KR20170003437A - Additive package for marine engine lubrication - Google Patents

Abstract

The purpose of the present invention is to reduce or solve a stability problem caused by gel or phase separation of a specific combination of salicylate and sulfonate cleansers. An additive package for two-stroke or four-stroke marine engine lubrication comprises: lubricant viscosity oil; salicylate and sulfonate cleansers of 90/10 to 10/90 ratio (represented by mmol of soap); and 1 to 1 wt% of a hydrocarbylphenol-aldehyde condensate.

Description

{ADDITIVE PACKAGE FOR MARINE ENGINE LUBRICATION}

The present invention relates to the lubrication of two-stroke and four-stroke marine diesel internal combustion engines (the former are commonly referred to as cross-head engines and the latter are referred to as trunk piston engines). Each lubricant for these applications is commonly known as marine diesel cylinder lubricant ("MDCL") and trunk piston engine oil (TPEO).

The cross-head engine is a low speed engine having a high to very high output range. This consists of two separately lubricated parts: a piston / cylinder assembly lubricated with total-loss lubrication by highly viscous oil (MDCL); And a crankshaft which is lubricated by a less viscous lubricant, commonly referred to as system oil.

Trunk piston engines can be used for ship, power and rail tow applications and are faster than cross-head engines. A single lubricant (TPEO) is used for crankcase and cylinder lubrication. All major drive components of the engine, namely main bearings and big end bearings, camshafts and valve gears, are lubricated by a pumped circulation system. The cylinder liner is partly lubricated by splash lubrication and in part from a circulating system that reaches the cylinder wall through a hole in the piston skirt by a connecting rod and a gudgeon pin. It is lubricated by oil.

Ship lubricants are typically formulated with metal detergent additives. A practical problem with the use of detergents for this purpose is that certain combinations of salicylate and sulfonate detergents exhibit stability problems exhibited by gel or phase separation.

It is an object of the present invention to reduce or overcome this problem.

It has now been found that the use of the additives exemplified by methylene-bridged alkylphenols can overcome this problem.

Thus, in one aspect,

Small amounts of lubricating viscosity oils;

(A) an overbased metal hydroxybenzoate detergent additive and (B) an overbased metal sulfonate detergent additive; And

(C) an oil-soluble hydrocarbylphenol-aldehyde condensate additive in an amount ranging from 1 to 10% by weight, preferably from 3 to 5% by weight,

, Wherein the ratio of (A) :( B) (expressed as mmol of soap) is from 90:10 to 10:90, preferably from And the additive package preferably has a TBN of from 100 to 450, more preferably from 150 to 400 when using ASTM D2896.

In a second embodiment, a two-stroke or four-stroke marine engine lubricant composition comprising a major amount of a lubricating viscosity oil blended with a small amount of the defined additive package, wherein the composition is ASTM Has a TBN of 10 to 120, preferably 40 to 100 when D2896 is used, and the composition has a TBN of 25 to 60 when using ASTM D2896 for a 4-stroke engine composition.

The additive package is preferably used at a throughput rate of 15 to 30 mass% to produce a 2-stroke composition, and at a throughput rate of 10 to 20 mass% in a 4-stroke engine composition.

The lubricating oil composition comprises from 0.15 to 1.5% by weight of an oil-soluble hydrocarbyl phenol-aldehyde condensate additive in the case of a two-stroke composition and from 0.1 to 1% by weight of an oil-soluble hydrocarbyl phenol - aldehyde condensate additive.

In a further aspect,

1 to 10% by mass of additives (A) and (B) in order to improve the stability of the additives (A) and (B) in the lubricant, in a marine diesel cylinder lubricant containing the additives (A) and (C); And

A method of lubrication of a cross-head marine diesel engine, comprising feeding a composition of an embodiment of the present invention during its operation to a piston / cylinder of a cross-head marine diesel engine.

.

In the present description, the following words and expressions, when used, have the meanings indicated below.

"Active ingredient" or "(a.i.)" refers to an additive material that is not a diluent or solvent.

"Comprising" or any similar word indicates the presence of stated features, steps or integers or components, but does not preclude the presence or addition of one or more other features, steps, integers, components or groups thereof; Or " consisting essentially of, " or " consisting essentially of, "or " consisting essentially of, " or & .

"Hydrocarbyl" means a substituent or group (such as an alkyl group) having a carbon atom and a predominantly hydrocarbon character attached directly to the remainder of the molecule. A heteroatom may be present, provided that it does not alter the intrinsic hydrocarbon character of the group.

The "major amount" means at least 40 mass% or at least 50 mass%, preferably at least 60 mass%, even more preferably at least 70 mass% and most preferably at least 80 mass% of the composition.

By "minor amount" is meant less than 50% by weight, preferably less than 40% by weight, more preferably less than 30% by weight, most preferably less than 20% by weight and most preferably less than 10% by weight of the composition.

"TBN" means the total base number measured by ASTM D2896.

Also, in this specification, when used:

"Calcium content" is measured by ASTM 4951;

"Phosphorus content" is measured by ASTM D5185;

The "sulphated ash content" is measured by ASTM D874;

"Sulfur Content" is measured by ASTM D2622;

"KV100" means the kinematic viscosity at 100 DEG C measured by ASTM D445.

It is also to be understood that not only essential but also various components which are optimally and conventionally used can be reacted under the conditions of compounding, storage or use, and that the present invention also provides the products obtainable or obtained as a result of any of the above reactions will be.

It is also understood that any amount, range, and upper and lower limits of the ratios shown herein can be combined independently.

The features of the present invention will be discussed in more detail below.

Lubricating viscosity oil

The lubricant composition contains a major amount of lubricating viscosity oil. Such lubricating oils may range in viscosity from light distillate mineral oil to heavy lubricating oil. Generally, the viscosity of the oil has a viscosity ranging from 2 to 40 mm 2 / sec, such as from 3 to 15 mm 2 / sec, and from 80 to 100, such as from 90 to 95, as measured at 100 ° C. The lubricating oil may comprise greater than 60% by weight of the composition, typically greater than 70% by weight.

Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil); Liquefied petroleum, and paraffinic, naphthenic and mixed paraffinic-naphthenic types of hydrogenated refined, solvent-treated or acid-treated mineral oils. Lubricating viscosity oils derived from coal or shale are also used as useful base oils.

Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutylene, poly ), Poly (1-octene), poly (1-decene)); Alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dynonylbenzene, di (2-ethylhexyl) benzene); Polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenols); And alkylated diphenyl ethers and alkylated diphenyl sulfides, and derivatives, analogs, and analogs thereof.

Alkylene oxide polymers and interpolymers, and derivatives thereof, in which the terminal hydroxyl groups are modified by esterification, etherification, etc., are another class of known synthetic lubricating oils. These include polyoxyalkylene polymers made by polymerization of ethylene oxide or propylene oxide, and alkyl and aryl ethers of polyoxyalkylene polymers (e.g., methyl-polyiso-propylene glycol ether having a molecular weight of 1000, Diphenyl ethers of poly-ethylene glycols having a molecular weight of 1500); And their mono- and polycarboxylic acid esters, such as the acetic acid esters of tetraethylene glycol, mixed C ₃ -C ₈ fatty acid esters and C ₁₃ oxo acid diesters.

Another suitable class of synthetic lubricating oils are dicarboxylic acids such as phthalic acid, succinic acid, alkyl succinic acid and alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, Alkylmalonic acid, alkenylmalonic acid) and esters of various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of the esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, Ethylhexyl diester of linoleic acid dimer, and a compound produced by the reaction of 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid Ester.

Esters useful as synthetic oils also include esters prepared from C ₅ to C ₁₂ monocarboxylic acids and polyols and polyol esters such as neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol and tripentaerythritol .

Silicone oils, such as polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxysilicon oils and silicate oils, constitute another useful class of synthetic lubricants, which include tetraethyl silicate, tetraisopropyl silicate, Tetra- (2-ethylhexyl) silicate, tetra- (4-methyl-2-ethylhexyl) silicate, tetra- (p- Poly (methyl) siloxane, and poly (methylphenyl) siloxane. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decyl phosphonic acid) and polymeric tetrahydrofuran.

Unrefined, refined and re-refined oils may be used in the lubricants of the present invention. Unrefined oils are those obtained directly from natural or synthetic sources without further purification treatment. For example, shale oil obtained directly from a retorting operation; Petroleum obtained directly from distillation; Or an ester oil obtained directly from esterification and used without further treatment is a non-refined oil.

The Institute of Petroleum Engineers ("API Oil"), Industry Services Department, Fourteenth Edition, December 1996, Addendum 1, December 1998 classifies base stocks as follows:

a) Group I base stocks contain less than 90% saturates and / or greater than 0.03% sulfur and have a viscosity index of 80 or greater but less than 120 when using the test method set forth in Table E-1 below.

b) Group II base stocks contain at least 90% saturates and up to 0.03% sulfur and have a viscosity index of 80 to less than 120 when using the test method specified in Table E-1 below.

c) Group III base stocks contain greater than 90% saturates and less than 0.03% sulfur and have a viscosity index of 120 or greater when using the test methods listed in Table E-1, below.

d) Group IV base stock is polyalphaolefin (PAO).

e) Group V base stock includes all other base stock not included in Group I, II, III or IV.

Analytical methods for the above-mentioned base stock are tabulated below.

[Table E-1]

The present invention preferably includes oils containing, for example, at least 90% saturates as a lubricating viscosity oil of Group II, III, IV or V and up to 0.03% sulfur. They also include base stocks derived from hydrocarbons synthesized by the Fischer-Tropsch process. In the Fischer-Tropsch process, syngas (or syngas) containing carbon monoxide and hydrogen are first produced and then converted to hydrocarbons using a Fischer-Tropsch catalyst. Such hydrocarbons typically require further processing in order to be useful as a base oil. For example, it can be hydroisomerized by methods known in the art; Hydrocracked and hydrogenated isomerization; Dewaxed; Or hydrogenation isomerization and dehydration. The fresh gas may be obtained from a gas such as natural gas or other gaseous hydrocarbons by, for example, reforming the steam if the base stock can be referred to as a gas-to-liquid or "GTL" base oil; From the vaporization of the biomass if the base stock can be referred to as a biomass-to-liquid or "BTL" or "BMTL" base oil; Or from the vaporization of coal if the base stock can be referred to as coal-to-liquid or "CTL " base oil. However, the present invention is not limited to the use of the above-described base stock, and may thus include, for example, the use of group I base stock and the use of bright stock.

Preferably, the lubricating viscosity oil of the present invention contains at least 50 mass% of the base stock. It may contain at least 60 mass%, such as 70, 80 or 90 mass%, of the above defined base stock or mixtures thereof. The lubricating viscous oil may be substantially all of the base stock or mixtures thereof.

The additives (A) and (B)

Each of these is a detergent that is an additive that reduces the formation of deposits, such as hot varnish and lacquer deposits, in the engine, which has acid-neutralizing properties and can keep the pulverized solids in a suspended state. The detergent is based on a metal "soap" which is a metal salt of an acidic organic compound and is sometimes referred to as a surfactant.

The detergent includes a polar head having a long hydrophobic tail. By providing an overbased detergent comprising a detergent neutralized as an outer layer of a metal base (e.g., carbonate) micelle by reacting an excess of a metal compound, such as an oxide or hydroxide, with an acid gas such as carbon dioxide A large amount of metal base is included.

The detergent is preferably an overbased oil-soluble or oil-dispersible surfactant selected from alkali metal or alkaline earth metal additives, for example phenol, sulfonic acid, carboxylic acid, salicylic acid and naphthenic acid. dispersible calcium, magnesium, sodium or barium salts wherein the overbasing is carried out in the presence of an oil-insoluble salt of a metal such as carbonates, basic carbonates, acetates, formates , ≪ / RTI > hydroxide or oxalate. The metal of the oil-soluble surfactant salt may be the same as or different from the metal of the oil-insoluble salt. Preferably, the metal or metal of the oil-soluble salt or the oil-insoluble salt is calcium.

The TBN of the detergent may be low (i.e., less than 50 mg KOH / g), moderate (i.e., 50-150 mg KOH / g) or higher (i.e., 150 mg KOH / g) as measured by ASTM D2896 g). Preferably, the TBN is medium or high (i.e., greater than 50 TBN). More preferably, the TBN is not less than 60, more preferably not less than 100, more preferably not less than 150, and not more than 500, such as not more than 350 mg KOH / g, as measured by ASTM D2896.

In detergent (A), the surfactant is selected from hydroxybenzoic acid, a specific example being salicylic acid, wherein the salt is salicylate. Salicylate detergents are known in the art.

In detergent (B), the surfactant is selected from sulfonic acid, wherein the salt is sulfonate. Sulfonate detergents are also known in the art.

Detergents that may be used include substituted hydrocarbyl (e.g., alkyl) detergents, such as detergents known in the art.

As mentioned above, the ratio of (A) to (B) (expressed as mmol of soap) is in the range of 90:10 to 10:90. As an example of the upper limit of the above range, 80:20 and 75:25 can be mentioned. As an example of the upper limit of the range, 25:75 can be mentioned. The upper and lower limits may be independently combined to provide a sub-range.

Additive (C): for example, methylene- Bridged  Alkyl phenol (" MBAP ")

Which is known in the art and can comprise an oil-soluble mixture of oxyalkylated hydrocarbyl phenol condensates, wherein the oxyalkyl groups prepared from the phenolic functional groups have the formula - (R'O) _{n- wherein} R ' Is an ethylene, propylene or butylene group and n is independently 0 to 10; Less than 45 mole%, preferably less than 30 mole% of the phenolic functional group of the condensate is non-oxyalkylated; More than 55 mole% of the phenolic functional group of the condensate is mono-oxyalkylated.

Such condensates can be represented by the following chemical structure:

In this formula,

x is 1 to 50, preferably 1 to 40, more preferably 1 to 30,

R ¹ and R ² are H, a hydrocarbyl group having 1 to 12 carbon atoms, or a hydrocarbyl group having 1 to 12 carbon atoms and at least one hetero atom;

R is a hydrocarbyl group having 9 to 100, preferably 9 to 70, most preferably 9 to 50 carbon atoms.

EP-A-2 374 866 describes these condensates in more detail. The MBAP constitutes one embodiment thereof.

As mentioned above, (C) is present in an amount ranging from 1 to 10% by mass, preferably from 3 to 5% by mass. As an example of the sub-range, 1 to 7 mass%, and 1 to 5 mass% may also be mentioned.

To prevent uncertainty, the MBAP used in the present invention may or may not be capped.

Ship lubricant

Ship diesel cylinder lubricant (" MDCL ")

The MDCL may be used in an amount of 10 to 35 mass%, preferably 13 to 30 mass%, most preferably 16 to 24 mass% of the concentrate or additive package, with the remainder being the base stock. Preferably it comprises at least 50% by weight, more preferably at least 60% by weight, even more preferably at least 70% by weight, based on the total weight of MDCL, of a lubricating viscosity oil. Preferably, the MDCL has a compositional TBN (using ASTM D2896) of 10 to 100, such as 70 to 100 or 40 to 100, preferably 60 to 90, more preferably 70 to 80.

An example of a typical proportion of additive in MDCL may be mentioned below.

Trunk piston engine oil (" TPEO ")

TPEO can be used in an amount of 7 to 35 mass%, preferably 10 to 28 mass%, more preferably 12 to 24 mass% of the concentrate or additive package, and the remainder is the base stock. Preferably, the TPEO has a composition TBN of 25 to 60, such as 25 to 55 (using ASTM D2896).

An example of a typical proportion of additive in TPEO may be mentioned below.

The term " oil-soluble " or " oil-dispersible " as used herein does not necessarily imply that the compound or additive may be soluble, soluble, miscible or suspended in total proportion to the oil. However, they mean that they are dissolved or stably dispersed in the oil to such an extent as to exert their intended effect, for example, in an environment where the oil is used. In addition, further incorporation of other additives may also allow incorporation of higher levels of certain additives, if desired.

The lubricant compositions of the present invention comprise individual (i.e., separate) components as defined, which may or may not remain the same chemically before and after mixing.

Although not required, it may be desirable to prepare one or more additive packages or concentrates, wherein the additive is simultaneously added to the lubricating viscosity oil to form a lubricating oil composition. Dissolving the additive package (s) in lubricating oil may be facilitated by solvent and by mixing with mild heating, but this is not necessary. Typically, when the additive package (s) are combined with a predetermined amount of base lubricant, the additives in the final formulation will be formulated in an amount sufficient to provide the desired concentration and / or perform the intended function.

Thus, the additives may be mixed with minor amounts of base oil or other compatible solvent and other desired additives to provide a suitable proportion of the additive, for example, from 2.5 to 90 mass%, preferably from 5 to 75 mass%, based on the additive package By weight, most preferably from 8 to 60% by weight, with the balance being base oil.

The final blend may typically contain from about 5 to 40 percent by weight of the additive package (s), with the balance being base oil.

Example

The invention is illustrated by way of the following non-limiting examples.

Stability test method

Various proportions of calcium salicylate detergent (basicity index 1.35) and calcium sulfonate detergent (basicity index 22.0) were mixed together at 75 DEG C for 30 minutes on a single stage equipped with a stirrer and a hot plate with 1% diluent oil. Thereby providing a mixture set.

Each of the resulting mixtures was poured into graduated glass stability tubes and tested at room temperature and 60 캜 for 12 weeks.

The stability tube was visually inspected for gel formation, phase separation, amount of sediment dripped to the bottom of the tube, and haziness as evidence of additive instability.

Tests were conducted on mixtures containing methylene-bridged dodecylphenoxyethanol (uncapped "MBAP") and mixtures not containing them.

result

Note:

OK: No additive stability problems observed.

Gel / phase separation ⁿ : additive instability (gel formation is more severe than phase separation).

Numbers: Number of weeks the stability performance is observed and reported (the first number is the test at room temperature; the second number is the test at 60 ° C).

The data show the following results:

1. In the ratio of 90/10, no stability problem was observed even in the absence of MBAP.

2. At a ratio of 75/25, problems were observed in the absence of MBAP; The room temperature test showed no stability problems at 1, 3 and 5 mass% MBAP; The 60 ° C test showed improvement at 1 and 3 mass% MBAP and no stability problems at 5 mass% MBAP.

3. Problems were observed in the ratio 50/50, in the absence of MBAP and at 1 mass% MBAP; The 3% by mass MBAP test showed some improvement; In the 5 mass% MBAP test, no stability problems were observed at room temperature and 60 ° C.

4. In the ratio 25/75, both at room temperature and at 60 ° C, problems were observed when MBAP was absent, the room temperature results being worse than the 60 ° C results; In the 5 mass% MBAP test, no stability problems were observed at room temperature and 60 ° C.

Claims (8)

Small amounts of lubricating viscosity oils;
(A) an overbased metal hydroxybenzoate detergent additive and (B) an overbased metal sulfonate detergent additive; And
(C) an oil-soluble hydrocarbylphenol-aldehyde condensate additive in an amount ranging from 1 to 10% by weight, preferably from 3 to 6% by weight,
, ≪ / RTI &
The ratio of (A) :( B) (expressed as mmol of soap) is 90:10 to 10:90, preferably 80:20 to 20:80,
Additive package for 2-stroke or 4-stroke marine engine lubricating oil composition. A two-stroke or four-stroke marine engine lubricant composition comprising a minor amount of a lubricating viscosity oil blended with an additive package as set forth in claim 1,
In the case of a two-stroke engine composition, the composition has a TBN of from 10 to 120, preferably from 40 to 100, when using ASTM D2896,
In the case of four-stroke engine compositions, the composition has a TBN of 25 to 60 using ASTM D2896, a two-stroke or four-stroke marine engine lubricant composition. 3. The method according to claim 1 or 2,
(A) is an overbased calcium salicylate detergent. 4. The method according to any one of claims 1 to 3,
(B) is an overbased calcium sulfonate detergent, additive package or composition. 5. The method according to any one of claims 1 to 4,
(C) is a methylene-bridged alkylphenol, the hydroxyl groups of which are capped or not capped. 6. The method according to any one of claims 2 to 5,
A composition in the form of a ship diesel cylinder lubricant. A lubricant composition for improving the stability of additives (A) and (B) in lubricant additives in marine diesel lubricant additives containing additives (A) and (B) as defined in claim 1, And 1 to 10% by mass of the additive (C) as defined in claim 5. A method for lubrication of a cross-head marine diesel engine, comprising feeding the composition of any one of claims 2 to 6 during its operation to a piston / cylinder of a cross-head marine diesel engine.