Method and use of a lubricating oil compositions for preventing or reducing pre-ignition in hydrogen fueled engines

Abstract

Method for preventing or reducing knock in a hydrogen fueled combustion engine is described. The steps of the method include lubricating the crankcase of the engine with a lubricating oil composition that includes from about 500 to about 2000 ppm of calcium from one or more phenolic-based calcium detergent, based on total weight of the lubricating oil composition.

Description

[0001] LUBRICATING OIL COMPOSITIONS FOR PREVENTING OR REDUCING PRE- IGNITION IN HYDROGEN FUELED ENGINES CROSS-REFERENCE TO RELATED APPLICATION [1] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 690,080, filed September 3, 2024, which is incorporated by reference herein in its entirety. FIELD OF THE INVENTION [2] This disclosure relates to a lubricating oil composition that prevents or reduces pre-ignition in hydrogen fueled engines. More particularly, this disclosure relates to a lubricating oil composition containing at least one oil-soluble or oil-dispersible phenolic-based calcium detergent. BACKGROUND OF THE INVENTION [3] While hydrogen fueled internal combustion engines offer potentially cost-effective means of reducing greenhouse gas emissions, there are some technical challenges. These hurdles include high risk of pre-ignition (knocking) due hydrogen’s high auto ignition temperature, low ignition energy, and wide flammability limits. [4] 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, medium and high speed conditions and not limited to low speed, high load conditions. [5] 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 Attorney Docket No.: T-12649-WO01 approach involves carefully designing lubricants that can reduce knocking or pre-ignition in hydrogen-fueled engines. SUMMARY [6] In one aspect, the present disclosure relates 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 500 to about 3000 ppm of calcium from one or more phenolic-based calcium detergent, based on total weight of the lubricating oil composition. [7] In another aspect, the present disclosure relates a use of one or more phenolic-based calcium detergent 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 [8] 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. Definitions [9] 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. Attorney Docket No.: T-12649-WO01

[0010] All percentages reported are weight % on an active ingredient basis (i.e., without regard to carrier or diluent oil) unless otherwise stated.

[0011] A “major amount” means in excess of about 50 wt. % of a composition.

[0012] “Active ingredients” or “actives” refer to additive material that is not diluent or solvent.

[0013] The term “ppm” means parts per million by weight, based on the total weight of the lubricating oil composition.

[0014] Kinematic viscosity at 100°C (KV100) was determined in accordance with ASTM D445.

[0015] An additive described as “oil-soluble” or “oil-dispersible” means that the amount needed to provide the desired level of activity or performance can be 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.

[0016] The term “metal” refers to alkali metals, alkaline earth metals, or mixtures thereof.

[0017] The term “alkali metal” refers to lithium, sodium, potassium, rubidium, and cesium.

[0018] The term “alkaline earth metal” refers to calcium, barium, magnesium, and strontium.

[0019] Calcium, magnesium, phosphorus, and sulfur contents were determined in accordance with ASTM D5185.

[0020] The term “olefins” refers to a class of unsaturated aliphatic hydrocarbons having one or more carbon-carbon double bonds, obtainable by a number of processes. Those containing one double bond are called mono-alkenes, and those with two double bonds are called dienes, alkyldienes, or diolefins. Alpha olefins are particularly reactive because the double bond is between the first and second carbons, e.g., 1-octene and 1-octadecene, and are used as the starting point for medium-biodegradable surfactants. Linear and branched olefins are also included in the definition of olefins. Attorney Docket No.: T-12649-WO01

[0021] The term “Normal Alpha Olefins” refers to olefins which are straight chain, non-branched hydrocarbons with carbon-carbon double bond present in the alpha or primary position of the hydrocarbon chain.

[0022] The term “Isomerized Normal Alpha Olefin” refers to an alpha olefin that has been subjected to isomerization conditions which results in an alteration of the distribution of the olefin species present and / or the introduction of branching along the alkyl chain. The isomerized olefin product may be obtained by isomerizing a linear alpha olefin containing from about 10 to about 40 carbon atoms, or from about 20 to about 28 carbon atoms, or from about 20 to about 24 carbon atoms.

[0023] The term “C10-40 Normal Alpha Olefins” defines a fraction of normal alpha olefins wherein the carbon numbers below 10 have been removed by distillation or other fractionation methods.

[0024] 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.

[0025] The term “overbased” is intended to define additives which contain a metal content in excess of that required by the stoichiometry of the particular metal and the particular organic acid used. The excess metal exists in the form of particles of inorganic base (e.g., a hydroxide or carbonate) surrounded by a sheath of metal salt. The sheath serves to maintain the particles in dispersion in a liquid oleaginous vehicle. The amount of excess metal is commonly expressed as the ratio of total equivalence of excess metal to equivalence of organic acid and is typically in a range of 0.1 to 30.

[0026] 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-12649-WO01 Description

[0027] The present disclosure relates to lubricating oil compositions for reducing or preventing knock (sometimes referred to as “pre-ignition”) in hydrogen-fueled engines (sometimes 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-fueled applications including on-road, off-road automobiles, marine vessels, railroad trains, stationary gas engines, gas cogeneration systems and the like.

[0028] In one embodiment, the lubricating oil composition includes an oil of lubricating viscosity and a phenolic-based calcium detergent. In an aspect, the present disclosure provides the use of one or more phenolic-based calcium detergents in a lubricating oil composition for preventing or reducing knock (pre-ignition) in a hydrogen fueled combustion engine.

[0029] 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.

[0030] 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 Attorney Docket No.: T-12649-WO01 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. %.

[0031] 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 about 1.60 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, Attorney Docket No.: T-12649-WO01 e.g., a level of sulfated ash of from about 0.10 to about 0.60 wt. % as determined by ASTM D 874.

[0032] 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).

[0033] Knock 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 500 to about 2500 rotations per minute (rpm), such as at engine speeds of from about 500 to 2000 rpm, such as at engine speeds of from about 500 to 1750 rpm, such as at engine speeds of from about 500 to 1500 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.

[0034] Knocking 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. Attorney Docket No.: T-12649-WO01

[0035] 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 200,000 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.

[0036] 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 phenolic-based calcium detergent.

[0037] 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 sulfurized calcium phenate detergent.

[0038] 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.

[0039] 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. Phenolic-Based Calcium Detergents

[0040] The lubricating oil composition of this disclosure includes one or more phenolic-based calcium detergent. Phenolic-based calcium detergents include hydrocarbyl-substituted calcium Attorney Docket No.: T-12649-WO01 phenates, hydrocarbyl-substituted calcium hydroxybenzoates, and calcium salts of Mannich base hydrocarbyl-substituted phenol.

[0041] The amount of calcium from the one or more phenolic-based calcium detergent is from about 500 to about 3000 ppm, such as from about 500 to about 2800 ppm, from about 500 to about 2600 ppm, from about 500 to about 2400 ppm, from about 500 to about 2200 ppm, from about 500 to about 2000 ppm, from about 500 to about 1800 ppm, from about 500 to about 1600 ppm, from about 500 to about 1500 ppm, from about 600 to about 3000 ppm, from about 600 to about 2800 ppm, from about 600 to about 2600 ppm, from about 600 to about 2400 ppm, from about 600 to about 2200 ppm, from about 600 to about 2000 ppm, from about 600 to about 1800 ppm, from about 600 to about 1600 ppm, or from about 600 to about 1500 ppm in the lubricating oil composition. Conventionally, the presence of calcium is believed to increase the probability of knocking events.

[0042] In some embodiments, the lubricating oil composition includes a detergent system solely comprising the one or more phenolic-based calcium detergent. That is, no other detergent is present in the lubricating oil composition or the lubricating oil composition is substantially free of any other detergents.

[0043] In one embodiment, the overbased calcium salt of a phenolic-based detergent is present in the lubricating oil composition in an amount of about 0.1 wt. % to about 3 wt. %, based on the total weight of the lubricating oil composition. In one embodiment, the overbased calcium salt of a phenolic-based detergent is present in the lubricating oil composition in an amount of about 0.2 wt. % to about 2 wt. %, based on the total weight of the lubricating oil composition. In one embodiment, the overbased metal salt of a phenolic-based detergent is present in the lubricating oil composition in an amount of about 0.5 wt. % to about 1.4 wt. %, based on the total weight of the lubricating oil composition.

[0044] Suitable phenolic-based detergents include substituted hydrocarbyl group(s) having about 5 to about 100 carbon atoms such as from about 5 to about 90 carbon atoms, from about 5 to about Attorney Docket No.: T-12649-WO01 80 carbon atoms, from about 5 to about 70 carbon atoms, from about 5 to about 60 carbon atoms, from about 5 to about 50 carbon atoms, from about 10 to about 100 carbon atoms, from about 10 to about 90 carbon atoms, from about 10 to about 80 carbon atoms, from about 10 to about 70 carbon atoms, from about 10 to about 60 carbon atoms, from about 10 to about 50 carbon atoms, and so forth.

[0045] According to an embodiment, the phenolic-based calcium detergent can be overbased. The overbased calcium salt of the phenolic-based detergent can have a TBN of from about 100 to about 600, or from about 150 to about 500, or from about 150 to about 450, or from about 200 to about 450, or from about 250 to about 450, or from about 300 to about 450, or from about 350 to about 450, or from about 300 to about 425, or from about 325 to about 425, or from about 350 to about 425 mg KOH / gram, on an oil free basis.

[0046] The phenolic-based calcium detergent includes one or more hydrocarbyl-substituted group such as linear or branched alkyl group, linear or branched olefinic oligomer group, isomerized olefin group, and the like.

[0047] More specifically, the hydrocarbyl-substituted group may be a branched olefinic propylene oligomers or mixture thereof. More specifically, the hydrocarbyl-substituted group may be a branched olefinic propylene oligomer or mixtures thereof. More specifically, the hydrocarbyl- substituted group may be a branched olefinic propylene oligomer or mixtures thereof.

[0048] In one embodiment, the isomerized olefins can contain branched-chain olefins. The branching may occur at a carbon atom that is part of the carbon-carbon double or at a carbon atom that does not form part of the double bond. Examples of the branched-chain olefins include, but are not limited to, the following: Attorney Docket No.: T-12649-WO01

[0049] The hydrocarbyl-substituted phenolic-based detergent may be derived from an isomerized normal alpha olefin having from about 10 to about 40 carbon atoms per molecule having an isomerization level (I) of the normal alpha olefin of from about 0.1 to about 0.4. In general, isomerized phenate detergents are useful for their detergency and antioxidant properties. In addition, metal salts of isomerized phenate detergents made from isomerized normal alpha olefin, have a reduced content of unreacted tetrapropenylphenate (TPP).

[0050] In one aspect of the present disclosure, the isomerization level (I) of the normal alpha olefin is between from about 0.10 to about 0.40, or from about 0.10 to about 0.30, or from about 0.12 to about 0.30, or from about 0.22 to about 0.30. In another embodiment, the isomerization level of the normal alpha olefin is about 0.24 to 0.28, and the normal alpha olefin has from about 20 to about 24 carbon atoms. The isomerization level (I) is defined as: I = m / (m+n) where m is NMR integral for methyl groups with chemical shifts between 0300.03 to 1.010.03 ppm, and n is NMR integral for methylene groups with chemical shifts between 1.010.03 to 1.38 0.10 ppm.

[0051] In one embodiment, isomerized olefin can be obtained by isomerizing normal alpha olefins via a catalyst. Examples of catalysts include solid, acidic catalysts comprising at least one metal oxide, and having an average pore size of less 5.5 angstroms. In one embodiment, the solid, acidic catalyst comprises a molecular sieve with a one-dimensional pore system. In another Attorney Docket No.: T-12649-WO01 embodiment, the catalyst is selected from the group consisting of molecular sieves SM-3, MAPO- 11, SAPO-11, SSZ-32, ZSM-23, MAPO-39, SAPO-39, ZSM-22, and SSZ-20. In one embodiment, the molecular sieves are SAPO-11 and SSZ-32. Other possible solid, acidic catalysts useful for isomerization include molecular sieves ZSM-35, SUZ4, NU-23, NU-87, and natural or synthetic ferrierites. These molecular sieves are well known in the art and are discussed in, for example, Rosemarie Szostak's Handbook of Molecular Sieves (New York, Van Nostrand Reinhold, 1992), and U.S. Pat. No.5,282,958, issued Feb.1, 1994 to Santilli et al., both of which are hereby incorporated by reference.

[0052] The hydrocarbyl-substituted group of the phenolic-based detergent can be derived from an isomerized normal alpha olefin having from about 10 to about 40 carbon atoms per molecule. In one aspect of the present disclosure, the alkyl group of the alkylated phenate detergent is derived from an isomerized normal alpha olefin having from about 14 to about 30, or from about 16 to about 30, or from about 18 to about 30, or from about 20 to about 28, or from about 20 to about 24, or from about 18 to about 28 carbon atoms per molecule. Calcium Phenate Detergent

[0053] The lubricating oil compositions may include a calcium phenate detergent. Suitable calcium phenate detergents include both sulfurized and un-sulfurized calcium phenates.

[0002] Attorney Docket No.: T-12649-WO01

[0054] Un-sulfurized calcium phenates can be represented by the following generalized structure, wherein each R is independently a hydrocarbyl-substituted group.

[0055] Sulfurized calcium phenates can be represented by the following generalized structure, wherein each R is independently a hydrocarbyl-substituted group.

[0056] The overbased calcium salt of a phenate detergent can be prepared any compatible method such as described in, for example, U.S. Patent No.8,580,717 which is herein incorporated in its entirety.

[0057] In an aspect, the present disclosure provides the use of at least one un-sulfurized or sulfurized calcium phenate detergent in a lubricating oil composition for preventing or reducing knock (pre-ignition) in a hydrogen fueled combustion engine. Hydroxybenzoate Detergents Attorney Docket No.: T-12649-WO01

[0058] The hydroxybenzoate detergent of this disclosure is a hydrocarbyl-substituted hydroxybenzoic acid such as a hydrocarbyl-substituted salicylic acid. In some embodiments, the hydrocarbyl-substituted hydroxybenzoic acid may be represented by the following generalized structure: wherein each R is independently a hydrocarbyl group.

[0059] In some embodiments, R is a linear or branched aliphatic group. In some embodiments, R is an alkyl group, including branched- or most preferably straight-chain alkyl groups. There may be more than one R group attached to the benzene ring. The COOM (M = Ca) group can be in the ortho, meta or para position with respect to the hydroxyl group; the ortho position is preferred. The R group can be in the ortho, meta or para position with respect to the hydroxyl group. In some embodiments, R is an isomerized olefin.

[0060] Hydroxybenzoic acids are typically prepared by the carboxylation, by the Kolbe-Schmitt process, of phenoxides, and in that case, will generally be obtained (normally in a diluent) in admixture with uncarboxylated phenol. Hydroxybenzoic acids may be non-sulphurized or sulphurized, and may be chemically modified and / or contain additional substituents. Processes for sulphurizing a hydrocarbyl-substituted hydroxybenzoic acid are well known to those skilled in the art, and are described, for example, in U.S. Publication No. 2007 / 0027057, which is hereby incorporated by reference. Mannich Base of Hydrocarbyl-Substituted Phenol Attorney Docket No.: T-12649-WO01

[0061] The phenolic-based detergent may be the calcium salt of a Mannich hydrocarbyl- substituted phenol. This Mannich product may be synthesized by any compatible method including via the reaction of a hydrocarbyl-substituted phenol with formaldehyde and a primary amine. The resulting product is then mixed with calcium hydroxide (lime) to form the calcium salt of the Mannich base hydrocarbyl-substituted phenol. Oil of lubricating viscosity

[0062] 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.

[0063] 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).

[0064] 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.

[0065] 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.

[0066] 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 Attorney Docket No.: T-12649-WO01 hydrocarbon terpenes such as myrcene, ocimene and farnesene which can also be co-polymerized with other olefins and further isomerized if desired.

[0067] 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.

[0068] Esters useful as synthetic oils also include those made from C5to C12monocarboxylic 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.

[0069] The base oil may be derived from Fischer-Tropsch synthesized hydrocarbons. Fischer- Tropsch synthesized hydrocarbons are made from synthesis gas containing H2and 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.

[0070] 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 Attorney Docket No.: T-12649-WO01 myrcene, ocimene, and farnesene. In some embodiments, the biobased hydrocarbon is produced from fatty acids or fatty esters.

[0071] 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.

[0072] 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 or reprocessed oils and often are additionally processed by techniques for approval of spent additive and oil breakdown products.

[0073] 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 I-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. Attorney Docket No.: T-12649-WO01(b)Determined in accordance with ASTM D2622, ASTM D3120, ASTM D4294 or ASTM D4927.(c)Determined in accordance with ASTM D2270.

[0074] 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.

[0075] 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

[0076] In addition to the sulfurized calcium phenate detergent compound described herein, the lubricating oil composition can comprise additional lubricating oil additives.

[0077] 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 Attorney Docket No.: T-12649-WO01 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. These additives, or their analogous compounds, can be employed for the preparation of the lubricating oil compositions of the disclosure by the usual blending procedures.

[0078] 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).

[0079] 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.

[0080] 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 Attorney Docket No.: T-12649-WO01 (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 products 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.

[0081] 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.

[0082] 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.

[0083] 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; Attorney Docket No.: T-12649-WO01 mono-, di- 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 C4to C75, or a C6to C24, or a C6to 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.

[0084] 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.

[0085] Preferred molybdenum-containing friction modifier is, for example, sulfurized oxymolybdenum dithiocarbamate, sulfurized oxymolybdenum dithiophosphate, amine- molybdenum complex compound, oxymolybdenum diethylate amide, and oxymolybdenum monoglyceride. Most preferred is a molybdenum dithiocarbamate friction modifier.

[0086] 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.

[0087] 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 oxidation inhibitor can be a hindered phenol oxidation inhibitor or a diarylamine oxidation inhibitor. The diarylamine Attorney Docket No.: T-12649-WO01 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.

[0088] 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).

[0089] 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.

[0090] 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).

[0091] 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.

[0092] 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 Attorney Docket No.: T-12649-WO01 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

[0093] 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 sulfurized calcium phenate detergent described herein. Optionally, one or more other additives in addition to the phenolic-based calcium detergent can be added. The phenolic-based calcium detergent compounds and the optional additives may be added to the base oil individually or simultaneously. In some embodiments, the phenolic-based calcium detergent 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 phenolic- based calcium detergent 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 phenolic-based calcium detergent 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.

[0094] 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, mixing 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 Attorney Docket No.: T-12649-WO01

[0095] 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, stationary gas engines or gas cogeneration systems), in a hydrogen fueled combustion engine, one that is susceptible to knock (pre-ignition).

[0096] 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

[0097] The following examples are intended for illustrative purposes only and do not limit in any way the scope of the present invention. Comparative Example 1

[0098] Comparative Example 1 is a 10W-30 viscosity grade oil with the following components: 1) mixture of Group 2 and Group 3 base oil 2) secondary dialkyl zinc dithiophosphates (770 ppm phosphorus based on total lubricating oil composition) 3) mixture of succinimide dispersants 4) molybdenum succinimide complex (130 ppm molybdenum based on total lubricating oil composition) 5) hindered phenol antioxidant 6) LOB calcium sulfonate (400 ppm Ca) 7) C20-C24 isomerized alpha olefin sulfurized calcium phenate (400 ppm Ca) Attorney Docket No.: T-12649-WO01 8) HOB magnesium sulfonate (1000 ppm Mg) 9) foam inhibitor 10) pour point depressant 11) olefin copolymer viscosity index improver The boron content of lubricating oil composition was 130 ppm from a borated succinimide dispersant; the zinc content was 840 ppm from the ZnDTP; the sulfated ash level was 0.89; and the TBN was 7.1. Comparative Example 2

[0099] Comparative Example 2 is a 10W-30 viscosity grade oil with the following components: 1) Group 3 base oil 2) secondary dialkyl zinc dithiophosphates (770 ppm phosphorus based on total lubricating oil composition) 3) mixture of succinimide dispersants 4) molybdenum succinimide complex (130 ppm molybdenum based on total lubricating oil composition) 5) hindered phenol antioxidant 6) mixture of calcium salicylates (2240 ppm Ca) 7) foam inhibitor 8) pour point depressant 9) olefin copolymer viscosity index improver The boron content of lubricating oil composition was 130 ppm from a borated succinimide dispersant; the zinc content was 840 ppm from the ZnDTP; the sulfated ash level was 0.89; and the TBN was 7.6. Comparative Example 3 Attorney Docket No.: T-12649-WO01

[0100] Comparative Example 3 is a 10W-30 viscosity grade oil with the following components: 1) Group 3 base oil 2) secondary dialkyl zinc dithiophosphates (770 ppm phosphorus based on total lubricating oil composition) 3) mixture of succinimide dispersants 4) molybdenum succinimide complex (130 ppm molybdenum based on total lubricating oil composition) 5) hindered phenol antioxidant 6) TBN 410 calcium sulfonate detergent (2260 ppm Ca) 7) foam inhibitor 8) pour point depressant 9) olefin copolymer viscosity index improver The boron content of lubricating oil composition was 130 ppm from a borated succinimide dispersant; the zinc content was 840 ppm from the ZnDTP; the sulfated ash level was 0.89; and the TBN was 7.4. Example 1

[0101] Example 1 is a 10W-30 viscosity grade oil with the following components: 1) mixture of Group 2 and Group 3 base oil 2) secondary dialkyl zinc dithiophosphates (770 ppm phosphorus based on total lubricating oil composition) 3) mixture of succinimide dispersants 4) molybdenum succinimide complex (130 ppm molybdenum based on total lubricating oil composition) 5) hindered phenol antioxidant 6) LOB calcium sulfonate (400 ppm Ca based on total lubricating oil composition) Attorney Docket No.: T-12649-WO01 7) C20-C24 isomerized alpha olefin sulfurized calcium phenate (890 ppm Ca based on total lubricating oil composition) 8) HOB magnesium sulfonate (680 ppm Mg based on total lubricating oil composition) 9) foam inhibitor 10) pour point depressant 11) olefin copolymer viscosity index improver The boron content of the lubricating oil composition was 130 ppm from a borated succinimide dispersant; the zinc content of 840 ppm from the ZnDTP; the sulfated ash level was 0.89; and the TBN was 7.0. Example 2

[0102] Example 2 is a 10W-30 viscosity grade oil with the following components: 1) Group 3 base oil 2) secondary dialkyl zinc dithiophosphates (770 ppm phosphorus based on total lubricating oil composition) 3) mixture of succinimide dispersants 4) molybdenum succinimide complex (130 ppm molybdenum based on total lubricating oil composition) 5) hindered phenol antioxidant 6) C20-C24 isomerized alpha olefin sulfurized calcium phenate (2240 ppm Ca based on total lubricating oil composition) 7) foam inhibitor 8) pour point depressant 9) olefin copolymer viscosity index improver Attorney Docket No.: T-12649-WO01 The boron content of the lubricating oil composition was 130 ppm from a borated succinimide dispersant; the zinc content of 840 ppm from the ZnDTP; the sulfated ash level was 0.89; and the TBN was 7.0. Hydrogen Engine Pre-Ignition (Knock) Test

[0103] The samples were tested in 12.8L hydrogen internal combustion events using a dedicated test methodology described in “The Role of Lubricant Formulation in Controlling Pre-Ignition Phenomena in a H2-ICE” 45th International Vienna Motor Symposium (https: / / doi.org / 10.62626 / 4r79-bfca).

[0104] 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 in 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.

[0105] The engine was operated for 1 hour - broken up into three 20 min segments (pre- conditioning, external oil dosing, and post-conditioning). The engine was operated at 1700 rpm and 12 bar. The engine ran for 200,000 combustion cycles in each stage, and pre-ignition events were counted.

[0106] 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.

[0107] The details of the oil formulations and test results are summarized below. Attorney Docket No.: T-12649-WO01

[0108] Referring to the table above, lowering the magnesium sulfonate detergent and increasing the sulfurized calcium phenate detergent (while keeping the sulfated ash fixed) resulted in significant reduction in number of high (cylinder max P > 115 bar) damage potential pre-ignition events. Higher magnitude pressure spike occurring during early part of crank rotation can cause severe damage to the engine, hence the severity of the PI events is classified based on the pressure spike magnitudes and the engine crank location. 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. This finding was surprising in that substituting magnesium for calcium to solve the problem of LSPI in downsized turbocharged gasoline engines does not work as a solution to the current problem.

[0109] 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.

[0110] 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. Attorney Docket No.: T-12649-WO01

[0111] 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.

[0112] The specification and illustrations of the embodiments described herein are intended to provide a general understanding of the structure of the various embodiments.

[0113] 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 the 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

1. Attorney Docket No.: T-12649-WO01 What 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 500 to about 3000 ppm of calcium from one or more phenolic-based calcium detergent, 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 one or more phenolic-based calcium detergent is a calcium phenate detergent, a sulfurized calcium phenate detergent, a calcium hydroxybenzoate detergent, or a calcium salt of Mannich base hydrocarbyl-substituted phenol.

5. The method of claim 4, wherein the one or more phenolic-based calcium detergent has a TBN of from about 100 to about 600 mg KOH / gram, on an oil free basis.

6. The method of claim 1, 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.Attorney Docket No.: T-12649-WO01 7. 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.

8. The method of claim 1, wherein the lubricating oil composition further comprises a molybdenum containing compound.

9. The method of claim 1, wherein the lubricating oil composition further comprises an ashless dispersant, an ashless antioxidant, a phosphorus-containing anti-wear additive, a friction modifier, or a polymeric viscosity modifier.

10. The method of claim 1, wherein the lubricating oil composition further comprises a magnesium detergent.

11. The method of claim 1, wherein the lubricating oil composition includes a detergent system solely comprising the one or more phenolic-based calcium detergent.

12. Use of one or more phenolic-based calcium detergent in a lubricating oil composition, wherein the lubricating engine oil composition prevents or reduces knock in a hydrogen fueled internal combustion engine.Attorney Docket No.: T-12649-WO01 13. Use of claim 12, wherein the one or more phenolic-based calcium detergent is present in from about 500 to about 3000 ppm of calcium, based on the total weight of the lubricating oil composition.

14. Use of claim 12, wherein the lubricating oil composition includes a detergent system solely comprising the one or more phenolic-based calcium detergent.

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