Lubricating oil composition for stationary gas engines and method for its production and use

Abstract

This invention relates to the field of lubricating oil technology, and more particularly to a lubricating oil composition for stationary gas engines, its preparation method, and its application. The lubricating oil composition includes a base oil, a composite additive, and a friction modifier; the composite additive includes one or more of anti-wear agents, detergents, antioxidants, and dispersants; the friction modifier includes a mixture of an organic friction reducer and an organic molybdenum friction modifier, wherein the weight ratio of the organic friction reducer to the organic molybdenum friction modifier is 1:(1~5). The lubricating oil composition for stationary gas engines, its preparation method, and its application provided by this invention can achieve a stationary gas engine oil composition that balances good resistance to high-temperature oxidation, nitration, and friction and wear.

Description

Technical Field

[0001] This invention relates to the field of lubricating oil technology, and more particularly to lubricating oil compositions for stationary gas engines, their preparation methods, and applications. Background Technology

[0002] Stationary gas engines are characterized by large size, high power, long operating cycle, high combustion chamber temperature, difficult lubrication of gaseous fuels, complex gas sources, and high nitrogen oxide content in exhaust gas. Therefore, stationary gas engine oils are required to have suitable ash content and superior anti-wear, anti-oxidation, anti-nitrification, and dispersing properties.

[0003] There is still room for improvement in the existing stationary gas engine oils, especially in terms of anti-wear performance during start-stop cycles, which has not been significantly improved. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a lubricating oil composition for stationary gas engines, its preparation method, and its application, thereby achieving a stationary gas engine oil composition that balances good resistance to high-temperature oxidation, nitration, and friction and wear.

[0005] Based on this, the present invention has the following technical solution: In a first aspect, the present invention provides a lubricating oil composition comprising a base oil, a composite additive, and a friction modifier; the composite additive comprising one or more of an anti-wear agent, a detergent, an antioxidant, and a dispersant; the friction modifier comprising a mixture of an organic friction reducer and an organic molybdenum friction modifier; the weight ratio of the organic friction reducer to the organic molybdenum friction modifier being 1:(1~5).

[0006] The present invention has discovered that by introducing the organic friction reducer and the organic molybdenum friction modifier in the above-mentioned dosage relationship into the lubricating oil composition, it is possible to effectively ensure compatibility in the lubricating oil formulation while exhibiting excellent film-forming properties, reducing engine wear, and improving engine service life.

[0007] Preferably, the organic friction reducer includes one or more of butyl stearate, butyl oleate, ethylene glycol oleate, oleamide, hexadecylamine, and benzotriazole octadecammonium salt.

[0008] More preferably, the organic friction reducer includes one or more of INF C9440, INF C9433, Perfad 3000, Perfad 3050, Perfad 3057, Perfad 3006, Perfad FM 3336 and Amadol 511.

[0009] Preferably, the organic molybdenum friction modifier includes one or more of molybdenum dialkyldithiocarbamate, molybdenum dialkyldithiophosphate oxydimethylphosphite, and molybdenum dialkyldithiocarbamate sulfide.

[0010] More preferably, the organic molybdenum friction modifier includes S525 and / or POUPC1002.

[0011] The present invention has found that, compared with other friction modifiers in the field, the above-mentioned friction modifier has not only superior oil film carrying capacity and anti-wear performance, but also good anti-oxidation performance, making it particularly suitable for lubrication conditions with high temperature, high pressure and high load. Most importantly, it has a more significant effect on reducing the coefficient of friction. It can decompose during the friction process and form a low-friction molybdenum compound film on the metal surface. This film can not only reduce the friction between metals and improve the fuel economy of the engine, but also provide a certain degree of anti-wear protection.

[0012] Preferably, the friction modifier is present in the lubricating oil composition at a content of 1 to 5 wt%.

[0013] Preferably, the base oil includes Group IV base oil; preferably, the content of Group IV base oil is 3-30% based on the total mass of the base oil, more preferably 5-15%.

[0014] Preferably, the base oil comprises a combination of any of the following base oils: 1) A mixture of Group I and Group IV base oils; 2) A mixture of Group II and Group IV base oils; 3) A mixture of Group III and Group IV base oils; 4) Blends of Group I, Group II, and Group IV base oils; 5) Blends of Group I, Group III, and Group IV base oils; 6) Blends of Group II, Group III and Group IV base oils; 7) A mixture of Group I, Group II, Group III and Group IV base oils.

[0015] More preferably, the base oil includes a mixture of Group I base oil and Group IV base oil, a mixture of Group II base oil and Group IV base oil, or a mixture of Group I base oil, Group II base oil and Group IV base oil.

[0016] Preferably, the content of the composite additive is 7-15 wt% based on the total weight of the lubricating oil composition.

[0017] Preferably, based on the total weight of the composite additives, the content of the anti-wear agent is 7~15-3.7xwt%; and / or, based on the total weight of the composite additives, the content of the detergent is 14~19+xwt%; and / or, based on the total weight of the composite additives, the content of the antioxidant is 47~54+xwt%; and / or, based on the total weight of the composite additives, the content of the dispersant is 18~25+7.5xwt%; wherein, 0 < x < 0.5.

[0018] Preferably, the detergent comprises a mixture of a calcium-containing detergent and a magnesium-containing detergent; the mass ratio of the calcium-containing detergent to the magnesium-containing detergent is (1~2):(1~2).

[0019] More preferably, the magnesium-containing detergent comprises high-alkalinity magnesium sulfonate and / or high-alkalinity alkyl salicylate; the calcium-containing detergent comprises a mixture of high-alkalinity calcium sulfonate, medium-alkalinity alkylphenol calcium sulfide and low-alkalinity calcium sulfonate; and even more preferably, the mass ratio of the high-alkalinity calcium sulfonate, medium-alkalinity alkylphenol calcium sulfide and low-alkalinity calcium sulfonate is (2~3):1:1.

[0020] Preferably, the antioxidant comprises a mixture of a primary antioxidant and a secondary antioxidant; the primary antioxidant comprises a mixture of shielding phenols and aromatic amine antioxidants; the secondary antioxidant comprises zinc dialkyl dithiophosphate and / or molybdenum dialkyl dithiocarbamate; more preferably, the mass ratio of the primary antioxidant to the secondary antioxidant is (3~4):2.

[0021] Preferably, the dispersant comprises high molecular weight succinimide.

[0022] Preferably, the anti-wear agent comprises one or more of dialkyl zinc dithiophosphate, diisooctyl zinc dithiophosphate, and secondary alkyl zinc dithiophosphate.

[0023] In a second aspect, the present invention provides a method for preparing the lubricating oil composition, comprising: mixing the base oil, dispersant, antioxidant and detergent at 50-60°C to obtain a first mixture; and then mixing the first mixture, the friction modifier and anti-wear agent at 65-68°C to obtain a second mixture.

[0024] In a preferred embodiment of the present invention, the method for preparing the lubricating oil composition includes: The base oil is heated to 50-60°C, and then the dispersant, antioxidant and detergent are added sequentially at 50-60°C and mixed for 10-20 minutes. Then the friction modifier is added and mixed for 10-20 minutes. Finally, the anti-wear agent is added and mixed for 70-90 minutes.

[0025] Thirdly, the present invention provides the application of the lubricating oil composition in stationary gas engine oil.

[0026] The lubricating oil composition for stationary gas engines, its preparation method, and its application provided by this invention can achieve a stationary gas engine oil composition that balances good resistance to high-temperature oxidation, nitration, and friction and wear. Detailed Implementation

[0027] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0028] Unless otherwise specified, all raw materials used in the examples and comparative examples are commercially available conventional raw materials, and the technical means used are conventional means well known to those skilled in the art.

[0029] Example 1 This embodiment provides a stationary gas engine oil lubricating oil composition, SAE 40 1#, which is composed of the following components: Table 1

[0030] Among them, INF C9440 was purchased from Runyinglian, S525 was purchased from Sakura, and POUPC1002 was purchased from Pacific Union.

[0031] This embodiment further provides a method for preparing the above-mentioned stationary gas engine oil lubricating oil composition, including: Heat the base oil to 50-60℃, then add the dispersant, antioxidant and detergent sequentially at 50-60℃ and mix for 10-20 minutes; then add the friction modifier and mix for 10-20 minutes; finally add the anti-wear agent and mix for 70-90 minutes.

[0032] Example 2 This embodiment provides a stationary gas engine oil lubricating oil composition, SAE 40 2#, which is composed of the following components: Table 2

[0033] The Perfad FM 3336 was purchased from Holland, and the S525 was purchased from Sakura.

[0034] This embodiment further provides a method for preparing the above-mentioned stationary gas engine oil lubricating oil composition, which is the same as the preparation method in Example 1.

[0035] Example 3 This embodiment provides a stationary gas engine oil lubricating oil composition, SAE 40 3#, which is composed of the following components: Table 3

[0036] This embodiment further provides a method for preparing the above-mentioned stationary gas engine oil lubricating oil composition, which is the same as the preparation method in Example 1.

[0037] Among them, Perfad FM 3336 was purchased from Croda, INF C9440 was purchased from Infineum, and POUPC1002 was purchased from Pacific Union.

[0038] Comparative Example 1 This comparative example provides a stationary gas engine oil lubricant composition SAE 40 3#, which differs from Example 1 only in that the content of organic friction reducer (Perfad FM 3336) is 4% and the content of organic molybdenum friction modifier (S525) is 1%.

[0039] Comparative Example 2 Commercially available stationary gas engine oil, model SAE 40.

[0040] Test case 1. Physicochemical property comparison analysis: Currently, there is no globally unified standard for gas engine oils. The physicochemical properties were compared and analyzed using the enterprise standard Q / SH 3031 0655. The results are shown in Table 4.

[0041] Table 4

[0042] The method for testing friction and wear performance includes: testing the oils used in the examples and comparisons using an HFRR (High Frequency Reciprocating Friction and Wear Tester). The test conditions are: contact load 100g, stroke 2mm, reciprocating frequency 20Hz, temperature 50℃, and continuous test time 60min. Evaluation is based on the coefficient of friction and the average wear scar diameter.

[0043] Table 5 Anti-wear performance of comparative oil and example oil

[0044] As can be seen from Table 5, the friction coefficients and average wear scar diameters of Examples 1, 2, and 3 are all lower than those of the control oil. The friction coefficients are reduced by approximately 24.43%, 37.40%, and 21.38% respectively compared to the control oil; the average wear scar diameters are reduced by approximately 23.70%, 27.41%, and 19.26% respectively compared to the control oil. Their anti-wear performance is superior to that of ordinary commercially available stationary gas engine oils.

[0045] The method for testing the frictional performance during start-stop states includes: testing the oils used in the examples and comparisons using an MTM friction and wear testing machine. The experimental conditions are 36 N, a test speed range of 3~0.05 m / s, a slip-roll ratio (SRP) of 50%, and an experimental temperature of 50℃. The frictional performance under start-stop conditions is evaluated based on the friction coefficient simulation.

[0046] Table 6. Friction performance of the comparative oil and the example oil during start-stop.

[0047] As can be seen from Table 6, the coefficients of friction of Examples 1, 2 and 3 are all lower than those of the control oil, with reduction rates of 35.26%, 44.23% and 33.97% respectively. Their friction performance at start-stop moments is far superior to that of ordinary commercially available stationary gas engine oils.

[0048] The low-temperature friction performance testing method includes: using a rotational rheometer to conduct low-temperature friction tests on the example and control oils. The test conditions are: temperature 0℃ and -20℃, running time 15 min. The friction performance under low-temperature cold start conditions is simulated and evaluated based on the friction coefficient.

[0049] Table 7. Tribological properties of the comparative oil and the example at low temperatures.

[0050] As can be seen from Table 7, the friction coefficients of Examples 1, 2, and 3 at low temperatures are all lower than those of the control oil. At 0°C, the decrease rates of friction coefficients of the Examples compared to the control oil are 52.43%, 56.80%, and 49.03%, respectively; at -20°C, the decrease rates of friction coefficients of the Examples compared to the control oil are 55.08%, 59.38%, and 55.86%, respectively. The tribological performance at low temperatures is far superior to that of ordinary commercially available stationary gas engine oils.

[0051] The high-temperature oxidation test method for heat pipes includes: injecting test oil into a high-temperature heat pipe, which is then vertically inserted into a heating furnace at a temperature of 280℃±1℃. Compressed air is introduced from the bottom of the heat pipe at a flow rate of 10.0 cm³ / min, and the oil injection rate is 0.31 cm³ / h. The test lasts for 16 hours, allowing the test oil to form a varnish film or deposit on the inner wall of the glass heat pipe. After the test, the heat pipe is cooled for about 5 minutes, then cleaned with n-heptane or other suitable petroleum solvent until the solvent color no longer changes. Finally, it is placed in an oven at 105℃ for 1 hour to dry. After drying, it is weighed and rated.

[0052] Table 8 High-Temperature Antioxidant Performance of Comparative Oils and Examples

[0053] As can be seen from Table 8, the adhesive weights of Examples 2 and 3 are 64.13% and 56.24% lower than those of the comparative example, respectively, indicating excellent high-temperature oxidation resistance.

[0054] The coking plate test method includes: using the coking plate test to test the oil samples of the examples and the comparison oils, with intermittent test at 320℃±1℃ and 100℃ for 1 hour; and continuous test at 330℃ and 150℃ for 6 hours. After the test, the high-temperature detergency performance of the oil samples of the examples and the comparison oils is evaluated based on the changes in the shape, color and weight of the coking plates.

[0055] Table 9. High-Temperature Detergent Performance of Comparative Oils and Examples

[0056] As can be seen from the test results in Table 9, the adhesive weight results of Examples 1 and 2 under both intermittent and continuous conditions are far superior to those of the control oil, demonstrating excellent high-temperature detergency performance.

[0057] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A lubricating oil composition, characterized in that, It includes base oil, compound additives and friction modifiers; the compound additives include one or more of anti-wear agents, detergents, antioxidants and dispersants; the friction modifiers include a mixture of organic friction reducers and organic molybdenum friction modifiers, wherein the weight ratio of the organic friction reducer to the organic molybdenum friction modifier is 1:(1~5).

2. The lubricating oil composition according to claim 1, characterized in that, The organic friction reducer includes one or more of butyl stearate, butyl oleate, ethylene glycol oleate, oleamide, hexadecylamine, and benzotriazole octadecammonium salt.

3. The lubricating oil composition according to claim 1 or 2, characterized in that, The organic molybdenum friction modifier includes one or more of dialkyl dithiocarbamate, dialkyl dithiophosphate molybdenum oxyphosphate, and dialkyl dithiocarbamate sulfide.

4. The lubricating oil composition according to any one of claims 1 to 3, characterized in that, The friction modifier is present in the lubricating oil composition at a content of 1-5 wt%.

5. The lubricating oil composition according to any one of claims 1 to 4, characterized in that, The base oil includes Group IV base oil; preferably, based on the total mass of the base oil, the content of the Group IV base oil is 3-30%, more preferably 5-15%; Preferably, the base oil comprises a combination of any of the following base oils: 1) A mixture of Group I and Group IV base oils; 2) A mixture of Group II and Group IV base oils; 3) A mixture of Group III and Group IV base oils; 4) Blends of Group I, Group II, and Group IV base oils; 5) Blends of Group I, Group III, and Group IV base oils; 6) Blends of Group II, Group III and Group IV base oils; 7) Blends of Group I, Group II, Group III and Group IV base oils; More preferably, the base oil includes a mixture of Group I base oil and Group IV base oil, a mixture of Group II base oil and Group IV base oil, or a mixture of Group I base oil, Group II base oil and Group IV base oil.

6. The lubricating oil composition according to any one of claims 1 to 5, characterized in that, Based on the total weight of the lubricating oil composition, the content of the composite additive is 7-15 wt%; Preferably, based on the total weight of the composite additives, the content of the anti-wear agent is 7~15-3.7x wt%; and / or, based on the total weight of the composite additives, the content of the detergent is 14~19+x wt%; and / or, based on the total weight of the composite additives, the content of the antioxidant is 47~54+x wt%; and / or, based on the total weight of the composite additives, the content of the dispersant is 18~25+7.5x wt%; wherein, 0 < x < 0.

5.

7. The lubricating oil composition according to any one of claims 1 to 6, characterized in that, The cleaning agent comprises a mixture of a calcium-containing cleaning agent and a magnesium-containing cleaning agent; the mass ratio of the calcium-containing cleaning agent to the magnesium-containing cleaning agent is (1~2):(1~2); Preferably, the magnesium-containing detergent comprises high-alkalinity magnesium sulfonate and / or high-alkalinity alkyl salicylate; the calcium-containing detergent comprises a mixture of high-alkalinity calcium sulfonate, medium-alkalinity alkylphenol calcium sulfide, and low-alkalinity calcium sulfonate; more preferably, the mass ratio of the high-alkalinity calcium sulfonate, medium-alkalinity alkylphenol calcium sulfide, and low-alkalinity calcium sulfonate is (2~3):1:

1.

8. The lubricating oil composition according to any one of claims 1 to 7, characterized in that, in, The antioxidant comprises a mixture of primary antioxidant and secondary antioxidant; the primary antioxidant comprises a mixture of shielding phenols and aromatic amine antioxidants; the secondary antioxidant comprises zinc dialkyl dithiophosphate and / or molybdenum dialkyl dithiocarbamate; preferably, the mass ratio of the primary antioxidant to the secondary antioxidant is (3~4):2; And / or, the dispersant includes a high molecular weight succinimide; And / or, the anti-wear agent comprises one or more of dialkyl zinc dithiophosphate, diisooctyl zinc dithiophosphate, and secondary alkyl zinc dithiophosphate.

9. A method for preparing the lubricating oil composition according to any one of claims 1 to 8, characterized in that, include: The base oil, dispersant, antioxidant, and detergent are mixed at 50-60°C to obtain a first mixture; The first mixture, the friction modifier, and the anti-wear agent are then mixed at 65-68°C to obtain a second mixture.

10. The use of the lubricating oil composition according to any one of claims 1 to 8 or the lubricating oil composition prepared by the preparation method according to claim 9 in stationary gas engine oil.

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