Chemicals, applications, and delivery methods for coke inhibition in fuel and oil systems

Abstract

Organometallic chemical-based compounds for preventing coke formation in hydrocarbon fluid systems. The organometallic chemical-based compounds include coordination complexes that interrupt autoxidation pathways of coke formation. Components and systems for reducing coke formation during transport or circulation of hydrocarbon fluids. The components include a contact surface configured to contact the hydrocarbon fluid. The contact surface is functionalized with an inhibitor ligand to form an inhibitor ligand-functionalized surface. The inhibitor ligand-functionalized surface interrupts autoxidation pathways of coke formation.

Description

Technical Field

[0001] The present disclosure relates to compositions, components, and systems that come into contact with hydrocarbon fluids, particularly compositions and components for use in gas turbine engines of aircraft, and methods of making the same. Background Art

[0002] Gas turbine engines include surfaces that come into contact with hydrocarbon fluids, such as fuel and lubricating oil. When exposed to hydrocarbon fluids at high temperatures, carbonaceous deposits (also known as coke) can form on these surfaces. This causes carbon to adhere and accumulate as deposits on surfaces in contact with the fuel or oil, resulting in reduced or blocked flow. BRIEF DESCRIPTION OF THE DRAWINGS

[0003] Features and advantages of the present disclosure will become apparent from the following description of various exemplary embodiments, as illustrated in the accompanying drawings, in which like reference numerals generally indicate identical, functionally similar, and / or structurally similar elements.

[0004] Figure 1 is a schematic perspective view of an aircraft having components for reducing coke formation during transport of hydrocarbon fluids according to one embodiment of the present disclosure.

[0005] Figure 2 Schematic diagram of a fuel system for reducing coke formation during hydrocarbon fluid delivery according to one embodiment of the present disclosure.

[0006] Figure 3 is a schematic diagram of a lubrication system for reducing coke formation during hydrocarbon fluid delivery according to one embodiment of the present disclosure.

[0007] Figure 4A and Figure 4B Schematic diagram of a controlled release assembly for reducing coke formation during hydrocarbon fluid transport according to one embodiment of the present disclosure.

[0008] Figure 5 A method for synthesizing M according to one embodiment of the present disclosure is shown. n+ Reaction scheme of radical inhibitors.

[0009] Figure 6 A method for synthesizing M according to one embodiment of the present disclosure is shown. n+ Reaction scheme of radical inhibitors. DETAILED DESCRIPTION

[0010] Features, advantages, and embodiments of the present disclosure are set forth or become apparent by considering the following detailed description, drawings, and claims. Furthermore, the following detailed description is exemplary and is intended to provide further explanation without limiting the scope of the claimed disclosure.

[0011] The terms "upstream" and "downstream" refer to the relative directions of fluid flow in a fluid path. For example, "upstream" refers to the direction from which a fluid is flowing, and "downstream" refers to the direction to which a fluid is flowing. The term "fluid" can be a gas or a liquid. The term "fluid communication" refers to the ability of a fluid to establish a connection between designated areas.

[0012] Unless otherwise indicated herein, the terms "coupled," "fixed," "attached to," and the like refer to both direct coupling, fixing, or attachment as well as indirect coupling, fixing, or attachment through one or more intermediate components or features.

[0013] The singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise.

[0014] As used herein, the terms “first,” “second,” and “third” may be used interchangeably to distinguish one component from another and are not intended to indicate the position or importance of each component.

[0015] The terms "fore" and "aft" refer to relative positions within a gas turbine engine or vehicle and to the normal operating altitude of the gas turbine engine or vehicle. For example, with respect to a gas turbine engine, "fore" refers to a position closer to the engine inlet, while "aft" refers to a position closer to the engine nozzle or exhaust.

[0016] Approximate language used throughout the specification and claims can be used to modify any quantitative expression that can be allowed to vary without causing a change in the basic function to which it is related. Therefore, the values ​​modified by terms such as "about", "approximately" and "substantially" are not limited to the precise values ​​specified. In at least some cases, approximate language can correspond to the precision of the instrument used to measure the value. For example, approximate language can be expressed as being within 1%, 2%, 4%, 5%, 10%, 15% or 20% of a single value, a range of values ​​and / or an endpoint defining a range of values. Here and throughout the specification and claims, range definitions can be combined and / or interchanged. Unless the context or language indicates otherwise, such ranges are definite and include all subranges contained therein.

[0017] As used herein, the term " n+ ” refers to a metal ion with a charge number of n. Similarly, the term “M (n+1)+ " refers to a metal ion with a charge number of (n+1).

[0018] As used herein, the term "organometallic compound" refers to an organometallic compound or coordination compound having at least one chemical bond between a metal and an organic ligand. The organic ligand may contain one or more heteroatoms, such as oxygen, nitrogen, sulfur, or phosphorus.

[0019] Various embodiments are discussed in detail below. Although specific embodiments are discussed, this is for illustrative purposes only. Those skilled in the relevant art will recognize that other components and arrangements may be used without departing from the spirit and scope of the present disclosure.

[0020] As described above, coke deposits may occur on surfaces of gas turbine engines that are exposed to hydrocarbon fluids (such as fuel and lubricating oil) at high temperatures. Such carbon deposits may form if a fluid circuit is operated or shut down without clearing out residual stagnant fuel. As the deposits accumulate, they can become large enough to reduce or even obstruct fluid flow. In the case of a fuel circuit, such carbon deposits can lead to reduced engine performance, reduced heat transfer efficiency, increased pressure drop, and increased material erosion rates, all of which may require the use of expensive decoking procedures or even replacement of fuel nozzles. The present disclosure discusses methods for preventing such carbon deposits on the surfaces of components that come into contact with hydrocarbon fluids, particularly such components used in gas turbine engines of aircraft. Aspects described herein relate to compositions, components, systems, and methods for preventing hydrocarbon fluids from generating carbon deposits at high temperatures. In particular, embodiments relate to modifying internal surfaces that are wetted or contacted by hydrocarbon fluids.

[0021] The formation of char involves certain autooxidative pathways that involve initiation, amplification, and termination of reactions in the presence of oxygen.

[0022] Trigger

[0023] RH→R· [Reaction 1]

[0024] ROOH→RO·+OH· [Reaction 2]

[0025] 2ROOH→RO2·+RO·+H2O [Reaction 3]

[0026] Amplification

[0027] R·+O2→RO2· [Reaction 4]

[0028] RO2·+RH→ROOH+R· [Reaction 5]

[0029] RO2·+RH→ROOR· [Reaction 6]

[0030] RO·+RH→free radical, product [Reaction 7]

[0031] termination

[0032] R·+R·→Product [Reaction 8]

[0033] R·+RO2·→Product [Reaction 9]

[0034] RO2·+RO2·→Product [Reaction 10]

[0035] Certain chemicals according to the present disclosure inhibit coke formation by interrupting one or more of the above-mentioned autoxidation pathways in hydrocarbon fluids. In one embodiment, the organometallic chemical-based compound or M n+ Radical inhibitors can interrupt more than one autooxidation pathway as follows:

[0036] RO2·+M n+ →M (n+1)+ + product [reaction 11]

[0037] R.+M (n+1)+ →M n+ + Product [Reaction 12]

[0038] Organometallic chemical compounds or M n+ The presence of a radical inhibitor can prevent the hydrocarbon radical intermediate generated by the initiation reaction from undergoing further amplification or termination reactions. n+ The metal-based inhibitor essentially acts as a catalyst, in other words, the inhibitor does not undergo consumption. Therefore, the presence of trace amounts (parts per billion (ppb) or parts per million (ppm)) of organometallic chemical compounds or M-based inhibitors in hydrocarbon fluids is not a problem. n+ In one embodiment, the organometallic chemical group compound or M n+ The concentration of the metal-based inhibitor is 100 ppb to 750 ppm, or 500 ppb to 400 ppm, or 1 ppm to 300 ppm, or 10 ppm to 90 ppm. Such concentration may depend on the oxygen concentration present in the hydrocarbon fluid (e.g., 0.1 ppm to 75 ppm). In addition, the organometallic chemical compound or M n+ Radical inhibitors can form adducts with ROOH or cause ROOH decomposition through non-radical mechanisms, thereby reducing free radicals in the system. Coke deposits on the internal surfaces of fuel and oil system components (e.g., flow paths, valves, and nozzles) can lead to reduced fuel flow and / or flow obstruction, resulting in system performance, maintenance, and safety issues. Coking occurs due to free radical-induced autooxidation of hydrocarbon fluids in the presence of oxygen or due to heteroatom-induced polymerization. The present disclosure describes the use and delivery of selected organometallic chemicals for inhibiting coke particle formation in bulk hydrocarbon fluids and coke deposition on such internal surfaces.

[0039] Embodiments of the present disclosure relate to certain organometallic chemicals that inhibit coke formation, delivery mechanisms for these coke-inhibiting chemicals, and / or coke-inhibiting chemicals on target surfaces. These organometallic chemicals (including organometallic chemical-based compounds or M n+Radical inhibitors) interrupt the autocatalytic coke formation reaction by minimizing the concentration of free radicals R· and RO2· over a wide range of temperatures (e.g., 25 to 430°C, or 50 to 300°C, or 90 to 200°C, or 25 to 100°C, or 100 to 200°C, or 200 to 300°C, or 300 to 430°C, or 200 to 430°C, or 230 to 430°C), pressures (e.g., up to 30 bar), and oxygen levels (e.g., 0.1 ppm to 75 ppm). These M n+ Applications of organometallic inhibitors include aviation or land-based hydrocarbon fluid delivery systems and nozzle components, which can be in the form of hydrocarbon fluid additives, metal surface coatings or controlled release capsules. n+ The radical inhibitors) can withstand operating temperatures up to approximately 430°C and can be used in a wide range of oxygen levels from 0.1 ppm to 75 ppm.

[0040] The components, systems, and methods discussed herein are particularly applicable to engines, such as gas turbine engines used on aircraft. Figure 1 FIG2 is a perspective view of an aircraft 10 in which various aspects of the present disclosure may be implemented. Aircraft 10 includes a fuselage 12, wings 14 connected to fuselage 12, and a tail 16. Aircraft 10 also includes a propulsion system that generates the propulsive thrust required to propel aircraft 10 in flight, during taxiing operations, etc. Figure 1 The propulsion system of the aircraft 10 shown includes a pair of engines 50. In this embodiment, each engine 50 is connected to one of the wings 14 via a pylon 18 located under the wing. Figure 1 The engine 50 is shown coupled to the wing 14 in an underwing arrangement, but in other embodiments, the engine 50 may have alternative arrangements and be coupled to other portions of the aircraft 10. For example, the engine 50 may additionally or alternatively include one or more aspects coupled to other portions of the aircraft 10, such as the tail 16 and the fuselage 12.

[0041] As will be referenced below Figure 2 Further described, Figure 1 The engines 50 shown in FIG are gas turbine engines, each of which is capable of selectively generating propulsive thrust for the aircraft 10. The amount of propulsive thrust can be controlled based at least in part on the volume of fuel provided to the engines 50 via the fuel system 100. The aviation turbine fuel in the embodiments discussed herein is a combustible hydrocarbon liquid fuel having a desired carbon number (e.g., kerosene-type fuel), Jet A, JetA1, JP-8, JP8+100, JP-5, sustainable aviation fuel (SAF), and deoxygenated fuel. The fuel is stored in a fuel tank 110 of the fuel system 100. As shown in FIG. Figure 1As shown, at least a portion of the fuel tank 110 is located in each wing 14, and a portion of the fuel tank 110 is located in the fuselage 12 between the wings 14. However, the fuel tank 110 may be located in other suitable locations in the fuselage 12 or wings 14. The fuel tank 110 may also be located entirely within the fuselage 12 or wings 14. The fuel tank 110 may also be separate tanks rather than a single, integral body, such as two tanks, each located within a respective wing 14.

[0042] although Figure 1 The aircraft 10 shown in the drawings is an airplane, but the embodiments described herein may also be applicable to other aircraft 10, including, for example, helicopters and unmanned aerial vehicles (UAVs). Preferably, the aircraft discussed herein are fixed-wing aircraft or rotary-wing aircraft, which generate lift through aerodynamic forces acting on, for example, fixed wings (such as wings 14) or rotary wings (such as the rotors of a helicopter) and are heavier-than-air aircraft, rather than lighter-than-air aircraft (such as airships).

[0043] like Figure 2 As shown, the engine 50 can operate with the fuel system 100 and receive a fuel flow from the fuel system 100. The fuel system 100 includes a fuel delivery assembly 120 in contact with the downstream fluid of the fuel tank 110, and the fuel delivery assembly 120 provides a fuel flow from the fuel tank 110 to the engine 50. The fuel delivery assembly 120 includes pipes, conduits, etc. to fluidly connect the various components of the fuel system 100 to the engine 50. The fuel system 100 may also include a fuel pump (not shown) connected to the fuel fluid in the fuel delivery assembly 120. The fuel pump is used to guide the fuel to flow through the fuel delivery assembly 120 to the engine 50. Generally, the fuel pump can be the main source of pressure increase in the fuel delivery assembly 120 between the fuel tank 110 and the engine 50. In one embodiment, the fuel delivery assembly 120 includes a controlled release assembly 150, which is capable of releasing an organometallic chemical-based compound or M in a controlled manner. n+ Radical inhibitors are released into the fuel.

[0044] The fuel is injected into the compressed air via the nozzle assembly 130 (in fluid contact with the downstream fuel delivery assembly 120) and mixed with the compressed primary air. The nozzle assembly 130 injects the fuel into the turbulent flow of the primary air, which promotes rapid mixing of the fuel and the primary air. The mixture of fuel and compressed air is burned in the combustion chamber, producing combustion gases (combustion products), which are accelerated as the combustion gases leave the combustion chamber. As the products are discharged through the outlet of the combustion chamber, the combustion products are accelerated to drive the engine 50. Non-limiting examples of fuels include Jet A, JetA1, JP-8, JP8+100, JP-5, SAF, and deoxygenated fuels synthesized from various non-fossil sources (e.g., biofuels).

[0045] The engine 50 also includes various accessory systems that assist in the operation of the engine 50 and / or an aircraft including the engine 50. For example, Figure 3 As shown, the engine 50 may include a lubrication system 200 configured to provide lubricant to, for example, bearings and gear meshes located at various components 220 of the engine 50 requiring lubrication. The lubricant provided by the lubrication system 200 may increase the useful life of such components 220 requiring lubrication and may remove a certain amount of heat from such components 220. In addition, the lubrication system 200 provides lubrication for an electric generator (not shown) and provides cooling / heat dissipation for the electric generator. The electric generator may provide electrical power, for example, to a starter motor for the engine 50 and / or various other electrical components of the engine 50 and / or an aircraft including the engine 50.

[0046] The lubrication system 200 is a closed fluid circuit that includes an oil tank 210 that provides oil flow from the oil tank 210 to a component 220 that requires lubrication. The lubrication system 200 includes pipes and conduits 202 to fluidly connect the various components of the lubrication system 200. The lubrication system 200 may also include an oil pump 230. The oil pump 230 is used to direct the flow of oil through the closed fluid circuit of the lubrication system 200. The oil pump 230 may generally be the primary source of pressure increase in the lubrication system 200. In one embodiment, the lubrication system 200 includes a controlled release assembly 250 that is capable of releasing an organometallic chemical-based compound or M-based compound in a controlled manner. n+ Radical inhibitors are released into the oil.

[0047] The lubrication system 200 for the engine 50 may be lubricated using a hydrocarbon fluid, such as oil, which is circulated through the inner surface of the oil removal line. Non-limiting examples of oil include lubricating oils used in aircraft turbines, such as Type II oils covered by MIL-PRF-23699 and SAE AS5780 specifications, lubricating oils used in land-based and sea-based power turbines, and engine and transmission lubricating oils used in automobiles.

[0048] The engine 50 discussed herein is provided by way of example only. In other embodiments, any other suitable engine may be used with aspects of the present disclosure. For example, in other embodiments, the engine may be any other suitable gas turbine engine, such as a turbofan engine, a turboshaft engine, a turboprop engine, a turbojet engine, or the like. In this manner, in other embodiments, the gas turbine engine may have other suitable configurations, such as other suitable numbers or arrangements of shafts, compressors, turbines, fans, and the like. In some embodiments, the engine 50 may be a direct-drive fixed-pitch turbofan engine. In other embodiments, the gas turbine engine may be a geared gas turbine engine, a variable-pitch gas turbine engine, or the like. Furthermore, in alternative embodiments, aspects of the present disclosure may be incorporated into or otherwise used with any other type of engine (e.g., a reciprocating engine) as described above. Furthermore, in other exemplary embodiments, the exemplary engine 50 may include or be operably connected to any other suitable accessory system. Additionally or alternatively, the exemplary engine 50 may not include or be operably connected to one or more of the aforementioned accessory systems.

[0049] As described above, various components of the engine 50 are exposed to hydrocarbon fluids (e.g., fuel and oil) at elevated temperatures and various oxygen levels. Figure 2 As shown, various components of the fuel system 100 come into contact with hydrocarbon fluids. Figure 3 As shown, various components of lubrication system 200 come into contact with hydrocarbon fluids. For example, the components may be tank 110, fuel delivery assembly 120, nozzle assembly 130, oil tank 210, component requiring lubrication 220, oil pump 230, and / or any other component configured to come into contact with hydrocarbon fluids, whether within engine 50 or within another system.

[0050] For example, Figure 2 As shown, the nozzle assembly 130 includes a fluid passage 134 (through which the hydrocarbon fluid is positioned and flows) and a containment wall 136. The containment wall 136 includes a contact surface 132. The contact surface 132 may form a boundary of the fluid passage 134 and, therefore, may be a wetted surface or contact surface that is wetted / contacted by the hydrocarbon fluid in the fluid passage 134. The contact surface 132 may include a cobalt-chromium alloy, a cobalt-based alloy, a nickel-based alloy, an iron-based alloy, or other suitable material capable of withstanding high temperatures. Non-limiting examples of cobalt-chromium alloys include Stellite alloys (e.g., Stellite-6B). Non-limiting examples of cobalt-based alloys include 188. Non-limiting examples of nickel-based alloys include 600, 625, 718, X-750, Rene N2, N4, N5, N500 and X. Non-limiting examples of iron-based alloys include stainless steels such as SS-304, SS-316, SS-340, SS-321, and SS-440. Those skilled in the art will recognize that certain alloys (e.g., ReneN5, N500, N4, N2, 718, X and 188) are known as superalloys that can withstand high operating temperatures. Similarly, for example Figure 3 The tubes and pipes 202 of the lubrication system 200 shown in the figure include fluid channels (through which hydrocarbon fluid is positioned and flows) (not shown) and containment walls (not shown), which include contact surfaces (not shown) that may form boundaries of the fluid channels and therefore may be wetted surfaces or contact surfaces that are wetted / contacted by the hydrocarbon fluid in the fluid channels.

[0051] Figure 4A A controlled release component 300 based on a porous material 320 is shown, the porous material 320 comprising an organometallic chemical-based compound or M n+ Base inhibitor 340. The controlled release assembly 300 includes a metal housing 310 having a fluid inlet 312 and a fluid outlet 314. The hydrocarbon fluid enters the interior of the metal housing 310 through the fluid inlet 312, contacts one or more layers of porous material 320, and leaves the interior of the metal housing 310 through the fluid outlet 314. Non-limiting examples of materials for the porous material 320 include: glass, ceramics, metals and polymers, such as cellulose acetate, cellulose nitrate, cellulose ester, polysulfone, polyethersulfone, polyacrylonitrile, polyamide, polyimide, polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride and polyvinyl chloride. These materials may undergo certain processes (such as powder sintering or polymer sponge replication) to produce a porous structure. Subsequently, using certain processes (such as melt impregnation and cooling, or slurry / solution impregnation and drying), the organometallic chemical base compound or M n+ Without being bound by any theory, the organometallic chemical compound or M n+ The rate of release of the metal-based inhibitor into the hydrocarbon fluid is determined by the metal-based compound or the metal-based compound containing the metal. n+ The exposed surface area of ​​the porous material 320 of the radical inhibitor is adjusted by the fuel flow rate through the controlled release assembly 300 .

[0052] Figure 4B A controlled release assembly 400 is shown that is based on a semipermeable membrane housing 430 that encapsulates an organometallic chemical-based compound or M n+The controlled release assembly 400 includes a metal housing 410 having a fluid inlet 412 and a fluid outlet 414. The hydrocarbon fluid enters the interior of the metal housing 410 through the fluid inlet 412, contacts one or more layers of the semipermeable membrane housing 430, and exits the interior of the metal housing 410 through the fluid outlet 414. Non-limiting examples of materials for the semipermeable membrane housing 430 include ceramics and polymers such as cellulose acetate, cellulose nitrate, cellulose esters, polysulfones, polyethersulfones, polyacrylonitrile, polyamides, polyimides, polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, and polyvinyl chloride. Without being bound by any theory, the organometallic chemical-based compound or M n+ The rate of release of the metal-based inhibitor into the hydrocarbon fluid is determined by the organometallic chemical group compound or M n+ The hydrocarbon solubility of the base inhibitor and the fuel flow rate through the controlled release assembly 400 are adjusted.

[0053] In one embodiment, the organometallic chemical-based compound or M n+ The organometallic chemical compound or M n+ Non-limiting examples of radical inhibitors include M(BuSal) n (including Co(BuSal)2, Cu(BuSal)2 and Zn(BuSal)2), M(PhSal) n (including Co(PhSal)2), M(DIPS) n (including Co(DIPS)2, Cu(DIPS)2, Ni(DIPS)2 and Cr(DIPS)3), [(BuP) m M(DG)] n+ (including [(BuP)2Co(DG)] n+ ) and M(bis-dithiol) n Coordination complexes (including NiS4C4Ph4, PdS4C4Ph4, PtS4C4Ph4, CoS4C4Ph4, CoS4C4(p-tolyl)4, CoS4C4(p-anisyl)4, CoS4C4Ph4.PPh3 and CoS4C4Ph4.PBu3, wherein Ph represents a phenyl group and Bu represents a butyl group) (with an inhibitor ligand). Non-limiting examples of M include Ni, Co, Fe, Cu, Zn, V, Re, Pt, Pd, Os, Ru, Cr, Mo and W. BuSal refers to an N-butyl salicylaldimine ligand (including its conjugate acid) having the following representative structure:

[0054]

[0055] PhSal refers to an N-phenylsalicylaldimine ligand (including its conjugate acid) having the following representative structure:

[0056]

[0057] DIPS refers to diisopropyl 3,5-salicylate (including its conjugate acid) having the following representative structure:

[0058]

[0059] BuP refers to an N-butylphosphonium ligand (including its conjugate base) having the following representative structure:

[0060]

[0061] DG refers to a dimethylglyoxime ligand (including its conjugate acid) having the following representative structure:

[0062]

[0063] The bis-dithiol ligand has the following representative structure (including its conjugate acid):

[0064]

[0065] R and R' are each independently hydrogen or a substituted or unsubstituted aryl or alkyl group. Non-limiting examples of aryl or alkyl groups include phenyl, methyl, ethyl, n-propyl (n-propanyl) and p-ClC6H4.

[0066] M(Bis-dithione) n The complex has the following structure:

[0067]

[0068] Wherein, R and R ' are each independently hydrogen or substituted or unsubstituted aryl or alkyl. Non-limiting examples of aryl or alkyl include phenyl, methyl, ethyl, n-propyl, p-CH3C6H4 (p-tolyl), p-OCH3C6H4 (p-anisyl) and p-ClC6H4.

[0069] Figure 5 The preparation of M (bis-dithione) from a molecule having a 2-hydroxy-1-ketone moiety and phosphorus pentasulfide is shown. n Example synthetic route of the complex. A molecule with a 2-hydroxy-1-ketone moiety reacts with phosphorus pentasulfide to give a thiophosphate intermediate. The thiophosphate intermediate then undergoes a chelation reaction with a metal cation (as the center of the coordination complex) to give M (bis-dithioketone). n Complex. For example, M (bis-dithiol) nThe synthesis of the complex CoS4C4Ph4 (Ph represents phenyl) comprises reacting benzoin and phosphorus pentasulfide at 110 to 140°C for 2 to 24 hours in the presence of xylene and nitrogen or argon by refluxing to obtain a thiophosphate intermediate. The subsequent reaction is carried out in the presence of xylene and nitrogen or argon using cobalt chloride or cobalt acetate by refluxing to convert the intermediate to obtain a bis-dithiobenzyl cobalt coordination complex. For the synthesis of NiS4C4Ph4, PdS4C4Ph4 and PtS4C4Ph4, dioxane solvent can be used instead of xylene.

[0070] In one embodiment, the hydrocarbon fluid occupying the fuel system 100 or the lubrication system 200 includes an organometallic chemical-based compound or M-based compound pre-dissolved or pre-suspended at a specific concentration. n+ In this way, it will be understood that the organometallic chemical group compound or M n+ The radical inhibitor may be an additive placed in the fuel or lubricant before loading into the aircraft 10. Alternatively, the fuel system 100 or the lubrication system 200 includes a controlled release assembly 300 that releases the organometallic chemical radical compound or M radical in a controlled manner in an isolated form. n+ The radical inhibitor is released into a hydrocarbon fluid at a certain concentration.

[0071] In one embodiment, the organometallic chemical-based compound or M n+ The metal-based inhibitor is present as a functionalized surface. The metal-based contact surface serves as the metal center of a coordination complex (rather than being present in isolated form) to which the inhibitor ligand is bonded.

[0072] Figure 6 An example synthetic route for functionalizing a metal surface with an inhibitor ligand to obtain an inhibitor ligand functionalized surface is shown. Figure 5 In the synthetic pathway shown in [1], a molecule with a 2-hydroxy-1-ketone moiety reacts with phosphorus pentasulfide to obtain a phosphorothioate intermediate. The metal-based contact surface is then exposed to a halide (e.g., chlorine) to obtain a halide-functionalized metal surface. Subsequently, as the phosphorothioate intermediate displaces the halide on the halide-functionalized metal surface, chelation occurs on the metal surface, resulting in functionalization of the metal surface with the inhibitor ligand.

[0073] In one embodiment, various components of the fuel system 100 or lubrication system 200, including the tank 110, the fuel delivery assembly 120, the nozzle assembly 130, the oil tank 210, the component requiring lubrication 220, and the oil pump 230 and / or any other component configured to come into contact with a hydrocarbon fluid, include an inhibitor ligand functionalized on a contact surface configured to come into contact with the hydrocarbon fluid.

[0074] In existing systems, coke deposits form on components that must then be cleaned or replaced during maintenance intervals. Aspects of the present disclosure can inhibit coke formation in systems such as aviation and land-based turbines. By inhibiting the formation of coke particles in the fuel or oil, coke deposition on surfaces throughout the system or circuit can be prevented.

[0075] Advantageously, the organometallic chemical group compound or M n+ The radical inhibitor resists decomposition over a wide range of operating temperatures and oxygen levels of the fuel system 100 or the lubrication system 200 .

[0076] Other aspects of the disclosure are provided by the subject matter of the following clauses.

[0077] An organometallic compound for preventing coke formation in a hydrocarbon fluid system, the organometallic compound comprising M(N-butyl salicylaldimine) n 、M(N-phenyl salicylaldimine) n 、M(3,5-diisopropyl salicylate) n 、[(N-butylphosphonium) m M (dimethylglyoxime)] n+ or M(bis-dithiol) n wherein the organic metal chemical compound or M n+ Radical inhibitors interrupt the autoxidation pathway of coke formation at temperatures between 230 and 430°C.

[0078] An organometallic chemical-based compound according to the preceding clause, wherein M comprises at least one of Ni, Co, Fe, Cu, Zn, V, Re, Pt, Pd, Os, Ru, Cr, Mo or W.

[0079] An organometallic compound according to any of the preceding clauses, wherein the coordination complex is M(bis-dithiol) having the structure n ,

[0080]

[0081] In the formula, R and R' are independently hydrogen or a substituted or unsubstituted aryl or alkyl group.

[0082] An organometallic compound according to any of the preceding clauses, wherein the aryl or alkyl group comprises at least one of phenyl, methyl, ethyl, n-propyl, p-tolyl, p-anisyl or p-ClC6H4.

[0083] An organometallic compound according to any of the preceding clauses, wherein the organometallic compound is present in a hydrocarbon fluid.

[0084] The organometallic chemical-based compound according to any of the preceding clauses, wherein the hydrocarbon fluid comprises at least one of JetA, JetAl, JP-8, JP8+100, JP-5, SAF, lubricating oil used in aviation turbines, lubricating oil used in power turbines, or engine and transmission lubricating oil used in automobiles.

[0085] An organometallic compound according to any of the preceding clauses, wherein the organometallic compound is released into the hydrocarbon fluid via a controlled release assembly.

[0086] The organometallic chemical-based compound according to any of the preceding clauses, wherein the controlled release component comprises a porous material comprising M n+ Base inhibitors.

[0087] The organometallic chemical-based compound according to any of the preceding clauses, wherein the controlled release component comprises a semipermeable membrane shell encapsulating the M n+ Base inhibitors.

[0088] A fuel system for reducing coke formation during hydrocarbon fluid delivery, the fuel system comprising: an organometallic chemical-based compound as described in any of the preceding clauses; a tank; a fuel delivery assembly, the fuel delivery assembly being fluidically connected to downstream of the tank; and a nozzle assembly, the nozzle assembly being fluidically connected to downstream of the fuel delivery assembly; wherein the organometallic chemical-based compound is present in the hydrocarbon fluid.

[0089] A fuel system according to any of the preceding clauses, wherein the fuel delivery assembly comprises a controlled release assembly for releasing the organometallic chemical-based compound into the hydrocarbon fluid.

[0090] A lubrication system for reducing coke formation during circulation of a hydrocarbon fluid, the lubrication system being a closed fluid circuit, the lubrication system comprising: an organometallic chemical-based compound as described in any one of the preceding clauses; a tank; a pump; and a component requiring lubrication; wherein the organometallic chemical-based compound is present in the hydrocarbon fluid.

[0091] A lubrication system according to any of the preceding clauses, wherein the lubrication system further comprises a controlled release assembly for releasing the organometallic chemical-based compound into a hydrocarbon fluid.

[0092] A component configured to contact a hydrocarbon fluid, the component comprising: a wall having a contact surface, the contact surface configured to contact the hydrocarbon fluid; wherein the contact surface is functionalized with an inhibitor ligand to form an inhibitor ligand functionalized surface, the inhibitor ligand functionalized surface interrupting the auto-oxidation pathway of coke formation at a temperature of 230 to 430°C.

[0093] The component according to the preceding clause, wherein the contact surface comprises at least one of a cobalt-chromium alloy, a cobalt-based alloy, a nickel-based alloy, or an iron-based alloy.

[0094] A component according to any of the preceding clauses, wherein the inhibitor ligand comprises at least one of N-butyl salicylaldimine, N-phenyl salicylaldimine, diisopropyl 3,5-salicylate, butylphosphonium, dimethylglyoxime, or bis-dithione.

[0095] A component according to any of the preceding clauses, wherein the inhibitor ligand is a bis-dithiol having the structure:

[0096]

[0097] In the formula, R and R' are independently hydrogen or a substituted or unsubstituted aryl or alkyl group.

[0098] A gas turbine engine comprising a nozzle assembly, wherein the component of any of the preceding clauses is the nozzle assembly and the contact surface is an inner surface of the nozzle assembly.

[0099] A fuel system for reducing coke formation during hydrocarbon fluid delivery, the fuel system comprising: a tank; a fuel delivery assembly, the fuel delivery assembly fluidly connected to a downstream portion relative to the tank; and a nozzle assembly, the nozzle assembly fluidly connected to a downstream portion relative to the fuel delivery assembly; wherein the component described in any one of the preceding clauses is one or more of the tank, the fuel delivery assembly and the nozzle assembly, and the contact surface is the inner surface of one or more of the tank, the fuel delivery assembly and the nozzle assembly.

[0100] A lubrication system for reducing coke formation during circulation of hydrocarbon fluids, the lubrication system being a closed fluid circuit, the lubrication system comprising a tank, a pump, and components to be lubricated, wherein the components described in any one of the preceding clauses are one or more of the tank, the pump, and the components to be lubricated, and the contact surface is the inner surface of one or more of the tank, the pump, and the components to be lubricated.

[0101] A method for preventing coke formation in a hydrocarbon fluid system, the method comprising introducing an organometallic chemical-based compound into the hydrocarbon fluid system, the organometallic chemical-based compound comprising M (N-butyl salicylaldimine) n、M(N-phenyl salicylaldimine) n 、M(3,5-diisopropyl salicylate) n 、[(N-butylphosphonium) m M (dimethylglyoxime)] n+ or M(bis-dithiol) n The invention relates to a coordination complex of at least one of the following: wherein the organometallic chemical-based compound interrupts the auto-oxidation pathway of coke formation at a temperature of 230 to 430°C.

[0102] The method of the preceding clause, wherein M comprises at least one of Ni, Co, Fe, Cu, Zn, V, Re, Pt, Pd, Os, Ru, Cr, Mo, or W.

[0103] A method according to any of the preceding clauses, wherein the coordination complex is M(bis-dithiol) having the structure n :

[0104]

[0105] In the formula, R and R' are independently hydrogen or a substituted or unsubstituted aryl or alkyl group.

[0106] The method according to any of the preceding clauses, wherein the aryl or alkyl group comprises at least one of phenyl, methyl, ethyl, n-propyl, p-tolyl, p-anisyl or p-ClC6H4.

[0107] A method according to any of the preceding clauses, wherein the organometallic compound is present in a hydrocarbon fluid.

[0108] The method according to any of the preceding clauses, wherein the hydrocarbon fluid comprises at least one of Jet A, JetAl, JP-8, JP8+100, JP-5, SAF, lubricating oil used in aviation turbines, lubricating oil used in power turbines, or engine and transmission lubricating oil used in automobiles.

[0109] A method according to any of the preceding clauses, wherein the organometallic compound is released into the hydrocarbon fluid via a controlled release assembly.

[0110] The method according to any of the preceding clauses, wherein the controlled release component comprises a porous material comprising M n+ Base inhibitors.

[0111] The method according to any of the preceding clauses, wherein the controlled release component comprises a semipermeable membrane housing enclosing the M n+ Base inhibitors.

[0112] A method for preventing coke formation in a hydrocarbon fluid system, the method comprising: functionalizing a contact surface of a component with an inhibitor ligand to form an inhibitor ligand-functionalized surface; and injecting or circulating a hydrocarbon fluid into the hydrocarbon fluid system so that the contact surface contacts the hydrocarbon fluid; wherein the inhibitor ligand-functionalized surface interrupts the auto-oxidation pathway for coke formation at a temperature of 230 to 430°C.

[0113] The method of the preceding clause, wherein the contact surface comprises at least one of a cobalt-chromium alloy, a cobalt-based alloy, a nickel-based alloy, or an iron-based alloy.

[0114] The method of any of the preceding clauses, wherein the inhibitor ligand comprises at least one of N-butyl salicylaldimine, N-phenyl salicylaldimine, diisopropyl 3,5-salicylate, butylphosphonium, dimethylglyoxime, or bis-dithione.

[0115] A method according to any of the preceding clauses, wherein the inhibitor ligand is a bis-dithiol having the structure:

[0116]

[0117] In the formula, R and R' are independently hydrogen or a substituted or unsubstituted aryl or alkyl group.

[0118] Although the foregoing description is directed to various exemplary embodiments, it should be noted that other changes and modifications may be made without departing from the spirit or scope of the present disclosure and will be apparent to those skilled in the art. In addition, features described in conjunction with one embodiment may be used in conjunction with other embodiments, even if not explicitly stated above.

Claims

1. A hydrocarbon fluid, wherein The hydrocarbon fluid contains an organometallic chemical-based compound, the organometallic chemical-based compound is used to prevent coke formation in the hydrocarbon fluid system, the organometallic chemical-based compound present in the hydrocarbon fluid includes: M(N-butyl salicylaldimine) n 、M(N-phenyl salicylaldimine) n 、M(3,5-diisopropyl salicylate) n 、[(N-butylphosphonium) m M(dimethylglyoxime)]n+ or M(bis-dithioketone) n At least one coordination complex of, M comprises at least one of Ni, Co, Fe, Cu, Zn, V, Re, Pt, Pd, Os, Ru, Cr, Mo or W; The organometallic chemical-based compound interrupts the auto-oxidation pathway of coke formation at a temperature of 230 to 430°C.

2. The hydrocarbon fluid according to claim 1, wherein The coordination complex is M (bis-dithiol) having the structure n : In the formula, R and R' are independently hydrogen or a substituted or unsubstituted aryl or alkyl group.

3. The hydrocarbon fluid according to claim 2, wherein The aryl or alkyl group includes at least one of phenyl, methyl, ethyl, n-propyl, p-tolyl, p-anisyl or p-ClC6H4.

4. The hydrocarbon fluid according to claim 1, wherein The hydrocarbon fluid comprises at least one of Jet A, JetA1, JP-8, JP8+100, JP-5, SAF, lubricating oil used in aviation turbines, lubricating oil used in power turbines, or engine and transmission lubricating oil used in automobiles.

5. The hydrocarbon fluid according to claim 1, wherein The organometallic chemical-based compound is released into the hydrocarbon fluid via a controlled release assembly.

6. The hydrocarbon fluid according to claim 5, wherein The controlled release component comprises a porous material comprising the organometallic chemical-based compound.

7. The hydrocarbon fluid according to claim 5, wherein The controlled-release component includes a semipermeable membrane housing that encapsulates the organometallic chemical-based compound.

8. A fuel system for reducing coke formation during transport of hydrocarbon fluids, the fuel system comprising: The hydrocarbon fluid of claim 1, wherein the hydrocarbon fluid comprises an organometallic chemical-based compound; Can; a fuel delivery assembly fluidly connected downstream of the tank; and a nozzle assembly fluidly connected downstream of the fuel delivery assembly; Wherein, the organometallic chemical-based compound exists in a hydrocarbon fluid.

9. The fuel system according to claim 8, wherein: The fuel delivery assembly includes a controlled release assembly for releasing the organometallic chemical-based compound into the hydrocarbon fluid.

10. A lubrication system for reducing coke formation during circulation of a hydrocarbon fluid, the lubrication system being a closed fluid circuit, the lubrication system comprising: The hydrocarbon fluid of claim 1, wherein the hydrocarbon fluid comprises an organometallic chemical-based compound; Can; pumps; as well as Parts that require lubrication; Wherein, the organometallic chemical-based compound exists in a hydrocarbon fluid.

11. The lubrication system according to claim 10, wherein: The lubrication system further includes a controlled release assembly for releasing the organometallic chemical-based compound into the hydrocarbon fluid.

12. A component configured to be in contact with the hydrocarbon fluid of claim 1, the component comprising: a wall having a contact surface configured to contact the hydrocarbon fluid, the contact surface being functionalized with an inhibitor ligand to form an inhibitor ligand functionalized surface; The inhibitor ligand functionalized surface interrupts the autoxidation pathway of coke formation at temperatures between 230 and 430°C.

13. The component according to claim 12, wherein The contact surface comprises at least one of a cobalt-chromium alloy, a cobalt-based alloy, a nickel-based alloy, or an iron-based alloy.

14. The component according to claim 12, wherein The inhibitor ligand comprises at least one of N-butyl salicylaldimine, N-phenyl salicylaldimine, 3,5-diisopropyl salicylate, butylphosphonium, dimethylglyoxime, or bis-dithione.

15. The component according to claim 14, wherein The inhibitor ligand is a bis-dithiol having the following structure: In the formula, R and R' are independently hydrogen or a substituted or unsubstituted aryl or alkyl group.

16. A gas turbine engine, comprising: The nozzle assembly, wherein the component according to claim 12 is the nozzle assembly, and the contact surface is the inner surface of the nozzle assembly.

17. A fuel system for reducing coke formation during transport of hydrocarbon fluids, the fuel system comprising: Can; a fuel delivery assembly fluidly connected downstream relative to the tank; as well as a nozzle assembly fluidly connected downstream relative to the fuel delivery assembly; The component according to claim 12 is one or more of a tank, a fuel delivery assembly and a nozzle assembly, and the contact surface is an inner surface of one or more of the tank, the fuel delivery assembly and the nozzle assembly.

18. A lubrication system for reducing coke formation during circulation of a hydrocarbon fluid, the lubrication system being a closed fluid circuit, the lubrication system comprising: Can; pumps; as well as Parts that require lubrication; The component described in claim 12 is one or more of a tank, a pump, and a component requiring lubrication, and the contact surface is an inner surface of one or more of a tank, a pump, and a component requiring lubrication.

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