CN107075404A - Marine diesel steam-cylinder lubrication fluid composition - Google Patents

Abstract

It disclosed herein is marine diesel steam-cylinder lubrication fluid composition, it includes (a) major amount of one or more II classes oil base stocks, cleaning agent composition (b), the cleaning agent composition includes the alkali salt of (i) one or more alkyl-substituted hydroxyaromatic carboxylic acids, its total base number (TBN) is more than 250, and (ii) one or more exceed alkalization alkyl aromatic sulfonic acid or its salt；Wherein the aromatic fractions of the alkyl aromatic sulfonic acid or its salt do not include hydroxyl；The wherein TBN about 5 about 120 of the marine diesel steam-cylinder lubrication fluid composition.

Description

Marine diesel steam-cylinder lubrication fluid composition

Priority

The provisional application Ser No.62/076 that the application requires to submit on November 6th, 2014 according to 35 U.S.C. § 119, 309 rights and interests, its content is expressly incorporated herein by reference.

Background of invention

1. technical field

Broad sense of the present invention is related to a kind of marine diesel steam-cylinder lubrication fluid composition, particularly for lubricating two stroke peculiar to vessel Crosshead diesel engine cylinder engine.

2. association area explanation

Not far in the past, quick cumulative cost of energy, particularly distill the crude oil with it is caused in liquid petroleum Those costs, become transport fuel user's such as ocean-going vessel shipowner and the heavy burden of operator.As response, this A little users selected to be operated avoid steam turbine propulsion plant and taken with the higher big marine diesel engine of fuel efficiency and Instead of.Diesel engine can be generally classified as at a slow speed, middling speed or high speed engine, the wherein slow class is used for largest deep axle Marine ship and some other commercial Applications.

Slow-speed diesel engines are unique in size and operating method.The engine is very big in itself, larger unit Weight is up to 200 tons and length more than 10 feets more than 45 feet.Engine speed per minute 60 is arrived under the conditions of about 200 turns The output of these engines may be up to 100000 brake horsepowers.They are generally crosshead design and run with two-stroke cycle. In addition, these engines are typically based on residual fuel operation, but some can also be based on distillate fuel operation, and it is comprising seldom Or without residue.

On the other hand, medium-speed engine is typically run in about 250- about 1100rpm scope, and can be based on Four strokes or two-stroke cycle are run.These engines can be plunger design or be sometimes crosshead designs.It Residual fuel is typically based on to run, but some can also be run based on distillate fuel just like low-speed diesel engine like that, It includes seldom or no residue.In addition, these engines can be used for propulsion on the steamer of deep-sea, assistance application Or the two.

Power plant's operation is also widely used for medium speed diesel engines at a slow speed.With two-stroke run at a slow speed or medium speed diesel Engine is usually the direct articulated of cross head design and directly to formula engine, uses diaphragm and one or more stuffing boxes So that actuating cylinder and crankcase be separated to prevent combustion product from entering crankcase and mixing with crankcase oils.Crankcase and combustion Being kept completely separate for region is burnt to have guided those skilled in the art with different lubricating oil to lubricate combustion chamber and crankcase.

In the large-sized diesel motor for ship and the crosshead type of heavy stationary applications, by cylinder and other hairs Motivation part is separately lubricated.Counted based on total losses and cylinder is lubricated, pass through the profit around cylinder liner Steam cylinder oil is injected separately into the spindle on each cylinder by sliding device.Lubricating coupler is distributed oil to pump, in Modern Engine design, Pump is started oil is directly applied on ring to reduce the waste of oil.

A problem related to these engines is that their manufacturer is commonly designed them to use a variety of diesel engines Fuel, intermediate of the scope from the high distillation fuel of better quality with low-sulfur and low asphalt content to poor quality or Heavy fuel residual fuel for example peculiar to vessel, it generally has high-sulfur and high asphalt content.

Generated in these engines and using the high stress encountered in residual fuel peculiar to vessel for high detergency With the demand of the lubricant of neutralising capacity, even if it is described oil only the short time be exposed to heat and other stress be also such.Generally Residual fuel for these diesel engines typically comprises substantial amounts of sulphur, and it combines to form sulfuric acid in combustion method with water, Its presence result in corrosion wear.Specifically, in two-cycle engine peculiar to vessel, the area around cylinder liner and piston ring Domain can be by acid attack and abrasion.So, it is important to the ability that diesel lubrication oil has the such corrosion of resistance and abrasion.

Therefore, during a major function of marine diesel lubricant cylinder is and in the stroke, diesel crosshead engines of low speed 2 The sulfenyl acidic components of middle burnt high sulphur fuel oil.This neutralization is by including in marine diesel lubricant cylinder Alkaline matter such as metal detergent is realized.Unfortunately, the basicity of marine diesel lubricant cylinder can be by peculiar to vessel The oxidation (by lubricant is within the engine undergone caused by heat and oxidation stress) of diesel engine cylinder lubricant reduces, because This reduces the neutralising capacity of lubricant.If marine diesel lubricant cylinder includes oxidation catalyst such as wear metal (it in engine operation process it is commonly known that be present in lubricant), then oxidation can be accelerated.

Two-stroke diesel engine lubricant cylinder peculiar to vessel must is fulfilled for performance requirement, to meet more modern relatively imperial palace thorax, two Harsh service condition needed for stroke, diesel crosshead engines marine engine, it is with height output and severe loadings and at higher temperature The cylinder liner of degree is run.

At present, marine industry is had been directed to the increasingly short of I classes oil base stock (being typically used for marine engine oil) Lack, and the relatively low-sulfur fuel level of law compulsion challenge.In addition to these challenges, two-stroke diesel engine cylinder profit peculiar to vessel Lubrication prescription must is fulfilled for performance requirement, come needed for meeting more modern relatively imperial palace thorax, two stroke, diesel crosshead engines marine engines Harsh service condition, it is run with the cylinder liner of height output and severe loadings and higher temperature.So, exist The further need for steam-cylinder lubrication fluid composition peculiar to vessel, the oil base stock of its right and wrong I class oil base stocks is compatible , while there is improved detergency and heat endurance high at high temperature, to meet the fuel based on the sulphur with wide scope Come the severe loadings condition of imperial palace thorax two-cycle engine run.

Recently, the be typically designed change and operating change in imperial palace thorax, low speed two-cycle engine (are all logical Fuel efficiency is crossed to drive) have resulted in the often serious cold corrosion of generation.Cold corrosion is as caused by sulfuric acid.By fuel (typically heavy oil, has for burning>2wt% sulphur) produced by oxysulfide by with the water that is formed in combustion process Sulfuric acid is formd with the water for coming from waste gas.When lining temperature descends below the dew point of sulfuric acid and water, caustic mixture is cold Coagulate in interior lining.Lubricant cylinder basicity, oily lubricant cylinder feeding rate, engine to cylinder liner are manufactured and class Type, engine load, Inlet Air Humidity and fuel sulfur content are such factors, and it can influence the amount of cold corrosion.High alkalinity Lubricant is used for neutralisation of sulphuric acid and avoids the cold corrosion on piston ring and cylinder liner surface.High alkalinity lubricant is (such as high to arrive 100BN, is measured by ASTM D2896 method of testings) sell to help to overcome serious cold corrosion at present.

Vulcanization, cross alkalization phenates and be due to their detergency and heat endurance and be widely used in the known of application peculiar to vessel Compound.But, low molecular weight alkyl phenolic compounds such as tetrapropylene benzene phenol (TPP) is often used as manufacturing these sulphur Change, cross the raw material for the phenates that alkalizes.The method for manufacturing alkalization phenates generally results in final reacting product and final last Lubricant oil composite in there is unreacted alkyl phenol.Nearest genotoxicity research is had shown that in high concentration not In the alkyl phenol of reaction, particularly TPP, it may be possible to which endocrine destructiveness material, it can cause phallic to masculinity and femininity Adverse effect.

In order to reduce for consumer any health risk and avoid potential problem of management, exist reduction or Person eliminate the amount of unreacted TPP and its unvulcanized metal salt present in lubricant oil composite it is other the need for.Institute With, or even it is more desirable that develop a kind of marine diesel steam-cylinder lubrication fluid composition, its there is no unreacted TPP and Its unvulcanized metal salt.

Summary of the invention

According to a kind of embodiment of the present invention, there is provided a kind of marine diesel cylinder engine lubricant oil composite, institute State lubricant oil composite and include (a) major amount of one or more II classes oil base stocks, and (b) cleaning agent composition, it is described clear Net agent composition includes the alkali salt of (i) one or more alkyl-substituted hydroxyaromatic carboxylic acids, and it has more than 250 Total base number (TBN), and (ii) one or more exceed alkalization alkyl aromatic sulfonic acid or its salt；Wherein the alkyl aromatic sulfonic acid or The aromatic fractions of its salt of person do not include hydroxyl；Wherein the marine diesel steam-cylinder lubrication fluid composition has about 5- about 120 TBN.

According to the second embodiment of the invention there is provided a kind of with the ship with improved high temperature detergency and heat endurance The method of two stroke cross-head diesels engine peculiar to vessel is lubricated with diesel engine cylinder lubricant compositions；Wherein this method includes The engine is run with marine diesel steam-cylinder lubrication fluid composition, the lubricant oil composite includes (a) major amount of one kind Or a variety of II classes oil base stocks, and (b) cleaning agent composition, the cleaning agent composition takes comprising (i) one or more alkyl The alkali salt of the hydroxyaromatic carboxylic acid in generation, it has the TBN more than 250, and (ii) one or more exceed alkalization alkyl Aromatic sulfonic acid or its salt；Wherein the aromatic fractions of the alkyl aromatic sulfonic acid or its salt do not include hydroxyl；Wherein this is peculiar to vessel Diesel engine cylinder lubricant oil composite has about 5- about 120 TBN.

The 3rd embodiment of the present invention is related to a kind of purposes of marine diesel steam-cylinder lubrication fluid composition, described group Compound includes (a) major amount of one or more II classes oil base stocks；Cleaning agent composition, the cleaning agent composition (b) The alkali salt of (i) one or more alkyl-substituted hydroxyaromatic carboxylic acids is included, it has the TBN more than 250, and (ii) One or more exceed alkalization alkyl aromatic sulfonic acid or its salt；Wherein the aromatic fractions of the alkyl aromatic sulfonic acid or its salt are not Include hydroxyl；Wherein the marine diesel steam-cylinder lubrication fluid composition has about 5- about 120 TBN, to improve two High temperature detergency and heat endurance in stroke crosshead marine diesel engine.

The present invention is based on so it has surprisingly been found that i.e., TBN is more than 250 one or more alkyl-substituted hydroxyls The alkali salt of base aromatic carboxylic acid is advantageously improved with one or more combinations for exceeding alkalization alkyl aromatic sulfonic acid or its salt Containing major amount of one or more class ii oil base stocks and for the bavin peculiar to vessel of two stroke crosshead marine diesel engines The high temperature detergency and heat endurance of oil machine steam-cylinder lubrication fluid composition；Wherein marine diesel lubricant cylinder tool about 5- is about 120 TBN.In addition, TBN is more than the alkali salt and one kind of 250 one or more alkyl-substituted hydroxyaromatic carboxylic acids Or a variety of combinations exceeded between alkalization alkyl aromatic sulfonic acid or salt advantageously improve marine diesel steam-cylinder lubrication fluid composition Storage stability, said composition include major amount of one or more II classes oil base stocks, its TBN is about 5- about 120, and Substantially free of TPP and its unvulcanized metal salt.

The detailed description of preferred embodiment

Definition

As used herein, term " marine diesel lubricant cylinder " or " marine diesel cylinder oil " should When the lubricant for being understood to mean the steam-cylinder lubrication for low speed or the stroke crosshead marine diesel of middling speed two.By the ship With diesel engine cylinder lubricant cylinder wall is supplied to by many injection points.Marine diesel lubricant cylinder can be in cylinder Serve as a contrast and film is provided between piston ring and keeps partially combusted fuel residue to suspend, thus promote engine washing with With the formed acid that burnt by the sulphur compound in such as fuel.

" residual fuel peculiar to vessel " refers to the material that can be burnt in large-scale marine engine, and it has such as International standardization group It is at least 2.5wt.% (for example, at least 5wt.% or at least 8wt.%) (relative to fuel to knit the carbon residue defined in (ISO) 10370 Gross weight), viscosity is more than 14.0cSt, such as International Organization for standardization's specification ISO8217 at 50 DEG C:2005, " oil product-fuel Residual fuel peculiar to vessel defined in (F classes)-marine fuel specification ", its content is fully incorporated herein.

" residual fuel " refers to meeting ISO 8217：The combustion for the residual marine fuel specification that 2010 international standards are proposed Material." low-sulfur marine fuel " refers to meeting ISO 8217：The fuel for the residual marine fuel specification that 2010 specifications are proposed, this Outer its has about 1.5wt% either lower or even about 0.5%wt% or lower sulphur, total relative to fuel Weight.

" distillation fuel " refers to meeting ISO 8217：The distillation marine fuel specification that 2010 international standards are proposed Fuel." low-sulfur distillation fuel " refers to meeting ISO 8217：The distillation marine fuel that 2010 international standards are proposed The fuel of specification, in addition its have that about 0.1wt% is either lower or even about 0.005wt% or lower sulphur, phase For the gross weight of fuel.

As used in those skilled in the art, term " bright stock " refers to such base oil, and it is deasphalting The direct product of petroleum vacuum residue is derived from deasphalting after other processing such as solvent extraction and/or dewaxing Petroleum vacuum residue.In the present invention, it also refers to the depitching distillation cut of vacuum residue method.Bright stock generally exists 100 DEG C of kinematic viscosity is 28-36mm²/s.One example of such bright stock is ESSO^TMCore2500 base oils.

Term " II races metal " or " alkaline-earth metal " refer to calcium, barium, magnesium and strontium.

Term " calcium alkali " refers to calcium hydroxide, calcium oxide, alkoxide calcium and their mixture.

Term " lime " refers to calcium hydroxide, also referred to as white lime or hydrated lime.

Term " alkyl phenol " refers to the phenolic group group with one or more alkyl substituents, the substitution of its at least one alkyl Base has enough carbon numbers to assign formed phenates additive with oily dissolubility.

Term " phenates " refers to the salt of phenol.

Term " lower alkanols alkanoic acid " refers to the alkanoic acid with 1 to 3 carbon atom, i.e. formic acid, acetic acid and propionic acid and its mixed Compound.

Term " polyalcohol accelerator " refers to the compound with two or more hydroxyl substituents, usually D-sorbite Type, such as aklylene glycol and its derivative, and functional equivalent, such as polyol ethers and hydroxycarboxylic acid.

Term " total base number " or " TBN " refer to the alkalinity levels in oil samples, and which show according to ASTM standard No.D2896 or equivalence program, composition persistently neutralize the ability of caustic acid.The test measures the change of conductance, and And result is (the equivalent milligram number of KOH needed for neutralizing 1 gram of product) expressed with mgKOH/g.Therefore, high TBN reflects mistake by force Alkalize product, and as a result, with higher alkaline reserve to neutralize acid.

As used herein, term " base oil " it should be understood that the mixing of oil base stock or oil base stock Thing, it is lubricant composition, and it is to be manufactured by single manufacturer with identical specification (independently of feed source or manufacturer Position)；It meets same manufacturer's specification；With its be by unique formula, product ID or the two recognize.

Term " be based on active material " refer to be not diluent oil or solvent additive material.

Term " alkene of isomerization " refers to the alkene obtained by isomerizing olefins.The alkene of usual isomerization is with spreading out Bearing the diverse location of their starting olefin has double bond, and can also take on a different character.

In one embodiment there is provided a kind of marine diesel steam-cylinder lubrication fluid composition, the lubricant oil composite bag Containing (a) major amount of one or more II classes oil base stocks, and (b) cleaning agent composition, the cleaning agent composition includes (i) The alkali salt of one or more alkyl-substituted hydroxyaromatic carboxylic acids, it has a TBN more than 250, and (ii) it is a kind of or It is a variety of to exceed alkalization alkyl aromatic sulfonic acid or its salt；Wherein the aromatic fractions of the alkyl aromatic sulfonic acid or its salt do not include hydroxyl Base；Wherein the marine diesel steam-cylinder lubrication fluid composition has about 5- about 120 TBN.

Generally, marine diesel steam-cylinder lubrication fluid composition of the invention is by the TBN with about 5- about 120.A kind of real Apply in scheme, marine diesel steam-cylinder lubrication fluid composition of the invention there can be about 20-100 TBN.In a kind of embodiment party In case, marine diesel steam-cylinder lubrication fluid composition of the invention can have about 40- about 100 TBN.In a kind of embodiment In, marine diesel steam-cylinder lubrication fluid composition of the invention can have about 55- about 80 TBN.In one embodiment, The marine diesel steam-cylinder lubrication fluid composition of the present invention can have about 60- about 80 TBN.In one embodiment, originally The marine diesel steam-cylinder lubrication fluid composition of invention can have about 10- about 40 TBN.In one embodiment, it is of the invention Marine diesel steam-cylinder lubrication fluid composition can have about 15- about 35 TBN.

In one embodiment, marine diesel steam-cylinder lubrication fluid composition of the invention there is no unvulcanized Tetrapropylene benzene phenolic compounds and its unvulcanized metal salt, such as TPP and its calcium salt.Term as used herein is " basic On do not have " represent the unvulcanized tetrapropylene benzene phenol and its unvulcanized gold of relatively low level (if any) Belong to salt, be, for example, less than the about 1.5wt% of marine diesel steam-cylinder lubrication fluid composition.In another embodiment, term " there is no " is less than the about 1wt% of marine diesel steam-cylinder lubrication fluid composition.In another embodiment, term " there is no " is less than the about 0.3wt% of marine diesel steam-cylinder lubrication fluid composition.In another embodiment, art Language " there is no " is less than the about 0.1wt% of marine diesel steam-cylinder lubrication fluid composition.In another embodiment, Term " there is no " is the about 0.0001- about 0.3wt% of marine diesel steam-cylinder lubrication fluid composition.

Due to the low speed of service and high load capacity in marine engine, it usually needs heavy oil is (for example, SAE40,50 With 60).The marine diesel steam-cylinder lubrication fluid composition of the present invention can have in 100 DEG C of centistokes of about 12.5- about 26.1 (cSt) kinematic viscosity.In another embodiment, the lubricant oil composite 100 DEG C of viscosity be about 12.5- about 21.9, or about 16.3- about 21.9cSt.The kinematic viscosity of the marine diesel steam-cylinder lubrication fluid composition is to pass through ASTM D445 measurements.

The marine diesel steam-cylinder lubrication fluid composition of the present invention can pass through any system well known by persons skilled in the art Shipbuilding is prepared with the method for diesel engine cylinder lubricant oil composite.The composition can add with any mode in any order Enter.Any suitable mixing or dispersal device can be used for being blended, mix or dissolving the composition.The blending, mixing or Person's dissolving can use blender, agitator, dispersion machine, blender (such as epicyclic mixer and double planetary mixers), homogenizer (such as Gaulin homogenizers or Rannie homogenizers), grinding machine (such as colloidal mill, ball mill or sand mill) or sheet Any other known mixing of field or dispersal device are carried out.

II classes oil base stock for this paper can be the oil base stock of the lubricant viscosity of any petroleum resources, and such as API goes out Version thing 1509, the 14th edition, defined in annex I (in December, 1998).API Guide defines the basis as lubricant composition Oil plant, it can use a variety of different methods to manufacture.II class oil base stocks are commonly referred to as the lubrication base of petroleum resources Oil, equal to or less than 300 parts, (ppm) (passes through ASTM D 2622, ASTM D 4294, ASTM D to its total sulfur content in parts per million 4297 or ASTM D 3120 are determined), saturate content is more than 90wt% (being determined by ASTM D 2007), and viscosity index (VI) (VI) it is more than or equal to 80 and less than 120 (being determined according to ASTM D 2270).

In one embodiment, one or more II classes oil base stocks can be with different molecular weight and viscosity Two or more, it is three or more, even four kinds or more kind II class oil base stocks blend or mixture, wherein should Blend is to process to produce with suitable performance (such as viscosity discussed above and TBN) in any suitable manner Base oil, for marine diesel.

One or more II classes oil base stocks for the diesel engine lubricating oil composite of the present invention are usual with master Presence is measured, about 50wt%, or greater than about 70wt% amount, the gross weight based on said composition is greater than.In one kind implementation In scheme, the amount of one or more class ii oil base stocks is 70wt%- about 95wt%, the gross weight based on said composition Amount.In one embodiment, the amount of one or more II classes oil base stocks is 70wt%- about 85wt%, based on the group The gross weight of compound.

If desired, the marine diesel engine oil composition of the present invention can be containing a small amount of except II classes basis Oil base stock outside oil plant.For example, the marine diesel engine oil composition can be containing a small amount of such as API publications 1509, the 16th edition, I the or III-V class oil base stocks defined in annex I (in October, 2009).IV class oil base stocks be poly- α- Alkene (PAO).

As described above, this is used for the marine diesel steam-cylinder lubrication fluid composition of marine diesel engine generally 100 DEG C kinematic viscosity be 12.5-26.1cSt.In order to prepare such lubricant, bright stock can be with light viscosity oil for example 100 DEG C viscosity for 4-6cSt oil combination.But, the supply of bright stock is gradually decreased, thus bright stock can not be relied on will be peculiar to vessel The viscosity of lubricant cylinder increases to the desired scope of manufacturer's recommendation.A solution of this problem is using thickening Agent such as such as polyisobutene (PIB) or viscosity index improver compound such as olefin copolymer thicken the marine diesel oil Machine steam-cylinder lubrication fluid composition.PIB comes from a kind of commercially available material of several manufacturers.The PIB is typically a kind of viscous oil Miscible liquid, its weight average molecular weight is about 1000- about 8000, or about 1500- about 6000, and viscosity is big About 2000- about 5000 or about 6000cSt (at 100 DEG C).The amount for being added to the PIB of marine diesel cylinder oil is led to Often by be finished lube about 1- about 20wt%, either finished lube about 2- about 15wt% or finished product The about 4- about 12wt% of lubricating oil.

I class oil base stocks typically refer to the lubricating base oil of petroleum resources, and its saturate content (passes through less than 90wt% ASTM D 2007 are determined) and/or total sulfur content (pass through ASTM D 2622, ASTM D 4294, ASTM D more than 300ppm 2749 or ASTM D 3120 are determined) and viscosity index (VI) (VI) be 80-120 (being determined by ASTM D 2270).

I classes oil base stock can side stream comprising the lightweight overhead fraction and heavy for coming from vacuum (distilling) column, and also Such as light neutral, medium neutral and heavy neutral base oil material can be included.The oil base stock of the petroleum resources can also be wrapped Include residual oil plant or bottom fraction, such as such as bright stock.Bright stock is a kind of high viscosity base oil, and it is typically by remaining Storing or bottoms are produced, and highly purified and dewaxing.Bright stock can be more than in 40 DEG C of kinematic viscosity About 180cSt, either in 40 DEG C of even greater than about 250cSt or in 40 DEG C of even about 500- about 1100cSt. In one embodiment, I classes oil base stock includes ExxonMobilExxonMobilExxonMobilOr ExxonMobilOr its mixture.

The usual total sulfur content of Group III base oil material is less than or equal to 0.03wt% (being determined by ASTM D 2270), saturation Thing content is more than or equal to 90wt% (being determined by ASTM D 2007), and viscosity index (VI) (VI) (passes through more than or equal to 120 ASTM D 4294, ASTM D 4297 or ASTM D 3120 are determined).In one embodiment, the oil base stock is Group III Oil base stock, or two or more different Group III base oil material mixture.

Generally, the Group III base oil material from oil is harsh hydrotreated mineral oil.Hydrogenation treatment is included hydrogen React to remove the hetero atom of dealkylation with pending oil base stock, alkene and aromatic hydrocarbons are reduced into alkane and cycloalkane respectively, and And in very harsh hydrogenation treatment, by cycloalkane ring structure be opened into it is acyclic just with isoalkane (" alkane ").One Plant in embodiment, the paraffinic carbon content (%C of Group III base oil material_p) it is at least about 70%, it is by method of testing ASTM D 3238-95 (2005), " Standard Test Method for Calculation of Carbon Distribution and Structural Group Analysis of Petroleum Oils by the n-d-M Method " is determined.In another embodiment, the paraffinic carbon content (%C of group iii oil base stock_p) it is at least about 72%.In another embodiment, the paraffinic carbon content (%C of Group III base oil material_p) it is at least about 75%.Another In embodiment, the paraffinic carbon content (%C of Group III base oil material_p) it is at least about 78%.In another embodiment, Paraffinic carbon content (the %C of Group III base oil material_p) it is at least about 80%.In another embodiment, Group III base oil Paraffinic carbon content (the %C of material_p) it is at least about 85%.

In another embodiment, the naphthenic carbon content (%C of Group III base oil material_n) it is not more than about 25%, it is Determined by ASTM D 3238-95 (2005).In another embodiment, the naphthenic carbon content of Group III base oil material (%C_n) it is not more than about 20%.In another embodiment, the naphthenic carbon content (%C of Group III base oil material_n) be not more than About 15%.In another embodiment, the naphthenic carbon content (%C of Group III base oil material_n) it is not more than about 10%.

Many Group III base oil material are commercially available, such as Chevron UCBO oil base stocks；Yukong Yubase bases Oil plant；ShellOil base stock and ExxonMobilOil base stock.

In one embodiment, the Group III base oil material for this paper is the base oil in Fischer-Tropsch source.Term " take- Support source " product is represented, cut or feed derive from what is either produced in some stages of Fischer-Tropsch process. For example Fischer-Tropsch base oils can be produced by such method, and the feed is the wax-like feed reclaimed from Fiscber-Tropscb synthesis, ginseng wherein See such as U.S. Patent Application Publication No.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；United States Patent (USP) No.7018525 and 7083713 and US application serial No.11/400570； 11/535165 and 11/613936, each of which is hereby incorporated by reference.Generally, this method includes hydrogenation completely or partially Isomerization dewaxing step, it uses Bifunctionalized catalyst or such catalyst, and it can selective isomerized alkanes Hydrocarbon.Hydrogenation isomerization dewaxing be by by it is wax-like feed with hydrogenation isomerization catalyst in isomerization zone in hydrogenation isomerization Under the conditions of contact realize.

Fischer-tropsch synthesis product can be obtained by known method, for example such as businessSlurry phase Fischer-Tropsch Technology, businessMedium distillation synthesis (SMDS) method or non-commercialSenior gas converts (AGC- 21) method.The details of these methods and other descriptions are in such as WO-A-9934917；WO-A-9920720；WO-A- 05107935；EP-A-776959；EP-A-668342；United States Patent (USP) No.4943672,5059299,5733839 and RE39073； In U.S. Patent Application Publication No.2005/0227866.The fischer-tropsch synthesis product, which can be included, has about 100 carbon of 1- Atom, or it is more than the hydrocarbon of 100 carbon atoms in some cases, and typically comprise alkane, alkene and oxidation product.

IV classes oil base stock or polyalphaolefin (PAO) are typically by low molecule amount alpha-olefin, such as containing at least 6 The oligomeric of the alpha-olefin of individual carbon atom manufactures.In one embodiment, the alpha-olefin be the α containing 10 carbon atoms- Alkene.PAO is the mixture of dimer, tripolymer, the tetramer etc., and accurate mixture depends on desired final base The viscosity of plinth oil plant.PAO is typically to hydrogenate to remove the degree of unsaturation of any residual after oligomeric.

V classes base oil includes all other base oils, and it is not included in I, II, III or IV class.

The marine diesel steam-cylinder lubrication fluid composition of the present invention further includes cleaning agent composition, the detersive group Compound includes the alkali salt of (i) one or more alkyl-substituted hydroxyaromatic carboxylic acids, and its TBN is more than 250, and (ii) one Kind or a variety of exceed alkalization alkyl aromatic sulfonic acid or its salt；The aromatic fractions of wherein the alkyl aromatic sulfonic acid or its salt are not wrapped Hydroxyl；

Generally, the alkali salt and one or more of one or more alkyl-substituted hydroxyaromatic carboxylic acids exceeds alkali Changing alkyl aromatic sulfonic acid or its salt is provided as the concentrate in each additive, and the additive is introduced into basic Upper inert, usually the organic diluent of liquid such as such as mineral oil, naphtha, benzene, toluene or dimethylbenzene is formed Multifunctional additive for lubricating oils.These concentrates generally comprise such diluent or about of the weight of about 10%- about 90% Such diluent of the weight of 20%- about 80%, and its surplus is the specific additive.Typically, it is viscous at 100 DEG C Spend about 4- about 8.5cSt and preferably will act as the diluent in 100 DEG C of viscosity about 4- about 6cSt neutral oil, although Artificial oil, and other organic liquids can also be used (it is compatible with the additive and final lubricating oil).

In one embodiment, the concentrate there is no unvulcanized tetrapropylene benzene phenolic compounds and its not The metal salt of vulcanization, such as TPP and its calcium salt.The relatively low level of term " there is no " expression as used herein is (such as Fruit have it is any if) unvulcanized tetrapropylene benzene phenol and its unvulcanized metal salt, be, for example, less than concentrate about 1.5wt%.In another embodiment, term " there is no " is less than the about 1wt% of concentrate.Implement another In scheme, term " there is no " is less than about 0.3wt%.In another embodiment, term " there is no " is Less than the about 0.1wt% of concentrate.In another embodiment, term " there is no " is the about 0.0001- of concentrate About 0.3wt%.

One or more are included for the cleaning agent composition in the marine diesel steam-cylinder lubrication fluid composition of the present invention The alkali salt of alkyl-substituted hydroxyaromatic carboxylic acid, it has the TBN more than 250.One or more alkali alkyl substitutions Hydroxyaromatic carboxylic acid alkali salt TBN be based on active material.In one embodiment, one or more alkyl The TBN of the alkali salt of substituted hydroxyaromatic carboxylic acid is more than 250 and is at most up to about 800.In one embodiment, should The TBN of the alkali salt of one or more alkyl-substituted hydroxyaromatic carboxylic acids is more than 250 and at most about 750.A kind of real Apply in scheme, the TBN of the alkali salt of one or more alkyl-substituted hydroxyaromatic carboxylic acids is more than 250 and at most about 700.In one embodiment, the TBN of the alkali salt of one or more alkyl-substituted hydroxyaromatic carboxylic acids is more than 250 and at most about 650.In one embodiment, the alkaline-earth metal of one or more alkyl-substituted hydroxyaromatic carboxylic acids The TBN of salt is more than 250 and at most about 600.In one embodiment, this kind or a variety of alkyl-substituted hydroxyaromatic carboxylic acids Alkali salt TBN be more than 250 and at most about 410.

In another embodiment, the alkali salt of one or more alkyl-substituted hydroxyaromatic carboxylic acids TBN is about 260- about 800.In one embodiment, the alkaline earth gold of one or more alkyl-substituted hydroxyaromatic carboxylic acids The TBN for belonging to salt is about 260- about 750.In one embodiment, one or more alkyl-substituted hydroxyaromatic carboxylic acids The TBN of alkali salt is about 260- about 700.In one embodiment, one or more alkyl-substituted hydroxyaromatics The TBN of the alkali salt of carboxylic acid is about 260- about 650.In one embodiment, one or more alkyl-substituted hydroxyls The TBN of the alkali salt of base aromatic carboxylic acid is about 260- about 600.In one embodiment, one or more alkyl take The TBN of the alkali salt of the hydroxyaromatic carboxylic acid in generation is about 260 and at most about 410.

In another embodiment, the alkali salt of one or more alkyl-substituted hydroxyaromatic carboxylic acids TBN is greater than or equal to about 300.In another embodiment, the alkali of one or more alkyl-substituted hydroxyaromatic carboxylic acids The TBN of earth metal salt about 300- about 800.In one embodiment, one or more alkyl-substituted hydroxyaromatic carboxylic acids Alkali salt TBN about 300- about 750.In one embodiment, one or more alkyl-substituted hydroxyaromatics The TBN of the alkali salt of carboxylic acid about 300- about 700.In one embodiment, one or more alkyl-substituted hydroxyls The TBN of the alkali salt of aromatic carboxylic acid about 300- about 650.In one embodiment, the one or more are alkyl-substituted The TBN of the alkali salt of hydroxyaromatic carboxylic acid about 300- about 600.In one embodiment, one or more alkyl take The TBN of the alkali salt of the hydroxyaromatic carboxylic acid in generation about 300- about 410.

In a preferred embodiment, the alkali salt of one or more alkyl-substituted hydroxyaromatic carboxylic acids It is the alkali salt of one or more alkyl-substituted hydroxybenzoic acids, its TBN is more than 250.In a preferred embodiment party In case, the alkali salt of one or more alkyl-substituted hydroxyaromatic carboxylic acids is alkyl substituted hydroxy alkyl carboxylic acid calcium, Its TBN is more than 250.In another preferred embodiment, the alkali of one or more alkyl-substituted hydroxyaromatic carboxylic acids Earth metal salt is the alkali salt of the hydroxyaromatic carboxylic acid with major amount of one or more monoalkyl substitutions, and its TBN is big In 250.

In a preferred embodiment, the alkali salt of one or more alkyl-substituted hydroxyaromatic carboxylic acids It is the alkali salt of one or more alkyl-substituted hydroxybenzoic acids, its TBN is greater than or equal to about 300.At one preferably Embodiment in, the alkali salt of one or more alkyl-substituted hydroxyaromatic carboxylic acids is alkyl substituted hydroxy alkyl Calcium carboxylates, its TBN is greater than or equal to about 300.In another preferred embodiment, one or more alkyl-substituted hydroxyls The alkali salt of base aromatic carboxylic acid is the alkaline earth of the hydroxyaromatic carboxylic acid with major amount of one or more monoalkyl substitutions Metal salt, its TBN is greater than or equal to about 300.

Suitable hydroxy aromatic compound includes monokaryon monohydroxy and polyhydroxy aromatic hydrocarbon, and it has 1-4, and preferably 1- 3 hydroxyls.Suitable hydroxy aromatic compound includes phenol, catechol, resorcinol, hydroquinones, pyrogaelol, cresols etc..It is preferred that Hydroxy aromatic compound be phenol.

The alkyl-substituted part of the alkali salt of the alkyl-substituted hydroxyaromatic carboxylic acid, which can be derived from, to be had greatly The alhpa olefin of about 80 carbon atoms of about 10-.In one embodiment, the alkaline earth gold of the alkyl-substituted hydroxyaromatic carboxylic acid The alhpa olefin with about 40 carbon atoms of about 10- can be derived from by belonging to the alkyl-substituted part of salt.In a kind of embodiment In, the alkyl-substituted part of the alkali salt of the alkyl-substituted hydroxyaromatic carboxylic acid, which can be derived from, has about 12- The alhpa olefin of about 28 carbon atoms.Alkene used can be that linear, isomerization is linear, branched or part branched linear 's.The alkene can be the mixture of linear alpha-olefin, the mixture of isomerization linear alpha-olefin, the mixture of branched olefin, part The mixture of branched linear alkene or foregoing arbitrary mixture.

In one embodiment, the mixture for the linear alpha-olefin that can be used is the mixture of positive alhpa olefin, the positive α Alkene is selected from alkene of each molecule with about 12- about 28, or about 20-28 carbon atom.In a kind of embodiment In, the positive alhpa olefin carrys out isomerization using at least one of solid or liquid catalyst.

In another embodiment, the alkene includes one or more alkene, and it is included selected from propylene, butylene or it is mixed The C of the monomer of compound₉-C₁₈Oligomer.Generally, one or more alkene will comprising it is major amount of selected from propylene, butylene or The C of the monomer of its mixture₉-C₁₈Oligomer.The example of such alkene includes the propylene tetramer, butylene tripolymer etc..Ability Field technique personnel are readily appreciated that there may be other alkene.For example except C₉-C₁₈Outside oligomer, other alkene that can be used Hydrocarbon includes linear alpha-olefin, cycloolefin, branched olefin such as butylene or isobutylene oligomer, the aryl olefin of non-propylene oligomer Deng and its mixture.Suitable linear alpha-olefin includes 1- hexenes, 1- nonenes, 1- decene, 1- dodecylenes etc. and its mixture.It is special Unsuitable linear alpha-olefin is the positive alpha-olefin of HMW such as C₁₆-C₃₀Positive alpha-olefin, it is low that it can be obtained from method such as ethene Poly- or wax destructive distillation.Suitable cycloolefin includes cyclohexene, cyclopentene, cyclo-octene etc. and its mixture.Suitable branched olefin Isobutylene oligomer including butene dimerization body or tripolymer or higher molecular weight etc. and its mixture.Suitable aryl alkene Hydrocarbon includes styrene, methyl styrene, 3- phenylpropens, 2- phenyl -2- butylene etc. and its mixture.

In one embodiment, the alkyl-substituted part of the alkali salt of the alkyl-substituted hydroxyaromatic carboxylic acid C can be included₁₂Alkyl and C₂₀-C₂₈The mixture of linear alpha-olefin.In one embodiment, the alkyl-substituted hydroxyaromatic The alkyl-substituted part of the alkali salt of carboxylic acid can include at most about 50wt% C₁₂Alkyl, it is and at least 50wt% C₂₀-C₂₈Linear alpha-olefin mixing.

In one embodiment, the alkyl-substituted part of the alkali salt of the alkyl-substituted hydroxyaromatic carboxylic acid At most 50wt% C can be included₂₀-C₂₈Linear alpha-olefin, it is the branched hydrocarbon with least 50wt% derived from propylene oligomer Base mixing.In another embodiment, the alkyl-substituted portion of the alkali salt of the alkyl-substituted hydroxyaromatic carboxylic acid At most 85wt% C can be included by dividing₂₀-C₂₈Linear alpha-olefin, it is branched with least 15wt% derived from propylene oligomer Alkyl mixing.

In one embodiment, it is at least big included in the alkali salt of the alkyl-substituted hydroxyaromatic carboxylic acid About 75mol% (for example, at least about 80mol%, at least about 85mol%, at least about 90mol%, at least about 95mol% Or at least about 99mol%) alkyl be C₂₀Alkyl or higher level.In another embodiment, the alkyl-substituted hydroxyl The alkali salt of base aromatic carboxylic acid is the alkali salt of alkyl-substituted hydroxybenzoic acid, and it is derived from alkyl-substituted hydroxyl Yl benzoic acid, wherein alkyl are containing at least 75mol% C₂₀Or the residue of the positive alpha-olefin of the positive alpha-olefin of higher level.

In another embodiment, in the alkali salt of the alkyl-substituted hydroxyaromatic carboxylic acid it is contained at least about 50mol% (for example, at least about 60mol%, at least about 70mol%, at least about 80mol%, at least about 85mol%, At least about 90mol%, at least about 95mol% or at least about 99mol%) alkyl be about C₁₄- about C₁₈。

The alkali salt of the alkyl-substituted hydroxyaromatic carboxylic acid with the TBN more than 250 formed can be adjacent Position and the mixture of para-isomer.In one embodiment, the product by the ortho isomer comprising about 1-99% and 99-1% para-isomer.In another embodiment, the product is by ortho isomer and 95- comprising about 5-70% 30% para-isomer.

The alkali salt of the alkyl-substituted hydroxyaromatic carboxylic acid is so alkyl-substituted hydroxyaromatic wherein The BN of the alkali salt of carboxylic acid for example adds alkali source (such as lime) by method and acidity crosses alkalization compound (for example Carbon dioxide) increase.The method of alkalization is crossed in the range of the understandability of those skilled in the art.

Generally, the TBN in TBN about 5- about 120 marine diesel steam-cylinder lubrication fluid composition is more than 250 one kind Or the amount of the alkali salt of a variety of alkyl-substituted hydroxyaromatic carboxylic acids based on active material be about 0.1wt%- about 35wt%, with the gross weight meter of the marine diesel steam-cylinder lubrication fluid composition.In one embodiment, TBN about 20- are big TBN in about 100 marine diesel steam-cylinder lubrication fluid composition is more than 250 one or more alkyl-substituted hydroxyaromatics The amount of the alkali salt of carboxylic acid may be about 1wt%- about 25wt% based on active material, be moistened with the marine diesel cylinder The gross weight meter of sliding oil composition.In one embodiment, TBN about 20- about 60 marine diesel cylinder oil The amount that TBN in composition is more than the alkali salt of 250 one or more alkyl-substituted hydroxyaromatic carboxylic acids is based on living Property material may be about 3wt%- about 20wt%, with the gross weight meter of the marine diesel steam-cylinder lubrication fluid composition.One Plant in embodiment, the TBN in TBN about 30- about 50 marine diesel steam-cylinder lubrication fluid composition is more than 250 one kind Or the amount of the alkali salt of a variety of alkyl-substituted hydroxyaromatic carboxylic acids may be about 3wt%- about based on active material 15wt%, with the gross weight meter of the marine diesel steam-cylinder lubrication fluid composition.

Cleaning agent composition for the marine diesel steam-cylinder lubrication fluid composition of the present invention also includes one or more Exceed alkalization alkyl aromatic sulfonic acid or its salt.The alkyl aromatic sulfonic acid or its salt include the alkylation by aromatic compounds The alkyl aromatic sulfonic acid or its salt obtained.The Alkylaromatics and then sulfonated form alkyl aromatic sulfonic acid.Such as Fruiting period hopes that the alkyl aromatic sulfonic acid can be with caustic and to obtain alkali metal or alkaline-earth metal alkyl aromatic sulfonates Compound.

The mixture of at least one aromatic compounds or aromatic compounds can be used for being formed alkyl aromatic sulfonic acid or Its salt.Suitable aromatic compounds or mixture of aromatic compounds include mononuclear aromatics, such as benzene,toluene,xylene, isopropyl At least one of base benzene or its mixture.In a preferred embodiment, the alkyl aromatic sulfonic acid or salt is at least One aromatic fractions does not include hydroxyl.In a preferred embodiment, the alkyl aromatic sulfonic acid or salt compound be extremely Few aromatic fractions are not phenol.In one embodiment, at least one aromatic compounds or aromatic compounds mixing Thing is toluene.

At least one Alkylaromatics or the mixture of aromatic compounds are commercially available or can be by these It is prepared by method known to field.

Alkylating agent for being alkylated the aromatic compounds can derive from a variety of sources.Such source includes positive α Alkene, linear alpha olefin, isomerization linear alpha olefin, dimerization and oligomeric alkene and the alkene derived from olefin metathesis.Should Alkene can be single carbon number, or it can be the mixture of linear alpha-olefin, it is the mixture of isomerization linear alpha-olefin, branched Mixture, the mixture of part branched olefin or the foregoing arbitrary mixture of alkene.Alkene can be derived from the another of its Source is by oil pyrolysis or fischer-tropsch wax.The fischer-tropsch wax can before cracking hydrogenation treatment.Other commercial source bags Such alkene is included, the paraffin dehydrogenation and oligomeric, methanol to olefins method (methanol decomposition of its derived from ethylene and other alkene Device) etc..

The alkene can be the alkene of about 8 carbon atom-about 60 carbon atoms selected from carbon number.In a kind of embodiment In, the alkene is selected from the alkene that carbon number is about 50 carbon atoms of about 10-.In one embodiment, the alkene is selected from carbon Number is the alkene of about 40 carbon atoms of about 12-.

In another embodiment, the alkene or alkene mixture are selected from the line containing about 60 carbon atoms of about 8- Property alhpa olefin or isomerisation of alpha alkene.In one embodiment, the alkene mixture, which is selected from, contains about 50 carbon of about 10- The linear alpha olefin or isomerisation of alpha alkene of atom.In one embodiment, the alkene mixture is selected from big containing about 12- The linear alpha olefin or isomerizing olefins of about 40 carbon atoms.

The linear alpha-olefin that can be used for alkylated reaction can a kind of positive alhpa olefin or its mixture, the positive alhpa olefin choosing From the alkene with about 60 carbon atom/molecules of about 8-.In one embodiment, the positive alhpa olefin, which is selected from, has about The alkene of about 50 carbon atom/molecules of 10-.In one embodiment, the positive alhpa olefin, which is selected from, has about 12- about 40 The alkene of individual carbon atom/molecule.

In one embodiment, the mixture of the branched olefin is selected from such polyolefin, and it can be derived from C₃Or The monoolefine of person's higher level (such as propylene oligomer, butene low polymers or copolymerized oligomer).In one embodiment, The mixture of the branched olefin is propylene oligomer or butene low polymers or its mixture.

In one embodiment, the aromatic compounds is with containing C₈-C₆₀The mixture of the positive alhpa olefin of carbon atom carrys out alkyl Change.In one embodiment, the aromatic compounds is with containing C₁₀-C₅₀The mixture of the positive alhpa olefin of carbon atom is alkylated. In another embodiment, the aromatic compounds is with containing C₁₂-C₄₀The mixture of the positive alhpa olefin of carbon atom is alkylated, to produce Raw aromatic alkylate.

Positive alhpa olefin for manufacturing the alkyl aromatic sulfonic acid or its salt is commercially available or can be by known in this field Method prepare.

In one embodiment, the positive alhpa olefin is to carry out isomerization using solid or liquid acid catalyst.Solid catalysis Preferably there is at least one metal oxide and average cell size to be less than 5.5 angstroms for agent.In one embodiment, the solid catalysis Agent is the molecular sieve with one-dimensional pore system, such as SM-3, MAPO-11, SAPO-11, SSZ-32, ZSM-23, MAPO-39, SAPO-39, ZSM-22 or SSZ-20.Other possible acidic solid catalysts for isomerization include ZSM-35, SUZ- 4th, NU-23, NU-87 and natural or synthetic ferrierite.These molecular sieves are it is known in the art that and in Rosemarie Carried out in Szostak Handbook of Molecular Sieves (New York, Van Nostrand Reinhold, 1992) Discuss, the reference for whole purposes is incorporated herein in it.The isomerization catalyst for the kind of liquid that can be used is pentacarbonyl Iron (Fe (CO)₅)。

Method for positive alhpa olefin isomerization can be with batches or continuous mode is carried out.This method temperature can be About 50 DEG C-about 250 DEG C.In batch mode, typical method used is stirred autoclave or glass flask, its Desired reaction temperature can be heated to.Continuation method in fixed-bed approach it is most useful that carry out.In fixed-bed approach Air speed can be about 0.1- about 10 or bigger weight (hourly) space velocity (WHSV).

In fixed-bed approach, isomerization catalyst is added in reactor, and at least 125 DEG C of temperature in vacuum Activation or dry in lower or flowing inertia dry gas.After activation, the temperature adjustment of the isomerization catalyst is expired The reaction temperature of prestige, and olefin stream is introduced into the reactor.Collect containing part is branched, isomerization alkene reaction Device effluent.The alkene that part is branched, isomerization alkene is comprising the alkene different from the non-isomerization distribution formed (that is, alhpa olefin, β alkene, internal olefin, trisubstituted alkene and vinylidene olefin) and branching content, and alternative condition obtains Obtain desired alkene distribution and the degree of branching.

Typically, the aromatic compounds of the alkylation can use Bu Langsi Taides acid catalyst, lewis acid catalyst Or prepared by solid acid catalyst.

Cloth Lanace Taide acid catalyst can be selected from hydrochloric acid, hydrofluoric acid, hydrobromic acid, sulfuric acid, perchloric acid, fluoroform sulphur Acid, fluosulfonic acid and nitric acid etc..In one embodiment, Bu Langsi Taides acid catalyst is hydrofluoric acid.

Lewis acid catalyst, which can be selected from, includes alchlor, alchlor, aluminium triiodide, boron trifluoride, tribromide The lewis acid of boron, triiodide boron etc..In one embodiment, the lewis acid catalyst is alchlor.

The solid acid catalyst can be selected from zeolite, sour clay and/or silica-alumina.Suitable solid is urged Agent is the cationic ion-exchange resin in its sour form, the sulfonic acid catalyst of such as crosslinking.The catalyst can be molecule Sieve.Suitable molecular sieve is silica-aluminophosphates molecular sieve or metal silicon/silicon dioxide-aluminophosphate molecular sieve, at it Middle metal may, for example, be iron, cobalt or nickel.Other suitable examples of solid acid catalyst are disclosed in United States Patent (USP) In No.7183452, its content is hereby incorporated by reference.

Cloth Lanace Taide acid catalyst can become inactivation at it, and (that is, catalyst loses it of all or part Catalytic activity) regenerated afterwards.Method well known in the art can be used for regenerating the acid catalyst such as hydrofluoric acid.

For produce the alkylation techniques of alkylaromatic hydrocarbon be included within about 300 DEG C of about 0- operation in batches, semi-batch Or Bu Langsi Taides acid and/or lewis acid and solid acid catalyst are used in continuation method.

When for continuation method, the acid catalyst can be recycled., should when for batch processes or continuation method Acid catalyst can be recycled or regenerated.

In one embodiment, the alkylation is such as progress of getting off：By at least one aromatics of the first amount The mixture of the olefin(e) compound of the mixture and the first amount of compound or aromatic compounds is in Bu Langsi Taides acid catalyst example As in the presence of hydrofluoric acid, reacted in first reactor (being kept stirring for wherein), thus produce the first reactant mixture. The first reactant mixture formed keeps time enough in the first alkylation zone under alkylating conditions, and alkene is turned It is melted into aromatic alkylate (that is, the first reaction product).After the desired time, by the first reaction product from alkylation zone Remove, and be supplied to second reactor, wherein at least one aromatic compounds of first reaction product and additional amount or The mixture of person's aromatic compounds and the acid catalyst of additional amount and the mixture optionally with the olefin(e) compound of additional amount enter Row reaction, wherein being kept stirring for.The second reactant mixture is produced, and is kept under alkylating conditions in the second alkylation zone Time enough, to convert alkenes to aromatic alkylate (that is, the second reaction product).Second reaction product is supplied to Liquid-liquid separator causes hydrocarbon (that is, organic) product to be separated with acid catalyst.The acid catalyst can be in closed cycle It is recycled to reactor.The hydrocarbon products further handle to remove excessive unreacted virtue from desired alkylate product Compounds of group and optional olefinic compounds.The excessive aromatic compounds can also be recycled to reactor.

In another embodiment, the reaction is carried out in more than two reactors, and it is arranged in series.Instead of should Second reaction product is supplied to Liquid-liquid separator, and second reaction product is supplied into the 3rd reactor, wherein this second The mixture and the acid catalyst of additional amount of at least one aromatic compounds or aromatic compounds of reaction product and additional amount Mixture optionally with the olefin(e) compound of additional amount is reacted, wherein being kept stirring for.Generate the 3rd reaction mixing Thing, and time enough is kept in tri-alkylated area under alkylating conditions, to convert alkenes to aromatic alkylation Thing (that is, the 3rd reaction product).The reaction multiple reactors necessary to desired alkylating aromatic reaction product is obtained It is middle to carry out.

For combined reactor, total charged molar ratio of Bu Langsi Taides acid catalyst and olefin(e) compound is about 0.1- about 1.In one embodiment, in first reactor Bu Langsi Taides acid catalyst and olefin(e) compound charging Mol ratio is not more than about 0.7- about 1 and is not less than about 0.3- about 1 in second reactor.

For combined reactor, total charged molar ratio of aromatic compounds and olefin(e) compound is about 7.5:1- is big About 1:1.In one embodiment, the charged molar ratio of aromatic compounds and olefin(e) compound is not less than in first reactor About 1.4:1- about 1:1 and in second reactor be not more than about 6.1:1- about 1:1.

The reactor configuration of many types can be used for reactor zone.They include but is not limited in batches and continuously stir groove Reactor, reactor riser construction, fluidized bed reactor and other reactor configurations well known in the art.It is many such anti- It is well known by persons skilled in the art to answer device, and suitable for alkylated reaction.Stirring is crucial for alkylated reaction, and Can dynamically it be mixed or this area by rotating vane (with or without baffle plate), static mixer, in riser Known any other agitating device is provided.The alkylation can be carried out at a temperature of about 0 DEG C-about 100 DEG C. This method is carried out at a pressure sufficient, i.e. most feed component is kept in the liquid phase.Typically, it is satisfactory Ground is will to be fed to be maintained at liquid phase with product with 0-150psig pressure.

Residence time in the reactor is such time, and it is enough most alkene changing into alkylation produce Thing.Required time is about 30 seconds to about 30 minutes.More accurate residence time can be used by those skilled in the art to be divided Batch stirred tank reactor is determined measuring the dynamics of alkylation.

The mixture and olefin(e) compound of at least one aromatic compounds or aromatic compounds can be injected separately into instead Answer in area or can be mixed before injection.It can use single and multiple reaction zones, and by the aromatic compounds One is injected with olefin(e) compound, in several or whole reaction zone.The reaction zone need not be maintained at identical processing bar Under part.Hydrocarbon feed for alkylation can include the mixture of aromatic compounds and olefin(e) compound, wherein aromatics The mol ratio of compound and alkene is about 0.5:1- about 50:1 or higher.Aromatic compounds and the mol ratio of alkene wherein> In the case of 1.0 to 1, excessive aromatic compounds is there is.In one embodiment, come using excessive aromatic compounds Increase reaction rate and improve selectivity of product.When excess aromatic compounds are used, in reactor effluent it is excessive not The aromatic hydrocarbons of reaction can be separated for example by distilling, and be recycled to reactor.

Once obtaining alkyl aromatic product as described above, then it further reacts to form alkyl aromatic sulfonic acid, and Then corresponding sulfonate can be neutralized into.The sulfonation of the Alkylaromatics can be by well known by persons skilled in the art Any method is carried out.The sulfonating reaction is typically being held in about 45 DEG C-about 75 DEG C of continuous falling liquid film tubular reactor It is middle to carry out.For example the Alkylaromatics are placed in reactor together with the sulfur trioxide of Dilution air, alkane is thus produced Base aryl sulfonic acid.Other sulfonating reaction things such as sulfuric acid, chlorosulfonic acid or sulfamic acid can also be used.In a kind of embodiment In, the Alkylaromatics are the sulfur trioxides with Dilution air come sulfonation.The charging of sulfur trioxide and alkylates rubs You are maintained at about 0.8- about 1.1 by ratio:1.

If desired, the neutralization of the alkyl aromatic sulfonic acid can pass through art technology in continuous or batch processes Any method of alkyl aromatic sulfonates is produced known to personnel to carry out.Typically, alkyl aromatic sulfonic acid be with alkali metal or Thus person's alkaline-earth metal or ammonia source produce alkyl aromatic sulfonates come what is neutralized.Suitable alkali metal not limiting example bag Include lithium, sodium, potassium, rubidium and caesium.In one embodiment, suitable alkali metal includes sodium and potassium.In another embodiment, close Suitable alkali metal is sodium.Suitable alkaline-earth metal not limiting example includes calcium, barium, magnesium or strontium etc..In one embodiment, Suitable alkaline-earth metal is calcium.In one embodiment, the source is alkali metal base such as alkali metal hydroxide, such as hydrogen Sodium oxide molybdena or potassium hydroxide.In one embodiment, the source is alkaline earth metal alkali such as alkaline earth metal hydroxide, such as hydrogen Calcium oxide.

One or more the alkyl aromatic sulfonic acid or its salt be one or more exceed alkalization alkyl aromatic sulfonic acid or Its salt.As described above, cross alkalization be so, the wherein TBN of alkyl aromatic sulfonic acid or its salt by method for example such as Alkali source (such as lime) and acid parlkaline compound (such as carbon dioxide) is added to improve.It is that this area is public to cross alkalization method Know.

The one or more exceed alkalization alkyl aromatic sulfonic acid or the TBN of its salt is more than 250.In a kind of embodiment In, the one or more exceed alkalization alkyl aromatic sulfonic acid or the TBN about 250- about 700 of its salt.In a kind of embodiment party In case, the one or more exceed the TBN of alkalization alkyl aromatic sulfonic acid or its salt greater than or equal to about 300.In one kind implementation In scheme, the one or more exceed alkalization alkyl aromatic sulfonic acid or the TBN about 300- about 700 of its salt.

Generally, the one or more in the marine diesel steam-cylinder lubrication fluid composition that TBN is about 5- about 120 exceed The amount of alkalization alkyl aromatic sulfonic acid or its salt may be about 0.1wt%- about 34wt% based on active material, with the bavin peculiar to vessel The gross weight meter of oil machine steam-cylinder lubrication fluid composition.In one embodiment, TBN is about 20- about 100 marine diesel oil One or more in machine steam-cylinder lubrication fluid composition exceed alkalization alkyl aromatic sulfonic acid or the amount of its salt is based on active material 1wt%- about 30wt% are may be about, with the gross weight meter of the marine diesel steam-cylinder lubrication fluid composition.In one kind implementation In scheme, the one or more in the marine diesel steam-cylinder lubrication fluid composition that TBN is about 20- about 60 exceed alkalization alkane The amount of base aromatic sulfonic acid or its salt may be about 2wt%- about 24wt% based on active material, with the marine diesel cylinder The gross weight meter of lubricant oil composite.In one embodiment, the marine diesel cylinder profit that TBN is about 30- about 50 One or more in sliding oil composition exceed alkalization alkyl aromatic sulfonic acid or the amount of its salt may be about based on active material 5wt%- about 16wt%, with the gross weight meter of the marine diesel steam-cylinder lubrication fluid composition.

The marine diesel steam-cylinder lubrication fluid composition of the present invention can also include conventional marine diesel steam-cylinder lubrication (it is different from the alkali that foregoing TBN is more than 250 one or more alkyl-substituted hydroxyaromatic carboxylic acids to fluid composition additive Earth metal salt and one or more exceed alkalization alkyl aromatic sulfonic acid or its salt), come assign miscellaneous function to wherein disperse or The marine diesel steam-cylinder lubrication fluid composition of these additives is dissolved.Such as marine diesel steam-cylinder lubrication fluid composition It can be passivated with antioxidant, ashless dispersant, other detersives, antiwear additive, antirust agent, fog remover, demulsifying agent, metal Agent, friction modifiers, pour-point depressant, defoamer, cosolvent, corrosion inhibitor, dyestuff, extreme pressure agent etc. and its mixture are carried out Blending.Multiple additives are known and commercially available.These additives or their similar compound can be used for by normal The blending program of rule come prepare the present invention marine diesel steam-cylinder lubrication fluid composition.

In one embodiment, marine diesel steam-cylinder lubrication fluid composition of the invention is substantially free of thickener (that is, viscosity index improver).

The example of antioxidant includes but is not limited to amine type, such as diphenylamine, phenyl-alpha-naphthyl-amine, N, N- bis- (alkyl phenyl) amine；With the phenylenediamine of alkylation；Phenol such as such as BHT, solid is obstructed the tertiary fourths of alkyl phenol such as 2,6- bis- Base phenol, DBPC 2,6 ditertiary butyl p cresol and 2,6- di-t-butyls -4- (2- octyl group -3- propionic acid) phenol；And its mixture.

Ashless dispersants immunomodulator compounds for the marine diesel steam-cylinder lubrication fluid composition of the present invention are generally used for making The insoluble material that formation is aoxidized during remains suspension, therefore prevents greasy filth flocculation and precipitation or be deposited on metal On part.Dispersant can be also used for reducing the change of lubricating oil viscosity by preventing the growth of big contaminant particles in lubricant Change.The dispersant for the present invention can be for any suitable ashless in marine diesel steam-cylinder lubrication fluid composition The mixture of dispersant or a variety of ashless dispersants.Ashless dispersant generally comprises oil-soluble polymerization hydrocarbon main chain, and it has energy Enough with treating the functional group that scattered particle is connected.

In one embodiment, ashless dispersant is one or more alkaline nitrogenous ashless dispersants.Nitrogen-containing basic without The base number or BN that grey (no metal) dispersant contribute to the lubricant oil composite that they are added thereto (can be by ASTM D 2896 measurements), without introducing other sulfate ash.Alkaline nitrogenous ashless dispersant available for the present invention includes alkyl Succinimide；Hydrocarbon succinic amide；The amber acylation agent replaced by alkyl progressively or the mixture with alkohol and amine and/ Or ester/acid amides of the mixing of the butanedioic acid of formed alkyl substitution is reacted with amino alcohol；The phenol of alkyl substitution, formaldehyde and polyamines The strange condensation product of Manny；Reacted with by high-molecular-weight aliphatic or alicyclic halides with amine such as polyalkylene polyamine The amine dispersant formed.The mixture of such dispersant can also be used.

The representational example of ashless dispersant includes but is not limited to amine, alcohols, amide-type or connected by bridging group It is connected to the ester polar portion on polymer backbone.The ashless dispersant of the present invention can be selected from the substitution of oil-soluble long chain hydrocarbons The salt of list or dicarboxylic acids or its acid anhydrides, ester, amino ester, acid amides, acid imide He oxazoline are long chain hydrocarbons, more with what is be directly connected to The thio carboxy acid ester derivative of the long chain aliphatic hydrocarbon of amine, and be condensed and shape by long-chain substituted phenol and formaldehyde and polyalkylene polyamine Into Mannich condensation product.

Carboxylic dispersants are following reaction products：Comprising at least about 34 and preferably at least about 54 carbon atoms Carboxylic acid acylating agent's (acid, acid anhydrides, ester etc.) and nitrogen-containing compound (such as amine), organic hydroxy compounds (such as aliphatic compound, Including monohydroxy and polyhydroxy-alcohol, or aromatic compounds, including phenol and naphthols), and/or alkaline inorganic material.These reactions Product includes acid imide, acid amides and ester.

Succinimide dispersants are a class carboxylic dispersants.They be the amber acylation agent that is replaced by alkyl with it is organic Hydroxy compounds, either with the amine comprising at least one hydrogen atom being connected on nitrogen-atoms or with hydroxy compounds and amine Mixture react to produce.Term " amber acylation agent " refers to the butanedioic acid of hydrocarbon substitution or produces the chemical combination of butanedioic acid Thing, the latter includes the acid itself.Such material typically comprises the butanedioic acid, acid anhydrides, ester (including half ester) of alkyl substitution And halide.

Amber base dispersant has extensive a variety of chemical constitutions.One class amber base dispersant can be represented with following formula：

Wherein each R¹Independent is alkyl, for example the group in polyolefin source.The typical alkyl is that alkyl for example gathers Isobutyl group.In other words, the R¹Group can include about 500 carbon atoms of about 40-, and these atoms can be with aliphatic shape Formula is present.R²It is alkylidene, typically ethylidene (C₂H₄).The example of succinimide dispersants includes description in such as U.S. Those in patent No.3172892,4234435 and 6165235.

The substituent is typically the carbon atoms of 2- about 16 derived from its polyolefin, and usual 2-6 carbon atom The homopolymer and interpretation of polymerizable alkylene hydrocarbon monomer.The amine that carboxylic dispersant composition is formed with amber acylation agent reaction can be with It is monoamine or polyamines.

Succinimide dispersants are referred to likewise, because they generally comprise and are mostly in imide functionalities' form Nitrogen, although amide functionality may be at the form of amine salt, acid amides, imidazoline and its mixture.It is sub- in order to prepare succinyl Amine dispersant, removes water one or more compounds for producing butanedioic acid and one or more amine heating and typically, optionally exists Carried out in the presence of substantially inert organic liquid solvent/diluent.The reaction temperature can be about 80 DEG C high to described mixed The decomposition temperature of compound or product, it typically falls into about 100 DEG C-about 300 DEG C.Succinyl for preparing the present invention The other details of the programs of imine dispersants and example include such as United States Patent (USP) No.3172892,3219666,3272746, 4234435th, those described in 6165235 and 6440905.

Suitable ashless dispersant can also include amine dispersant, its be relatively high molecular weight aliphatic halide and The reaction product of amine, preferably polyalkylene polyamine.The example of such amine dispersant includes description in such as United States Patent (USP) Those in No.3275554,3438757,3454555 and 3565804.

Suitable ashless dispersant may further include " the strange dispersant of Manny ", and it is alkyl phenol (wherein alkyl bag Containing at least about 30 carbon atoms) reaction product with aldehyde (particularly formaldehyde) and amine (being particularly polyalkylene polyamine).So The example of dispersant include that in such as United States Patent (USP) No.3036003,3586629,3591598 and 3980569 of description A bit.

Suitable ashless dispersant can also be the succinimide of the ashless dispersant such as post processing of post processing, for example Post-processing approach including borate or ethylene carbonate, as disclosed in United States Patent (USP) No.4612132 and 4746446；Deng Deng and other post-processing approach.The alkenyl succinimide of carbonic ester processing is polybutylene succinimide, and it is derived from tool There is the polybutene of following molecular weight：About 450- about 3000, preferably approximately 900- about 2500, more preferably from about 1300- is big About 2400, and most preferably from about 2000- about 2400, and these molecular weight mixing.It is preferred that it is by reactive bar Under part, by the acid reactant copolymer of the unsaturation of polybutene succinic acid derivative, unsaturated acids reactant and alkene and polyamines Mixture react come what is prepared, be for example disclosed in United States Patent (USP) No.5716912, its content is hereby incorporated by reference.

It is containing metal or act as detersive into grey detersive and deposit and act as sour neutralization to reduce or remove Both agent or antirust agent, thus reduce abrasion and corrosion and extend engine life.Detersive is generally comprised with length The polar head of hydrophobic tail.The polar head includes the metal salt of acidic organic compound.The salt can include substantially stoichiometry The metal of proportion, they are commonly described as just or neutral salt in this case, and typically total base number or TBN (can be with Measured by ASTM D2896) it is 0- about 80.Substantial amounts of metal base can by excessive metallic compound (for example oxide or Person's hydroxide) react to introduce with sour gas (such as carbon dioxide).The alkalization detersive of crossing formed includes neutralization clearly Net agent as metal base (such as carbonate) micella outer layer.It is such cross alkalization detersive TBN can be about 50 or Bigger, either TBN is that about 100 or bigger or TBN is about 200 or bigger, or TBN be about 250- about 450 or bigger.

The representative of other metal detergents in the marine diesel steam-cylinder lubrication fluid composition of the present invention can be included in Property example include phenates, aliphatic sulfonate, its TBN and be equal to or alkyl-substituted hydroxyaromatic carboxylic acid equal to less than 250 Alkali salt, the alkali metal salt of alkyl-substituted hydroxyaromatic carboxylic acid, phosphonate and phosphinate.The alkyl-substituted hydroxyl The salt of aromatic carboxylic acid can be as described above.

Commercially available prod is commonly referred to as neutral or crosses alkalization.Alkalization metal detergent is crossed typically by making hydrocarbon, detersive Acid is (for example：Sulfonic acid, carboxylate etc.), metal oxide or hydroxide (such as calcium oxide or calcium hydroxide) and accelerator The mixture of (such as dimethylbenzene, first alcohol and water) is carbonated to produce.For example, in order to prepare alkaline calcium sulfonate, in carbonic acid In change, calcium oxide or calcium hydroxide are reacted with gaseous carbon dioxide to form calcium carbonate.By the excessive CaO of the sulfonic acid or Ca(OH)₂Neutralize, to form sulfonate.

It can be that low cross is alkalized to cross alkalization detersive, and the BN for for example crossing alkalization salt is less than about 100.In a kind of embodiment party In case, the low BN for crossing alkalization salt can be about 5- about 50.In another embodiment, the low BN for crossing alkalization salt can be big About 10- about 30.In another embodiment still, the low BN for crossing alkalization salt can be about 15- about 20.

It can be that medium cross is alkalized to cross alkalization detersive, and the BN for for example crossing alkalization salt is about 100- about 250.One Plant in embodiment, the medium BN for crossing alkalization salt can be about 100- about 200.In another embodiment, it is medium to cross alkali The BN of salt dissolving can be about 125- about 175.

Alkalization can be exceeded by crossing alkalization detersive, and the BN for for example crossing alkalization salt is higher than 250.In a kind of embodiment In, the BN for exceeding alkalization salt can be about 250- about 550.

The example of antirust agent includes but is not limited to non-ionic polyoxyalkylene reagent, such as polyoxyethylene lauryl ether, poly- It is the senior alcohol ether of oxygen ethene, ethylene nonyl phenyl ether, NONIN HS 240, polyoxyethylene octyl stearyl base ether, poly- Oxygen ethene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene 80 sorbitan monooleate and polyethyleneglycol Oleate；Stearic acid and other aliphatic acid；Dicarboxylic acids；Metallic soap；Aliphatic acid amine salt；The metal salt of heavy sulfonic acid；Polyhydroxy-alcohol Inclined carboxylate；Phosphate；(short chain) alkenyl succinic acid；Its partial ester and its nitrogen containing derivative；Synthesize alkylaryl sulfonate for example Metal dinonylnaphthalene sulfonic acid salt；Etc. and its mixture.

The example of friction modifiers includes but is not limited to alkoxylated fats amine；Borated fatty epoxides；It is fatty sub- Phosphate/ester, fat epoxide, fatty amine, borated alkoxylated fatty amine, the metal salt of aliphatic acid, fatty acid amide, Glyceride, borated glycerol esters；And fatty imidazolines, as disclosed in United States Patent (USP) No.6372696, its content is incorporated herein It is used as reference；Friction modifiers are obtained from C₄-C₇₅, preferably C₆-C₂₄Most preferably C₆-C₂₀Fatty acid ester and selected from ammonia and alkanolamine example The reaction product of the nitrogen-containing compound of such as list or dialkanol amine and its mixture.

The example of antiwear agents includes but is not limited to zinc dialkyl dithiophosphate and zinc diaryl dithiophosphates, for example Description is in paper Born et al., title " Relationship between Chemical Structure and Effectiveness of Some Metallic Dialkyl-and Diaryl-dithiophosphates in Different Lubricated Mechanisms ", appear in Lubrication Science 4-2, in 1 month 1992 Those, see, for example, the 97-100 pages；Aryl phosphate ester/salt and aromatic yl phosphite/salt, containing thioesters, phosphorus sulphur compound, metal Or ashless dithiocarbamate/salt, xanthate/salt, alkyl sulfur compounds etc. and its mixture.

The example of defoamer includes but is not limited to methacrylate polymer；Polymer of dimethyl organosilicon etc. And its mixture.

The example of pour-point depressant includes but is not limited to polymethacrylates, acrylate polymers, methyl-prop Olefin(e) acid alkylester polymers, two (four alkane phenol) phthalic acid esters, condensation product, chlorinated paraffin and the naphthalene of four alkane phenol Condensation product and combinations thereof.In some embodiments, the pour-point depressant includes vinyl-vinyl acetate copolymer, chlorination Condensation product, alkyl styrenes of alkane and phenol etc. and combinations thereof.The amount of pour-point depressant can be big in about 0.01wt%- About 10wt% changes.

The example of demulsifying agent includes but is not limited to anion surfactant (such as alkyl-naphthalenesulfonate salts/ester, alkyl Benzene sulfonate/ester etc.), Nonionic alkoxylated alkyl phenol resin, polymer (such as PEO, polycyclic oxygen of alkylene oxide Propane, ethylene oxide propylene oxide block copolymer etc.), the ester of oil-soluble acid, polyoxyethylene sorbitan esters and combinations thereof.Instead The amount of emulsifying agent can change in the range of about 0.01wt%- about 10wt%.

The example of corrosion inhibitor includes but is not limited to the half ester or acid amides of dodecyl succinate, phosphate, thio Phosphate/salt, alkyl imidazoline, methyl amimoacetic acid etc. and combinations thereof.The amount of the corrosion inhibitor can be in about 0.01wt%- about Change in the range of 0.5wt%.

The example of extreme pressure agent includes but is not limited to vulcanization animal or plant fat or oil, vulcanization animal or vegetable butter Fat acid esters, the ester being completely or partially esterified of the trivalent of phosphorus or pentahydric acid, olefine sulfide, dihydrocarbyl polysulfide, vulcanization Diels-alder adducts, vulcanization bicyclopentadiene, fatty acid ester and single unsaturated olefin it is vulcanization or co-vulcanization Mixture, aliphatic acid, the mixture of the co-vulcanization of fatty acid ester and alpha-olefin, dihydrocarbyl polysulfide, the sulphur of functionalization substitution For the co-vulcanization mixture and many sulphur of aldehyde, thio ketone, table thio-compounds, the acetal derivant of sulfur-bearing, terpenes and non-ring olefin Change amine salt of olefin product, phosphate or thiophosphate etc. and combinations thereof.The amount of extreme pressure agent can be about 0.01wt%- about 5wt% change.

Each aforementioned additive is used with functionalization effective dose when in use, to assign lubricant desired performance. Therefore for example, if additive is friction modifiers, the functionalization effective dose of this friction modifiers will be enough to assign profit Lubrication prescription changes the amount of characteristic with desired friction.Generally, the concentration of these every kind of additives when in use is about 0.001wt%- about 20wt%, are about 0.01wt%- about 10wt% in one embodiment, based on the lubricating oil group The gross weight of compound.

In addition, foregoing marine diesel steam-cylinder lubrication fluid composition additive can come as additive bag or concentrate There is provided, wherein introduce the additive into it is substantially inert, in liquids in general organic diluent, as described above.The additive bag The different additives of one or more will be typically comprised, as described above, promoting with desired amount and ratio and necessary amounts Lubricant viscosity oily direct combination.

In one embodiment, marine diesel steam-cylinder lubrication fluid composition of the invention there is no or not have Any dispersant and/or zinc compound, such as zinc dithiophosphate.It is used as used herein, term " there is no " expression The every kind of dispersant and/or zinc compound of relatively low level (if any), are, for example, less than marine diesel cylinder The about 0.5wt% of lubricant oil composite every kind of dispersant and/or zinc compound.In another embodiment, term is " basic On do not have " be less than marine diesel steam-cylinder lubrication fluid composition about 0.1wt% every kind of dispersant and/or zinc impregnation close Thing.In another embodiment, term " there is no " is less than marine diesel steam-cylinder lubrication fluid composition about 0.01wt% every kind of dispersant and/or zinc compound.

As disclosed herein with it is exemplified hereinafter the present invention marine diesel steam-cylinder lubrication fluid composition in it is total TPP and its unvulcanized metal salt (i.e. " total TPP " or " total remnants TPP ") and hydroxyaromatic group containing alkyl monosulfide substitution The lubricant of the salt of compound and the concentration of oil additive are measured with reversed-phased high performace liquid chromatographic (HPLC).In HPLC methods In, precise 80 to 120mg samples, with dchloromethane to scale mark, is mixed until sample into 10ml volumetric flasks It is completely dissolved, prepares the sample for analysis.

HPLC system used includes a HPLC pump, constant temperature HPLC column compartment, the inspection of HPLC fluorescence in HPLC methods Survey device and the chromatographic signal sampling system based on PC.Described specific system is based on ChemStation softwares Agilent 1200 HPLC.HPLC column is 5 μm of (2) 150 × 4.6mm of Phenomenex Luna C8,P/N 00F4249E0。

Set in analysis operation using following system：

Pump discharge=1.0ml/min

Maximum pressure=200bars

Wavelength of fluorescence：225 excite 313 transmittings:Gain=9

Column oven temperature=25C

The μ L of injection volume=1 dilute sample

Elute type：Gradient, it is anti-phase

Gradient：The methanol/water of 0-7 minutes 85/15 switches to the linear gradient elution of 100% methanol.

Run time：17 minutes

Gained chromatogram generally comprises several peaks.Belong to free unvulcanized alkyl hydroxy aromatic compounds (that is, TPP) Peak be usually to be eluted together in early stage retention time, and belong to the peak of the alkyl hydroxy aromatic compounds of vulcanization typically will be Longer retention time elution.In order to quantitative, free unvulcanized alkyl hydroxy aromatic compounds and its unvulcanized metal are determined The area at the single largest peak of salt, then determined with this area total free unvulcanized alkyl hydroxy aromatic compounds and its The concentration of unvulcanized metal salt species.It is assumed that the form of alkyl hydroxy aromatic compounds does not change, if alkyl hydroxy aromatics The form of compound is changed really, then have to re-calibrate.

The area at selected peak be compared with calibration curve to obtain free alkyl phenol and free alkyl phenol The wt% of sulphurizing salt.Calibration curve is the chromatogram obtained with the free unvulcanized alkyl hydroxy aromatic compounds for preparing phenates product Same peak is formulated in figure.

Following non-limiting example is used to illustrate the present invention.

For following each embodiment, high temperature detergency and degree of heat stability are to use following little Song heat pipes (" KHT ") tests to evaluate.The result of each embodiment is shown in table 1.

Little Song heat pipes (KHT) are triedTest

The test of little Song heat pipes is a kind of industrial platform test of lubrication, and it measures the detergency of lubricating oil and hot and oxidation-stabilized Property.Detergency is such performance zones with heat and oxidation stability, and it is industrially generally acknowledged for meeting the whole of lubricating oil It is necessary for body performance.In the test process, the test oil of ormal weight is pumped upward through glass tube, the glass tube is put In being arranged in the baking oven of some temperature.Before oil enters glass tube, introduce air into oil stream, and together with oily to Upper flowing.The evaluation of marine diesel cylinder oil is carried out at a temperature of 300-330 DEG C.Test result is as got off Determine：By the amount for the paint being deposited on glass test tube and from 1.0 (non-normally-black) to the grade scale of 10.0 (especially clean) It is compared.Result is multiplied by 0.5 to report.It is following deposit to block, and very thick and most of glass is painted in this case Glass pipe is blocked, and testing tube is flowed through which prevent normal oil and air.Although blocking the knot for being considered and being worse than 1.0 grades Really, but its incidence can be mainly by other testing tubes of test be blocked and influenceed simultaneously in same test run.

Marine diesel steam-cylinder lubrication fluid composition is prepared with following components below.

Chevron 600N RLOP:II class based lubricating oils are Chevron 600N RLOP oil base stocks, obtained from Chevron Products Company(San Ramon,CA.)。

ExxonMobil2500BS：I class based lubricating oils are ExxonMobil2500BS oil base stocks, Obtained from ExxonMobil (Irving, TX.).

Detersive used in the embodiment of table 1 is described below：

Detersive A：The oil concentrate of neutral (non-cross is alkalized) alkyl hydroxy calcium benzoate additive, the additive has Derived from C₂₀-C₂₈The alkyl substituent of linear alpha-olefin, it is the institute of embodiment 1 according to U.S. Patent application 2007/0027043 Prepared by the method stated, but without subsequent mistake alkalinization step.Ca of this multifunctional additive for lubricating oils comprising 2.17wt% and big About 43.0wt% diluent oil, and TBN are 61.Based on active material, the TBN (diluent oil is not present) of this additive is 107。

Detersive B：The oil concentrate for crossing the calcium sulfide phenates that alkalizes of the derived from propylene tetramer.This additive is included 9.6wt% Ca and about 31.4wt% diluent oil, and TBN is 260.The weight of detersive based on the preparation, clearly Net agent B is it is believed that total TPP contents with about 5-7wt%, i.e. TPP and its unvulcanized metal salt.

Detersive C：The oil concentration of additive comprising the unvulcanized non-phenol distillation for crossing alkalization alkyl hydroxy benzoate Thing, the additive has the C derived from about 50wt%₂₀-C₂₈The branched hydrocarbyl radical propylene tetramer of linear alpha-olefin and 50wt% Alkyl substituent, it is prepared by method according to the embodiment 1 of U.S. Patent application 2004/0235686.It is this to add Plus Ca and about 33.0wt% of the agent comprising 5.00wt% diluent oil, and TBN is 140.It is this to add based on active material Plus the TBN of agent (diluent oil is not present) is 210.The weight of detersive based on the preparation, detersive C are it is believed that with about 2- 3wt% total TPP contents, i.e. TPP and its unvulcanized metal salt.

Detersive D：The oil concentrate of alkalization alkyl hydroxy calcium benzoate additive is crossed, the additive, which has, to be derived from C₂₀-C₂₈The alkyl substituent of linear alpha-olefin, it is the side according to the embodiment 1 of U.S. Patent application 2007/0027043 Prepared by method.Ca and about 35.0wt% of this additive comprising 5.35wt% diluent oil, and TBN is 150.It is based on Active material, the TBN of this additive (diluent oil is not present) is 230.

Detersive E：The oil concentrate of alkalization alkyl hydroxy calcium benzoate additive is crossed, the addition, which has, is derived from C₂₀- C₂₈The alkyl substituent of linear alpha-olefin, it is the method system according to the embodiment 1 of U.S. Patent application 2007/0027043 Standby.Ca and about 33.0wt% of this additive comprising 12.5wt% diluent oil, and TBN is 350.Based on activity Material, the TBN of this additive (diluent oil is not present) is 522.

Detersive F：Cross the oil concentrate of alkalization alkyl toluene sulfonic acids calcium detersive；The wherein alkyl derivative is from C₂₀-C₂₄Line Property alhpa olefin.This multifunctional additive for lubricating oils includes 16.1wt% Ca and about 38.7wt% diluent oil, and TBN is 420.Based on active material, the TBN of this additive (diluent oil is not present) is 685.

Detersive G：The oil concentrate of alkalization alkyl hydroxy calcium benzoate additive is crossed, wherein the alkyl substituent derives From C₁₄-C₁₈Linear alpha olefin.Ca and about 41.0wt% of this multifunctional additive for lubricating oils comprising 6.25wt% diluent oil, and And TBN is 175.Based on active material, the TBN of this additive (diluent oil is not present) is 296.

Embodiment 1-3 and Comparative examples A-J

Embodiment 1-3 and comparative example A-J marine diesel engine oil composition is as shown in table 1 below to prepare 's.Embodiment 1 and comparative example A-J every kind of marine diesel engine oil composition are SAE40 viscosity grades oil, and it is transported Kinetic viscosity is that 100 DEG C of about 14.5cSt@and TBN are about 40mgKOH/g.Embodiment 2 is SAE50 viscosity grades oil, its kinematic viscosity It is that 100 DEG C of 18.7cSt@are about 70mgKOH/g with TBN.Embodiment 3 is SAE50 viscosity grades oil, and its kinematic viscosity is 100 DEG C of 18.9cSt@and TBN are about 20mgKOH/g.Embodiment 1-3 and comparative example A-J marine diesel engine lubricating oil Composition is combined using detersive defined in major amount of class ii oil base stock, a small amount of I classes oil base stock, table 1 Thing and 0.04wt% defoamers are prepared.Comparative example D further includes the oil of 0.57wt% double amber imide dispersant Concentrate, the dispersant is derived from 1000MW polyisobutylene succinic anhydrides (PIBSA) and heavy polyamine (HPA)/diethylidene Triamine (DETA), the oil concentrate has about 31.7wt% diluent oil.Every kind of diesel engine cylinder in embodiment 1-3 Lubricant oil composite is free of TPP and its unvulcanized metal salt.

Shown in result as shown in table 1, the marine diesel engine oil composition relative to comparative example A-J, bag The embodiment 1-3 of cleaning agent composition containing present invention marine diesel engine oil composition shows astonishing Improved cleansing performance.This is shown by higher KHT values, its be in higher temperature range it is constant, this Show that embodiment 1-3 marine diesel engine oil composition shows excellent detergency and heat in heat pipe test Stability, because they generate oil ageing or the catabolite of seldom pollution pipe.In addition, embodiment 1-3 It is substantially free of TPP and its unvulcanized metal salt.

It is to be understood that carrying out different changes to embodiment disclosed herein.So description above should not It is construed to restricted, and as just the example of preferred embodiment.As described above, and it is optimal as the present invention The function of embodiment is merely for illustrative purposes.Other arrangements and method can be performed by those skilled in the art, and The scope and spirit of the present invention are not departed from.In addition, those skilled in the art are possible to expect being in be additional to its claim Scope and spirit in other change.

Claims (15)

1. a kind of marine diesel steam-cylinder lubrication fluid composition, it includes (a) major amount of one or more II classes oil base stocks, Cleaning agent composition, the cleaning agent composition includes the alkali of (i) one or more alkyl-substituted hydroxyaromatic carboxylic acids (b) Earth metal salt, its have more than 250 total base number (TBN), and (ii) one or more exceed alkalization alkyl aromatic sulfonic acid or Its salt；The aromatic fractions of wherein described alkyl aromatic sulfonic acid or its salt do not include hydroxyl；Wherein described marine diesel vapour Cylinder lubricating oil composition has about 5- about 120 TBN.

2. marine diesel steam-cylinder lubrication fluid composition according to claim 1, it has about 20- about 100 TBN.

3. marine diesel steam-cylinder lubrication fluid composition according to claim 1, it has about 10- about 40 TBN.

4. the marine diesel steam-cylinder lubrication fluid composition according to any one of claim 1-3, it is substantially free of four Polypropylene-base phenol (TPP) and its unvulcanized metal salt.

5. the marine diesel steam-cylinder lubrication fluid composition according to any one of claim 1-4, wherein it is described a kind of or The alkali salt of a variety of alkyl-substituted hydroxyaromatic carboxylic acids is the calcium of one or more alkyl-substituted hydroxyaromatic carboxylic acids Salt.

6. the marine diesel steam-cylinder lubrication fluid composition according to any one of claim 1-5, wherein the alkyl takes The alkyl substitution part of the alkali salt of the hydroxyaromatic carboxylic acid in generation is C₁₀-C₄₀Alkyl.

7. the marine diesel steam-cylinder lubrication fluid composition according to any one of claim 1-6, wherein it is described a kind of or The alkali salt of a variety of alkyl-substituted hydroxyaromatic carboxylic acids has the TBN more than 250 and at most about 800.

8. the marine diesel steam-cylinder lubrication fluid composition according to any one of claim 1-7, wherein it is described a kind of or A variety of alkalization alkyl aromatic sulfonic acid or its salt of exceeding are that one or more exceed alkalization alkaline-earth metal alkyl aromatic sulfonates.

9. the marine diesel steam-cylinder lubrication fluid composition according to any one of claim 1-8, wherein it is described a kind of or A variety of alkalization alkyl aromatic sulfonic acid or its salt of exceeding are that one or more exceed alkalization alkyl aromatic sulfonic acid calcium salt.

10. the marine diesel steam-cylinder lubrication fluid composition according to any one of claim 1-9, wherein it is described a kind of or A variety of alkalization alkyl aromatic sulfonic acid or its salt of exceeding have the TBN for being more than 250.

11. the marine diesel steam-cylinder lubrication fluid composition according to any one of claim 1-10, it is included：

With the gross weight meter of the marine diesel steam-cylinder lubrication fluid composition, about 0.1- about 35wt% based on active material The alkali salt of one or more alkyl-substituted hydroxyaromatic carboxylic acids, it has the TBN more than 250；With

With the gross weight meter of the marine diesel steam-cylinder lubrication fluid composition, about 0.1- about 34wt% based on active material The one or more exceed alkalization alkyl aromatic sulfonic acid or its salt.

12. the marine diesel steam-cylinder lubrication fluid composition according to any one of claim 1-11, it is further included The one or more marine diesel steam-cylinder lubrication fluid composition additives being selected from the group：It is antioxidant, ashless dispersant, peace and quiet Agent, antirust agent, fog remover, demulsifying agent, matal deactivator, friction modifiers, pour-point depressant, defoamer, cosolvent, corrosion Inhibitor, dyestuff, extreme pressure agent and its mixture.

13. the marine diesel steam-cylinder lubrication fluid composition according to any one of claim 1-12, its substantially free of Any dispersant and/or zinc compound.

14. a kind of method for lubricating two stroke cross-head diesels engine peculiar to vessel, wherein methods described will including the use of such as right The marine diesel steam-cylinder lubrication fluid composition any one of 1-13 is asked to run the engine.

15. the purposes of the marine diesel steam-cylinder lubrication fluid composition according to any one of claim 1-13, it is used for Improve the high temperature detergency and heat endurance in two stroke crosshead marine diesel engines.