Preparation method of long-life extreme pressure anti-wear ship engine oil

Abstract

The invention discloses a preparation method of long-life extreme pressure anti-wear ship engine oil. The preparation method comprises the following steps: S1, stirring at least one of 150SN base oil and 500N base oil and 150BS base oil for 1-2 hours at normal pressure and at the temperature of 60-80 DEG C; s2, esterified modified graphene oxide and an organic molybdenum multifunctional anti-wear agent are dissolved and diluted with dipentaerythritol ester, a diluted mixed solution is added after stirring in the step S1 is completed, and stirring continues to be conducted for 1-2 h; s3, after stirring in the step S2 is completed, a diesel engine oil complexing agent, high-base-number calcium alkyl salicylate, a polyether amine purification dispersant and polymethacrylate are sequentially added, stirring continues to be conducted in the environment at the normal pressure and the temperature of 50-60 DEG C till the mixture is uniform and transparent, and the additive is obtained. The prepared marine engine oil is good in cleaning and dispersing performance and high in abrasion resistance, in-cylinder abrasion of a marine engine in a long-time working stroke can be effectively reduced, the engine oil burning phenomenon of a diesel engine is reduced, and the oil change period and the service life of the marine diesel engine are prolonged.

Description

Technical Field

[0001] The invention relates to the technical field of engine oils, and in particular to a long-life extreme pressure and anti-wear ship engine oil and a preparation method thereof. Background Art

[0002] With the continuous development of global trade, the scale of the shipping industry continues to expand, driving the steady growth of the market demand for ship engine oil. According to a report by QYResearch, during the period 2019-2024, the global market for high-speed marine engine lubricants showed a good development trend, with key indicators such as production capacity, output, and sales increasing.

[0003] With the continuous advancement of ship engine technology, the performance indicators of engines such as power and speed are constantly improving, and the performance requirements for engine oil are becoming increasingly stringent. Lubricant companies have begun to develop and produce oils with better antioxidant, anti-wear and clean dispersibility to adapt to the high-load operation and harsh working environment of the engine. In recent years, the international community has paid more and more attention to environmental protection, and ship emission regulations have become increasingly stringent, which has had a profound impact on the development of ship engine oil. In order to meet the requirements of low-sulfur emissions, the sulfur content of ship fuel oil has gradually decreased. Accordingly, ship engine oil also needs to adjust the formula, reduce the base number to adapt to low-sulfur fuel, and at the same time improve the cleaning performance, reduce the formation of sediments, and prevent clogging of exhaust gas treatment devices.

[0004] At present, the following problems are common in marine engine oil: Insufficient oxidation resistance: The working environment of ship engines is harsh and the oil temperature is high. During long-term operation, if the engine oil has poor oxidation resistance, oxidation reactions are likely to occur. This will cause the oil to deteriorate and generate sludge and paint film. For example, sludge will clog the oil filter and oil channel, causing poor oil circulation and affecting the normal lubrication and heat dissipation of the engine; paint film will adhere to the surface of components such as pistons and valves, affecting their normal operation and reducing the efficiency of the engine.

[0005] Anti-wear performance needs to be improved: The piston, crankshaft and other moving parts of the ship engine will produce severe friction when running under high load. If the anti-wear performance of the engine oil is not good enough, it cannot form an effective lubricating film on the surface of these parts, which will easily cause part wear. The dimensional accuracy of the worn parts will decrease, which will lead to a decrease in the power output of the engine, an increase in fuel consumption, and even cause engine failure.

[0006] Limited cleanliness and dispersibility: Various impurities are generated during the operation of ship engines, such as carbon deposits from combustion, metal wear particles, etc. Engine oil needs to disperse these impurities in the oil to prevent them from gathering and settling. However, the cleanliness and dispersibility of some engine oils are limited. When impurities gather to a certain extent, they will form deposits inside the engine, such as carbon deposits in the piston ring groove, causing the piston ring to get stuck, affecting the sealing of the engine, and thus reducing the power of the engine.

[0007] In the future, ship engines will develop towards higher power, lower fuel consumption and greater reliability, which requires ship engine oil to have higher performance. For example, improving the anti-oxidation stability of the oil to extend the oil change cycle; enhancing the anti-wear performance to reduce the wear of engine parts and improve the reliability and service life of the engine; optimizing the detergency and dispersibility to keep the engine clean and reduce maintenance costs.

[0008] Extending the service life of ship engine oil has become one of the main trends in the development of ship engine oil. This requires the engine oil to have excellent antioxidant properties and be able to resist oil aging and deterioration caused by high temperature, oxygen and other factors during long-term use. Base oil quality: Long-life ship engine oil usually uses high-quality base oil. The methods to improve the service life of ship engine oil mainly include improving base oil and additives. Synthetic base oil has more stable performance and stronger antioxidant ability. It is an ideal base oil component for long-life engine oil. However, some ship operating companies still choose traditional engine oil due to price concerns or distrust of new technologies. Therefore, the screening and development of traditional ship engine oil additives to extend the service life of ship engine oil still has huge market potential.

[0009] Usually, the way to improve the lubrication efficiency of engine oil and reduce engine wear is mainly to add anti-wear additives. Anti-wear agents are classified according to typical elements, mainly sulfur anti-wear agents, phosphorus anti-wear agents, boron anti-wear agents, halogen anti-wear agents and organic metal anti-wear agents. A single anti-wear additive is difficult to meet the complex equipment working conditions, and multiple additives need to be compounded and used. The use of multiple additives must take into account both the effect and compatibility issues. With the increase in the amount of anti-wear composite additives, while improving the anti-wear properties, it often causes the anti-corrosion and anti-emulsification properties of the anti-wear engine oil to decrease and increase the tendency of carbon deposits to form. Therefore, the amount of anti-wear additives used in hydraulic oil is controlled within a certain range, which limits the method of further improving the anti-wear effect of engine oil.

[0010] Organic molybdenum anti-wear agents and graphene additives are commonly used anti-wear additives for engine oils. They can form a chemical adsorption film on the friction surface, repair the wear of the friction surface, effectively reduce wear, and extend the service life of the equipment. However, traditional organic molybdenum anti-wear agents are mostly acidic anti-wear agents. During long-term use, they react with alkaline additives in engine oils, such as petroleum calcium sulfonates, to produce sludge. Graphene anti-wear additives disperse solid graphene or modified graphene in base oil. During the application process, graphene or modified graphene is physically adsorbed on the surface of the equipment to play a role in reducing wear and resisting wear. However, graphene dispersions are unstable dispersion systems. As the amount of addition increases, graphene will agglomerate and settle, which will also cause sludge formation. Therefore, the use of both additives in base oils is limited. Summary of the invention

[0011] In order to overcome the deficiencies of the prior art, the object of the present invention is to provide a method for preparing a long-life extreme pressure and anti-wear marine engine oil, so as to prepare a marine engine oil with high cleanliness and high anti-wear properties.

[0012] The technical solution adopted by the present invention is as follows: A method for preparing a long-life extreme pressure and anti-wear marine engine oil comprises the following steps: S1. Stir at least one of 150SN base oil and 500N base oil and 150BS base oil at 60-80° C. under normal pressure for 1-2 hours; S2, dissolving and diluting the esterified modified graphene oxide and the organic molybdenum multifunctional anti-wear agent using dipentaerythritol ester, adding the diluted mixed solution after the stirring in step S1 is completed, and continuing to stir for 1-2 hours; S3, after the stirring in step S2 is completed, add diesel engine oil compound, high base value alkyl calcium salicylate, polyether amine detergent dispersant, and polymethacrylate in sequence, and continue stirring at normal pressure and temperature of 50-60°C until the mixture is uniform and transparent; The raw material components in the above steps are: 0-100 parts of 150SN base oil, 0-100 parts of 500N base oil, wherein the above single base oil or mixed base oil is 90-100 parts; 10-50 parts of 150BS base oil, 0.05-0.5 parts of esterified modified graphene oxide, 1-5 parts of dipentaerythritol ester, 0.05-0.5 parts of organic molybdenum multifunctional antiwear agent, 1-4 parts of diesel engine oil compound, 0.05-2 parts of high base number alkyl calcium salicylate, 0.05-0.5 parts of polyetheramine detergent dispersant, and 0.05-0.50 parts of polymethacrylate.

[0013] As a preferred embodiment of the present invention, the preparation of the organic molybdenum multifunctional anti-wear agent includes the following steps: using butyl acrylate as a raw material, polymerizing it through RAFT, and then capping it with ethanolamine for esterification. The esterified capped butyl acrylate and molybdenum trioxide are subjected to a catalytic reaction in an environment where N,N-dimethylformamide, xylene solvent and hydrazine hydrate are present to obtain the product.

[0014] As a preferred embodiment of the present invention, the preparation of the esterified modified graphene oxide includes the following steps: using graphene oxide and butanol as raw materials and p-toluenesulfonic acid as a catalyst for esterification reaction, and after the reaction is completed, adding ester base oil and stirring and mixing to obtain.

[0015] As a preferred embodiment of the present invention, the dipentaerythritol ester is dipentaerythritol oleate or dipentaerythritol isostearate.

[0016] Beneficial effects of the present invention: The present invention uses the organic molybdenum multifunctional anti-wear agent and esterified modified graphene oxide independently developed by the company, wherein the organic molybdenum multifunctional anti-wear agent itself has good anti-wear and cleaning and dispersing effects, which can enhance the anti-wear performance while reducing the generation of sludge. The esterified modified graphene oxide also has a good anti-wear effect and good oil solubility, and can be evenly and stably dispersed in the base oil to reduce agglomeration and precipitation. The present invention can obtain a ship engine oil with high cleanliness and high anti-friction properties by combining the above-mentioned organic molybdenum multifunctional anti-wear agent and esterified modified graphene oxide according to certain conditions and proportions.

[0017] The organic molybdenum multifunctional anti-wear agent and the esterified modified graphene oxide are dispersed in the dipentaerythritol ester. The two can form a stable dispersion by synergistic cooperation, reduce agglomeration and sedimentation, and then further compound the high-performance polyetheramine detergent dispersant, which can reduce the generation of engine oil sludge and carbon deposition to a greater extent, extend the oil change cycle of the engine oil, and reduce maintenance costs. Traditional organic molybdenum anti-wear agents and graphene anti-wear additives will generate sludge after long-term use, and because the traditional graphene anti-wear additives have poor dispersion stability in the base oil and are easy to agglomerate, if the product obtained by combining these two traditional materials is selected, the sludge generation may be aggravated. The present invention uses the self-developed organic molybdenum multifunctional anti-wear agent and esterified modified graphene oxide. The two materials are further compounded on the basis of their own good performance, which can achieve a synergistic effect, further improve the anti-wear and friction reduction performance of the product, and reduce the sludge generation.

[0018] In addition, the present invention can form a physical-chemical adsorption film on the surface of the equipment when the organic molybdenum multifunctional anti-wear agent and the esterified modified graphene oxide are used in conjunction, which can not only repair small scratches on the friction surface, but also repair larger wear marks on the friction surface. While reducing equipment wear, it can increase the airtightness between the engine piston and the cylinder closure, reduce the problems of blowby and oil burning in old engines, reduce the engine operating oil temperature, and achieve the purpose of extending the service life of the engine. DETAILED DESCRIPTION

[0019] Typical embodiments that embody the features and advantages of the present invention will be described in detail in the following description. It should be understood that the present invention can have various changes in different embodiments without departing from the scope of the present invention, and the descriptions and illustrations therein are essentially used for illustration purposes rather than for limiting the present invention.

[0020] The diesel engine oil compound used in the following examples is RF6066 diesel engine oil compound purchased from the market, produced by Xinxiang Ruifeng New Materials Co., Ltd.

[0021] High base number calcium alkyl salicylate (T109D) was purchased from the market and produced by Xinxiang Ruifeng New Materials Co., Ltd.

[0022] Polymethacrylate (PMA) was purchased from the market and produced by Xinxiang Ruifeng New Materials Co., Ltd.

[0023] The polyetheramine detergent dispersant (FL-1000) was purchased from the market and produced by Xinxiang Ruifeng New Materials Co., Ltd. The organic molybdenum multifunctional anti-wear agent was independently developed by the company. The preparation of the organic molybdenum multifunctional anti-wear agent includes the following steps: butyl acrylate is used as a raw material for RAFT polymerization, and then esterification and capping are performed with ethanolamine. The esterified capped butyl acrylate and molybdenum trioxide are catalyzed in the presence of N,N-dimethylformamide, xylene solvent and hydrazine hydrate to obtain the product.

[0024] The esterified modified graphene oxide is independently developed by the company. The preparation of the esterified modified graphene oxide includes the following steps: using graphene oxide and butanol as raw materials and p-toluenesulfonic acid as a catalyst to carry out an esterification reaction, and after the reaction is completed, adding an ester base oil and stirring and mixing to obtain the product.

[0025] Example 1 This embodiment discloses a method for preparing a long-life extreme pressure and anti-wear marine engine oil, comprising the following steps: S1. Add 55 parts of 150SN base oil, 40 parts of 500N base oil and 40 parts of 150BS base oil into a stirring kettle and stir for 2 hours at 60°C under normal pressure.

[0026] S2. 0.2 parts of esterified modified graphene oxide and 0.2 parts of organic molybdenum multifunctional anti-wear agent were mixed and diluted with 2 parts of dipentaerythritol isostearate, and then put into a stirring tank and continued to stir for 2 hours.

[0027] S3. After the stirring in step S2 is completed, 4 parts of RF6066 diesel engine oil compound, 0.8 parts of high base value alkyl calcium salicylate (T109D), 0.3 parts of polyetheramine detergent dispersant (FL-1000), and 0.05 parts of polymethacrylate (PMA) are added in sequence, and the mixture is stirred at 50-60°C under normal pressure until the mixture is uniform and transparent.

[0028] Example 2 This embodiment discloses a method for preparing a long-life extreme pressure and anti-wear marine engine oil, comprising the following steps: S1. Put 45 parts of 150SN base oil, 55 parts of 500N base oil and 35 parts of 150BS base oil into a stirring kettle and stir for 2 hours at 60°C under normal pressure.

[0029] S2. 0.1 part of esterified modified graphene oxide and 0.3 part of organic molybdenum multifunctional anti-wear agent are mixed and diluted with 1 part of dipentaerythritol oleate, and then put into a stirring tank and continue stirring for 2 hours.

[0030] S3. After the stirring in step S2 is completed, 4 parts of RF6066 diesel engine oil compound, 1.5 parts of high base value alkyl calcium salicylate (T109D), 0.5 parts of polyetheramine detergent dispersant (FL-1000), and 0.2 parts of polymethacrylate (PMA) are added in sequence, and the mixture is stirred at 50-60°C under normal pressure until the mixture is uniform and transparent.

[0031] Example 3 This embodiment discloses a method for preparing a long-life extreme pressure and anti-wear marine engine oil, comprising the following steps: S1. Add 90 parts of 150SN base oil and 15 parts of 150BS base oil into a stirring kettle and stir for 2 hours at 60°C under normal pressure.

[0032] S2. 0.05 parts of esterified modified graphene oxide and 0.05 parts of organic molybdenum multifunctional anti-wear agent were mixed and diluted with 1 part of dipentaerythritol isostearate, and then put into a stirring tank and continued to stir for 2 hours.

[0033] S3. After the stirring in step S2 is completed, 1 part of RF6066 diesel engine oil compound, 0.1 part of high base value alkyl calcium salicylate (T109D), 0.1 part of polyether amine detergent dispersant (FL-1000), and 0.15 part of polymethacrylate (PMA) are added in sequence, and the mixture is stirred at 50-60°C under normal pressure until the mixture is uniform and transparent.

[0034] Example 4 This embodiment discloses a method for preparing a long-life extreme pressure and anti-wear marine engine oil, comprising the following steps: S1. Add 95 parts of 500N base oil and 48 parts of 150BS base oil into a stirring kettle and stir for 2 hours at 60°C under normal pressure.

[0035] S2. 0.15 parts of esterified modified graphene oxide and 0.25 parts of organic molybdenum multifunctional anti-wear agent were mixed and diluted with 1.5 parts of dipentaerythritol oleate, and then put into a stirring tank and continued to stir for 2 hours.

[0036] S3. After the stirring in step S2 is completed, 3.5 parts of RF6066 diesel engine oil compound, 2 parts of high base value alkyl calcium salicylate (T109D), 0.35 parts of polyetheramine detergent dispersant (FL-1000), and 0.45 parts of polymethacrylate (PMA) are added in sequence, and the mixture is stirred at 50-60°C under normal pressure until the mixture is uniform and transparent.

[0037] Example 5 This embodiment discloses a method for preparing a long-life extreme pressure and anti-wear marine engine oil, comprising the following steps: S1. Put 100 parts of 150SN base oil and 48 parts of 150BS base oil into a stirring kettle and stir for 2 hours at 60°C under normal pressure.

[0038] S2. 0.45 parts of esterified modified graphene oxide and 0.5 parts of organic molybdenum multifunctional anti-wear agent were mixed and diluted with 5 parts of dipentaerythritol oleate, and then put into a stirring tank and continued to stir for 2 hours.

[0039] S3. After the stirring in step S2 is completed, 3 parts of RF6066 diesel engine oil compound, 1.5 parts of high base value alkyl calcium salicylate (T109D), 0.5 parts of polyetheramine detergent dispersant (FL-1000), and 0.5 parts of polymethacrylate (PMA) are added in sequence, and the mixture is stirred at 50-60°C under normal pressure until the mixture is uniform and transparent.

[0040] Performance Testing The main indexes of the marine engine oils prepared in Examples 1-5 were tested, and the results are shown in Table 1. The kinematic viscosity at different temperatures in Table 1 was measured according to the method of "Method for Determination of Kinematic Viscosity of Petroleum Products and Calculation of Dynamic Viscosity": GB / T 265; the viscosity index was measured according to the method of "Method for Calculation of Petroleum Viscosity Index": GB / T 1995; the base number (TBN) was measured according to the "Petrochemical Industry Standard": SH / T 0251; the low temperature dynamic viscosity was measured according to the "Determination of Apparent Viscosity of Engine Oil": GB / T 6538; the high temperature and high shear viscosity was measured according to the "Petrochemical Industry Standard": SH / T 0703; the flash point (opening) and pour point were measured according to the method of "Determination of Pour Point of Petroleum Products": GB / T3535; the water content was measured according to the method of "Determination of Water Content of Petroleum Products by Distillation": GB / T 260; the mechanical impurities were measured according to the method of "Determination of Mechanical Impurities in Petroleum, Petroleum Products and Additives": GB / T The friction coefficient is measured according to the Petrochemical Industry Standard: SH / T0762-2005 method; the wear spot diameter is measured according to the Petrochemical Industry Standard: NB / SH / T 0189-2017 method.

[0041] Table 1

[0042] The above-mentioned embodiments are only preferred embodiments of the present invention and cannot be used to limit the scope of protection of the present invention. Any non-substantial changes and substitutions made by technicians in this field on the basis of the present invention shall fall within the scope of protection required by the present invention.

Claims

1. A method for preparing a long-life extreme pressure and anti-wear marine engine oil, characterized in that: The following steps are involved: S1. Stir at least one of 150SN base oil and 500N base oil and 150BS base oil at 60-80° C. under normal pressure for 1-2 hours; S2, dissolving and diluting the esterified modified graphene oxide and the organic molybdenum multifunctional anti-wear agent using dipentaerythritol ester, adding the diluted mixed solution after the stirring in step S1 is completed, and continuing to stir for 1-2 hours; S3, after the stirring in step S2 is completed, add diesel engine oil compound, high base value alkyl calcium salicylate, polyether amine detergent dispersant, and polymethacrylate in sequence, and continue stirring at normal pressure and temperature of 50-60°C until the mixture is uniform and transparent; The raw material components in the above steps are: 0-100 parts of 150SN base oil and 0-100 parts of 500N base oil, wherein the above single base oil or mixed base oil is 90-100 parts; 150BS base oil 10-50 parts, esterified modified graphene oxide 0.05-0.5 parts, dipentaerythritol ester 1-5 parts, organic molybdenum multifunctional antiwear agent 0.05-0.5 parts, diesel engine oil compound 1-4 parts, high base number alkyl calcium salicylate 0.05-2 parts, polyether amine detergent dispersant 0.05-0.5 parts, polymethacrylate 0.05-0.50 parts.

2. The preparation method according to claim 1, characterized in that: The preparation of the organic molybdenum multifunctional anti-wear agent comprises the following steps: taking butyl acrylate as a raw material, polymerizing it through RAFT, and then capping it with ethanolamine for esterification; and catalyzing the reaction of the capped butyl acrylate and molybdenum trioxide in an environment with N,N-dimethylformamide, xylene solvent and hydrazine hydrate to obtain the organic molybdenum multifunctional anti-wear agent.

3. The preparation method according to claim 1, characterized in that: The preparation of the esterified modified graphene oxide comprises the following steps: using graphene oxide and butanol as raw materials and using p-toluenesulfonic acid as a catalyst to carry out an esterification reaction, and after the reaction is completed, adding an ester base oil and stirring and mixing to obtain the esterified modified graphene oxide.

4. The preparation method according to claim 1, characterized in that: The dipentaerythritol ester is dipentaerythritol oleate or dipentaerythritol isostearate.

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