Lubricating oil compositions for preventing or reducing knock in a hydrogen fueled engine

Abstract

A method for preventing or reducing knock in a hydrogen fueled combustion engine is described. The method involves lubricating the crankcase of the engine with a lubricating oil composition that includes about 50 to about 3000 ppm of zirconium from one or more zirconium compound, based on total weight of the lubricating oil composition.

Description

T-12650-W001LUBRICATING OIL COMPOSITIONS FOR PREVENTING OR REDUCING KNOCK IN A HYDROGEN FUELED ENGINECROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 684,616, filed August 19, 2024, which is incorporated by reference herein in its entirety.FIELD OF THE INVENTION

[0002] This disclosure relates to a lubricating oil composition that prevents knock in hydrogen fueled engine. More particularly, this disclosure relates to a lubricant composition containing an oil-soluble or oil-dispersible zirconium compound and methods of using the lubricating oil composition thereof.BACKGROUND OF THE INVENTION

[0003] While hydrogen fueled internal combustion engines offer potentially cost- effective means of reducing greenhouse gas emissions, there are some technical challenges. Some of these challenges include high risk of pre-ignition (knocking) due hydrogen’s high auto ignition temperature, low ignition energy, and wide flammability limits.

[0004] Because of differences in combustion characteristics, pre-ignition in hydrogen engines is very different from low-speed pre-ignition in gasoline engines. For example, pre-ignition phenomenon in hydrogen engines is more prevalent at high load, high speed conditions and not limited to low speed, high load conditions.Attorney Docket No.: T-12650-W001

[0005] Because hydrogen (as a fuel) presents pre-ignition challenges in engines, it is important to make design choices that can reduce or minimize pre-ignition in hydrogen engines. Some of these design choices are hardware considerations including spark plug, spark plug gap, piston bowl design, cooling of spark plug, valve timing, turbocharger sizing, and the like. Another viable approach involves carefully designing lubricants that can reduce knocking or pre-ignition in hydrogen-fueled engines.SUMMARY

[0006] In one aspect, the present disclosure is related to a method for preventing or reducing knock in a hydrogen fueled combustion engine, wherein the method comprises the step of: lubricating the crankcase of the engine with a lubricating oil composition comprising from about 50 to about 3000 ppm of zirconium from one or more zirconium compound, based on total weight of the lubricating oil composition.

[0007] In another aspect, the present disclosure is related to a lubricating engine oil composition for a direct injected, boosted, spark ignited internal combustion engine comprising from about 50 to about 3000 ppm of zirconium from one or more zirconium compound, based on total weight of the lubricating oil composition.

[0008] In yet another aspect, the present disclosure is related to a use of one or more zirconium compound in a lubricating oil composition, wherein the lubricating engine oil composition prevents or reduces knock in a hydrogen fueled internal combustion engine.DETAILED DESCRIPTION OF THE INVENTION

[0009] While the disclosure is susceptible to various modifications and alternative forms, specific embodiments thereof are herein described in detail. It should beAttorney Docket No.: T-12650-W001 understood, however, that the description herein of specific embodiments is not intended to limit the disclosure to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the disclosure as defined by the appended claims.Definitions

[0010] To facilitate the understanding of the subject matter disclosed herein, a number of terms, abbreviations or other shorthand as used herein are defined below. Any term, abbreviation or shorthand not defined is understood to have the ordinary meaning used by a skilled artisan contemporaneous with the submission of this application.

[0011] As used herein, the following terms have the following meanings, unless expressly stated to the contrary. In this specification, the following words and expressions, if and when used, have the meanings given below.

[0012] Unless otherwise specified, all percentages are in weight percent.

[0013] Throughout the specification and claims the expression oil-soluble or dispersible is used. By oil soluble or dispersible is meant that an amount needed to provide the desired level of activity or performance can be incorporated by being dissolved, dispersed or suspended in an oil of lubricating viscosity. Usually, this means that at least about 0.001% by weight of the material can be incorporated in a lubricating oil composition. For a further discussion of the terms oil soluble and dispersible, particularly "stably dispersible", see U.S. Pat. No. 4,320,019 which is expressly incorporated herein by reference for relevant teachings in this regard.

[0014] The term “Total Base Number” or “TBN” as used herein refers to the amount of base equivalent to milligrams of KOH in one gram of sample. Thus, higher TBN numbers reflect more alkaline products, and therefore a greater alkalinity. TBN was determined using ASTM D 2896 test.Attorney Docket No.: T-12650-W001

[0015] The term “sulfated ash” as used herein refers to the non-combustible residue resulting from detergents and metallic additives in lubricating oil. Sulfated ash may be determined using ASTM Test D874.Description

[0016] The present disclosure relates to lubricating oil compositions for reducing or preventing knock or pre-ignition in hydrogen-fueled engines (also referred to as “hydrogen engines”) and methods of using the compounds thereof. It is contemplated that as technology matures, hydrogen fueled combustion engines will be increasingly adopted in various types of gaseous-fuled application including on-road, off-road automobiles, marine vessels, railroad trains, stationary gas engines, gas cogeneration systems and the like.

[0017] In one embodiment, the lubricating oil composition includes an oil of lubricating viscosity and a zirconium compound. In an aspect, the present disclosure provides the use of at least one zirconium compound in a lubricating oil composition for preventing or reducing knock (pre-ignition) in a hydrogen fueled combustion engine.

[0018] In one embodiment, the level of sulfur in the lubricating oil compositions of the present invention is less than or equal to about 0.7 wt. %>, based on the total weight of the lubricating oil composition, such as a level of sulfur of about 0.01 wt. % to about 0.70 wt. %>, 0.01 to 0.6 wt.%, 0.01 to 0.5 wt.%, 0.01 to 0.4 wt.%, 0.01 to 0.3 wt.%, 0.01 to 0.2 wt.%, 0.01 wt. % to 0.10 wt. %. In one embodiment, the level of sulfur in the lubricating oil compositions of the present invention is less than or equal to about 0.60 wt. %, less than or equal to about 0.50 wt. %, less than or equal to about 0.40 wt. %, less than or equal to about 0.30 wt. %, less than or equal to about 0.20 wt. %, less than or equal to about 0.10 wt. % based on the total weight of the lubricating oil composition.Attorney Docket No.: T-12650-W001

[0019] In one embodiment, the level of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.12 wt. %>, based on the total weight of the lubricating oil composition, such as a level of phosphorus of about 0.01 wt. % to about 0.12 wt. %>. In one embodiment, the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.11 wt. %>, based on the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.11 wt. %>. In one embodiment, the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.10 wt. %>, based on the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.10 wt. %>. In one embodiment, the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.09 wt. %>, based on the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.09 wt. %>. In one embodiment, the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.08 wt. %>, based on the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.08 wt. %>. In one embodiment, the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.07 wt. %>, based on the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.07 wt. %>. In one embodiment, the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.05 wt. %>, based on the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.05 wt. %>.

[0020] In one embodiment, the level of sulfated ash produced by the lubricating oil compositions of the present invention is less than or equal to about 1.60 wt. % as determined by ASTM D 874, e.g., a level of sulfated ash of from about 0.10 to aboutAttorney Docket No.: T-12650-W0011 .60 wt. % as determined by ASTM D 874. In one embodiment, the level of sulfated ash produced by the lubricating oil compositions of the present invention is less than or equal to about 1.00 wt. % as determined by ASTM D 874, e.g., a level of sulfated ash of from about 0.10 to about 1.00 wt. % as determined by ASTM D 874. In one embodiment, the level of sulfated ash produced by the lubricating oil compositions of the present invention is less than or equal to about 0.80 wt. % as determined by ASTM D 874, e.g. , a level of sulfated ash of from about 0.10 to about 0.80 wt. % as determined by ASTM D 874. In one embodiment, the level of sulfated ash produced by the lubricating oil compositions of the present invention is less than or equal to about 0.60 wt. % as determined by ASTM D 874, e.g., a level of sulfated ash of from about 0.10 to about 0.60 wt. % as determined by ASTM D 874.

[0021] In one embodiment, the present lubricating oil composition may have a total base number (TBN) of 4 to 15 mg KOH / g (e.g., 5 to 12 mg KOH / g, 6 to 12 mg KOH / g, or 8 to 12 mg KOH / g).

[0022] Knock (pre-ignition) is most likely to occur in hydrogen fueled combustion engines that, in operation, generate a break mean effective pressure (BMEP) level of greater than about 12 bar (peak torque), such as at least about 13 bar, at least about 14 bar, at least about 15 bar, at least about 16 bar , at least about 17 bar, particularly at least about 20 bar at engine speeds of from about 1500 to about 2500 rotations per minute (rpm), such as at engine speeds of from about 1500 to about 2000 rpm, such as at engine speeds of from about 1700 to about 2500 rpm, such as at engine speeds of from about 1700 to about 2000 rpm. As used herein, break mean effective pressure (BMEP) is defined as the work accomplished during one engine cycle, divided by the engine swept volume; the engine torque normalized by engine displacement. The word "brake" denotes the actual torque / power available at the engine flywheel, as measured on a dynamometer. Thus, BMEP is a measure of the useful power output of the engine.Attorney Docket No.: T-12650-W001

[0023] Knocking (pre-ignition) events, while comparatively uncommon, may be catastrophic in nature. Hence drastic reduction or even elimination of these events during normal or sustained operation of a hydrogen fueled engine is desirable. These events can be divided into three categories, small damage potential pre-ignition events, medium damage potential events, and high damage potential events. Small damage potential events are those in that the pressure in the cylinder max out at 107 bar. Medium damage potential events are those in which the pressure cylinder max is greater than 107 bar and less than 115 bar. Finally, high damage potential events are those in which the pressure cylinder max is greater than 115 bar.

[0024] Thus, one goal is to limit the high damage potential events as much as possible. In one aspect, a goal is to limit pre-ignition such that there are less than 55 high damage potential events per 100,000 combustion events such as less than 50 high damage potential events per 200,000 combustion events, less than 45 high damage potential events per 200,000 combustion events, less than 40 high damage potential events per 200,000 combustion events, less than 35 high damage potential events per 200,000 combustion events, less than 30 high damage potential events per 200,000 combustion events, less than 25 high damage potential events per 200,000 combustion events, or there may be less than 20 high damage potential events per 200,000 combustion events.

[0025] Therefore, in an aspect the present disclosure provides a method for preventing or reducing knock in a hydrogen fueled engine, said method comprising the step of lubricating the crankcase of the engine with a lubricating oil composition comprising one or more zirconium compound. In one embodiment, the amount of zirconium from the one or more zirconium compound is from about 50 to about 3000 ppm, from about 100 to about 3000 ppm, from about 200 to about 3000 ppm, from about 250 to about 2500 ppm, from about 300 to about 2500 ppm, from about 350 to about 2500 ppm,Attorney Docket No.: T-12650-W001 from about 400 ppm to about 2500 ppm, from about 500 to about 2500 ppm, from about 600 to about 2500 ppm, from about 700 to about 2500 ppm, from about 700 to about 2000 ppm, from about 700 to about 1500 ppm in the lubricating oil composition. In one embodiment, the amount of zirconium from the zirconium compound is no more than about 2000 ppm or no more than 1500 ppm in the lubricating oil composition.

[0026] In one embodiment, the method of the invention provides a reduction in the number of high damage potential events per 200,000 combustion events of at least 10 percent, or at least 20 percent, or at least 30 percent, or at least 50 percent, or at least 60 percent, or at least 70 percent, or at least 80 percent, or at least 90 percent, or at least 95 percent, compared to an oil that does not contain the one or more zirconium compound.

[0027] In one embodiment, the lubricating oil composition of this disclosure may be a monograde engine oil, e.g., a SAE 20, SAE 30, SAE 40, SAE 50 or SAE 60 viscosity grade engine oil.

[0028] In one embodiment, the lubricating oil composition of this disclosure may be a multi-grade engine oil, e.g., an engine oil with a SAE viscosity grade of 0W-X, 5W-X, 10W-X, 15W-X, 20W-X or 25W-X, where X may be selected from 8, 12, 16, 20, 30, 40, 50, or 60.Zirconium Compounds

[0029] The lubricating oil compositions includes one or more zirconium compounds (may also be referred to as “zirconium-containing compound”) as described herein.

[0030] The zirconium compounds compatible with the present disclosure are generally oil-soluble or oil-dispersible and include zirconium complexes prepared by reacting a tetravalent zirconium reactant with a suitable ligand. Suitable examples of zirconium reactants include, but are not limited to, zirconium(IV) n-butoxide, zirconium(IV) t- butoxide, zirconium(IV) n-propoxide, zirconium(IV) i-propoxide, zirconium(IV)Attorney Docket No.: T-12650-W001 ethoxide, zirconium(IV) oxide, zirconium(IV) hydrogenphosphate, zirconium (IV) chloride, tetrachlorobis(tetrahydrofuran)zirconium, zirconium (IV) dichloride oxide hydrate, zirconium(IV) bromide, zirconium(IV) iodide, zirconium(IV) fluoride, tetrabenzylzirconium, tetrakis(diethylamino)zirconium, zirconium(IV) acetylacetonate, or similar zirconium compounds. It is also possible that the zirconium reactants disclosed herein can be used as the zirconium compound in the lubricating oil composition.

[0031] A more detailed discussion of zirconium compounds can be found in Cardin et al., “Chemistry of Organo-Zirconium and -Hafnium Compounds”, 1st Edition, Chichester, Ellis Norwood Limited, (1986), which is incorporated herein by reference. The following is a non -exhaustive list of suitable zirconium compounds.Zirconium Alkoxides

[0032] In accordance with the present disclosure, the zirconium compound can be a zirconium alkoxide. In some embodiments, the zirconium alkoxides can be described by the following generalized formula:Zr(ORA)nL% (Formula 1 ) where RA is independently a linear, cyclic, or branched, saturated or unsaturated, aliphatic hydrocarbon moiety having from 1 to about 30 carbon atoms, n is an integer from 0 to 4, L is absent or a ligand that saturates the coordination sphere of zirconium, and x is an integer from 0 to 4, wherein n + x =4. Ligand, L, can independently be water, hydroxide, alkoxide, oxo, phosphine, phosphite, ammonia, amino, amido, halide, or combinations thereof.Colloidal DispersionAttorney Docket No.: T-12650-W001

[0033] In accordance with the present disclosure, the zirconium compound can be a colloidal dispersion of zirconia. For example, zirconia has the net molecular formula of ZrO .

[0034] In certain embodiments, the colloidal dispersion of zirconia will comprise nanoparticle, wherein the nanoparticle has an average particle size less than 100 nm as determined by TEM. Practically speaking, a solvent can be added to improve the dispersion of the colloidal particles. Examples of suitable solvents include glycol ethers such as Propyl CELLOSOLVE™ (Dow), Butyl CELLOSOLVE™ (Dow), Hexyl CELLOSOLVE™ (Dow), CARBITOL™ (Dow), Methyl CARBITOL™ (Dow), Butyl CARBITOL™ (Dow), Hexyl CARBITOL™ (Dow), Methoxytriglycol (Dow), Ethoxytrigylcol (Dow), Butoxytriglycol (Dow), Eastman™ DB Solvent, Eastman™ DE Solvent, Eastman™ DP Solvent, Eastman™ EP Solvent, Eastman™ EP Solvent, Eastman™ EEH Solvent, or related species. In some embodiments, the solvents can be reduced or unsaturated fatty acids such as oleic acid, lauric acid, stearic acid, and palmitic acid and related species, or synthetic carboxylic acids such as ExxonMobil™ neopentanoic acid, ExxonMobil™ neodecanoic acid, Eastman™ 2-Ethylhaxanoic Acid, or other related species. If solvent is used, the amount of the colloidal dispersion of zirconia can be from about 0.01 wt. % to about 5 wt. %>.Zirconium Amido Compounds

[0035] In accordance with the present disclosure, the zirconium compound can be a zirconium amido compound. In some embodiments, the zirconium amido compound can be described the following generalized formula:Zr(NRB)nL% (Formula 2) where RB is independently a linear, cyclic, or branched, and saturated or unsaturated, aliphatic hydrocarbon moiety having from 1 to about 30 carbon atoms, n is an integerAttorney Docket No.: T-12650-W001 from 0 to 4, L is absent or a ligand that saturates the coordination sphere of zirconium, and x is an integer from 0 to 4, wherein n + x = 4. In certain embodiments, the Ligand, L, is independently selected from the group consisting of water, hydroxide, alkoxide, oxo, phosphine, phosphite, ammonia, amino, amido, halide, and combinations thereof.Zirconium Acetylacetonates

[0036] In accordance with the present disclosure, the zirconium compound can be a zirconium acetylacetonate compound. In some embodiments, the zirconium acetylacetonate can be described by the following generalized formula:(Formula 3),Where each Rc can independently be a symmetric or asymmetric linear, cyclic, or branched, saturated or unsaturated, aliphatic hydrocarbon moiety having from 1 to about 30 carbon atoms, or an aromatic moiety, n is an integer from 0 to 4, L is absent or a ligand that saturates the coordination sphere of zirconium, x is an integer from 0 to 4, and n + x = 4. In certain embodiments the Ligand, L, is independently selected from the group consisting of water, hydroxide, alkoxide, oxo, phosphine, phosphite, ammonia, amino, amido, halide, and combinations thereof.Zirconium Carboxylates

[0037] In accordance with the present disclosure, the zirconium compound can be a zirconium carboxylate. In some embodiments, the zirconium carboxylate can be described the following generalized formula:Attorney Docket No.: T-12650-W001(Formula 4), where RD is independently a linear, cyclic, or branched, saturated or unsaturated, aliphatic hydrocarbon moiety having from 1 to about 30 carbon atoms, or aromatic and alkylaromatic rings with alkyl groups that can be linear, cyclic, or branched, and saturated or unsaturated, aliphatic hydrocarbon moiety having from 1 to about 30 carbon atoms, n is an integer from 0 to 4, L is a ligand that saturates the coordination sphere of zirconium, x is an integer from 0 to 4, and n + x = 4. In certain embodiments, the Ligand, L, is independently absent or selected from the group consisting of water, hydroxide, alkoxide, oxo, phosphine, phosphite, ammonia, amino, amido, halide, and combinations thereof. For example, the zirconium carboxylate can be Zirconium (IV) 2-ethylhexanoate or a zirconium fatty acid such as zirconium (IV) stearate.Zirconium Salicylates

[0038] In accordance with the present disclosure, the zirconium compound can be a zirconium salicylate. In some embodiments, the zirconium carboxylate can be described by the following generalized formula:(Formula 5), where RE is independently a hydrogen atom, a linear, cyclic, or branched, saturated or unsaturated, aliphatic hydrocarbon moiety having from 1 to about 40 carbon atoms, p is independently an integer from 1 to 4, n is an integer from 0 to 4, L is absent or a ligand that saturates the coordination sphere of zirconium, x is an integer from 0 to 4,Attorney Docket No.: T-12650-W001 and n + x = 4. In some embodiments, n is an integer from 0 to 2. In certain embodiments, the Ligand, L, is independently selected from the group consisting of water, hydroxide, alkoxide, oxo, phosphine, phosphite, ammonia, amino, amido, halide, and combinations thereof. In some embodiments, alkali earth metals such as magnesium, calcium, strontium, and barium may be added. Alkali earth metals are typically basic salts which can include, but are not limited to, metal oxides, metal alkoxides, metal carbonates, and metal bicarbonates.Zirconium Arylsulfonates

[0039] In accordance with the present disclosure, the zirconium compound can be a zirconium arylsulfonate. In some embodiments, the zirconium arylsufonate can be described the following generalized formula:(Formula 6), where Rj is independently a hydrogen atom, a linear, cyclic, or branched, saturated or unsaturated, aliphatic hydrocarbon moiety having from 1 to about 40 carbon atoms, p is independently an integer from 1 to 5, n is an integer from 0 to 4, L is a ligand that saturates the coordination sphere of zirconium, x is an integer from 0 to 4, and n + x = 4. In certain embodiments the Ligand, L, is independently absent or selected from the group consisting of water, hydroxide, alkoxide, oxo, phosphine, phosphite, ammonia, amino, amido, halide, and combinations thereof. In some embodiments, alkali earth metals such as magnesium, calcium, strontium, and barium may be added. Alkali earth metals are typically basic salts which can include, but are not limited to, metal oxides, metal alkoxides, metal carbonates, and metal bicarbonates.Attorney Docket No.: T-12650-W001Zirconium Phenates

[0040] In accordance with the present disclosure, the zirconium compound can be a zirconium phenate (including zirconium sulfurized or unsulfurized phenate). In some embodiments, the zirconium sulfurized or unsulfurized phenate can be described the following generalized formula:(Formula 7) where RK is independently a hydrogen atom, a linear, cyclic, or branched, saturated or unsaturated, aliphatic hydrocarbon moiety having from 1 to about 40 carbon atoms, x’ is independently 0 or an integer from 1 to about 8, n is an integer from 0 to about 4, L is absent or a ligand that saturates the coordination sphere of zirconium, and x is an integer from 0 to 4. In some embodiments, there is no sulfur present. In some embodiments, calcium carbonate may be added. In certain embodiments, the Ligand, L, is independently selected from the group consisting of water, hydroxide, alkoxide, oxo, phosphine, phosphite, ammonia, amino, amido, halide, and combinations thereof.Dithiocarbamato Zirconium Complexes

[0041] In accordance with the present disclosure, the zirconium compound can be a dithiocarbamato zirconium complex. In some embodiments, the zirconium dithiocarbamato can be described by the following generalized formula:Attorney Docket No.: T-12650-W001(Formula 8), where each RG is independently a linear, cyclic, or branched, saturated or unsaturated, aliphatic hydrocarbon moiety having from 1 to about 30 carbon atoms, n is an integer from 0 to 4, L is absent or a ligand that saturates the coordination sphere of zirconium, x is an integer from 0 to 4, and n + x = 4. In certain embodiments the Ligand, L, is independently selected from the group consisting of water, hydroxide, alkoxide, oxo, phosphine, phosphite, ammonia, amino, amido, halide, and combinations thereof.Dithiophosphato Zirconium Complexes

[0042] In accordance with the present disclosure, the zirconium compound can be a dithiophosphato zirconium complex. In some embodiments, the zirconium dithiophosphato complex can be described by the following generalized formula:(Formula 9), where each RH and Rj is independently a linear, cyclic, or branched, saturated or unsaturated, aliphatic hydrocarbon moiety having from 1 to about 30 carbon atoms, n is an integer from 0 to 4, L absent or is a ligand that saturates the coordination sphere of zirconium, x is an integer from 0 to 4, and n + x = 4. In certain embodiments, the Ligand, L, is independently selected from the group consisting of water, hydroxide,Attorney Docket No.: T-12650-W001 alkoxide, oxo, phosphine, phosphite, ammonia, amino, amido, halide, and combinations thereof.Salen Zirconium Complexes

[0043] In accordance with the present disclosure, the zirconium compound can be a salen zirconium complex. In some embodiments, the salen zirconium complexes can be described by the following generalized formula:(Formula 10), where each RM, RM’, RN, RN>, RP, RP’ is independently a hydrogen atom, or a linear, cyclic, or branched, saturated or unsaturated, hydrocarbon moiety having from 1 to about 40 carbon atoms, each X or Y is independently -C(R ” )Z where each R ” is independently a hydrogen atom, a linear, cyclic, or branched, saturated or unsaturated, aliphatic hydrocarbon moiety having from 1 to about 20 carbon atoms, or an aromatic ring, z is 1 or 2 when each N is imido or amino, respectively, each RP or Rp> is independently a hydrogen atom, a linear, cyclic, or branched, saturated or unsaturated, aliphatic chains hydrocarbon moiety having from 1 to about 20 carbon atoms, or taken together with the atoms to which they are connected form a 5-, 6-, or 7-membered ring (can be aromatic, completely saturated, or contain varying levels of unsaturation), n is an integer from 0 to 2, L is absent or a ligand that saturates theAttorney Docket No.: T-12650-W001 coordination sphere of zirconium, and x is an integer from 0 to 4. In certain embodiments the Ligand, L, is independently selected from the group consisting of water, hydroxide, alkoxide, oxo, phosphine, phosphite, ammonia, amino, amido, halide, and combinations thereof.Phosphorus-Containing Zirconium Complexes

[0044] In accordance with the present disclosure, the zirconium compound can be a phosphate ester, phospinate, or phosphinite zirconium complex. In some embodiments, the zirconium phosphate esters, phosphite, phospinates, or phosphinites can be described by the following generalized formula:(Formula 11 ), where each W is independently an oxo or an unbonded pair of electrons when the phosphorous atom is in the +5 or +3 oxidation state, respectively, each Roor Ro> is independently a linear, cyclic, or branched, saturated or unsaturated, aliphatic hydrocarbon moiety having from 1 to about 30 carbon atoms, an aromatic ring or an alkoxide moiety, n is an integer from 0 to 4, L is independently absent or a ligand that saturates the coordination sphere of zirconium, x is an integer from 0 to 4, and n + x = 4. In some embodiments, the zirconium phosphate esters, phosphite, phospinates, and phosphinites structures are dimeric with bridging ligand groups. In certain embodiments the Ligand, L, is independently selected from the group consisting of water, hydroxide, alkoxide, oxo, phosphine, phosphite, ammonia, amino, amido, halide, and combinations thereof.Attorney Docket No.: T-12650-W001Additional Aryl Zirconium Complexes

[0045] In accordance with the present disclosure, the zirconium compound can be pyridyl, polypyridyl, and quinolinolato zirconium complexes. In some embodiments, pyridyl, polypyridyl, and quinolinolato complexes of zirconium can be described by the following generalized formula:(Formula 12), where each Rq, Rq>, or Rq” is independently a hydrogen atom or a linear, cyclic, or branched, saturated or unsaturated, aliphatic hydrocarbon moiety having from 1 to about 40 carbon atoms, or a pyridyl ring typically substituted at the 2 position which can be unfunctionalized or can be connected to the other functionalized pyridyl rings to make fused ring systems commonly referred to 8-hydroxyquinolines, quinolines, or phenanthrolines, n is an integer from 0 to 4, L is absent or a ligand that saturates the coordination sphere of zirconium, x is an integer from 0 to 4, and n + x = 4. In certain embodiments the Ligand, L, is independently selected from the group consisting of water, hydroxide, alkoxide, oxo, phosphine, phosphite, ammonia, amino, amido, halide, and combinations thereof.Other Zirconium Complexes

[0046] In accordance with the present disclosure, the zirconium compound can be a dialkyl, dihalo or thiocarbamto, thiophosphato bis(cyclopentadienyl)zirconiumAttorney Docket No.: T-12650-W001 compound. Other related zirconium metallocene complexes are known to a person of ordinary skill in the art and may be used in the lubricating oil compositions disclosed herein. In some embodiments, the zirconium metallocene can be described by the following generalized formula:(Formula 13), where each RF is independently a hydrogen atom, a linear, cyclic, or branched, saturated or unsaturated, aliphatic hydrocarbon moiety having from 1 to about 30 carbon atoms, n is an integer from 0 to 5, X is a linear, cyclic, or branched, saturated or unsaturated, aliphatic hydrocarbon moiety having from 1 to about 30 carbon atoms;a halogen substituent selected from fluoride, chloride, bromide, and iodide, or thiocarbamto ligand of the following generalized formula:(Formula 14), where each RG is independently selected from a linear, cyclic, or branched, saturated or unsaturated, aliphatic hydrocarbon moiety having from 1 to about 30 carbon atoms; or thiophosphato ligand of following generalized formula: ,ORHOS- RORh(Formula 15), where each RH is independently selected from linear, cyclic, or branched, saturated or unsaturated, aliphatic hydrocarbon moiety having from 1 to about 30 carbon atoms. Those skilled in the art will appreciate the zirconium metallocene will contain the appropriate number of X ligands to result in a formally neutral complex.

[0047] In accordance with the present disclosure, a zirconium reactant can be complexed to a basic nitrogen dispersant succinimide. The basic nitrogen succinimideAttorney Docket No.: T-12650-W001 used to prepare the zirconium complexes has at least one basic nitrogen and is preferably oil-soluble. The succinimide compositions may be post-treated with, e.g., boron, using procedures well known in the art so long as the compositions continue to contain basic nitrogen. The mono and polysuccinimides that can be used to prepare the zirconium complexes described herein are disclosed in numerous references and are well known in the art. Certain fundamental types of succinimides and the related materials encompassed by the term of art "succinimide" are taught in U.S. Pat. No’s. 3,219,666; 3,172,892; and 3,272,746, the disclosures of which are hereby incorporated by reference. The term "succinimide" is understood in the art to include many of the amide, imide, and amidine species which may also be formed. The predominant product however is a succinimide and this term has been generally accepted as meaning the product of a reaction of an alkenyl substituted succinic acid or anhydride with a nitrogen-containing compound. Preferred succinimides, because of their commercial availability, are those succinimides prepared from a hydrocarbyl succinic anhydride, wherein the hydrocarbyl group contains from about 24 to about 350 carbon atoms, and an ethylene amine, said ethylene amines being especially characterized by ethylene diamine, diethylene triamine, triethylene tetramine, and tetraethylene pentamine. Particularly preferred are those succinimides prepared from polyisobutenyl succinic anhydride of 70 to 128 carbon atoms and tetraethylene pentamine or triethylene tetramine or mixtures thereof. Also included within the term "succinimide" are the cooligomers of a hydrocarbyl succinic acid or anhydride and a poly secondary amine containing at least one tertiary amino nitrogen in addition to two or more secondary amino groups. Ordinarily this composition has between 1 ,500 and 50,000 average molecular weight. A typical compound would be that prepared by reacting polyisobutenyl succinic anhydride and ethylene dipiperazine.Attorney Docket No.: T-12650-W001

[0048] Succinimides having an average molecular weight of 1000 or 1300 or 2300 and mixtures thereof are most preferred.

[0049] In accordance with the present disclosure, the zirconium compound can be a stable colloidal suspension. For example, US Pat. 7,884,058 incorporated herein by reference, discloses stable colloidal suspensions of various inorganic oxides. These can be prepared in the presence of an oil phase with a dispersing agent that includes polyalkylene succinic anhydrides, non-nitrogen containing derivatives of a polyalkylene succinic anhydride selected from the group consisting of a polyalkylene succinic acid, a Group I and / or Group II mono- ordi-salt of a polyalkylene succinic acid, a polyalkylene succinate ester formed by the reaction of a polyalkylene succinic anhydride or an acid chloride with an alcohol and mixtures thereof, and mixtures thereof and a diluent oil, wherein the stable colloidal suspension is substantially clear.

[0050] In one embodiment, the amount of zirconium from the at least one zirconium compound is from about 50 to about 3000 ppm, from about 100 to about 3000 ppm, from about 200 to about 3000 ppm, or from about 250 to about 2500 ppm, from about 300 to about 2500 ppm, from about 350 to about 2500 ppm, from about 400 ppm to about 2500 ppm, from about 500 to about 2500 ppm, from about 600 to about 2500 ppm, from about 700 to about 2500 ppm, from about 700 to about 2000 ppm, from about 700 to about 1500 ppm. In one embodiment, the amount of zirconium from the zirconium containing compound is no more than about 2000 ppm or no more than about 1500 ppm.

[0051] In one embodiment, the zirconium-containing compound can be combined with conventional lubricating oil detergent additives (e.g., a carboxylate, salicylate, phenate, or sulfonate detergent) which contain magnesium and / or calcium. In one embodiment the calcium detergent(s) can be added in an amount sufficient to provide the lubricating oil composition from 0 to about 2400 ppm of calcium metal, from 0 toAttorney Docket No.: T-12650-W001 about 2200 ppm of calcium metal, from 100 to about 2000 ppm of calcium metal, from 200 to about 1800 ppm of calcium metal, or from about 100 to about 1800 ppm, or from about 200 to about 1500 ppm, or from about 300 to about 1400 ppm, or from about 400 to about 1400 ppm, of calcium metal in the lubricating oil composition. In one embodiment the magnesium detergent(s) can be added in an amount sufficient to provide the lubricating oil composition from about 100 to about 1000 ppm of magnesium metal, or from about 100 to about 600 ppm, or from about 100 to about 500 ppm, or from about 200 to about 500 ppm of magnesium metal in the lubricating oil composition.Oil of lubricating viscosity

[0052] The lubricating oil composition includes oil of lubricating viscosity. In some embodiments, the oil of lubricating viscosity is present from 1 wt.% to 99 wt.% based on total weight of the lubricating oil composition.

[0053] When added to finished oil, the oil of lubricating viscosity (sometimes referred to as “base stock” or “base oil”) is the primary liquid constituent of a lubricant, into which additives and possibly other oils are blended, for example to produce a final lubricant (or lubricant composition).

[0054] A base oil is also useful for making concentrates (i.e., additive package) as well as for making lubricating compositions therefrom and may be selected from natural and synthetic lubricating oils and combinations thereof.

[0055] Natural oils include animal and vegetable oils, liquid petroleum oils and hydrorefined, solvent-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.Attorney Docket No.: T-12650-W001

[0056] Synthetic lubricating oils include hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1 -hexenes), poly(1 -octenes), poly(1 - decenes); alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes; polyphenols (e.g., biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogues and homologues thereof. Polymerized olefins can also be derived from bio-derived sources such as hydrocarbon terpenes such as myrcene, ocimene and farnesene which can also be co-polymerized with other olefins and further isomerized if desired.

[0057] Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., malonic acid, alkyl malonic acids, alkenyl malonic acids, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, fumaric acid, azelaic acid, suberic acid, sebacic acid, adipic acid, linoleic acid dimer, phthalic acid) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2- ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these esters include dibutyl adipate, di (2 -ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.

[0058] Esters useful as synthetic oils also include those made from C5 to C12 monocarboxylic acids and polyols, and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol. Esters from bio-derived sources may also be useful as synthetic oils.Attorney Docket No.: T-12650-W001

[0059] The base oil may be derived from Fischer-Tropsch synthesized hydrocarbons. Fischer-Tropsch synthesized hydrocarbons are made from synthesis gas containing H2 and CO using a Fischer-Tropsch catalyst. Such hydrocarbons typically require further processing in order to be useful as the base oil. For example, the hydrocarbons may be hydroisomerized; hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed; using processes known to those skilled in the art.

[0060] The base oil may be a renewable or bio-derived base oil. Examples of such base oils are disclosed in WO2016061050 and US20190338211 , which is incorporated herein by reference. According to some embodiments, the renewable or bio-derived base oil includes a biobased hydrocarbon, such as an isoparaffinic hydrocarbon derived from hydrocarbon terpenes, such as myrcene, ocimene, and farnesene. In some embodiments, the biobased hydrocarbon is produced from fatty acids or fatty esters.

[0061] Unrefined, refined and re-refined oils can be used in the present lubricating composition. Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further treatment would be unrefined oil. Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration and percolation are known to those skilled in the art.

[0062] By applying similar refining processes to already- refined oils that have been used in service as those processes that are used to obtain those refined oils in the first place, re-refined oils may be obtained. Such re-refined oils are also known as reclaimed orAttorney Docket No.: T-12650-W001 reprocessed oils and often are additionally processed by techniques for approval of spent additive and oil breakdown products.

[0063] Hence, the base oil which may be used to make the present lubricating composition may be selected from any of the base oils in Groups l-V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines (API Publication 1509). Such base oil groups are summarized in Table 1 below:Table 1<a> Determined in accordance with ASTM D2007.W Determined in accordance with ASTM D2622, ASTM D3120, ASTM D4294 or ASTM D4927.Determined in accordance with ASTM D2270.

[0064] Base oils suitable for use herein are any of the variety corresponding to API Group II, Group III, Group IV, and Group V oils and combinations thereof. In one embodiment, the base oil is a Group I base oil or a blend of two or more different Group I base oils. Suitable Group I base oils include any light overhead cuts from a vacuum distillation column, such as, for example, any Light Neutral, Medium Neutral, and Heavy Neutral base stocks. The base oil may also include residual base stocks or bottoms fractions such as bright stock. Bright stock is a high viscosity base oil which has been conventionally produced from residual stocks or bottoms and has been highly refined and dewaxed.Attorney Docket No.: T-12650-W001

[0065] In one embodiment, the base oil is a Group II base oil or a blend of two or more different Group II base oils. Suitable Group II base oils include, for example, paraffinic mineral oils obtained by a suitable combination of refining processes such as hydrorefining and dewaxing in respect of lubricating oil fractions obtained by atmospheric distillation of crude oil.Additional Lubricating Oil Additives

[0066] In addition to the zirconium compound described herein, the lubricating oil composition can comprise additional lubricating oil additives.

[0067] The lubricating oil compositions of the present disclosure may also contain other conventional additives that can impart or improve any desirable property of the lubricating oil composition in which these additives are dispersed or dissolved. Any additive known to a person of ordinary skill in the art may be used in the lubricating oil compositions disclosed herein. Some suitable additives have been described in Mortier et al., “Chemistry and Technology of Lubricants”, 2nd Edition, London, Springer, (1996); and Leslie R. Rudnick, “Lubricant Additives: Chemistry and Applications”, New York, Marcel Dekker (2003), both of which are incorporated herein by reference. For example, the lubricating oil compositions can be blended with antioxidants (including ashless antioxidants), anti-wear agents, metal detergents, rust inhibitors, dehazing agents, demulsifying agents, metal deactivating agents, friction modifiers, viscosity modifiers (including polymeric viscosity modifiers), pour point depressants, antifoaming agents, co-solvents, corrosion-inhibitors, ashless dispersants, multifunctional agents, dyes, extreme pressure agents and the like and mixtures thereof. A variety of the additives are known and commercially available. TheseAttorney Docket No.: T-12650-W001 additives, or their analogous compounds, can be employed for the preparation of the lubricating oil compositions of the disclosure by the usual blending procedures.

[0068] The lubricating oil composition of the present invention can contain one or more detergents. Metal-containing or ash-forming detergents function as both detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life. Detergents generally comprise a polar head with a long hydrophobic tail. The polar head comprises a metal salt of an acidic organic compound. The salts may contain a substantially stoichiometric amount of the metal in which case they are usually described as normal or neutral salts. A large amount of a metal base may be incorporated by reacting excess metal compound (e.g., an oxide or hydroxide) with an acidic gas (e.g., carbon dioxide).

[0069] Detergents that may be used include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates and other oil-soluble carboxylates of a metal, particularly the alkali or alkaline earth metals, e.g., barium, sodium, potassium, lithium, calcium, and magnesium. The most commonly used metals are calcium and magnesium, which may both be present in detergents used in a lubricant, and mixtures of calcium and / or magnesium with sodium.

[0070] The lubricating oil composition of the present invention can contain one or more anti-wear agents that can reduce friction and excessive wear. Any anti-wear agent known by a person of ordinary skill in the art may be used in the lubricating oil composition. Non-limiting examples of suitable anti-wear agents include zinc dithiophosphate, metal (e.g., Pb, Sb, Mo and the like) salts of dithiophosphates, metal (e.g., Zn, Pb, Sb, Mo and the like) salts of dithiocarbamates, metal (e.g., Zn, Pb, Sb and the like) salts of fatty acids, boron compounds, phosphate esters, phosphite esters, amine salts of phosphoric acid esters or thiophosphoric acid esters, reaction productsAttorney Docket No.: T-12650-W001 of dicyclopentadiene and thiophosphoric acids and combinations thereof. The amount of the anti-wear agent may vary from about 0.01 wt. % to about 5 wt. %>, from about 0.05 wt. % to about 3 wt. %>, or from about 0.1 wt. % to about 1 wt. %>, based on the total weight of the lubricating oil composition.

[0071] In certain embodiments, the anti-wear agent is or comprises a dihydrocarbyl dithiophosphate metal salt, such as zinc dialkyl dithiophosphate compounds. The metal of the dihydrocarbyl dithiophosphate metal salt may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper. In some embodiments, the metal is zinc. In other embodiments, the alkyl group of the dihydrocarbyl dithiophosphate metal salt has from about 3 to about 22 carbon atoms, from about 3 to about 18 carbon atoms, from about 3 to about 12 carbon atoms, or from about 3 to about 8 carbon atoms. In further embodiments, the alkyl group is linear or branched.

[0072] The amount of the dihydrocarbyl dithiophosphate metal salt including the zinc dialkyl dithiophosphate salts in the lubricating oil composition disclosed herein is measured by its phosphorus content. In some embodiments, the phosphorus content of the lubricating oil composition disclosed herein is from about 0.01 wt. % to about 0.14 wt. %>, based on the total weight of the lubricating oil composition.

[0073] The lubricating oil composition of the present invention can contain one or more friction modifiers that can lower the friction between moving parts. Any friction modifier known by a person of ordinary skill in the art may be used in the lubricating oil composition. Non-limiting examples of suitable friction modifiers include fatty carboxylic acids; derivatives (e.g., alcohol, esters, borated esters, amides, metal salts and the like) of fatty carboxylic acid; mono-, di- or tri-alkyl substituted phosphoric acids or phosphonic acids; derivatives (e.g., esters, amides, metal salts and the like) of mono-, di- or tri-alkyl substituted phosphoric acids or phosphonic acids; mono-, di-Attorney Docket No.: T-12650-W001 or tri-alkyl substituted amines; mono- or di-alkyl substituted amides and combinations thereof. In some embodiments examples of friction modifiers include, but are not limited to, alkoxylated fatty amines; borated fatty epoxides; fatty phosphites, fatty epoxides, fatty amines, borated alkoxylated fatty amines, metal salts of fatty acids, fatty acid amides, glycerol esters, borated glycerol esters; and fatty imidazolines as disclosed in U.S. Patent No. 6,372,696, the contents of which are incorporated by reference herein; friction modifiers obtained from a reaction product of a C4 to C75, or a C& to C24, or a C& to C20, fatty acid ester and a nitrogen-containing compound selected from the group consisting of ammonia, and an alkanolamine and the like and mixtures thereof. The amount of the friction modifier may vary from about 0.01 wt. % to about 10 wt. %>, from about 0.05 wt. % to about 5 wt. %>, or from about 0.1 wt. % to about 3 wt. %>, based on the total weight of the lubricating oil composition.

[0074] The lubricating oil composition of the disclosure can contain a molybdenum- containing friction modifier. The molybdenum-containing friction modifier can be any one of the known molybdenum-containing friction modifiers or the known molybdenum-containing friction modifier compositions.

[0075] Preferred molybdenum-containing friction modifier is, for example, sulfurized oxymolybdenum dithiocarbamate, sulfurized oxymolybdenum dithiophosphate, aminemolybdenum complex compound, oxymolybdenum diethylate amide, and oxymolybdenum monoglyceride. Most preferred is a molybdenum dithiocarbamate friction modifier.

[0076] The lubricating oil composition of the invention generally contains the molybdenum-containing friction modifier in an amount of 0.01 to 0.15 wt. % in terms of the molybdenum content.

[0077] The lubricating oil composition of the invention preferably contains an organic oxidation inhibitor in an amount of 0.01 -5 wt. %>, preferably 0.1 -3 wt. %>. The oxidationAttorney Docket No.: T-12650-W001 inhibitor can be a hindered phenol oxidation inhibitor or a diarylamine oxidation inhibitor. The diarylamine oxidation inhibitor is advantageous in giving a base number originating from the nitrogen atoms. The hindered phenol oxidation inhibitor is advantageous in producing no NOx gas.

[0078] Examples of the hindered phenol oxidation inhibitors include 2,6-di-t-butyl-p- cresol, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-methylenebis(6-t-butyl-o-cresol), 4,4'-isopropylidenebis(2,6-di-t-butylphenol), 4,4'-bis(2,6-di-t-butylphenol), 2,2'- methylenebis(4-methyl-6-t-butylphenol), 4,4'-thiobis(2-methyl-6-t-butylphenol), 2,2- thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octyl 3-(3, 5-di-t- butyl-4-hydroxyphenyl)propionate, octadecyl 3-(3,5-di-t-butyl-4- hydroxyphenyl)propionate, and octyl 3-(3,54-butyl-4-hydroxy-3- methylphenyl)propionate, and commercial products such as, but not limited to, Irganox L135® (BASF), Naugalube 531® (Chemtura), and Ethanox 376® (SI Group).

[0079] Examples of the diarylamine oxidation inhibitors include alkyldiphenylamine having a mixture of alkyl groups of 4 to 9 carbon atoms, p,p'-dioctyldiphenylamine, phenyl-naphthylamine, phenyl-naphthylamine, alkylated-naphthylamine, and alkylated phenyl-naphthylamine.

[0080] Each of the hindered phenol oxidation inhibitor and diarylamine oxidation inhibitor can be employed alone or in combination. If desired, other oil soluble oxidation inhibitors can be employed in combination with the above-mentioned oxidation inhibitor(s).

[0081] The lubricating oil composition of the invention may further contain an oxymolybdenum complex of succinimide, particularly a sulfur-containing oxymolybdenum complex of succinimide. The sulfur-containing oxymolybdenum complex of succinimide can provide increased oxidation inhibition when it is employed in combination with the above-mentioned phenolic or amine oxidation inhibitors.Attorney Docket No.: T-12650-W001

[0082] In the preparation of lubricating oil formulations, it is common practice to introduce the additives in the form of 10 to 80 wt. % active ingredient concentrates in hydrocarbon oil, e.g. mineral lubricating oil, or other suitable solvent. Usually, these concentrates may be diluted with 3 to 100, e.g., 5 to 40, parts by weight of lubricating oil per part by weight of the additive package in forming finished lubricants, e.g. crankcase motor oils. The purpose of concentrates is to make the handling of the various materials less difficult and awkward as well as to facilitate solution or dispersion in the final blend.Preparing Lubricating Oil Compositions

[0083] The lubricating oil compositions disclosed herein can be prepared by any method known to a person of ordinary skill in the art for making lubricating oils. In some embodiments, the base oil can be blended or mixed with the zirconium-containing compounds described herein. Optionally, one or more other additives in additional to the zirconium-containing compounds can be added. The zirconium-containing compounds and the optional additives may be added to the base oil individually or simultaneously. In some embodiments, the zirconium-containing compounds and the optional additives are added to the base oil individually in one or more additions and the additions may be in any order. In other embodiments, the zirconium-containing compounds and the additives are added to the base oil simultaneously, optionally in the form of an additive concentrate. In some embodiments, the solubilizing of the zirconium-containing compounds or any solid additives in the base oil may be assisted by heating the mixture to a temperature from about 25 °C to about 200 °C, from about 50 °C to about 150 °C or from about 75 °C to about 125 °C.

[0084] Any mixing or dispersing equipment known to a person of ordinary skill in the art may be used for blending, mixing or solubilizing the ingredients. The blending, mixingAttorney Docket No.: T-12650-W001 or solubilizing may be carried out with a blender, an agitator, a disperser, a mixer (e.g., planetary mixers and double planetary mixers), a homogenizer (e.g., Gaulin homogenizers and Rannie homogenizers), a mill (e.g., colloid mill, ball mill and sand mill) or any other mixing or dispersing equipment known in the art.Application of the Lubricating Oil Compositions

[0085] The lubricating oil composition disclosed herein may be suitable for use as motor oils (that is, engine oils or crankcase oils), or in stationary applications (that is, station gas engines or gas cogeneration systems), in a hydrogen fueled combustion engine, one that is susceptible to knock (pre-ignition).

[0086] The following examples are presented to exemplify embodiments of the invention but are not intended to limit the invention to the specific embodiments set forth. Unless indicated to the contrary, all parts and percentages are by weight. All numerical values are approximate. When numerical ranges are given, it should be understood that embodiments outside the stated ranges may still fall within the scope of the invention. Specific details described in each example should not be construed as necessary features of the invention.EXAMPLES

[0087] The following examples are intended for illustrative purposes only and do not limit in any way the scope of the present invention.Baseline Formulation

[0088] The base line formulation (10-30W viscosity grade) contained a mixture of Group 2 and Group 3 base oil, a secondary dialkyl zinc dithiophosphates (in an amount to provide 770 ppm phosphorus to the lubricating oil composition), a mixture ofAttorney Docket No.: T-12650-W001 succinimide dispersants, a molybdenum succinimide complex (in an amount to provide 130 ppm molybdenum to the lubricating oil composition), a hindered phenol antioxidant, a calcium sulfonate, a calcium phenate, and a magnesium sulfonate (such that there is 1290 ppm Ca and 690 ppm Mg), a foam inhibitor, a pour point depressant, and an olefin copolymer viscosity index improver. The boron content level was 130 ppm (from a borated succinimide dispersant), the sulfur content level was 2580 ppm, while zinc content level was 840 ppm. The formulation had a sulfated ash level of 0.89 and a TBN of 7.Zirconium compound A

[0089] Zirconium compound A was commercially-obtained zirconium(IV) 2- ethylhexanoate (6% Zr) with the chemical formula Zr(CsHi5O2)4.Example 1

[0090] A lubricating oil composition was prepared according to the baseline, the only difference being the addition of 0.3 wt.% of zirconium-containing compound A (180 ppm of Zr based on total weight of the finished oil).Hydrogen Engine Pre-lgnition (Knock) Test

[0091] The samples were tested in 12.8L hydrogen internal combustion events using a dedicated test methodology as described in “The Role of Lubricant Formulation in Controlling Pre-lgnition Phenomena in a H2-ICE” 45th International Vienna Motor Sym posi u m ( h tips : / / dpi,.. o

[0092] To study the lubricant effect on pre-ignition (PI), the engine was modified to inject controlled amount(s) of oil before the intake valve of one of the six cylinders. The pre-ignition events were monitored via pressure sensors before the oil dosing inAttorney Docket No.: T-12650-W001 the next cylinder, during the oil dosing and after the oil dosing. The intensity of the pre-ignition events was determined by the magnitude of the pressure spikes and then classified as low damage potential, medium damage potential and high damage potential pre-ignition events.

[0093] The engine was operated for 1 hour - broken up into three 20 min segments (preconditioning, external oil dosing, and post-conditioning). The engine was operated at 1700 rpm and 12 bar. The engine ran for 20 minutes in each stage, and pre-ignition events were counted. The results were normalized to 200,000 engine cycles and 1g of oil dosed.

[0094] These events can be divided into three categories, small damage potential pre- ignition events, medium damage potential events, and high damage potential events. When pressure in the cylinder max out at 107 bar, the event is considered small damage potential event. When the pressure cylinder max is greater than 107 bar and less than 115 bar, the event is considered medium damage potential event. High damage potential events are events wherein the pressure cylinder max is greater than 115 bar.

[0095] The details of the oil formulations and test results are summarized below.

[0096] Referring to the table above, the addition of 0.3wt% of zirconium compound A reduces the number of high damage potential (in-cylinder pressure spike > 115bar) byAttorney Docket No.: T-12650-W001 over 21%. This can have a huge impact on the durability and life of the engine whilst allowing OEMs to push for higher torque operating points for higher engine efficiency.

[0097] While the disclosure is susceptible to various modifications and alternative forms, specific embodiments thereof are herein described in detail. It should be understood, however, that the description herein of specific embodiments is not intended to limit the disclosure to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the disclosure as defined by the appended claims.

[0098] Note that not all of the activities described in the general description or the examples are required, that a portion of a specific activity may not be required, and that one or more further activities may be performed in addition to those described. Still further, the order in which activities are listed is not necessarily the order in which they are performed.

[0099] Benefits, other advantages, and solutions to problems have been described herein with regard to specific embodiments. However, the benefits, advantages, solutions to problems, and any feature(s) that may cause any benefit, advantage, or solution to occur or become more pronounced are not to be construed as a critical, required, or essential feature of any or all the claims.

[0100] The specification and illustrations of the embodiments described herein are intended to provide a general understanding of the structure of the various embodiments.

[0101] The specification and illustrations are not intended to serve as an exhaustive and comprehensive description of all the elements and features of formulations, compositions, apparatus and systems that use the structures or methods described herein. Separate embodiments may also be provided in combination in a single embodiment, and conversely, various features that are, for brevity, described in theAttorney Docket No.: T-12650-W001 context of a single embodiment, may also be provided separately or in any subcombination. Further, reference to values stated in ranges includes each and every value within that range. Many other embodiments may be apparent to skilled artisans only after reading this specification. Other embodiments may be used and derived from the disclosure, such that a structural substitution, logical substitution, or another change may be made without departing from the scope of the disclosure. Accordingly, the disclosure is to be regarded as illustrative rather than restrictive.

Claims

Attorney Docket No.: T-12650-W001What is Claimed:

1. A method for preventing or reducing knock in a hydrogen fueled combustion engine, wherein the method comprises the step of: lubricating the crankcase of the engine with a lubricating oil composition comprising from about 50 to about 3000 ppm of zirconium from one or more zirconium compound, based on total weight of the lubricating oil composition.

2. The method of claim 1 , wherein the engine is operated under a load with a break mean effective pressure (BMEP) of from about 12 to about 30 bars.

3. The method of claim 1 , wherein the engine is operated at speeds between 500 and 3,000 rpm.

4. The method of claim 1 , wherein the zirconium compound is a zirconium alkoxide compound; colloidal dispersion of zirconia; zirconium amido compound; zirconium acetylacetonate compound; zirconium carboxylate; zirconium salicylate; zirconium arylsulfonate; zirconium sulfurized or unsulfurized phenate; dialkyl, dihalo or thiocarbamto, thiophosphato bis(cyclopentadienyl)zirconium compound; dithiocarbamato zirconium complex; dithiophosphato zirconium complex; salen zirconium complex; phosphate ester, phospinate, or phosphinite zirconium complex; pyridyl, polypyridyl, or quinolinolato zirconium complex; zirconium succinimide complex; or zirconium colloidal suspension.

5. The method of claim 1 , wherein the lubricating oil further comprises a detergent selected from calcium detergents, magnesium detergents, or a combination thereof.

6. The method of claim 5, wherein the detergent is a carboxylate, salicylate, phenate, or sulfonate detergent.

7. The method of claim 1 , wherein the lubricating oil further comprises a molybdenum containing compound.Attorney Docket No.: T-12650-W0018. The method of claim 1, wherein the lubricant composition further comprises at least one other additive selected from an ashless dispersant, an ashless antioxidant, a phosphorus-containing anti-wear additive, a friction modifier, and a polymeric viscosity modifier.

9. The method of claim 1 , wherein the hydrogen fueled combustion engine operates an on-road automobile, off-road automobile, marine vessel, stationary gas engine or gas cogeneration system or railroad train.

10. A lubricating engine oil composition for a direct injected, boosted, spark ignited internal combustion engine comprising from about 50 to about 3000 ppm of zirconium from one or more zirconium compound, based on total weight of the lubricating oil composition.

11. The lubricating engine oil of claim 10, wherein the zirconium compound is a zirconium alkoxide compound; colloidal dispersion of zirconia; zirconium amido compound; zirconium acetylacetonate compound; zirconium carboxylate; zirconium salicylate; zirconium arylsulfonate; zirconium sulfurized or unsulfurized phenate; dialkyl, dihalo or thiocarbamto, thiophosphato bis(cyclopentadienyl)zirconium compound; dithiocarbamato zirconium complex; dithiophosphato zirconium complex; salen zirconium complex; phosphate ester, phospinate, or phosphinite zirconium complex; pyridyl, polypyridyl, or quinolinolato zirconium complex; zirconium succinimide complex; or zirconium colloidal suspension.

12. The lubricating engine oil composition of claim 10, wherein the lubricating oil composition further comprises a detergent selected from calcium detergent, magnesium detergent, and combinations thereof.Attorney Docket No.: T-12650-W00113. The lubricating engine oil composition of claim 12, wherein the detergent is a carboxylate, salicylate, phenate, or sulfonate detergent.

14. The lubricating engine oil composition of claim 10, wherein the lubricating oil composition further comprises a molybdenum containing compound.

15. The lubricating engine oil composition of claim 10, wherein the lubricating oil composition further comprises at least one other additive selected from an ashless dispersant, an ashless antioxidant, a phosphorus-containing anti-wear additive, a friction modifier, and a polymeric viscosity modifier.

16. Use of one or more zirconium compound in a lubricating oil composition, wherein the lubricating engine oil composition prevents or reduces knock in a hydrogen fueled internal combustion engine.

17. Use of claim 16, wherein the one or more zirconium compound is present in from about 50 to about 3000 ppm of zirconium from the one or more zirconium compound, based on the total weight of the lubricating oil composition.

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