A dispersed low-base-number marine cylinder oil composition, its preparation method and application

Abstract

The present invention relates to the field of lubricating oil technology and provides a dispersed low-base-number marine cylinder oil composition, a preparation method thereof, and applications thereof. The dispersed low-base-number marine cylinder oil composition comprises 10 to 25 parts by weight of a detergent, 1 to 10 parts by weight of a dispersant, 0.5 to 5 parts by weight of an antioxidant, and 70 to 85 parts by weight of a base oil. The nitrogen content of the dispersant is not less than 300 ppm, and the base number of the composition is 30 to 50 mgKOH / g. The dispersed low-base-number marine cylinder oil composition provided by the present invention has excellent dispersibility and detergency, and is suitable for lubricating the cylinder area of ​​a marine low-speed two-stroke crosshead diesel engine using fuel with a sulfur content of less than 0.5%.

Description

Technical Field

[0001] The present invention relates to the technical field of lubricating oils, and more particularly to a dispersed low-base-number marine cylinder oil composition, a preparation method thereof, and an application thereof. Background Art

[0002] As environmental conditions become increasingly severe, the International Maritime Organization (IMO) has implemented a cap on fuel sulfur content. Effective January 1, 2020, the 0.5% international sulfur limit will take full effect. Except for vessels operating within ECA (Emission Control Areas) using fuel capped at 0.1%, and vessels equipped with desulfurization equipment, all other vessels must use fuel with a sulfur content below 0.5%. International OEMs recommend using 40BN cylinder oil for vessels operating fuel with a sulfur content below 0.5%, necessitating the development of low-base-number (LBN) cylinder oils that can run on fuel with a sulfur content below 0.5%. Currently, the low-sulfur fuel currently used in large two-stroke, low-speed engines is low-sulfur residual oil, which is of lower quality than higher-sulfur fuel and more prone to forming piston deposits. This places higher demands on the cleanliness performance of low-base-number (LBN) cylinder oils.

[0003] The cleanliness of traditional cylinder oil is positively correlated with the amount of metal detergent in the formula. The more metal detergent, the better the cylinder oil's cleanliness, and the less varnish, carbon deposits, and other deposits on the piston ring surface and in the piston ring grooves. This is mainly due to the cleaning effect of the detergent. Traditional high-alkalinity cylinder oil has better cleanliness due to the higher amount of detergent in the formula. The IMO sulfur limit has made low-sulfur fuel the mainstream, thus limiting the alkalinity of cylinder oil to a level that cannot be too high. Excessive alkalinity in cylinder oil can easily form white calcium deposits on the top of the piston. These deposits act as abrasive particles, scratching and scuffing the surfaces of the piston and cylinder liner, and even causing the cylinder wall surface to become polished. The deposits can also enter the gaps in the ring grooves, hindering the movement of the piston rings. In severe cases, they may cause seizures and cylinder scuffing. Therefore, it is impossible to improve the cleanliness of cylinder oil simply by increasing the amount of detergent. Researchers have turned the research direction of improving the cleanliness of cylinder oil to improving the dispersion performance of cylinder oil, dispersing and suspending the oxidation products of cylinder oil under high temperature conditions, as well as the combustion products and incompletely burned colloids and asphalts that reach the piston area through blowby gas, thereby inhibiting and reducing further condensation reactions between substances to generate varnish, carbon deposits and other deposits that are deposited on the piston ring, ring land surface or ring groove, so as to achieve the purpose of keeping the engine piston area clean. Summary of the Invention

[0004] The purpose of the present invention is to provide a dispersed low-base number marine cylinder oil composition and its preparation method and application, so as to solve the technical problem that the dispersion performance of low-base number marine cylinder oil in the prior art is not ideal.

[0005] To achieve the above object, the technical solution adopted by the present invention is:

[0006] In a first aspect, the present invention provides a dispersed low base number marine cylinder oil composition comprising the following components in parts by weight:

[0007] 10-25 parts of detergent;

[0008] 1 to 10 parts of dispersant;

[0009] 0.5-5 parts of antioxidant;

[0010] 70-85 parts of base oil;

[0011] The nitrogen content of the dispersant is not less than 300 ppm;

[0012] The alkalinity of the composition is 30 to 50 mgKOH / g.

[0013] According to some embodiments of the present invention, the nitrogen content of the antioxidant is 0 to 1000 ppm.

[0014] According to some preferred embodiments of the present invention, the nitrogen content of the antioxidant is 0 to 600 ppm, preferably 0 to 440 ppm.

[0015] According to some embodiments of the present invention, the detergent is selected from at least one of sulfurized alkyl phenol salts, sulfonates, and salicylates.

[0016] According to some embodiments of the present invention, the detergent is a mixture of sulfonate and sulfurized alkyl phenate.

[0017] According to some embodiments of the present invention, the weight ratio of the sulfonate to the sulfurized alkyl phenate is 1 to 12:1.

[0018] According to some embodiments of the present invention, the sulfonate is selected from at least one of petroleum calcium sulfonate and synthetic calcium sulfonate.

[0019] According to some embodiments of the present invention, the petroleum calcium sulfonate is selected from at least one of low-alkalinity petroleum calcium sulfonate, medium-alkalinity petroleum calcium sulfonate, high-alkalinity petroleum calcium sulfonate, and ultra-overalkalinity petroleum calcium sulfonate; and / or the synthetic calcium sulfonate is selected from at least one of low-alkalinity synthetic calcium sulfonate, medium-alkalinity synthetic calcium sulfonate, high-alkalinity synthetic calcium sulfonate, and ultra-overalkalinity synthetic calcium sulfonate.

[0020] According to some embodiments of the present invention, the sulfurized alkylphenate includes at least one of high base value sulfurized alkylphenate calcium and medium base value sulfurized alkylphenate calcium.

[0021] According to some embodiments of the present invention, the dispersant is selected from at least one of a polymer ashless dispersant, a succinimide dispersant, and a boronated ashless dispersant.

[0022] According to some preferred embodiments of the present invention, the dispersant is selected from at least one of polymer polyisobutylene succinimide, diene succinimide, monoalkenyl succinimide, high nitrogen diene succinimide, and boronated succinimide.

[0023] According to some embodiments of the present invention, the antioxidant is selected from at least two of amine antioxidants, sulfur-phosphorus zinc salts, and carbamate antioxidants.

[0024] According to some preferred embodiments of the present invention, the antioxidant is selected from at least two of octyl / butyl diphenylamine, dioctyl zinc thiophosphate, butyl octyl zinc thiophosphate, and carbamate.

[0025] According to some embodiments of the present invention, the base oil is selected from at least one of HVI I base oil and HVI II base oil.

[0026] According to some embodiments of the present invention, the composition comprises the following components in parts by weight:

[0027] 10-25 parts of detergent;

[0028] 1.5-8 parts of dispersant;

[0029] 0.5-4 parts of antioxidant;

[0030] 70-85 parts of base oil.

[0031] According to some embodiments of the present invention, the composition further comprises 0 to 1 parts by weight of a rust inhibitor.

[0032] According to some embodiments of the present invention, the rust inhibitor is selected from at least one of dinonylnaphthalenesulfonic acid metal salt and zinc naphthenate.

[0033] According to some preferred embodiments of the present invention, the rust inhibitor is selected from at least one of zinc naphthenate and dinonylnaphthalene sulfonate.

[0034] In a second aspect, the present invention provides a method for preparing the above-mentioned dispersed low-base-number marine cylinder oil composition, comprising: adding other components other than the base oil to the base oil at 50-60°C, stirring until all components are dissolved, to obtain the dispersed low-base-number marine cylinder oil composition.

[0035] In a second aspect, the present invention provides the use of the above-mentioned dispersed low-base number marine cylinder oil composition or the above-mentioned dispersed low-base number marine cylinder oil composition prepared by the above-mentioned preparation method in a marine low-speed two-stroke diesel engine fueled by low-sulfur fuel with a sulfur content of less than 0.5%.

[0036] The beneficial effects of the present invention are at least:

[0037] The present invention provides a dispersed low-base number marine cylinder oil composition, which has excellent dispersibility and detergency and is suitable for lubricating the cylinder part of a marine low-speed two-stroke crosshead diesel engine using fuel with a sulfur content of less than 0.5%. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 This is a black and white photograph of oil spots taken during a filter paper spot dispersion test of the dispersed low base number marine cylinder oil composition of Example 1.

[0039] Figure 2 This is a black and white photograph of oil spots taken in a filter paper spot dispersion test of the marine cylinder oil composition of Comparative Example 1. DETAILED DESCRIPTION

[0040] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments. It should be understood that the specific embodiments described herein are only used to illustrate this patent in detail and do not limit the scope of protection of the present invention in any way.

[0041] Example 1

[0042] A dispersed low-base-number marine cylinder oil composition is prepared from the following components in parts by weight:

[0043] (1) Detergent: 4 parts of super-high base synthetic calcium sulfonate T106 (base value 410 mgKOH / g)

[0044] High base synthetic calcium sulfonate T106B (base value 316 mgKOH / g), 3 parts

[0045] Medium base value sulfurized alkyl phenol calcium T121 (base value 160mgKOH / g), 8 parts

[0046] 2 parts of low base synthetic calcium sulfonate T104 (base value 25mgKOH / g)

[0047] (2) Dispersant: Diolefin succinimide T154, 0.2 parts

[0048] Monoalkenyl succinimide T151, 1 part

[0049] Boronated succinimide KT1356PB, 0.4 parts

[0050] (3) Antioxidant: 0.3 parts of dioctyl zinc thiophosphate T203

[0051] Octyl / butyl diphenylamine T557, 0.7 parts

[0052] (4) Base oil: 1b 500, 34.5 parts

[0053] 120BS, 45.7 parts

[0054] (5) Rust inhibitor: Zinc naphthenate T704, 0.2 parts

[0055] The preparation method is as follows: each component is added to the base oil at 50-60° C., and stirred for 1-4 hours until all components are dissolved, thereby obtaining a dispersed low-base-number marine cylinder oil composition.

[0056] Example 2

[0057] A dispersed low-base-number marine cylinder oil composition is different from Example 1 only in that no rust inhibitor (0.2 parts of zinc naphthenate T704) is added.

[0058] Example 3

[0059] A dispersed low-base-number marine cylinder oil composition is prepared from the following components in parts by weight:

[0060] (1) Detergent: 7 parts of super-high base synthetic calcium sulfonate T106 (base value 410 mgKOH / g)

[0061] 3 parts of high base value sulfurized alkyl phenate calcium S206 (base value 280mgKOH / g)

[0062] 6 parts of low base value petroleum calcium sulfonate T101 (base value 25mgKOH / g)

[0063] (2) Dispersant: Polyisobutylene Succinimide T161, 3 parts

[0064] 2 parts of bis(vinyl)succinimide T154

[0065] (3) Antioxidant: dioctyl zinc thiophosphate T203, 0.5 parts

[0066] Octyl / butyl diphenylamine T557, 1 part

[0067] Carbamate T531, 0.5 parts

[0068] (4) Base oil: 1b 500, 47.1 parts

[0069] 120BS, 29.5 parts

[0070] (5) Rust inhibitor: Nonylnaphthalenesulfonate T705A, 0.4 parts

[0071] The preparation method is the same as that in Example 1.

[0072] Example 4

[0073] A dispersed low-base-number marine cylinder oil composition is prepared from the following components in parts by weight:

[0074] (1) Detergent: 2 parts of super-high base synthetic calcium sulfonate T106 (base value 410 mgKOH / g)

[0075] High base synthetic calcium sulfonate T106B (base value 316 mgKOH / g), 5 parts

[0076] 2 parts of high base value sulfurized alkyl phenate calcium S206 (base value 280mgKOH / g)

[0077] Medium base value sulfurized alkyl phenol calcium T121 (base value 160mgKOH / g), 5 parts

[0078] 5 parts of low base value petroleum calcium sulfonate T101 (base value 25mgKOH / g)

[0079] (2) Dispersant: 2 parts of high molecular weight polyisobutylene succinimide T161

[0080] Monoalkenyl succinimide T151, 1 part

[0081] 2.5 parts of high nitrogen diene succinimide T146

[0082] (3) Antioxidant: 1 part of 1-octylthiophosphonate T202

[0083] Octyl / butyl diphenylamine T557, 1 part

[0084] (4) Base oil: 1b 500, 46.2 parts

[0085] 120BS, 27.0 parts

[0086] (5) Rust inhibitor: Zinc naphthenate T704, 0.3 parts

[0087] The preparation method is the same as that in Example 1.

[0088] Example 5

[0089] A dispersed low-base-number marine cylinder oil composition is prepared from the following components in parts by weight:

[0090] (1) Detergent: 1 part of super-high base synthetic calcium sulfonate T106 (base value 410 mgKOH / g)

[0091] High base synthetic calcium sulfonate T106B (base value 316 mgKOH / g), 9 parts

[0092] 1.5 parts of high base value sulfurized alkyl phenate calcium S206 (base value 280mgKOH / g)

[0093] 8 parts of low base synthetic calcium sulfonate T104 (base value 25mgKOH / g)

[0094] (2) Dispersant: Diolefin succinimide T154, 1 part

[0095] 1 part of high nitrogen diene succinimide T146

[0096] Monoalkenyl succinimide T151, 0.2 parts

[0097] (3) Antioxidant: dioctyl zinc thiophosphate T203, 0.5 parts

[0098] Carbamate T531, 1 part

[0099] (4) Base oil: 1b 500, 45.3 parts

[0100] 120BS, 31.5 parts

[0101] The preparation method is the same as that in Example 1.

[0102] Comparative Example 1

[0103] A marine cylinder oil composition is prepared from the following components in parts by weight:

[0104] (1) Detergent: 2 parts of super-high base synthetic calcium sulfonate T106 (base value 410 mgKOH / g)

[0105] High base synthetic calcium sulfonate T106B (base value 316 mgKOH / g), 5 parts

[0106] 2 parts of high base value sulfurized alkyl phenate calcium S206 (base value 280mgKOH / g)

[0107] Medium base value sulfurized alkyl phenol calcium T121 (base value 160mgKOH / g), 5 parts

[0108] 5 parts of low base value petroleum calcium sulfonate T101 (base value 25mgKOH / g)

[0109] (2) Dispersant: Monoalkenyl succinimide T151, 0.5 parts

[0110] (3) Antioxidant: 1 part of 1-octylthiophosphonate T202

[0111] Octyl / butyl diphenylamine T557, 1 part

[0112] (4) Base oil: 1b 500, 46.2 parts

[0113] 120BS, 32.0 parts

[0114] (5) Rust inhibitor: Zinc naphthenate T704, 0.3 parts

[0115] The preparation method is the same as that in Example 1.

[0116] Comparative Example 2

[0117] A marine cylinder oil composition is prepared from the following components in parts by weight:

[0118] (1) Detergent: 2 parts of super-high base synthetic calcium sulfonate T106 (base value 410 mgKOH / g)

[0119] High base synthetic calcium sulfonate T106B (base value 316 mgKOH / g), 4.5 parts

[0120] 2 parts of high base value sulfurized alkyl phenate calcium S206 (base value 280mgKOH / g)

[0121] Medium base value sulfurized alkylphenol calcium T121 (base value 160mgKOH / g), 3.5 parts

[0122] (2) Dispersant: 2 parts of high molecular weight polyisobutylene succinimide T161

[0123] Monoalkenyl succinimide T151, 1 part

[0124] 2.5 parts of high nitrogen diene succinimide T146

[0125] (3) Antioxidant: 1 part of 1-octylthiophosphonate T202

[0126] Octyl / butyl diphenylamine T557, 1 part

[0127] (4) Base oil: 1b 500, 48.2 parts

[0128] 120BS, 29.0 parts

[0129] (5) Rust inhibitor: Zinc naphthenate T704, 0.3 parts

[0130] The preparation method is the same as that in Example 1.

[0131] Comparative Example 3

[0132] A marine cylinder oil composition is prepared from the following components in parts by weight:

[0133] (1) Detergent: High base synthetic calcium sulfonate T106B (base value 316 mgKOH / g), 5 parts

[0134] 2 parts of high base value sulfurized alkyl phenate calcium S206 (base value 280mgKOH / g)

[0135] Medium base value sulfurized alkylphenol calcium T121 (base value 160mgKOH / g), 1.5 parts

[0136] (2) Dispersant: 2 parts of high molecular weight polyisobutylene succinimide T161

[0137] Monoalkenyl succinimide T151, 1 part

[0138] 2.5 parts of high nitrogen diene succinimide T146

[0139] (3) Antioxidant: 1 part of 1-octylthiophosphonate T202

[0140] Octyl / butyl diphenylamine T557, 1 part

[0141] (4) Base oil: 1b 500, 51.7 parts

[0142] 120BS, 32.0 parts

[0143] (5) Rust inhibitor: Zinc naphthenate T704, 0.3 parts

[0144] The preparation method is the same as that in Example 1.

[0145] Table 1

[0146]

[0147]

[0148]

[0149]

[0150] The high antioxidant low base number marine cylinder oil compositions of each embodiment and the marine cylinder oil compositions of each comparative example were subjected to a paper spot dispersion test and a Komatsu heat pipe test. The test results are shown in Tables 2 and Figure 1-2 .

[0151] (1) The filter paper spot dispersion test (ASTM D7899) measures the dispersibility of a cylinder oil composition for low-sulfur fuel. The cylinder oil composition is mixed evenly with a certain proportion of low-sulfur fuel and then dripped onto a specially prepared filter paper. After being placed in an 80°C oven for 1 hour, the mixture is photographed and rapidly measured using a DT100 dispersibility tester. The dispersion merit value (0-100, with 100 being the ideal value) characterizes the degree of dispersion of suspended matter in the oil spot. A larger value indicates better dispersibility of the test oil.

[0152] (2) The Komatsu hot pipe test examines the high-temperature cleanliness and dispersibility of oil products. During the test, the test oil is pumped into a high-temperature glass test tube at a fixed speed by air. The oil flows upward with the air until it is pumped out of the test tube. During the test, new oil is continuously pumped into the test tube and old oil is pumped out. After the test, the cleanliness level of the paint-like substance on the inner wall of the test tube is compared (0-10 levels) to evaluate the high-temperature cleanliness and dispersibility of the test oil. The higher the test result, the less sediment in the tube and the better the cleanliness and dispersibility of the oil. The test temperature is 310℃ and the test time is 16 hours.

[0153] Table 2 Oil detergency and dispersibility test results

[0154] Group filter paper spot dispersion test Komatsu heat pipe test Example 1 91 8.5 Example 2 89 8.5 Example 3 93 9 Example 4 94 8 Example 5 89 9 Comparative Example 1 85 7 Comparative Example 2 85 7 Comparative Example 3 85 6

[0155] The above results indicate that the dispersed low base number marine cylinder oil composition provided by the present invention has excellent dispersibility and high-temperature detergency by simultaneously controlling the nitrogen content of the dispersant and antioxidant, limiting the nitrogen content of the dispersant to no less than 300 ppm and the nitrogen content of the antioxidant to 0 to 1000 ppm, when the base number of the composition is 30 to 50 mgKOH / g.

[0156] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation of 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 words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein. On the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A dispersed low base number marine cylinder oil composition, characterized in that: The composition comprises the following components in parts by weight: 10-25 parts of detergent; 1 to 10 parts of dispersant; 0.5-5 parts of antioxidant; Base oil 70~85 parts; The nitrogen content of the dispersant is 600 to 880 ppm; The base value of the composition is 30 to 50 mgKOH / g; The nitrogen content of the antioxidant is 0 to 440 ppm; The antioxidant is selected from at least two of amine antioxidants, sulfur-phosphorus zinc salts, and carbamate antioxidants; The dispersant is selected from at least one of a polymer ashless dispersant, a succinimide dispersant, and a boronized ashless dispersant; The detergent is a mixture of sulfonate and sulfurized alkylphenol salt; the weight ratio of the sulfonate to the sulfurized alkylphenol salt is (13:3) to (12:1).

2. The composition according to claim 1, characterized in that The sulfonate is selected from at least one of petroleum calcium sulfonate and synthetic calcium sulfonate.

3. The composition according to claim 2, characterized in that The petroleum calcium sulfonate is selected from at least one of low-base petroleum calcium sulfonate, medium-base petroleum calcium sulfonate, high-base petroleum calcium sulfonate, and ultra-overbased petroleum calcium sulfonate; and / or the synthetic calcium sulfonate is selected from at least one of low-base synthetic calcium sulfonate, medium-base synthetic calcium sulfonate, high-base synthetic calcium sulfonate, and ultra-overbased synthetic calcium sulfonate.

4. The composition according to any one of claims 1 to 3, characterized in that The base oil is selected from at least one of HVI Class I base oil and HVI Class II base oil.

5. The composition according to any one of claims 1 to 3, characterized in that The composition comprises the following components in parts by weight: 10-25 parts of detergent; 1.5-8 parts of dispersant; 0.5-4 parts of antioxidant; 70~85 parts of base oil.

6. The composition according to any one of claims 1 to 3, characterized in that The composition further comprises 0 to 1 parts by weight of a rust inhibitor.

7. The composition according to claim 6, characterized in that The rust inhibitor is selected from at least one of dinonylnaphthalenesulfonic acid metal salt and zinc naphthenate.

8. A method for preparing the composition according to any one of claims 1 to 7, characterized in that: include: The other components except the base oil are added to the base oil at 50-60° C. and stirred until all components are dissolved to obtain the dispersed low base number marine cylinder oil composition.

9. Use of the composition according to any one of claims 1 to 7 or the composition prepared by the preparation method according to claim 8 in a marine low-speed two-stroke diesel engine fueled by low-sulfur fuel oil with a sulfur content of less than 0.5%.

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