons, and having one or more carbon-carbon triple bonds. Alkynyl groups include, but are not limited to, ethynyl, propynyl, and butynyl. Alkynyl groups can be unsubstituted or substituted by one or more suitable substituents as defined above.

[0069] The term "alkoxy," as used herein, refers to an alkyl group, as defined herein, appended to the parent molecular moiety through an oxygen atom.

[0070] The term "aryl," as used herein, means a monocyclic, bicyclic, or tricyclic aromatic radical, such as phenyl, naphthyl, tetrahydronaphthyl, indanyl, and the like, optionally substituted by one or more suitable substituents, preferably 1 to 5 suitable substituents, as defined above.

[0071] The term "arylalkyl," as used herein, refers to an aryl group attached to the parent molecular moiety through an alkyl group. An arylalkyl group can be unsubstituted or substituted with one or more suitable substituents, as defined above.

[0072] The term "cycloalkyl" as used herein refers to a monocyclic, bicyclic or tricyclic carbocyclic radical (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclopentenyl, cyclohexenyl, bicyclo[2.2.1]heptanyl, bicyclo[3.2.1]octanyl, bicyclo[5.2.0]nonanyl, and the like), optionally containing one or two double bonds. Cycloalkyl groups can be unsubstituted or substituted with one or more suitable substituents, preferably 1 to 5 suitable substituents, as defined above.

[0073] The term "halo" or "halogen" as used herein refers to a fluoro, chloro, bromo, or iodo radical.

[0074] The term "heteroaryl" as used herein refers to a monocyclic, bicyclic, or tricyclic aromatic heterocyclic group containing within the ring one or more heteroatoms (e.g., 1 to 3 heteroatoms) selected from O, S, and N. Heteroaryl groups include, but are not limited to, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, thienyl, furyl, imidazolyl, pyrrolyl, oxazolyl (e.g., 1,3-oxazolyl, 1,2-oxazolyl), thiazolyl (e.g., 1,2-thiazolyl, 1,3-thiazolyl), pyrazolyl, tetrazolyl, triazolyl (e.g., 1,2,3-triazolyl, 1,2,4-triazolyl), oxadiazolyl (e.g., 1,2,3-oxadiazolyl), thiadiazolyl (e.g., 1,3,4-thiadiazolyl), quinolyl, isoquinolyl, benzothienyl, benzofuryl, and indolyl. A heteroaryl group can be unsubstituted or optionally substituted with one or more suitable substituents, preferably 1 to 5 suitable substituents, as defined above.

[0075] The term "heterocycle" or "heterocyclyl" as used herein refers to a monocyclic, bicyclic, or tricyclic group containing 1 to 4 heteroatoms selected from N, O, S(O)n, P(O)n, PRz, NH, or NRz, where Rz is a suitable substituent. Heterocyclic groups optionally contain one or two double bonds. Heterocyclic groups include, but are not limited to, azetidinyl, tetrahydrofuranyl, imidazolidinyl, pyrrolidinyl, piperidinyl, piperazinyl, oxazolidinyl, thiazolidinyl, pyrazolidinyl, thiomorpholinyl, tetrahydrothiazinyl, tetrahydro-thiadiazinyl, morpholinyl, oxetanyl, tetrahydrodiazinyl, oxazinyl, oxathiazinyl, indolinyl, isoindolinyl, quinuclidinyl, chromanyl, isochromanyl, and benzoxazinyl. Examples of monocyclic saturated or partially saturated ring systems are tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, imidazolidin-1-yl, imidazolidin-2-yl, imidazolidin-4-yl, pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, piperidin-1-yl, piperidin-2-yl, piperidin-3-yl, piperazin-1-yl, piperazin-2-yl, piperazin-3-yl, 1,3-oxazolidin-3-yl, isothiazolidine-1-yl, tetrahydrofuran-3-yl, imidazolidin-1-yl, imidazolidin-2-yl, imidazolidin-4-yl, pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, piperidin-1-yl, piperazin-2-yl, piperazin-3-yl, 1,3-oxazolidin-3-yl, isothiazolidine-1-yl, lysine, 1,3-thiazolidin-3-yl, 1,2-pyrazolidin-2-yl, 1,3-pyrazolidin-1-yl, thiomorpholin-yl, 1,2-tetrahydrothiazin-2-yl, 1,3-tetrahydrothiazin-3-yl, tetrahydrothiadiazin-yl, morpholin-yl, 1,2-tetrahydrodiazin-2-yl, 1,3-tetrahydrodiazin-1-yl, 1,4-oxazin-2-yl, and 1,2,5-oxathiazin-4-yl. The heterocyclic group may be unsubstituted or substituted by one or more suitable substituents as defined above, preferably 1 to 3 suitable substituents.

[0076] As used herein, the term "hydroxy" refers to an --OH group.

[0077] As used herein, the terms "comprise," "include," "having," "has," "can," "contain," and variations thereof are intended to be open-ended transitional phrases, terms, or words that do not exclude the possibility of additional acts or structures. The singular forms "a," "and," and "the" include plural referents unless the context clearly dictates otherwise. The present disclosure also contemplates other embodiments that "comprise," "consist," and "consist essentially of" the embodiments or elements presented herein, whether or not expressly stated.

[0078] Having described the invention in detail, it will be apparent that modifications and variations are possible without departing from the scope of the invention as defined in the appended claims. EXAMPLES

[0079] The following non-limiting examples are provided to further illustrate the present invention.

[0080] Example 1: High Temperature Liquid Process Simulator (HLPS) HLPS is an industry accepted test method for evaluating antifoulant chemical performance. The test uses desalted crude oil. The test conditions used were: (a) rod temperature: 400°C, flow rate: 1 mL / min, pressure: 500 psi, and reaction time: 80 min.

[0081] In the HLPS test, a homogenized crude oil sample is passed through a heating zone at a given flow rate. During the test, the inlet, outlet, and rod temperatures are measured and recorded. Foulant precursors are destabilized during passage through the heating zone and tend to precipitate and adhere to the heating rod, resulting in a decrease in the outlet temperature. The test is repeated with antifoulant-spiked desalted crude oil having an antifoulant concentration of 3000 ppm. The fouling curves from these tests are then compared for performance improvement. Results for an antifouling composition containing Product 1 (50 wt. % polyisobutenyl succinic acid pentaerythritol ester (Comparative Chemical 1)) and 50 wt. % 4-nonylphenol formaldehyde resin (Comparative Chemical 2)) and 3000 ppm dosage of polyisobutenyl succinic acid pentaerythritol ester (Comparative Chemical 1) and 4-nonylphenol formaldehyde resin (Comparative Chemical 2) are shown in FIG. 1. The results for an antifouling composition containing Product 2 (43.5 wt. % polyisobutenyl succinic acid pentaerythritol ester (Comparative Chemical 1), 43.5 wt. % 4-nonylphenol formaldehyde resin (Comparative Chemical 2), and 13 wt. % N,N'-disalicylidene-1,2-propanediamine in xylene) and the results for 3000 ppm polyisobutenyl succinic acid pentaerythritol ester (Comparative Chemical 1) and 4-nonylphenol formaldehyde resin (Comparative Chemical 2) are shown in FIG. 2.

[0082] Example 2: Asphaltene Dispersity Test (ADT) 500 μL of crude oil is taken in a test tube. The first tube remains "blank" while the other tubes are spiked with 50 ppm of antifoulant chemical. The amount of precipitate in each test tube is recorded and compared to the blank. The results for the antifouling composition containing Product 1 (50 wt. % polyisobutenyl succinic acid pentaerythritol ester (Comparative Chemical 1) and 50 wt. % 4-nonylphenol formaldehyde resin (Comparative Chemical 2)) as well as polyisobutenyl succinic acid pentaerythritol ester (Comparative Chemical 1), Comparative Chemical 3, and Comparative Chemical 4 at a 50 ppm dosage are shown in FIG. 3. The Product 1 antifouling composition exhibited the best asphaltene dispersancy among the agents tested, as evidenced by the least precipitate and the clearest solution.

[0083] The results for the antifouling composition containing Product 2 (43.5 wt. % polyisobutenyl succinic acid pentaerythritol ester (Comparative Chemical 1), 43.5 wt. % 4-nonylphenol formaldehyde resin (Comparative Chemical 2), and 13 wt. % N,N'-disalicylidene-1,2-propanediamine) as well as the results for the antifouling compositions containing each of Comparative Chemical 1 and Comparative Chemical 2 alone at a dosage of 50 ppm are shown in Figure 4. The Product 2 antifouling composition demonstrated advantageous asphaltene dispersancy as evidenced by the amount of precipitate and the clarity of the solution.

[0084] When introducing elements of the present invention or preferred embodiments thereof, the articles "a", "an", "the" and "said" are intended to mean that there are one or more of the elements. The terms "comprising", "including" and "having" are intended to be inclusive and mean that there may be additional elements other than the elements listed therein.

[0085] In view of the above, it will be seen that the several objects of the invention are achieved and other advantageous results attained.

[0086] Because various changes can be made in the compositions and methods described above without departing from the scope of the invention, it is intended that all matter contained in the above description and illustrated in the accompanying drawings be interpreted in an illustrative and not a limiting sense.

Claims

1. 1. An antifouling composition for inhibiting fouling of structural parts in a petroleum refining system exposed to a hydrocarbon fluid, the antifouling composition comprising: an effective amount of a resin comprising an alkylphenol-aldehyde resin; and an effective amount of a polyolefin comprising a polyalkylene ester, a polyolefinamide alkenamine, a polyethylene polyamine, a polyalkylene imine, or a combination thereof.

2. 10. The antifouling composition of claim 1 further comprising an effective amount of a polyalkyleneimide, an amine-substituted polyalkyleneimide, or a combination thereof, and / or further comprising an effective amount of a chelating compound comprising N,N'-disalicylidene-1,2-propanediamine.

3. 3. The antifouling composition according to claim 1 or 2, wherein the alkylphenol-aldehyde resin comprises an alkylphenol-formaldehyde resin, preferably the alkylphenol-aldehyde resin comprises a C1 to C16 alkylphenol-aldehyde resin, more preferably the alkylphenol-aldehyde resin comprises a C3 to C12 alkylphenol-aldehyde resin, even more preferably the alkylphenol-aldehyde resin comprises a C6 to C12 alkylphenol-aldehyde resin.

4. 4. The antifouling composition of any one of claims 1 to 3, comprising a polyalkylene ester, the polyalkylene ester comprising a polyalkylene succinic ester, a polyalkylene succinic anhydride, a polyalkylene succinic acid, or a combination thereof, optionally the polyalkylene ester comprising a polyethylene succinic ester, a polyethylene succinic anhydride, a polyethylene succinic acid, a polypropylene succinic ester, a polypropylene succinic anhydride, a polypropylene succinic acid, a polyisobutylene succinic ester, a polyisobutylene succinic anhydride, a polyisobutylene succinic acid, or a combination thereof, preferably the polyalkylene ester comprises a polyisobutylene succinic ester.

5. 5. The antifouling composition of claim 4, wherein the polyisobutylene succinate ester is derived from the reaction of polyisobutylene succinic anhydride with a polyol; optionally, the polyol comprises pentaerythritol, triethanolamine, glycerol, glucose, sucrose, arabitol, erythritol, maltitol, mannitol, ribitol, sorbitol, xylitol, threitol, galactitol, isomalt, iditol, lactitol, or a combination thereof, preferably the polyol comprises pentaerythritol.

6. 4. The antifouling composition according to any one of claims 2 to 3, comprising the polyalkyleneimide or the amine-substituted polyalkyleneimide, wherein the polyalkyleneimide is a polyalkylene succinimide, wherein the amine-substituted polyalkyleneimide is an amine-substituted polyalkylene succinimide, preferably the polyalkylene succinimide is a polyethylene succinimide, a polyisopropylene succinimide, a polyisobutylene succinimide, or a combination thereof, and / or the amine-substituted polyalkylene succinimide is an amine-substituted polyethylene succinimide, an amine-substituted polyisopropylene succinimide, a polyisobutylene succinimide, or a combination thereof.

7. 7. The antifouling composition according to any one of claims 1 to 6, wherein the resin is present at a concentration of about 1 to about 99% by weight and the polyolefin is present at a concentration of about 1 to about 99% by weight, based on the total weight of the resin and the polyolefin, preferably the resin is present at a concentration of about 20 to about 80% by weight and the polyolefin is present at a concentration of about 20 to about 80% by weight, based on the total weight of the resin and the polyolefin.

8. 7. The antifouling composition according to any one of claims 3 to 6, wherein the resin is present at a concentration of about 10 to about 80% by weight, the polyolefin is present at a concentration of about 10 to about 80% by weight, and the chelating agent is present at a concentration of about 1 to about 25% by weight, based on the total weight of the resin, the polyolefin, and the chelating agent, and preferably the resin is present at a concentration of about 20 to about 70% by weight, the polyolefin is present at a concentration of about 20 to about 70% by weight, and the chelating agent is present at a concentration of about 5 to about 15% by weight, based on the total weight of the resin, the polyolefin, and the chelating agent.

9. 9. A method for reducing or preventing fouling of a structural part in a petroleum refinery system exposed to a hydrocarbon fluid, said method comprising contacting said structural part with an effective amount of an antifouling composition according to any one of claims 1 to 8.

10. Use of the antifouling composition according to any one of claims 1 to 8 to reduce or prevent fouling of structural parts in a petroleum refining system exposed to hydrocarbon fluids.

11. 11. The method or use of claim 9 or 10, wherein the hydrocarbon fluid is a petrochemical fluid, optionally the petrochemical fluid comprises asphaltenes, paraffins, waxes, scales, naphthenates, coke, or combinations thereof.

12. 12. The method or use according to claim 11, wherein the antifouling composition is contacted with the petrochemical fluid in an amount effective to disperse contaminant precursors and / or the antifouling composition is contacted with the petrochemical fluid in an amount effective to prevent or reduce the deposition of contaminants.

13. 12. The method or use of claim 11, wherein the antifouling composition is contacted with the petrochemical fluid in an amount effective to disperse asphaltenes, or the antifouling composition is contacted with the structural part in an amount effective to prevent or reduce coke deposition.

14. 14. The method or use according to any one of claims 9 to 13, wherein the structural part comprises parts of production, storage units, heat exchangers, pipes, pumps, flow meters, valves, desalters, furnaces, cokers, distillation columns, fractionation columns, atmospheric columns, pipe stills, debutanizers, reactors, fluid catalytic crackers, fluid catalytic cracking slurry settlers, hydrocrackers, steam crackers, thermal crackers, visbreakers, reflux units, condensers, scrubbers, or combinations thereof, preferably the structural part comprises parts of heat exchangers, crude oil processors, fluid catalytic crackers, fluid catalytic cracking slurry settlers, hydrocrackers, steam crackers, thermal crackers, visbreakers, or combinations thereof, more preferably the structural part comprises parts of heat exchangers, crude oil processors, fluid catalytic crackers, visbreakers, or combinations thereof.

15. 15. The method or use according to any one of claims 9 to 14, wherein the effective amount of the antifouling composition is from about 1 ppm to about 50,000 ppm, preferably the effective amount of the antifouling composition is from about 1 ppm to about 500 ppm, based on the total amount of the hydrocarbon fluid.

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