Aftertreatment system friendly engine oil formulations

Abstract

The present disclosure describes a method of reducing catalyst poisoning in a diesel engine equipped with an aftertreatment system including a selective catalytic reduction device. The method includes lubricating the engine with a lubricating oil composition. The lubricating oil composition comprises a major amount of an oil of lubricating viscosity; and a calcium salicylate or magnesium salicylate detergent, wherein the lubricating oil composition is free of a calcium sulfonate detergent.

Description

Cross-reference to related applications

[0001] This application claims priority to U.S. Provisional Application 63 / 451,669, filed March 13, 2023, the disclosure of which is incorporated herein by reference. Technical Field

[0002] This disclosure relates to engine oil formulations. More specifically, the present invention relates to engine oil formulations designed to reduce emissions from internal combustion engines. Background Technology

[0003] Reduce emissions from compression-ignition internal combustion engines, such as carbon monoxide (CO) and nitrogen oxides (NOx). x Efforts to reduce emissions are ongoing. Aftertreatment systems are methods or devices designed to reduce harmful exhaust emissions from internal combustion engines. Some aftertreatment systems (ATS) may employ diesel particulate filters (DPFs) to capture particulate matter in emissions.

[0004] Another ATS method (which can be used in combination with DPF) is Selective Catalytic Reduction (SCR). SCR removes nitrogen oxides (NOx) from the exhaust pipe. x Selective catalytic reduction (SCR) converts nitrogen (N2) and water via catalytic conversion. A potential drawback of SCR is its susceptibility to clogging and poisoning by soot and ash. Specifically, the presence of metals in engine oil can poison the catalyst used in selective catalytic reduction. Summary of the Invention

[0005] In one aspect, a method is provided for reducing catalyst poisoning in a diesel engine aftertreatment system including a selective catalytic reduction device, the method comprising: lubricating the engine with a lubricating oil composition comprising: a major amount of an oil having a lubricating viscosity; and a calcium salicylate or magnesium salicylate detergent; wherein the lubricating oil composition is free of calcium sulfonate detergent.

[0006] In another aspect, the use of a lubricating oil composition for reducing catalyst poisoning in a diesel engine aftertreatment system including a selective catalytic reduction device is provided, the lubricating oil composition comprising: a principal amount of an oil having a lubricating viscosity; and a calcium salicylate or magnesium salicylate detergent; wherein the lubricating oil composition is free of sulfonate detergents. Detailed Implementation

[0007] It should be understood that when combinations, subsets, groups, etc. of elements are disclosed (e.g., combinations of components in a composition, or combinations of steps in a method), each of these elements is specifically considered and described herein, although specific references to each of the various individual and collective combinations and arrangements of these elements may not be explicitly disclosed.

[0008] Modern engines are typically equipped with aftertreatment systems designed to reduce harmful exhaust emissions from internal combustion engines. These aftertreatment systems may feature selective catalytic reduction (SCR), which uses a catalyst to remove nitrogen oxides (NOx). x A device that converts exhaust gas into diatomic nitrogen (N2) and water (H2O). This reduction chemical reaction occurs when exhaust gas passes through a catalytic converter. A reducing agent is injected and mixed with the exhaust gas before it enters the catalytic converter. The reducing agent (usually ammonia) or its precursors (e.g., ammonia solution, urea) is typically provided by diesel exhaust fluid (DEF). The catalyst contains oxides of base metals (such as molybdenum and tungsten), zeolites, metals, or activated carbon.

[0009] This disclosure relates to a lubricating oil composition formulated to enhance or improve the performance of aftertreatment systems, particularly those equipped with selective catalytic reduction systems. The specific formulation of these lubricating oil compositions is crucial because the metals in commonly used lubricant additives (such as detergents (e.g., salicylates, sulfonates, phenolates) or anti-wear agents (e.g., zinc dithiophosphate)) are considered catalyst poisoning compounds.

[0010] As an advantage, the lubricating oil composition disclosed herein reduces harmful emissions by minimizing poisoning of the catalyst used to convert harmful emissions into less harmful compounds. In another aspect, the lubricating oil composition improves the performance of selective catalytic reduction systems. Other advantages will be apparent from the disclosure herein.

[0011] This disclosure provides a method for reducing catalyst poisoning in a diesel engine equipped with an aftertreatment system including a selective catalytic reduction (SCR) system. In some embodiments, this disclosure provides a method for improving the performance of a diesel engine equipped with an SCR system. In some embodiments, this disclosure provides the use of a lubricating oil composition for a diesel engine equipped with an SCR system.

[0012] The method disclosed herein includes lubricating an engine with a lubricating composition comprising a major amount of an oil having a lubricating viscosity and a detergent system comprising calcium salicylate or magnesium salicylate detergents. The lubricating oil composition is typically free of calcium sulfonate because it has been inadvertently found that calcium sulfonate can lead to relatively high levels of emissions. Therefore, the lubricating oil composition is free of calcium sulfonate. In some embodiments, the lubricating oil composition contains a total of about 50 ppm or less of calcium derived from sulfonate detergents.

[0013] Detergent systems The lubricating oil compositions disclosed herein comprise a detergent system containing one or more salicylates. In some embodiments, the lubricating oil compositions comprising the detergent system unexpectedly improve ATS conversion or NO. x Conversion efficiency. Cleaning agents compatible with this disclosure include calcium salicylate or magnesium salicylate cleaning agents. Incompatible cleaning agents include sulfonate cleaning agents. Optional cleaning agents include phenolic salt cleaning agents.

[0014] Salicylate detergents Salicylate detergents can be prepared by reacting an alkali metal compound with at least one carboxylic acid and removing water from the reaction product.

[0015] Useful salicylates include hydrocarbon-substituted salicylates, such as long-chain alkyl salicylates. The term "hydrocarbon" refers to a chemical group or part derived from a hydrocarbon (including saturated and unsaturated hydrocarbons). Examples of hydrocarbon groups include alkenyl, alkyl, polyalkenyl, polyalkyl, phenyl, etc. Hydrocarbon-substituted salicylates can be prepared from phenols via the Kolbe reaction (see U.S. Patent No. 3,595,791). Metal salts of hydrocarbon-substituted salicylates can be prepared by metathesis of the metal salt in polar solvents such as water or alcohols.

[0016] Typical detergents are anionic materials containing the long-chain hydrophobic portion of the molecule and the smaller anionic or oleophobic hydrophilic portion of the molecule. The anionic portion of salicylate detergents is derived from carboxylic acids. The counterions are calcium or magnesium.

[0017] Salts containing stoichiometric amounts of metal are described as neutral salts and have a total base number (TBN) ranging from 0 mg KOH / g to 80 mg KOH / g as measured according to ASTM D-2896.

[0018] Many cleaning agents are highly alkaline and contain large amounts of metallic bases, which is achieved by reacting an excess of a metallic compound (e.g., a metal hydroxide or metal oxide) with an acid-rich gas (e.g., carbon dioxide).

[0019] Useful detergents can be neutral, slightly alkaline, or highly alkaline.

[0020] In some implementations, at least some of the detergents used in the detergent system may be highly alkaline. Highly alkaline detergents help neutralize acidic impurities generated during combustion and retained in the oil. The degree of alkalinity typically depends on the ratio of the metal ion to the anionic portion of the detergent, expressed in equivalence.

[0021] According to ASTM D-2896, highly alkaline detergents typically have a TBN of 10 mg KOH / g or higher, such as 15 mg KOH / g or higher, 25 mg KOH / g or higher, 50 mg KOH / g or higher, 75 mg KOH / g or higher, 100 mg KOH / g or higher, 125 mg KOH / g or higher, 150 mg KOH / g or higher, 175 mg KOH / g or higher, 200 mg KOH / g or higher, 225 mg KOH / g or higher, 250 mg KOH / g or higher, 275 mg KOH / g or higher, 300 mg KOH / g or higher, 325 mg KOH / g or higher, 350 mg KOH / g or higher, 375 mg KOH / g or higher, 400 mg KOH / g or higher, 425 mg KOH / g or higher, 450 mg KOH / g or higher, 475 mg KOH / g or higher. KOH / g or higher, 500 mg KOH / g or higher, 525 mg KOH / g or higher, 550 mg KOH / g or higher, 575 mg KOH / g or higher, 600 mg KOH / g or higher and 650 mg KOH / g or higher.

[0022] In some implementations, the highly alkaline detergent has a TBN of 10 mg KOH / g to 650 mg KOH / g, as measured according to ASTM D-2896, such as 10 mg KOH / g to 600 mg KOH / g, 10 mg KOH / g to 550 mg KOH / g, 10 mg KOH / g to 500 mg KOH / g, 10 mg KOH / g to 450 mg KOH / g, 10 mg KOH / g to 400 mg KOH / g, 10 mg KOH / g to 350 mg KOH / g, 10 mg KOH / g to 300 mg KOH / g, 10 mg KOH / g to 250 mg KOH / g, 10 mg KOH / g to 200 mg KOH / g, 10 mg KOH / g to 150 mg KOH / g, 10 mg KOH / g to 100 mg KOH / g, and 10 mg KOH / g to 50 mg KOH / g. KOH / g, 50 mg KOH / g to 650 mg KOH / g, 50 mg KOH / g to 600 mgKOH / g, 50 mg KOH / g to 550 mg KOH / g, 50 mg KOH / g to 500 mg KOH / g, 50 mg KOH / g to 450 mgKOH / g, 50 mg KOH / g to 400 mg KOH / g, 50 mg KOH / g to 350 mg KOH / g, 50 mg KOH / g to 300 mg KOH / g, 50 mg KOH / g to 250 mg KOH / g, 50 mg KOH / g to 200 mg KOH / g, 50 mg KOH / g to 150 mgKOH / g, 50 mg KOH / g to 100 mg KOH / g, 100 mg KOH / g to 650 mg KOH / g, 100 mg KOH / g to 600mg KOH / g, 100 mg KOH / g to 550 mg KOH / g, 100 mg KOH / g to 500 mg KOH / g, 100 mg KOH / g to 450 mg KOH / g, 100 mg KOH / g to 400 mg KOH / g, 100 mg KOH / g to 350 mg KOH / g, 100 mgKOH / g to 300 mg KOH / g, 100 mg KOH / g to 250 mg KOH / g, 100 mg KOH / g to 200 mg KOH / g, 100 mg KOH / g to 150 mg KOH / g, 150 mg KOH / g to 650 mg KOH / g, 150 mg KOH / g to 600 mg KOH / g, 150 mgfrom 550 mg KOH / g to 550 mg KOH / g, from 150 mg KOH / g to 500 mg KOH / g, from 150 mg KOH / g to 450 mg KOH / g, from 150 mg KOH / g to 400 mg KOH / g, from 150 mg KOH / g to 350 mg KOH / g, from 150 mg KOH / g to 300 mg KOH / g, from 150 mg KOH / g to 250 mg KOH / g, from 150 mg KOH / g to 200 mg KOH / g, from 200 mg KOH / g to 650 mg KOH / g, from 200 mg KOH / g to 600 mg KOH / g, from 200 mg KOH / g to 550 mg KOH / g, from 200 mg KOH / g to 500 mg KOH / g, from 200 mg KOH / g to 450 mg KOH / g, from 200 mg KOH / g to 400 mg KOH / g, from 200 mg KOH / g to 350 mg KOH / g, from 200 mg KOH / g to 300 mg KOH / g, from 250 mg KOH / g to 650 mg KOH / g, from 250 mg KOH / g to 600 mg KOH / g, from 250 mg KOH / g to 550 mg KOH / g, from 250 mg KOH / g to 500 mg KOH / g, from 250 mg KOH / g to 450 mg KOH / g, from 250 mg KOH / g to 400 mg KOH / g, from 250 mg KOH / g to 350 mg KOH / g, from 300 mg KOH / g to 650 mg KOH / g, from 300 mg KOH / g to 600 mg KOH / g, from 300 mg KOH / g to 550 mg KOH / g, from 300 mg KOH / g to 500 mg KOH / g, from 300 mg KOH / g to 450 mg KOH / g, from 300 mg KOH / g to 400 mg KOH / g, from 300 mg KOH / g to 350 mg KOH / g, from 350 mg KOH / g to 650 mg KOH / g, from 350 mg KOH / g to 600 mg KOH / g, from 350 mg KOH / g to 550 mg KOH / g, from 350 mg KOH / g to 500 mg KOH / g, from 350 mg KOH / g to 450 mg KOH / g, from 350 mg KOH / g to 400 mg KOH / g, from 400 mg KOH / g to 650 mgKOH / g, 400 mg KOH / g to 600 mg KOH / g, 400 mg KOH / g to 550 mg KOH / g, 400 mg KOH / g to 500 mg KOH / g, 400 mg KOH / g to 450 mg KOH / g, 450 mg KOH / g to 650 mg KOH / g, 450 mg KOH / g to 600 mg KOH / g, 450 mg KOH / g to 550 mg KOH / g, 450 mg KOH / g to 500 mg KOH / g, 500 mg KOH / g to 650 mg KOH / g, 500 mg KOH / g to 600 mg KOH / g, 500 mg KOH / g to 550 mg KOH / g, 550 mg KOH / g to 650 mg KOH / g, 550 mg KOH / g to 600 mg KOH / g, or 600 mg KOH / g to 650 mg KOH / g.

[0023] In some embodiments, the highly alkaline detergent has a TBN of 10 mg KOH / g to 150 mg KOH / g, such as 10 mg KOH / g to 140 mg KOH / g, 10 mg KOH / g to 130 mg KOH / g, 10 mg KOH / g to 120 mg KOH / g, 10 mg KOH / g to 110 mg KOH / g, 10 mg KOH / g to 100 mg KOH / g, 10 mg KOH / g to 90 mg KOH / g, 10 mg KOH / g to 80 mg KOH / g, 10 mg KOH / g to 70 mg KOH / g, 10 mg KOH / g to 60 mg KOH / g, 10 mg KOH / g to 50 mg KOH / g, 10 mg KOH / g to 40 mg KOH / g, 10 mg KOH / g to 30 mg KOH / g, 10 mg KOH / g to 20 mg KOH / g. KOH / g, 20 mg KOH / g to 150 mg KOH / g, 20 mg KOH / g to 140 mg KOH / g, 20 mg KOH / g to 130 mg KOH / g, 20 mg KOH / g to 120 mg KOH / g, 20 mg KOH / g to 110 mg KOH / g, 20 mg KOH / g to 100 mg KOH / g, 20 mg KOH / g to 90 mg KOH / g, 20 mg KOH / g to 80 mg KOH / g, 20 mg KOH / g to 70 mg KOH / g, 20 mg KOH / g to 60 mg KOH / g, 20 mg KOH / g to 50 mgKOH / g, 20 mg KOH / g to 40 mg KOH / g, 20 mg KOH / g to 30 mg KOH / g, 30 mg KOH / g to 150 mgKOH / g, 30 mg KOH / g to 140 mg KOH / g, 30 mg KOH / g to 130 mg KOH / g, 30 mg KOH / g to 120 mgKOH / g, 30 mg KOH / g to 110 mg KOH / g, 30 mg KOH / g to 100 mg KOH / g, 30 mg KOH / g to 90 mgKOH / g, 30 mg KOH / g to 80 mg KOH / g, 30 mg KOH / g to 70 mg KOH / g, 30 mg KOH / g to 60 mgKOH / g, 30 mg KOH / g to 50 mg KOH / g, 30 mg KOH / g to 40 mg KOH / g, 40 mg KOH / g to 150 mgKOH / g, 40 mgfrom 40 mg KOH / g to 140 mg KOH / g, from 40 mg KOH / g to 130 mg KOH / g, from 40 mg KOH / g to 120 mg KOH / g, from 40 mg KOH / g to 110 mg KOH / g, from 40 mg KOH / g to 100 mg KOH / g, from 40 mg KOH / g to 90 mg KOH / g, from 40 mg KOH / g to 80 mg KOH / g, from 40 mg KOH / g to 70 mg KOH / g, from 40 mg KOH / g to 60 mg KOH / g, from 40 mg KOH / g to 50 mg KOH / g, from 50 mg KOH / g to 150 mg KOH / g, from 50 mg KOH / g to 140 mg KOH / g, from 50 mg KOH / g to 130 mg KOH / g, from 50 mg KOH / g to 120 mg KOH / g, from 50 mg KOH / g to 110 mg KOH / g, from 50 mg KOH / g to 100 mg KOH / g, from 50 mg KOH / g to 90 mg KOH / g, from 50 mg KOH / g to 80 mg KOH / g, from 50 mg KOH / g to 70 mg KOH / g, from 50 mg KOH / g to 60 mg KOH / g, from 60 mg KOH / g to 150 mg KOH / g, from 60 mg KOH / g to 140 mg KOH / g, from 60 mg KOH / g to 130 mg KOH / g, from 60 mg KOH / g to 120 mg KOH / g, from 60 mg KOH / g to 110 mg KOH / g, from 60 mg KOH / g to 100 mg KOH / g, from 60 mg KOH / g to 90 mg KOH / g, from 60 mg KOH / g to 80 mg KOH / g, from 60 mg KOH / g to 70 mg KOH / g, from 80 mg KOH / g to 150 mg KOH / g, from 80 mg KOH / g to 140 mg KOH / g, from 80 mg KOH / g to 130 mg KOH / g, from 80 mg KOH / g to 120 mg KOH / g, from 80 mg KOH / g to 110 mg KOH / g, from 80 mg KOH / g to 100 mg KOH / g, from 80 mg KOH / g to 90 mg KOH / g, from 90 mg KOH / g to 150 mg KOH / g, from 90 mg KOH / g to 140 mg KOH / g, from 90 mg KOH / g to 130 mg KOH / g, from 90 mg KOH / g to 120 mg KOH / g, from 90 mg KOH / g to 110 mg KOH / g, 90 mgKOH / g to 100 mg KOH / g, 100 mg KOH / g to 150 mg KOH / g, 100 mg KOH / g to 140 mg KOH / g, 100 mg KOH / g to 130 mg KOH / g, 100 mg KOH / g to 120 mg KOH / g, 100 mg KOH / g to 110 mg KOH / g, 110 mg KOH / g to 150 mg KOH / g, 110 mg KOH / g to 140 mg KOH / g, 110 mg KOH / g to 130 mg KOH / g, 110 mg KOH / g to 120 mg KOH / g, 120 mg KOH / g to 150 mg KOH / g, 120 mg KOH / g to 140 mg KOH / g, 120 mg KOH / g to 130 mg KOH / g, 130 mg KOH / g to 150 mg KOH / g, 130 mg KOH / g to 140 mg KOH / g or 140 mg KOH / g to 150 mg KOH / g.

[0024] Salicylates can be calcium or magnesium salicylates. In some embodiments, the detergent system comprises a mixture of calcium salicylate and magnesium salicylate.

[0025] The presence of calcium salicylate can provide the lubricating oil composition with approximately 500 ppm to approximately 5000 ppm, such as approximately 500 ppm to approximately 4500 ppm, 500 ppm to 4000 ppm, 500 ppm to 3500 ppm, 500 ppm to 3000 ppm, 500 ppm to 2500 ppm, 500 ppm to 2000 ppm, 500 ppm to 1500 ppm, 500 ppm to 1000 ppm, 1000 ppm to 5000 ppm, 1000 ppm to 4500 ppm, 1000 ppm to 4000 ppm, 1000 ppm to 3500 ppm, 1000 ppm to 3000 ppm, 1000 ppm to 2500 ppm, 1000 ppm to 2000 ppm, 1000 ppm to 1500 ppm. ppm, 1500 ppm to 5000 ppm, 1500 ppm to 4500 ppm, 1500 ppm to 4000 ppm, 1500 ppm to 3500 ppm, 1500 ppm to 3000 ppm, 1500 ppm to 2500 ppm, 1500 ppm to 2000 ppm, 2000 ppm to 5000 ppm, 2500 ppm to 4500 ppm, 2500 ppm to 3500 ppm, 2500 ppm to 3000 ppm, 3000 ppm to 5000 ppm, 3000 ppm to 4500 ppm, 3000 ppm to 4000 ppm, 3000 ppm to 3500 ppm, 3500 ppm to 5000 ppm, 3500 ppm Calcium concentrations ranging from ppm to 4500 ppm, 3500 ppm to 4000 ppm, 4000 ppm to 5000 ppm, 4000 ppm to 4500 ppm, or 4500 ppm to 5000 ppm.

[0026] The presence of magnesium salicylate can provide the lubricating oil composition with approximately 500 ppm to approximately 5000 ppm, such as approximately 500 ppm to approximately 4500 ppm, 500 ppm to 4000 ppm, 500 ppm to 3500 ppm, 500 ppm to 3000 ppm, 500 ppm to 2500 ppm, 500 ppm to 2000 ppm, 500 ppm to 1500 ppm, 500 ppm to 1000 ppm, 1000 ppm to 5000 ppm, 1000 ppm to 4500 ppm, 1000 ppm to 4000 ppm, 1000 ppm to 3500 ppm, 1000 ppm to 3000 ppm, 1000 ppm to 2500 ppm, 1000 ppm to 2000 ppm, 1000 ppm to 1500 ppm. ppm, 1500 ppm to 5000 ppm, 1500 ppm to 4500 ppm, 1500 ppm to 4000 ppm, 1500 ppm to 3500 ppm, 1500 ppm to 3000 ppm, 1500 ppm to 2500 ppm, 1500 ppm to 2000 ppm, 2000 ppm to 5000 ppm, 2500 ppm to 4500 ppm, 2500 ppm to 3500 ppm, 2500 ppm to 3000 ppm, 3000 ppm to 5000 ppm, 3000 ppm to 4500 ppm, 3000 ppm to 4000 ppm, 3000 ppm to 3500 ppm, 3500 ppm to 5000 ppm, 3500 ppm Magnesium in the range of ppm to 4500 ppm, 3500 ppm to 4000 ppm, 4000 ppm to 5000 ppm, 4000 ppm to 4500 ppm, or 4500 ppm to 5000 ppm.

[0027] In some embodiments, the total amount of calcium salicylate and magnesium salicylate results in a total calcium and magnesium content in the lubricating oil composition of about 500 ppm to about 5000 ppm, such as about 500 ppm to about 4500 ppm, 500 ppm to 4000 ppm, 500 ppm to 3500 ppm, 500 ppm to 3000 ppm, 500 ppm to 2500 ppm, 500 ppm to 2000 ppm, 500 ppm to 1500 ppm, 500 ppm to 1000 ppm, 1000 ppm to 5000 ppm, 1000 ppm to 4500 ppm, 1000 ppm to 4000 ppm, 1000 ppm to 3500 ppm, 1000 ppm to 3000 ppm, 1000 ppm to 2500 ppm, 1000 ppm to 2000 ppm. ppm, 1000 ppm to 1500 ppm, 1500 ppm to 5000 ppm, 1500 ppm to 4500 ppm, 1500 ppm to 4000 ppm, 1500 ppm to 3500 ppm, 1500 ppm to 3000 ppm, 1500 ppm to 2500 ppm, 1500 ppm to 2000 ppm, 2000 ppm to 5000 ppm, 2500 ppm to 4500 ppm, 2500 ppm to 4000 ppm, 2500 ppm to 3500 ppm, 2500 ppm to 3000 ppm, 3000 ppm to 5000 ppm, 3000 ppm to 4500 ppm, 3000 ppm to 4000 ppm, 3000 ppm to 3500 ppm, 3500 ppm to 5000 ppm, 3500 ppm to 4500 ppm, 3500 ppm to 4000 ppm, 4000 ppm to 5000 ppm, 4000 ppm to 4500 ppm or 4500 ppm to 5000 ppm.

[0028] The ppm value is based on the total weight of the lubricating oil composition.

[0029] Generally, the total amount of Ca and Mg present in a lubricating oil composition is about 5000 ppm or less.

[0030] In one embodiment, the hydrocarbon-substituted salicylate is a long-chain alkyl salicylate represented by the following general formula: Where R” is a C1 to C30 (e.g., C13 to C30) alkyl group; n is an integer from 1 to 4; and M is an alkaline earth metal (e.g., Ca or Mg).

[0031] In one aspect of this disclosure, the salicylate is derived from a C10-C40 isomerized n-alpha olefin (NAO) and is prepared from an alkylphenol having an alkyl group derived from the isomerized NAO, the isomerized NAO having an isomerization level of (i) about 0.10 to about 0.40, about 0.10 to about 0.35, preferably about 0.10 to about 0.30, about 0.12 to about 0.30, about 0.12 to about 0.25, about 0.12 to about 0.23, about 0.12 to about 0.22, about 0.12 to about 0.20, about 0.13 to about 0.19, about 0.14 to about 0.18, or about 0.15 to about 0.17.

[0032] Succinimides The lubricating oil compositions of the present invention may optionally contain nitrogen-containing dispersants. These include polyolefin succinimide dispersants, such as those described herein. Generally, based on the lubricating oil composition, the nitrogen content in the nitrogen-containing dispersant is from about 0.010 wt% to about 0.30 wt%, such as from about 0.050 wt% to about 0.25 wt%, from about 0.050 wt% to about 0.20 wt%, and from about 0.050 wt% to about 0.15 wt%.

[0033] In one embodiment, the polyolefinic bis(succinimide) can be derived from a succinic anhydride by substituting the following polyolefinic groups: (Where R is a polyolefin substituent derived from a polyolefin group with a number average molecular weight of about 500 to about 3000) is obtained by reacting with a polyamine. In one embodiment, R is a polyolefin substituent derived from a polyolefin group with a number average molecular weight of about 1000 to about 2500. In one embodiment, R is a polyisobutylene substituent derived from polyisobutylene with a number average molecular weight of about 500 to about 3000. In another embodiment, R is a polyisobutylene substituent derived from polyisobutylene with a number average molecular weight of about 1000 to about 2500.

[0034] Suitable polyamines for preparing bissuccinimide dispersants include polyalkylene polyamines. These polyalkylene polyamines typically contain about 2 to about 12 nitrogen atoms and about 2 to 24 carbon atoms. Particularly suitable polyalkylene polyamines are those having the following formula: H₂N—(R´NH)x—H, where R´ is a straight-chain or branched alkylene group having 2 or 3 carbon atoms, and x is 1 to 9. Representative examples of suitable polyalkylene polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and heavy polyamines (e.g., ethyleneeneamine E-100, available from Huntsman Company).

[0035] Generally, polyalkenyl-substituted succinic anhydride is reacted with a polyamine at a temperature of about 130°C to about 220°C (e.g., 145°C to 175°C). The reaction can be carried out under an inert atmosphere, such as nitrogen or argon. Generally, a suitable molar charge ratio of polyamine to polyalkenyl-substituted succinic anhydride is about 0.35:1 to about 0.6:1 (e.g., 0.4:1 to 0.5:1). As used herein, “molar charge ratio of polyamine to polyalkenyl-substituted succinic anhydride” means the ratio of the number of moles of polyamine to the number of succinic acid groups in the succinic anhydride reactant.

[0036] A suitable class of polyolefinic succinimides can be represented by the following: Where R and R' are as described above and y is from 1 to 11.

[0037] Post-treatment of polyalkenyl succinimides In some implementations, the succinimide dispersant may be post-treated with a reactive boron compound or an organic carbonate.

[0038] Suitable boron compounds that can be used as boron sources include, for example, boric acid, borates, and borate esters. Representative examples of boric acid include orthoboric acid, metaboric acid, and p-boric acid. Representative examples of borates include ammonium borate, such as ammonium metaborate, ammonium tetraborate, ammonium pentaborate, and ammonium octaborate. Representative examples of borate esters include monomethyl borate, dimethyl borate, trimethyl borate, monoethyl borate, diethyl borate, triethyl borate, monopropyl borate, dipropyl borate, tripropyl borate, monobutyl borate, dibutyl borate, and tributyl borate.

[0039] Anti-wear agents The lubricating oil compositions disclosed herein may optionally contain one or more anti-wear agents. Anti-wear agents reduce wear on metal parts. Suitable anti-wear agents include dialkyl dithiophosphate metal salts, such as zinc dialkyl dithiophosphate (ZDDP) having the following structure: Zn[S–P(=S)(OR1)(OR2)]2 R1 and R2 can be the same or different hydrocarbon groups having 1 to 18 (e.g., 2 to 12) carbon atoms, and include groups such as alkyl, alkenyl, aryl, aralkyl, alkylaryl, and alicyclic groups. Particularly preferred groups as R1 and R2 are alkyl groups having 2 to 8 carbon atoms (e.g., alkyl groups can be ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl). To obtain oil solubility, the total number of carbon atoms (i.e., R1 + R2) should be at least 5. Therefore, dialkyl zinc dithiophosphate can contain dialkyl zinc dithiophosphate. Dialkyl zinc dithiophosphate is primary, secondary, or a combination thereof. ZDDP can be present at 3% by weight or less (e.g., 0.1% to 1.5% by weight, or 0.5% to 1.0% by weight) of the lubricating oil composition.

[0040] Antioxidants In one embodiment, the lubricating oil composition may optionally include an antioxidant compound. In one embodiment, the antioxidant is an aromatic amine antioxidant. Typical aromatic amine antioxidants have at least two aromatic groups directly attached to an amine nitrogen atom. Typical aromatic amine antioxidants have alkyl substituents containing at least six carbon atoms.

[0041] Examples of aromatic amine antioxidants that may be used herein include 4,4'-dioctyldiphenylamine, 4,4'-dinonyldiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, and N-(4-octylphenyl)-1-naphthylamine. The antioxidant may be present in 0.01 to 5% by weight (e.g., 0.1 to 2% by weight) of the said lubricating oil composition.

[0042] Lubricating oils A lubricating viscosity oil (sometimes referred to as a "base oil" or "base oil") is the main liquid component of a lubricant. Additives and possibly other oils are blended into the main liquid component, for example, to produce the final lubricant (or lubricant composition). The base oils that can be used to prepare concentrates and lubricant compositions thereof can be selected from natural (vegetable, animal, or mineral) lubricating oils and synthetic lubricating oils and mixtures thereof.

[0043] The oil used as the base oil is selected or blended according to the desired end use and the additives in the finished oil to obtain the desired grade of engine oil, such as a lubricant composition with a Society of Automotive Engineers (SAE) grade. In one embodiment, the lubricant composition is a multi-grade oil for heavy-duty vehicles or passenger cars. The multi-grade oil may have the following SAE viscosity grades: 0W-8, 0W-12, 0W-16, 0W-20, 0W-30, 0W-40, 0W-50, 0W-60, 5W, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W, 10W-20, 10W-30, 10W-40, 10W-50, 15W, 15W-20, 15W-30, or 15W-40.

[0044] The definitions of base oils and base oils in this disclosure are the same as those in Appendix E of American Petroleum Institute (API) Publication 1509 (“API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils,” December 2016). Using the test methods specified in Table E-1, Group I base oils contain less than 90% saturated hydrocarbons and / or more than 0.03% sulfur, and have a viscosity index greater than or equal to 80 and less than 120. Using the test methods specified in Table E-1, Group II base oils contain more than or equal to 90% saturated hydrocarbons and less than or equal to 0.03% sulfur, and have a viscosity index greater than or equal to 80 and less than 120. Using the test methods specified in Table E-1, Group III base oils contain more than or equal to 90% saturated hydrocarbons and less than or equal to 0.03% sulfur, and have a viscosity index greater than or equal to 120. Group IV base oils are polyalphaolefins (PAO). Category V base oils include all other base oils not included in Categories I, II, III, or IV.

[0045] Natural oils include animal fats, vegetable oils (e.g., castor oil and lard), and mineral oils. Animal and vegetable oils with good thermal oxidative stability can be used. Among natural oils, mineral oils are preferred. Mineral oils vary considerably regarding their crude oil source (e.g., whether they are alkanes, cycloalkanes, or a mixture of alkanes and cycloalkanes). Oils derived from coal or shale are also useful. Natural oils also vary regarding the methods used for their production and purification (e.g., their distillation range) and whether they are straight-run or cracked, hydrorefined, or solvent-extracted.

[0046] Synthetic oils include hydrocarbon oils. Hydrocarbon oils include oils such as polymerized and interpolymerized olefins (e.g., polybutene, polypropylene, propylene-isobutylene copolymers, ethylene-olefin copolymers, and ethylene-α-olefin copolymers). Polyalphaolefin (PAO) oil base stocks are commonly used synthetic hydrocarbon oils. For example, oils derived from C8 to C999 can be used. 14 Alkenes, such as C8, C6, and C7 olefins 10 C 12 C 14 PAO of olefins or mixtures thereof.

[0047] Other useful fluids used as base oils include non-conventional or unconventional base oils that have been processed (preferably catalytically processed) or synthesized to provide high-performance properties.

[0048] Unconventional or superconducting base oils / base oils include one or more of the following: mixtures of base oils derived from one or more natural gas liquefaction (GTL) materials; isomer / isodewaxate base oils derived from natural waxes or waxy feedstocks; mineral and / or non-mineral waxy feedstocks such as loose waxes; natural waxes and waxy feedstocks such as gas oils; waxy fuel hydrocracker bottom residues; waxy residues; hydrocracking products; thermal cracking products; or other mineral, mineral oil, or even non-petroleum-derived waxy materials such as waxy materials obtained from coal liquefaction or shale oil; and mixtures of such base oils. Other base oils include coal-to-liquids (CTL) products and alkylnaphthalenes.

[0049] The base oil used in the lubricating oil compositions of this disclosure is any kind of oil corresponding to API Group I, II, III, IV and V oils and mixtures thereof, preferably API Group II, III, IV and V oils and mixtures thereof, more preferably Group III to V base oils, because they have superior volatility, stability, viscosity and cleanliness characteristics.

[0050] The lubricating oil composition may have a high-temperature shear (HTHS) viscosity at 150°C of 3.7 cP or less, such as 3.6 cP or less, 3.5 cP or less, 3.4 cP or less, 3.3 cP or less, 3.2 cP or less, 3.1 cP or less, 3.0 cP or less, 2.9 cP or less, 2.8 cP or less, 2.7 cP or less, 2.6 cP or less, 2.5 cP or less, 2.4 cP or less, 2.3 cP or less, 2.2 cP or less, 2.1 cP or less, 2.0 cP or less, 1.9 cP or less, 1.8 cP or less, 1.7 cP or less, 1.6 cP or less, 1.5 cP or less, 1.4 cP or less, 1.3 cP or less, 1.2 cP or less, 1.1 cP or less, 1.0 cP or less. cP or less, 1.0 cP to 2.9 cP, 1.3 cP to 2.9 cP, 1.0 cP to 2.6 cP, 1.3 cP to 2.6 cP, 1.0 cP to 2.3 cP, 1.3 cP to 2.3 cP, 1.0 cP to 2.0 cP, 1.3 cP to 2.3 cP, 1.0 cP to 1.7 cP, or 1.3 cP to 1.7 cP.

[0051] The lubricating oil composition may have a viscosity index of at least 135 (e.g., 135 to 400, or 135 to 250), at least 150 (e.g., 150 to 400, or 150 to 250), at least 165 (e.g., 165 to 400, or 165 to 250), at least 190 (e.g., 190 to 400, or 190 to 250), or at least 200 (e.g., 200 to 400, or 200 to 250). If the viscosity index of the lubricating oil composition is less than 135, it may be difficult to improve fuel efficiency while maintaining the HTHS viscosity at 150°C. If the viscosity index of the lubricating oil composition exceeds 400, the evaporative properties may decrease, and defects may occur due to insufficient solubility of additives and inadequate compatibility with sealing materials.

[0052] The base oil has a kinematic viscosity (ASTM D445) of up to 1.4 mm at 100°C. 2 / s to 20 mm 2 / s, such as 3 mm 2 / s to 12 mm 2 / s, such as 3 mm 2 / s to 11 mm 2 / s, 3 mm 2 / s to 10 mm 2 / s, 3 mm 2 / s to 9 mm2 / s, 3 mm 2 / s to 8 mm 2 / s, 3 mm 2 / s to 7 mm 2 / s, 3 mm 2 / s to 6 mm 2 / s, 3 mm 2 / s to 5 mm 2 / s, 3 mm 2 / s to 4 mm 2 / s, 4 mm 2 / s to 12 mm 2 / s, 4 mm 2 / s to 11 mm 2 / s, 4 mm 2 / s to 10 mm 2 / s, 4 mm 2 / s to 9 mm 2 / s, 4 mm 2 / s to 8 mm 2 / s, 4 mm 2 / s to 7 mm 2 / s, 4 mm 2 / s to 6 mm 2 / s, 4 mm 2 / s to 5 mm 2 / s, 5 mm 2 / s to 12 mm[[ID=ID=56]] 2 / s, 5 mm 2 / s to 11 mm 2 / s, 5 mm 2 / s to 10 mm 2 / s, 5 mm 2 / s to 9 mm 2 / s, 5 mm 2 / s to 8 mm 2 / s, 5 mm 2 / s to 7 mm 2 / s, 5 mm 2 / s to 6 mm 2 / s, 6 mm 2 / s to 12 mm 2 / s, 6 mm 2 / s to 11 mm 2 / s, 6 mm 2 / s to 10 mm 2 / s, 6 mm 2 / s to 9 mm 2 / s, 6 mm 2 / s to 8 mm2 / s, 6 mm 2 / s to 7 mm 2 / s, 7 mm 2 / s to 12 mm 2 / s, 7mm 2 / s to 11 mm 2 / s, 7 mm 2 / s to 10 mm 2 / s, 7 mm 2 / s to 9 mm 2 / s, 7 mm 2 / s to 10 mm 2 / s, 7 mm 2 / s to 9mm 2 / s, 7 mm 2 / s to 8 mm 2 / s, 8 mm 2 / s to 12 mm 2 / s, 8 mm 2 / s to 11 mm 2 / s, 8 mm 2 / s to 10 mm 2 / s, 8mm 2 / s to 9 mm 2 / s, 9 mm 2 / s to 12 mm 2 / s, 9 mm 2 / s to 11 mm 2 / s, 9 mm 2 / s to 10 mm 2 / s, 10 mm 2 / s to 12 mm 2 / s, 10 mm 2 / s to 11 mm 2 / s or 11 mm 2 / s to 12 mm 2 within the range of / s.

[0053] In some embodiments, the lubricating oil composition contains 0.8 wt% to 1.5 wt%, such as 0.8 wt% to 1.4 wt%, 0.8 wt% to 1.3 wt%, 0.8 wt% to 1.2 wt%, 0.8 wt% to 1.1 wt%, 0.8 wt% to 1.0 wt%, 0.8 wt% to 0.9 wt%, 0.9 wt% to 1.5 wt%, 0.9 wt% to 1.4 wt%, 0.9 wt% to 1.3 wt%, 0.9 wt% to 1.2 wt%, 0.9 wt% to 1.1 wt%, 0.9 wt% to 1.0 wt%, 1.0 wt%. Ash content of 1.5 wt%, 1.0 wt% to 1.4 wt%, 1.0 wt% to 1.3 wt%, 1.0 wt% to 1.2 wt%, 1.0 wt% to 1.1 wt%, 1.1 wt% to 1.5 wt%, 1.1 wt% to 1.4 wt%, 1.1 wt% to 1.3 wt%, 1.1 wt% to 1.2 wt%, 1.2 wt% to 1.5 wt%, 1.2 wt% to 1.4 wt%, 1.2 wt% to 1.3 wt%, 1.3 wt% to 1.5 wt%, 1.3 wt% to 1.4 wt%, and 1.4 wt% to 1.5 wt%.

[0054] In some embodiments, the lubricating oil composition contains phosphorus at concentrations greater than 600 ppm, such as greater than 650 ppm, greater than 700 ppm, greater than 750 ppm, greater than 800 ppm, greater than 850 ppm, greater than 900 ppm, greater than 950 ppm, and greater than 1000 ppm.

[0055] Other additives The lubricating oil compositions of the present invention may also contain conventional lubricant additives for imparting auxiliary functions, to obtain finished lubricating oil compositions in which these additives are dispersed or dissolved. For example, the lubricating oil compositions may be blended with antioxidants, ashless dispersants, anti-wear agents, rust inhibitors, demisting agents, demulsifiers, friction modifiers, metal deactivators, pour point depressants, viscosity modifiers, defoamers, cosolvents, packaging compatibilizers, corrosion inhibitors, dyes, extreme pressure agents, and mixtures thereof. Many additives are known and commercially available. These additives or similar compounds may be used to prepare the lubricating oil compositions of the present invention through conventional blending procedures.

[0056] When used, each of the aforementioned additives is used in a functionally effective amount to impart the desired properties to the lubricant. Therefore, for example, if the additive is an ashless dispersant, the functionally effective amount of such an ashless dispersant will be sufficient to impart the desired dispersive properties to the lubricant. Generally, unless otherwise specified, when used, the concentration of each of these additives can range from about 0.001 wt% to about 20 wt%, such as from about 0.01 wt% to about 10 wt%.

[0057] The following non-limiting embodiments are illustrative of the invention. A brief description of how to prepare the embodiments is provided.

[0058] Example Baseline formulations All samples (Examples 1 to 7) comprised the following baseline formulation: SAE 10-30W viscosity grade heavy-duty vehicle diesel lubricant compositions prepared by blending the following components: a) A mixture of boronized and non-boronized succinimides b) Diphenylamine antioxidant c) A mixture of primary and secondary ZnDTP d) Detergent systems containing calcium sulfonate / magnesium sulfonate, calcium phenolate and / or calcium salicylate / magnesium salicylate The remainder of the lubricating oil composition includes a base oil, a viscosity index improver, and a pour point depressant. Each sample underwent a NOx conversion bench test as described below.

[0059] NOx conversion bench test This test measures the decrease in NOx conversion of an SCR catalyst after it has been contaminated with lubricating oil. Prior to the SCR test, the catalyst must be prepared, which involves collecting a solid vanadium EU6 catalyst stock, followed by crushing, filtering, hydrothermal aging, and impregnation / calcination of the material.

[0060] Once the catalyst material is pulverized and filtered, it is immersed in an oil sample and hot-filtered until the oil disappears. The oil-immersed catalyst is then calcined under a positive gas flow to remove hydrocarbons. SCR tests are conducted under typical diesel engine exhaust conditions (temperatures jump from 175°C to 550°C). More specifically, the SCR catalyst material is contacted with a simulated gas feed, which is a mixture of NO (500 ppm), NH3 (500 ppm), H2O (5%), O2 (10%), and the balance N2.

[0061] SCR was run at 10 different temperature steps (200℃, 220℃, 240℃, 260℃, 280℃, 300℃, 320℃, 350℃, 400℃, 500℃). The ATS conversion rate (NOx conversion efficiency) of the effluent was evaluated based on ICP analysis.

[0062] While lubricants with lower TBN may exhibit better ATS performance in certain situations, the trade-off is that lower TBN can lead to poorer detergency and make them unsuitable for engine lubrication. From a formulation perspective, careful balancing of TBN and ATS is crucial.

[0063] For the sake of brevity, this document only explicitly discloses certain ranges. However, a range starting from any lower limit can be combined with any upper limit to enumerate ranges not explicitly listed, and a range starting from any lower limit can be combined with any other lower limit to enumerate ranges not explicitly listed, just as a range starting from any upper limit can be combined with any other upper limit to enumerate ranges not explicitly listed. Furthermore, each point or individual value within a range is included, even if not explicitly listed. Therefore, each point or individual value can act as its own lower or upper limit to be combined with any other point or individual value or any other lower or upper limit to enumerate ranges not explicitly listed.

[0064] Similarly, the term "comprising" is considered synonymous with the term "including". Likewise, whenever a composition, element, or group of elements is preceded by the transitional phrase "comprising", it should be understood that we also consider the same composition or group of elements that is preceded by the transitional phrase "substantially composed of", "composed of", "selected from the group consisting of", or "is" before the description of the composition, element, or multiple elements, and vice versa.

[0065] As used herein, the terms “a / kind” and “described” should be understood to encompass both plural and singular forms.

[0066] Various terms have been defined above. If a term used in the claims is not defined above, it should be given the broadest definition that a person skilled in the art has given to that term, as reflected in at least one printed publication or granted patent. Furthermore, all patents, test procedures, and other documents cited in this application are incorporated in their entirety by reference to the extent that such disclosure does not conflict with this application and to all jurisdictions that permit such incorporation.

[0067] The foregoing description of this disclosure illustrates and describes the present disclosure. Furthermore, this disclosure shows and describes only preferred embodiments, but as mentioned above, it should be understood that this disclosure is applicable to various other combinations, modifications, and environments, and can be changed or modified within the scope of the concepts expressed herein, commensurate with the foregoing teachings and / or the technology or knowledge in related fields. While the foregoing is directed to embodiments of this disclosure, other and additional embodiments of this disclosure may be devised without departing from the essential scope of this disclosure, which is defined by the appended claims.

[0068] It should be understood that when combinations, subsets, groups, etc. of elements are disclosed (e.g., combinations of components in a composition, or combinations of steps in a method), each of these elements is specifically considered and described herein, although specific references to each of the various individual and collective combinations and arrangements of these elements may not be explicitly disclosed.

[0069] The embodiments described above are further intended to explain the known best mode of practice and to enable others skilled in the art to utilize this disclosure in such or other embodiments, as well as with various modifications required for a particular application or use. Therefore, this specification is not intended to limit it to the form disclosed herein. Furthermore, the appended claims are intended to be construed as including alternative embodiments.

Claims

1. A method for reducing catalyst poisoning in a diesel engine aftertreatment system including a selective catalytic reduction device, the method comprising: The engine is lubricated using a lubricating oil composition, the lubricating oil composition comprising: The main component is oil with lubricating viscosity; and Calcium salicylate or magnesium salicylate detergent; The lubricating oil composition therein does not contain calcium sulfonate detergent.

2. The method of claim 1, wherein the lubricating oil composition contains 500 ppm to 5000 ppm Ca from the calcium salicylate detergent.

3. The method of claim 1, wherein the lubricating oil composition contains 500 ppm to 5000 ppm of Mg from the magnesium salicylate detergent.

4. The method of claim 1, wherein the lubricating oil composition contains 0.8% to 1.5% by weight of ash.

5. The method of claim 1, wherein the lubricating oil composition contains more than 600 ppm of phosphorus.

6. The method of claim 1, wherein the lubricating oil composition contains 500 ppm to 5000 ppm of Ca and Mg.

7. The method of claim 1, wherein the lubricating oil composition contains 50 ppm or less of Ca or Mg derived from a sulfonate detergent.

8. The use of a lubricating oil composition for reducing catalyst poisoning in a diesel engine aftertreatment system including a selective catalytic reduction device, said lubricating oil composition comprising: The main quantity of oil with lubricating viscosity; and Calcium salicylate or magnesium salicylate detergent; The lubricating oil composition therein does not contain sulfonate detergents.

9. The use as claimed in claim 8, wherein the lubricating oil composition contains 500 ppm to 5000 ppm Ca from the calcium salicylate detergent.

10. The use as claimed in claim 8, wherein the lubricating oil composition contains 500 ppm to 5000 ppm Mg from the magnesium salicylate detergent.

11. The use as claimed in claim 8, wherein the lubricating oil composition contains 0.8% to 1.5% by weight of ash.

12. The use as claimed in claim 8, wherein the lubricating oil composition contains more than 600 ppm of phosphorus.

13. The use as claimed in claim 8, wherein the lubricating oil composition contains 500 ppm to 5000 ppm of Ca and Mg.

14. The use as claimed in claim 8, wherein the lubricating oil composition contains 50 ppm or less of Ca or Mg derived from a sulfonate detergent.

Images