WO2016123548A1

WO2016123548A1 - Combination of low/no ash oil and emission control catalysts for improved emission control durability and performance

Info

Publication number: WO2016123548A1
Application number: PCT/US2016/015775
Authority: WO
Inventors: Kevin A. Hallstrom; Roger Kuhlman; Sandip D. SHAH; Kenneth E. Voss; Michael Hoey; Kevin Desantis; Alfred Jung; Patrick HASENHUETL
Original assignee: Basf Corporation
Priority date: 2015-01-30
Filing date: 2016-01-29
Publication date: 2016-08-04

Abstract

Lubricating oils and oil additive packages that reduce the amount of ash generated by an internal combustion engine are described. Reducing the amount of ash generated by the internal combution engines significantly aids in the maintenance of the catalytic exhaust system, which would otherwise exhibit a decrease in the treatment efficiency of exhaust gas emissions. A low ash catalytic exhaust system of the invention includes an engine oil used by an internal combustion engine associated with the low ash catalytic exhaust system, wherein the engine oil comprises a base oil and an additive package. The additive package includes a hindered secondary amine detergent, an anti-wear additive in the amount of about 0.1% to about 5% by weight of the engine oil, and at least one epoxide as a seal compatibility additive. Furthermore, the low ash catalytic exhaust system includes a monolithic honeycomb with a catalytic metal.

Description

COMBINATION OF LOW/NO ASH OIL AND EMISSION CONTROL CATALYSTS FOR IMPROVED EMISSION CONTROL DURABILITY AND PERFORMANCE

TECHNICAL FIELD OF THE INVENTION

Principles and embodiments of the present invention relate generally to low ash or ashless lubricating oils that reduce the amount of clogging and fouling of catalytic converters.

BACKGROUND OF THE INVENTION

Lubricating oils are required to protect moving parts from wear that would otherwise result from their direct contact by forming an intervening film between such parts. Such oils may also function to protect the parts from the heat and chemical environment in which they operate. Lubricating oils comprise multiple components including a base oil stock, and one or more additives that affect the formulated oil's chemical and physical properties.

Some of these additives include:

a. Detergents. Detergents have been added to lubricating oils to control the accumulation of deposits in internal combustion engines and keep sludge and carbon suspended in the oil to reduce the wear caused by such materials. Deposits may be generated from the partial combustion of fuel and lubricating oil, and sludges may be formed through oxidation of the oil. Combustion products, such as soot, may enter the crank case from the engine cylinders, where such combustion products may be treated by the detergents in the engine oil.

b. Calcium sulfonates. Calcium sulfonates are widely used detergent additives, an example of which would be a neutral calcium alkylbenzene sulfonate, as shown in general formula I. Two sulfonates interact with the calcium 2+ ion.

FORMULA (I)

The alkyl group is of sufficient length and structure to provide oil solubility, while the polar head may interact with salts, ions, and polar molecules. Calcium carbonate may be dispersed in the oil in excess, and form micelles with the alkylbenzene sulfonate to form 'overbased' sulfonates, where the ratio of calcium carbonate (N_Caco₃) to calcium ions ( ca2₊) in the calcium alkylbenzene sulfonate may be up to 30:1. The CaC0₃ provides a base for neutralizing acidic compounds in the oil, and the amount present determines the total base number (TBN). In some instances magnesium may be used in place of the Ca²⁺. Calcium phenates may also be used.

c. Oxidation inhibitors and anti-wear additives. Oxidation inhibitors and anti-wear additives are also added to lubricating oils. One class of anti-wear additives are phosphorous compounds, which may be an organo-thiophosphate compound, for example 0-[(lR)-l,3-dimethylbutyl] O-(l-methylethyl) hydrogen dithiophosphate and 0-(4,5-dimethylhexyl) 0-(6-methylheptyl) hydrogen phosphorodithioate, or a zinc organo-thiophosphate, for example zinc di-thiophosphates (ZnDTP) or zinc di-alkyl di-thiophosphates (ZDDP). The organo-thiophosphonates and zinc di-thiophosphates, such as ZDDP can act as an anti-wear additive and various ZDDP decomposition products may act as both a peroxide inhibitor and a radical scavenger. Many engine oils include ZnDTP or ZDDP and salts thereof (e.g., amine salts) as an anti-wear additive.

One measure of a lubricating oil's chemical properties is the Total Base Number (TBN), which indicates the lubricating oil's available alkalinity in milligrams of potassium hydroxide per gram of lubricant. The TBN relates to the lubricating oil's ability to reduce the corrosive effects of acidic material in the oil. This value is measured by two ASTM titration methods, ASTM D2896 and ASTM D4739.

A particular area in which lubricating oils are used is in internal combustion engines, where the operating environment can lead to combustion of a portion of the lubricating oil to generate ash. In internal combustion engines these oils and additives are typically used to lubricate the various moving parts, such as the pistons, cylinders, connecting rods, crankshaft, camshaft, valves, and bearings. The internal combustion engine may comprise a combustion system, a fuel injection system, an ignition system, a cooling system, an exhaust system, a lubricating system, and a control system.

The consumption of lubricating oil by the internal combustion engine described above and subsequent ash accumulation in the engine system and can have a significant impact on a number of aspects related to engine emissions, performance and maintenance. For example, lubricating oils can contribute to increased engine -out emissions in the exhaust aftertreatment system in diesel engines. In particular, lubricating oil can be a significant source of hydrocarbon (HC) and carbon monoxide (CO) emissions, especially in smaller engines, and total particulate matter (PM) mass and particle number emissions.

The consumption of lubricating oil and subsequent ash accumulation can have a significant impact on the diesel particulate filters (DPF). In various instances over 90% of the incombustible ash in a diesel particle filter (DPF) can come from inorganic lubricant additives, where ash may comprise incombustible inorganic materials. Keeping lubricating oil consumption low allows smaller DPFs to be fitted to the engine due to lower ash accumulation rate, less frequent regeneration (and fuel economy penalty) to avoid excessive pressure drop, and less deterioration of DPF ceramic substrates. Excessive accumulation of oil-derived hydrocarbons in the DPF can also lead to uncontrolled regeneration and subsequent DPF damage. In addition, sulfur present in engine exhaust gas is known to poison precious metal catalysts, such as platinum group metals, present in various components of the internal combustion engine. Similarly, inorganic materials such as zinc, calcium, magnesium, and phosphorous may accumulate in the catalytic exhaust gas system and may deactivate any catalysts.

All emission control catalysts must therefore be designed— in terms of sizing and precious metal loading— to account for catalyst activity loss due to exposure to oil-derived catalyst poisons and, in the case of SCR catalysts, to oil-derived hydrocarbons as well as other sources that can contribute to loss of catalytic activity, i.e., the presence of sulfur. For example, the platinum group metal loading of monolithic catalytic substrates may be 15 to 250 g/ft³ for light duty vehicles, and about 0.1 g/ft³ to about 300 g/ft³ for heavy duty vehicles (HDV). In some cases the platinum group metal loading (e.g., Pt, Pd, Rh) is in the range of about 15 g/ft³ to about 70 g/ft³ for LDV and about 5 g/ft³ to about 60 g/ft³ for HDV.

Regulated species of exhaust emissions include carbon monoxide (CO), oxides of nitrogen (NO_x), hydrocarbons (HCs), including volatile organic compounds (VOCs), and particulate matter (PM). The Environmental Protection Agency (EPA) Tier 3 March 2014 rules and regulations, which apply to passenger cars, light-duty trucks, medium-duty passenger vehicles, and some heavy-duty vehicles govern the emission of such gases from these sources, including the emission of greenhouse gases.

The EPA FTP NMOG+NOX Tier 3 regulations have two separate sets of declining fleet-average standards, with light duty vehicles (LDVs) and small light trucks (LDT) in one category that begins at 86 milligrams per mile (mg/mi) for MY 2017, and heavier light trucks and MDPVs in a second category that begins at 101 milligrams per mile (mg/mi) for MY 2017, that converge at 30 milligrams per mile (mg/mi) in MY 2025 and later.

EPA Tier 3 Regulations being introduced include PM standards evaluated over the US06 driving cycle (the US06 is one part of the Supplemental Federal Test SFTP) procedure) of 10 mg/mi through MY 2018 and of 6 mg/mi for 2019 and later model years, for light-duty vehicles.

EPA Tier 3 Regulations being introduced also include FTP PM standards of 8 mg/mi and 10 mg/mi for Class 2b and Class 3 HDVs.

The final EPA Tier 3 standards are in most cases identical to those of California's LEVIII program.

In addition, heavy duty trucks, buses, and engines are regulated by the EPA. These EPA emission standards apply to engines installed in all vehicles with Gross Vehicle Weight Ratings above 14,000 pounds, and to some engines installed in vehicles with Gross Vehicle Weight Rating between 8,500 and 14,000 pounds.

These are referred to as the heavy duty diesel (HDD) standards, and set a PM standard of 0.01 g- bhp-hr for a useful life of 22,000 hrs/10 yrs/435,000 miles for MY 2007+ vehicles. Further details of the standards are available from the EPA.

Due to emission regulations becoming more stringent, there is an ongoing need to provide products with lower oil consumption and hence lower ash production. SUMMARY OF THE INVENTION

Various embodiments are listed below. It will be understood that the embodiments listed below may be combined not only as listed below, but in other suitable combinations in accordance with the scope of the invention.

One aspect of the invention describes a low ash catalytic exhaust system comprising an engine oil used by an internal combustion engine associated with the low ash catalytic exhaust system, wherein the engine oil comprises a base oil and an additive package, wherein the additive package comprises a secondary amine detergent, an anti-wear additive in the amount of about 0.1 % to about 5% by weight of the engine oil, and at least one epoxide as a seal compatibility additive; and a monolithic honeycomb substrate comprising a quantity of catalytic metal components, wherein the monolithic honeycomb substrate exhibits an intended operating lifetime that is extended by about 5% to about 400% as compared with the lifetime of a monolithic substrate used with an engine oil containing an additive package with no secondary amine detergent, wherein the additive package is otherwise comparable to the additive package described herein.

In some embodiments, the secondary amine detergent comprises a secondary amine of general formula (II),

wherein R¹ is a branched or straight chain Q-Cis alkyl, and R² is a branched or straight chain Q-Cis alkyl, or R¹ and R² are joined to form a substituted heterocyclic compound.

In some embodiment, the secondary amine comprises a secondary amine sterically hindered by at least one substituent on at least one of the carbons alpha or beta to the nitrogen.

In some embodiments, the secondary amine is selected from the group comprising general formula

IV,

FORMULA (IV)

wherein R³, R⁴, R⁵, and R⁶ are each independently a hydrogen or a C C6 alkyl group; and

R¹¹ and R¹² are independently a C Ci₆ alkyl group, with the proviso that R¹¹ and R¹² are longer alkyl chains than R³, R⁴, R⁵, and R⁶. In some embodiments, the secondary amine is selected from the group comprising general formula

V,

wherein R⁷, R⁸, R⁹,and R¹⁰ are independently a hydrogen or C C6 alkyl group; and

11 12 1 1 12

R and R are independently a C Ci6 alkyl group, with the proviso that each of R and R are longer alkyl chains than R⁷, R⁸, R⁹,and R¹⁰.

In some embodiments, the secondary amine t is selected from the group comprising general formula

VI,

FORMULA (VI)

wherein R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ are each independently a hydrogen or a C C6 alkyl group, and wherein R¹¹ is a C₁ -C 16 alkyl group, and R¹² is a C Ci6 alkyl group.

In some embodiments, the secondary amine is a heterocyclic compound selected from the group comprising general formulas VIIA, VIIB, VIII, IX A, IXB, and X,

FORMULA (VIIA) FORMULA (VIIB) FORMULA (VIII)

wherein R³, R⁴, R⁵, and R⁶ are each independently hydrogen or a C₁-C4 saturated alkyl, with the proviso that at least two of R³, R⁴, R⁵, and R⁶ are Q-C4 saturated alkyl; and

wherein R¹³ is a hydrogen, a Q-Cis alkyl group or CpCn ester group.

In some embodiment, the catalytic exhaust system further comprises a diesel particulate filter (DPF), a gasoline particulate filter (GPF), particle oxidation catalyst (POC), a catalyzed soot filter (CSF), or combinations thereof, for removing particulate matter from the exhaust gases; and wherein the additive package extends the time period between cleaning or replacement of the DPF, the GPF, the POC, the CSF, or combinations thereof, in the range of about 5% to about 400% compared to a catalytic exhaust system operatively associated with an internal combustion engine containing an engine and an additive package with no hindered secondary amine detergent, wherein the additive package is otherwise comparable to the additive package described herein.

In some embodiments, the reduction in ash-producing components from the additive package produces a reduction in clogging and fouling of the monolithic catalytic substrate in the range of about 5% to about 80%.

In some embodiments, the monolithic catalytic substrate comprises an amount of about 1 % to about 80% less PGM loading than a monolithic catalytic substrate sized and loaded with catalytic material to provide the intended emission reduction for the intended operating lifetime.

Another aspect of the invention describes a method of reducing ash introduced into an exhaust system comprising:

introducing an engine oil having an additive package, wherein the additive package comprises a hindered secondary amine detergent, an anti-wear additive in the amount of about 0.1% to about 5% by weight of the engine oil, and at least one epoxide as a seal compatibility, to a lubricating system of an internal combustion system.

In some embodiments, the overbased sulfonates of alkaline earth metals, overbased phenates of alkaline earth metals, and overbased salicylates of alkaline earth metals are excluded from the engine oil.

Another aspect of the invention describes an internal combustion engine system comprising:

an internal combustion engine having a size and a lubricating system, wherein the lubricating system comprises an engine oil with a base oil, a hindered secondary amine detergent, an anti-wear additive in an amount of about 0.1% to about 5% by weight of the engine oil, and at least one epoxide as a seal compatibility additive; and

a catalytic exhaust system comprising a monolithic catalytic substrate operatively associated and in fluid communication with the internal combustion engine, wherein the monolithic catalytic substrate has a volume in the range of about 5% to about 75% smaller, and a catalytic material loading in the range of about 1% to about 80% less than a monolithic catalytic substrate sized and loaded with catalytic material for an equally sized internal combustion engine that utilizes a lubricating oil comprising one or more of calcium carbonate, calcium alkylbenzene sulfonate, calcium salicylate, calcium phenate, magnesium sulfonate, and magnesium salicylate.

In some embodiments, an internal combustion engine system also comprises:

an internal combustion engine having a size and a lubricating system, wherein the lubricating system comprises an engine oil and an additive package, wherein the additive package comprises a secondary amine detergent, an anti-wear additive in the amount of about 0.1% to about 5% by weight of the engine oil, and at least one epoxide as a seal compatibility additive; and

a catalytic exhaust system comprising a monolithic catalytic substrate operatively associated and in fluid communication with the internal combustion engine, wherein the monolithic catalytic substrate has a volume in the range of about 5% to about 75% smaller, and a catalytic material loading in the range of about 1% to about 80% less than a monolithic catalytic substrate sized and loaded with catalytic material for an equally sized internal combustion engine that utilizes a lubricating system comprising engine oil containing the additive package with no secondary amine detergent.

In some embodiments, the monolithic catalytic substrate has a volume in the range of about 20% to about 75% smaller compared to a monolithic catalytic substrate sized to provide the intended emission reduction for the intended operating lifetime for an equally sized an internal combustion engine that utilizes a lubricating oil comprising one or more of calcium carbonate, calcium alkylbenzene sulfonate, calcium salicylate, calcium phenate, magnesium sulfonate, and magnesium salicylate.

In some embodiments, the monolithic catalytic substrate has a catalytic material loading in an amount of about 10% to about 75% less than the monolithic catalytic substrate would have for an internal combustion engine of the intended size based on the expected exhaust output.

In some embodiments, the internal combustion engine generates from about 10% to about 75% less ash-producing components and reduces or prevents clogging or fouling of a monolithic catalytic substrate.

One or more aspects of the present invention describes a low ash catalytic exhaust system comprising an engine oil used by the internal combustion engine associated with the low ash catalytic exhaust system containing an additive package including a secondary amine detergent; an anti-wear additive in the range of 0.1% and 5% of the engine oil; and at least one epoxide as a seal compatibility additive in the engine oil, and a monolithic honeycomb substrate present in the catalytic exhaust system comprising a quantity of catalytic metal components, optimized for operation with the internal combustion engine using the additive package and enabled to meet prescribed emission limits for at least 99,420 miles as an intended operating lifetime extended by about 5% to about 400% when used with the engine oil containing the additive package in the internal combustion engine.

One or more aspects of the present invention describes an internal combustion system comprising an internal combustion engine and a catalytic exhaust system, wherein the internal combustion engine comprises a lubricating system utilizing an engine oil for reducing friction between moving parts of the internal combustion engine, and a lubricating oil, wherein the engine oil comprises a low SAPS engine oil comprising a base oil and an additive package, wherein the additive package comprises a secondary amine antacid, an anti-wear additive, and a seal compatibility additive and reduces the amount of ash-producing components produced in the internal combustion engine.

BRIEF DESCRIPTION OF THE DRAWINGS

The disclosure may be more completely understood in consideration of the following detailed description of various embodiments of the disclosure in connection with the accompanying drawing, in which:

Fig. 1 illustrates an exemplary embodiment of an engine system comprising an internal combustion engine and a catalytic exhaust system.

DETAILED DESCRIPTION OF THE INVENTION

Before describing several exemplary embodiments of the invention, it is to be understood that the invention is not limited to the details of construction or process steps set forth in the following description. The invention is capable of other embodiments and of being practiced or being carried out in various ways and combinations, which are considered to fall within the scope of the claims.

Reference throughout this specification to "one embodiment," "certain embodiments," "various embodiments," "one or more embodiments" or "an embodiment" means that a particular feature, structure, material, or characteristic described in connection with the embodiment may be included in at least one embodiment of the invention. Thus, the appearances of the phrases such as "in one or more embodiments," "in certain embodiments," "in various embodiments," "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily referring to the same embodiment of the invention. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments.

A particular role that lubricating oils play is in internal combustion engines is to reduce friction between moving parts, remove/transfer heat and prevent corrosion. These engine oils are subject to particular operating environments that place particular demands on the oil performance and composition. Often small amounts of these lubricating oils are consumed by internal combustion engines to ash, which accumulates in the internal combustion engine and travels into the catalytic exhaust system. In the catalytic exhaust system ash can interfere with the treatment of gas emissions by reducing the activity of various components in the catalytic exhaust system. As such, additive packages are added to lubricating oils to minimize ash formation in the engine and hence lower the amount of ash present in the catalytic exhaust system.

Principles and embodiments of the present invention relate generally to new additives that may be combined as an additive package and provide suitable engine treatment, lubricating performance, and compatibility with new and existing catalytic exhaust systems. Examples of such additives include detergent additives, corrosion and rust additives, metal deactivators, viscosity modifiers, friction modifiers/reducers, antiwear additives, oxidation inhibitors, dispersants, anti-foam agents, antimisting agents, was crystal modifiers, and seal conditioners. For example, some common additives to lubricating oils used in internal combustion engines have included calcium and magnesium detergent additives, zinc di-thiophosphates (ZnDTP), which is also referred to as zinc di-alkyl di-thiophosphates (ZDDP).

In one or more embodiments, the engine oil formulation comprises about 51% to about 99%, or about 70% to about 99%, or about 80% to about 99%, or about 80% to about 95% by weight of a base oil, where the balance of the oil formulation comprises three or more different additives. In various embodiments, the three different additives include a secondary amine, ZDDP, and a SCA, which comprise at least about 5%, or in the range of about 3% to about 20%, by weight of the engine oil.

In one or more embodiments, a secondary amine, as shown in general formula II, provides detergent, dispersant, and antacid functionality to a base oil to which the secondary amine is added.

FORMULA (II)

In various embodiments, R¹ may be a Q-Cis alkyl substituent, an alicyclic substituent, or a combination thereof.

In various embodiments, R² may be a C Ci₈ alkyl substituent, an alicyclic substituent, or a combination thereof.

In one or more embodiments, the R¹ and/or R² alkyl group is a saturated hydrocarbon, and may comprise a straight chain or a branched chain Q-Cis alkyl group. In various embodiments, a branched alkane may comprise one or more alkyl side chains, where one to three alkyl substituents may be attached to the same backbone carbon.

In one or more embodiments, the R¹ and R² may be the same or different substituents.

In some embodiment, the R¹ and/or R² alkyl group is a saturated hydrocarbon, and may comprise a straight chain or a branched chain Ci-C₇ alkyl group such as methyl, ethyl, propyl, isopropyl, 2- methylpropyl, 2-dimethylbutyl, butyl, pentyl, hexyl, or heptyl.

In some embodiment, the R¹ and/or R² alkyl group is a saturated hydrocarbon, and may comprise a straight chain or a branched chain Cs-Qs alkyl group such as

ra-octyl, ra-nonyl, ra-decyl, ra-undecyl, ra-dodecyl, ra-tridecyl, ra-tetradecyl, ra-pentadecyl, re-hexadecyl, ra-heptadecyl, or ra-octadecyl.

A non-limiting example of a secondary amine is dinonylamine given by formula III.

FORMULA (III)

In various embodiments, R¹ and R² may be connected through a carbon-carbon bond to form a cyclic aliphatic, where the cyclic ring may comprise 4 to 8 carbons.

In various embodiments, the monomeric acyclic amine compound or the monomeric cyclic amine compound may be a sterically hindered amine compound, wherein at least one alkyl substituent is bonded to at least one of the carbons alpha to the nitrogen.

In various embodiments, the monomeric acyclic amine compound may be a sterically hindered amine compound, wherein at least one alkyl substituent is bonded to at least one of the carbons beta to the nitrogen. In various embodiments, the monomeric acyclic amine compound may be sterically hindered by at least two alkyl substituents, wherein at least one alkyl substituent may be bonded to at least one of the carbons alpha to the nitrogen and/or at least one alkyl substituent may be bonded to at least one of the carbons beta to the nitrogen.

In various embodiments, the secondary amine may have the formula R'-NH-R², wherein R¹ is a C Ci8 alkyl group having 0 to 8 alkyl substituents, and R² is a Q-Cis alkyl group having 0 to 8 alkyl substituents. The carbon atoms of R¹ and R² that do not indicate the presence of a substituent or multiple carbon-carbon bonds are presumed to be saturated carbons bonded to hydrogen atoms.

In various embodiments, the alkyl substituents may be bonded to the alpha and/or beta carbon of the backbone.

In one or more embodiments, the secondary amine may be a branched chain alkyl having one or more substituents at the carbons alpha to the nitrogen, wherein R³, R⁴, R⁵, and R⁶ are each independently a hydrogen or a C C6 alkyl group, and wherein R¹¹ is a C C i6 alkyl group, and R¹² is a C C i6 alkyl group, as shown in formula IV. In various embodiments, R¹¹ and R¹² are longer alkyl chains than R³, R⁴, R⁵, and R⁶.

FORMULA (IV)

In various embodiments, the secondary amine may be a branched chain alkyl having one or more substituents at the carbons beta to the nitrogen, wherein R⁷, R⁸, R⁹, and R¹⁰ are each independently a hydrogen or a C C₆ alkyl group, and wherein R¹¹ is a C Ci₆ alkyl group, and R¹² is a C Ci₆ alkyl group. In

1 1 12 7 8 9 10 various embodiments, R and R are longer alkyl chains than R , R , R , and R , as shown in general formula V.

In some embodiment, the R¹¹ and/or R¹² alkyl group is a saturated hydrocarbon, and may comprise a straight chain or a branched chain Ci-C₇ alkyl group such as methyl, ethyl, propyl, isopropyl, 2- methylpropyl, 2-dimethylbutyl, butyl, pentyl, hexyl, or heptyl.

In some embodiment, the R¹¹ and/or R¹² alkyl group is a saturated hydrocarbon, and may comprise a straight chain or a branched chain Cs-Qs alkyl group such as ra-octyl, ra-nonyl, ra-decyl, ra-undecyl, ra-dodecyl, ra-tridecyl, ra-tetradecyl, ra-pentadecyl, or ra- hexadecyl.

FORMULA (V)

In various embodiments, the secondary amine may be a branched chain alkyl having one alkyl substituent at each of the carbons beta to the nitrogen, and one alkyl substituent at each of the carbons alpha to the nitrogen, or two substituents at both alpha carbons and one substituent at each of the beta carbons, or two substituents at both beta carbons and one substituent at each of the alpha carbons, or two substituents at both alpha and both beta carbons.

In one or more embodiments, the secondary amine may be a branched chain alkyl having one or more substituents, wherein R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ are each independently a hydrogen or a C C6 alkyl group, and wherein R¹¹ is a C Ci₆ alkyl group, and R¹² is a C Ci₆ alkyl group, as shown in formula VI. In various embodiments, R¹¹ and R¹² are longer alkyl chains than R³, R⁴, R⁵, and R⁶.

In some embodiment, the R¹¹ and/or R¹² alkyl group is a saturated hydrocarbon, and may comprise a straight chain or a branched chain Cs-C^ alkyl group such as

ra-octyl, ra-nonyl, ra-decyl, ra-undecyl, ra-dodecyl, ra-tridecyl, ra-tetradecyl, ra-pentadecyl, or ra- hexadecyl.

FORMULA (VI)

In one or more embodiments, R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ may be the same or different alkyl groups.

In one or more embodiments R¹¹ and R¹² may be the same or a different C C i6 alkyl group. In various embodiments, additional C C6 alkyl substituents may be bonded to R¹¹ and/or R¹² to form a branched alkyl. In some embodiment, the R¹¹ and/or R¹² alkyl group is a saturated hydrocarbon, and may comprise a straight chain or a branched chain Q-C7 alkyl group such as methyl, ethyl, propyl, isopropyl, 2- methylpropyl, 2-dimethylbutyl, butyl, pentyl, hexyl, or heptyl.

In some embodiment, the R¹¹ and/or R¹² alkyl group is a saturated hydrocarbon, and may comprise a straight chain or a branched chain C₈-Ci₆ alkyl group such as

In one or more embodiments, the secondary amine is a nitrogen-containing heterocyclic moiety having a saturated carbon ring of C₄ to C₇, where the two carbons alpha to the nitrogen on the ring may have from 0 to 2 alkyl substituents.

In one or more embodiments, the nitrogen is in a C4 ring, wherein R³, R⁴, R⁵, and R⁶ are each independently a hydrogen or a C C6 alkyl group, and wherein R¹³ is a hydrogen, a Q-Cis alkyl group or C C i7 ester group, as shown in general formulas VIIA, VIIB.

In some embodiment, the R³, R⁴, R⁵ and R⁶ alkyl group alkyl groups are independently selected saturated hydrocarbons, and may comprise a straight chain or a branched chain C C6 alkyl group such as methyl, ethyl, propyl, isopropyl, 2-methylpropyl, 2-dimethylbutyl, butyl, or pentyl, hexyl.

In some embodiment, the R¹³ is a Q-Cis alkyl group and may comprise a straight chain or a branched chain C Ci₈ alkyl group such as methyl, ethyl, propyl, isopropyl, 2-methylpropyl, 2- dimethylbutyl, butyl, or pentyl, hexyl, ra-octyl, ra-nonyl, ra-decyl, ra-undecyl, ra-dodecyl, ra-tridecyl, ra- tetradecyl, ra-pentadecyl, or ra-hexadecyl.

FORMULA (VIIA) FORMULA (VIIB)

In one or more embodiments, R₃, R4, R₅, and R₆ may be the same or different.

In one or more embodiments, the nitrogen is in a C5 ring, wherein R³, R⁴, R⁵, and R⁶ are each independently a hydrogen or a C C6 alkyl group, and wherein R¹³ is a hydrogen, a Q-Cis alkyl group or C C i7 ester group, as shown in general formula VIII.

FORMULA (VIII)

In one or more embodiments, the nitrogen is in a C ring, wherein R³, R⁴, R⁵, and R⁶ are each independently a hydrogen or a C C₆ alkyl group, and wherein R¹³ is a Ci-Ci₈ alkyl group or C Ci₇ ester group, as shown in general formulas XIA, XIB.

In some embodiment, the R¹³ is a Q-Cis alkyl group and may comprise a straight chain or a branched chain Q-Cis alkyl group such as methyl, ethyl, propyl, isopropyl, 2-methylpropyl, 2- dimethylbutyl, butyl, or pentyl, hexyl, ra-octyl, ra-nonyl, ra-decyl, ra-undecyl, ra-dodecyl, ra-tridecyl, ra- tetradecyl, ra-pentadecyl, or ra-hexadecyl.

In one or more embodiments, the nitrogen is in a C7 ring, wherein R³, R⁴, R⁵, and R⁶ are each independently a hydrogen or a C C6 alkyl group, and wherein R¹³ is a hydrogen, a Q-Cis alkyl group or C C i7 ester group, as shown in general formula X.

In one or more embodiments, the secondary amine is a heterocyclic moiety selected from the group consisting of pyrrolidine, piperidine, azapane, and azocane.

In one or more embodiments, the secondary amine is pyrrolidine or piperidine, wherein each of the alpha carbons have from 0 to 2 substituents indicated as R³, R⁵ and R⁴, R⁶, wherein R³, R⁴, R⁵, and R⁶, may be a straight-chain alkyl substituent.

In one or more embodiments, the heterocyclic moiety may have a substituent, R¹³, on the heterocyclic ring bonded to a carbon on a side opposite the nitrogen. . In various embodiments, R¹³, may be a C₁ -C 18 alkyl group, or a CpCn ester group.

In some embodiment, the R¹³ is a Q-Cis alkyl group and may comprise a straight chain or a branched chain Q-Cis alkyl group such as methyl, ethyl, propyl, isopropyl, 2-methylpropyl, 2- dimethylbutyl, butyl, or pentyl, hexyl, re-octyl, re-nonyl, re-decyl, re-undecyl, re-dodecyl, re-tridecyl, re- tetradecyl, re-pen tadecyl, or re-hexadecyl.

In some embodiment, the R¹³ is a Q-Cis alkyl group and may comprise a straight chain or a branched chain Q-Cis alkyl group such as methyl, ethyl, propyl, isopropyl, 2-methylpropyl, 2- dimethylbutyl, butyl, or pentyl, hexyl, re-octyl, re-nonyl, re-decyl, re-undecyl, re-dodecyl, re-tridecyl, re- tetradecyl, re-pentadecyl, or re-hexadecyl.

A non-limiting example of the hindered secondary amine is bis(2-ethylhexyl)amine given by formula XI.

Another non-limiting example of the hindered secondary amine is bis(l-methyl-2- ethyldodecyl) amine given by formula (XII), wherein according to formula R³ and R⁴ at the alpha carbons are both a -CH₃ (methyl) group, R⁷ and R⁸ at the beta carbons are both a -CH₂CH₃ (ethyl) group, and R¹¹ and R¹² are both C₈H₁₇ (octyl) group as described in general formula VI.

In the non-limiting example of formula XII, both R¹¹ and R¹² are larger alkyl substituents than R³ and R⁴, and R⁷ and R⁸, (C₈H₁₇ > C₂H₅; C₈H₁₇ > CH₃) as described in general formula VI.

Another non-limiting example of the hindered secondary amine is N-(2,2, -dimethyl butyl)- 1- octylamine given by formula XIII.

Another non-limiting example of the hindered secondary amine is (2,2,6,6-tetramethyl piperidin-^ yl) dodecanoate given by formula XIV, wherein R₃, R4, R₅, and R₆ are methyl (-CH₃) groups and R₁₃ is a C ester group as described in general formula VIII.

In one or more embodiments, the compounds described by formulae II, IV, V, VI, VIIA, VIIB, VIII, XIV, XV, X may be single enantiomers and/or diastereomers. In one or more embodiments, the compounds described by formulae II, IV, V, VI, VIIA, VIIB, VIII, XIV, XV, X may be mixtures of at least two enantiomers. In one or more embodiments, the compounds described by formulae II, IV, V, VI, VIIA, VIIB, Vm, XIV, XV, X may be mixtures of at least two enantiomers. In one or more embodiments, the compounds described by formulae II, IV, V, VI, VIIA, VIIB, VIII, XIV, XV, X may be mixtures of at least two diastereomers.

In one or more embodiments, the secondary amine does not contribute to the sulfated ash composition of the exhaust products.

In some embodiments, the additives for the engine oil provide a detergent and an antacid functionality without excess calcium and/or magnesium. In various embodiments, a secondary amine compound may take the place of a detergent such as calcium carbonate, calcium alkylbenzene sulfonate, calcium salicylate, calcium phenate, magnesium sulfonate, and magnesium salicylate to at least reduce the amount of calcium and/or magnesium present in the engine oil that may form ash, and for achieving an intended TBN.

In some embodiments of the present invention the secondary amine functions as a base by acting as an electron pair donor (Lewis Base) or a hydrogen ion acceptor (Bronstead-Lowry Base) to neutralize acids present in the lubricating oil, where the acids may be generated by the partial combustion and/or oxidation processes within an engine. These acids may cause corrosion to metal parts and otherwise deteriorate polymeric components such as seals. In various embodiments the secondary amine may react with acids present in the engine oil, and/or function as a detergent by forming micelles around insoluble combustion byproducts that may be in the lubricating oil. The secondary amines, however, may have detrimental effects on fluoropolymer seals, which may be prevented or alleviated by the addition of seal compatibility additives that may protect the seals.

In various embodiments, the secondary amine compound has a TBN value of at least about 80 mg KOH/g when tested according to ASTMD4739. Alternatively, the amine compound may have a TBN value of at least about 90, at least about 100, at least about 110, at least about 120, at least about 130, at least about 140, at least about 150, or at least about 160, mg KOH/g, when tested according to ASTM D4739. Alternatively still, the amine compound may have a TBN value of from about 80 to about 500, or about 80 to about 400, or about 80 to about 200, or about 90 to about 190, or about 100 to about 180, or about 100 to about 150, mg KOH g, when tested according to ASTM D4739.

In one or more embodiments, additional additives introduced into the lubricating oil may increase the TBN value above the value achieved by the secondary amine introduced to the lubricating oil alone.

In one or more embodiments, a lubricating oil comprising an additive package may be prepared by substituting at least one secondary amine and/or at least one hindered secondary amine into the engine oil for overbased sulfonates of alkaline earth metals, overbased phenates of alkaline earth metals, and overbased salicylates of alkaline earth metals. In some embodiments, the additive further includes an anti-wear additive, for example ZDDP, and amine salts thereof and other phosphorus and sulfur containing anti-wear additives, for example an organo-thiophosphate, in the amount from about 0.1% to about 5% by weight in the engine oil and at least one epoxide as a seal compatibility additive (SCA).

In various embodiments, the anti-wear additive may be ZDDP, the amine salt of ZDDP, an organo- thiophosphate, and combinations thereof, wherein the organo-thiophosphate may be a dithiophosphate alkyl ester. In one or more embodiments, an organo-thiophosphate anti-wear additive may be selected from the group consisting of 0-[(lR)-l,3-dimethylbutyl] O-(l-methylethyl) hydrogen dithiophosphate, 0-(2- methylpropyl) O-pentyl hydrogen phosphorodithioate, 0-(4-methylpentan-2-yl) 0-(2-methylpropyl) hydrogen phosphorodithioate, O-butan-2-yl 0-(6-methylheptyl) hydrogen phosphorodithioate, 0-(2- ethylhexyl) 0-(2-methylpropyl) hydrogen phosphorodithioate, 0,0-bis(4-methylpentan-2-yl) hydrogen phosphorodithioate, 0,0-bis(2-ethylhexyl) hydrogen phosphorodithioate, 0-(4,5-dimethylhexyl) 0-(6- methylheptyl) hydrogen phosphorodithioate, 0,0-bis(6-methylheptyl) hydrogen phosphorodithioate, and combinations thereof.

In one or more embodiments, the additive package includes at least one epoxide compound as the seal compatibility additive. In various embodiments, the epoxide compound may be represented by general formula XV. FORMULA (XV)

In one or more embodiments, each R may independently be a hydrogen atom or a hydrocarbyl group. Multiple groups designated by R¹⁴ may be bonded together to form a cyclic structure.

In one or more embodiments, each hydrocarbyl group designated by R¹⁴ may independently be substituted or unsubstituted, straight or branched, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkylaryl, arylalkyl group, or combinations thereof. In various embodiments, each hydrocarbyl group designated by R¹⁴ may independently include from 1 to 100, 1 to 50, 1 to 40, 1 to 30, 1 to 20, 1 to 15, 1 to 10, 1 to 6, or 1 to 4, carbon atoms. Alternatively, each hydrocarbyl group designated by R¹⁴ may independently include less than 20, less than 15, less than 12, or less than 10, carbon atoms.

In one or more embodiments, the epoxide compound described by formula XV is only one enantiomer or diastereomer. In some embodiments, the epoxide may be a mixture of at least two enantiomers. In some embodiments, the epoxide may be a mixture of at least two diastereomers.

In one or more embodiments, the seal compatibility additive epoxide compound may include one or more oxirane ring. The oxirane ring may be a terminal oxirane ring or an internal oxirane ring. The term "terminal oxirane ring" means that one of the carbon atoms which form the oxirane ring must contain two hydrogen atoms, or that two carbons which form the oxirane ring also form part of a cyclic ring. The term "internal oxirane ring" means that neither of the carbon atoms which form the oxirane ring is bonded to more than one hydrogen atom. The epoxide compound may be free from internal oxirane rings, or may include fewer than 4, 3, 2, or 1, internal oxirane rings. Alternatively, the epoxide compound may include 1, 2, 3, 4, or more internal oxirane rings. Alternatively still, the epoxide compound may include at least 1, at least 2, at least 3, at least 4 terminal oxirane rings. In certain embodiments, at least one, or at least two, oxirane rings may be terminal and may be cyclic, i.e., the carbons of the oxirane rings are part of a cyclic ring.

A non-limiting example of the epoxide seal compatibility additive is 2,2'-[benzene-l,3- diylbis(oxymethanediyl)] dioxirane given by formula XVIII.

FORMULA (XVIII)

In various embodiments, the SCA may be an epoxide compound having two or more oxirane ring wherein at least one of the oxirane rings is terminal. In one or more embodiments, each hydrocarbyl group designated by R in formula XV may be independently substituted, and include one or more heteroatoms, such as oxygen, nitrogen, sulfur, chlorine, fluorine, bromine, or iodine, and/or one or more heterogroups, such as pyridyl, furyl, thienyl, and imidazolyl. Alternatively, or in addition to including heteroatoms and heterogroups, each hydrocarbyl group designated by R¹⁴ may independently include one or more substituent groups selected from alkoxy, amide, amine, carboxyl, epoxy, ester, ether, hydroxyl, keto, metal salt, sulfuryl, and thiol groups. Alternatively, each hydrocarbyl group designated by R¹⁴ may be independently unsubstituted.

In certain embodiments, the seal compatibility additive epoxide compound is a cyclic epoxide compound. The cyclic epoxide compound may be represented by general formula XVI.

FORMULA XVI)

In one or more embodiments for general formula (XVI), Z represents the type and number of atoms necessary to complete the cyclic ring of general formula (XVI). The ring designated by Z may include from 1 to 20, 3 to 15, 5 to 15, carbon atoms. For example, the ring designated by Z may include 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbons, not accounting for the number of carbon atoms in any substituent groups. Z may be a substituted or unsubstituted, branched or unbranched, divalent hydrocarbon group that may include one or more heteroatoms, such as oxygen, nitrogen, sulfur, chlorine, fluorine, bromine, or iodine, or one or more heterogroups, such as pyridyl, furyl, thienyl, and imidazolyl. In addition to, or alternatively to, including heteroatoms and/or heterogroups, the ring designated by Z may include one or more hydrocarbyl substituent groups, such as those described for R¹ in general formula (I). The divalent hydrocarbon group designated by Z may be aliphatic or aromatic. In some embodiments, the divalent hydrocarbon group designated by Z may be exemplified by: cyclopropyl, cyclopentyl, cyclohexyl, phenyl, naphthalenyl, benzyl, phenylethyl, and (2- naphthyl)-methyl groups. It should be appreciated that the heteroatoms, heterogroups, and/or substituent groups described above may be bonded to various atoms in the ring designated by Z; for example, the hydrocarbyl substituent groups may be bonded directly to one or more carbons in the ring designated by Z that form part of the oxirane ring. Alternatively, the substituent groups, heterogroups, and heteroatoms may be bonded to other carbon atoms in the hydrocarbon group, such as carbons that are not part of the oxirane ring. In some embodiments, the cyclic epoxide compound of general formula (XVI) may be a cycloaliphatic epoxide compound having at least two terminal oxirane rings.

In one or more embodiments, the seal compatibility additive may be a polyepoxide compound may be represented by general formula XVII. FORMULA (XVII)

In one or more embodiments, each Z may have the same meaning as described above with respect to general formula (XVI). In various embodiments for general formula (XVII), R¹⁵ is a divalent hydrocarbon group. R¹⁵ may have the same meaning as described above with respect to R¹⁴ in general formula (XV). It should be appreciated that the divalent hydrocarbon group designated by R¹⁵ may be bonded to various atoms in the divalent hydrocarbon group designated by Z. For example, the divalent hydrocarbon group designated by R¹⁵ may be bonded directly to one or more oxirane ring carbons in certain embodiments. Alternatively, the divalent hydrocarbon group designated by R¹⁵ may be bonded to non-oxirane ring carbon atoms in the hydrocarbon group designated by Z.

In various embodiments, overbased sulfonates of alkaline earth metals, overbased phenates of alkaline earth metals, and overbased salicylates of alkaline earth metals are excluded from the engine oil formulation and additive package. That is, no overbased sulfonates of alkaline earth metals, overbased phenates of alkaline earth metals, and overbased salicylates of alkaline earth metals are intentionally added to the oil formulation. In some embodiments, at least one overbased sulfonates of alkaline earth metals, overbased phenates of alkaline earth metals, and overbased salicylates of alkaline earth metals present in the addivitve package is replaced with the secondary amines described by formula II.

In various embodiments, the base oil is selected from the group of API Group I base oils, API Group II base oils, API Group III base oils, API Group IV base oils, API Group V base oils, and combinations thereof. In one or more embodiments, the base oil includes an API Group II base oil.

The base oil is classified in accordance with the American Petroleum Institute (API) Base Oil Interchange ability Guidelines. Under Appendix E of the guidelines, the base oil may be described as one of five types of base oils with particular criteria: Group I (sulphur content >0.03 wt. %, and/or <90 wt. % saturates, viscosity index 80-119); Group II (sulphur content less than or equal to 0.03 wt. %, and greater than or equal to 90 wt. % saturates, viscosity index 80-1 19); Group III (sulphur content less than or equal to 0.03 wt. %, and greater than or equal to 90 wt. % saturates, viscosity index greater than or equal to 1 19); Group IV (all polyalphaolefins (PAO's)); and Group V (all others not included in Groups I, II, III, or IV).

The base oil may be further defined as a crankcase lubricant oil for spark-ignited and compression- ignited internal combustion engines, including automobile and truck engines, two-cycle engines, aviation piston engines, marine engines, and railroad diesel engines, as well as stationary industrial engines operated on natural gas, compressed natural gas and landfill gas. Alternatively, the base oil can be further defined as an oil to be used in gas engines, diesel engines, stationary power engines, and turbines. The base oil may be further defined as heavy or light duty engine oil. In various embodiments, the additives may be one or more of detergents, anti-oxidants, antacids, anti-wear agents, anti-foaming agents, seal compatibility additives, pour-point depressants, viscosity modifiers, dispersants, and combinations thereof. In various embodiments, the dispersants may be for example secondary amines, poly-ether amines, polyisobutyl amines, succinimides, and/or polyisobutyl succinimides.

In one or more embodiments, the engine oil formulation comprises about 80% to about 99% by weight of a base oil, about 1% to about 15% by weight of a secondary amine, about 0.2% to about 3.0% by weight of ZDDP and/or salts thereof, and about 0.01% to about 5.0% by weight of a seal compatibility additive (SCA).

In one or more embodiments, the engine oil formulation comprises about 80% to about 99% by weight of a base oil, about 1% to about 12% by weight of a secondary amine, about 0.2% to about 2.0% by weight of ZDDP and/or salts thereof, and about 0.01 % to about 8.0% by weight of a seal compatibility additive (SCA).

In one or more embodiments, the combination of the secondary amine, the ZDDP, and the SCA comprise at least about 3% or at least about 5% by weight of the lubricating oil, up to about 20% by weight of the lubricating oil, or in the range of about 3% to about 20%, or about 5% to about 15% by weight of the lubricating oil.

Various amine additives have been disclosed and described in U.S. Patent Application No. 13/966,740 filed by DeSantis et al. on Aug. 14, 2013, and published as US 2014/0051621 Al on Feb. 20, 2014, which is incorporated herein by reference in its entirety for all purposes.

Various epoxide additives and amine additives have been disclosed and described in U.S. Patent Application No. 14/081,373 filed by DeSantis et al. on Nov. 15, 2013, and published as US 2014/0142008 Al on May 22, 2014, which is incorporated herein by reference in its entirety for all purposes. Additional epoxide additives and amine additives have been disclosed and described in U.S. Patent Application No. 14/081,531 filed by DeSantis et al. on Nov. 15, 2013, and published as US 2014/0142009 Al on May 22, 2014, which is incorporated herein by reference in its entirety for all purposes.

Various lubricating oil compositions comprising epoxide additives and amine additives have been disclosed and described in U.S. Patent Application No. 14/081,551 filed by DeSantis et al. on Nov. 15, 2013, and published as US 2014/0142010 Al on May 22, 2014, which is incorporated herein by reference in its entirety for all purposes. Additional lubricating oil compositions comprising epoxide additives and amine additives have been disclosed and described in U.S. Patent Application No. 14/081,360 filed by DeSantis et al. on Nov. 15, 2013, and published as US 2014/0142011 Al on May 22, 2014, which is incorporated herein by reference in its entirety for all purposes.

In various embodiments, the additional additives may include one or more anti-oxidant(s), where the anti-oxidant(s) may be an amine anti-oxidant. In various embodiments, the amine anti-oxidant may comprise about 0.7% to about 1% by weight of the lubricating oil. In various embodiments, the additional additives may include one or more dispersant(s), where the dispersant(s) may be an amine based dispersant(s). In various embodiments, the amine based dispersant(s) may comprise about 1% to about 3% of the lubricating oil, where the amine based dispersant(s) may be secondary amines.

As a non-limiting example, an additive package may comprise about 5% by weight hindered secondary amine detergent, about 0.8% by weight amine anti-oxidant, about 3% by weight of amine based dispersant, about 0.8% by weight anti-wear additive as ZDDP, and about 0.5% SCA by weight of the lubricating oil.

In the various embodiments, a lubricating oil refers to an oil formulation that may be effective in various operating environments, which may include an internal combustion engine, whereas an engine oil refers to a lubricating oil formulated for use in an internal combustion engine operating environment and may be effective in other operating environments.

As engine life and emission durability requirements have increased in recent years the interaction between the oil additive package and the emission control catalyst system has become a critical factor for emission performance and durability in part due to the reduction of ash formation. Because the presence of ash-forming materials in engine oils results in clogging and fouling of the catalytic system, which may be described as chemical aging of the catalytic system, "low ash " lubricating oils have been developed. "Low ash" lubricating oils retard chemical aging and restore the performance loss caused by clogging and poisoning of catalytic components due to ash. In addition "low ash" lubricating oils are more resistant to heat and leave lower amounts of ash deposits when burnt off during the combustion process. The lower ash content of the oil enables the diesel particulate filter (DPF), for example, to reach the EPA mandated 4,500 hour ash cleaning service interval for engines above 174 hp (130 kW).

Additional substances such as phosphorous compounds may also react with oxygen to form 'glasses' that coat and/or clog catalytic substrates and filters, which may reduce porosity. Deposits on the inlet openings of the catalytic substrate comprising a honeycomb cell structure may narrow the cell openings, thereby reducing gas flow through the catalytic exhaust system and increasing back pressure. In contrast, thermal aging may occur due to prolonged time at raised and/or operating temperatures that may result in sintering of catalytic components and/or a loss in catalytic surface area. As such "low SAPS" lubricating oils have been developed. The requirement of the "Low SAPS" (Sulphated Ash, Phosphorus, Sulfur) designation restricts the amount of traditional calcium and magnesium based detergents found in the lubricating oil composition. The calcium and magnesium incorporated into the lubricating oil through their use in the overbased metal soaps form ash when combusted, where an ash is a non-combustible residue that may be comprised of inorganic oxides, such as CaO and MgO. In addition, low SAPS oil requires reduced amounts of total phosphorous and sulfur. These lubricating oil components may be introduced to the combustion chamber from the crank case around the piston heads and piston rings or by leaking past valve seals. By greatly reducing the amount of ash producing components in the engine oil, the catalytic exhaust system life may be extended, the time between cleaning or replacement of the various particulate filters used may also be extended and the chemical aging of various catalyst components may be reduced.

Therefore, in some embodiments of the present invention relates generally to a low ash catalytic exhaust system comprising an engine oil used by the internal combustion engine associated with the low ash catalytic exhaust system containing an additive package, which includes a secondary amine detergent, an anti-wear additive in an amount from about 0.1% to about 5% by weight of the engine oil, and at least one epoxide as a seal compatibility additive. In some embodiments, the low ash catalytic exhaust system comprises a monolithic honeycomb substrate with a quantity of catalytic metal components, which have an extended intended operating lifetime by about 5% to about 400% when used with the engine oil with an additive package containing a secondary amine detergent compared to a catalytic exhaust system comprising an engine oil with an additive package containing no secondary amine detergent, wherein the additive package is otherwise comparable to the additive package described therein. For example, the composition of the two additive packages referenced herein are the same with the exception that the additive package of the current invention comprises a secondary amine detergent.

In various embodiments, the catalytic exhaust system may comprise at least one component selected from two-way catalysts, three-way catalysts (TWC) (used primarily on stoichiometric-burning gasoline engines), diesel oxidation catalysts (DOC) (used primarily on lean-burning diesel engines), selective catalytic reduction (SCR) catalysts, lean nitrous oxide catalysts (LNC), ammonia slip catalysts (ASC), ammonia oxidation catalysts (AMOC), NOX absorbers, lean NO_x trap (LNT), diesel particulate filters (DPF), gasoline particulate filters (GPF), particle oxidation catalysts (POC), and catalyzed soot filters (CSF), as well as combinations thereof, which can include catalytic metal components.

In various embodiments, the catalytic exhaust system may include but not be limited to a Lean NOx trap (LNT), Passive NOx Absorber (PNA), Selective catalytic reduction (SCR) with an associated ammonia injection and AMOX catalyst, which can include catalytic metal components.

In various embodiments, the secondary amine may at least partially replace overbased sulfonates of alkaline earth metals, overbased phenates of alkaline earth metals, and overbased salicylates of alkaline earth metals in the engine oil formulation and additive package to reduce the amount of sulfated ash produced by the oil. Sulfated ash from lubricating oils may be measured and determined by standard method ASTM D874-13a, as would be known in the art.

In some embodiments, alkaline earth metal sulfonates, alkaline earth metal phenates, alkaline earth metal salicylates, and/or overbased sulfonates of alkaline earth metals, overbased phenates of alkaline earth metals, and overbased salicylates of alkaline earth metals may be added as dispersants and/or detergents to the engine oil formulation and additive package.

In various embodiments, molybdenum-containing compounds are excluded from the engine oil formulation and additive package. Elimination and/or avoidance of molybdenum-containing compounds can avoid poisoning of catalysts by the molybdenum from the oil. In various embodiments, bisdithiocarbamate compounds are excluded from the engine oil formulation and additive package.

Embodiments of an engine oil that consist essentially of a secondary amine antacid, an anti-wear additive, and a seal compatibility additive, are essentially free of overbased sulfonates of alkaline earth metals, over based phenates of alkaline earth metals, over based salicylates of alkaline earth metals, and molybdenum-containing compounds. In various embodiments, the anti-wear additive may be ZDDP and amine salts thereof, and/or phosphorus and/or sulfur containing anti-wear additives. In various embodiments, the secondary amine may be substituted for the overbased sulfonates of alkaline earth metals, over based phenates of alkaline earth metals, and/or over based salicylates of alkaline earth metals, to achieve an intended TBN, while some overbased sulfonates of alkaline earth metals, over based phenates of alkaline earth metals, and/or over based salicylates of alkaline earth metals may be incorporated as detergents and/or dispersants in the oil formulation. In such embodiments, the overbased sulfonates of alkaline earth metals, over based phenates of alkaline earth metals, and/or over based salicylates of alkaline earth metals may be reduced but not completely eliminated from the oil.

In various embodiments, a combustion engine is intended to have an operating lifetime of at least

99,420 miles (160,000 km), or at least 100,000 miles (160,935 km), or at least 120,000 miles (193,121 km), or at least 125,000 miles (201,168 km), or at least 150,000 miles (241,402 km), or at least 435,000 miles (700,065 km), or at least 500,000 miles (804,672 km), or at least 1,000,000 miles (1,609,350 km).

In one or more embodiments, the combustion engine has an operating lifetime extended by about 5% to about 400%, or about 5% to about 300%, or about 5% to about 200%, or about 5% to about 100%, by using the additive package described herein.

In various embodiments, the catalytic exhaust system may comprise a diesel particulate filter (DPF), a gasoline particulate filter (GPF), particle oxidation catalyst (POC), a catalyzed soot filter (CSF), or combinations thereof, for removing particulate matter from the exhaust gases, and wherein the additive package extends the time period between cleaning or replacement of the DPF, the GPF, the POC, the CSF, or combinations thereof, in the range of at least 5%, or by about 5% to about 400%, or about 5% to about 300%, or about 5% to about 200%, or about 5% to about 100%, or about 5% to about 50%, or by at least 10%, or about 10% to about 400%, or about 10% to about 300%, or about 10% to about 200%, or about 10% to about 100%, by about 50% to about 400%, or about 50% to about 300%, or about 25% to about 200%, or about 20% to about 100%, or up to about 400%, compared to a catalytic exhaust system operatively associated with an internal combustion engine using engine oil comprising an additive package with no secondary amine detergent, wherein the additive package is otherwise comparable to the additive package described therein. In some embodiments, the additive package reduces the chemcial aging of the DPF, the GPF, the POC, the CSF, or combinations thereof, in the range of at least 5%, or by about 5% to about 400%, or about 5% to about 300%, or about 5% to about 200%, or about 5% to about 100%, or about 5% to about 50%, or by at least 10%, or about 10% to about 400%, or about 10% to about 300%, or about 10% to about 200%, or about 10% to about 100%, by about 50% to about 400%, or about 50% to about 300%, or about 25% to about 200%, or about 20% to about 100%, or up to about 400%, compared to a catalytic exhaust system operatively associated with an internal combustion engine using an engine oil comprising with an additive package containing no secondaryamine detergent, wherein the addtive package is otherwise comparable to the additive package described therein.

In one or more embodiments, the catalytic exhaust system may comprise a diesel particulate filter

(DPF), a gasoline particulate filter (GPF), particle oxidation catalyst (POC), a catalyzed soot filter (CSF), or combinations thereof, for removing particulate matter from the exhaust gases, and wherein the additive package extends the catalytic exhaust system life by about 5% to about 400%, or about 5% to about 300%, or about 5% to about 200%, or about 5% to about 100%, or about 5% to about 50%, or by at least 10%, or about 10% to about 400%, or about 10% to about 300%, or about 10% to about 200%, or about 10% to about 100%, by about 50% to about 400%, or about 50% to about 300%, or about 25% to about 200%, or about 20% to about 100%, or up to about 400%, compared to a catalytic exhaust system operatively associated with an internal combustion engine using and engine oil comprising an additive package with no secondary amine detergent, wherein the additive package is otherwise comparable to the additive package described therein.

Principles and embodiments of the present invention also relate to an internal combustion system comprising an internal combustion engine and a catalytic exhaust system, wherein the internal combustion engine comprises a lubricating system utilizing an engine oil for reducing friction between moving parts of the internal combustion engine, and a lubricating oil. In some embodiments, the engine oil comprises a low SAPS engine oil, wherein the low SAPS engine oil comprises a base oil and an additive package, wherein the additive package comprises a secondary amine antacid, an anti-wear additive, and a seal compatibility additive, which reduces the amount of ash-producing components produced in the internal combustion engine.

In various embodiments, the lubricating system may further comprise a lubricating oil composition that includes a collective amount of acids, amine curing agents, anhydrides, triazoles, and/or oxides which are less than about 0.01, or about 0.001, or about 0.0001 wt. %, based on the total weight of the lubricating oil composition. Alternatively, the lubricating oil composition may be free of acids, amine curing agents, anhydrides, triazoles, and/or oxides.

In one or more embodiments, the internal combustion engine utilizing a low SAPS engine oil, as described herein, produces exhaust gases containing about 10% or about 20% or about 30% or about 40% or about 50% less total zinc, phosphorous, calcium, and sulfur compounds than an engine utilizing a non-SAPS engine oil containing an overbased detergent, which may become deposited on the cell walls of the catalytic substrate.

In one or more embodiments, a low SAPS engine oil comprising a secondary amine, a zinc- phosphorus-based anti-wear additive, and an epoxide seal compatibility additive may be introduced into a lubricating system of the internal combustion engine to reduce the amount of ash-producing components by at least about 5%, or about 5% to about 75%, or about 5% to about 80%, or at least 10%, or about 10% to about 50%, or about 10% to about 75%, or about 15% to about 40%, or at least 20%, or about 20% to about 30%, or about 20% to about 50%, or at least 25%, or about 30% to about 50%, or at least 33%, or about 33% to about 75%, or at least 50%, or about 50% to about 80% by weight.

In various embodiments, the additive package, as described herein, may reduce the amount of ash- producing components to 1/2 compared to the amount of ash-producing components produced by a non-low SAPS engine oil, thereby increasing intended operating lifetime by about 100%. In various embodiments, the additive package, as described herein, may reduce the amount of ash-producing components to 1/3 compared to the amount of ash-producing components produced by a non-low SAPS engine oil, thereby increasing intended operating lifetime by about 200%. In various embodiments, the additive package, as described herein, may reduce the amount of ash-producing components to 1/4 compared to the amount of ash-producing components produced by a non-low SAPS engine oil, thereby increasing intended operating lifetime by about 300%. In various embodiments, the additive package, as described herein, may reduce the amount of ash-producing components to 1/5 compared to the amount of ash-producing components produced by a non-low SAPS engine oil, thereby increasing intended operating lifetime by about 400%.

The internal combustion engine may comprise a combustion system, a fuel injection system, an ignition system, a cooling system, an exhaust system, a lubricating system, and a control system. An internal combustion engine typically has a size that may be defined by horse-power output (e.g., 200 HP, 500 HP, etc.), cylinder displacement (e.g., 1.3 liter, 1.8 liter, 2.4 liter, 3.0 liter, 3.5 liter, 5.7 liter, 13 liter, 15 liter, etc.), or a combination thereof, where the size of the internal combustion engine has a relationship with the amount of exhaust gases produced by combustion of fuel (e.g., gasoline, diesel, natural gas), as well as the composition of the exhaust gases.

In one or more embodiments, a catalytic exhaust system includes a monolithic catalytic substrate which may be sized to abate pollutants from an intended amount exhaust gases produced from an internal combustion engine. The monolithic catalytic substrate has a catalytic material loading effective to reduce emissions to governmental regulated limits. The catalytic substrate also is designed to be used for intended operating lifetime for the amount and composition of the exhaust gases to be treated, where an intended operating lifetime is a statistical average of the duration that a component is expected to properly function before needing replacement. Intended operating lifetime may be described in distance (e.g., miles, km) or in time (e.g., hours, years). In various embodiments, the actual and/or intended operating lifetime may be extended by using the oil additive package described herein in an engine operatively associated with the monolithic catalytic substrate.

In one or more embodiment, the catalytic exhaust system comprises a monolithic catalytic substrate having a length, a width, a height, and a precious metal loading. In various embodiments, the monolithic catalytic substrate has a shape that may be cylindrical, having a diameter that defines a cross-sectional area, and a length; elliptical, having a major axis and a minor axis that defines a cross-sectional area, and a length; or oblong, having a chief axis and a transverse diameter that defines a cross-sectional area, and a length, and wherein the monolithic catalytic substrate has a precious metal loading to provide an intended level of catalytic activity.

In one or more embodiments, the monolithic catalytic substrate comprises a honeycomb cell structure with a length, a cross-sectional area, an inlet end and an outlet end, and an amount of oxidation catalyst loaded on the cell walls. In various embodiments, the cell walls may be porous thereby forming a wall-flow substrate and/or particulate filter. It should be understood that the term " monolithic catalytic substrate" is intended to encompass both flow-through and wall-flow (e.g., diesel particulate filters (DPF), a gasoline particulate filter (GPF), particle oxidation catalyst (POC), a catalyzed soot filter (CSF), etc.) substrate types, where the monolithic catalytic substrate provides surfaces that can support one or more washcoat layers and/or catalytic materials. The term "monolithic catalytic substrate" is therefore used throughout the application for simplicity and convenience without intending to narrow the scope of the claimed invention.

In various embodiments, a monolithic catalytic substrate may be coated with at least one washcoat layer containing one or more catalytic metals that may be selected from the platinum group metals, precious metals, base metals, and their metal oxides, and the substrate housed within a shell.

The catalytic material loading on the substrate may include a first washcoat layer and a second washcoat layer, the first washcoat layer comprising a palladium (Pd) component and first refractory metal oxide support including cerium; and the second washcoat layer comprising a second refractory oxide support, and a platinum (Pt) component.

In various embodiments, the monolithic catalytic substrate has a cross-sectional area, a length, and a catalytic material loading, that is reduced in volume and/or catalyst loading. In one more embodiments, the reduction in volume and/or catalytic loading is in an amount of about 1 % to about 75% by volume/ by g/in³ less when compared with a monolithic catalytic substrate that is required to meet the same emissions limits and does not utilize a lubricating system including a low SAPS engine oil according to one or more embodiments of the invention present in the internal combustion engine. In other words, utilization of a low SAPS engine oil according to one or more embodiments enables a reduction in catalytic substrate volume and/or loading by about 1% to 50% by volume and/or g/in³ while maintaining the same catalytic activity for the reduction of pollutants compared with an internal combustion system that does not utilize a low SAPS engine oil and utilizes a standard, higher catalytic substrate volume or higher loading required to reduce emissions to regulated limits.

In various embodiments, the internal combustion system using a low SAPS engine oil utilizes a monolithic catalytic substrate, which has a catalytic material loading that is in an amount of about 5% to about 75% by g/in³ less than a monolithic catalytic substrate in an internal combustion system that uses a different engine oil and having the same engine size. In various embodiments, the internal combustion system using low SAPS engine oil utilizes a monolithic catalytic substrate that has a catalytic material loading in an amount of about 10% to about 50% by g/in³ less than a monolithic catalytic substrate in an internal combustion system that does not use low SAPS engine oil and having the same engine size. In various embodiments, a catalytic exhaust system comprising a monolithic catalytic substrate operatively associated and in fluid communication with the internal combustion engine comprising a lubricating system of the current invention, has a monolithic catalytic substrate with a volume in the range of about 5% to about 75% by volume smaller, and/or a catalytic material loading in the range of about 1% to about 75% g/in³ less compared to a catalytic exhaust system comprising a monolithic catalytic substrate sized and loaded with catalytic material for an equally sized internal combustion engine utilizing a lubricating system comprising one or more of calcium carbonate, calcium alkylbenzene sulfonate, calcium salicylate, calcium phenate, magnesium sulfonate, and magnesium salicylate.

In one or more embodiments, the volume of the monolithic catalytic substrate may be reduced in the range of about 1% to about 80%, or at least about 5%, or about 5% to about 80%, or about 5% to about 75%, or from about 10% to about 80%, or from about 10% to about 75%, or from about 10% to about 50%, or from about 20% to about 50%, or from about 30% to about 75%, where the reduction in size is due to a reduction of the amount of catalytic material loading being applied to the monolithic catalytic substrate.

In one or more embodiments, the amount of catalytic material loading being applied to the monolithic catalytic substrate may be reduced in the range of about 1% to about 80%, or at least about 5%, or about 5% to about 80%, or about 5% to about 75%, or from about 10% to about 80%, or from about 10% to about 75%, or from about 10% to about 50%, or from about 20% to about 50%, or from about 30% to about 75%, where the reduction in the amount of catalytic material loading being applied to the monolithic catalytic substrateis due to a reduction in volume of the monolithic catalytic substrate.

In various embodiments, an additive package comprising a hindered secondary amine detergent, ZDDP in the amount of about 0.1% to about 5% by weight of the engine oil, and at least one epoxide as a seal compatibility additive is added to the engine oil. In some embodiments, the engine oil containing such an additive package generates from about 10% to about 50% less ash-producing components, which reduces or prevents clogging and/or fouling of a monolithic catalytic substrate, and may reduce chemical aging and extend the intended lifetime of the monolithic catalytic substrate. In various embodiments, the additive package comprises a hindered secondary amine detergent, ZDDP in the amount of about 0.1% to about 5% by weight of the engine oil, and at least one epoxide as a seal compatibility additive and generates at least about 5%, or about 5% to about 80%, or about 5% to about 75%, or at least 10%, or about 10% to about 75%, or about 10% to about 50%, or about 20% to about 80%, or about 20% to about 50% less ash- producing components. The improved performance of various embodiments may be more pronounced and observed towards the end of the component lifetime, particularly compared to a catalytic component operatively associated with an engine utilizing oil with overbased sulfonates of alkaline earth metals, overbased phenates of alkaline earth metals, and/or overbased salicylates of alkaline earth metals.

In various embodiments, the monolithic catalytic substrate may be configured and dimensioned to treat engine exhaust gas comprising about 5% to about 80%, or about 5% to about 75%, or at least 10%, or about 10% to about 75%, or about 10% to about 50%, or about 20% to about 80%, or about 20% to about 50% less ash-producing components produced by a low SAPS engine oil. In some embodiments, the low SAPS engine oil comprises a secondary amine, a zinc -phosphorus-based anti-wear additive, and an epoxide seal compatibility additive and is introduced into a lubricating system of the internal combustion engine operatively associated with the monolithic catalytic substrate.

In various embodiments, the catalytic exhaust system is part of an exhaust system, which may comprise an exhaust manifold, an exhaust pipe (or a down pipe, or a Y-pipe), a muffler, and a tailpipe. Various components of the catalytic exhaust system may be inserted into the Y-pipe and/or exhaust pipe to treat the exhaust gas from the internal combustion engine prior to the gases exiting the tailpipe to the atmosphere.

In one or more embodiments, the catalytic metal loading may comprise one or more platinum group metals, one or more base metals, one or more precious metals (e.g., Ag, Au), and/or one or more base metal oxides, or a combination thereof.

Principles and embodiments of the present invention also relate to an internal combustion system comprising an internal combustion engine and a catalytic exhaust system, wherein the catalytic exhaust system has a reduced size and/or a reduced amount of precious metal loading compared to a catalytic exhaust system sized for an internal combustion system that does not utilize a lubricating system in their internal combustion engine comprising an addtivie package containing a secondary amine detergent, wherein the additive package is otherwise comparable to the additive package therein.

In various embodiments, the catalyst is sized to efficiently convert exhaust gases generated by the internal combustion engine having a space velocity in the range of about 30,000 per hour to about 120,000 per hour. In addition, a catalysts substrate may be sized to reduce the backpressure by increasing the cross- sectional area (A) and open frontal area (OF A).

In one or more embodiments, the monolithic catalytic substrate of a catalytic exhaust system has an operating lifetime extended by an amount of about 5% to about 400%, or about 5% to about 300%, or about 5% to about 200%, or about 5% to about 100%, by using the additive package described herein or a a low SAPS additive package. In one or more embodiments, the monolithic catalytic substrate of a catalytic exhaust system has an operating lifetime extended by about 50% to about 400%, or about 50% to about 300%, or about 25% to about 200%, or about 10% to about 100%, by using the additive package described herein or by using a low SAPS additive package. A low SAPS additive package contains low amounts of sulfur and phosphorous and is able to produce little if no amounts of ash when used in an internal combution engine. In one or more embodiments, the monolithic catalytic substrate of a catalytic exhaust system has an operating lifetime extended by at least about 10%, or extended by at least about 20%, or by at least about 30%, or by at least about 40%, or by at least about 50% by using the additive package described herein or the low SAPS additive package describes therein, where for example a catalytic substrate having an intended operating lifetime of about 100,000 miles that is extended by at least about 20% would still provide the same level of emission reductions at about 120,000 miles, as the intended emission reductions at about 100,000 miles. Similarly, a catalytic substrate having an intended operating lifetime of about 435,000 miles that is extended by at least about 30% would still provide the same level of emission reductions at about 565,500 miles, as the emission reductions at about 435,000 miles intended to meet prescribed emission limits. Similarly, a catalytic substrate having an intended operating lifetime of about 150,000 miles for a light duty vehicle that is extended by at least about 100% would still provide the same level of emission reductions at about 300,000 miles, as the emission reductions at about 150,000 miles intended to meet prescribed emission limits.

In one or more embodiments, a monolithic honeycomb substrate comprising a quantity of catalytic metal components is optimized for operation with the additive package and enabled to meet prescribed emission limits for at least about 99,420 miles at an operating lifetime of at least about 120,000 miles when used with the engine oil containing the additive package.

In one or more embodiments, the catalytic exhaust system is configured and dimensioned to have a volume sufficient to treat a volume of exhaust over an operating intended lifetime, and/or at an intended space velocity.

In some embodiments, the use of a lubricating system comprising an engine oil and additive package as described by the current invention may extend the life of the catalytic exhaust system. For example, in one or more embodiments, the catalytic exhaust system may comprise a diesel particulate filter (DPF), a gasoline particulate filter (GPF), particle oxidation catalyst (POC), a catalyzed soot filter (CSF), or combinations thereof, for removing particulate matter from the exhaust gases, and wherein the additive package extends the catalytic exhaust system life by about 5% to about 400%, or about 5% to about 300%, or about 5% to about 200%, or about 5% to about 100%, or about 5% to about 50%, or by at least 10%, or about 10% to about 400%, or about 10% to about 300%, or about 10% to about 200%, or about 10% to about 100%, by about 50% to about 400%, or about 50% to about 300%, or about 25% to about 200%, or about 20% to about 100%, or up to about 400%, compared to a catalytic exhaust system operatively associated with an internal combustion engine using an engine oil comprising an additive package with no secondary amine detergent, wherein the additive package is otherwise comparable to the additive package described therein. The catalytic exhaust system life is measured by operating time (hours or minutes) and/or miles traveled.

In one or more embodiments, the time period between cleaning and/or replacement of various components of the catalytic exhaust system may be extended with the use of a lubricating system containing an engine oil and an additive package as described by the current invention. For example, In various embodiments, the catalytic exhaust system may comprise a diesel particulate filter (DPF), a gasoline particulate filter (GPF), particle oxidation catalyst (POC), a catalyzed soot filter (CSF), or combinations thereof, for removing particulate matter from the exhaust gases, and wherein the additive package extends the time period between cleaning or replacement of the DPF, the GPF, the POC, the CSF, or combinations thereof, in the range of at least 5%, or by about 5% to about 400%, or about 5% to about 300%, or about 5% to about 200%, or about 5% to about 100%, or about 5% to about 50%, or by at least 10%, or about 10% to about 400%, or about 10% to about 300%, or about 10% to about 200%, or about 10% to about 100%, by about 50% to about 400%, or about 50% to about 300%, or about 25% to about 200%, or about 20% to about 100%, or up to about 400%, compared to a catalytic exhaust system operatively associated with an internal combustion engine using an engine oil comprising an additive package with no secondary amine detergent, wherein the additive package is otherwise comparable to the additive package descibed therein. In some embodiments, the additive package reduces the chemical aging of the DPF, the GPF, the POC, the CSF, or combinations thereof, in the range of at least 5%, or by about 5% to about 400%, or about 5% to about 300%, or about 5% to about 200%, or about 5% to about 100%, or about 5% to about 50%, or by at least 10%, or about 10% to about 400%, or about 10% to about 300%, or about 10% to about 200%, or about 10% to about 100%, by about 50% to about 400%, or about 50% to about 300%, or about 25% to about 200%, or about 20% to about 100%, or up to about 400%, compared to a catalytic exhaust system operatively associated with an internal combustion engine using an engine oil comprising an additive package with no secondary amine detergent, wherein the additive package is otherwise comparable to the additive package described therein. The catalytic exhaust system life is measured by operating time (hours or minutes) and/or miles traveled.

In one or more embodiments, the use of the low SAPS engine oil in the internal combustion engine allows the monolithic catalytic substrate of a catalytic exhaust system to maintain overall conversion efficiency over an intended operating lifetime at or above the prescribed emission limits, while utilizing a lower loading of catalytic metal(s). In various embodiments, the loading of catalytic metals (e.g., platinum group metal (PGM), base metals) may be reduced by about 10% to about 75%, or about 10% to about 50%, or reduced by at least 20%, or by at least 30%, or by at least 40%, or about 40% to about 75% by g/in³ by using the low SAPS additive package described herein.

In one or more embodiments, a monolithic catalytic substrate precious metal loading (e.g., of Pt, Pd, and Rh) does not require additional amounts of catalytic materials to meet the intended operating lifetimes at the intended space velocities.

In one or more embodiments, a monolithic catalytic substrate configured, dimensioned, and with a precious metal loading sufficient to meet prescribed emission limits for at least about 99,420 miles has an operating lifetime of at least about 120,000 miles if a low SAPS engine oil comprising the additive package is utilized in the lubricating system of the internal combustion engine operably associated with the monolithic catalytic substrate.

In one or more embodiments, a monolithic catalytic substrate configured, dimensioned, and with a precious metal loading sufficient to meet prescribed emission limits for at least about 120,000 miles has an operating lifetime of at least about 150,000 miles if a low SAPS engine oil comprising the described additive package is utilized in the lubricating system of the internal combustion engine operably associated with the monolithic catalytic substrate.

In one or more embodiments, a monolithic catalytic substrate configured, dimensioned, and with a precious metal loading sufficient to meet prescribed emission limits for at least about 435,000 miles has an operating lifetime of at least about 522,000 miles if a low SAPS engine oil comprising the described additive package is utilized in the lubricating system of the internal combustion engine operatively associated with the monolithic catalytic substrate.

The intented operating lifetime of a monolithic catalytic substrate is at least 50,000 miles with any engine oil. For example, the intented operating lifetime for a internal combustion passenger car is at least about 120,000 to about 150,000 miles, whereas for a heavy duty diesel engine the the intented operating lifetime is at least about 435,000 miles. In some embodiments, the intented operating lifetime of a monolithic catalytic substrate is at least about 50,000 miles or at least about 100,000 miles or at least about 150,000 miles, or at least about 200,000 miles or at least about 250,000 miles or at least about 300,000 miles or at least about 350,000 miles or at least about 400,000 miles or at least about 450,000 miles or at least about 500,000 miles.

In one or more embodiments, an engine oil containing an additive package generates from about 10% to about 80% less ash-producing components, wherein the additive package comprises a hindered secondary amine detergent, an anti-wear additive in an amount of about 0.1% to about 5% by weight of the engine oil and at least one epoxide as a seal compatibility additive, compared to an engine oil containing an additive package with no secondary amine detergent, wherein the additive package is otherwise comparable to the additie package described therein. In some embodiments, the anti-wear additive may be ZDDP. In some embodiments, the engine oil containing such an additive package reduces or prevents clogging and/or fouling of a monolithic catalytic substrate operatively associated and in fluid communication with an internal combustion engine. The reduction or prevention of clogging and/or fouling of a catalytic substrate delays and/or avoids increases in the amount of backpressure produced by the catalytic substrate over time. For example, a monolithic catalytic substrate operatively associated and in fluid communication with an internal combustion engine utilizing an engine oil with an additive package comprising a secondary amine detergent, wherein the secondary amine is present in an amount of about 1% to about 15% by weight, or in an amount of about 1% to about 12% by weight, or in an amount of about 5% by weight of the engine oil, an an ti- wear additive, where the anti-wear additive may be ZDDP, in an amount of about 0.1% to about 5% by weight, or in an amount of about 1.5% by weight of the engine oil, and at least one epoxide produces less backpressure at about 50,000 miles than the same internal combustion engine utilizing an engine oil containing overbased sulfonates of alkaline earth metals, overbased phenates of alkaline earth metals, and/or overbased salicylates of alkaline earth metals in the engine oil and no additive package as described by the current invention.

In one or more embodiments, the reduction in ash-producing components produces a reduction in clogging and fouling of the monolithic catalytic substrate in an amount of at least about 5%, or about 5% to about 80%, or about 5% to about 75%, or about 5% to about 50%, or at least 10%, or about 10% to about 50%, or about 10% to about 75%, or about 15% to about 40%, or at least 20%, or about 20% to about 30%, or about 20% to about 50%, or at least 25%, or about 30% to about 50%, or at least 33%, or about 33% to about 75%, or at least 50%, or about 50% to about 80%. In some embodiments, the reduction in ash- producing components allows a reduction of PGM loading on the monolithic catalytic substrate in an amount of about 1% to about 80%, or at least about 5%, or about 5% to about 80%, or about 5% to about 75%, or from about 10% to about 80%, or from about 10% to about 75%, or from about 10% to about 50%, or from about 20% to about 50%, or from about 20% to about 40%,or from about 30% to about 75%.

In various embodiments, the size, dimensions, and catalytic material loading of the monolithic catalytic substrate may be maintained at the same size, dimensions, and catalytic material loading for an internal combustion engine using an engine oil containing the additive package of the invention, to provide higher catalytic activity and/or an extended lifetime due to lower clogging and fouling by the reduction in ash-producing components.

In one or more embodiments, a catalytic exhaust system in fluid communication with an internal combustion engine comprises a reduced-size monolithic catalytic substrate, where reduced size refers to a catalytic substrate that is in the range of about 1 % to about 50% less in volume and/or catalytic loading than a monolithic catalytic substrate sized to provide an intended emission reduction for an intended operating lifetime that is not used in combination with the same engine oil in accordance with embodiments of the invention. In various embodiments, the reduced-size monolithic catalytic substrate may also comprise in an amount of about 1 % to about 80% less PGM loading than a monolithic catalytic substrate sized to provide the intended emission reduction for the intended operating lifetime that is not used together with the same engine oil in accordance with embodiments of the invention.

In one or more embodiments, a catalytic exhaust system in fluid communication with an internal combustion engine comprising a monolithic catalytic substrate provides increase emission reduction and/or an increase operating lifetime with the same volume and/or catalytic loading, as a monolithic catalytic substrate sized to provide an intended emission reduction for an intended operating lifetime that does not operate in combination with a low SAPS engine oil in accordance with embodiments of the invention. In various embodiments, the monolithic catalytic substrate operatively associated with an internal combustion engine using a low SAPS engine oil in accordance with various embodiments of the invention may provide an amount of about 1% to about 50% greater exhaust emission reduction at the same PGM loading as a monolithic catalytic substrate sized to provide the intended emission reduction for the intended operating lifetime that is not used together with a low SAPS engine oil in accordance with embodiments of the invention. In various embodiments, the emission reduction for the intended operating lifetime is in the range of about 5% to about 50% greater, or at least 20% greater, or by at least 30%, or by at least 40% greater, by using the additive package described herein. The use of the additive package described herein may increase the operating lifetime of the catalytic substrate and provide superior performance over the operating lifetime of the monolithic catalytic substrate.

In one or more embodiments, the catalytic exhaust system is exposed to less ash conveyed to the monolithic catalytic substrate from an operatively associated internal combustion engine due to a reduction in ash-producing components in the engine oil from the additive package, wherein the substitution of an overbased detergent with one or more secondary amines produces a reduction of ash in the exhaust gases in the amount of at least 5%, or about 75% to about 40%, or from about 10% to about 50%, or from about 20% to about 50%, or from about 30% to about 50% compared to the amount of ash produced from an internal combustion engine with an engine oil and no additive package. In various embodiments, only a first component, for example a filter and/or catalytic substrate, in a catalytic exhaust system comprising a plurality of catalytic substrates experiences a reduction in chemical aging and higher catalytic activity and/or an extended lifetime due to lower clogging and fouling by the reduction in ash-producing components.

In various embodiments, the chemical aging of a catalytic substrate and/or particle filter may be reduced by at least about 5%, or about 5% to about 80%, or about 5% to about 75%, or about 5% to about 50%, or at least 10%, or about 10% to about 50%, or about 10% to about 75%, or about 15% to about 40%, or at least 20%, or about 20% to about 30%, or about 20% to about 50%, or at least 25%, or about 30% to about 50%, or at least 33%, or about 33% to about 75%, or at least 50%, or about 50% to about 80% when an engine oil with an additive package is used compared to a catalytic substrate in communication with an internal combustion engine using an engine oil and an additive package with no secondary amine detergent, wherein the additive package is otherwise comparable to the additive package described therein.

In one or more embodiments, the monolithic catalytic substrate comprises an amount of about 1 % to about 80% less PGM loading, or about 5% to about 80% less PGM loading, or about 5% to about 75% less PGM loading, or about 10% to about 80% less PGM loading, or about 10% to about 75% less PGM loading, or about 10% to about 50% less PGM loading, or about 20% to about 50% less PGM loading, or about 20% to about 40% less PGM loading, or about 30% to about 75% less PGM loading than a monolithic catalytic substrate sized and loaded with catalytic material to provide the intended emission reduction for the intended operating lifetime using no low SAPS engine oil as described by the current inventions and/or no low SAPS additive package as described by the current invention.

FIG. 1 illustrates an exemplary embodiment of an engine system 10 comprising an internal combustion engine 100 (e.g., gasoline, diesel, natural gas) and a catalytic exhaust system 200. The internal combustion engine 100 may comprise a combustion system, which may include an engine block 110 having one or more engine cylinders (combustion chambers), a cylinder head, a piston for each cylinder, piston rings, one or more air intake valves per cylinder, and one or more exhaust valves per cylinder. The internal combustion system may further comprise a fuel injection system, which may include a fuel tank, a fuel pump, a fuel line, and a fuel injector per cylinder. The internal combustion system may further comprise an ignition system, which may include a battery, an alternator, an ignition wire and spark plug or glow plug per cylinder, and one or more sensors. The internal combustion system may further comprise a cooling system, which may include a radiator for containing cooling fluid, cooling fluid, a water pump, an outlet radiator hose, an inlet radiator hose, a thermostat, and conduits and cooling jackets in the engine block. The internal combustion system may further comprise an exhaust system, which may include one or more exhaust manifolds 120 mounted to the engine block 110, an exhaust pipe 122 (also referred to as a down pipe or a Y- pipe) operatively connected to the one or more exhaust manifolds 120, a catalytic exhaust system 200 (also referred to as a catalytic converter) comprising a monolithic catalytic substrate within a housing 250 that is operatively associated and in fluid communication with the exhaust pipe 122, an extension pipe 124, a muffler 125, and a tailpipe 128. The internal combustion system may further comprise a lubricating system, which may include an oil pan 151 for containing engine oil, an oil pump, an oil filter 152, one or more feeds to bearings, shafts, and cylinders, and a return to the oil pan.

The internal combustion system may further comprise a control system, which may include an engine control unit, one or more actuators, one or more sensors, and hardware, software, and firmware to control the various systems, components, and functions of the engine.

In one or more embodiments, engine oil containing an additive package comprising or consisting essentially of a secondary amine, ZDDP, and an epoxide seal compatibility additive is introduced into the lubricating system of an internal combustion engine 100 to reduce the ash generated by the engine through combustion of the oil and additives. In various embodiments, a catalytic exhaust system 200 is operably associated with the internal combustion engine 100 and comprises a monolithic catalytic substrate, which is configured, dimensioned and loaded with a catalytic material (e.g., PGM) sufficient to provide an intended emission reduction for an intended operating lifetime.

In one or more embodiments, the catalytic converter may comprise a monolithic catalytic substrate encased within a shell having an inlet and an outlet, wherein the shell may be housed within a housing that may be operatively associated and in fluid communication with an exhaust system of an internal combustion engine. Although the invention herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It will be apparent to those skilled in the art that various modifications and variations can be made to the method and apparatus of the present invention without departing from the spirit and scope of the invention. Thus, it is intended that the present invention include modifications and variations that are within the scope of the appended claims and their equivalents.

Claims

What is claimed is:

1. A low ash catalytic exhaust system comprising:

an engine oil used by an internal combustion engine associated with the low ash catalytic exhaust system, wherein the engine oil comprises a base oil and an additive package, wherein the additive package comprises a secondary amine detergent, an anti-wear additive in the amount of about 0.1% to about 5% by weight of the engine oil, and at least one epoxide as a seal compatibility additive; and

a monolithic honeycomb substrate comprising a quantity of catalytic metal components, wherein the monolithic honeycomb substrate exhibits an intended operating lifetime that is extended by about 5% to about 400% as compared with the lifetime of a monolithic substrate used with an engine oil containing the additive package with no secondary amine detergent.

2. The low ash catalytic exhaust system of claim 1, wherein the secondary amine detergent comprises a secondary amine of general formula (II),

FORMULA (II)

3. The low ash catalytic exhaust system of claim 2, wherein the secondary amine comprises a hindered secondary amine sterically hindered by at least one substituent on at least one of the carbons alpha or beta to the nitrogen.

4. The low ash catalytic exhaust system of claim 3, wherein the secondary amine is selected from the group comprising general formula IV,

FORMULA (IV)

wherein R³, R⁴, R⁵, and R⁶ are each independently a hydrogen or a C C6 alkyl group; and 11 12 11 12

R and R are independently a C Ci6 alkyl group, with the proviso that R and R are longer alkyl chains than R³, R⁴, R⁵, and R⁶.

5. The low ash catalytic exhaust system of claim 3, wherein the secondary amine is selected from the group comprising general formula V,

11 12 1 1 12

6. The low ash catalytic exhaust system of claim 3, wherein the secondary amine is selected from the group comprising general formula VI,

FORMULA (VI)

wherein R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ are each independently a hydrogen or a C C6 alkyl group, and wherein R¹¹ is a C 1 -C 16 alkyl group, and R¹² is a C C i6 alkyl group.

7. The low ash catalytic exhaust system of claim 3, wherein the secondary amine is a heterocyclic compound selected from the group comprising general formulas VIIA, VIIB, VIII, IXA, ΓΧΒ, and X,

FORMULA (VIIA) FORMULA (VIIB) FORMULA (VIII)

wherein R³, R⁴, R⁵, and R⁶ are each independently hydrogen or a C₁-C4 saturated alkyl, with the proviso that at least two of R³, R⁴, R⁵, and R⁶ are C C₄ saturated alkyl; and

wherein R¹³ is a hydrogen, a Q-Cis alkyl group or CpCn ester group.

8. The low ash catalytic exhaust system of claim 1, wherein the catalytic exhaust system further comprises a diesel particulate filter (DPF), a gasoline particulate filter (GPF), particle oxidation catalyst (POC), a catalyzed soot filter (CSF), or combinations thereof, for removing particulate matter from the exhaust gases; and

wherein the additive package extends the time period between cleaning or replacement of the DPF, the GPF, the POC, the CSF, or combinations thereof, in the range of about 5% to about 400% compared to a catalytic exhaust system operatively associated with an internal combustion engine not using engine oil comprising an additive package with a hindered secondary amine detergent.

9. The low ash catalytic exhaust system of claim 1, wherein the reduction in ash-producing components from the additive package produces a reduction in clogging and fouling of the monolithic catalytic substrate in the range of about 5% to about 80%.

10. The low ash catalytic exhaust system of claim 9, wherein the monolithic catalytic substrate comprises an amount of about 1 % to about 80% less PGM loading than a monolithic catalytic substrate sized and loaded with catalytic material to provide the intended emission reduction for the intended operating lifetime.

11. A method of reducing ash introduced into an exhaust system comprising:

13. The method of claim 11, wherein the overbased sulfonates of alkaline earth metals, overbased phenates of alkaline earth metals, and overbased salicylates of alkaline earth metals are excluded from the engine oil.

14. The method of claim 11, wherein the hindered secondary amine detergent is selected from the group comprising general formula IV,

FOMRULA (IV)

wherein R³, R⁴, R⁵, and R⁶ are independently a hydrogen or a C C6 alkyl group; and

R 11 and R12 are independently a C Ci6 alkyl group, with the proviso that R 11 and R12 are longer alkyl chains than R³, R⁴, R⁵, and R⁶.

15. The method of claim 11, wherein the hindered secondary amine detergent is selected from the group comprising general formula V,

FORMULA (V)

R 11 and R12 are independently a C 1 1 12

C i6 alkyl group, with the proviso that each of R and R are longer alkyl chains than R⁷, R⁸, R⁹, and R¹⁰.

16. The method of claim 11, wherein the hindered secondary amine detergent is selected from the group comprising general formula VI,

FORMULA (VI)

wherein R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ are each independently a hydrogen or a C C6 alkyl group, and wherein R¹¹ is a C₁ -C 16 alkyl group, and R¹² is a C Ci6 alkyl group

17. The method of claim 11, wherein the hindered secondary amine detergent is a heterocylic compound selected from the group comprising general formulas VIIA, VIIB, VIII, IXA, ΓΧΒ, and X,

FORMULA (VIIA) FORMULA (VIIB)

wherein R³, R⁴, R⁵, and R⁶ are each independently hydrogen or a C₁-C4 saturated alkyl, with the proviso that at least two of R³, R⁴, R⁵, and R⁶ are C₁-C4 saturated alkyl; and

wherein R¹³ is a hydrogen, a C Ci₈ alkyl group or C Ci₇ ester group.

18. An internal combustion engine system comprising:

a catalytic exhaust system comprising a monolithic catalytic substrate operatively associated and in fluid communication with the internal combustion engine, wherein the monolithic catalytic substrate has a volume in the range of about 5% to about 75% smaller, and a catalytic material loading in the range of about 1 % to about 80% less than a monolithic catalytic substrate sized and loaded with catalytic material for an equally sized internal combustion engine that utilizes a lubricating system comprising engine oil and one or more of calcium carbonate, calcium alkylbenzene sulfonate, calcium salicylate, calcium phenate, magnesium sulfonate, and magnesium salicylate.

19. An internal combustion engine system comprising:

19. The internal combustion engine system of claim 19, wherein the monolithic catalytic substrate has a volume in the range of about 20% to about 75% smaller compared to a monolithic catalytic substrate sized to provide the intended emission reduction for the intended operating lifetime for an equally sized an internal combustion engine that utilizes a lubricating oil comprising one or more of calcium carbonate, calcium alkylbenzene sulfonate, calcium salicylate, calcium phenate, magnesium sulfonate, and magnesium salicylate.

20. The engine system of claim 19, wherein the monolithic catalytic substrate has a catalytic material loading in an amount of about 10% to about 75% less than the monolithic catalytic substrate would have for an internal combustion engine of the intended size based on the expected exhaust output.

21. The engine system of claim 19, wherein the internal combustion engine generates from about 10% to about 75% less ash-producing components and reduces or prevents clogging or fouling of a monolithic catalytic substrate.