阅读说明：本技术 双循环十字头型柴油发动机用汽缸润滑油组合物和其用途 (Cylinder lubricating oil composition for two-cycle crosshead diesel engine and use thereof ) 是由 金子佳亮 于 2018-06-11 设计创作，主要内容包括：双循环十字头型柴油发动机用汽缸润滑油组合物和其用途,润滑油组合物含有：(A)润滑油基础油、(B)酚钙、(C)磺酸钙和(D)无灰分散剂,其为烯基琥珀酰亚胺或烷基琥珀酰亚胺和/或其硼衍生物,以该润滑油组合物总量基准计,(B)酚钙的含有比率2～10质量％、(C)磺酸钙的含有比率1.5～35质量％、(D)无灰分散剂的含有比率0.1～3.0质量％,润滑油组合物的碱值15～150mgKOH/g,100℃下的运动粘度18.0mm<Sup>2</Sup>/s以上且低于21.9mm<Sup>2</Sup>/s,以该润滑油组合物总量基准计Ca成分0.5～5.5质量％、N成分0.002～0.075质量％。该润滑油组合物可同时达成高水平的高温清净性和耐磨耗性。(A cylinder lubricating oil composition for a two-cycle crosshead diesel engine and its use, the lubricating oil composition comprising: (A) a lubricating oil base oil, (B) calcium phenate, (C) calcium sulfonate, and (D) an ashless dispersant which is an alkenylsuccinimide or an alkylsuccinimide and/or a boron derivative thereof, wherein the content of (B) calcium phenate is 2 to 10% by mass, the content of (C) calcium sulfonate is 1.5 to 35% by mass, the content of (D) an ashless dispersant is 0.1 to 3.0% by mass, the base number of the lubricating oil composition is 15 to 150mgKOH/g, and the kinematic viscosity at 100 ℃ is 18.0mm 2 More than s and less than 21.9mm 2 And/s, 0.5 to 5.5 mass% of Ca component and 0.002 to 0.075 mass% of N component based on the total amount of the lubricating oil composition. The lubricating oil composition can achieve both high-temperature detergency and wear resistance at high levels.)

1. a cylinder lubricating oil composition for a two-cycle crosshead diesel engine, comprising:

(A) A lubricant base oil,

(B) Calcium phenate,

(C) Calcium sulfonate, and

(D) An ashless dispersant which is an alkenyl succinimide or an alkyl succinimide and/or a boron derivative thereof,

The content ratio of the calcium phenate (B) is 2-10% by mass based on the total amount of the lubricating oil composition,

the content ratio of the calcium sulfonate (C) is 1.5-35% by mass based on the total amount of the lubricating oil composition,

The content of the ashless dispersant (D) is 0.1-3.0% by mass based on the total amount of the lubricating oil composition,

The base number of the lubricating oil composition is 15 to 150mgKOH/g,

The kinematic viscosity of the lubricating oil composition at 100 ℃ is 18.0mm²more than s and less than 21.9mm²/s，

The Ca component in the lubricating oil composition is 0.5-5.5 mass% based on the total amount of the lubricating oil composition,

The N component in the lubricating oil composition is 0.002-0.075% by mass based on the total amount of the lubricating oil composition.

2. The lubricating oil composition according to claim 1,

The base number of the calcium phenate (B) is 60-350 mgKOH/g,

the base number of the calcium sulfonate (C) is 60-500 mgKOH/g.

3. The lubricating oil composition according to claim 1 or 2,

The kinematic viscosity of the lubricating base oil (A) at 100 ℃ is 10.0-20.0 mm²/s。

4. The lubricating oil composition according to claim 3,

The lubricant base oil (A) is grade I base oil and/or grade II base oil.

5. The lubricating oil composition according to any one of claims 1 to 4,

And (E) ZnDTP, wherein the content of (E) ZnDTP is 0.05-0.5% by mass based on the total amount of the lubricating oil composition.

6. The lubricating oil composition according to any one of claims 1 to 5,

The P component in the lubricating oil composition is 50 to 500 ppm by mass based on the total amount of the lubricating oil composition.

7. The lubricating oil composition according to any one of claims 1 to 6,

Further contains (F) an antioxidant, and the content of the (F) antioxidant is 0.1 to 1.0 mass% based on the total amount of the lubricating oil composition.

8. The lubricating oil composition according to any one of claims 1 to 7,

And at least 1 or more selected from the group consisting of rust preventive, pour point depressant, metal deactivator and extreme pressure agent, and the content ratio thereof is 0.05 to 2 mass% based on the total amount of the lubricating oil composition.

9. the lubricating oil composition according to any one of claims 1 to 8,

And a dimethyl silicone type defoaming agent, wherein the content ratio of the defoaming agent is 10-100 mass ppm based on the total amount of the lubricating oil composition.

10. The application of lubricating oil composition in cylinder lubricating oil for double-circulation crosshead diesel engine,

The lubricating oil composition contains:

(A) A lubricant base oil,

(B) Calcium phenate,

(C) calcium sulfonate, and

(D) an ashless dispersant which is an alkenyl succinimide or an alkyl succinimide and/or a boron derivative thereof,

The content ratio of the calcium phenate (B) is 2-10% by mass based on the total amount of the lubricating oil composition,

The content ratio of the calcium sulfonate (C) is 1.5-35% by mass based on the total amount of the lubricating oil composition,

The content of the ashless dispersant (D) is 0.1-3.0% by mass based on the total amount of the lubricating oil composition,

the base number of the lubricating oil composition is 15 to 150mgKOH/g,

The kinematic viscosity of the lubricating oil composition at 100 ℃ is 18.0mm²More than s and less than 21.9mm²/s，

The Ca component in the lubricating oil composition is 0.5-5.5 mass% based on the total amount of the lubricating oil composition,

The N component in the lubricating oil composition is 0.002-0.075% by mass based on the total amount of the lubricating oil composition.

Technical Field

The present invention relates to a cylinder lubricating oil composition for a two-cycle crosshead diesel engine.

Background

A crosshead type diesel engine uses cylinder oil for lubricating between a cylinder and a piston, and system oil for lubricating and cooling other parts. In cylinder oil for a marine two-cycle crosshead engine, a function of maintaining detergency required for properly moving a piston and a piston ring is required. Further, as important performance required for the cylinder oil for a marine two-cycle crosshead engine, wear resistance is cited.

On the other hand, in recent crosshead diesel engines, for further improvement in performance, for example, there is a tendency to increase the cylinder diameter of 70cm or more in size, increase the piston stroke such as an ultra-long stroke in which the average piston velocity is 8m/s or more, and increase the combustion pressure such as for making the net effective pressure (BMEP) 1.8MPa or more. Since the increase in the combustion pressure causes the sulfuric acid dropping point to rise, the sulfuric acid corrosion of the cylinder is likely to occur. Further, as a measure for preventing the corrosion by sulfuric acid, for example, the cylinder wall temperature may be raised to 250 ℃ or higher, and the amount of lubricating oil to be injected into the cylinder may be gradually reduced from the viewpoint of economy, and therefore, the lubricating environment of the cylinder is further increased in strictness.

Chinese patent application publication CN105754685A discloses the following technology: by using the marine cylinder oil containing calcium naphthenate as a metal detergent, the detergent composition is excellent in detergency and the like. Further, chinese patent application publication CN103184092B discloses the following technology: the cylinder oil for ships, which contains calcium naphthenate as a main metal detergent and other additives such as calcium phenolsulfide, is excellent in detergency and the like.

Conventional marine cylinder lubricating oil compositions have room for improvement in terms of high-temperature detergency and wear resistance, and in order to further improve these properties, a significant increase in cost associated with an increase in the amount of an additive is inevitable. In particular, in order to improve the heat resistance to 320 ℃ or higher, a large increase in the amount of a detergent dispersant or an antioxidant is required.

Disclosure of Invention

The present invention has been made in view of the above circumstances, and an object thereof is to provide: a cylinder lubricating oil composition for a two-cycle crosshead engine which is low in cost and can achieve both high-temperature detergency and wear resistance at high levels.

Inventive pairA cylinder lubricating oil for a circulating cross-head engine (hereinafter, also simply referred to as a lubricating oil composition) comprising: (A) a lubricating oil base oil, (B) calcium phenate, (C) calcium sulfonate, and (D) an ashless dispersant which is an alkenylsuccinimide or an alkylsuccinimide and/or a boron derivative thereof, wherein the content ratio of (B) calcium phenate is 2 to 10% by mass, the content ratio of (C) calcium sulfonate is 1.5 to 35% by mass, and the content ratio of (D) the ashless dispersant is 0.1 to 3.0% by mass, based on the total amount of the composition, the lubricating oil composition has a base number of 15 to 150mgKOH/g and a kinematic viscosity at 100 ℃ of 18.0mm²More than s and less than 21.9mm²The lubricating oil composition contains 0.5 to 5.5 mass% of Ca component and 0.002 to 0.075 mass% of N component, based on the total mass of the composition.

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that: the present invention has been completed based on the finding that the use of the above lubricating oil composition can achieve both high-temperature detergency and wear resistance at low cost.

The lubricant base oil (a) used in the lubricant composition is not particularly limited, and a mineral base oil and/or a synthetic base oil used in a general lubricant can be used. The base oil (a) is preferably a base oil classified into class I or class II according to the classification of the base oil classification by API (american petroleum institute), and may contain both of the class I base oil and the class II base oil. The base oil (A) is particularly preferably a grade I mineral oil or a grade II mineral oil.

The kinematic viscosity of the lubricant base oil (A) is not particularly limited, and the kinematic viscosity at 100 ℃ is preferably 10 to 20mm²(ii) s, more preferably 12 to 18mm²And s. The kinematic viscosity of the lubricant base oil at 100 ℃ is more than 20mm²At s, the low-temperature viscosity characteristics may deteriorate, while the kinematic viscosity is less than 10mm²In the case of/s, a predetermined kinematic viscosity as a cylinder lubricating oil composition may not be obtained. In the present invention, the kinematic viscosity at 100 ℃ means the kinematic viscosity at 100 ℃ specified in ASTM D-445.

the above lubricating oil (A)The base oil can have a kinematic viscosity of 10-14 mm at 100 DEG C²The lubricating oil base oil has a kinematic viscosity of 20-40 mm at 100 DEG C²a mixed base oil of lubricating base oil/s. Under the above conditions, the kinematic viscosity at 100 ℃ is 10-14 mm²The content ratio of the lubricant base oil/s is not particularly limited, and is preferably 40% by mass or more, more preferably 50% by mass or more, based on the total amount of the lubricant base oil.

The viscosity index of the lubricant base oil (a) is not particularly limited, but is preferably 85 or more, more preferably 90 or more, and still more preferably 95 or more, in order to obtain excellent viscosity characteristics from low temperatures to high temperatures. The upper limit of the viscosity index is not particularly limited. In the present invention, the viscosity index is a viscosity index measured in accordance with JIS K2283-1993.

The lubricating oil composition contains (B) calcium phenate, (C) calcium sulfonate, and (D) an ashless dispersant (alkenyl succinimide or alkyl succinimide and/or a boron derivative thereof) as essential additive components.

The content ratio of the calcium phenate (B) used in the lubricating oil composition is 2 to 10 mass%, preferably 3 to 9 mass%, more preferably 4 to 8 mass% based on the total amount of the lubricating oil composition. If the content of the calcium phenate (B) is less than 2% by mass, the detergency may be poor, while if it exceeds 10% by mass, the content of the calcium sulfonate (C) may be low, the wear resistance may be poor.

The base number of the calcium phenate (B) is not particularly limited, but is preferably 60mgKOH/g or more, more preferably 100mgKOH/g or more, and is preferably 350mgKOH/g or less, more preferably 320mgKOH/g or less, and still more preferably 300mgKOH/g or less. When the base number of the calcium phenate (B) is less than 60mgKOH/g, the acid neutralization property may be poor, and when it exceeds 350mgKOH/g, the detergency may be poor. In the present invention, the base number refers to a base number measured by the perchloric acid method in accordance with JIS K2501 "petroleum products and lubricating oils-neutralization number test method" of 7.

The content ratio of the calcium sulfonate (C) used in the lubricating oil composition is 1.5 to 35% by mass, preferably 1.7 to 30% by mass, and more preferably 1.9 to 25% by mass based on the total amount of the lubricating oil composition. When the content ratio of the calcium sulfonate (C) is less than 1.5% by mass, the abrasion resistance may be poor, while when it exceeds 35% by mass, the content ratio of the calcium phenate (B) may be low, the detergency may be poor.

The base number of the calcium sulfonate (C) is not particularly limited, but is preferably 60mgKOH/g or more, more preferably 100mgKOH/g or more, and is preferably 500mgKOH/g or less, more preferably 450mgKOH/g or less. When the base number of the calcium sulfonate (C) is less than 60mgKOH/g, the acid neutralization property may be poor, and when it exceeds 500mgKOH/g, the detergency may be poor.

the ashless dispersant (D) used in the lubricating oil composition is alkenyl succinimide or alkyl succinimide and/or a boron derivative thereof, and exhibits a high level of detergency by being used in combination with calcium phenate (B) and calcium sulfonate (C).

The number of carbons of the alkyl group or alkenyl group is not particularly limited, but is preferably 40 to 400, more preferably 60 to 350. When the number of carbon atoms of the alkyl group or alkenyl group is less than 40, the solubility of the lubricant base oil may be lowered, while when the number of carbon atoms of the alkyl group or alkenyl group exceeds 400, the low-temperature fluidity of the lubricant composition may be deteriorated. The alkyl group or alkenyl group may be linear or branched.

The ashless dispersant (D) may or may not contain boron, but preferably contains boron in view of seizure resistance and high-temperature stability.

The content of the ashless dispersant (D) is 0.1 to 3.0% by mass, preferably 0.2 to 2.5% by mass, more preferably 0.4 to 2.0% by mass based on the total amount of the lubricating oil composition. If the content of the ashless dispersant (D) is less than 0.1% by mass, the detergency may be insufficient, while if it exceeds 3.0% by mass, the content may cause deposits.

When the ashless dispersant (D) contains boron, the content thereof is not particularly limited, but the B component based on the ashless dispersant (D) is preferably 0.005 to 0.1% by mass, more preferably 0.01 to 0.05% by mass, based on the total amount of the lubricating oil composition. If the B component based on the ashless dispersant (D) is less than 0.005% by mass, there is a fear that detergency and seizure resistance due to boron are not exhibited, while if it exceeds 0.1% by mass, there is a fear that friction loss increases.

From the viewpoint of wear resistance and oxidation resistance, the lubricating oil composition may further contain (E) zinc dialkyldithiophosphate (hereinafter, also referred to as ZnDTP). When the lubricating oil composition contains (E) ZnDTP, the content thereof is preferably 0.05 to 0.5 mass%, more preferably 0.1 to 0.4 mass%, based on the total amount of the lubricating oil composition, from the viewpoint of wear resistance and oxidation resistance.

the (E) ZnDTP is not particularly limited, and may contain a compound represented by the following formula (1).

in the above formula (1), R₁each independently represents a hydrocarbon group having 2 to 24 carbon atoms, and the hydrocarbon group having 2 to 24 carbon atoms may be a straight-chain or branched alkyl group or an allyl group. The hydrocarbon group preferably has 3 or more carbon atoms, and preferably has 13 or less carbon atoms. The alkyl group may be a primary alkyl group or a secondary alkyl group, and a secondary alkyl group is preferable.

the method for producing (E) ZnDTP is not particularly limited, and can be synthesized, for example, as follows: so as to have the same structure as the above-mentioned R₁the corresponding alkyl alcohol reacts with phosphorus pentasulfide to synthesize thiophosphoric acid, which is neutralized with zinc oxide to synthesize the thiophosphoric acid.

The lubricating oil composition may further contain (F) an antioxidant. When the lubricating oil composition contains (F) an antioxidant, the content thereof is preferably 0.1 to 1.0% by mass based on the total amount of the lubricating oil composition, from the viewpoint of maintaining high-temperature detergency.

Examples of the antioxidant (F) include phenolic and aromatic amine antioxidants. Specific examples thereof include 4, 4-methylenebis (2, 6-di-tert-butylphenol), 4-bis (2-methyl-6-tert-butylphenol), 2-methylenebis (4-ethyl-6-tert-butylphenol), 4-butylidenebis (3-methyl-6-tert-butylphenol), 4-isopropylidenebis (2, 6-di-tert-butylphenol), 2-methylenebis (4-methyl-6-nonylphenol), 2-isobutylidenebis (4, 6-dimethylphenol), 2-methylenebis (4-methyl-6-cyclohexylphenol), 2, 6-di-tert-butyl-4-methylphenol, 2, 6-di-tert-butyl-4-ethylphenol, 2, 4-dimethyl-6-tert-butylphenol, 2, 6-di-tert- α -dimethylamino-p-cresol, 2, 6-di-tert-butyl (N, N-dimethylaminomethylphenol), 4-thiobis (3-methyl-6-tert-butylphenol), 2-thiobis (4-methyl-6-tert-butylphenol), bis (3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide, bis (3, 5-di-tert-butyl-4-hydroxybenzyl) sulfide, 2-dithio-diethylenebis [3(3, 5-di-tert-butyl-4-hydroxyphenol) propionate ], (methyl-ethyl-2, 6-di-tert-butyl-4-dimethylphenol) propionate), Tridecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol-tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and the like. Specific examples of the aromatic amine antioxidant include phenyl- α -naphthylamine, alkylphenyl- α -naphthylamine, dialkyldiphenylamine and N, N-diphenyl-p-phenylenediamine, and the alkylated diphenylamine is preferably contained from the viewpoint of maintaining oxidation resistance at high temperatures.

The lubricating oil composition may further contain any additives for the purpose of further improving the performance thereof or imparting other desired properties. Examples of the optional additives include rust inhibitors, defoaming agents, pour point depressants, metal deactivators, and extreme pressure agents. When the lubricating oil composition contains any of these additives, the content thereof is preferably 0.05 to 2.0% by mass based on the total amount of the lubricating oil composition.

Examples of the rust inhibitor include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinate, and polyol ester.

Examples of the defoaming agent include silicone oils, alkenyl succinic acid derivatives, esters of polyhydroxyaliphatic alcohols and long-chain fatty acids, methyl salicylate and o-hydroxybenzyl alcohol, aluminum stearate, potassium oleate, N-dialkyl-allylamine nitroaminoalkanols, aromatic amine salts of isopentyl octyl phosphate, alkylalkylene diphosphate, metal derivatives of thioether, metal derivatives of disulfide, fluorine compounds of aliphatic hydrocarbons, triethylsilane, dichlorosilane, alkylphenyl polyglycol ether sulfide, and fluoroalkyl ethers, and from the viewpoints of insolubility, stability, and the like, a defoaming agent containing dimethylsilicone is preferable.

Examples of the pour point depressant include polymethacrylates, poly-alpha-olefins, polyesters, and alkylnaphthalenes.

Examples of the metal deactivator include imidazoline, pyrimidine derivatives, alkylthiadiazole, mercaptobenzothiazole, benzotriazole or derivatives thereof, 1,3, 4-thiadiazole polythioether, 1,3, 4-thiadiazolyl-2, 5-dialkyldithiocarbamate, 2- (alkyldithio) benzimidazole, and β - (o-carboxybenzylthio) propionitrile.

as the anti-wear agent or extreme pressure agent other than the above, for example, ashless friction modifiers such as fatty acid ester-based, fatty amine-based, and fatty acid amide-based; metal-based friction modifiers such as molybdenum dithiocarbamate and molybdenum dithiophosphate; sulfur-based, phosphorus-based, sulfur-phosphorus-based extreme pressure agents, and the like. More specifically, there may be mentioned phosphites, thiophosphites, dithiophosphates, trithiophosphites, phosphates, thiophosphates, dithiophosphates, trithiophosphates, amine salts thereof, metal salts thereof, derivatives thereof, dithiocarbamates, zinc dithiocarbamates, molybdenum dithiocarbamates, dithioethers, polythioethers, sulfurized olefins, sulfurized oils and fats, and the like.

The lubricating oil composition must have a base number required as a cylinder lubricating oil composition for a two-cycle crosshead diesel engine, and the base number is 15 to 150mgKOH/g (perchloric acid method), preferably 35 to 130mgKOH/g, and more preferably 65 to 105 mgKOH/g. When the base number of the lubricating oil composition is less than 15mgKOH/g, detergency may be insufficient, while when it exceeds 150mgKOH/g, an excessive alkali component may be accumulated in the piston to inhibit oil film formation, thereby causing burnishing and scratching.

As described aboveThe lubricating oil composition must have a viscosity required as a cylinder lubricating oil composition for a two-cycle crosshead diesel engine and a kinematic viscosity at 100 ℃ of 18.0mm²more than s, preferably 19.0mm²More than s. On the other hand, the kinematic viscosity at 100 ℃ of the lubricating oil composition is less than 26.1mm²S, preferably less than 21.9mm²S, more preferably less than 21.0mm²And s. The kinematic viscosity at 100 ℃ of the lubricating oil composition is less than 18mm²At/s, the oil film forming ability is insufficient, and sintering of the rings and the liners (Japanese: sintering き つ く) is feared, while 21.9mm²If the viscosity is more than s, the startability may be deteriorated due to the high viscosity.

The lubricating oil composition contains 0.5 to 5.5% by mass, preferably 0.6 to 5.0% by mass of Ca, based on the total amount of the lubricating oil composition. If the Ca content of the lubricating oil composition is less than 0.5 mass%, the detergency may be poor, while if it exceeds 5.5 mass%, excessive Ca may be deposited on the piston.

the N content of the lubricating oil composition is 0.002 to 0.075 mass%, preferably 0.005 to 0.07 mass%, based on the total amount of the lubricating oil composition. If the N content of the lubricating oil composition is less than 0.002 mass%, detergency at low temperatures may be poor, while if it exceeds 0.075 mass%, detergency at high temperatures may be poor.

The composition of the present invention is preferably used as a cylinder lubricating oil for a crosshead diesel engine. The cylinder oil is particularly suitable for the cylinder oil for the double-circulation crosshead type diesel engine which requires wear resistance and high-temperature detergency under the severe lubricating conditions of piston rings and cylinder sleeves.

Detailed Description

the present invention will be described in more detail below based on examples and comparative examples, but the present invention is not limited to these examples.