KR101662350B1 - Marine engine lubrication - Google Patents

Abstract

In the case where heavy fuel oil is supplied as fuel to the engine, the lubrication of the engine for the trunk piston marine vessel has a lubrication viscosity of 50 mass% or more containing a large amount of a basic raw material containing 90% or more of cargo and 0.03% Hydrocarbyl-substituted hydroxybenzoate detergent other than a detergent having a basicity of less than 2 and a degree of basicity of 80% or more and a hydrocarbyl-substituted carboxylic acid in an amount of 1% by mass or more, or Ester, or amide thereof. The precipitation of asphaltenes in the lubricant caused by the presence of the polluting heavy fuel oil is prevented or suppressed.

Description

LUBRICATION OF MARINE ENGINE LUBRICATION

The present invention relates to an engine lubrication composition for trunk piston marine engines for medium speed four stroke compression-ignition (diesel) marine engines and to the lubrication of such engines.

Generally, trunk piston marine engines use heavy fuel oil (HFO) for offshore operation. Heavy fuel oil is the heaviest fraction of petroleum distillates and contains 15% or less asphaltene, defined as a fraction of petroleum distillate which is insoluble in excess aliphatic hydrocarbons (e.g., heptane) but soluble in aromatic solvents (such as toluene) ≪ / RTI > The asphaltene can enter the engine lubricant as a contaminant via the cylinder or fuel pump and injector, and then asphaltene precipitates appearing in the "black paint" or "black sludge" in the engine can occur. The presence of such carbonaceous deposits on the piston surface can act as an insulating layer, which can form a crack propagating through the piston. When the crack moves through the piston, the hot combustion gas enters the crankcase and a crankcase explosion may occur.

Therefore, trunk piston engine oil (TPEO) would be more desirable to prevent or inhibit asphaltene precipitation. The prior art has described a method for performing this.

International Patent Application Publication No. WO 96/26995 discloses the use of hydrocarbyl-substituted phenols to reduce "black paint" in diesel engines. International Patent Application Publication No. WO 96/26996 discloses the use of demulsifiers for water-in-oil emulsions, such as polyoxyalkylene polyols, to reduce "black paint" in diesel engines. US Patent No. 7,053,027 discloses the use of one or more overbased metal carboxylate detergents in combination with a wear resistant additive in dispersant-free TPEO.

Asphaltene precipitation problems become more severe at higher base raw material saturation levels. International Patent Application Publication No. WO 2008/128656 describes the use of an overbased metal hydrocarbyl-substituted hydroxybenzoate detergent with a basicity of less than 2 and a degree of carbonation of less than 80% in engine lubricants for trunk piston marine engines to provide asphaltene precipitation The above problem is solved. Here, lubricants including Group III and Group IV base materials are mentioned but not exemplified, and lubricants containing Group II base raw materials are exemplified, and all of these base materials have a high saturation level.

However, the solution described above is limited to certain types of cleaning agents. Now, the present invention addresses the problem in International Patent Application Publication No. WO 2008/128656 by using a range of overbased metal carboxylate detergents with a hydrocarbyl-substituted carboxylic acid, anhydride, ester or amide in a high saturated base stock .

International Patent Application Publication No. WO 2008/021737 describes lubrication of an internal combustion engine using a composition comprising at least 0.5% by weight of a carboxylic acid or an anhydride thereof. The composition was illustrated as comprising an overbased phenate and an overbased sulfonate and provided panel coker test data. However, the presence of heavy fuel oil in the composition is not addressed.

A first aspect of the present invention is an engine lubricating oil composition for a trunk piston marine engine for improving handling of asphaltene during use of the lubricating oil composition during operation of the engine when fuel is supplied by heavy fuel oil, And 0.03% or less of sulfur or a mixture thereof, and an oil having a lubricating viscosity of 50% or more by mass containing a basic raw material containing less than (A) a basicity of less than 2 and a cleaning agent having a degree of carbonization of 80% Or hydrocarbyl-substituted carboxylic acids, or anhydrides, esters or amides thereof, of the hydrocarbyl-substituted hydroxybenzoate detergents and (B) hydrocarbyl-substituted carboxylic acids, wherein the degree of carbonization is in mol% Substituted hydroxybenzoate detergent represented by the formula < RTI ID = 0.0 > Wherein at least one of the hydrocarbyl groups in (B) contains at least 8 carbon atoms and the acid, anhydride, ester or amide constitutes at least 1% by mass of the lubricating oil composition.

A second aspect of the present invention relates to a detergent A (A) in combination with a carboxylic acid, anhydride, ester or amide (B) in an amount as defined in the first aspect of the present invention and defined therein in a lubricant composition for a trunk piston marine vessel for medium speed compression ignition marine engines , Said composition comprising a large amount of oil having a lubricating viscosity and containing at least 50% by mass of a basic raw material containing not less than 90% of a charge and not more than 0.03% of sulfur or a mixture thereof, The handling of the asphaltenes and the lubricity by the composition are improved during operation of the engine in which the fuel is supplied by the heavy fuel oil, as compared to a similar operation when the engine oil (A) is used in the absence of (B).

The third aspect of the present invention includes the steps of (i) supplying fuel to the engine using heavy fuel oil, and (ii) lubricating the crankcase of the engine using the composition defined in the first aspect of the present invention A method for operating a trunk piston medium speed compression ignition marine engine.

A fourth aspect of the present invention is a process for producing a fuel oil comprising the steps of (i) providing a composition as defined in the first aspect of the present invention, (ii) providing the composition in a combustion chamber, (iii) , And (iv) combusting the heavy fuel oil in the combustion chamber, and during the operation of the engine, the asphalt is dispersed in the lubricating oil composition for the trunk piston marine vessel during operation of the combustion chamber of the medium speed compression ignition vessel engine.

In the present invention, when the following terms are used, they have the following meanings:

The term " active ingredient "or" a. I. &Quot; refers to an additive material that is not a diluent or solvent.

The word "comprising" or any similar term specifies the presence of stated features, steps, integers or components but does not preclude the presence or addition of one or more other features, steps, integers, components or groups. The term " consisting essentially of, "or similar term, may be included in" comprising "or similar terms, wherein" consisting essentially "includes materials that do not materially affect the characteristics of the composition to which it is applied .

The term "large amount" means 50% by mass or more of the composition.

The term "minor amount" means less than 50% by weight of the composition.

The term "TBN" means the total base weight as measured by ASTM D2896.

In addition, the following is used herein:

"Calcium content" is measured by ASTM 4951.

The "phosphorus content" is measured by ASTM D5185.

The "sulfated ash content" is measured by ASTM D874.

The "sulfur content" is measured by ASTM D2622.

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

It will also be understood that the various components used, which are optional, conventional and necessary, can be reacted under the conditions of compounding, storage or use, and that the present invention also provides products obtained and obtained by any such reaction.

It is also understood that the amounts, ranges, and ratios of any upper and lower limits disclosed herein may be combined independently.

The features of the present invention will now be described in more detail.

Oil with a lubricating viscosity

The lubricating oil may have a viscosity range from the hard distillate mineral oil to the heavy lubricating oil. In general, the viscosity of the lubricating oil ranges from 2 to 40 mm ² / sec when measured at 100 ° C.

Natural oils include animal and vegetable oils (e.g., castor oil, lard oil); Liquid petroleum oil and hydrogenated refined, solvent-treated or acid-treated paraffinic, naphthenic and mixed paraffinic-naphthenic type mineral oils. In addition, an oil having a lubricating viscosity derived from coal or shale acts as a useful base oil.

Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins such as polybutylene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutylene, poly (1- Hexene), 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 in which terminal hydroxyl groups are modified by esterification, etherification, and the like, and their interpolymers and derivatives constitute other types of known synthetic lubricating oils. These include polyoxyalkylene polymers prepared by the 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, A diphenyl ether of polyethylene glycol having a molecular weight of 1500); And their mono- and polycarboxylic acid esters, such as acetic acid esters of tetraethylene glycol, mixed C ₃ -C ₈ fatty acid esters and C ₁₃ oxo acid diesters.

Other suitable synthetic lubricating oils include dicarboxylic acids such as phthalic acid, succinic acid, alkylsuccinic acid and alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer (Such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol monomethyl ether, Glycoll) and the esters. Specific examples of such 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 complex ester formed by reacting 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid .

Esters useful as synthetic oils also include those derived from C ₅ to C ₁₂ monocarboxylic acids and polyols and polyol esters such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and dipentaerythritol, And so on.

Silicone oils such as polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxysilicon oils and silicate oils constitute another class of useful synthetic lubricants, such as tetraethyl silicate, tetraisopropyl silicate, tetra - (2-ethylhexyl) silicate, tetra- (4-methyl-2-ethylhexyl) silicate, tetra- (p- Siloxane, 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 refined oils can be used in the lubricants of the present invention. Unrefined oils are obtained directly from natural or synthetic sources without further purification treatment. For example, shale oil directly obtained from a retorting operation, petroleum oil obtained directly from distillation, or an ester oil obtained directly from esterification and used without further treatment is an unrefined oil .

Purified oils are similar to unrefined oils, except that the oil is further treated in one or more purification steps to improve one or more characteristics. Many of these purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration and permeation, are known to those skilled in the art. The refined oil is obtained by a process similar to the process used to provide the refined oil, but is undertaken using the oil already used during operation. These refined oils are also known as regenerated or reprocessed oils and are often subjected to further processing using techniques for removing spent additives and oil consumption products.

The American Petroleum Institute (API), Engine Oil Licensing and Certification System, Industry Services Department, Fourteenth Edition, December 1996, Addendum 1, December 1998 classifies basic raw materials as follows:

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

b) Group II base stocks contain not less than 90% saturates and not more than 0.03% sulfur, and have a viscosity of not less than 80 and less than 120 when using the test method specified in Table E-1.

c) Group III base stocks contain not less than 90% saturates and not more than 0.03% sulfur, and have a viscosity of not less than 120 when using the test method specified in Table E-1.

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

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

The analytical methods for the basic raw materials are shown in the following table:

For example, the present invention includes Group II, Group III and Group IV base stocks and also basic raw materials derived from hydrocarbons synthesized by the Fischer-Tropsch process. In the Fischer-Tropsch process, synthesis gas (or "syngas") containing carbon monoxide and hydrogen is first produced and then converted to hydrocarbons using a Fischer-Tropsch catalyst. These hydrocarbons typically require further processing for use as a base oil. For example, they can be hydrogenated by methods known in the art; Hydrogenolysis and hydrogenation isomerization; Dewaxing; Or hydrogenated isomerization and dewaxing. For example, a syngas can be produced from a gas such as natural gas or other gaseous hydrocarbons by steam modification, if the base feed can be referred to as a gas to liquid (GTL) base oil; From the gasification of the biomass if the base stock can be referred to as a biomass to liquid (BTL or BMTL) base oil; Or from the gasification of coal if the base feedstock can be referred to as a coal-to-liquid (CTL) base oil.

As shown, the oil having a lubricating viscosity in the present invention contains at least 50 mass% of the defined basic raw materials or a mixture thereof. Preferably, it contains 60 mass%, such as 70, 80 or 90 mass% or more of the defined basic raw materials or mixtures thereof. The oils having a lubricating viscosity may be substantially all of the defined base stocks or mixtures thereof.

The overbased metal detergent (A)

Metal cleaners are additives based on the so-called metal "soap ", i.e. metal salts of acidic organic compounds, often referred to as surfactants. These typically include polar heads with long hydrophobic tails. An overbased metal detergent comprising a neutralized metal detergent as an outer layer of a metal base (e.g., carbonate) micelle is prepared by incorporating a large amount of a metal base by reacting an excess of a metal base, such as an oxide or hydroxide, with an acidic gas, .

In the present invention, the overbased metal cleanser (A) is an overbased metal hydrocarbyl-substituted hydroxybenzoate, preferably a hydrocarbyl-substituted salicylate cleanser.

"Hydrocarbyl" means a group or radical containing carbon and a hydrogen atom bound to the remainder of the molecule through a carbon atom. In the present application, hydrocarbyl may contain heteroatoms, i.e., atoms other than carbon and hydrogen, provided that they do not inherently alter the properties of the hydrocarbon and group. As an example of hydrocarbyl, there may be mentioned alkyl and alkenyl. The overbased metal hydrocarbyl-substituted hydroxybenzoates typically have the structure of Formula 1:

[Chemical Formula 1]

In this formula,

R is a linear or branched aliphatic hydrocarbyl group, more preferably an alkyl group containing a linear or branched alkyl group. More than one R group attached to the benzene ring may be present. M is an alkali metal (e.g., lithium, sodium or potassium) or an alkaline earth metal (e.g., calcium, magnesium, barium or strontium). Calcium or magnesium is preferable, and calcium is particularly preferable. The COOM group may be ortho, meta or para to the hydroxyl group and ortho position is preferred. The R group may be ortho, meta or para to the hydroxyl group.

Hydroxybenzoic acid is typically prepared by carboxylation by the Kolbe-Schmitt process of phenoxide, in which case it will generally be obtained as a mixture with non-carboxylated phenols (typically in a diluent). Hydroxybenzoic acid can be non-sulfated or sulfated and can be chemically modified and / or contain additional substituents. Methods for sulfiding hydrocarbyl-substituted hydroxybenzoic acids are known to those skilled in the art and are described, for example, in U.S. Patent No. 2007/0027057.

In the hydrocarbyl-substituted hydroxybenzoic acid, the hydrocarbyl group is preferably alkyl (including straight chain or branched chain alkyl groups), and the alkyl group advantageously has 5 to 100, preferably 9 to 30, especially 14 to 24 Lt; / RTI > carbon atoms.

The term " overbased "is generally used to describe metal detergents wherein the ratio of the number of equivalents of metal residues to the number of equivalents of acid residues is greater than one. The term "low basic" is used to describe a metal detergent having an equivalent ratio of metal residues to acid residues of more than 1 and less than or equal to about 2.

The term " overbased calcium salt of a surfactant "means an overbased detergent wherein the metal cation of the oil-insoluble metal salt is essentially a calcium cation. Typically, at least 80 mol%, more typically at least 90 mol%, such as at least 95 mol% of the cations of the oil-insoluble metal salt are calcium ions, although small amounts of other cations may be present in the oil-insoluble metal salt. Other cations other than calcium may be derived, for example, by use in the preparation of an overbased detergent of a surfactant salt wherein the cation is a metal other than calcium. Preferably, the metal salt of the surfactant is also calcium.

Carbonated overbased metal cleaners typically include amorphous nanoparticles. In addition, there are presentations of nanoparticulate materials comprising crystalline carbonate and carbonate in the form of crystalline calcite.

The basicity of the detergent may be expressed as the total base (TBN). The total base is the amount of acid needed to neutralize the basicity of the overbased base. TBN can be measured using ASTM standard D2896 or equivalent procedure. The detergent may have a low TBN (i.e., TBN of less than 50), an intermediate TBN (i.e., TBN of 50 to 150) or a high TBN (i.e., TBN of more than 150, e.g., 150 to 500). In the present invention, basicity and degree of carbonization can be used. The basicity is the molar ratio of total base to total soap in an overbased detergent. The degree of carbonization is the ratio of carbonate present in the overbased detergent expressed as mole percent relative to the total overbases in the detergent.

The overbased metal hydrocarbyl-substituted hydroxybenzoates may be prepared by any technique used in the art. The general method is as follows:

1. neutralizing a hydrocarbyl-substituted hydroxybenzoic acid using a molar excess of a metallic base to produce a slight overbased metal hydrocarbyl-substituted hydroxybenzoate complex in a solvent mixture of volatile hydrocarbons, alcohols and water ;

2. Post-Carbonization Reaction - Post-production to produce a colloidal-dispersed metal carbonate;

3. removing the remaining solid that is not colloidally dispersed; And

4. Stripping to remove the process solvent.

The overbased metal hydrocarbyl-substituted hydroxybenzoate may be prepared by a batch or continuous overbasing process.

The metal base (e.g., metal hydroxide, metal oxide or metal alkoxide), preferably lime (calcium hydroxide), can be charged in one or more stages. The charge can be the same or different, and the charge of carbon dioxide can be: When an additional calcium hydroxide charge is added, it is not necessary to complete the treatment of the previous step of carbon dioxide. As the carbonization progresses, the dissolved hydroxide is converted into colloidal carbonate particles dispersed in a mixture of volatile hydrocarbon solvent and non-volatile hydrocarbon oil.

The carbonization can be carried out in one or more steps over a range of room temperature to the reflux temperature of the alcohol promoter. The addition temperatures may be similar or different, or may vary during each addition step. The timing at which the temperature is selectively reduced after the elevation can precede the additional carbonization step.

The volatile hydrocarbon solvent of the reaction mixture is preferably a normal liquid aromatic hydrocarbon having a boiling point of about 150 캜 or less. Aromatic hydrocarbons have been found to provide certain advantages such as improved filtration rate, examples of suitable solvents being toluene, xylene and ethylbenzene.

The alkanol is preferably methanol, but other alcohols such as ethanol may be used. It is important to select the ratio of alkanol to hydrocarbon solvent and the water content of the initial reaction mixture accurately to obtain the desired product.

An oil may be added to the reaction mixture, in which case a suitable oil may be a hydrocarbon oil, especially those of inorganic origin. An oil having a viscosity of 15 to 30 mm ² / sec at 38 ° C is very suitable.

After final treatment with carbon dioxide, the reaction mixture is typically heated to an elevated temperature, such as, for example, greater than 130 ° C to remove volatiles (water and any remaining alkanols and hydrocarbon solvents). When the synthesis is complete, the crude product is turbid because of the presence of the suspended precipitate. It is purified, for example, by filtration or centrifugation. Such measures may be used before or at the midpoint or after solvent removal.

Generally, the product is used as an oil liquid. If the reaction mixture contains insufficient oil to retain the oil after removal of the volatiles, additional oil should be added. This may occur before or at the midpoint, or after solvent removal.

In the present invention, (A) comprises (A1) a basicity of 2 or more and a degree of carbonization of 80% or more; (A2) a basicity of 2 or more and a degree of carbonization of less than 80%; Or (A3) a basicity of less than 2 and a degree of carbonization of less than 80%.

Carboxylic acid, or an anhydride, ester or amide thereof (B)

As indicated, the acid, or an anhydride, ester or amide thereof, accounts for at least 1% by weight of the lubricating oil composition. Preferably 1.5% by mass, such as 10% by mass or less, for example, 2% by mass to 10% by mass, for example, 3% by mass to 6% by mass. (B) may be a mixture.

The acid may be a mono or polycarboxylic acid, preferably a dicarboxylic acid. The hydrocarbyl group preferably has 8 to 400 carbon atoms, for example 8 to 100 carbon atoms.

(B), an anhydride of a dicarboxylic acid is preferable.

The ester may be a half or a diaster when the acid is a dicarboxylic acid. The ester group may include alkyl, aryl, or aralkyl, and the amide group may be unsubstituted or may have one or more alkyl, aryl, or aralkyl groups.

The general structure of exemplary monocarboxylic and dicarboxylic acids, and their anhydrides, esters or amides, may be represented by the formula (I) or (II)

(I)

[In the above formula,

R ¹ represents a C ₈ to C ₁₀₀ branched or linear hydrocarbyl, such as a polyalkenyl, alkyl or alkaryl group,

X and Y are each independently OR ² and OR ³ , wherein each of R ² and R ³ independently represents a hydrogen atom, or an alkyl, aryl or aralkyl group, or X and Y together represent -O- .]

≪ RTI ID = 0.0 &

R ¹ CH ₂ COR ⁴

[In the above formula,

R ⁴ represents OR ⁵ or NR ⁶ R ⁷ , wherein each of R ⁵ , R ⁶ and R ⁷ independently represents a hydrogen atom or an alkyl group.

Preferably, the hydrocarbyl group is a polyalkenyl group. Such polyalkenyl moieties may have a number average molecular weight of from 200 to 3000, preferably from 350 to 950.

Suitable hydrocarbons or polymers used in the formation of the acid / derivatives of the present invention include homopolymers, interpolymers or low molecular weight hydrocarbons. One such group of polymers comprises polymers of ethylene and / or one or more C ₃ to C ₂₈ alpha-olefins having the formula H ₂ C = CHR ¹ , wherein R ¹ is a straight or branched chain alkyl group containing from 1 to 26 carbon atoms Branched alkyl radical, and the polymer has a carbon-to-carbon unsaturation, preferably a high terminal ethylenic unsaturation. Advantageously, the polymer is one or more alpha-ethylene and Formula-comprising a cross-polymer of an olefin, wherein R ¹ is more preferably 1 to 8 having a carbon atom alkyl, having 1 to 18 carbon atoms Alkyl, even more preferably alkyl having 1 to 2 carbon atoms. Thus, useful alpha-olefin monomers and comonomers are, for example, propylene, butene-1, hexene-1, octene-1, 4- methylpentene-1, decene-1, dodecene- 1, heptadecene-1, octadecene-1, nonadecene-1 and mixtures thereof (for example, a mixture of propylene and butene-1, etc.) . Examples of such polymers are propylene homopolymers, butene-1 homopolymers, ethylene-propylene copolymers, ethylene-butene-1 copolymers, propylene-butene copolymers, etc. where the polymer has at least some terminal and / . Preferred polymers are ethylene and propylene and unsaturated copolymers of ethylene and butene-1. The interpolymer of the present invention may contain minor amounts, such as from 0.5 to 5 mole percent of C ₄ to C _{18 non-} conjugated diolefin comonomers. However, it is preferred that the polymers of the present invention comprise only interpolymers of alpha-olefin homopolymers, interpolymers of alpha-olefin comonomers and copolymers of ethylene and alpha-olefin comonomers. The ethylene molar content of the polymer used in the present invention is preferably 0 to 80%, more preferably 0 to 60%. When propylene and / or butene-1 are used as comonomers with ethylene, the ethylene content of the copolymer is preferably between 15 and 50%, but more or less ethylene may be present.

Such polymers may be prepared by reacting a mixture comprising alpha-olefin monomers, or alpha-olefin monomers, or a mixture comprising ethylene and one or more C ₃ to C ₂₈ alpha-olefin monomers with one or more metallocenes (e.g., cyclopentadienyl- Metal compounds) and an alumoxane compound in the presence of a catalyst system. By using such a process, polymers in which 95% or more of the polymer chains have terminal ethylenidene-type unsaturation can be provided. The proportion of polymer chains exhibiting terminal ethynylidene unsaturation can be determined by FTIR spectroscopic titration or C ¹³ NMR. The latter type of interpolymer may be characterized by the formula poly-C (R ¹ ) = CH ₂ where R ¹ is C ₁ to C ₂₆ alkyl, preferably C ₁ to C ₁₈ alkyl, C ₁ to C ₈ alkyl, most preferably C ₁ to C ₂ alkyl (e.g., methyl or ethyl), and poly represents a polymer chain. The chain length of the R < ¹ > alkyl group will vary depending on the monomer selected for use in the polymerization. A small amount of the polymer chain is at the terminal ethenyl, i.e., vinyl, unsaturation, i.e., may contain poly -CH = CH _2, some of the polymer may contain internal monounsaturated, such as poly -CH = CH (R ¹⁾ , Wherein R < ¹ > is as defined above. Such terminally unsaturated interpolymers can be prepared by known metallocene chemistry and can be prepared by known metallocene chemistry as described in U.S. Patent Nos. 5,498,809, 5,663,130, 5,705,577, 5,814,715, 6,022,929, and 6,030,930 .

Another class of useful polymers are polymers made by cationic polymerization such as isobutene, styrene, and the like. Conventional polymers from this class include C ₄ refinery streams having a butene content of about 35 to about 75 mass% and an isobutene content of about 30 to about 60 mass% with a Lewis acid catalyst such as aluminum trichloride or boron trifluoride ≪ / RTI > A preferred source of monomer for making poly-n-butene is a petroleum feed stream, such as Raffinate II. Such feedstocks are disclosed in the art, such as U.S. Patent No. 4,952,739. Polyisobutylene is the most preferred backbone of the present invention because it can be readily utilized by cationic polymerization from a butene stream (e.g., using an AlCl ₃ or BF ₃ catalyst). Such polyisobutylene generally contains residual unsaturation in an amount of about one ethylenic double bond per polymer chain disposed along the chain. A preferred embodiment produces a reactive isobutylene polymer having a terminal vinylidene olefin using a pure isobutylene stream or a polyisobutylene produced from a raffinate I stream. Preferably, such a polymer, referred to as highly reactive polyisobutylene (HR-PIB), has a terminal vinylidene content of at least 65%, such as at least 70%, more preferably at least 80%, and most preferably at least 85% . The preparation of such polymers is described, for example, in U.S. Patent No. 4,152,499. HR-PIB is well known and HR-PIB is available under the trade name Glissopal TM (obtained from BASF) and Ultravis TM (obtained from BP-Amoco) .

The polyisobutylene polymers that can be used are generally based on hydrocarbon chains of 400 to 3000. Methods for producing polyisobutylene are known. The polyisobutylene can be functionalized by free radical grafting using halogenated (e.g., chlorinated), thermal "ene" reactions or catalysts such as peroxides as described below.

(B), the hydrocarbon or polymer backbone may be optionally substituted at the carbon-to-carbon unsaturation moiety on the polymer or hydrocarbon chain using any of the above-mentioned three optional processes or combinations thereof in any order, (Acid or anhydride moiety) at random.

Methods of reacting polymeric hydrocarbons with unsaturated carboxylic acids, anhydrides or esters and methods of making derivatives from such compounds are described in U.S. Patent Nos. 3,087,936, 3,172,892, 3,215,707, 3,231,587, 3,272,746, 3,275,554 , 3,381,022, 3,442,808, 3,565,804, 3,912,764, 4,110,349, 4,234,435, 5,777,025, 5,891,953 and EP 0 382 450 B1, Canadian Patent 1,335,895 and British Patent A-1,440,219. Polymers or hydrocarbons can be used to remove functionalized moieties or agents, i. E., Acid, anhydride, ester moieties, etc., primarily by carbon-to-carbon unsaturation (or ethylenic or < (Acid or anhydride) by reacting a polymer or hydrocarbon under conditions such that it is added to the polymer or hydrocarbon chain at the site (hereinafter referred to as olefinic unsaturation).

The optional functionalization is carried out by passing chlorine or bromine through the polymer at a temperature of from 60 to 250 DEG C, preferably from 110 to 160 DEG C, for example from 120 to 140 DEG C, for from about 0.5 to 10 hours, preferably from 1 to 7 hours, can be achieved by halogenating, for example, chlorinating or brominating the? -olefin polymer with about 1 to 8% by weight, preferably 3 to 7% by weight, of chlorine or bromine, based on the weight of the polymer or hydrocarbon. The halogenated polymer or hydrocarbon (and hence the backbone) is then added to the backbone in the required number of functional moieties at 100-250 ° C, typically about 180-235 ° C, for about 0.5-10 hours, such as 3-8 hours , The resulting product will contain the monounsaturated carboxylic acid reactant per mole of halogenated backbone at the desired mole number. Alternatively, the backbone and monounsaturated carboxylic acid reactants are mixed and heated while adding chlorine to the hot material.

Typically, chlorination assists in increasing the reactivity of the starting olefin polymer by the monounsaturated functional reactants, but it is also possible to add a portion of the polymer or hydrocarbon considered to be used in the present invention, especially to the desired polymer or hydrocarbon with high terminal bonding content and reactivity It is not absolutely necessary. Thus, preferably, the backbone and monounsaturated functional reactants, such as carboxylic acid reactants, are contacted at elevated temperatures to induce an initial thermal "Yen" reaction. The reaction is well known.

The hydrocarbon or polymer backbone can be functionalized by random attachment of functional moieties along the polymer chain by a variety of methods. For example, the polymer in solution or solid form can be grafted with the monounsaturated carboxylic acid reactants described above in the presence of a free radical initiator. When the grafting is carried out in solution, the grafting takes place at an elevated temperature ranging from about 100 to 260 캜, preferably from 120 to 240 캜. Preferably, the free radical initiated grafting is achieved in an inorganic lubricating oil solution containing, for example, from 1 to 50 mass%, preferably from 5 to 30 mass%, based on the initial total oil solution.

Free radical initiators that may be used are those which have peroxides, hydroperoxides and azo compounds, preferably boiling above about 100 < 0 > C and thermally decomposing within the grafting temperature range to provide free radicals. Representative free radical initiators are azobutyronitrile, 2,5-dimethylhex-3-ene-2,5-bis-tert-butyl peroxide, and dicumene peroxide. The initiator, if used, is typically used in an amount of from 0.005 to 1% by weight, based on the weight of the reaction mixture solution. Typically, the monounsaturated carboxylic acid reactant materials and free radical initiators described above are used in a weight ratio range of from about 1.0: 1 to 30: 1, preferably from 3: 1 to 6: 1. Grafting is preferably carried out under an inert atmosphere, such as a nitrogen blanket. The resulting grafted polymer is characterized by having a randomly attached carboxylic acid (or derivative) moiety along the polymer chain. Of course, it is understood that some of the polymerization chain remains ungrafted. The above-described free radical grafting can be used for other polymers and hydrocarbons of the present invention.

The preferred monounsaturated reactants used to functionalize the backbone are mono- and dicarboxylic acid materials, i.e., (i) (a) the carboxyl group is adjacent (i.e., is located at a neighboring carbon atom), (b) one of the neighboring carbon atoms Monounsaturated C ₄ to C ₁₀ dicarboxylic acids, preferably both of which are part of monounsaturated; (ii) a derivative of (i) above, such as an anhydride or C ₁ to C ₅ alcohol derived mono- or diester of (i); (iii) monounsaturated C ₃ to C ₁₀ monocarboxylic acids wherein the carbon-carbon double bond is conjugated with a carboxy group (i.e., -C = C-CO- structure); And (iv) an acid or acid derivative material, including derivatives of the above (iii), such as C ₁ to C ₅ alcohol derived mono- or diesters of (iii). Mixtures of monounsaturated carboxylic acid materials (i) to (iv) may also be used. Upon reaction with the backbone, the monounsaturation of the monounsaturated carboxylic acid reactant is saturated. Thus, for example, maleic anhydride becomes backbone-substituted succinic anhydride and acrylic acid becomes backbone-substituted propionic acid. Examples of such monounsaturated carboxylic acid reactants are fumaric acid, itaconic acid, maleic acid, maleic anhydride, chloromaleic acid, chloromaleic anhydride, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid and lower alkyl ₁ to C ₄ alkyl) acid esters such as methyl maleate, ethyl fumarate and methyl fumarate.

In order to provide the required functionality, the monounsaturated carboxylic acid reactant, preferably maleic anhydride, is typically used in an amount of from about equimolar to about 100% by weight, preferably from 5 to 50% by weight, based on the moles of the polymer or hydrocarbon Range. Unreacted excess monounsaturated carboxylic acid reactants can be removed from the final dispersant product, if desired, for example by stripping, typically under vacuum.

The treatment ratio of the additives (A) and (B) contained in the lubricating oil composition may be, for example, 1 to 2.5 mass%, preferably 2 to 20 mass%, and more preferably 5 to 18 mass%.

Co-additive

The lubricating oil composition of the present invention may contain, in addition to (A) and (B), further additives different from (A) and (B). Such further additives may include, for example, ashless dispersants, other metal cleaners, antiwear agents such as zinc dihydrocarbyl dithiophosphate, antioxidants and anti-fogging agents.

Although not required, it may be desirable to prepare one or more additive packages or concentrates containing additives, wherein additives (A) and (B) may be simultaneously added to the base oil to form a lubricant composition. The dissolution of the additive package with the lubricating oil can be facilitated by the solvent and by the mixing accompanied by mild heating, but is not necessary. Typically, when the additive package is combined with a predetermined amount of the base lubricant, the additive package is formulated containing the additive in the proper amount to provide the desired concentration and / or to perform the intended function in the final formulation. Thus, the additives (A) and (B) according to the invention can be mixed with minor amounts of base oils or other compatibilizing solvents together with other preferred additives to provide, for example, from 2.5 to 90% by weight, Preferably from 5 to 75% by mass, most preferably from 8 to 60% by mass, and the balance being base oil.

The final formulation as a trunk piston engine oil typically contains 30% by weight, preferably 10 to 28% by weight, more preferably 12 to 24% by weight, of the additive package and the balance is base oil. Preferably, the trunk piston engine oil has a constituent TBN of 20 to 60, such as 25 to 55 (using ASTM D2896).

Example

The present invention is illustrated by the following examples, but it is not limited thereto.

ingredient

The following ingredients are used:

Component (A):

(A1) a calcium salicylate detergent having a TBN of 350 (a basicity of 2 or more; a degree of carbonization of 80% or more);

(A2) a calcium salicylate detergent having a TBN of 225 (2 or more basic degrees; less than 80% carbide);

(A3) Calcium salicylate detergent having a TBN of 65 (less than 2 basicity; less than 80% carbidity).

Component (B):

Polyisobutene succinic anhydride ("PIBSA") derived from polyisobutene having a number average molecular weight of 950 (72% active ingredient)

Base oil II: API Group II 600R base material from Chevron

Base Oil III: API Group III base oil known as XHV 182

Base oil IV (1): API group IV base oil known as DURASYN82

Base oil IV (2): API group IV base oil known as SPECTRAPA0100

HFO: heavy fuel oil, ISO-F-RMK 380

slush

The above components were selected and blended to provide a range of engine lubricants for trunk piston marine engines. Some lubricants are embodiments of the present invention, and others are control examples for comparison. For each containing HFO, the composition of the tested lubricant is presented in the table entitled "Results" below.

exam

Panel Cocker Test

Panel Coker test was used to evaluate the performance of the test lubricant. The test method involves dropping the oil on the heated metal plate by spinning the metal comb-like device in an oil sump containing the oil during the test. At the end of the test, the formed deposits can be evaluated by visual inspection and weight of the plate's exterior.

The test was carried out using a panel coker tester Model PK-S supplied by Yoshida Kagaku KiKai Co., Osaka, Japan. The test panels were thoroughly cleaned and weighed prior to placing in the apparatus. The test oil was mixed with 2.5% HFO and 225 g of the resulting mixture was added to the oil sump of the apparatus. When the temperature of the oil was 100 占 폚 and the temperature of the test plate was 320 占 폚, the metal comb-like device was automatically rotated to cause the oil to fall onto the test plate.

The test sequence lasted for 120 cycles, each cycle consisting of 15 seconds of falling time to oil and 45 seconds of non-falling time.

At the end of the test, the plate was washed with n-heptane, dried, reweighed and visually inspected. The weight of the deposit was recorded.

Light scattering

In addition, the test lubricant was evaluated for asphaltene dispersibility using light scattering in accordance with the Focused Beam Reflectance Method (FBRM), which predicts asphaltene aggregation and hence "black sludge" formation.

The FBRM test method was disclosed at the seventh international symposium on marine engineering in Tokyo, Japan from October 24 to 28, 2005, and the Benifits of Salicylate Detergents in TPEO Application with Variety of Base Stocks . More details were presented at the CIMAC meeting in Vienna, Austria, on May 21-24, 2007, and as a conference newsletter [Meeting the Challenge of the New Base Fluids for the Lubrication of Medium Speed Marine Engines - An Additive Approach] Respectively. In the latter article, the FBRM method is used to predict the performance of a lubricant system based on base stocks containing greater than or less than 90% saturates and greater than or equal to 0.03% sulfur, Quantitative results can be obtained. Prediction of relative performance from FBRM was confirmed by engine testing in marine diesel engines.

The FBRM probe contains a fiber optic cable that moves the laser light to reach the probe tip. At the tip, the lens focuses the laser light to a small point. The lens is rotated to scan the focused path for a circular path between the probe window and the sample. As the particles flow past the window, they cross the scanning path and provide backscattered light from the individual particles.

The scanning laser light travels much faster than the particles, which means that the particles are effectively stopped. As the focused light reaches one edge of the particle, the amount of backscattered light increases, and the amount will decrease as the focused light reaches the other edge of the particle.

The machine measures the time of increased backscattering. The time of backscattering from one particle is increased by the scan speed, and the result is distance or string length. The string length is a straight line between any two points at the edge of the particle. This is shown as a graph of the number of string lengths (particles) measured as a function of string length distribution, i. E., A function of the string length dimension in microns. As the measurement is performed in real time, distribution statistics can be calculated and tracked. Typically, the FBRM measures tens of thousands of strings per second, resulting in an established number of string length distributions. This method provides an absolute measure of the particle size distribution of the asphaltene particles.

The focused beam reflectance probe (FBRM) and the model Lasentec D600L are supplied by Mettler Toledo, Leicester, UK. The machine was used in a configuration to provide particle size decomposition of 1 [mu] m to 1 mm. Data from the FBRM can be presented in several ways. The study suggested that an average count per second could be used as a quantitative determination of asphaltene dispersion. This value is a function of both the average size and the level of aggregate. In the present application, the average count rate (for the entire size range) was monitored using a measurement time of one second per sample.

The test lubricant formulation was heated to 60 DEG C and stirred at 400 rpm. When the temperature reached 60 ° C, the FBRM probe was placed in the sample and measured for 15 minutes. Heavy fuel oil aliquots (10% w / w) were introduced into the lubricant blend under agitation using a four-bladed agitator (400 rpm). The average count value per second was taken when the count rate reached an equilibrium value (typically overnight).

result

Panel Cocker Test

Panel Coker test results are summarized in the following table, where the numbers are% by mass unless otherwise indicated.

Example Ca salicylate (A1) PIBSA (B) Base Oil III Base Oil IV (1) Base Oil IV (2) The deposit (g) One 5.71 6.1 72.21 15.98 0.0484 X 5.71 77.59 16.71 0.0916 2 5.71 6.1 70.96 17.23 0.0738 Y 5.71 75.43 18.56 0.1062

Each lubricant contained 44.6 mM of soap and had a TBN of 30. Further, each of the lubricants contained 0.5% by mass of HFO.

The results show that the embodiments of the present invention (Examples 1 and 2) result in much less deposits. That is, the asphaltene dispersibility is improved compared to the corresponding example without PIBSA (Examples X and Y, respectively) and also with the Group IV base oil without PIBSA (Example Y).

Light scattering

The FBRM test results are summarized in Tables 2 to 4 below.

Base oil II Example Ca salicylate (A)
(Mass% of active ingredient) Component (B)
(Mass% of active ingredient) Particle count / sec Control Example -
A1 (2.6)
A1 (2.6) 2.6
-
2.6 13,710
15,888
4,355 Control Example -
A2 (2.1)
A2 (2.1)
A2 (2.1) 2.1
-
2.1
2.6 15,191
8,782
6,149
3,438 Control Example -
A3 (1.8)
A3 (1.8)
A3 (1.8) 1.8
-
1.8
2.6 15,564
10,748
5,803
3,629

Base Oil III Example Ca salicylate (A)
(Mass% of active ingredient) Component (B)
(Mass% of active ingredient) Particle count / sec Control Example -
A1 (5.2)
A1 (5.2) 6.1
-
6.1 19,478
24,647
11,889 Control Example A2 (4.2)
A2 (4.2) -
6.1 22,953
13,168 Control Example A3 (3.6)
A3 (3.6) -
6.1 20,170
13,724

Base oil IV (I) Example Ca salicylate (A)
(Mass% of active ingredient) Component (B)
(Mass% of active ingredient) Particle count / sec Control Example -
A1 (5.2)
A1 (5.2) 6.1
-
6.1 15,386
20,585
10,094 Control Example A2 (4.2)
A2 (4.2) -
6.1 22,366
9,385 Control Example A3 (3.6)
A3 (3.6) -
6.1 16,440
7,528

The results show that in each of the base oils II, III and IV (I), (A) in combination with (B) (denoted A1, A2 and A3, respectively) are superior to (A) alone and (B) alone.

Claims (18)

1. An engine lubricating oil composition for a trunk piston marine engine for improving handling of asphaltenes during use of a lubricating oil composition in operation of an engine for supplying heavy fuel oil as fuel,
Wherein the composition comprises
At least 50% by mass of a basic raw material containing 90% or more of a charge and 0.03% or less of sulfur or a mixture thereof,
(A) an overbased metal hydrocarbyl-substituted hydroxybenzoate detergent other than a detergent having a basicity of less than 2 and a degree of carbonization of 80%
(B) a hydrocarbyl-substituted carboxylic acid or an anhydride thereof
In a small amount, or by mixing them,
The degree of carbonization is the proportion of carbonate present in the overbased metal hydrocarbyl-substituted hydroxybenzoate detergent, expressed as mole percent relative to the total overblock of the detergent,
Wherein at least one hydrocarbyl group in (B) contains at least 8 carbon atoms and the acid or anhydride comprises at least 1% by weight of the lubricating oil composition,
Composition. The method according to claim 1,
(A)
(A1) a basicity of 2 or more and a degree of carbonization of 80% or more,
(A2) a basicity of at least 2 and a degree of carbonization of less than 80%, or
(A3) a basicity of less than 2 and a degree of carbonation of less than 80%
≪ / RTI > The method according to claim 1,
(B) is represented by formula (I) or formula (II): < EMI ID =
Formula I

[In the above formula,
R ¹ represents a C ₈ to C ₁₀₀ branched or linear hydrocarbyl group,
X and Y are each independently OR ² and OR ³ , wherein each of R ² and R ³ independently represents a hydrogen atom, or X and Y together represent -O-;
(II)
R ¹ CH ₂ COR ⁴
[In the above formula,
R < ¹ > is as defined above,
R ⁴ represents OR ⁵ , wherein R ⁵ represents a hydrogen atom. The method according to claim 1,
Wherein the metal in (A) is calcium. The method according to claim 1,
Wherein the hydrocarbyl-substituted hydroxybenzoate in (A) is salicylate. The method according to claim 1,
Wherein the oil having a lubricating viscosity contains more than 60% by mass of a basic raw material containing 90% or more of a charge and 0.03% or less of sulfur or a mixture thereof. The method according to claim 1,
(B) the hydrocarbyl group has from 8 to 400 carbon atoms. The method according to claim 1,
In the acid or derivative of (B), the hydrocarbyl substituent is derived from a polyolefin. The method according to claim 1,
(B) is succinic acid or succinic anhydride. 10. The method of claim 9,
(B) is polyisobutene succinic acid or anhydride. The method according to claim 1,
Wherein the total base (TBN) is from 20 to 60. The method according to claim 1,
Wherein the acid or anhydride in (B) accounts for at least 1.5% by mass of the lubricating oil composition. The method of claim 3,
Wherein R < ¹ > represents a polyalkenyl, alkyl or alkaryl group. 8. The method of claim 7,
(B) the hydrocarbyl group has from 12 to 100 carbon atoms. 8. The method of claim 7,
(B) the hydrocarbyl group has from 16 to 64 carbon atoms. 12. The method of claim 11,
Wherein the total base number (TBN) is 25 to 55. CLAIMS 1. A method of operating an engine for a medium speed compression ignition marine engine of a trunk piston,
(i) supplying heavy fuel oil to the engine, and
(ii) lubricating the crankcase of the engine using the composition according to any one of claims 1 to 16
≪ / RTI > CLAIMS 1. A method of lubricating a combustion chamber surface of a medium speed compression ignition marine engine and dispersing asphaltenes in a lubricant composition for a trunk piston marine vessel during operation of the engine,
(i) providing a composition according to any one of claims 1 to 16,
(ii) providing said composition in said combustion chamber,
(iii) providing the heavy fuel oil in the combustion chamber, and
(iv) combusting the heavy fuel oil in the combustion chamber
≪ / RTI >