Lubricating oil composition, method for producing the same, marine engine lubricating oil, and use thereof

Abstract

The present application relates to the technical field of lubricating oil, and provides a lubricating oil composition, a preparation method thereof, a marine engine lubricating oil and application thereof.The lubricating oil composition comprises, in parts by weight, 1-5 parts of a detergent, 1-5 parts of an antioxidant, 0.01-1 parts of an extreme pressure and antiwear agent, 0.01-2 parts of a metal deactivator and 81.5-96.98 parts of base oil; the antioxidant is at least one selected from zinc dithiophosphate, an amine antioxidant and a phenolic antioxidant; and the metal deactivator is at least one selected from benzotriazole derivatives, thiadiazole derivatives and heterocyclic compounds.The present application selects suitable additive types and compositions, and uses the same as marine engine oil to meet the working condition requirements of ammonia fuel engines, and the product has excellent oxidation resistance, wear resistance and corrosion resistance.

Description

Technical Field

[0001] This invention relates to the field of lubricating oil technology, and more specifically to lubricating oil compositions and their preparation methods, marine engine lubricating oils and their applications. Background Technology

[0002] Due to its zero-carbon properties, ammonia is poised to become an alternative fuel for the shipping industry, prompting engine manufacturers to dedicate themselves to developing new ammonia-fueled engines.

[0003] Ammonia is corrosive and can corrode some metals. Ammonia gas readily combines with water vapor to form ammonia water, which can form complex ions with many metal ions, making the metals more susceptible to oxidation and corrosion by oxygen in the air. Ammonia gas in the engine combustion chamber leaks through the gap between the cylinder liner and piston rings, dissolving in the lubricating oil and affecting its quality and lubrication performance. Simultaneously, ammonia antagonizes the use of zinc dialkyl dithiophosphate (ZDDP), a commonly used extreme pressure anti-wear agent in engine oils, causing ZDDP to become ineffective and thus affecting the oil's antioxidant and anti-wear properties.

[0004] Therefore, ammonia has significant differences in physicochemical properties compared to traditional fuels. Traditional engine oils are not well-suited for ammonia fuels, and there are currently no lubricating oils specifically designed for ammonia-fueled engines. Summary of the Invention

[0005] This invention provides a lubricating oil composition, which selects appropriate types and compositions of additives, and is used as a marine engine oil to meet the operating conditions of ammonia fuel engines. The product has excellent anti-oxidation, anti-wear, and anti-corrosion properties.

[0006] This invention provides a lubricating oil composition, comprising, by weight: 1-5 parts detergent; 1-5 parts dispersant; 1-5 parts antioxidant; 0.01-1 part anti-wear agent; 0.01-2 parts metal deactivator; and 81.5-96.98 parts base oil. The metal deactivator includes at least one of benzotriazole derivatives, thiadiazole derivatives, and heterocyclic compounds. The antioxidant includes at least one of amine antioxidants and phenolic antioxidants.

[0007] By optimizing the types and proportions of oil detergents, dispersants, antioxidants, anti-wear agents, and metal deactivators, an engine oil composition with superior overall performance is provided. Through examples and comparative examples, it is found that this composition has excellent antioxidant, anti-wear, and anti-corrosion properties, meeting the operating conditions of ammonia-fueled marine engines.

[0008] As a specific embodiment of the present invention, the metal deactivator is preferably at least one of T551, T553, T561, and T571.

[0009] As a specific embodiment of the present invention, the antioxidant is preferably at least one of T534, T557, and T508.

[0010] As a specific embodiment of the present invention, the detergent is at least one selected from sulfonates, sulfide alkylphenol salts, and salicylates, preferably at least one selected from T105, T106, T109, and T122.

[0011] The extreme pressure anti-wear agent includes at least one of ammonium phosphate salt, phosphate ester, and zinc dithiophosphate, preferably at least one of T204, T323, PA24, and PY438.

[0012] The base oil is either a Group I or Group II base oil.

[0013] The lubricating oil composition further includes 0.01 to 0.5 parts of an antifoaming agent, preferably selected from methyl silicone oil antifoaming agents.

[0014] The present invention also provides a method for preparing lubricating oil: raw material components containing detergent, antioxidant, dispersant, extreme pressure anti-wear agent, metal deactivator, antifoaming agent and base oil are mixed at 50°C to 80°C for 0.5 to 3 hours to obtain the lubricating oil composition.

[0015] As a preferred embodiment of the present invention, the raw material components containing base oil, detergent, dispersant, antioxidant, anti-wear agent and metal deactivator are mixed at 50°C to 80°C for 0.5 to 2 hours, then an antifoaming agent is added, and the mixture is mixed for another 0.5 to 2 hours to obtain the lubricating oil composition.

[0016] As a specific embodiment of the present invention, detergent, dispersant, antioxidant, anti-wear agent and metal deactivator are added to base oil, heated to 60°C, stirred at a rate of 500 rpm for 1 hour, and after being mixed evenly, antifoaming agent is added, and stirring is continued for 1 hour to obtain the lubricating oil composition.

[0017] The present invention also provides marine engine lubricating oil containing any of the above-described lubricating oil compositions.

[0018] This invention also provides the application of marine engine lubricating oil for ammonia-fueled marine engines.

[0019] The beneficial effects of the lubricating oil composition obtained by the present invention are as follows:

[0020] (1) Excellent water separation performance, which can maintain good performance in water-containing environments;

[0021] (2) Excellent antioxidant and anti-wear properties, avoiding the negative impact of ammonia on additive ZDDP, giving the oil excellent antioxidant and anti-wear properties.

[0022] (3) Excellent corrosion resistance, which can protect the engine from the corrosion of metal by ammonia. Detailed Implementation

[0023] The technical solution of the present invention will be further described below with reference to specific embodiments. The scope of protection of the present invention is not limited to the following embodiments; these examples are provided for illustrative purposes only and do not limit the present invention in any way.

[0024] Example 1

[0025] Component ratio of lubricating oil suitable for ammonia-fueled marine engines:

[0026] Detergent: 0.6 parts high-alkalinity synthetic calcium sulfonate T106, 0.6 parts high-alkalinity alkylphenol calcium sulfide T122;

[0027] Antioxidant: 1 part alkyl diphenylamine T534, 0.4 parts phenolic ester antioxidant T508;

[0028] Extrusion anti-wear agent: 0.5 parts thiocarbamate T323, 0.5 parts ammonium phosphate salt PY438;

[0029] Metal deactivator: 0.1 parts of thiadiazole derivative T561;

[0030] Base oil: 95.3 parts of Group I base oil.

[0031] Preparation method: Add detergent, dispersant, antioxidant, anti-wear agent and metal deactivator to base oil, heat to 60°C, stir at 500 rpm for 1 hour, add antifoaming agent T901 after uniform mixing, and continue stirring for 1 hour to obtain the lubricating oil composition suitable for ammonia fuel marine engines.

[0032] Example 2

[0033] Component ratio of lubricating oil suitable for ammonia-fueled marine engines:

[0034] Detergent: 0.8 parts medium-alkalinity synthetic calcium sulfonate T105, 0.8 parts high-alkalinity alkylphenol calcium sulfide T122;

[0035] Antioxidant: 1 part alkyl diphenylamine T534;

[0036] Extrusion anti-wear agent: 1 part thiocarbamate T323;

[0037] Metal deactivator: 0.1 parts heterocyclic derivative T553;

[0038] Base oil: Group I base oil 96.3 parts.

[0039] Preparation method: Add detergent, dispersant, antioxidant, anti-wear agent and metal deactivator to base oil, heat to 60°C, stir at 500 rpm for 1 hour, add antifoaming agent T901 after uniform mixing, and continue stirring for 1 hour to obtain a lubricating oil composition suitable for ammonia fuel marine engines.

[0040] Example 3

[0041] Component ratio of lubricating oil suitable for ammonia-fueled marine engines:

[0042] Detergent: 0.8 parts high-alkalinity calcium salicylate T109, 0.8 parts high-alkalinity alkylphenol calcium sulfide T122;

[0043] Antioxidant: 1.4 parts octylbutyldiphenylamine T557;

[0044] Extrusion anti-wear agent: 1 part phosphate ester PA24;

[0045] Metal deactivator: 0.1 parts of benzotriazole derivative T551;

[0046] Base oil: 95.5 parts of Group II base oil.

[0047] Preparation method: Add detergent, dispersant, antioxidant, anti-wear agent and metal deactivator to base oil, heat to 60°C, stir at 500 rpm for 1 hour, add antifoaming agent T901 after uniform mixing, and continue stirring for 1 hour to obtain a lubricating oil composition suitable for ammonia fuel marine engines.

[0048] Example 4

[0049] Component ratio of lubricating oil suitable for ammonia-fueled marine engines:

[0050] Detergent: 0.3 parts high-alkalinity synthetic calcium sulfonate T106, 0.3 parts high-alkalinity alkylphenol calcium sulfide T122;

[0051] Antioxidant: 1 part alkyl diphenylamine T534, 0.4 parts octylbutyl diphenylamine T557;

[0052] Extrusion anti-wear agent: 1 part ammonium phosphate salt PY438;

[0053] Metal deactivator: 0.1 parts heterocyclic derivative T571;

[0054] Base oil: Group I base oil 96.9 parts.

[0055] Preparation method: Add detergent, dispersant, antioxidant, anti-wear agent and metal deactivator to base oil, heat to 60°C, stir at 500 rpm for 1 hour, add antifoaming agent T901 after uniform mixing, and continue stirring for 1 hour to obtain a lubricating oil composition suitable for ammonia fuel marine engines.

[0056] Example 5

[0057] Component ratio of lubricating oil suitable for ammonia-fueled marine engines:

[0058] Detergent: 0.8 parts high-alkalinity synthetic calcium sulfonate T106, 0.4 parts high-alkalinity alkylphenol calcium sulfide T122;

[0059] Antioxidant: 0.4 parts octylbutyldiphenylamine T557, 1 part phenolic ester antioxidant T508;

[0060] Extrusion anti-wear agent: 0.5 parts primary / secondary alkyl dithiophosphate zinc T204, 0.5 parts thiocarbamate T323;

[0061] Metal deactivator: 0.1 parts heterocyclic derivative T553;

[0062] Base oil: Group II base oil 96.3 parts.

[0063] Preparation method: Add detergent, dispersant, antioxidant, anti-wear agent and metal deactivator to base oil, heat to 60°C, stir at 500 rpm for 1 hour, add antifoaming agent T901 after uniform mixing, and continue stirring for 1 hour to obtain a lubricating oil composition suitable for ammonia fuel marine engines.

[0064] Comparative Example 1

[0065] Lubricating oil composition ratio:

[0066] Detergent: 1 part high-alkalinity alkylphenol calcium sulfide T122;

[0067] Antioxidant: 1 part alkyl diphenylamine T534, 0.4 parts phenolic ester antioxidant T508;

[0068] Extrusion anti-wear agent: 1 part primary / secondary alkyl dithiophosphate zinc T204;

[0069] Metal deactivator: 0.1 parts of benzotriazole derivative T551;

[0070] Base oil: 96.5 parts of Group I base oil.

[0071] Preparation method: Add detergent, dispersant, antioxidant, anti-wear agent and metal deactivator to base oil, heat to 60°C, stir at 500 rpm for 1 hour, add antifoaming agent T901 after mixing evenly, and continue stirring for 1 hour to obtain lubricating oil composition.

[0072] Comparative Example 2

[0073] Lubricating oil composition ratio:

[0074] Detergent: 1 part high-alkalinity synthetic calcium sulfonate T106;

[0075] Antioxidant: 0.4 parts octylbutyldiphenylamine T557;

[0076] Extrusion anti-wear agent: 1 part thiocarbamate T323;

[0077] Base oil: Group II base oil 97.6 parts.

[0078] Preparation method: Add detergent, dispersant, antioxidant, anti-wear agent and metal deactivator to base oil, heat to 60°C, stir at 500 rpm for 1 hour, add antifoaming agent T901 after mixing evenly, and continue stirring for 1 hour to obtain lubricating oil composition.

[0079] Comparative Example 3

[0080] Lubricating oil composition ratio:

[0081] Detergent: 0.6 parts high-alkalinity synthetic calcium sulfonate T106, 0.6 parts high-alkalinity alkylphenol calcium sulfide T122;

[0082] Antioxidant: 1 part alkyl diphenylamine T534, 0.4 parts phenolic ester antioxidant T508;

[0083] Extrusion anti-wear agent: 1 part phosphate ester PA24;

[0084] Base oil: Group II base oil 96.4 parts.

[0085] Preparation method: Add detergent, dispersant, antioxidant, anti-wear agent and metal deactivator to base oil, heat to 60°C, stir at 500 rpm for 1 hour, add antifoaming agent T901 after mixing evenly, and continue stirring for 1 hour to obtain lubricating oil composition.

[0086] Comparative Example 4

[0087] Lubricating oil composition ratio:

[0088] Detergent: 0.8 parts medium-alkalinity synthetic calcium sulfonate T105, 0.8 parts high-alkalinity alkylphenol calcium sulfide T122;

[0089] Antioxidant: 1 part octylbutyldiphenylamine T557, 0.4 parts phenolic ester antioxidant T508;

[0090] Extrusion anti-wear agent: 0.5 parts thiocarbamate T323, 0.5 parts ammonium phosphate salt PY438;

[0091] Base oil: 96 parts of Group I base oil.

[0092] Preparation method: Add detergent, dispersant, antioxidant, anti-wear agent and metal deactivator to base oil, heat to 60°C, stir at 500 rpm for 1 hour, add antifoaming agent T901 after mixing evenly, and continue stirring for 1 hour to obtain lubricating oil composition.

[0093] Table 1. Composition of Lubricating Oil Composition

[0094]

[0095] The lubricating oil compositions in the examples and comparative examples were subjected to water separation tests using the marine oil-water separation test method (SH / T 0619-1995). The results are listed in Table 2.

[0096] Table 2. Results of water separation tests for the examples and comparative examples.

[0097]

[0098] The lubricating oil compositions of the examples and comparative examples were incorporated with 1% by mass of ammonia water to conduct antioxidant tests on the oils in an ammonia-containing environment. The results are listed in Table 3.

[0099] Table 3. Antioxidant performance of the examples and comparative examples in an ammonia-containing environment.

[0100] Example number Oxidation induction period (200℃, min) Example 1 48 Example 2 18 Example 3 28 Example 4 32 Example 5 28 Comparative Example 1 42 Comparative Example 2 16 Comparative Example 3 41 Comparative Example 4 22

[0101] The lubricating oil compositions of the examples and comparative examples were mixed with 1% by mass of ammonia water, and the anti-wear properties of the oils in an ammonia-containing environment were tested. The test method was: determination of lubricant load-carrying capacity - four-ball method (GB / T3142-2019). The steel balls used in the method were pre-soaked in the ammonia-containing oil at room temperature for 24 hours, and the results are listed in Table 4.

[0102] Table 4. Wear resistance of the examples and comparative examples in an ammonia-containing environment.

[0103]

[0104]

[0105] The lubricating oil compositions of the examples and comparative examples were mixed with 1% by mass of ammonia water, and the corrosion resistance of the oils in an ammonia-containing environment was tested. The test method was the copper strip corrosion method for petroleum products (GB / T 5096-2017), and the results are listed in Table 5.

[0106] Table 5. Corrosion resistance of the examples and comparative examples in an ammonia-containing environment.

[0107] Example number Copper sheet rating Example 1 1b Example 2 1b Example 3 1b Example 4 1b Example 5 1b Comparative Example 1 1b Comparative Example 2 4b Comparative Example 3 4b Comparative Example 4 4b

[0108] Water ingress and emulsification in marine engine oil can lead to a decline in oil performance. Therefore, the oil must possess excellent water separation properties. A water separation test can verify the oil's water separation ability; the more water layer and the less emulsion layer in the test, the better the water separation performance. The polar groups of detergents in additives can adversely affect the water separation performance of the oil. The water separation performance of lubricating oil is closely related to the type and ratio of detergents.

[0109] Engine operating conditions require engine oils to have excellent anti-oxidation and anti-wear properties. The anti-wear and anti-oxidation properties of the oils are tested by the four-ball test and the oxidation induction period test, respectively. The higher the maximum non-seize load and sintering load in the four-ball test, the better the anti-wear performance. The longer the oxidation induction period, the better the anti-oxidation performance.

[0110] Ammonia exhibits significant corrosion to metals, especially copper. The corrosion resistance of oils is evaluated using the copper strip corrosion test; the higher the copper strip rating, the more pronounced the corrosion.

[0111] Data from Examples 1, 2, 3, and 5 show that, among the lubricating oil compositions of the present invention, Example 1 exhibits better water separation performance. The use of high-alkalinity synthetic calcium sulfonate T106 and high-alkalinity sulfurized alkylphenol calcium T122 in combination can improve the water separation performance of the oil while maintaining its cleaning properties.

[0112] Data from Examples 1 and 3 and Comparative Examples 3 and 4 show that, in the lubricating oil composition of the present invention, Example 1 has better water separation performance, while PA24 has poor water separation performance.

[0113] Data from Examples 1, 2, 4, 5 and Comparative Examples 1, 3 show that the T534 and T508 compound system in the lubricating oil composition of the present invention has better antioxidant properties.

[0114] Data from Examples 1-5 and Comparative Examples 1 and 4 show that in the lubricating oil composition of the present invention, the combination of extrusion anti-wear agents T323 and PY438 has better extreme pressure anti-wear performance, while ZDDP will fail in an ammonia-containing environment.

[0115] Data from Examples 1-5 and Comparative Examples 1-4 show that in the lubricating oil composition of the present invention, the metal deactivator can reduce the corrosion of copper sheets by ammonia and improve the corrosion resistance of the oil. Currently commercially available products cannot effectively resist the corrosion of metals by ammonia.

[0116] Data from Examples 1 and Comparative Examples 1 and 4 show that in the lubricating oil composition of the present invention, the metal deactivator and antioxidant have a synergistic effect, which can effectively improve the antioxidant performance of the oil.

[0117] Data from Examples 1-5 and Comparative Examples 1-4 show that, in the lubricating oil compositions of the present invention, the base oil does not have a significant impact on the oil performance.

Claims

1. A lubricating oil composition, comprising, by weight: 1-5 parts cleaning agent; Antioxidant 1-5 parts; Extreme pressure anti-wear agent 0.01 to 1 part; Metal deactivating agent 0.01-2 parts; Base oil 81.5–96.98 parts; The antioxidant is selected from at least one of zinc dithiophosphate, amine antioxidant, and phenolic antioxidant. The metal deactivator is selected from at least one of benzotriazole derivatives, thiadiazole derivatives, and heterocyclic compounds.

2. The lubricating oil composition according to claim 1, characterized in that, The detergent is selected from at least one of sulfonates, sulfide alkylphenol salts, and salicylates.

3. The lubricating oil composition according to claim 1, characterized in that, The extreme pressure anti-wear agent is selected from at least one of zinc dithiophosphate, ammonium phosphate, and phosphate.

4. The lubricating oil composition according to claim 1, characterized in that, The base oil is selected from at least one of HVI Group I base oil or HVI Group II base oil.

5. The lubricating oil composition according to claim 1, characterized in that, The lubricating oil composition also includes 0.01 to 0.5 parts of an antifoaming agent.

6. The lubricating oil composition according to claim 5, characterized in that, The antifoaming agent is selected from methyl silicone oil antifoaming agents.

7. A method for preparing the lubricating oil composition according to any one of claims 1-6, characterized in that, The raw material components containing detergents, antioxidants, dispersants, extreme pressure anti-wear agents, metal deactivators, antifoaming agents and base oils are mixed at 50°C to 80°C for 0.5 to 3 hours to obtain the lubricating oil composition.

8. The preparation method according to claim 7, characterized in that, The raw material components containing detergent, antioxidant, dispersant, extreme pressure anti-wear agent, metal deactivator, antifoaming agent and base oil are mixed at 50℃~80℃ for 0.5~2 hours, and then the antifoaming agent is added and the mixture is mixed for another 0.5~2 hours to obtain the lubricating oil composition.

9. A marine engine lubricating oil, characterized in that it contains the lubricating oil composition according to any one of claims 1-6.

10. The application of the marine engine lubricating oil according to claim 9, characterized in that, Used in ammonia-fueled marine engines.

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