High speed diesel engine oil composition, method of making and marine diesel engine oil

Abstract

The present application relates to the field of lubricating oil technology, and provides a high-speed diesel engine oil composition, a preparation method thereof and a marine diesel engine oil, which comprises components: base oil, detergent, dispersant, antioxidant, viscosity index improver, pour point depressant and antifoaming agent; the detergent is composed of calcium sulfonate and calcium sulfide alkyl phenol; the calcium sulfonate is composed of high-alkali-value calcium sulfonate and low-alkali-value calcium sulfonate, and the mass ratio of the high-alkali-value calcium sulfonate to the low-alkali-value calcium sulfonate is 1:1-2; the mass ratio of the medium-alkali-value calcium sulfide alkyl phenol to the high-alkali-value calcium sulfide alkyl phenol is 1:1.5-2.5.The marine high-speed diesel engine oil composition has better detergency and dispersibility, and can meet the working conditions of the marine high-speed diesel engine with poor quality fuel.

Description

Technical Field

[0001] This invention relates to the field of lubricating oil technology, and more specifically, to marine high-speed diesel engine oil compositions, preparation methods thereof, and marine diesel engine oils. Background Technology

[0002] High-speed marine diesel engines typically operate at speeds exceeding 1000 rpm and can be used as main engines on fishing vessels. High-speed engine oil is used for crankcase and cylinder lubrication, and can lubricate all major moving parts and seals of the diesel engine.

[0003] Marine high-speed engine oil circulates within the engine and must cope with the poor combustion conditions caused by the inconsistent quality of fuel used on fishing vessels, reducing the formation of deposits on engine parts. Therefore, improved detergency and dispersancy are particularly necessary. Fishing vessels generally use diesel fuel, but to save costs, in some remote or underdeveloped areas abroad, fishing vessels use substandard diesel fuel or fuel mixed with heavy residue oil, resulting in significantly higher sulfur content than diesel. The combustion of such fuel produces more sludge and deposits; therefore, this places higher demands on the detergency and dispersancy of engine oils.

[0004] Chinese invention patent application CN201510680031.0 discloses the use of a CF-4 grade diesel engine oil composition, which comprises, by weight percentage: 1-10 parts detergent; 1-15 parts dispersant; 1-10 parts antioxidant; 0-20 parts thickener; 0.03-2 parts pour point depressant; 0.01-1 part antifoaming agent; and 50-88 parts base oil. It provides a new use for this diesel engine oil composition in a light diesel / natural gas dual-fuel four-stroke marine high-speed engine. However, this diesel engine oil composition is only intended for use in light diesel / natural gas dual-fuel high-speed engines with relatively good fuel quality. There is room for further optimization of the detergent performance of marine high-speed diesel engine oils formulated with additives and base oils.

[0005] Chinese invention patent application CN202011058717.3 discloses a diesel engine oil compound and its preparation method. The compound contains 30-60% ashless succinimide dispersant, 19-34% metal detergent, 6-17% antioxidant, 5-19% zinc dialkyl dithiophosphate, and 0-2% friction modifier. It provides a method for preparing a CH-4 and CI-4 diesel engine oil composition to improve the oxidation resistance, wear resistance, and high-temperature detergency of diesel engine oil. However, this composition does not take into account the detergency and dispersancy performance of diesel engine oil under complex fuel conditions (e.g., light diesel oil mixed with heavy fuel oil). Summary of the Invention

[0006] The purpose of this invention is to provide a marine high-speed diesel engine oil composition, its preparation method, and the marine diesel engine oil, so as to improve its detergency and dispersancy performance and solve the technical problem that the detergency performance of existing high-speed diesel engine oils used on fishing vessels needs to be further improved.

[0007] To achieve the above objectives, in a first aspect, the present invention provides a diesel engine oil composition comprising: a base oil, a detergent, a dispersant, an antioxidant, a viscosity index modifier, a pour point depressant, and an antifoaming agent; wherein the detergent is composed of calcium sulfonate (preferably synthetic calcium sulfonate) and calcium alkylphenolate sulfide; wherein the calcium sulfonate is composed of high-base-value calcium sulfonate and low-base-value calcium sulfonate, the high-base-value calcium sulfonate having a base value ≥300 mgKOH / g; and the low-base-value calcium sulfonate having a base value of 10–30 mgKOH / g; wherein the calcium alkylphenolate sulfide… It is composed of medium-alkalinity alkylphenol calcium sulfide and high-alkalinity alkylphenol calcium sulfide. The medium-alkalinity alkylphenol calcium sulfide has an alkalinity greater than or equal to 145 mg KOH / g and less than 245 mg KOH / g; the high-alkalinity alkylphenol calcium sulfide has an alkalinity range of ≥245 mg KOH / g; the mass ratio of high-alkalinity synthetic calcium sulfonate to low-alkalinity synthetic calcium sulfonate is 1:0.8-1.5; the mass ratio of medium-alkalinity alkylphenol calcium sulfide to high-alkalinity alkylphenol calcium sulfide is 1:1.5-2.5.

[0008] According to some embodiments of the present invention, the diesel engine oil composition comprises, by weight, 70-85 parts base oil; 3-8 parts detergent; 5-10 parts dispersant; 2-5 parts antioxidant; and 5-10 parts viscosity index agent.

[0009] According to some embodiments of the present invention, in the diesel engine oil composition, the base oil accounts for 70-85 wt% by mass, the detergent accounts for 3-8 wt% by mass, the dispersant accounts for 5-10 wt% by mass, the antioxidant accounts for 2-5 wt% by mass, the viscosity index agent accounts for 5-10 wt% by mass, and the pour point depressant accounts for 0.1-1.0 wt% by mass.

[0010] According to some embodiments of the present invention, the mass ratio of the synthesized calcium sulfonate to calcium alkylphenol sulfide can be 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, etc.

[0011] According to some embodiments of the present invention, the detergent accounts for 3 to 7 wt% by mass.

[0012] According to some embodiments of the present invention, the dispersant accounts for 5 to 9 wt% by mass.

[0013] According to some embodiments of the present invention, the antioxidant accounts for 2 to 4 wt% of the mass.

[0014] According to some embodiments of the present invention, the dispersant includes at least one of high molecular weight succinimide and monoalkenyl succinimide, wherein the molecular weight of the high molecular weight succinimide is 2200 to 2700.

[0015] According to some embodiments of the present invention, the dispersant comprises monoalkenyl succinimide.

[0016] According to some embodiments of the present invention, the antioxidant includes at least one of zinc diisooctyl dithiophosphate, diphenylamine ashless antioxidant, phenolic ester antioxidant, and thioether-type hindered phenol.

[0017] According to some embodiments of the present invention, the base oil includes at least one of Group I base oil and Group II base oil.

[0018] Secondly, the present invention provides a method for preparing the above-mentioned diesel engine oil composition, comprising the steps of: mixing and stirring the components at 55-60°C to obtain the diesel engine oil composition.

[0019] Thirdly, the present invention provides a marine diesel engine oil containing the diesel engine oil composition described in the first aspect, including base oil, detergents, dispersants, antioxidants, viscosity index depressants, pour point depressants, and antifoaming agents, etc., that is, providing the application of the diesel engine oil composition in marine high-speed engines, which can improve the detergency of marine high-speed diesel engine oil and is suitable for marine engine operating conditions using poor quality fuel.

[0020] The beneficial effects of the present invention are at least as follows: the marine high-speed diesel engine oil provided by the present invention has superior detergency and dispersancy properties, which can meet the usage requirements of marine high-speed diesel engines with poor fuel quality. Detailed Implementation

[0021] To make the technical problem to be solved, the technical solution, and the beneficial effects of this invention clearer, the invention will be further described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are merely for illustrating this patent and do not limit the scope of protection of this invention in any way.

[0022] Unless otherwise defined, the technical terms used in the following embodiments have the same meaning as commonly understood by those skilled in the art. Unless otherwise specified, the reagents used in the following embodiments are conventional biochemical reagents; the raw materials, instruments, and equipment used in the following embodiments can all be obtained commercially or by existing methods; unless otherwise specified, the reagent dosages are those used in routine experimental operations; unless otherwise specified, the experimental methods are conventional methods.

[0023] In the embodiments and comparative examples of this invention, the sources of raw materials used to prepare the lubricating oil are as follows:

[0024] Cleaning agent:

[0025] High-base-value synthetic calcium sulfonate T106B, base value 316, was purchased from Wuxi Southern Petroleum Additives Co., Ltd.

[0026] Low-base-value synthetic calcium sulfonate T104B, base value 25, was purchased from Wuxi Southern Petroleum Additives Co., Ltd.

[0027] High-base-value alkylphenol calcium S206, base value 255, purchased from Wuxi Southern Petroleum Additives Co., Ltd.

[0028] Medium-alkalinity alkylphenol calcium sulfide T121, alkalinity 150, purchased from Wuxi Southern Petroleum Additives Co., Ltd.

[0029] Dispersant:

[0030] High molecular weight succinimide T161 was purchased from Wuxi Southern Petroleum Additives Co., Ltd.

[0031] Monoalkenyl succinimide T151 was purchased from Wuxi Southern Petroleum Additives Co., Ltd.

[0032] Antioxidants:

[0033] Zinc diisooctyl dithiophosphate T203 was purchased from Wuxi Southern Petroleum Additives Co., Ltd.

[0034] Diphenylamine ashless antioxidant T534, purchased from Beijing Xingpu;

[0035] Phenolic ester antioxidant T512, purchased from Shanghai Qike;

[0036] Thioether-type hindered phenol T535, purchased from Shanghai Qike;

[0037] Group II base oil III-6, purchased from Sinopec;

[0038] Group I base oil 150BS, purchased from Sinopec.

[0039] The fuel oil is a mixture of high-sulfur heavy fuel oil (sulfur content 3.0%) and light diesel oil (0# diesel), both purchased from Sinopec.

[0040] Marine high-speed diesel engine oils for each example and comparative example were prepared according to the formulations shown in Table 1 (parts by weight).

[0041] The alkalinity determination method follows SH / T 0251, using a perchloric acid-glacial acetic acid standard titration solution for potentiometric titration, with the endpoint being the point of potential jump in the titration curve. Alkalinity indirectly reflects the content of detergent-dispersant in the oil and is an important control indicator for marine engine oils.

[0042] Table 1

[0043]

[0044] Examples 1-8

[0045] Preparation process: According to the component ratio in Table 1, the detergent, dispersant, antioxidant, pour point depressant, viscosity index depressant, antifoaming agent and base oil are mixed to obtain a mixture. The mixture is stirred at 60°C for 1 hour until it is completely homogeneous, and the marine high-speed diesel engine oil composition is obtained.

[0046] Comparative Examples 1-5

[0047] Preparation process: According to the component ratio in Table 1, the detergent, dispersant, antioxidant, pour point depressant, viscosity index depressant, antifoaming agent and base oil are mixed to obtain a mixture. The mixture is stirred at 60°C for 1 hour until it is completely homogeneous, and the diesel engine oil composition is obtained.

[0048] Test case

[0049] The performance of the diesel engine oil compositions of each embodiment and comparative example was tested, and the test results are shown in Table 2. The methods are as follows:

[0050] (1) High-temperature detergency: Crankcase simulation test method SH / T 0300, the coke weight of the test aluminum plate surface is measured. The smaller the coke weight, the better the high-temperature detergency performance.

[0051] (2) High-temperature cleaning performance: Komatsu heat pipe SH / T 0906-2015 method, by continuously circulating the oil in the high-temperature heat pipe, the final cleaning performance of the heat pipe is evaluated. The higher the score, the better the high-temperature cleaning performance of the oil.

[0052] (3) Dispersibility: Soot dispersion was investigated by oil spot dispersion test according to ASTM D7899 method. The dispersibility value characterizes the uniformity of distribution of black soot particles in the oil spot throughout the spot. The larger the value, the better the dispersibility and the more uniform the dispersion. The ideal value is 100.

[0053] Table 2

[0054]

[0055] Oil change interval refers to the time from when the customer's engine oil is changed to the end of its service life. According to the national standard GB / T7607-2010, the iron content exceeds 150ppm.

[0056] The above test results show that the marine high-speed diesel engine oil composition provided by the present invention improves the detergency and dispersancy of the product by using a combination of synthetic calcium sulfonate and calcium sulfide, making the product better able to meet the operating conditions of marine high-speed diesel engines with poor fuel quality (light diesel mixed with high-sulfur heavy fuel oil).

[0057] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A diesel engine oil composition characterized in that, The components include base oil, detergent, dispersant, antioxidant, viscosity index improver, pour point depressant, and antifoam agent; The detergent is composed of calcium sulfonate and calcium sulfide alkyl phenol; The calcium sulfonate is composed of high base number calcium sulfonate and low base number calcium sulfonate, the base number of the high base number calcium sulfonate is ≥300mgKOH / g; The base number of the low base number calcium sulfonate is 10-30mgKOH / g; The calcium sulfide alkyl phenol is composed of medium base number calcium sulfide alkyl phenol and high base number calcium sulfide alkyl phenol, the base number of the medium base number calcium sulfide alkyl phenol is ≥145mgKOH / g and <245mgKOH / g, and the base number of the high base number calcium sulfide alkyl phenol is ≥245mgKOH / g; The mass ratio of the high base number calcium sulfonate to the low base number calcium sulfonate is 1:1-2; The mass ratio of the medium base number calcium sulfide alkyl phenol to the high base number calcium sulfide alkyl phenol is 1:1.5-2.

5.

2. The diesel oil composition according to claim 1, wherein the components of the diesel oil composition include, by weight: 70-85 parts of base oil; 3-8 parts of detergent; 5-10 parts of dispersant; 2-5 parts of antioxidant; 5-10 parts of viscosity index improver; 0.1-1.0 parts of pour point depressant; and 0.1-1.0 parts of antifoam agent.

3. The diesel oil composition according to claim 1 or 2, wherein the dispersant is at least one selected from the group consisting of succinimide dispersant and high molecular weight ashless dispersant.

4. The diesel oil composition according to any one of claims 1-3, wherein the dispersant includes at least one selected from the group consisting of high molecular weight succinimide and bis-olefin succinimide; and the high molecular weight succinimide has a molecular weight of 2200-2700.

5. The diesel oil composition according to any one of claims 1-4, wherein the antioxidant includes at least one selected from the group consisting of zinc diisooctyl dithiophosphate, diphenylamine ashless antioxidant, phenol ester type antioxidant, and thioether type steric phenol.

6. The diesel oil composition according to any one of claims 1-5, wherein the base oil includes at least one selected from the group consisting of Group I base oil and Group II base oil.

7. A method for preparing the diesel oil composition according to any one of claims 1-6, comprising the step of mixing and stirring the components at 55-60°C to obtain the diesel oil composition.

8. Marine diesel oil containing the diesel oil composition according to any one of claims 1-6. ​ ​ ​ ​ ​ ​ ​

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