JP6810033B2 - Diesel Cylinder Lubricating Oil Composition for Ships - Google Patents

Description

Priority This application claims benefits under 35 USC 119 for US Provisional Application No. 62 / 076,309 filed on November 6, 2014, which is hereby referred to herein. Invite.

Background of the invention 1. Technical Fields The present invention generally relates to marine diesel cylinder lubricating oil compositions, and in particular to marine lubricating oil compositions for lubricating marine two-stroke crosshead diesel cylinder engines.

2. 2. Description of Related Technologies In the not-so-distant past, the sharply rising energy costs, especially the costs of distilling crude and liquid oil, have placed a heavy burden on transport fuel users such as marine vessel owners and operators. It has become. Correspondingly, those users have steered their operations by moving away from steam turbine propulsion units and favoring fuel-efficient large marine diesel engines. Diesel engines can generally be categorized as low speed, medium speed, or high speed engines, the low speed type being used for the largest deep shaft vessels and certain other industrial applications.

Low-speed diesel engines are unique in terms of size and operating method. The engine itself is large, with larger units weighing nearly 200 tons, and can be 10 feet long and over 45 feet high. The output of these engines can reach as high as 100,000 brake horsepower, with engine speeds ranging from 60 to about 200 revolutions per minute. They are typically crosshead designs and operate in a two-stroke cycle. In addition, these engines typically operate on residual fuels, but some can also operate on distillate fuels that contain little or no residue.

On the other hand, medium speed engines typically operate in the range of about 250 to about 1100 rpm and can operate in either 4-stroke or 2-stroke cycles. These engines may have a trunk piston design or sometimes a crosshead design. They usually operate on residual fuels, much like low speed diesel engines, but some can operate on distillate fuels that contain little or no residue. These engines can also be used for propulsion of deep-sea vessels, auxiliary applications, or both.

Low and medium speed diesel engines are also widely used in the operation of power plants. A low or medium speed diesel engine operating in a two-stroke cycle is typically a direct-coupled and direct reversing engine with a crosshead construction, which has one or more stuffing boxes and diaphragms that separate the power cylinder from the crankcase. Provided, which prevents combustion products from entering the crankcase and mixing with the crankcase oil. By highly completely separating the crankcase from the combustion zone, those skilled in the art have begun to lubricate the combustion chamber and crankcase with different lubricants.

In large crosshead diesel engines used in marine and heavy stationary applications, the cylinder is lubricated separately from the other engine components. Cylinders are lubricated on a total loss basis by separately injecting cylinder oil into the quill of each cylinder using a lubricator located around the cylinder liner. The oil is pumped to the lubricator and, in current engine designs, is moved to apply the oil directly to the ring to reduce oil waste.

One problem associated with these engines is that engine manufacturers typically make them from good quality high distillate fuels with low sulfur and low asphaltene content to ships with generally high sulfur and higher asphaltene content. It is designed to use a variety of diesel fuels, ranging from lower quality intermediate or heavy fuels such as residual fuels.

The high stresses encountered in these engines and the use of marine residual fuels require lubricants with high cleanliness and neutralization capacity, even if the oil is only briefly exposed to heat and other stresses. Residual fuels commonly used in these diesel engines typically contain significant amounts of sulfur, which combine with water to form sulfuric acid during the combustion process and therefore corrode wear in the presence of it. Is caused. In particular, in a two-stroke engine for ships, the area around the cylinder liner and piston ring can be corroded and worn by the acid. Therefore, it is important that the diesel engine lubricating oil has a resistance to such corrosion and wear.

Therefore, the main function of marine diesel cylinder lubricants is to neutralize the sulfur-based acidic components of high sulfur fuel oils burned in low speed 2-stroke crosshead diesel engines. This neutralization is achieved by including basic species such as metal detergents in marine diesel cylinder lubricants. Unfortunately, the basicity of marine diesel cylinder lubricants can be reduced by the oxidation of marine diesel cylinder lubricants (due to the heat and oxidative stress the lubricant receives in the engine), thereby The neutralizing capacity of the lubricant is reduced. Oxidation may be accelerated if the marine diesel cylinder lubricant contains an oxidation catalyst such as a wear metal that is generally known to be present in the lubricant during engine operation.

Marine 2-stroke diesel cylinder lubricants meet the rigorous operating conditions required for more modern, large-diameter, large-diameter 2-stroke crosshead diesel marine engines that operate at high powers and cylinder liner loads and higher temperatures. Performance requirements must be met in order to meet.

Currently, the shipping industry is addressing an increasing shortage of basestock in the Group I category, typically used for marine engine oils, and lower sulfur fuel levels required by law. In addition to these challenges, marine 2-stroke diesel cylinder lubricants are required for more modern large-diameter 2-stroke cross-head diesel marine engines operated on high power and high load as well as hotter cylinder liners. In order to meet the harsh operating conditions, marine 2-stroke diesel cylinder lubricants must meet performance requirements. Therefore, it is compatible with basestocks other than Group I basestocks, while improving cleanliness and thermal stability at high temperatures to meet the harsh load conditions of large diameter 2-stroke engines operating on fuels with a wide range of sulfur content. There is a further need for marine cylinder lubricant compositions.

Recently, severe cold corrosion has frequently occurred due to overall design changes and operational changes (both imposed by fuel efficiency) of large-diameter low-speed two-stroke engines. Cold corrosion is caused by sulfuric acid. Sulfur oxides resulting from the combustion of fuel (typically heavy fuel oils containing> 2% by weight sulfur) will form sulfuric acid, along with the water formed during combustion and the water from the scavenger. .. When the liner temperature drops below the dew point of sulfuric acid and water, the corrosive mixture condenses on the liner. Cylinder lubricant basicity, cylinder lubricant supply rate of oil to the cylinder liner, engine build and type, engine load, inlet air humidity and fuel sulfur content are among the factors that can affect the amount of cold corrosion. Alkaline lubricants are used to neutralize sulfuric acid and avoid cold corrosion of piston ring and cylinder liner surfaces. Alkalinity lubricants (eg, up to 100 BN by the ASTM D2896 test method) are currently commercially available to help overcome severe cold corrosion.

Hyperbasic sulphide phenate is a known compound widely used in marine applications due to its cleanliness and thermal stability. However, low molecular weight alkylphenol compounds such as tetrapropenylphenol (TPP) are often used as raw materials in the production of these hyperbasic sulphide phenols. The process of producing a hyperbasic phenato generally results in the presence of unreacted alkylphenols in the final reaction product and, ultimately, in the finished lubricating oil composition. Recent reproductive toxicity studies have shown that high concentrations of unreacted alkylphenols, especially TPP, may be endocrine disruptors that can adversely affect the reproductive organs of men and women.

Reduce the amount of unreacted TPP and its unsulfided metal salts present in the lubricating oil composition to reduce potential health hazards to customers and avoid potential regulatory issues There is a further need to do or eliminate. Therefore, it would be more desirable to develop a marine diesel cylinder lubricant composition that is substantially free of unreacted TPP and its unsulfided metal salts.

Outline of the Invention According to one embodiment of the present invention.
(A) One or more Group II basestocks of a major amount, and (b) (i) one or more alkyl-substituted hydroxyaromatic carboxylic acids having a total base value (TBN) of greater than 250. Alkaline earth metal salt, and (ii) one or more highly hyperbasic alkyl aromatic sulfonic acids or salts thereof, a cleaning agent composition;
Is a marine diesel cylinder engine lubricating oil composition containing:
The aromatic portion of the alkyl aromatic sulfonic acid or a salt thereof does not contain a hydroxyl group; and the marine diesel cylinder lubricant composition has a TBN of about 5 to about 120.
The lubricating oil composition is provided.

According to the second embodiment of the present invention.
A method of lubricating a marine two-stroke crosshead diesel engine with a marine diesel cylinder lubricant composition having improved high temperature cleanliness and thermal stability; the method comprises the engine.
(A) Major amounts of one or more Group II basestocks, and (b) (i) one or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids with TBN greater than 250, and (ii). ) A detergent composition containing one or more highly hyperbasic alkyl aromatic sulfonic acids or salts thereof;
Is a marine diesel cylinder lubricant composition containing:
The aromatic portion of the alkyl aromatic sulfonic acid or a salt thereof does not contain a hydroxyl group; and the marine diesel cylinder lubricant composition has a TBN of about 5 to about 120, said lubricant. Provided are methods that include lubrication with the composition.

A third aspect of the present invention is to improve high temperature cleanliness and thermal stability in a two-stroke crosshead marine diesel engine.
(A) Major amounts of one or more Group II basestocks, and (b) (i) one or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids with TBN greater than 250, and (ii). ) A detergent composition containing one or more highly hyperbasic alkyl aromatic sulfonic acids or salts thereof;
Is a marine diesel cylinder lubricant composition containing:
The aromatic portion of the alkyl aromatic sulfonic acid or a salt thereof does not contain a hydroxyl group; and the marine diesel cylinder lubricant composition has a TBN of about 5 to about 120, said lubricant. Regarding the use of the composition.

The present invention comprises a combination of one or more alkaline earth metal salts of alkyl substituted hydroxyaromatic carboxylic acids with a TBN greater than 250 and one or more highly hyperbasic alkyl aromatic sulfonic acids or salts thereof. A marine diesel cylinder lubricating oil composition containing a major amount of one or more Group II basestocks and used in a two-stroke crosshead marine diesel engine, said marine diesel cylinder lubricant. Based on the surprising finding that the high temperature cleanliness and thermal stability of said lubricating oil composition, having a TBN of about 5 to about 120, is advantageously improved. In addition, the combination of one or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids with a TBN greater than 250 and one or more highly hyperbasic alkyl aromatic sulfonic acids or salts thereof is predominant. Storage stability of marine diesel cylinder lubricating oil compositions containing an amount of one or more Group II basestocks and having a TBN of about 5 to about 120 is also advantageously improved.

Detailed description of preferred embodiments
Definition

The terms "marine diesel cylinder lubricant" or "marine diesel cylinder lubricant" as used herein are used to lubricate the cylinders of low-speed or medium-speed two-stroke crosshead marine diesel engines. It shall be understood to mean the lubricant to be used. Marine diesel cylinder lubricants are supplied to the cylinder wall through a number of injection points. Marine diesel cylinder lubricants form a film between the cylinder liner and the piston ring and retain partially burned fuel residues in the suspension, thereby promoting engine cleanliness, and For example, the acid formed by the combustion of sulfur compounds in fuel can be neutralized.

"Marine Residual Fuel" is defined in the International Organization for Standardization Standards ISO 8217: 2005, "Petroleum Products-Fuels (class F) -Specialities of Marine Fuels", and the like, as defined by the International Organization for Standardization (ISO) 10370. Has a carbon residue defined in at least 2.5% by weight (eg, at least 5% by weight, or at least 8% by weight) (with respect to the total weight of the fuel) and has a viscosity greater than 14.0 cSt at 50 ° C. Means a flammable material in a large marine engine, the entire contents of which are incorporated herein by reference.

"Residual fuel" means a fuel that meets the specifications of residual marine fuel as defined in ISO 8217: 2010 International Standard. The "low sulfur marine fuel" conforms to the specifications of the residual marine fuel specified in the ISO 8217: 2010 specification, and in addition, is about 1.5% by weight or less, or about 1.5% by weight, based on the total weight of the fuel. It means a fuel having 0.5% by weight or less of sulfur.

“Distilled fuel” means a fuel that meets the specifications of the distillate ship fuel specified in the ISO 8217: 2010 International Standard. The "low sulfur distillate fuel" conforms to the specifications of the distillate marine fuel specified in the ISO 8217: 2010 international standard, and in addition, is about 0.1% by weight or less or about 0.1% by weight based on the total weight of the fuel. It means a fuel having 0.005% by weight or less of sulfur.

The term "bright stock" as used by those skilled in the art is the direct production of base oil or deasphalt petroleum decompressed residual oil derived from deasphalt petroleum decompression residue after further treatment such as solvent extraction and / or dewaxing. It means the base oil that is a thing. For the purposes of the present invention, it also means deasphalt distillate cut in the vacuum residue process. Brightstock generally has a kinematic viscosity of 28 to 36 mm ² / s at 100 ° C. An example of such a bright stock is ESSO ™ Core 2500 Base Oil.

The terms "group II metals" or "alkaline earth metals" mean calcium, barium, magnesium and strontium.

The term "calcium base" means calcium hydroxide, calcium oxide, calcium alkoxide, etc. and mixtures thereof.

The term "lime" means calcium hydroxide, also known as slaked lime or slaked lime.

The term "alkylphenol" is a phenol having one or more alkyl substituents, wherein at least one of the alkyl substituents has a sufficient number of carbon atoms to impart oil solubility to the resulting phenolic additive. It means a phenol group having.

The term "phenato" means a salt of phenol.

The term "lower alkanoic acid" means an alkanoic acid having 1 to 3 carbon atoms, ie formic acid, acetic acid and propionic acid and mixtures thereof.

The term "polyol accelerator" also means compounds having two or more hydroxy substituents, generally sorbitol types such as alkylene glycols and derivatives thereof, and functional group equivalents such as polyol ethers and hydroxycarboxylic acids. To do.

The term "total base value" or "TBN" means the level of alkalinity in an oil sample, which is a composition that continues to neutralize corrosive acids according to ASTM Standard No. D2896 or equivalent procedure. Show ability. The test measures changes in electrical conductivity and expresses the results as mgKOH / g (milligram equivalents of KOH required to neutralize 1 gram of product). Thus, a high TBN represents a strong overbasic product and, as a result, a higher base reserve for neutralizing the acid.

The term "base oil" as used herein is manufactured by a single manufacturer to the same specifications (regardless of the source or manufacturer's location); conforms to the specifications of the same manufacturer; and It shall be understood to mean a basestock or a blend of basestocks, which are lubricant components identified by a unique formulation, product identification number, or both.

The term "by activity criteria" means an additive material that is neither a diluent nor a solvent.

The term "isomerized olefin" means an olefin obtained by isomerizing an olefin. In general, isomerized olefins have double bonds at different positions than the starting olefins from which they are derived, and may also have different properties.

In one embodiment, (a) a major amount of one or more Group II basestocks, and (b) (i) one or more alkaline earth metals of alkyl substituted hydroxyaromatic carboxylic acids with a TBN greater than 250. A marine diesel cylinder lubricating oil composition comprising a salt and (ii) a cleaning agent composition comprising one or more highly hyperbasic alkyl aromatic sulfonic acids or salts thereof:
The aromatic portion of the alkyl aromatic sulfonic acid or a salt thereof does not contain a hydroxyl group; and the marine diesel cylinder lubricant composition has a TBN of about 5 to about 120, said lubricant. The composition is provided.

In general, the marine diesel cylinder lubricant composition of the present invention will have a TBN of about 5 to about 120. In one embodiment, the marine diesel cylinder lubricant composition of the present invention can have from about 20 to about 100 TBN. In one embodiment, the marine diesel cylinder lubricant composition of the present invention can have from about 40 to about 100 TBN. In one embodiment, the marine diesel cylinder lubricant composition of the present invention can have about 55 to about 80 TBN. In one embodiment, the marine diesel cylinder lubricant composition of the present invention can have about 60 to about 80 TBN. In one embodiment, the marine diesel cylinder lubricant composition of the present invention can have about 10 to about 40 TBN. In one embodiment, the marine diesel cylinder lubricant composition of the present invention can have about 15 to about 35 TBN.

In one embodiment, the marine diesel cylinder lubricating oil composition of the present invention is substantially free of unsulfated tetrapropenylphenol compounds and unsulfated metal salts thereof, such as TTP and calcium salts thereof. The term "substantially free" as used herein refers to relatively low levels, eg, marine diesel cylinder lubricant compositions, in the presence of unsulfurized tetrapropenylphenol and its unsulfated metal salts. It means less than about 1.5% by weight in the product. In another embodiment, the term "substantially free" is less than about 1% by weight in the marine diesel cylinder lubricant composition. In another embodiment, the term "substantially free" is less than about 0.3% by weight in the marine diesel cylinder lubricant composition. In another embodiment, the term "substantially free" is less than about 0.1% by weight in the marine diesel cylinder lubricant composition. In another embodiment, the term "substantially free" is from about 0.0001% to about 0.3% by weight in the marine diesel cylinder lubricant composition.

Due to the low operating speed and high load of marine engines, high viscosity oils (eg SAE 40, 50, and 60) are typically required. The marine diesel cylinder lubricant composition of the present invention can have kinematic viscosities in the range of about 12.5 to about 26.1 centimeters Stokes (cSt) at 100 ° C. In another embodiment, the lubricating oil composition has a viscosity of about 12.5 to about 21.9, or about 16.3 to about 21.9 cSt at 100 ° C. The kinematic viscosity of the marine diesel cylinder lubricant composition is measured by ASTM D445.

The marine diesel cylinder lubricating oil composition of the present invention can be prepared by a method known to those skilled in the art for producing a marine diesel cylinder lubricating oil composition. The ingredients can be added in any order and in any way. Any suitable mixing or dispersing device can be used to blend, mix or solubilize the ingredients. Blending, mixing or solubilization can be done with blenders, stirrers, dispersers, mixers (eg planetary mixers and double planetary mixers), homogenizers (eg Gaulin homogenizers or Rannie homogenizers), mills (eg , Colloid mill, ball mill or sand mill) or any other mixing or dispersing device known in the art.

The Group II basestock for use in the present invention can be a petroleum-derived base oil with a lubricating viscosity as defined in API Publication 1509, 14th Edition, Addendum I, December 1998. The API guidelines define basestock as a lubricant component that can be manufactured using a variety of different processes. Group II basestocks generally have a total sulfur content of 300 ppm or less (ppm: parts per million) (quantified by ASTM D2622, ASTM D4294, ASTM D4297 or ASTM D3120) and a saturation content of 90% by weight or more (ASTM D2007). (Quantitated by ASTM D2270) and means petroleum-induced lubricating base oil with a viscosity index (VI) between 80 and 120 (quantified by ASTM D2270).

In one embodiment, one or more Group II basestocks can be a blend or mixture of two or more Group II basestocks with different molecular weights and viscosities, or four or more Group II basestocks. In this case, the blend is processed in a manner suitable for producing a base oil having suitable properties (such as the viscosity and TBN values discussed above) for use in marine diesel engines.

One or more Group II basestocks for use in the marine diesel engine lubricating oil compositions of the present invention are typically in a major amount, eg, about 50% by weight, based on the total weight of the composition. Excess amount, or about 70% by weight excess. In one embodiment, one or more Group II basestocks are present in an amount of 70% to about 95% by weight based on the total weight of the composition. In one embodiment, one or more Group II basestocks are present in an amount of 70% to about 85% by weight, based on the total weight of the composition.

If desired, the marine diesel engine lubricating oil composition of the present invention may contain a minor amount of basestock other than the Group II basestock. For example, a marine diesel engine lubricating oil composition can contain a small amount of Group I or III-V basestock as defined in API Publication 1509, 16th Edition, Addendum I, October 2009. .. The base oil of Group IV is polyalphaolefin (PAO).

As described above, marine diesel cylinder lubricant compositions for use in marine diesel engines have kinematic viscosities in the range of 12.5 to 26.1 cSt at 100 ° C. To formulate such lubricants, Brightstock can be combined with low viscosity oils, such as oils having a viscosity of 4 to 6 cSt at 100 ° C. However, as the supply of bright stock is declining, it is not possible to rely on bright stock to increase the viscosity of marine cylinder lubricants to the desired range recommended by the manufacturer. One solution to this problem is to use a thickener compound such as polyisobutylene (PIB) or a viscosity index improver compound such as an olefin copolymer to enrich the marine diesel cylinder lubricant composition. is there. PIB is a material commercially available from several manufacturers. PIBs typically have a weight average molecular weight in the range of about 1,000 to about 8,000, or about 1,500 to about 6,000, and about 2,000 to about 5,000 or about 6,000 cSt. A viscous oil-miscible liquid having a viscosity in the range (at 100 ° C.). The amount of PIB added to the marine diesel cylinder lubricant composition is typically about 1 to about 20% by weight of the final oil, or about 2 to about 15% by weight of the final oil, or the final. It will be about 4 to about 12% by weight of the oil.

Group I base oils generally have a saturation content of less than 90% by weight (quantified by ASTM D2007) and / or a total sulfur content of more than 300 ppm (quantified by ASTM D2622, ASTM D4294, ASTM D4297 or ASTM D3120). Yes, and means a petroleum-induced lubricating base oil having a viscosity index (VI) of 80 or greater and less than 120 (quantified by ASTM D2270).

Group I base oils can include light overhead cuts and heavier side cuts from vacuum distillation columns, and can also include, for example, light neutral, medium neutral and heavy neutral basestocks. In addition, petroleum-derived base oils can also include residue stocks such as bright stocks or bottom fractions. Brightstock is a highly refined and dewaxed high viscosity base oil traditionally produced from residual stock or bottom. Brightstock can have kinematic viscosities in the range of about 180 cSt over 40 ° C, or about 250 cSt at 40 ° C, or about 500 to about 1100 cSt at 40 ° C. In one embodiment, the Group I basestock comprises ExxonMobil CORE® 100, ExxonMobil CORE® 150, ExxonMobil CORE® 600, ExxonMobil CORE® 2500 or a mixture thereof. Is done.

Group III Betstock generally has a total sulfur content of 0.03% by weight or less (quantified by ASTM D2270), a saturation content of 90% by weight or more (quantified by ASTM D2007), and a viscosity index (VI) of 120. The above (quantified by ASTM D4294, ASTM D4297 or ASTM D3120). In one embodiment, the basestock is a group III basestock or a blend of two or more different group III basestocks.

In general, Group III basestocks derived from petroleum oils are highly hydrogenated mineral oils. The hydrogenation process involves reacting hydrogen with the basestock to be treated to remove heteroatoms from the hydrocarbons, reducing olefins and aromatics to alkanes and cycloparaffins, respectively, and a very advanced hydrogenation process. Includes opening the naphthenic cyclic structure into acyclic normals and isoalkanes (“paraffins”). In one embodiment, Group III base stocks, have at least about 70% paraffinic carbon content (% _{C p),} which is the test method ASTM D3238-95 (2005), "Standard Test Method for Calculation of Carbon It is quantified by "Distribution and Structural Group Analysis of Petroleum Oils by the n-d-M Method". In another embodiment, the Group III basestock has a paraffinic carbon content (% _Cp ) of at least about 72%. In another embodiment, the Group III basestock has a paraffinic carbon content (% _Cp ) of at least about 75%. In another embodiment, the Group III basestock has a paraffinic carbon content (% _Cp ) of at least about 78%. In another embodiment, the Group III basestock has a paraffinic carbon content (% _Cp ) of at least about 80%. In another embodiment, the Group III basestock has a paraffinic carbon content (% _Cp ) of at least about 85%.

In another embodiment, Group III base stocks have a naphthenic carbon content of less than about 25% (% _{C n),} which is quantified by the ASTM D3238-95 (2005). In another embodiment, Group III base stocks have a naphthenic carbon content of less than about 20% (% _{C n).} In another embodiment, Group III base stocks have a naphthenic carbon content of less than about 15% (% _{C n).} In another embodiment, Group III base stocks have a naphthenic carbon content of less than about 10% (% _{C n).}

Many of the Group III basestocks are commercially available, such as the Chevron UCBO basestock; the Yukong Hubase basestock; the Shell XHVI® basestock; and the ExxonMobil Exxsin® basestock.

In one embodiment, the Group III basestock for use in the present invention is a Fischer-Tropsch-induced base oil. The term "Fischer-Tropsch induction" means that a product, fraction, or feed is produced from the Fischer-Tropsch process or at some stage by the Fischer-Tropsch process. For example, Fisher Tropsch base oil can be produced from a process in which the feed is a waxy feed recovered from Fisher Tropsch synthesis, eg, US Patent Application Publication Nos. 2004/0159582; 2005/0077208. No. 2005/01333407; No. 2005/01333409; No. 2005/0139513; No. 2005/0139514; No. 2005/0241990; No. 2005/0261145; No. 2005/0261146; No. 2005/0261147; No. 2006/0016721; 2006/0016724; 2006/0076267; 2006/013210; 2006/0201851; 2006/020185 and 2006/0289337; US Pat. Nos. 7,018,525 And 7,083,713 and US Application Nos. 11 / 400,570; 11 / 535, 165 and 11 / 613,936, each of which is incorporated herein by reference. To do. Generally, the process involves a complete or partial hydrogenation isomerization dewaxing step utilizing a catalyst capable of selectively isomerizing paraffin or a dual function catalyst. Hydrogenation isomerization dewaxing is achieved by contacting a waxy feed with a hydrogenation isomerization catalyst in the isomerization zone under hydrogenation isomerization conditions.

The products of Fischer-Tropsch synthesis are well-known processes such as, for example, the commercial SASOL® Slurry Phase Fisher-Tropsch technology, the commercial SHELL® Middle Distilate Synthesis (SMDS) process, or non-commercial. It can be obtained by a typical EXXON® Advanced Gas Conversion (AGC-21) process. These processes and other details are described, for example, in International Publication No. 9934917; International Publication No. 9920720; International Publication No. 05107935; European Patent Application Publication No. 7769959; European Patent Application Publication No. 668342; US Patent No. 4,943. , 672, 5,059,299; 5,733,839; and US Reissue Patent No. 39073; and US Patent Application Publication No. 2005/0227866. The product of Fischer-Tropsch synthesis can contain hydrocarbons with 1 to about 100 carbon atoms, and in some cases more than 100 carbon atoms, typically paraffin, olefins and oxygenated products. Is included.

Group IV basestocks, or polyalphaolefins (PAOs), are typically made by oligomerizing low molecular weight alphaolefins, such as alphaolefins containing at least 6 carbon atoms. In one embodiment, the alpha olefin is an alpha olefin containing 10 carbon atoms. PAO is a mixture of dimers, trimers, tetramers, etc., which is precisely mixed according to the desired viscosity of the final base stock. PAOs are typically hydrogenated after oligomerization to remove the remaining unsaturated.

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

The marine diesel cylinder lubricating oil composition of the present invention further comprises.
(I) One or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids having a TBN of more than 250, and (ii) one or more highly hyperbasic alkyl aromatic sulfonic acids or salts thereof. A cleaning agent composition containing, wherein the aromatic portion of the alkyl aromatic sulfonic acid or a salt thereof contains a cleaning agent composition containing no hydroxyl group.

Generally, one or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids and one or more highly hyperbasic alkyl aromatic sulfonic acids or salts thereof are provided as concentrates, and each of the additives is provided as a concentrate. , For example mineral oil, naphtha, benzene, toluene or xylene, etc., are mixed in a substantially inert, normally liquid organic diluent to form an additive concentrate. These concentrates typically contain from about 10% to about 90% by weight such diluent or from about 20% to about 80% by weight such diluent, with the remaining amount being a particular additive. is there. Typically, neutral oils having viscosities of about 4 to about 8.5 cSt at 100 ° C. and preferably about 4 to about 6 cSt at 100 ° C. will be used as diluents, but synthetic oils, as well as additives. Other organic liquids that are compatible with the agent and the final lubricant can also be used.

In one embodiment, the concentrate is substantially free of unsulfated tetrapropenylphenol compounds and unsulfated metal salts thereof, such as TPP and calcium salts thereof. The term "substantially free" as used herein refers to relatively low levels, eg, about 1.5 weight in concentrate, in the presence of unsulfurized tetrapropenylphenol and its unsulfated metal salts. Means less than%. In another embodiment, the term "substantially free" is less than about 1% by weight in the concentrate. In another embodiment, the term "substantially free" is less than about 0.3% by weight in the concentrate. In another embodiment, the term "substantially free" is less than about 0.1 in the concentrate. In another embodiment, the term "substantially free" is from about 0.0001 to about 0.3% by weight in the concentrate.

The cleaning agent composition used in the marine diesel cylinder lubricating oil composition of the present invention contains one or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids having a TBN of more than 250. The TBN of one or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids is the activity criterion. In one embodiment, one or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids have a TBN greater than 250 and up to about 800. In one embodiment, one or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids have a TBN greater than 250 and up to about 750. In one embodiment, one or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids have a TBN greater than 250 and up to about 700. In one embodiment, one or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids have a TBN greater than 250 and up to about 650. In one embodiment, one or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids have a TBN greater than 250 and up to about 600. In one embodiment, one or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids have a TBN greater than 250 and up to about 410.

In another embodiment, one or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids have a TBN of about 260 to about 800. In one embodiment, one or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids have a TBN of about 260 to about 750. In one embodiment, one or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids have a TBN of about 260 to about 700. In one embodiment, one or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids have a TBN of about 260 to about 650. In one embodiment, one or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids have a TBN of about 260 to about 600. In one embodiment, one or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids have a TBN of about 260 to about 410.

In another embodiment, one or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids have a TBN of about 300 or more. In one embodiment, one or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids have a TBN of about 300 to about 800. In one embodiment, one or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids have a TBN of about 300 to about 750. In one embodiment, one or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids have a TBN of about 300 to about 700. In one embodiment, one or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids have a TBN of about 300 to about 650. In one embodiment, one or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids have a TBN of about 300 to about 600. In one embodiment, one or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids have a TBN of about 300 to about 410.

In one preferred embodiment, the one or more alkaline earth metal salts of the alkyl substituted hydroxyaromatic carboxylic acid is one or more alkaline earth metal salts of the alkyl substituted hydroxybenzoic acid having a TBN greater than 250. In one preferred embodiment, the one or more alkaline earth metal salts of the alkyl-substituted hydroxyaromatic carboxylic acids are calcium alkyl-substituted hydroxyaromatic carboxylates with a TBN greater than 250. In another preferred embodiment, one or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids are one or more of mono-alkyl-substituted hydroxyaromatic carboxylic acids with a major amount of TBN greater than 250. It has an alkaline earth metal salt.

In one preferred embodiment, the one or more alkaline earth metal salts of the alkyl substituted hydroxyaromatic carboxylic acid is one or more alkaline earth metal salts of the alkyl substituted hydroxybenzoic acid having about 300 or more TBN. .. In one preferred embodiment, the one or more alkaline earth metal salts of the alkyl-substituted hydroxyaromatic carboxylic acids are calcium alkyl-substituted hydroxyaromatic carboxylic acids having a TBN of about 300 or more. In another preferred embodiment, the one or more alkaline earth metal salts of the alkyl-substituted hydroxyaromatic carboxylic acid is one or more of the monoalkyl-substituted hydroxyaromatic carboxylic acids having a major amount of about 300 or more TBN. It has an alkaline earth metal salt.

Suitable hydroxy aromatic compounds include mononuclear monohydroxy and polyhydroxy aromatic hydrocarbons having 1 to 4 and preferably 1 to 3 hydroxyl groups. Suitable hydroxy aromatic compounds include phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol and the like. A preferred hydroxy aromatic compound is phenol.

Alkyl Substitution The alkyl substituted moiety of an alkaline earth metal salt of a hydroxyaromatic carboxylic acid can be derived from an alpha olefin having about 10 to about 80 carbon atoms. In one embodiment, the alkyl substituted moiety of the alkaline earth metal salt of the alkyl substituted hydroxyaromatic carboxylic acid can be derived from an alpha olefin having about 10 to about 40 carbon atoms. In one embodiment, the alkyl substituted moiety of the alkaline earth metal salt of the alkyl substituted hydroxyaromatic carboxylic acid can be derived from an alpha olefin having about 12 to about 28 carbon atoms. The olefins utilized may be linear, isomerized linear, branched or partially branched linear. The olefin may be a mixture of linear olefins, a mixture of isomerized linear olefins, a mixture of branched olefins, a mixture of partially branched linear olefins, or any mixture of the above.

In one embodiment, the mixture of linear olefins that can be used is a mixture of normal alpha olefins selected from olefins having about 12 to about 28, or about 20 to 28 carbon atoms per molecule. .. In one embodiment, the normal alpha olefin is isomerized using at least one solid or liquid catalyst.

In another embodiment, the olefin comprises one or more olefins comprising C ₉ to C ₁₈ oligomers of monomers selected from propylene, butylene or mixtures thereof. Generally, one or more olefins will contain major amounts of C ₉ to C ₁₈ oligomers of monomers selected from propylene, butylene or mixtures thereof. Examples of such olefins include propylene tetramers, butylene trimers and the like. Other olefins may be present, as will be readily appreciated by those skilled in the art. For example, other olefins that can be used in addition to the C ₉ to C ₁₈ oligomers include branched olefins other than propylene oligomers such as linear olefins, cyclic olefins, butylene or isobutylene oligomers, arylalkylenes and the like, and theirs. Contains a mixture. Suitable linear olefins include 1-hexene, 1-nonene, 1-decene, 1-dodecene and the like and mixtures thereof. Particularly suitable linear olefins are high molecular weight normal alpha olefins such as C ₁₆ to C ₃₀ normal alpha olefins, which can be obtained from processes such as ethylene oligomerization or wax cracking. Suitable cyclic olefins include cyclohexene, cyclopentene, cyclooctene and the like and mixtures thereof. Suitable branched olefins include butylene dimers or trimers or even higher molecular weight isobutylene oligomers and mixtures thereof. Suitable arylalkylenes include styrene, methylstyrene, 3-phenylpropene, 2-phenyl-2-butene and the like and mixtures thereof.

In one embodiment, the alkyl-substituted moiety of the alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acids may contain a mixture of C ₁₂ alkyl and C ₂₀ and C ₂₈ linear olefins. In one embodiment, the alkyl substituted moiety of the alkaline earth metal salt of the alkyl substituted hydroxyaromatic carboxylic acid is mixed with at least 50% by weight C ₂₀ to C ₂₈ linear olefins to about 50% by weight C ₁₂ alkyl. Can contain groups.

In one embodiment, the alkyl-substituted moiety of the alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid is up to 50% by weight mixed with at least 50% by weight of branched hydrocarbyl radicals derived from the propylene oligomer. It can contain C ₂₀ to C ₂₈ linear olefins. In another embodiment, the alkyl-substituted portion of the alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid is mixed with at least 15% by weight of branched hydrocarbyl radicals derived from propylene oligomers up to 85% by weight. C ₂₀ to C ₂₈ linear olefins can be contained.

In one embodiment, at least about 75 mol% (eg, at least about 80 mol%, at least about 85 mol%, at least about 90 mol%) of the alkyl groups contained in the alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid. , at least about 95 mole%, or at least about 99 mole%) _is a _{C 20} or greater alkyl group. In another embodiment, the alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid is an alkaline earth metal salt of the alkyl-substituted hydroxybenzoic acid derived from the alkyl-substituted hydroxybenzoic acid, the alkyl group being at least 75. It is a residue of a normal alpha olefin containing a molar% of C ₂₀ or more of a normal alpha olefin.

In another embodiment, at least about 50 mol% (eg, at least about 60 mol%, at least about 70 mol%, at least about 80 mol%) of the alkyl groups contained in the alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid. %, At least about 85 mol%, at least about 90 mol%, at least about 95 mol%, or at least about 99 mol%) is about C ₁₄ to about C ₁₈ .

The resulting alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid with a TBN greater than 250 can be a mixture of ortho and para-isomers. In one embodiment, the product will contain from about 1 to 99% ortho isomer and 99 to 1% para isomer. In another embodiment, the product will contain from about 5 to 70% ortho isomer and 95 to 30% para isomer.

The alkaline earth metal salt of the alkyl-substituted hydroxy aromatic carboxylic acid is derived from the BN of the alkaline earth metal salt of the alkyl-substituted hydroxy aromatic carboxylic acid as a base source (eg, lime) and an acidic hyperbasic compound (eg, carbon dioxide). ) Was added by a process such as addition. The method of superbasement is within the understanding of those skilled in the art.

Generally, the amount of one or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids with more than 250 TBN present in marine diesel cylinder lubricant compositions with about 5 to about 120 TBN Based on the total weight of the marine diesel cylinder lubricant composition, it can range from about 0.1% by weight to about 35% by weight on an activity basis. In one embodiment, a marine diesel cylinder lubricant composition having a TBN of about 20 to about 100, one or more of alkyl substituted hydroxyaromatic carboxylic acids having a TBN greater than 250 present in the marine diesel cylinder lubricant composition. The amount of alkaline earth metal salt in the above can range from about 1% to about 25% by weight on an activity basis, based on the total weight of the marine diesel cylinder lubricant composition. In one embodiment, a marine diesel cylinder lubricant composition having a TBN of about 20 to about 60 and one of the alkyl substituted hydroxyaromatic carboxylic acids having a TBN greater than 250 present in the marine diesel cylinder lubricant composition. The amount of the above alkaline earth metal salt can be in the range of about 3% by weight to about 20% by weight based on the activity standard based on the total weight of the marine diesel cylinder lubricating oil composition. In one embodiment, a marine diesel cylinder lubricant composition having a TBN of about 30 to about 50, one or more of alkyl substituted hydroxyaromatic carboxylic acids with a TBN greater than 250 present in the marine diesel cylinder lubricant composition. The amount of alkaline earth metal salt in the above can range from about 3% to about 15% by weight on an activity basis, based on the total weight of the marine diesel cylinder lubricant composition.

The detergent composition used in the marine diesel cylinder lubricating oil composition of the present invention also contains one or more highly hyperbasic alkyl aromatic sulfonic acids or salts thereof. Alkyl aromatic sulfonic acids or salts thereof include alkyl aromatic sulfonic acids obtained by alkylation of aromatic compounds or salts thereof. Alkyl aromatic compounds are then sulfonated to form alkyl aromatic sulfonic acids. If desired, the alkyl aromatic sulfonic acid can be neutralized with caustic to give an alkyl aromatic sulfonate compound of alkali or alkaline earth metal.

At least one aromatic compound or mixture of aromatic compounds can be used to form alkyl aromatic sulfonic acids or salts thereof. Suitable aromatic compounds or mixtures of aromatic compounds include at least one monocyclic aromatic such as benzene, toluene, xylene, cumene or mixtures thereof. In one preferred embodiment, at least one aromatic moiety of the alkyl aromatic sulfonic acid or salt does not contain a hydroxyl group. In one preferred embodiment, at least one aromatic portion of the alkyl aromatic sulfonic acid or salt compound is not phenol. In one embodiment, the at least one aromatic compound or mixture of aromatic compounds is toluene.

At least one alkyl aromatic compound or mixture of aromatic compounds can be commercially available or prepared by methods well known in the art.

Alkylating agents used to alkylate aromatic compounds can be derived from a variety of sources. Such sources include normal alpha olefins, linear alpha olefins, isomerized linear alpha olefins, dimerized and oligomerized olefins, and olefins derived from olefin metathesis. The olefin may be a single carbon number olefin, or a mixture of linear olefins, a mixture of isomerized linear olefins, a mixture of branched olefins, partially branched. It may be a mixture of olefins of the above, or a mixture of any of the above. Another source of olefin induction is by cracking petroleum or Fischer-Tropsch wax. Fischer-Tropsch wax may be hydrogenated prior to cracking. Other commercially available sources include paraffin dehydrogenation and oligomerization of ethylene and other olefins, olefins derived from MTO (methanol-to-olefin) processes (methanol crackers) and the like.

The olefin can be selected from olefins having a carbon number in the range of about 8 carbon atoms to about 60 carbon atoms. In one embodiment, the olefin is selected from olefins having a carbon number in the range of about 10 to about 50 carbon atoms. In one embodiment, the olefin is selected from olefins having a carbon number in the range of about 12 to about 40 carbon atoms.

In another embodiment, the olefin or mixture of olefins is selected from linear alpha olefins or isomerized alpha olefins containing from about 8 to about 60 carbon atoms. In one embodiment, the olefin mixture is selected from linear alpha olefins or isomerized alpha olefins containing from about 10 to about 50 carbon atoms. In one embodiment, the olefin mixture is selected from linear alpha olefins or isomerized olefins containing from about 12 to about 40 carbon atoms.

The linear olefins that can be used for the alkylation reaction can be one or a mixture of normal alpha olefins selected from olefins having about 8 to about 60 carbon atoms per molecule. In one embodiment, the normal alpha olefin is selected from olefins having about 10 to about 50 carbon atoms per molecule. In one embodiment, the normal alpha olefin is selected from olefins having about 12 to about 40 carbon atoms per molecule.

In one embodiment, the mixture of branched olefins, C ₃ or which higher monoolefin (e.g., propylene oligomer, butylene oligomers or co-oligomers and the like) is selected from polyolefins can be derived from. In one embodiment, the mixture of branched olefins is either a propylene oligomer or a butylene oligomer or a mixture thereof.

In one embodiment, the aromatic compounds are alkylated with a mixture of normal alpha olefins containing C ₆₀ carbon atoms from C _8. In one embodiment, the aromatic compound is alkylated with a mixture of normal alpha olefins containing C ₁₀ to C ₅₀ carbon atoms. In another embodiment, the aromatic compounds are alkylated with a mixture of normal alpha olefins from C ₁₂ containing C ₄₀ carbon atoms, produce aromatic alkylate.

The normal alpha olefins utilized to make alkyl aromatic sulfonic acids or salts thereof can be commercially available or prepared by methods well known in the art.

In one embodiment, the normal alpha olefin is isomerized using a solid or liquid acid catalyst. The solid catalyst preferably has at least one metal oxide and an average pore size of less than 5.5 angstroms. In one embodiment, the solid catalyst is a one-dimensional sieve such as SM-3, MAPO-11, SAPO-11, SSZ-32, ZSM-23, MAPO-39, SAPO-39, ZSM-22 or SSZ-20. Molecular sieves with a pore system. Other possible acidic solid catalysts useful for isomerization include ZSM-35, SUZ-4, NU-23, NU-87 and natural or synthetic ferrierite. These molecular sieves are well known in the art and are described by Rosemary Szostak, Handbook of Molecular Sieves (New York, Van Nostrand Reinhold, 1992), for all purposes. Incorporated herein. A liquid type isomerization catalyst that can be used is iron pentacarbonyl (Fe (CO) ₅ ).

The isomerization process for normal alpha olefins can be carried out in batch or continuous fashion. The process temperature can range from about 50 ° C to about 250 ° C. In the batch formula, the typical method used is a stirring autoclave or a glass flask, which can be heated to the desired reaction temperature. The continuous process is most efficient in the fixed floor process. Space velocities in fixed floor processes can range from about 0.1 to about 10 or more weight space velocities per unit time.

In the fixed bed process, the isomerization catalyst is placed in a reactor and activated or dried at a temperature of at least 125 ° C. under reduced pressure or while flowing an inert dry gas. After activation, the temperature of the isomerization catalyst is adjusted to the desired reaction temperature and a stream of olefins is introduced into the reactor. Reactor effluent containing partially branched isomerized olefins is recovered. The resulting partially branched isomerized olefin contains a different olefin distribution (ie, alpha olefin, beta olefin, internal olefin, trisubstituted olefin, and vinylidene olefin) and branched content than the unisomerized olefin. The conditions are selected to obtain the desired olefin distribution and branching degree.

Typically, alkylated aromatic compounds can be prepared using Bronsted acid catalysts, Lewis acid catalysts, or solid acid catalysts.

The blended acid catalyst can be selected from the group containing hydrochloric acid, hydrofluoric acid, hydrofluoric acid, sulfuric acid, perchloric acid, trifluoromethanesulfonic acid, fluorosulfonic acid, nitric acid and the like. In one embodiment, the Bronsted acid catalyst is hydrofluoric acid.

The Lewis acid catalyst can be selected from the group of Lewis acids including aluminum trichloride, aluminum tribromide, aluminum triiodide, boron trifluoride, boron tribromide, boron triiodide and the like. In one embodiment, the Lewis acid catalyst is aluminum trichloride.

The solid acidic catalyst can be selected from the group containing zeolite, acid clay, and / or silica alumina. A desirable solid catalyst is an acid form of a cation exchange resin, such as a crosslinked sulfonic acid catalyst. The catalyst can be molecular sieves. Suitable molecular sieves are silica aluminophosphate molecular sieves or metallic silica aluminophosferate molecular sieves, the metal of which can be, for example, iron, cobalt or nickel. Other suitable examples of solid acidic catalysts are disclosed in US Pat. No. 7,183,452, the contents of which are incorporated herein by reference.

Bronsted acid catalysts can be regenerated after deactivation (ie, after the catalyst loses all or part of its catalytic activity). Methods well known in the art can be used to regenerate acid catalysts such as hydrofluoric acid.

Alkylation techniques used to produce alkyl aromatics include Bronsted acid catalysts and / or Lewis acid catalysts used in batch, semi-batch or continuous processes operating between about 0 and about 300 ° C. , As well as solid acid catalysts.

Acid catalysts can be recycled if used in a continuous process. Acid catalysts can be recycled or regenerated when used in batch or continuous processes.

In one embodiment, the alkylation process involves a first amount of a mixture of at least one aromatic compound or aromatic compound, a first amount of a mixture of olefin compounds and a Bronsted acid catalyst, eg, fluoride. This is done by reacting in the presence of a hydride in a first reactor where stirring is maintained, thereby producing a first reaction mixture. The resulting first reaction mixture is held in a first alkylation zone under alkylation conditions for a time sufficient to convert the olefin to an aromatic alkylene (ie, the first reaction product). After the desired time, the first reaction product is removed from the alkylation zone and fed to the second reactor, where the first reaction product is added in an additional amount of at least one aromatic. A mixture of group or aromatic compounds and an additional amount of acid catalyst, and optionally an additional amount of a mixture of olefin compounds, are reacted with continuous stirring. A second reaction mixture is obtained, which is held in the second alkylation zone under alkylation conditions for a time sufficient to convert the olefin to an aromatic alkylene (ie, the second reaction product). .. A second reaction product can be fed into a liquid-liquid separator to separate the hydrocarbon (ie, organic) product from the acid catalyst. The acid catalyst can be recycled to the reactor (s) during the closed loop cycle. Hydrocarbon products are further treated to remove excess unreacted aromatic compounds and optionally olefinic compounds from the desired alkyrates product. Excess aromatic compounds can also be recycled into reactors (s).

In another embodiment, the reaction takes place in more than two reactors arranged in series. Instead of feeding the second reaction product to the liquid-liquid separator, the second reaction product is fed to the third reactor, where the second reaction product is added in at least one additional amount. Reacts with an aromatic compound or a mixture of aromatic compounds and an additional amount of acid catalyst, and optionally an additional amount of a mixture of olefin compounds, with continued stirring. A third reaction mixture is obtained, which is held in the third alkylation zone under alkylation conditions for a time sufficient to convert the olefin to an aromatic alkylene (ie, the third reaction product). .. The reaction is carried out in the number of reactors required to obtain the desired alkylated aromatic reaction product.

The total molar ratio of Bronsted acid catalyst to olefin compound charged is from about 0.1 to about 1 in the combined reactor. In one embodiment, the Bronsted acid-catalyzed to olefin compound charge molar ratio is from about 0.7 or less to about 1 in the first reactor and from about 0.3 to about 1 in the second reactor. Is.

The total molar ratio of aromatic compound to olefin compound charged is from about 7.5: 1 to about 1: 1 in the combined reactor. In one embodiment, the charged molar ratio of aromatic compound to olefin compound is from about 1.4: 1 or greater to about 1: 1 in the first reactor and about 6.1: 1 in the second reactor. From 1 or less to about 1: 1.

Many types of reactor shapes can be used for reactor zones. These include, but are not limited to, batch and continuous stirring tank reactors, reactor riser shapes, ebulating bed reactors, and other reactor shapes well known in the art. Many such reactors are known to those of skill in the art and are suitable for alkylation reactions. Stirring is important for alkylation reactions and is performed by a rotating impeller with or without a baffle, a static mixer, kinetic mixing in a riser, or any other stirrer known in the art. be able to. The alkylation process can be carried out at a temperature of about 0 ° C to about 100 ° C. The process is carried out under sufficient pressure so that a substantial portion of the feed component remains in the liquid phase. Typically, a pressure of 0 to 150 psig is sufficient to maintain the feed and product in the liquid phase.

The residence time in the reactor is sufficient to convert a substantial portion of the olefin into an alkyrate product. The time required is from about 30 seconds to about 30 minutes. More accurate residence times can be determined by one of ordinary skill in the art using a batch stirring tank reactor to measure the reaction rate of the alkylation process.

The at least one aromatic compound or mixture of aromatic compounds and the olefin compound may be injected separately into the reaction zone or mixed prior to injection. Both single and multiple reaction zones can be used to inject aromatic and olefin compounds into one, several, or all reaction zones. The reaction zone need not be maintained under the same process conditions. The hydrocarbon feed for the alkylation process can include a mixture of aromatic and olefin compounds having an aromatic to olefin compound molar ratio of about 0.5: 1 to about 50: 1 or more. When the molar ratio of aromatic compound to olefin is> 1.0: 1, there is an excess amount of aromatic compound. In one embodiment, excess aromatic compounds are used to increase reaction rate and improve product selectivity. When excess aromatic compounds are used, the excess unreacted aromatics in the reactor effluent can be separated, for example by distillation, and recycled to the reactor.

Once the alkyl aromatic product is obtained as described above, it can be further reacted to form an alkyl aromatic sulfonic acid and then neutralized to give the corresponding sulfonate. Sulfonation of alkyl aromatic compounds can be carried out by any method known to those of skill in the art. The sulfonate reaction is typically carried out in a continuous flowing film tubular reactor maintained at about 45 ° C to about 75 ° C. For example, an alkyl aromatic compound is placed in a reactor with air-diluted sulfur trioxide, thereby producing an alkylaryl sulfonic acid. Other sulfonates such as sulfuric acid, chlorosulfonic acid or sulfamic acid can also be utilized. In one embodiment, the alkyl aromatic compound is sulfonated with air-diluted sulfur trioxide. The sulfur trioxide to alchilate charge molar ratio is maintained from about 0.8 to about 1.1: 1.

If desired, neutralization of the alkyl aromatic sulfonic acid can be carried out in a continuous or batch process by any method known to those of skill in the art to produce the alkyl aromatic sulfonate. Typically, alkyl aromatic sulfonic acids are neutralized with a source of alkali metal or alkaline earth metal or ammonia, thereby producing alkyl aromatic sulfonates. Non-limiting examples of suitable alkali metals include lithium, sodium, potassium, rubidium, and cesium. In one embodiment, suitable alkali metals include sodium and potassium. In another embodiment, a suitable alkali metal is sodium. Non-limiting examples of suitable alkaline earth metals include calcium, barium, magnesium, strontium and the like. In one embodiment, a suitable alkaline earth metal is calcium. In one embodiment, the source is an alkali metal hydroxide, such as an alkali metal base such as sodium hydroxide or potassium hydroxide. In one embodiment, the source is an alkaline earth metal hydroxide, eg, an alkaline earth metal base such as calcium hydroxide.

One or more alkyl aromatic sulfonic acids or salts thereof is one or more highly hyperbasic alkyl aromatic sulfonic acids or salts thereof. As mentioned above, hyperbasification is enhanced by a process such as the addition of an alkyl aromatic sulfonic acid or a salt thereof, for example, a base source (eg, lime) and an acidic superbasic compound (eg, carbon dioxide). Is to be done. The method of superbasement is well known in the art.

In one embodiment, one or more highly hyperbasic alkyl aromatic sulfonic acids or salts thereof will have a TBN greater than 250. In one embodiment, one or more highly hyperbasic alkyl aromatic sulfonic acids or salts thereof will have a TBN of about 250 to about 700. In one embodiment, one or more highly hyperbasic alkyl aromatic sulfonic acids or salts thereof will have about 300 or more TBN. In one embodiment, one or more highly hyperbasic alkyl aromatic sulfonic acids or salts thereof will have a TBN of about 300 to about 700.

Generally, the amount of one or more highly hyperbasic alkyl aromatic sulfonic acids or salts thereof present in a marine diesel cylinder lubricant composition having a TBN of about 5 to about 120 is a marine diesel cylinder lubricant. Based on the total weight of the oil composition, it can range from about 0.1% to about 34% by weight on an activity basis. In one embodiment, the amount of one or more highly hyperbasic alkyl aromatic sulfonic acids or salts thereof present in a marine diesel cylinder lubricant composition having about 20 to about 100 TBN is a marine diesel cylinder. Based on the total weight of the lubricating oil composition, it can range from about 1% to about 30% by weight on an activity basis. In one embodiment, the amount of one or more highly hyperbasic alkyl aromatic sulfonic acids or salts thereof present in a marine diesel cylinder lubricant composition having about 20 to about 60 TBN is a marine diesel cylinder. Based on the total weight of the lubricating oil composition, it can range from about 2% to about 24% by weight on an activity basis. In one embodiment, the amount of one or more highly hyperbasic alkyl aromatic sulfonic acids or salts thereof present in a marine diesel cylinder lubricant composition having about 30 to about 50 TBN is a marine diesel cylinder. Based on the total weight of the lubricating oil composition, it can range from about 5% to about 16% by weight on an activity basis.

The marine diesel cylinder lubricating oil composition of the present invention comprises one or more alkaline earth metal salts of the above-mentioned alkyl-substituted hydroxyaromatic carboxylic acids having a TBN of more than 250 and one or more highly hyperbasic alkyl aromatics. Other than group sulfonic acids or salts thereof, additives of conventional marine diesel cylinder lubricant compositions can also be contained, which impart ancillary functions and these additives are dispersed or dissolved. This is to provide a marine diesel cylinder lubricating oil composition. For example, marine diesel cylinder lubricant compositions include antioxidants, ashless dispersants, other cleaning agents, anti-wearing agents, rust inhibitors, defoaming agents, anti-emulsifiers, metal deactivators, friction modifiers, etc. It can be blended with flow point lowering agents, antifoaming agents, auxiliary solvents, corrosion inhibitors, dyes, extreme pressure agents and the like and mixtures thereof. A variety of additives are known and commercially available. These additives or similar compounds thereof can be utilized in the preparation of the marine diesel cylinder lubricant composition of the present invention by ordinary blending procedures.

In one embodiment, the marine diesel cylinder lubricant composition of the present invention is essentially free of thickeners (ie, viscosity index improvers).

Examples of antioxidants include, but are not limited to, amines such as diphenylamine, phenyl-alpha-naphthyl-amine, N, N-di (alkylphenyl) amine; and alkylated phenylene-diamine; phenols such as phenols. , BHT, steric disorder alkylphenols such as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl-4- (2-octyl-). 3-Proanoic acid) phenol; and mixtures thereof.

The ashless dispersant compounds utilized in the marine diesel cylinder lubricant compositions of the present invention are commonly used to maintain insoluble materials resulting from oxidation during use in suspensions, thus sludge. Prevent agglomeration and sedimentation or deposition on metal parts. The dispersant can also exert a function of reducing changes in lubricating oil viscosity by hindering the growth of large pollutant particles in the lubricant. The dispersant used in the present invention may be any suitable ashless dispersant for use in marine diesel cylinder lubricant compositions or a mixture of multiple ashless dispersants. The ashless dispersant is generally composed of an oil-soluble polymer hydrocarbon backbone having a functional group capable of binding to the particles to be dispersed.

In one embodiment, the ashless dispersant is one or more basic nitrogen-containing ashless dispersants. Nitrogen-containing basic ashless (metal-free) dispersants can be added to the base value or BN (which can be measured by ASTM D2896) of the lubricating oil composition to which it is added, without introducing additional sulphate ash. Contribute. Basic nitrogen-containing ashless dispersants useful in the present invention include hydrocarbyl succinimide; hydrocarbyl succinamide; hydrocarbyl-substituted succinate acylating agents, either stepwise or with a mixture of alcohols and amines and / or with aminoalcohol. Mixed ester / amide of hydrocarbyl-substituted succinic acid formed by; Mannig condensation product of hydrocarbyl-substituted phenol, formaldehyde and polyamine; and reaction of high molecular weight aliphatic or alicyclic halides with amines such as polyalkylene polyamine. Includes amine dispersants formed by. Mixtures of such dispersants can also be used.

Representative examples of ashless dispersants include, but are not limited to, amines, alcohols, amides, or ester polar moieties attached to the polymer backbone via crosslinkers. The ashless dispersants of the present invention include, for example, oil-soluble salts of long-chain hydrocarbon-substituted monos and dicarboxylic acids or their anhydrides, esters, aminoesters, amides, imides, and oxazolines; thiocarboxylate derivatives of long-chain hydrocarbons. , Long-chain aliphatic hydrocarbons with directly bound polyamines; and Mannig condensation products formed by condensing long-chain substituted phenols with formaldehyde and polyalkylene polyamines.

The carboxylic acid dispersant includes a carboxylic acid acylating agent (acid, anhydride, ester, etc.) containing at least about 34, preferably at least about 54 carbon atoms, a nitrogen-containing compound (amine, etc.), and an organic hydroxy compound (amine, etc.). Aliphatic compounds containing monovalent and polyhydric alcohols, aromatic compounds containing phenol and naphthol, etc.), and / or reaction products with basic inorganic materials. These reaction products include imides, amides, and esters.

The succinimide dispersant is a kind of carboxylic acid dispersant (carboxylic dispersant). They are produced by reacting a hydrocarbyl-substituted succinate acylating agent with an organic hydroxy compound, or with an amine containing at least one hydrogen atom attached to a nitrogen atom, or with a mixture of the hydroxy compound and the amine. The term "succinic acylating agent" means a hydrocarbon-substituted succinic acid or a succinic acid-producing compound, the latter of which includes the acid itself. Such materials typically include hydrocarbyl-substituted succinic acids, anhydrides, esters (including semi-esters) and halides.

Succinic acid-based dispersants have a wide variety of chemical structures. One class of amber dispersants can be expressed by the following formula:

In the formula, each R ¹ is independently a hydrocarbyl group such as a polyolefin inducing group. Typically, the hydrocarbyl group is an alkyl group such as a polyisobutyl group. Alternatively, ^one R group can contain from about 40 to about 500 carbon atoms, and these atoms can exist in an aliphatic form. R ² is an alkylene group, generally an ethylene (C ₂ H ₄ ) group. Examples of succinimide dispersants include, for example, those described in US Pat. Nos. 3,172,892, 4,234,435 and 6,165,235.

Substituent-derived polyalkenes are typically homopolymers and interpolymers of polymerizable olefin monomers with 2 to about 16 carbon atoms, usually 2 to 6 carbon atoms. The amine that reacts with the succinic acid acylating agent to form the carboxylic acid dispersant composition can be a monoamine or a polyamine.

Although amide functional groups can take the form of amine salts, amides, imidazolines and mixtures thereof, succinimide dispersants usually contain nitrogen in the form of imide functional groups, so succinimide dispersants are It is called like this. To prepare a succinimide dispersant, one or more succinic acid-producing compounds and one or more amines are heated to typically remove water, which is optionally, substantially inert. This is done in the presence of an organic liquid solvent / diluent. The reaction temperature can range from about 80 ° C. to the decomposition temperature of the mixture or product, which typically falls between about 100 ° C. and about 300 ° C. Additional details and examples of procedures for preparing the succinimide dispersants of the present invention include, for example, US Pat. Nos. 3,172,892, 3,219,666, 3,272,746, 4. , 234, 435, 6, 165, 235 and 6, 440, 905.

Suitable ashless dispersants can also include amine dispersants, which are reaction products of relatively high molecular weight aliphatic halides with amines, preferably polyalkylene polyamines. Examples of such amine dispersants are described, for example, in US Pat. Nos. 3,275,554, 3,438,757, 3,454,555 and 3,565,804. Things are included.

Suitable ashless dispersants can further include "Mannich dispersants", which include alkylphenols with alkyl groups containing at least about 30 carbon atoms and aldehydes (particularly formaldehyde) and amines (particularly formaldehyde). In particular, it is a reaction product with polyalkylene polyamine). Examples of such dispersants include those described in US Pat. Nos. 3,036,003, 3,586,629, 3,591,598 and 3,980,569. Including.

Suitable ashless dispersants can also be post-treated ashless dispersants, such as post-treated succinimide, for example, for post-treatment processes, eg, US Pat. Nos. 4,612,132 and 4, Examples thereof include post-treatment processes involving borate or ethylene carbonate disclosed in No. 746, 446 and the like, as well as other post-treatment processes. Carbonate-treated alkenyl succinimide has a molecular weight of about 450 to about 3000, preferably about 900 to about 2500, more preferably about 1300 to about 2400, and most preferably about 2000 to about 2400, and a mixture of these molecular weights. It is a polybutene succinimide derived from the polybutene. Preferably, it is prepared by reacting a polybutene succinic acid derivative, an unsaturated acidic reagent copolymer with an olefin, and a polyamine under reaction conditions, for example, US Pat. , 716,912, the contents of which are incorporated herein by reference.

Metal-containing or ash-forming cleaners act as both cleaners that reduce or remove deposits, as well as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life. Detergents are generally composed of a polar head with a long hydrophobic tail. The polar head contains a metal salt of an acidic organic compound. Salts can contain substantially stoichiometric amounts of metals, in which case they are usually described as positive or neutral salts, and typically 0 to about 80 total bases. It will have a valence, ie TBN (which can be measured by ASTM D2896). Large amounts of metal bases can be incorporated by reacting excess metal compounds (eg, oxides or hydroxides) with acid gases (eg, carbon dioxide). The resulting hyperbasic cleaning agent includes a cleaning agent neutralized as an outer layer of metal base (eg, carbonate) micelles. Such a hyperbasic detergent can have about 50 or more TBNs, or about 100 or more TBNs, or about 200 or more TBNs, or about 250 to about 450 or more TBNs.

Representative examples of other metal detergents that can be included in the marine diesel cylinder lubricating oil composition of the present invention are phenate, aliphatic sulfonates, alkyl substituted hydroxyaromatic carboxylic acids with a TBN of 250 or less. Includes alkaline earth metal salts, alkali metal salts of alkyl-substituted hydroxyaromatic carboxylic acids, phosphonates, and phosphinates. Salts of alkyl-substituted hydroxyaromatic carboxylic acids can be as described above.

Commercially available products are commonly referred to as neutral or hyperbasic. Perbasic metal cleaners are generally hydrocarbons, detergent acids, eg: sulfonic acids, carboxylates, etc., metal oxides or hydroxides (eg calcium oxide or calcium hydroxide) and promoted. It is produced by carbonating a mixture of agents such as xylene, methanol and water. For example, in carbonatization, calcium oxide or calcium hydroxide is reacted with gaseous carbon dioxide to form calcium carbonate in order to prepare perbasic calcium sulfonate. Sulfonic acid is neutralized with excess CaO or Ca (OH) ₂ to form sulfonate.

The hyperbasic detergent can be a hyperbasic salt with low hyperbasicity, eg, less than about 100 BN. In one embodiment, the BN of the low hyperbasic salt can be from about 5 to about 50. In another embodiment, the BN of the low hyperbasic salt can be from about 10 to about 30. In yet another embodiment, the BN of the low hyperbasic salt can be from about 15 to about 20.

The superbasic detergent can be a medium hyperbasic, eg, a superbasic salt having a BN of about 100 to about 250. In one embodiment, the BN of the medium hyperbasic salt can be from about 100 to about 200. In another embodiment, the BN of the medium hyperbasic salt can be from about 125 to about 175.

The hyperbasic detergent can be a highly hyperbasic salt, eg, a hyperbasic salt having a BN greater than 250. In one embodiment, the BN of the highly hyperbasic salt can be from about 250 to about 550.

Examples of rust preventives include, but are not limited to, nonionic polyoxyalkylenes such as polyoxyethylene lauryl ethers, polyoxyethylene higher alcohol ethers, polyoxyethylene nonylphenyl ethers, polyoxyethylene octylphenyl ethers, etc. Polyoxyethylene octylstearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostealto, polyoxyethylene sorbitol monooleate, and polyethylene glycol monooleate; stearic acid and other fatty acids; dicarboxylic acid; metal sulpens; fatty acids Amin salts; metal salts of heavy sulfonic acids; partial carboxylic acid esters of polyhydric alcohols; phosphoric acid esters; (short chain) alkenyl succinic acids; their partial esters and their nitrogen-containing derivatives; synthetic alkaline sulfonates, eg , Dinonylnaphthalene sulfonic acid metal salt; etc. and mixtures thereof.

Examples of friction modifiers include, but are not limited to, alkoxylated fatty amines; borated aliphatic epoxides; aliphatic phosphite, aliphatic epoxides, aliphatic amines, booxide alkoxylated aliphatics. Amin, metal salts of fatty acids, fatty acid amides, glycerol esters, glycerol esters; and aliphatic imidazolines, which are disclosed in US Pat. No. 6,372,696, the contents of which are described herein by reference. incorporated) to; _{C 4 C 75} from, preferably from _{C 6 C 24,} and most preferably a fatty acid ester to _{C 20 C 6,} ammonia and alkanolamines (e.g. mono - or di-alkanolamines), etc. and their Includes friction modifiers and the like obtained from reaction products with nitrogen-containing compounds selected from the group consisting of mixtures.

Examples of anti-wear agents are described, but not limited to, zinc dialkyl dithiophosphates and zinc diaryl dithiophosphates, such as Sulfide Science 4-2 (January 1992) (see, eg, pp. 97-100). Title by Born et al "Relationship between Chemical Structure and Effectiveness of Some Metallic Dialkyl- and Diaryl-dithiophosphates in Different Lubricated Mechanisms" according to article ones; aryl phosphates and phosphites, sulfur-containing esters, phospho sulfur (phosphosulfur) compound, Metal or ashless dithiocarbamate, xanthate, alkyl sulfide, etc. and mixtures thereof are included.

Examples of antifoaming agents include, but are not limited to, polymers of alkylmethacrylates; polymers of dimethylsilicone and the like and mixtures thereof.

Examples of flow point depressants include, but are not limited to, polymethacrylates, alkylacrylate polymers, alkylmethacrylate polymers, di (tetra-paraffinphenol) phthalates, tetra-paraffinphenol condensates, chlorinated paraffins and naphthalene. Condensates with and combinations thereof are included. In one embodiment, the pour point lowering agent includes ethylene-vinyl acetate copolymer, condensate of chlorinated paraffin and phenol, polyalkylstyrene and the like, and combinations thereof. The amount of pour point depressant can vary from about 0.01% to about 10% by weight.

Examples of anti-emulsifiers include, but are not limited to, anionic surfactants (eg, alkyl-naphthalene sulfonate, alkylbenzene sulfonate, etc.), nonionic alkoxylated alkylphenol resins, alkylene oxide polymers (eg, polyethylene oxide, etc.). (Block copolymers such as polypropylene oxide, ethylene oxide and propylene oxide), oil-soluble acid esters, polyoxyethylene sorbitan esters and the like, and combinations thereof are included. The amount of anti-emulsifier can be varied from about 0.01% to about 10% by weight.

Examples of corrosion inhibitors include, but are not limited to, semiesters or amides of dodecylsuccinic acid, phosphate esters, thiophosphates, alkylimidazolines, sarcosine and the like and combinations thereof. The amount of corrosion inhibitor can vary from about 0.01% by weight to about 0.5% by weight.

Examples of extreme pressure agents include, but are not limited to, sulfurized animal or vegetable fats and oils, sulfurized animal or vegetable fatty acid esters, or trivalent or pentavalent acids of phosphorus, wholly or partially. Estelized esters, olefin sulfides, dihydrocarbyl polysulfides, deal-sulfur sulfide adducts, dicyclopentadiene sulfides, sulfurized or co-sulfided mixtures of fatty acid esters and monounsaturated olefins, co-sulfurized blends of fatty acids, fatty acid esters and alpha olefins, Functional group-substituted dihydrocarbyl polysulfides, thiaaldehydes, thiaketones, epithio compounds, sulfur-containing acetal derivatives, co-sulfide blends of terpen and acyclic olefins, polysulfide olefin products, amine salts of phosphate esters or thiophosphate esters, etc. Combinations are included. The amount of extreme pressure agent can be varied from about 0.01% by weight to about 5% by weight.

Each of the above additives, when used, is used in a functionally effective amount to impart the desired properties to the lubricant. Thus, for example, if the additive is a friction modifier, the functionally effective amount of this friction modifier will be sufficient to impart the desired friction modifier to the lubricant. Generally, the concentration of each of these additives, when used, is from about 0.001% to about 20% by weight, and in one embodiment about 0, based on the total weight of the lubricating oil composition. It ranges from 0.01% by weight to about 10% by weight.

In addition, the additives in the marine diesel cylinder lubricant composition can be provided as additive packages or concentrates, the additives being substantially inert and usually liquid organic dilutions as described above. It is mixed in the agent. The additive package will typically contain one or more of the various additives as described above, in the desired amount and ratio to facilitate direct combination with the required amount of lubricating oil.

In one embodiment, the marine diesel cylinder lubricant composition of the present invention is substantially free or free of dispersants and / or zinc compounds such as zinc dithiophosphate. As used in the present invention, the term "substantially free", when included, means that each of the dispersants and / or zinc compounds is at relatively low levels, eg, dispersants in marine diesel cylinder lubricant compositions. And / or each of the zinc compounds is less than about 0.5% by weight. In another embodiment, the term "substantially free" means that each of the dispersants and / or zinc compounds in the marine diesel cylinder lubricant composition is less than about 0.1% by weight. In another embodiment, the term "substantially free" means that each of the dispersants and / or zinc compounds in the marine diesel cylinder lubricant composition is less than about 0.01% by weight.

All TPPs and their unsulfided metal salts (ie, "total TPPs" or "total residual TPPs") and lubricants in the marine diesel cylinder lubricant compositions of the present invention disclosed herein and exemplified below. And the concentration of the oil additive containing the salt of the alkyl sulfide substituted hydroxy aromatic composition is measured by reverse phase high performance liquid chromatography (HPLC). In the HPLC method, a sample for analysis was prepared by weighing exactly 80 to 120 mg of the sample into a 10 ml volumetric flask, diluting with methylene chloride to the level mark, and mixing until the sample was completely dissolved.

The HPLC system used in the HPLC method includes an HPLC pump, a thermostat HPLC column compartment, an HPLC fluorescence detector, and a PC-based chromatography data acquisition system. The particular system described is based on Agilent 1200 HPLC with ChemStation software. The HPLC column was Phenomenex Luna C8 (2) 150 × 4.6 mm 5 μm 100 Å, P / N00F4249E0.

The following system settings were used to perform the analysis:

Pump flow rate = 1.0 ml / min

Maximum pressure = 200 bar

Fluorescence wavelength: 225 excitation 313 emission: gain = 9

Column thermostat temperature = 25 ° C

Injection size = 1 μL diluted sample

Elution type: gradient, reverse phase

Gradient: Switch 85/15 methanol / water to 100% methanol linear gradient in 0 to 7 minutes.

Experiment time: 17 minutes

The resulting chromatograph typically contains several peaks. Peaks due to free unsulfided alkylhydroxyaromatic compounds (ie, TPP) typically elute together with a fast retention time; while peaks due to alkylalkylsulfide aromatic compounds typically elute together. , Elute with a longer retention time. For quantification purposes, the area of a single maximum peak of a free unsulfided alkyl hydroxy aromatic compound and its unsulfided metal salt is then measured and then the area is determined by its total free unsulfided alkyl hydroxy aromatic compound and its unsulfided alkyl hydroxy aromatic compound. It was used to quantify the concentration of unsulfided metal salt species. It is assumed that the species of the alkylhydroxy aromatic compound does not change, but if something changes the species of the alkyl hydroxy aromatic compound, recalibration is required.

The area of the selected peaks is compared to the calibration curve to obtain free alkylphenols and% by weight of free unsulfated salts of alkylphenols. Calibration curves were created using the same peaks on the chromatograph obtained for the free unsulfided alkylhydroxyaromatic compounds used to make the phenate product.

The present invention will be described by the following non-limiting examples.

The degree of high temperature cleanliness and thermal stability was evaluated for each of the following examples using the Komatsu Hot Tube (“KHT”) test described below. The results of each of the examples are listed in Table 1.

Komatsu Hot Tube (KHT) Test

The Komatsu Hot Tube Test is a lubrication industry bench test that measures the cleanliness and thermal and oxidative stability of lubricating oils. Cleanliness as well as thermal and oxidative stability are performance areas generally accepted by the industry as essential to the satisfactory overall performance of lubricating oils. During the test, a specific amount of test oil is pumped upward through a glass tube placed in an oven set at a specific temperature. Before the oil enters the glass tube, air is introduced into the oil stream and flows upward with the oil. Evaluation of marine diesel cylinder lubricants was performed at temperatures between 300 and 330 ° C. The test results are determined by comparing the amount of lacquer deposited on the glass tube with a rating scale in the range 1.0 (very black) to 10.0 (completely clean). Results are reported in multiples of 0.5. The blockage is a deposited state, in which the lacquer is very thick and most of the glass test tubes are blocked, obstructing the normal flow of oil and air through the test tubes. Blocking can be considered to be inferior to a rating of 1.0, but its occurrence can be highly affected by blocking of other tubes tested simultaneously in the same test experiment.

The following ingredients are used as follows when blending a marine diesel cylinder lubricant composition.

Chevron 600N RLOP: A Group II based lubricant was the Chevron 600N RLOP Basestock, which was available from the Chevron Products Company (San Ramon, CA).

ExxonMobil CORE® 2500BS: Group I-based lubricants were ExxonMobil CORE® 2500BS basestock and were available from ExxonMobil, Irving, Texas.

The cleaning agents used in the examples in Table 1 are listed below.

Cleaner A: An oil concentrate of a neutral (non-hyperbasic) calcium benzoate additive having an alkyl substituent derived from C ₂₀ to C ₂₈ linear olefins, US Patent Application No. 2007/0027043. It was prepared according to the method described in Example 1 of No. 1, but no subsequent hyperbasification step was performed. The additive concentrate contained 2.17% by weight of Ca and about 43.0% by weight of diluted oil, and had a TBN of 61. By activity criteria, the TBN of this additive (without diluent oil) is 107.

Detergent B: An oil concentrate of perbasic calcium sulfide phenate derived from a propylene tetramer. The additive contained 9.6% by weight Ca and about 31.4% by weight of diluted oil, and had a TBN of 260. Cleaner B is believed to have a total TPP content of about 5-7% by weight, ie TPP and its unsulfided metal salts, based on the weight of the cleansant produced.

Detergent C: Unsulfided, non-perbasic alkylhydroxy with alkyl substituents derived from about 50% by weight C ₂₀ to C ₂₈ linear olefins and 50% by weight branched hydrocarbyl radical propylene tetramer. An oil concentrate containing a benzoate and a phenol radical additive, prepared according to the method described in Example 1 of US Patent Application No. 2004/0235686. The additive contained 5.00% by weight Ca and about 33.0% by weight diluted oil and had a TBN of 140. By activity criteria, the TBN of this additive (without diluent oil) is 210. Cleaner C is believed to have a total TPP content of about 2-3 wt%, ie TPP and its unsulfided metal salts, based on the weight of the cleansant produced.

Cleaner D: An oil concentrate of a perbasic alkylhydroxycalcium benzoate additive having an alkyl substituent derived from a C ₂₀ to C ₂₈ linear olefin, as described in Example 1 of US Patent Application 2007/0027043. This additive, prepared according to the method described above, contained 5.35% by weight of Ca and about 35.0% by weight of diluted oil, and had a TBN of 150. By activity criteria, the TBN of this additive (without diluent oil) is 230.

Cleaner E: An oil concentrate of a perbasic alkylhydroxycalcium benzoate additive having an alkyl substituent derived from a C ₂₀ to C ₂₈ linear olefin, Example 1 of US Patent Application No. 2007/0027043. Prepared according to the method described in. The additive contained 12.5% by weight Ca and about 33.0% by weight of diluted oil, and had a TBN of 350. By activity criteria, the TBN of this additive (without diluent oil) is 522.

Detergent F: An oil concentrate of a perbasic calcium alkyltoluenesulfonate detergent in which the alkyl group is derived from C ₂₀ to C ₂₄ linear alpha olefins. This additive concentrate contained 16.1% by weight Ca and about 38.7% by weight of diluted oil, and had a TBN of 420. By activity criteria, the TBN of this additive (without diluent oil) is 685.

Cleaner G: An oil concentrate of a perbasic alkylhydroxycalcium benzoate additive having an alkyl substituent derived from C ₁₄ to C ₁₈ linear alpha olefins. This additive contained 6.25% by weight Ca and about 41.0% by weight of diluted oil, and had a TBN of 175. By activity criteria, the TBN of this additive (without diluent oil) is 296.

Examples 1 to 3 and Comparative Examples A to J
The marine diesel engine lubricating oil compositions of Examples 1 to 3 and Comparative Examples A to J were prepared as shown in Table 1 and the following. The marine diesel engine lubricating oil compositions of Examples 1 and Comparative Examples A to J are SAE 40 viscosity grade oils, the kinematic viscosity is about 14.5 cSt at 100 ° C., and the TBN is about 40 mgKOH / g. It was. Example 2 was a SAE 50 viscosity oil with a kinematic viscosity of about 18.7 cSt at 100 ° C. and a TBN of about 70 mgKOH / g. Example 3 was a SAE 50 viscosity oil with a kinematic viscosity of about 18.9 cSt at 100 ° C. and a TBN of about 20 mgKOH / g. The marine diesel engine lubricating oil compositions of Examples 1 to 3 and Comparative Examples A to J include a major amount of Group II base stock and a small amount of Group I base stock, the cleaning agent composition specified in Table 1, and 0. It was formulated using a .04 wt% foam inhibitor. Comparative Example D is an oil concentrate of a bissuccinimide dispersant derived from 1000 MW of polyisobutylene succinic anhydride (PIBSA) and dipolyamine (HPA) / diethylenetriamine (DETA), which has about 31.7% by weight of diluted oil. It further contained 0.57 wt%. Each of the marine diesel cylinder lubricant compositions of Examples 1-3 did not contain TPP and its unsulfided metal salts.

As the results shown in Table 1 show, the marine diesel cylinder lubricating oil compositions of Examples 1 to 3 containing the cleaning agent composition of the present invention are the marine diesel cylinder lubricating oil compositions of Comparative Examples A to J. It showed surprisingly improved cleaning properties. This is indicated by higher KHT values held over a higher temperature range, and the marine diesel cylinder lubricant compositions of Examples 1-3 are such that the compositions are hot tubes. It has been shown to exhibit excellent cleanliness and thermal stability in hot tube tests in that it produces very little oxidation or decomposition products of contaminating lubricating oil. Furthermore, Examples 1 to 3 are substantially free of TPP and its unsulfided metal salts.

It will be appreciated that various modifications can be made to the embodiments disclosed herein. Therefore, the above description should be construed as merely exemplifying preferred embodiments, not as limiting. For example, the functions described above and implemented as the best mode for performing the present invention are for illustrative purposes only. Those skilled in the art can implement other configurations and methods without departing from the scope and nature of the invention. In addition, one of ordinary skill in the art will recall other changes within the scope and nature of the claims attached herein.
The following contents are further disclosed in connection with the present invention.
[1]
(A) Major amounts of one or more Group II basestocks, as well as
(B) (i) One or more alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids having a total base value (TBN) of more than 250, and (ii) one or more highly hyperbasic alkyl aromatics. Detergent composition containing sulfonic acids or salts thereof;
Is a marine diesel cylinder lubricant composition containing:
The aromatic portion of the alkyl aromatic sulfonic acid or a salt thereof does not contain a hydroxyl group; and the marine diesel cylinder lubricant composition has a TBN of about 5 to about 120.
The lubricating oil composition.
[2]
The marine diesel cylinder lubricant composition according to [1], which has a TBN of about 20 to about 100.
[3]
The marine diesel cylinder lubricant composition according to [1], which has a TBN of about 10 to about 40.
[4]
The marine diesel cylinder lubricating oil composition according to any one of [1] to [3], which is substantially free of tetrapropenylphenol (TPP) and its unsulfided metal salt.
[5]
The item according to any one of [1] to [4], wherein the one or more alkaline earth metal salts of the alkyl-substituted hydroxy aromatic carboxylic acid are one or more calcium salts of the alkyl-substituted hydroxy aromatic carboxylic acid. The marine diesel cylinder lubricating oil composition described.
[6]
The marine diesel cylinder according to any one of [1] to [5], wherein the alkyl-substituted portion of the alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid is a C ₁₀ to C ₄₀ alkyl group. Lubricating oil composition.
[7]
The marine diesel cylinder according to any one of [1] to [6], wherein the one or more alkaline earth metal salts of the alkyl-substituted hydroxyaromatic carboxylic acid have a TBN of more than 250 and up to about 800. Lubricating oil composition.
[8]
Any of [1] to [7], wherein the one or more highly hyperbasic alkyl aromatic sulfonic acids or salts thereof are one or more highly hyperbasic alkyl aromatic sulfonic acid alkaline earth metals. The marine diesel cylinder lubricating oil composition according to paragraph 1.
[9]
The item according to any one of [1] to [8], wherein the one or more highly hyperbasic alkyl aromatic sulfonic acids or salts thereof is one or more highly hyperbasic alkyl aromatic sulfonic acid calcium. The marine diesel cylinder lubricating oil composition described.
[10]
The marine diesel cylinder lubricating oil composition according to any one of [1] to [9], wherein the one or more highly superbasic alkyl aromatic sulfonic acids or salts thereof have a TBN of more than 250. ..
[11]
One or more alkalis of alkyl substituted hydroxyaromatic carboxylic acids with a TBN greater than 250, from about 0.1 to about 35% by weight based on activity criteria, based on the total weight of the marine diesel cylinder lubricant composition. Earth metal salts; and
One or more highly hyperbasic alkyl aromatic sulfonic acids or salts thereof, based on the total weight of the marine diesel cylinder lubricating oil composition, from about 0.1 to about 34% by weight based on activity criteria.
The marine diesel cylinder lubricating oil composition according to any one of [1] to [10], which comprises.
[12]
Antioxidants, ashless dispersants, lubricants, rust inhibitors, defrosting agents, anti-emulsifiers, metal inactivating agents, friction modifiers, flow point lowering agents, defoamers, auxiliary solvents, corrosion inhibitors, dyes, The marine diesel according to any one of [1] to [11], further comprising one or more marine diesel cylinder lubricating oil composition additives selected from the group consisting of extreme pressure agents and mixtures thereof. Cylinder lubricant composition.
[13]
The marine diesel cylinder lubricating oil composition according to any one of [1] to [12], which is substantially free of a dispersant and / or a zinc compound.
[14]
A method for lubricating a two-stroke crosshead diesel engine for ships, wherein the engine is made using the diesel cylinder lubricating oil composition for ships according to any one of [1] to [13]. Methods, including working.
[15]
Use of the marine diesel cylinder lubricating oil composition according to any one of [1] to [13] for improving high temperature cleanliness and thermal stability in a two-stroke crosshead marine diesel engine.

Claims (11)

(A) Based on the total weight of the composition, based on the base stock of one or more Group II in excess of 50% by weight, and (b) (i) based on the total weight of the marine diesel cylinder lubricant composition. Alkaline earth metal salts of one or more alkyl-substituted hydroxyaromatic carboxylic acids having a total base value (TBN) of more than 250, from 3% to 15% by weight based on activity, and (ii) marine diesel cylinders. A detergent composition comprising one or more highly hyperbasic alkyl aromatic sulfonic acids or salts thereof, based on the total weight of the lubricating oil composition, from 5% to 16% by weight on an activity basis;
Is a marine diesel cylinder lubricant composition containing:
The one or more highly hyperbasic alkyl aromatic sulfonic acids or salts thereof have a TBN of more than 250 and
The aromatic portion of the alkyl aromatic sulfonic acid or salt thereof does not contain a hydroxyl group; and the marine diesel cylinder lubricant composition has a TBN of 20 to 70 .
The lubricating oil composition. The marine diesel cylinder lubricating oil composition according to claim 1 , wherein tetrapropenylphenol (TPP) and an unsulfided metal salt thereof are contained in the marine diesel cylinder lubricating oil composition in an amount of less than 1.5% by weight, if present. Stuff. The invention according to any one of claims 1 to 2 , wherein the one or more alkaline earth metal salts of the alkyl-substituted hydroxy aromatic carboxylic acid are one or more calcium salts of the alkyl-substituted hydroxy aromatic carboxylic acid. Marine diesel cylinder lubricating oil composition. The marine diesel cylinder lubricating oil according to any one of claims 1 to 3 , wherein the alkyl-substituted portion of the alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid is a C ₁₀ to C ₄₀ alkyl group. Composition. The marine diesel cylinder lubricating oil composition according to any one of claims 1 to 4 , wherein the one or more alkaline earth metal salts of the alkyl-substituted hydroxyaromatic carboxylic acid have a TBN of more than 250 and up to 800. Stuff. Any one of claims 1 to 5 , wherein the one or more highly hyperbasic alkyl aromatic sulfonic acids or salts thereof are one or more highly hyperbasic alkyl aromatic sulfonic acid alkaline earth metals. The marine diesel cylinder lubricating oil composition according to. The invention according to any one of claims 1 to 6 , wherein the one or more highly hyperbasic alkyl aromatic sulfonic acids or salts thereof are one or more highly hyperbasic alkyl aromatic sulfonic acid calcium. Diesel cylinder lubricating oil composition for ships. Antioxidants, ashless dispersants, lubricants, rust inhibitors, defrosting agents, anti-emulsifiers, metal inactivating agents, friction modifiers, flow point lowering agents, defoamers, auxiliary solvents, corrosion inhibitors, dyes, The marine diesel cylinder lubricant according to any one of claims 1 to 7 , further comprising one or more marine diesel cylinder lubricating oil composition additives selected from the group consisting of extreme pressure agents and mixtures thereof. Oil composition. Any one of claims 1-8 , each containing less than 0.5% by weight of the dispersant and / or zinc compound, if any, in the marine diesel cylinder lubricant composition. The marine diesel cylinder lubricating oil composition according to. A method of lubricating a two-stroke crosshead diesel engine for a ship, wherein the engine is operated by using the diesel cylinder lubricating oil composition for a ship according to any one of claims 1 to 9. The method, including that. Use of the marine diesel cylinder lubricating oil composition according to any one of claims 1 to 9 for improving high temperature cleanliness and thermal stability in a two-stroke crosshead marine diesel engine.