KR20170082544A - Marine diesel cylinder lubricant oil compositions - Google Patents

Abstract

Disclosed herein is a diesel cylinder lubricating oil composition for marine use which comprises (a) a major amount of one or more Group II base stocks, and (b) an alkyl-substituted hydroxyaromatic group having a total base (TBN) At least one alkaline earth metal salt of a carboxylic acid, and (ii) at least one highly overbased alkyl aromatic sulfonic acid or salt thereof, wherein the aromatic moiety of the alkyl aromatic sulfonic acid or salt thereof is selected from the group consisting of hydroxides And the marine diesel cylinder lubricating oil composition has a TBN of about 5 to about 120. [

Description

{MARINE DIESEL CYLINDER LUBRICANT OIL COMPOSITIONS}

preference

This application claims the benefit of 35 U.S.C. U.S. Provisional Application Serial No. 62 / 076,309 filed on November 6, 2014 under §119, the contents of which are incorporated herein by reference.

1. Technical Field

The present application relates generally to marine diesel cylinder lubricant compositions for lubricating marine two-stroke crosshead diesel cylinder engines.

2. Description of Related Technology

In recent years, soaring energy costs, especially those that occur in distillation of crude oil and liquid petroleum, have become a burden on the users of transportation fuels, such as owners and operators of navigation vessels. Correspondingly, users have avoided the steam turbine cooing unit and coordinated its operation for a more fuel efficient large marine diesel engine. Diesel engines can be generally classified as low speed, medium speed, or high speed engines, while those of the low speed type are used for maximum deep shaft shafts and certain other industrial applications.

Low speed diesel engines are unique in size and operating method. The engine itself is large and these units can weigh up to 200 tons in weight, 10 feet in length and 45 feet in height. The output of such an engine can reach as high as 100,000 brake horsepower at an engine speed of 60 to about 200 revolutions per minute. This is typically of a crosshead design and operates in a two-stroke cycle. In addition, such an engine usually operates with residual fuels, but some can also be operated as distillate fuels with or without a small number of residues.

On the other hand, medium speed engines are typically operated in the range of about 250 to about 1100 rpm and can operate in a four-stroke or two-stroke cycle. Such an engine may be of a trunk piston design or, in some cases, of a crosshead design. This can usually be operated with heavy oil, such as a low-speed diesel engine, but some can also be operated with distillate fuels, which may or may not contain a small number of residues. These engines can also be used for propulsion, deep ancillary applications, or both for deep-sea vessels.

Low- and medium-speed diesel engines are also widely used in power plant operations. A low or medium speed diesel engine operating in a two-stroke cycle typically includes at least one stuffing boxe that separates the power cylinder from the crankcase and prevents combustion products from entering the crankcase and mixing with the crankcase oil, And a direct-coupled and direct-reversing engine. The remarkable complete separation of the crankcase from the combustion zone has resulted from those skilled in the art to lubricate the combustion chamber and the crankcase with different lubricants.

In large cross-head diesel engines used in marine and heavy stationary applications, cylinders are lubricated separately from other engine components. The cylinder is lubricated with a total loss basis on which the cylinder oil is injected separately into the quills on each cylinder by lubricators located around the cylinder liner. The oil is distributed to the lubricator by a pump, which operates to apply oil directly to the ring to reduce the consumption of oil in modern engine structures.

One problem associated with such engines is that their manufacturers generally design to use a variety of diesel fuels because they are less expensive than high distillate fuels of good quality with low sulfur and low asphaltene content Poorer quality intermediate or beavy fuels, such as marine heavy oil generally having high sulfur and high asphaltene content.

The use of high stress and marine heavy oils encountered in such engines results in the need for lubricants with high detergency and neutralizing capability despite the oils being exposed only to thermal and other stresses in a short period of time . Heavy oil commonly used in such diesel engines typically contains significant amounts of sulfur, which in combination with water forms a sulfuric acid in the combustion process, and its presence causes corrosive wear. Particularly, in a two-stroke engine for a ship, the space around the cylinder liner and the piston ring can be corroded and abraded by the acid. Thus, it is important that diesel engine lubricants have such a resistance to corrosion and abrasion.

Thus, the main function of marine diesel cylinder lubricants is to neutralize the sulfur-based acidity of the high-sulfur fuel oil burned in low speed 2-stroke crosshead diesel engines. This neutralization is achieved by the intervention of basic species marine diesel cylinder lubricants, such as metallic detergents. Unfortunately, the basicity of marine diesel cylinder lubricants can be reduced by oxidation of marine diesel cylinder lubricants (caused by thermal and oxidative stresses experienced by the engine in the lubricant), and thus the neutralizing ability of the lubricant is reduced do. Oxidation can be accelerated if the marine diesel cylinder lubricant contains a commonly known wear metal as being present in the lubricant, such as in an oxidation process (contain oxidation), e.g., during engine operation.

The marine two-stroke diesel cylinder lubricant is required for a more modern, larger bore, 2-stroke, cross-head diesel marine engine that is operated at higher throughputs and at higher temperatures of severe loads and cylinder liners Performance requirements must be met to adhere to severe operating conditions.

Currently, the marine industry has traditionally addressed the increasing shortage of Group I category basestocks used in marine engine oils, as well as overcoming the low sulfur fuel levels imposed by law. In addition to these overcoming challenges, the marine two-stroke diesel cylinder lubricant has been designed to meet the extreme operating conditions required for a more modern large bore, two-stroke, cross-head diesel marine engine to be operated at higher throughputs and at higher temperatures of extreme loads and cylinder liner To meet the performance requirements. Thus, a marine cylinder that can be used with a base stock other than the I-base stock, while having improved cleaning power and high thermal stability at high temperatures to meet extreme loading conditions of a large bore two-stroke engine operating with a fuel with a wide range of sulfur There is a further need for lubricant compositions.

In recent years, changes in operation, both induced by fuel efficiency, as well as general structural changes in large bore, low speed, two-stroke engines have contributed to the frequent occurrence of extreme cold corrosion. Low temperature corrosion is caused by sulfuric acid. Sulfur oxides resulting from the combustion of fuel (typically a heavy oil fuel with> 2 wt% sulfur) will form sulfuric acid with water from the combustion process and water from the scavenge air. When the liner temperature is lowered below the dew point of sulfuric acid and water, the corrosion mixture is condensed on the liner. The cylinder lubricant basicity, cylinder lubricant feed rate of the oil to the cylinder liner, engine manufacturing type, engine load, inlet air humidity and fuel sulfur content are factors that can affect the amount of low temperature corrosion. High alkaline lubricants are used to neutralize sulfuric acid and avoid low temperature corrosion of piston rings and cylinder liner surfaces. High alkaline lubricants (e.g., up to 100 BN by the ASTM D2896 test method) are commercially available to help overcome extreme low temperature corrosion.

Sulfated, overbased phenates are well known compounds widely used in marine applications for their cleansing properties and thermal stability. However, low molecular weight alkylphenol compounds such as tetrapropenyl phenol (TPP) are generally used as raw materials in the preparation of such sulfated, overbased vaporized phenates. The process of preparing the overbased phenate generally results in the presence of unreacted alkyl phenol in the final reaction product and in the ultimately finished lube oil composition. Recent reproductive toxicity studies may be endocrine disruptive materials at high concentrations of unreacted alkylphenol, especially TPP, which can cause side effects in female and male reproductive organs.

There is a further need to reduce or eliminate the amount of unreacted TPP and its unsalified metal salts present in the lubricating oil composition to reduce any potential health risks to the consumer and avoid potential regulatory problems. Thus, it would be even more desirable to develop marine diesel cylinder lubricant compositions that are substantially free of unreacted TPP and its unsulfided metal salts.

SUMMARY OF THE INVENTION

According to one embodiment of the present invention, there is provided a marine diesel cylinder engine lubricant composition comprising: (a) a major amount of one or more Group II base stocks; and (b) At least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid, and (ii) at least one highly overbased alkylaromatic sulfonic acid or salt thereof, A cleaning composition comprising; Wherein the aromatic moiety of the alkyl aromatic sulfonic acid or salt does not contain a hydroxyl group; The marine diesel cylinder lubricating oil composition has a TBN of about 5 to about 120.

According to a second embodiment of the present invention there is provided a method for lubricating a marine two-stroke crosshead diesel with a marine diesel cylinder lubricant composition having improved high temperature cleaning and thermal stability; (I) at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid having a TBN of greater than 250, and (ii) at least one alkaline earth metal salt of an alkyl- ) Driving the engine with a marine diesel cylinder lubricant composition comprising a cleaning composition comprising at least one highly overbased alkyl aromatic sulfonic acid or salt thereof; Wherein the aromatic moiety of the alkyl aromatic sulfonic acid or salt thereof does not contain a hydroxyl group; The marine diesel cylinder lubricating oil composition has a TBN of from about 5 to about 120 to improve high temperature cleaning and thermal stability in a two-stroke crosshead marine diesel engine.

(I) one or more Group II base stocks of a major amount and (b) an alkyl-substituted hydroxyaromatic carboxyl group having a total base of greater than 250 with a TBN At least one alkaline earth metal salt of an acid, and (ii) at least one highly overbased alkyl aromatic sulfonic acid or salt thereof; Wherein the marine diesel cylinder lubricant composition has a TBN of about 5 to about 120 to improve high temperature cleanliness and thermal stability in a two-stroke crosshead marine diesel engine.

The present invention is directed to the combination of at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid having a TBN of greater than 250 and at least one highly overbased alkylaromatic sulfonic acid or salt thereof advantageously in a two- Improving the high temperature cleaning and thermal stability of marine diesel cylinder lubricating oil compositions used in engines and containing a major amount of one or more Group II base stocks; Wherein the marine diesel cylinder lubricant is based on an amazing discovery having a TBN of from about 5 to about 120. It is also preferred that the combination of at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid having a TBN of greater than 250 and at least one highly overbased alkylaromatic sulfonic acid or salt thereof advantageously comprises a major amount of one or more Group II Base stock and improves the thermal stability of a marine diesel cylinder lubricant composition having a TBN of from about 5 to about 120.

Justice

The term " marine diesel cylinder lubricant "or" marine diesel cylinder lubricating oil "as used herein is used for cylinder lubrication of low or medium speed two-stroke crosshead marine diesel engines. Quot; lubricant " as used herein. The marine diesel cylinder lubricant is supplied to the cylinder wall through a number of injection points. The marine diesel cylinder lubricant supplies the film between the cylinder liner and the piston rings and maintains the partially burned fuel residue in the suspension whereby the engine cleanliness for example, by neutralizing the acid formed by the combustion of sulfur compounds in the fuel.

"Marine residual fuel" means at least 2.5 wt.% (Eg, at least 5 wt.%, Or at least 8 wt.%) Of the total weight of the fuel, as defined in International Organization for Standardization (ISO) Carbon residues, combustible materials in engines for large marine vessels with a viscosity of more than 14.0 cSt at 50, such as the International Standardization Organization ISO 8217: 2005, "Petroleum products - Fuels (class F) - Specifications of marine fuels" It is about defined marine fuel oil, the contents of which are included in this text.

"Residual fuel" refers to fuels that meet the specifications of marine fuel oil as described in the International Standard ISO 8217: 2010. "Low sulfur distillate fuel" refers to a fuel that meets the specifications of marine heavy fuel oil as specified in the ISO 8217: 2010 specification, which is also less than about 1.5 wt%, or even about 0.5% wt% or less sulfur.

"Distillate fuel" refers to fuels that meet the specifications of distillate marine fuels as described in the International Standard ISO 8217: 2010. "Low sulfur distillate fuel" refers to a fuel that meets the specifications of distillate marine fuels as described in the International Standard ISO 8217: 2010, which is also less than or equal to about 0.1 wt% It has less than about 0.005 wt% sulfur.

The term "bright stock " used by those skilled in the art is a direct product of a de-asphalted petroleum vacuum residue, or may be a further product, such as solvent extraction and / / RTI > The present invention relates to a base oil derived from a deasphalted petroleum vacuum residue after being dewaxed and / or dewaxed. For the purposes of the present invention, this also relates to a deasphalted distillate cut of a vacuum residue process. The brightstock generally has a kinematic viscosity of 28 to 36 mm ² / s at 100. An example of such a brightstock is ESSO ^TM Core 2500 Base Oil.

The term "Group II metal" or "alkaline earth metal" is calcium, barium, magnesium, and strontium.

The term " calcium base "refers to calcium hydroxide, calcium oxide, calcium alkoxide, and the like, and mixtures thereof.

The term "lime" also relates to calcium hydroxide, also known as slaked lime or hydrated lime.

The term "alkylphenol" relates to a phenolic group having at least one alkyl substituent having a sufficient number of carbon atoms, at least one of which imparts utility to the resulting phenate additive.

The term "phenate" refers to a salt of phenol.

The term " lower alkanoic acid "refers to alkanoic acids having from 1 to 3 carbon atoms, i.e., formic acid, acetic acid and propionic acid, ≪ / RTI >

The term "polyol promoter" refers to compounds having two or more hydroxy substituents, generally sorbitol types, such as alkylene glycols, and also derivatives and functional equivalents thereof, such as polyol ethers (polyol ethers) and hydroxycarboxylic acids.

The term " Total Base Number "or" TBN "relates to the level of alkalinity in the oil sample, indicating the ability of the composition to continue neutralizing the corrosive acid according to ASTM Standard D2896 or equivalent procedure . The test measures the change in electrical conductivity and the result is expressed in mg KOH / g (the equivalent number of milligrams of KOH needed to neutralize 1 gram of product). Thus, the high TBN strongly reflects the overbased product, and as a result, the higher base serves to neutralize the acid.

As used herein, the term "base oil" is identified by a unique chemical formula, product identification number, or both; Manufacturing It shall be understood to mean a blend of base raw materials or base raw materials which is a lubricating component manufactured by the same manufacturer with the same specifications (independent of feedstock or manufacturer's location) that meet the specifications of the same manufacturer.

The term " on an actives basis "relates to an additive material that is not a diluent oil or solvent.

The term "isomerized olefins" relates to olefins obtained by isomerization of olefins. In general, isomerized olefins have double bonds at positions different from the starting olefin from which they are derived, which may also have different properties.

(I) at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid having a TBN of greater than 250, and (ii) at least one alkaline earth metal salt of an alkyl- ii) a cleaning composition comprising at least one highly overbased alkyl aromatic sulfonic acid or salt thereof; Wherein the aromatic moiety of the alkyl aromatic sulfonic acid or salt thereof does not contain a hydroxyl group; The marine diesel cylinder lubricating oil composition has a TBN of about 5 to about 120.

Generally, the marine diesel cylinder lubricating oil composition of the present invention will have a TBN of from about 5 to about 120. In one embodiment, the marine diesel cylinder lubricating oil composition of the present invention may have a TBN of from about 20 to about 100. In one embodiment, the marine diesel cylinder lubricating oil composition of the present invention may have a TBN of from about 40 to about 100. In one embodiment, the marine diesel cylinder lubricating oil composition of the present invention may have a TBN of from about 55 to about 80. [ In one embodiment, the marine diesel cylinder lubricating oil composition of the present invention may have a TBN of about 60 to about 80. In one embodiment, the marine diesel cylinder lubricating oil composition of the present invention may have a TBN of about 10 to about 40. In one embodiment, the marine diesel cylinder lubricating oil composition of the present invention may have a TBN from about 15 to about 35. [

In one embodiment, the marine diesel cylinder lubricating oil composition of the present invention comprises an unsulfurized tetrapropenyl phenol compound and its unsulfurized metal salt, such as TPP and its calcium salt, . The term "substantially free " as used herein refers to the relatively low level of unsulfided tetrapropenyl phenol and its unsulfided metal salt in marine diesel cylinder lubricating oil composition, if present, For example, less than about 1.5 wt%. In another embodiment, the term "substantially free" is less than about 1 wt% in a marine diesel cylinder lubricating oil composition. In other embodiments, the term "substantially free" is less than about 0.3 wt% in a marine diesel cylinder lubricating oil composition. In another embodiment, the term "substantially free" is less than about 0.1 wt% in a marine diesel cylinder lubricating oil composition. In other embodiments, the term "substantially free" is from about 0.0001 to about 0.3 wt% in the marine diesel cylinder lubricating oil composition.

Due to low-operating speeds and high loads in marine engines, high-speed oils (e.g., SAE 40, 50, and 60) are typically required. The marine diesel cylinder lubricating oil composition of the present invention may have a kinematic viscosity in the range of about 12.5 to about 26.1 centistokes (cSt) at 100. In another embodiment, the lubricating oil composition has a viscosity of from about 12.5 to about 21.9, or from about 16.3 to about 21.9 cSt at 100. The kinematic viscosity of a marine diesel cylinder lubricating oil composition is measured by ASTM D445.

The marine diesel cylinder lubricating oil compositions of the present invention can be prepared by any method known to those skilled in the art for making marine diesel cylinder lubricating oil compositions. The components may be added in any order and in any manner. Any suitable mixing or dispensing equipment may be used to blend, mix, or solubilize the ingredients. Blending, mixing or solubilizing may be carried out in a blender, an agitator, a disperser, a mixer (for example, planetary mixers and dual (E.g., double planetary mixers), homogenizers (e.g., Gaulin homogenizer or Rannie homogenizer), mills (e.g., colloid mills colloid mill, ball mill or sand mill) or any other mixing or dispensing equipment known in the art.

Group II base stocks for use herein are described in API Publication 1509, 14th Edition, Addendum I, Dec. 1998], the oil viscosity of any lubricating viscosity may be unique. API guidelines define the base stock as a lubricant component that can be prepared using a variety of different processes. The Group II base stock generally has a total sulfur content of less than 300 parts per million (ppm) (as determined by ASTM D 2622, ASTM D 4294, ASTM D 4927 or ASTM D 3120), a saturation content of at least 90 wt% (As determined by ASTM D 2007) and a viscosity index (VI) of 80 to 120 (as determined by ASTM D 2270).

In one embodiment, the one or more Group II base stocks may be a blend or a mixture of two or more, three or more, or even four or more Group II base stocks having different molecular weights and viscosities, wherein the blend is applied to a marine diesel engine Is treated in any suitable manner to produce a base oil having properties suitable for use (e.g., the viscosity and TBN values discussed above).

One or more Group II base stocks for use in the marine diesel engine lubricating oil composition of the present invention are typically present in a major amount, e.g., greater than about 50 wt%, greater than about 70 wt%, based on the total weight of the composition do. In one embodiment, the at least one Group II base stock is present in an amount of from about 70 wt% to about 95 wt%, based on the total weight of the composition. In one embodiment, the at least one Group II base stock is present in an amount of from about 70 wt% to about 85 wt%, 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 base stock other than a Group II base stock. For example, a marine diesel engine lubricant composition can contain minor amounts of Group I or III-V base stocks as defined in API Publication 1509, 16 ^th Edition, Addendum I, Oct., 2009 ≪ / RTI > The IV base oil is polyalphaolefin (PAO).

As mentioned above, marine diesel cylinder lubricating oil compositions for use in marine diesel engines have a kinematic viscosity in the range of 100 to 12.5 to 26.1 cSt. To formulate such a lubricant, the brightstock may be combined with a low viscosity oil, for example an oil having a viscosity of 100 to 4 to 6 cSt. However, the supply of bright stock is reduced, so that bright stock may not be needed to increase the viscosity of the marine cylinder lubricant to the desired range recommended by the manufacturer. One solution to this problem is to use thickeners to thicken the marine diesel cylinder lubricating oil composition, such as polyisobutylene (PIB) or viscosity index improver compounds such as olefin copolymers . PIB is a commercially available material from a number of manufacturers. PIB typically has a weight average molecular weight ranging from about 1,000 to about 8,000, or from about 1,500 to about 6,000, and a viscous oil-miscibility (from 100) having a viscosity ranging from about 2,000 to about 5,000 or about 6,000 cSt oil-miscible liquid. The amount of PIB added to the marine diesel cylinder lubricating oil composition is generally from about 1 to about 20 wt% of the finished oil, or from about 2 to about 15 wt% of the finished oil, or from about 4 to about 15 wt% 12 wt%.

The Group I base oil generally has a total sulfur content of less than 90 wt% (as determined by ASTM D 2007) and / or 300 ppm (determined by ASTM D 2622, ASTM D 4294, ASTM D 4297 or ASTM D 3120) Based lubricating base oil having a viscosity index (VI) of 80 to less than 120 (determined by ASTM D 2270).

The Group I base oil may include light overhead cuts and heavier side cuts derived from a vacuum distillation column and may also include, for example, Light Neutral, , Medium Neutral, and Heavy Neutral base stock. In addition, the oil-based base stock may include residual stocks or bottoms fractions such as, for example, bright stock. The brightstock is a high viscosity base oil, which is conventionally manufactured from residual stock or from the bottom, is highly comminuted, and is desiccated. The brightstock may have a kinematic viscosity in the range of from about 40 to about 180 cSt, even from about 40 to about 250 cSt, or even from about 40 to about 500 to about 1100 cSt. In one embodiment, the Group I base stock comprises ExxonMobil CORE ^® 100, ExxonMobil CORE ^® 150, ExxonMobil CORE ^® 600, or ExxonMobil CORE ^® 2500, or mixtures thereof.

Group III base stocks generally have a total sulfur content of less than 0.03 wt% (determined by ASTM D 2270), saturates content of greater than or equal to 90 wt% (determined by ASTM D 2007), and 120 (ASTM D 4294, (Determined by ASTM D 4297 or ASTM D 3120) or higher. In one embodiment, the base stock is a Group III base stock, or a blend of two or more different Group III base stocks.

Generally, group III base stocks derived from petroleum oils are highly hydrotreated mineral oils. Hydrotreating involves the reduction of olefins and aromatics into alkanes and cycloparaffins, respectively, by removing heteroatoms from the hydrocarbons by reacting the treated base stock with hydrogen , In extreme hydrotreating, opening naphthenic ring structures into non-cyclic normal and iso-alkanes ("paraffins") (open up. In one embodiment, the Group III base stock is at least about 70 wt%, as determined by Test Method ASTM D 3238-95 (2005), "Standard Test Method for Calculation of Carbon Distribution and Structural Group Analysis of Petroleum Oil by the ndM Method & % Of paraffinic carbon content (% C _p ). In another embodiment, the Group III base stock has a paraffinic carbon content (% C _p ) of at least about 72%. In another embodiment, the Group III base stock has a paraffinic carbon content (% C _p ) of at least about 75%. In another embodiment, the Group III base stock has a paraffinic carbon content (% C _p ) of at least about 78%. In another embodiment, the Group III base stock has a paraffinic carbon content (% C _p ) of at least about 80%. In another embodiment, the Group III base stock has a paraffinic carbon content (% C _p ) of at least about 85%.

In another embodiment, the Group III base stock has a naphthenic carbon content (% C _n ) of less than or equal to about 25% as determined in ASTM D 3238-95 (2005). In another embodiment, the Group III base stock has a naphthene-based carbon content (% C _n ) of about 20% or less. In another embodiment, the Group III base stock has a naphthene carbon content (% C _n ) of about 15% or less. In another embodiment, the Group III base stock has a naphthene carbon content (% C _n ) of about 10% or less.

Many Group III base stocks include, for example, commercially available Chevron UCBO base stocks; Yukong Yubase base stock; Shell XHVI ^® base stock; And ExxonMobil Exxsyn® base stock.

In one embodiment, the Group III base stock for use herein is a Fischer-Tropsch derived base oil. The term "Fischer-Tropsch derived" means that a product, fraction, or feed is derived from the Fischer-Tropsch process or is produced at some stage. For example, the Fischer Tropsch base oil may be prepared from a process wherein the feed is a waxy feed recovered from a Fischer-Tropsch synthesis, see for example, U.S. Patent Application Publication Nos. 2004/0159582; 2005/0077208; 2005/0133407; 2005/0133409; 2005/0139513; 2005/0139514; 2005/0241990; 2005/0261145; 2005/0261146; 2005/0261147; 2006/0016721; 2006/0016724; 2006/0076267; 2006/013210; 2006/0201851; 2006/020185, and 2006/0289337; U.S. Patent Nos. 7,018,525 and 7,083,713 and U.S. Serial No. 11 / 400,570; 11 / 535,165 and 11 / 613,936, each of which is incorporated herein by reference. In general, the process may be a complete or partial hydroisomerization dewaxing process using a dual-functional catalyst or catalyst capable of selectively isomerizing paraffins selectively, step. Hydrotreating isomerization is accomplished by contacting the hydrotreating isomerization catalyst with the wax feed in the isomerization zone under hydrotreating isomerization conditions.

Fischer-Tropsch synthesis product is, for example, for example SASOL commercially available ^® slurry phase Fischer-Tropsch technology, that are not, or commercially available by the commercial SHELL ^® middle distillate Synthesis (SMDS) process is EXXON ^® Advanced Gas Conversion (AGC -21) process. A detailed description of these processes and others can be found, for example, in WO-A-9934917; WO-A-9920720; WO-A-05107935; EP-A-776959; EP-A-668342; U.S. Patent Nos. 4,943,672, 5,059,299; 5,733,839; And RE39073; And United States Patent Application Publication No. 2005/0227866. The Fischer-Tropsch synthesis product may contain from 1 to about 100 carbon atoms, or, in some cases, hydrocarbons having more than 100 carbon atoms and typically comprises paraffins, olefins, and oxygenated products.

IV base stocks, or polyalphaolefins (PAOs) are commonly used in the oligomerization of low molecular weight alpha-olefins, such as alpha-olefins containing at least 6 carbon atoms Lt; / RTI > In one embodiment, the alpha-olefin is an alpha-olefin containing 10 carbon atoms. PAO is a mixture of dimers, trimers, tetramers, etc., and the exact mixing depends on the viscosity of the desired final base stock. The PAO is typically hydrotreated after oligomerization to remove any residual unsaturation.

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

The marine diesel cylinder lubricating oil composition of the present invention further comprises (i) at least one alkaline earth metal salt of an alkyl-substituted hydroaromatic carboxylic acid having a TBN of greater than 250, and (ii) at least one highly overbased alkylaryl sulfonic acid Or a salt thereof; The aromatic moiety of the alkyl aromatic sulfonic acid or its salt does not contain a hydroxyl group.

In general, at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid and at least one highly overbased alkylaromatic sulfonic acid or salt thereof is dissolved in a conventional liquid organic diluent in which each additive is substantially inert, diluent such as a concentrate which is incorporated in, for example, mineral oil, naphtha, benzene, toluene or xylene to form an additive concentrate . Such concentrates usually contain from about 10% to about 90% by weight of such a diluent or from 20% to 80% by weight of such a diluent, the rest being specific additives. Typically, a neutral oil having a viscosity of from about 4 to about 8.5 cSt at 100 and preferably from about 4 to about 6 cSt at 100 will be used as a diluent, while other synthetic oils, as well as other additives compatible with the additive and finished lubricant Organic liquids may also be used.

In one embodiment, the concentrate is substantially free of unsulfurized tetrapropenyl phenol compound and its unsulfided metal salts, such as TPP and its calcium salt. The term "substantially free " as used herein, when present, refers to the relatively low level of unsulfided tetrapropenyl phenol and its unsulfated metal salt, for example, Less than 1.5 wt%. In other embodiments, the term "substantially free" is less than about 1 wt% in the concentrate. In other embodiments, the term "substantially free" is less than about 0.3 wt% in the concentrate. In another embodiment, the term "substantially free" is less than about 0.1 wt% in the concentrate. In other embodiments, the term "substantially free" is from about 0.0001 to about 0.3 wt% in the concentrate.

The detergent composition used in the marine diesel cylinder lubricating oil composition of the present invention comprises at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid having a TBN of greater than 250, earth metal salts. TBN of at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid is on an activated water basis. In one embodiment, the at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid has a TBN of at least 250 and up to about 800. In one embodiment, the at least one alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid has a TBN greater than 250 and up to about 750. In one embodiment, the at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid has a TBN greater than 250 and up to about 700. In one embodiment, the at least one alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid has a TBN of greater than 250 and up to about 650. In one embodiment, the at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid has a TBN greater than 250 and up to about 600. [ In one embodiment, the at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid has a TBN greater than 250 and up to about 410. [

In another embodiment, the at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid has a TBN of from about 260 to about 800. In one embodiment, the at least one alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid has a TBN of from about 260 to about 750. In one embodiment, the at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid has a TBN of from about 260 to about 700. In one embodiment, the at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid has a TBN of from about 260 to about 650. In one embodiment, the at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid has a TBN of from about 260 to about 600. In one embodiment, the at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid has a TBN of from about 260 to about 410.

In another embodiment, the at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid has a TBN of about 300 or greater. In another embodiment, the at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid has a TBN of from about 300 to about 800. In one embodiment, the at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid has a TBN of from about 300 to about 750. In one embodiment, the at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid has a TBN of from about 300 to about 700. In one embodiment, the at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid has a TBN of about 300 to about 650. In one embodiment, the at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid has a TBN from about 300 to about 600. In one embodiment, the at least one alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid has a TBN of from about 300 to about 410.

In one preferred embodiment, the at least one alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid is at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid having a TBN greater than 250. In one preferred embodiment, the at least one alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid is a calcium alkyl-substituted hydroxyaromatic carboxylic acid having a TBN of greater than 250. In another preferred embodiment, the at least one alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid has a major amount of mono-alkyl-substituted hydroxyaromatic carboxylic acid having a TBN of greater than 250, hydroxyaromatic carboxylic acid).

In one preferred embodiment, the at least one alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid is at least one alkaline earth metal salt of an alkyl-substituted hydroxybenzoic acid having a TBN of at least 300 . In one preferred embodiment, the at least one alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid is a calcium alkyl-substituted hydroxyaromatic carboxylic acid having a TBN of at least 300. In another preferred embodiment, the at least one alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid comprises at least one alkaline earth metal salt of a major amount of a mono-alkyl-substituted hydroxyaromatic carboxylic acid having a TBN of at least 300 I have.

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

The alkyl-substituted moiety of an alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid may be derived from an alpha olefin having from about 10 to about 80 carbon atoms. In one embodiment, the alkyl-substituted moiety of an alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid may be derived from an alpha olefin having from about 10 to about 40 carbon atoms. In one embodiment, the alkyl-substituted moiety of the alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid may be derived from an alpha olefin having from about 12 to about 28 carbon atoms. The olefins used 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 types, or a mixture of any of the foregoing.

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

In further embodiments, the olefin comprises at least one olefin-containing C ₉ to C ₁₈ oligomers of monomers selected from a mixture of propylene, butylene or mixtures thereof. Generally, the one or more olefins will contain a major amount of C ₉ to C ₁₈ oligomers of monomers selected from propylene, butylene, or mixtures thereof. Examples of such olefins include propylene tetramer, butylene trimer, and the like. Other olefins may be present, as will be readily appreciated by those skilled in the art. For example, other olefins that may be used besides C ₉ to C ₁₈ oligomers include, but are not limited to, linear olefins, cyclic olefins, branched olefins such as butylene, Isobutylene oligomers, arylalkylenes, and the like, and mixtures thereof. 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, common alpha-olefins such as C ₁₆ to C ₃₀ common 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 dimer or trimer or high molecular weight isobutylene oligomers, and the like, and mixtures thereof. Suitable arylalkylenes include, but are not limited to, styrene, methyl styrene, 3-phenylpropene, 2-phenyl-2-butene, ≪ / RTI >

In one embodiment, the alkyl-substituted moiety of the alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid may contain a mixture of a C ₁₂ alkyl group and a C ₂₀ to C ₂₈ linear olefin. In one embodiment, the alkyl-substituted hydroxy aromatic carboxylic alkaline earth metal salt of an alkyl acid-substituted moiety is at least about 50% by weight of C ₂₀ to C ₂₈ of at most about 50% by weight in a mixture with linear olefin C It may contain a _12-alkyl group.

In one embodiment, the alkyl-substituted moiety of the alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid is at least 50% by weight of a branched branched hydrocarbyl radical derived from a propylene oligomer. up to 50% by weight in the mixture having a hydrocarbyl radical) to about ₂₀ C may contain a C ₂₈ linear olefins. In another embodiment, the alkyl-substituted moiety of the alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid is a mixture of up to 85 weight percent of a mixture having at least 15 weight percent branched hydrocarbyl radical derived from propylene oligomer % Of C ₂₀ to C ₂₈ linear olefins.

In one embodiment, at least about 75 mole% (e.g., at least about 80 mole%, at least about 85 mole%, at least about 90 mole%, at least about 90 mole% At least about 95 mol%, or at least about 99 mol%) is an alkyl group of C ₂₀ or more. In another embodiment, the alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid is an alkaline earth metal salt of an alkyl-substituted hydroxybenzoic acid derived from an alkyl-substituted hydroxybenzoic acid wherein the alkyl group has at least 75 moles Is a residue of normal alpha-olefins containing more than ₂₀ % C alpha-olefins.

In other embodiments, at least about 50 mole% (e.g., at least about 60 mole%, at least about 70 mole%, at least about 80 mole%, at least about 80 mole% At least about 85 mole percent, at least about 90 mole percent, at least about 95 mole percent, or at least about 99 mole percent) of the alkyl groups is from about _C14 to about _C18 .

The resulting alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids having a TBN of greater than 250 may be a mixture of ortho and para isomers. In one embodiment, the product will contain about 1 to 99% ortho isomer and 99 to 1% para isomer. In other embodiments, the product will contain about 5 to 70% ortho and 95 to 30% para isomer.

The alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids are prepared by reacting BN of an alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid with a base source (e.g., lime) Is increased by processes such as the addition of vaporized compounds (e. G., Carbon dioxide). Methods for overbasing are within the purview of those skilled in the art.

Generally, the amount of at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid having a TBN greater than 250 present in a marine diesel cylinder lubricating oil composition having a TBN of from about 5 to about 120 is greater than the total of the marine diesel cylinder lubricating oil composition And may range from about 0.1 wt% to about 35 wt% based on the weight of active material. In one embodiment, the amount of at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid having a TBN of greater than 250 present in a marine diesel cylinder lubricating oil composition having a TBN of from about 20 to about 100, To about 25 wt% based on the active water based on the total weight of the composition. In one embodiment, the amount of at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid having a TBN of greater than 250 present in a marine diesel cylinder lubricating oil composition having a TBN of from about 20 to about 60, Based on the total weight of the active ingredients. ≪ RTI ID = 0.0 > [0035] < / RTI > In one embodiment, the amount of at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid having a TBN greater than 250 present in a marine diesel cylinder lubricating oil composition having a TBN of from about 30 to about 50, Based on the total weight of the active ingredients. ≪ RTI ID = 0.0 > [0031] < / RTI >

In addition, the cleaning composition used in the marine diesel cylinder lubricating oil composition of the present invention comprises at least one highly overbased alkyl aromatic sulfonic acids or salts thereof. Alkyl aromatic sulfonic acids or salts thereof include alkyl aromatic sulfonic acids or salts thereof obtained by alkylation of aromatic compounds. The alkyl aromatic compound is then sulfonated to form an alkyl aromatic sulfonic acid. If desired, the alkyl aromatic sulfonic acid may be caustically neutralized to yield an alkaline or alkaline earth metal alkyl aromatic sulfonate compound.

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

Mixtures of at least one alkylaromatic compound or aromatic compound are commercially available or can be prepared by methods well known in the art.

The alkylating agent used to alkylate the aromatics may be derived from a variety of sources. Such sources include, but are not limited to, normal alpha olefins, linear alpha olefins, isomerized linear alpha olefins, dimerized and oligomerized olefins, and And olefins derived from olefin metathesis. The olefin may be a single carbon number olefin or it may be a mixture of linear olefins, a mixture of isomerized linear olefins, a mixture of branched olefins, Partially branched olefins, or a mixture of any of the foregoing. Another source from which olefins can be derived is through cracking of petroleum or Fischer-Tropsch waxes. The Fischer-Tropsch wax can be hydrotreated prior to cracking. Other commercially available sources include olefins derived from paraffinic dehydrogenation and oligomerization of ethylene and other olefins, methanol-to-olefin processes (such as methanol crackers) .

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

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

In one embodiment, the mixture of branched olefins is selected from polyolefins that can be derived from C ₃ or higher monoolefins (e.g., propylene oligomers, butylene oligomers, or co-oligomers). In one embodiment, the mixture of branched olefins is propylene oligomers or butylenes oligomers or mixtures thereof.

In one embodiment, the aromatic compound is alkylated with a mixture of common alpha olefins containing C ₈ to C ₆₀ carbon atoms. In one embodiment, the aromatic compound is alkylated with a mixture of common alpha olefins containing C ₁₀ to C ₅₀ carbon atoms. In another embodiment, the aromatic compound is alkylated with a mixture of common alpha olefins containing C ₁₂ to C ₄₀ carbon atoms to yield an aromatic alkylate.

The normal alpha olefins used to prepare the alkyl aromatic sulfonic acids or their salts are either commercially available or can be prepared by methods known in the art.

In one embodiment, normal alpha olefins are isomerized using solid and liquid acid catalysts. 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 comprises a molecular sieve having a one-dimensional pore system such as SM-3, MAPO-11, SAPO-11, SSZ-32, ZSM-23, MAPO- -39, ZSM-22 or SSZ-20. Other possible acidic solid catalysts useful for isomerization include ZSM-35, SUZ-4, NU-23, NU-87 and natural or synthetic ferrierites. Such molecular sieves are well known in the art and are discussed in Rosemarie Szostak's Handbook of Molecular Sieves (New York, Van Nostrand Reinhold, 1992), which is incorporated herein by reference for all purposes. The liquid type isomerization catalyst that can be used is iron pentacarbonyl (Fe (CO) ₅ ).

The process for isomerization of common alpha olefins can be carried out in a batch or continuous manner. The process temperature may range from about 50 to about 250. In the batch mode, the conventional method used is a stirred autoclave or glass flask, which can be heated to the desired reaction temperature. The continuous process is most efficiently carried out in the fixed bed process. The space rate in the fixed bed process may range from a space velocity of from about 0.1 to about 10 or more per weight hour.

In a fixed bed process, the isomerization catalyst is charged to the reactor and activated or dried at a temperature of at least 125 under a flowing inert, flowing, dry gas. After activation, the temperature of the isomerization catalyst is adjusted to the desired reaction temperature, and a constant flow rate of olefin is injected into the reactor. A reactor effluent containing partially branched and isomerized olefins is collected. The reactor effluent containing the partially branched and isomerized olefins obtained has an olefin distribution that is different from that of the unisomerized olefins (i.e., alpha olefins, beta olefins, beta olefin, an internal olefin, a tri-substituted olefin, and a vinylidene olefin) and branching content, the conditions varying according to the olefin distribution and degree of branching desired Is selected for obtaining.

Typically, the alkylated aromatic compound can be prepared using a Bronsted acid catalyst, a Lewis acid catalyst, or a solid acidic catalysts.

The Bronsted acid catalyst may be selected from the group consisting of hydrochloric acid, hydrofluoric acid, hydrobromic acid, sulfuric acid, perchloric acid, trifluoromethane sulfonic acid, Fluorosulfonic acid, and 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 consisting of 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 may be selected from the group comprising zeolites, acid clays, and / or silica-alumina. A suitable solid catalyst is a cation exchange resin in its acidic form, for example a crosslinked sulfonic acid catalyst. The catalyst may be a molecular sieve. Suitable molecular sieves are silica-aluminophosphate molecular sieves or metal silica-aluminophosphate molecular sieves, where the metals are, for example, iron, cobalt cobalt or nickel. Another suitable example of a solid acid catalyst is disclosed in U.S. Patent No. 7,183,452, the contents of which are incorporated herein by reference.

The Bronsted acid catalyst may be regenerated after it has been regenerated (i.e., the catalyst has lost all or part of its catalytic activity). Methods well known in the art can be used to regenerate acidic catalysts, such as hydrofluoric acid.

The alkylation techniques used to prepare the alkylaromatics may be used in batches, semi-batch or continuous processes operating at about 0 to about 300, as well as Bronsted and / or Lewis acids. Lt; RTI ID = 0.0 > acidic < / RTI >

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

In one embodiment, the alkylation process is carried out in a first reactor where agitation is maintained in the presence of a Bronsted acid catalyst, such as hydrofluoric acid, in the presence of a first amount of at least one aromatic compound or mixture of aromatic compounds, By reacting a mixture of olefinic compounds, thereby preparing a first reaction mixture. The resulting first reaction mixture is maintained in the first alkylation section under alkylation conditions for a period of time sufficient to convert the olefin to an aromatic alkylate (i.e., the first reaction product). After the desired time, the first reaction product is removed from the alkylation section and fed to a second reactor wherein the first reaction product comprises an additional amount of at least one aromatic compound or mixture of aromatic compounds and an additional amount of an acidic catalyst and Optionally with a mixture of additional amounts of olefinic compounds, wherein shaking is maintained. A second reaction mixture is formed and is maintained in the second alkylation section under alkylation conditions for a time sufficient to convert the olefin to an aromatic alkylate (i.e., a second reaction product). The second reaction product is fed to a liquid-liquid separator to cause the hydrocarbon (i.e., organic) product to separate from the acidic catalyst. The acidic catalyst can be recycled to the reactor (s) in a closed loop cycle. The hydrocarbon product is further treated to remove excess unreacted aromatics and optionally olefinic compounds from the desired alkylate product. In addition, excess aromatic compounds can be recycled to the reactor (s).

In another embodiment, the reaction occurs in more than two reactors located in series. Instead of feeding the second reaction product to the liquid-liquid separator, the second reaction product is fed to a third reactor, wherein the second reaction product is a mixture of an additional amount of at least one aromatic compound or aromatic compound and an additional amount Of an acidic catalyst and optionally a further amount of an olefinic compound, wherein the agitation is maintained. A third reaction mixture is formed and maintained in the third alkylation section under alkylation conditions for a period of time sufficient to convert the olefin to the aromatic alkylate (i.e., the third reaction product). The reaction takes place in a number of reactors as required to obtain the desired alkylated aromatic reaction product.

The total charge mole ratio of the Bronsted acid catalyst to the olefinic compound is from about 0.1 to about 1 for the combined reactors. In one embodiment, the total charged mole ratio of the Bronsted acid catalyst to the olefin compound is from about 0.7 to about 1 in the first reactor and from about 0.3 to about 1 or more in the second reactor.

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

Many types of reactor configurations can be used for the reactor zone. These include, but are not limited to, batch and continuous stirred tank reactors, reactor riser configurations, ebullated bed reactors, and other reactor structures well known in the art. Numerous such reactors are well known to those skilled in the art and are suitable for alkylation reactions. Shaking is important for alkylation reactions and can be achieved by using baffles, static mixers, kinetic mixing in risers, or any other agitation device known in the art But can be provided by rotating impellers. The alkylation process may be carried out at a temperature of from about 0 to about 100. The process is carried out under sufficient pressure that a substantial portion of the feed components remain in the liquid phase. Typically, pressures of 0 to 150 psig are sufficient to maintain the feed and product in the liquid phase.

The residence time in the reactor is a sufficient time for a significant portion of the olefin to convert to an alkylate product. The time required is about 30 seconds to about 30 minutes. A more accurate residence time can be determined by those skilled in the art using a batch stirred tank reactor to determine the kinetics of the alkylation process.

The mixture of at least one aromatic compound or aromatic compound and the olefin compound may be injected separately into the reactor section or may be mixed prior to injection. Both single and multiple reaction zones can be used for the injection of aromatic compounds and olefinic compounds into one, many, or all reaction zones. The reaction zone does not have to be maintained under the same process conditions. The hydrocarbon feed to the alkylation process may comprise a mixture of an aromatic compound and an olefin compound, wherein the molar ratio of aromatic compound to olefin is from about 0.5: 1 to about 50: 1 or greater. When the molar ratio of aromatic compound to olefin is > 1.0 to 1, excess aromatic compound is present. In one embodiment, an excess of aromatic compound is used to increase the rate of reaction and improve product selectivity. If excess aromatic compounds are used, excess unreacted aromatics in the reactor effluent can be separated by, for example, distillation and recycled to the reactor.

If an alkyl aromatic product is obtained as described above, it may be further reacted to form an alkyl aromatic sulfonic acid and then neutralized with the corresponding sulfonate. The sulfonation of alkylaromatics can be carried out by any method known to those skilled in the art. The sulfonation reaction is typically carried out in a continuous falling film tubular reactor maintained at about 45 to about 75. For example, an alkylaromatic compound is placed in a reactor with sulfur trioxide diluted with air to produce an alkylaryl sulfonic acid. Other sulfonation reagents such as sulfuric acid, chlorosulfonic acid or sulfamic acid may also be used. In one embodiment, the alkylaromatic compound is sulfonated with air diluted sulfur trioxide. The charge molar ratio of sulfur trioxide to alkylate is maintained at about 0.8 to about 1.1: 1.

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

The at least one alkylaromatic sulfonic acid or salt thereof is at least one highly overbased alkylaromatic sulfonic acid or salt thereof. As discussed above, the overbasing is carried out in such a way that the TBN of the alkylaromatic sulfonic acid or its salt is converted to a salt of a base such as, for example, a base source (for example, lime) and an acidic and basic compound (for example, carbon dioxide) And is increased by a process such as addition. Methods of overbasing are well known in the art.

In one embodiment, the at least one highly overbased alkyl aromatic sulfonic acid or salt thereof will have a TBN of greater than 250. In one embodiment, the at least one highly overbased alkyl aromatic sulfonic acid or salt thereof will have a TBN of from about 250 to about 700. In one embodiment, the at least one highly overbased alkyl aromatic sulfonic acid or salt thereof will have a TBN of greater than about 300. In one embodiment, the at least one highly overbased alkyl aromatic sulfonic acid or salt thereof will have a TBN from about 300 to about 700.

In general, at least one highly overbased alkylaromatic sulfonic acid or salt thereof present in a marine diesel cylinder lubricating oil composition having a TBN of from about 5 to about 120 may be present in an amount of about < RTI ID = 0.0 > And may range from 0.1 wt% to about 34 wt%. In one embodiment, the at least one highly overbased alkylaromatic sulfonic acid or salt thereof present in a marine diesel cylinder lubricating oil composition having a TBN of from about 20 to about 100, based on the total weight of the marine diesel cylinder lubricating oil composition, To about 30 wt%, based on the total weight of the composition. In one embodiment, the at least one highly overbased alkylaromatic sulfonic acid or salt thereof present in a marine diesel cylinder lubricating oil composition having a TBN of from about 20 to about 60 comprises, based on the total weight of the marine diesel cylinder lubricant composition, To about 24 wt%, based on the total weight of the composition. In one embodiment, the at least one highly overbased alkyl aromatic sulfonic acid or salt thereof present in a marine diesel cylinder lubricating oil composition having a TBN of from about 30 to about 50, based on the total weight of the marine diesel cylinder lubricating oil composition, To about 16 wt%, based on the total weight of the composition.

In addition, the marine diesel cylinder lubricating oil composition of the present invention is a conventional marine diesel cylinder lubricating oil composition other than the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid having a TBN of greater than 250 Additives and at least one highly overbased alkyl aromatic sulfonic acid that imparts auxiliary functions to the marine diesel cylinder lubricating oil composition in which such additives are dispersed or dissolved. For example, marine diesel cylinder lubricating oil compositions can be formulated with antioxidants, ashless dispersants, other detergents, anti-wear agents, rust inhibitors, dehazing agents, antifoaming agents, co-solvents, anticorrosive agents, antifoaming agents, demulsifying agents, metal deactivating agents, friction modifiers, pour point depressants, antifoaming agents, corrosion-inhibitors, dyes, extreme pressure agents, and the like, and mixtures thereof. Various additives are known and are commercially available. These additives, or similar compounds thereof, can be used for the preparation of the marine diesel cylinder lubricating oil composition of the present invention by a common blending process.

In one embodiment, the marine diesel cylinder lubricating oil composition of the present invention essentially does not contain a thickener (i.e., a viscosity index improver).

Examples of antioxidants include, but are not limited to, amine-based types, such as diphenylamine, phenyl-alpha-napthyl-amine, N, (N, N-di (alkylphenyl) amines); And alkylated phenylene-diamines; Phenolics such as, for example, BHT, sterically hindered alkyl phenols such as 2,6-di-tert-butylphenol, 2,6- Di-tert-butyl-p-cresol and 2,6-di-tert-4- (2-octyl-3-propanoyl) phenol 2,6-di-tert-butyl-4- (2-octyl-3-propanoic) phenol); And mixtures thereof.

The ashless dispersant compound used in the marine diesel cylinder lubricating oil composition of the present invention generally retains the insoluble materials produced by oxidation during use in suspension and is useful for sludge flocculation and metal parts To prevent precipitation or deposition on the substrate. The dispersant can also serve to prevent the growth of large contaminant particles in the lubricant, thereby reducing the change in lubricant viscosity. The dispersant used in the present invention may be any suitable ashless dispersant or a mixture of many ashless dispersants for use in marine diesel cylinder lubricating oil compositions. The ashless dispersant generally comprises a soluble polymeric hydrocarbon backbone having functional groups that can associate with the particles to be dispersed.

In one embodiment, the ashless dispersant is at least one basic nitrogen-containing ashless dispersant. The nitrogen-containing basic ashless (metal-free) dispersants contribute to the base of the lubricating oil composition to which they are added, or BN (which can be measured by ASTM D 2896) without the addition of additional sulfuric acid ash. Basic nitrogen-containing ashless dispersants useful in the present invention include hydrocarbyl succinimides; Hydrocarbyl succinamides; A hydrocarbyl-substituted succinic acid formed by reacting a hydrocarbyl-substituted succinic acylating agent either stepwise or with a mixture of alcohols and amines, and / or with an amino alcohol, mixed ester / amides of hydrocarbyl-substituted succinic acids; Mannich condensation products of hydrocarbyl-substituted phenols, formaldehyde and polyamines; And amine dispersants formed by reacting with high molecular weight aliphatic or alicyclic halides and amines such as polyalkylene polyamines. Mixtures of such dispersants may also be used.

Representative examples of ashless dispersants include, but are not limited to, ester polar moieties attached to the polymer backbone through amines, alcohols, amides, or bridging groups. do. The ashless dispersants of the present invention can be used in the form of, for example, long-chain hydrocarbon substituted mono and dicarboxylic acids or their anhydrides, oil soluble salts, esters, ), Amino-esters, amides, imides, and oxazolines; Thiocarboxylate derivatives of long chain hydrocarbons, long-chain aliphatic hydrocarbons having a polyamine directly attached thereto; And Mannich condensation products formed by condensation of long chain substituted phenols with formaldehyde and polyalkylene polyamines.

Carboxylic acid dispersants include carboxylic acid alkylating agents (acids, anhydrides, esters, etc.) containing at least about 34 and preferably at least about 54 carbon atoms and nitrogen containing compounds such as amines (for example, amines), organic hydroxy compounds (e.g., aliphatic compounds including monohydric and polyhydric alcohols, or aromatic compounds including phenol and naphthol), and / It is the reaction product with the substance. Such reaction products include imides, amides, and esters.

Succinimide dispersants are a type of carboxylic acid dispersant. This may be achieved by reacting a hydrocarbyl-substituted succinic acylating agent with an organohydroxy compound, or an amine comprising at least one hydrogen atom attached to the nitrogen atom, or a mixture of a hydroxy compound and an amine ≪ / RTI > The term " succinic acylating agent "relates to a hydrocarbon-substituted succinic acid or a succinic acid-producing compound, the latter including an acid itself. Such materials typically include hydrocarbyl-substituted succinic acids, anhydrides, esters (including half esters), and halides.

Succinic-based dispersants have a wide chemical structure. One class of succinic acid-based dispersants can be represented by the formula:

Wherein each R < ^{1 >} is independently a hydrocarbyl group, such as a polyolefin-derived group. Typically, the hydrocarbyl group is an alkyl group, such as a polyisobutyl group. Alternatively, the R < ¹ > groups may contain from about 40 to about 500 carbon atoms, and these atoms may be present in aliphatic form. R ² is an alkylene group, generally an ethylene (C ₂ H ₄ ) group. Examples of succinimide dispersants include those described, for example, in U.S. Patent Nos. 3,172,892, 4,234,435, and 6,165,235.

The polyalkenes from which the substituents are derived are homopolymers and interpolymers of polymerizable olefin monomers, typically of from 2 to about 16 carbon atoms, and usually from 2 to 6 carbon atoms. The amine that reacts with the succinic acid alkylating agent to form the carboxylic acid dispersant composition may be monoamines or polyamines.

The succinimide dispersants are thus mentioned and the amide functional groups may be present in the form of amine salts, amides, imidazolines as well as mixtures thereof, Because it mostly contains nitrogen. In order to prepare a succinimide dispersant, one or more succinic acid-producing compounds and one or more amines are heated and typically water is optionally removed in the presence of a substantially inert organic liquid solvent / diluent. The reaction temperature may typically range from about 80 to the maximum mixture or product decomposition temperature, which is in the range of from about 100 to about 300. Additional descriptions and examples of processes for preparing the succinimide dispersants of the present invention include those described, for example, in U.S. Patent Nos. 3,172,892, 3,219,666, 3,272,746, 4,234,435, 6,165,235, and 6,440,905.

Suitable ashless dispersants may also include amine dispersants, which are the reaction products of relatively high molecular weight aliphatic halides and amines, preferably polyalkylene polyamines. Examples of such amine dispersants include those described in, for example, U.S. Patent Nos. 3,275,554, 3,438,757, 3,454,555, and 3,565,804.

Suitable ashless dispersants may further include "Mannich dispersants ", which may include alkylphenols and aldehydes (especially formaldehyde) and amines (where the alkyl group contains at least about 30 carbon atoms) Particularly polyalkylene polyamines). ≪ / RTI > Examples of such dispersants include those described in, for example, U.S. Patent Nos. 3,036,003, 3,586,629, 3,591,598, and 3,980,569.

Suitable non-ashless dispersants can also be post-treated ashless dispersants, such as post-treated succinimide, for example, the post-treatment process can be carried out using borate as disclosed in U.S. Patent Nos. 4,612,132 and 4,746,446 ) Or ethylene carbonate and the like and other post-treatment processes. The carbonate-treated alkenyl succinimide has a weight average 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 Polybutenes succinimide derived from polybutenes having a molecular weight of 2400 and a blend of these molecular weights. Preferably, it is an unsaturated acidic reagent copolymer of a polybutene succinic acid derivative, an unsaturated acidic reagent and an olefin, and an unsaturated acid labile copolymer, Is prepared by reacting a mixture of polyamines such as those disclosed in Patent No. 5,716,912, the contents of which are incorporated herein by reference.

Metal-containing or ash-forming detergents act as both detergents and acid neutralizers or rust inhibitors for reducing or eliminating deposits, Thereby reducing wear and corrosion and extending engine life. The detergent generally comprises a polar head with a long hydrophobic tail. The polar head includes a metal salt of an acidic organic compound. The salt may contain a substantially stoichiometric amount of the metal, in which case it is usually described as a normal or neutral salt, which is typically from 0 to about 80 total bases or TBN (can be measured by ASTM D2896 ). A large amount of the metal base may be incorporated by reacting an excess of a metal compound (e.g., oxide or hydroxide) with an acidic gas (e.g., carbon dioxide). The resulting overbased detergent includes a neutralized detergent, such as an outer layer of a metal base (e.g., carbonate) micelle. Such an overbased detergent may have a TBN of about 50 or more, or TBN of about 100 or more, or TBN of about 200 or more, or TBN of about 250 to about 450. [

Representative examples of other metal cleaners that may be included in the marine diesel cylinder lubricating oil composition of the present invention include phenates, aliphatic sulfonates, alkyl-substituted hydroxyaromatic carboxylic acids having a TBN of less than 250 Alkyllithium metal salts, alkali metal salts of alkyl-substituted hydroxyaromatic carboxylic acids, phosphonates, and phosphinates. Salts of alkyl-substituted hydroxyaromatic carboxylic acids may be as described above.

Commercially available products are generally referred to as neutral or overbased. The overbased metal cleansing agent is generally selected from the group consisting of hydrocarbons, detergent acids such as sulfonic acids, carboxylates, metal oxides or hydroxides, (For example, calcium oxide or calcium hydroxide) and promoters such as xylene, methanol and water. For example, in order to prepare an overbased calcium sulfonate, at the time of carbonization, calcium oxide or calcium hydroxide is reacted with gaseous carbon dioxide to form calcium carbonate. The sulfonic acid is neutralized with excess CaO or Ca (OH) ₂ to form the sulfonate.

The overbased detergent can be an overbased salt, for example, an overbased salt having a BN of less than about 100. In one embodiment, the BN of the low overbased salt may be from about 5 to about 50. In other embodiments, the BN of the overbased salt may be from about 10 to about 30. In other embodiments, the BN of the overbased salt may be from about 15 to about 20.

The overbased detergent may be an overbased salt medium, for example, an overbased salt having a BN of about 100 to about 2.5 million. In one embodiment, the BN of the intermediate overbased salt may be from about 100 to about 200. In other embodiments, the intermediate overbased BN may be from about 125 to about 175.

The overbased detergent can be highly overbased and, for example, an overbased salt having a BN of greater than 250. In one embodiment, the BN of the highly overbased salt may be from about 250 to about 550.

Examples of rust inhibitors include, but are not limited to, nonionic polyoxyalkylene agents such as polyoxyethylene lauryl ether, polyoxyethylene higher alcohol < RTI ID = 0.0 > ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene octyl stearyl ether, polyoxyalkylene oleyl ether, But are not limited to, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol monooleate, and polyethylene glycol monooleate; Stearic acid and other fatty acids; Dicarboxylic acids; Metal soaps; Fatty acid amine salts; Metal salts of heavy sulfonic acid; Partial carboxylic acid esters of polyhydric alcohols; Phosphoric esters; (Short chain) alkenyl succinic acids ((short-chain) alkenyl succinic acids); Partial esters thereof and nitrogen-containing derivatives thereof; Synthetic alkarylsulfonates, such as metal dinonylnaphthalene sulfonates, and the like, and mixtures thereof.

Examples of friction modifiers include, but are not limited to, alkoxylated fatty amines; Borated fatty epoxides; Fatty phosphites, fatty epoxides, fatty amines, borated alkoxylated fatty amines, metal salts of fatty acids, fatty acids, Fatty acid amides, glycerol esters, borated glycerol esters; And fatty imidazolines disclosed in U.S. Patent No. 6,372,696, the contents of which are incorporated herein by reference; C ₄ to C ₇₅ , preferably C ₆ to C ₂₄ , most preferably C ₆ to C ₂₀ , fatty acid esters (fatty acid-containing compound obtained from the reaction product of a nitrogen-containing compound selected from the group consisting of an acid ester and ammonia, and an alkanolamine, such as mono- or dialkanolamine, Friction modifiers, and mixtures thereof.

Examples of antiwear agents include, but are not limited to, zinc dialkyldithiophosphates and zinc diaryldithiophosphates, such as those described in Born et al., Entitled "Some Metallic &Quot; The relationship between the chemical structure and effect of dialkyl- and diaryl-dithiophosphates ", published in Lubrication Science 4-2, 1992, see for example pages 97-100); Aryl phosphates and phosphites, sulfur-containing esters, phosphosulfur compounds, metals, or ash-free dithiocarbamates ), Xanthates, alkyl sulfides, and the like, and mixtures thereof.

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

Examples of pour point depressants include, but are not limited to, polymethacrylates, alkyl acrylate polymers, alkyl methacrylate polymers, di (tetra-paraffin phenol) phthalate tetra-paraffin phenol phthalate, condensates of tetra-paraffin phenol, condensates of chlorinated paraffin and naphthalene, and combinations thereof. In one embodiment, the pour point depressant is selected from the group consisting of an ethylene-vinyl acetate copolymer, a condensate of chlorinated paraffin and phenol, a polyalkyl styrene, and the like, . The amount of the pour point depressant may vary from about 0.01 wt% to about 10 wt%.

Examples of demulsifiers include, but are not limited to, anionic surfactants (e.g., alkyl-naphthalene sulfonates, alkyl benzene sulfonates, etc.), non-ionic surfactants Nonionic alkoxylated alkylphenol resins, polymers of alkylene oxides (for example, polyethylene oxide, polypropylene oxide, ethylene oxide, Block copolymers of propylene oxide and the like, esters of oil soluble acids, polyoxyethylene sorbitan ester, and the like, and combinations thereof. The amount of demulsifier may vary from about 0.01 wt% to about 10 wt%.

Examples of corrosion inhibitors include, but are not limited to, half esters or amides of dodecylsuccinic acid, phosphate esters, thiophosphates, alkyl imidazolines, Sarcosines, and the like, and combinations thereof. The amount of corrosion inhibitor may vary from about 0.01 wt% to about 0.5 wt%.

Examples of extreme pressure include, but are not limited to, sulphurised animal or vegetable fats or oils, sulphated animal or vegetable fatty acid esters, esters in which all or part of the trivalent or pentavalent acids of phosphorus are esterified, But are not limited to, sulfurized olefins, dihydrocarbyl polysulfides, sulfurized Diels-Alder adducts, sulfurized dicyclopentadiene, fatty esters and mono-unsaturated olefins Sulfide or co-sulfurized mixtures of fatty acids, co-sulphated blends of fatty acids, fatty acid esters and alpha-olefins, functionally-substituted dihydrocarbyl polysulfides, thia-aldehydes -aldehydes, thia-ketones, epithio compounds, sulfur-containing compounds (sulfur-containing compounds) acetal derivatives thereof, co-sulfurized blends of terpene and acyclic olefins, and polysulfide olefin products, phosphoric acid esters or thiophosphoric acid esters. acid esters, and the like, and combinations thereof. The amount of extreme pressure may vary from about 0.01 wt% to about 5 wt%.

When used, each of these additives is used in an amount that is functionally effective to impart the desired properties to the lubricant. Thus, for example, when the additive is a friction modifier, the functionally effective amount of the friction modifier will be sufficient to impart the desired friction modifying properties to the lubricant. Generally, when used, the concentration of each such additive ranges from about 0.001 wt.% To about 20 wt.%, And in one embodiment from 0.01 wt.% To about 10 wt.%, Based on the total weight of the lubricating oil composition.

In addition, the marine diesel cylinder lubricating oil composition additive may be provided as an additive package or concentrate incorporated in a substantially inert, liquid, liquid organic diluent as described above . The additive package will typically contain one or more of the various additives mentioned above in desired amounts and proportions to facilitate direct combination with the required amount of oil of lubricating viscosity.

In one embodiment, the marine diesel cylinder lubricating oil composition of the present invention is substantially free or free of any dispersants and / or zinc compounds, such as zinc dithiophosphates. As used herein, the term " substantially free "means that, when present, the relative low level of each dispersant and / or zinc compound, e.g., the respective dispersant in the marine diesel cylinder lubricant composition, Or less than about 0.5 wt% of the zinc compound. In another embodiment, the term "substantially free" is less than about 0.1 wt% of each dispersant and / or zinc compound in the marine diesel cylinder lubricating oil composition. In other embodiments, the term "substantially free" is less than about 0.01 wt% of each dispersant and / or zinc compound in the marine diesel cylinder lubricating oil composition.

(I. E., "Total TPP" or "Total Residual TPP") of the diesel cylinder lubricating oil composition of the present invention as disclosed herein and illustrated below, and the total amount of TPP and its sulfurized metal salt The concentration of the salt containing lubricant and oil additive is determined by High Performance Liquid Chromatography (HPLC). In the HPLC method, samples are precisely weighed from 80 to 120 mg of sample in a 10 ml volumetric flask, diluted to the level indicated using methylene chloride, and mixed until complete dissolution of the sample .

The HPLC system used in the HPLC method was a HPLC pump, a thermostatted HPLC column compartment, an HPLC fluorescence detector, and a PC-based chromatographic data acquisition system (PC -based chromatography data acquisition system). The specific system described is based on Agilent 1200 HPLC using ChemStation software. The HPLC column was Phenomenex Luna C8 (2) 150 x 4.6 mm 5 m 100 ANGSTROM, P / N 00F4249E0.

The following system settings were used in the analysis:

Pump flow = 1.0 ml / min

Maximum pressure = 200 bars

Fluorescence wavelength: 225 excitation 313 emission: gain = 9

Column Thermostat temperature = 25C

Injection Size = 1 μL diluted sample.

Elution type: Gradient, reverse phase,

Gradient: 0-7 min 85/15 methanol / water that is converted to a methanol linear gradient to 100% methanol

Run time: 17 minutes

The resulting chromatograph typically has a number of peaks. Peaks due to free unsulfurized alkylhydroxyaromatic compounds (i.e., TPP) are typically eluted together at early retention times; While peaks due to sulfurized alkylhydroxyaromatic compounds are typically eluted at longer retention times. For the purposes of quantitation, the area of the single maximum peak of the free sulfated alkylhydroxy aromatic compound and its metal sulfide metal salt was measured, after which the area was determined as the total free sulfhydrylized alkylhydroxy aromatic compound and its concentration . Under the assumption that the speciation of the alkylhydroxyaromatic compound is not changed; If the speciation of the alkylhydroxyaromatic compound is changed by a specific one, then recalibration is required.

The area of the selected peak was compared with the calibration curve to reach wt-% of the free sulfhydryl salts of free alkylphenols and alkylphenols. The calibration curve was developed using the same peak in the chromatograph obtained for the free sulfated alkylhydroxyaromatic compound used to prepare the phenate product.

The following non-limiting examples illustrate the invention.

The high temperature detergency and thermal stability were evaluated for each of the following examples using the Komatsu High Temperature Tube ("KHT") test described below. The results of each example are shown in Table 1.

Komatsu High Temperature Tube ("KHT") Test

Komatsu High Temperature Tube (Komatsu Hot Tube) is a lubrication industry bench test that measures the cleanliness and heat and oxidation stability of lubricating oil. Cleanliness and heat and oxidation stability are the performance categories generally accepted in the essential industry for overall performance that is satisfactory to lubricants. In the test procedure, a certain amount of test oil is pumped upward through a glass tube placed in an oven set at a certain temperature. Air is injected into the oil stream before the oil enters the glass tube and flows upward with the oil. The evaluation of marine diesel cylinder lubricant was carried out at 300-330. The test results were determined by comparing the amount of lacquer deposited on a glass test tube at a scale scale of 1.0 (very black) to 10.0 (perfectly clean). Record the result as a product of 0.5. Blockage is a deposit when the lacquer is very thick, and most of the glass test tube is occluded, preventing normal oil and air from passing through the test tube. Clogging can be considered as an inferior result of 1.0 grade and its occurrence can have a significant impact by occluding other test tubes being tested simultaneously in the same test run.

The following components are used to formulate a marine diesel cylinder lubricating oil composition as follows.

The Chevron 600N RLOP: Group II-based lubricant was a Chevron 600N RLOP base stock available from Chevron Products Company (San Ramon, Calif.).

ExxonMobil CORE ^® 2500BS: Group I-based lubricant was an ExxonMobil CORE ^® 2500BS base stock available from ExxonMobil (Irving, TX.).

The detergents used in the examples of Table 1 are described below.

Cleanser A: An oil concentrate of a neutral (non-overbased) calcium alkylhydroxybenzoate additive with an alkyl substituent derived from a C ₂₀ to C ₂₈ linear olefin is subjected to a subsequent over- Was prepared according to the method described in Example 1 of U.S. Patent Application 2007/0027043. The additive concentrate contained 2.17 wt% Ca and about 43.0 wt% diluent oil and had a TBN of 61. On an activated water basis, the TBN of this additive (dilute oil component) is 107.

Cleanser B: The oil concentrate of the overbased vaporized calcium sulfinate phenate was derived from propylene tetramer. These additives included 9.6 wt% Ca, and about 31.4 wt% diluent oil and had a TBN of 260. Detergent B is believed to have a total TPP content, i. E. About 5 to 7 wt.% TPP and its metal sulfide based on the weight of the detergent prepared.

Detergent C: unsulfurized, non-basicized alkylhydroxybenzoate having an alkyl substituent derived from about 50 wt% C ₂₀ to C ₂₈ linear olefin and 50 wt% branched hydrocarbyl radical propylene tetramer An oil concentrate of a non-overbased alkylhydroxybenzoate-containing, phenol-distilled additive was prepared according to the method described in Example 1 of U.S. Patent Application 2004/0235686. This additive contained 5.00 wt% Ca, and about 33.0 wt% diluted oil and had a TBN of 140. On an activated water basis, the TBN of this additive (dilute oil component) is 210. Detergent C is believed to have a total TPP content, i. E. About 2 to 3 wt% TPP and its metal sulfide based on the weight of the detergent prepared.

Cleanser D: An oil concentrate of an overbased calcium alkylhydroxybenzoate additive having an alkyl substituent derived from a C ₂₀ to C ₂₈ linear olefin was added to the oil concentrate of Example 1 of U.S. Patent Application 2007/0027043 ≪ / RTI > This additive contained 5.35 wt% Ca, and about 35.0 wt% diluent oil and had a TBN of 150. On an activated water basis, the TBN of this additive (dilute oil component) is 230.

Cleanser E: An oil concentrate of an overbased calcium alkylhydroxybenzoate additive having an alkyl substituent derived from a C ₂₀ to C ₂₈ linear olefin was added to the oil concentrate of Example 1 of US Patent Application 2007/0027043 ≪ / RTI > This additive contained 12.5 wt% Ca, and about 33.0 wt% diluent oil and had a TBN of 350. On an activated water basis, the TBN of this additive (dilute oil component) is 522.

Cleanser F: An oil concentrate of an overbased calcium alkyltoluene sulfonate detergent in which the alkyl group is derived from a C ₂₀ to C ₂₄ linear alpha olefin. This additive contained 16.1 wt% Ca, and about 38.7 wt% diluent oil and had a TBN of 420. On an activated water basis, the TBN of this additive (dilute oil component) is 685.

Cleanser G: An oil concentrate of an overbased calcium alkylhydroxybenzoate additive having an alkyl substituent derived from a C ₁₄ to C ₁₈ linear alpha olefin. This additive contained 6.25 wt% Ca, and about 41.0 wt% diluent oil and had a TBN of 175. On an active basis, the TBN of this additive (absent diluent oil) is 296.

Examples 1-3 and Comparative Examples A-J

The marine diesel engine lubricant compositions of Examples 1-3 and Comparative Examples A-J were prepared as described in Table 1 below. Each marine diesel engine lubricant composition of Example 1 and Comparative Examples A-J was a SAE 40 viscosity grade oil having a kinematic viscosity of about 14.5 cSt @ 100 and a TBN of 40 mg KOH / g. Example 2 was a SAE 50 viscosity oil having a kinematic viscosity of about 18.7 cSt @ 100 and a TBN of about 70 mg KOH / g. Example 3 was a SAE 50 viscosity oil having a kinematic viscosity of about 18.9 cSt @ 100 and a TBN of about 20 mg KOH / g. The marine diesel engine lubricant compositions of Examples 1-3 and Comparative Example AJ were prepared using a major amount of Group II base stock and a minor amount of Group I base stock, a cleaning composition as defined in Table 1, and a 0.04 wt% Lt; / RTI > Comparative Example D comprises 1000 MW polyisobutylene succinic anhydride (PIBSA) with about 31.7 wt% diluent oil and heavy polyamine (HPA) / diethylene triamine (DETA Lt; / RTI > oil concentrate of the bissuccinimide detergent derived from the oil-in-water emulsion. Each marine diesel cylinder lubricating oil composition of Examples 1-3 did not contain TPP and its metal sulfide salts.

As shown by the results shown in Table 1, the marine diesel cylinder lubricating oil composition of Example 1-3 containing the cleaning composition of the present invention surprisingly showed improved cleaning performance for the marine diesel cylinder lubricating oil composition of Comparative Example AJ . This is exemplified by the high KHT value maintained over the high temperature range, demonstrating that the marine diesel cylinder lubricating oil compositions of Example 1-3 exhibit excellent cleaning and thermal stability in high temperature tube testing, Little oil oxidation or deterioration products were produced. Further, Example 1-3 is substantially free of TPP and its metal sulfide salt.

It will be appreciated that various changes can be made in making the embodiments disclosed herein. Accordingly, the above description should be construed as merely illustrative of preferred embodiments, rather than limitation. For example, the functions described and enforced above as the best mode for operating the present invention are for illustrative purposes only. Other arrangements and methods may be practiced by those skilled in the art without departing from the scope and spirit of the invention. Those skilled in the art will also realize other modifications within the scope and spirit of the claims appended hereto.

Claims (15)

A marine diesel cylinder lubricating oil composition,
(a) a major amount of at least one Group II base stock, and
(b) at least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid having a total base of greater than 250 (TBN), and (ii) at least one highly overbased alkylaromatic sulfonic acid or A cleaning composition comprising a salt,
Wherein the aromatic moiety of the alkyl aromatic sulfonic acid or salt thereof does not contain a hydroxyl group and the marine diesel cylinder lubricating oil composition has a TBN of about 5 to about 120. The diesel cylinder lubricating oil composition of claim 1, The marine diesel cylinder lubricating oil composition of claim 1 having a TBN of from about 20 to about 100. The marine diesel cylinder lubricating oil composition of claim 1 having a TBN of about 10 to about 40. The marine diesel cylinder lubricating oil composition according to any one of claims 1 to 3, which is substantially free from tetrapropenyl phenol (TPP) and its metal sulfide metal salt. 5. A process according to any one of claims 1 to 4, wherein the at least one alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid is at least one calcium salt of an alkyl-substituted hydroxyaromatic carboxylic acid, Diesel cylinder lubricating oil composition. The marine diesel cylinder lubricating oil composition according to any one of claims 1 to 5, wherein the alkyl-substituted moiety of the alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid is a C ₁₀ to C ₄₀ alkyl group. 7. The marine diesel cylinder lubricating oil composition according to any one of claims 1 to 6, wherein the at least one alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid has a TBN of greater than 250 and up to about 800. 8. The marine diesel cylinder lubricating oil composition according to any one of claims 1 to 7, wherein said at least one highly overbased alkyl aromatic sulfonic acid or salt thereof is at least one highly overbased alkaline earth metal alkyl aromatic sulfonate. 9. The marine diesel cylinder lubricating oil composition according to any one of claims 1 to 8, wherein the at least one highly overbased alkylaromatic sulfonic acid or salt thereof is at least one highly overbased calcium alkylaromatic sulfonate. 10. The marine diesel cylinder lubricating oil composition according to any one of claims 1 to 9, wherein the at least one highly overbased alkylaromatic sulfonic acid or salt thereof has a TBN of greater than 250. 11. The method according to any one of claims 1 to 10,
At least one alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid of from about 0.1 wt% to about 35 wt%, based on the active, having a TBN of greater than 250, based on the total weight of the marine diesel cylinder lubricating oil composition, ; And
Based on the total weight of the marine diesel cylinder lubricating oil composition, from about 0.1 wt% to about 34 wt% of at least one highly overbased alkylaromatic sulfonic acid or salt thereof
Wherein the lubricating oil composition is a lubricant. 12. The composition according to any one of claims 1 to 11, wherein the antioxidant, the ashless dispersant, the detergent, the rust inhibitor, the dehazing agent, the detackifier, the metal deactivator, the friction modifier, the pour point depressant, , A corrosion inhibitor, a dye, an extreme pressure agent, and mixtures thereof. ≪ RTI ID = 0.0 > 18. < / RTI > 13. The marine diesel cylinder lubricating oil composition according to any one of claims 1 to 12, which is substantially free of any dispersant and / or zinc compound. A method of lubricating a two-stroke crosshead diesel engine for a marine,
Comprising operating the engine with the marine diesel cylinder lubricant composition of any one of claims 1 to 13. 13. Use of a marine diesel cylinder lubricating oil composition according to any one of claims 1 to 13 for improving high temperature cleaning and thermal stability in a two-stroke crosshead marine diesel engine.