Cylinder lubricant for two-stroke marine engine. RU patent 2507245.

FIELD: chemistry.

SUBSTANCE: invention relates to a cylinder lubricant, having a base number (BN) determined according to standard ASTM D-2896 greater than or equal to 15 mg KOH/g of lubricant, containing: one or more lubricating base oils for marine engines, at least one detergent based on alkali or alkali-earth metals, overbased with metal carbonates, optionally in combination with one or more neutral detergents, one or more oil-soluble fatty amines containing 16-22 carbon atoms and having BN determined according to standard ASTM D-2896 from 150 to 600 mg KOH/g. The present invention also relates to use of the cylinder lubricant (versions) and an additive concentrate for preparing the cylinder lubricant.

EFFECT: obtaining a lubricant having neutralisation power with respect to sulphuric acid formed during combustion of high-sulphur liquid fuel, while limiting formation of deposits during use of low-sulphur liquid fuel.

29 cl, 4 ex, 2 tbl, 2 dwg

Field of the invention

The present invention relates to grease substance for cylinder two-stroke marine engine which can be used with sour liquid fuel and liquid fuel. More particularly, the invention relates to grease the substance, possessing sufficient neutralizing force in respect of sulfuric acid formed during the combustion of high-sulphur liquid fuel, and the formation of deposits when using low sulphur liquid fuels is limited.

Prior art

In the document FR 2094182 describes lubricants containing the additive, formation of rust and corrosion, which is based on connections, including C18 Amin. Use a very small number of Amin. In addition, indicate that the connection used to ensure the basicity of the lubricant, is a carbonate.

Ship oils used in low-speed two-stroke engines are of two types. First, it is a cylinder oil, providing lubrication site piston-cylinder and, secondly, oil system, providing lubrication of moving parts except the node piston-cylinder. Node piston-cylinder residual combustion products containing acid gases, are in contact with lubricating oil.

Acid gases are formed as a result of combustion of liquid fuel; they in particular are sulfur oxides (SO2 , SO3 ), which are then subjected to hydrolysis in contact with moisture present in the combustion products and/or oil. Such hydrolysis leads to the formation of sulphurous (HSO 3 ) or sulphuric acid (H 2 SO 4 ) acid.

To protect the surface of piston cylinder liners, and to avoid excessive wear due to corrosion, these acid must be neutralized, that, as a rule, is carried out by interaction with major groups, are part of the lubricant.

The ability of the oil to the fallback measure its or alkaline number, characterising its basicity. It is measured in accordance with ASTM D 2896 and is expressed as the equivalent mass of potassium hydroxide in grams butter or mg KOH/g is a standard criterion, allowing to adjust the basicity of the cylinder lubricating oils in accordance with the content of sulphur in the use of liquid fuel, in order to give the opportunity to neutralize all of the sulphur in liquid fuels, and the ability to transform into a sulfuric acid by combustion and hydrolysis.

Thus, the more the content of sulphur in fuel oils, the higher should be ship oil. Therefore, the market presents ship oils, having , located in the range from 5 to 100 mg KOH/g This basicity is provided detergents, which insoluble salts of metals, in particular, metal carbonates. Detergents, mainly anionic type are, for example metal-containing soap , , , type etc. that form micelles, which in suspension are insoluble particles of salts of metals. Ordinary detergents inherently possess , typically 150 to 700 mg KOH per gram of detergent. Their mass content in per cent in the lubricating substance is fixed depending on the required value .

Some of the values can also be provided or "neutral detergent, having , as a rule, less than 150. However, it is impossible to imagine production composition of the lubricant for cylinder ship's engine, where fully secured by a "neutral detergent: actually be necessary to include them in excessive amounts, which may worsen the other properties of the lubricant and are unrealistic from the economic point of view.

Insoluble metal salts detergents, such as calcium carbonate, thus, contribute significantly to conventional lubricants. It can be assumed that approximately at least 50%, as a rule 75% of the value lubricant for cylinder, thus providing these insoluble salts.

The part that really is a detergent, or metallic Soaps available in the composition of both neutral and detergents, as a rule, provide most of the rest of the .

Care for environment has led in some areas, particularly in coastal regions, to the demands associated with the limitation of the sulphur content in liquid fuel, used by ships.

So, in may 2005, entered into force Annex 6 of MARPOL (the international Convention for the prevention of pollution from ships), released by the IMO (international Maritime organization). It installs a generic limit of 4.5% of mass for sulfur content in heavy fuel oil) and also sets the zone, which is controlled by the emission of sulfur oxides, called SECA (SOx Emission Control Areas). The ships coming in these zones must use liquid fuel with a maximum sulphur content of 1.5% of mass or any other alternative treatment, intended to limit emissions of SOx (sulphur oxides), in order to meet the requirements concerning the emission values. The value in wt.% denotes the mass content of the connection relative to the total mass of liquid fuel or lubricating composition, in which it is located.

Later, the marine environment protection Committee (MEPC) meeting in April 2008 approved the proposed changes to Annex 6 to MARPOL. These suggestions are summarized in the following table. They reflect a scenario in which the restriction on the maximum sulphur content is becoming stricter, and the total for the whole world the maximum sulfur content with 2012 should decline from 4.5% of mass up to 3.5%of mass. SECA (zone, which is controlled by the emission of sulfur oxides) will zones with controlled emissions - ENA (Emission Control Areas). In these areas the maximum permitted content of sulphur 2010 decreased from 1.5 wt% up to 1,0% mass and introduced new restrictions in respect of content of nitrogen oxide (MOX) and particles.

Acting rules under Annex 6 to MARPOL

Maximum sulphur content

The total limit

The limit for SECA zones

4,50%of mass

1,50%of mass

Changes to Annex 6 of MARPOL (MEPC meeting №57, April 2008)

Maximum sulphur content

The total limit

Limit zones ENA

3,5% of mass to 1.01.2012

1 wt.% to 1.03.2010

0,5% mass to 1.01.2020

0,1 mass% to 1.01.2015

Ships to challenge overland routes already use several types of heavy fuel oil depending on local restrictions related to environmental protection, with the ability to optimize their operational costs. The situation will remain such, whatever the level of maximum sulphur content allowed in liquid fuel.

This condition is established for most container ships that currently design for the use of different fuel tanks for liquid fuel to the open sea with a high sulfur content, and for liquid fuel for use in hazardous areas "SECA" with sulfur content no more than 1.5%of mass.

The transition from one to the other of the two following categories of liquid fuel may require adaptation of the operating regimes of the engine, in particular the use of appropriate lubricants for cylinders.

Currently in the presence of liquid fuel with high sulphur content of 3.5% of mass and more) use of marine lubricants, having about 70.

In the presence of liquid fuel with low sulphur content (1.5 wt% and less) is used marine lubricants, having about 40 (this value should be reduced in the future).

In both these cases is sufficient neutralizing ability, as they provide the necessary concentration of the main groups at the expense of detergents marine lubricant, but it is necessary to change the lubricant every time you change the type of liquid fuel.

In addition, each of these lubricants are the restrictions on use of, arising from the following observations:

use a lubricant for cylinders with a value 70 in the presence of liquid fuel with low sulphur content (1,5 wt.% and less) and a fixed level of lubrication lead to a substantial excess of the main groups (high ) and risk of destabilization of unused detergent micelles, which contain insoluble salts of metals. Such destabilization results in formation of insoluble salts of metals with a high degree of hardness (for example, calcium carbonate), mainly in the area above the piston ring, and for a long period lead to the risk of excessive wear on the type of polishing liner piston.

Thus, the optimization cylinder lubrication of low-speed two-stroke engine requires a choice of lubricant with , suitable for liquid fuel to the engine operation. This optimization reduces the flexibility of the engine and requires significant technical skills of the crew to identify the conditions under which should be the replacement of one type of lubricant on the other.

Thus, to simplify operations may be desirable to have one lubricant for cylinder two-stroke marine engine which can be used with sour liquid fuel and liquid fuel.

The present invention relates to the lubricating preparations, possessing high enough to effectively neutralize sulfuric acid produced using liquid fuel with high sulphur content, where a significant portion of the specified provided particles that do not lead to the formation of metal deposits for partially expenditure in the case of the use of low sulphur fuel.

Thus, the present invention relates to a grease substance for cylinders with defined in accordance with ASTM D 2896, greater than or equal to 15, preferably 20 or higher, preferably greater than or equal to 30, most preferably greater than or equal to 40 milligrams of sodium hydroxide of potassium per gram lubricant containing:

- one or more main lubricating oil for marine engines

- at least one detergent based on alkaline or alkaline earth metals, metal carbonates, possibly in combination with one or more than one neutral detergent,

- one or more bold Amin and/or derivative fatty amine, having defined in accordance with ASTM D 2896, ranging from 150 to 600 milligrams of sodium hydroxide of potassium per gram, preferably ranging from 200 to 500 milligrams of sodium hydroxide of potassium per gram,

moreover, the mass content in percentage of fatty amines and their derivatives with respect to the total mass of the lubricant is chosen so that the contribution of provided by these compounds, in General specified lubricant for cylinder was at least 10 milligrams of sodium hydroxide of potassium per gram lubrication, preferably at least 20 milligrams hydroxide potassium per gram, preferably at least 30 milligrams of sodium hydroxide of potassium per gram, more preferably at least 40 milligrams of sodium hydroxide of potassium per gram of lubricant, and

mass content in per cent detergents respect to the total mass of the lubricant is chosen so that the contribution of provided by carbonates metals, in General specified lubricant for cylinder was, as a maximum, 20 milligrams of sodium hydroxide of potassium per gram of lubricant.

The Complainant discovered that it is possible to create the composition of the lubricant substances for cylinder, in which the major part of provided fatty amines, and there is a level of product quality, comparable with standard compositions with an equivalent .

The required characteristics in particular represent the ability to neutralize sulfuric acid, which measured using a test enthalpy described in the following examples.

However, it is impossible to completely eliminate the contribution in make insoluble metal particles detergents: they are the "last reserve of" mandatory basicity when operating with sour liquid fuel (e.g. more than 3 wt.%, or even 3.5%of mass).

In addition, these insoluble salts of metals have a favorable anti-aging effect, if they are supported in state in the lubricating substance in the form of stable micelles.

In addition, it was found that the inclusion of too high content of Amina leads to a significant reduction of viscosity of the lubricant, so that it almost ceases to be suitable for use as a lubricant for cylinders. In addition, this may have an adverse effect on the toxicity of the specified lubricant.

The applicant also suddenly discovered that when there are a significant contribution to value by these fatty amines, too great contribution in (more than 20 mg hydroxide potassium per gram lubricant) from insoluble detergents with metals (usually metal carbonates)has an adverse effect in respect of neutralizing capacity of the lubricant for cylinders.

In standard lubricating substances for cylinders with a value 40, the composition of which is dimensioned for use with liquid fuel value provided insoluble salts of metals, as a rule, is of the order of 30 mg hydroxide potassium per gram of lubricant.

Thanks alternative contribution to provided fatty amines, do not form a solid metal deposits, resulting in wear of parts, in combination with and perhaps neutral detergents, lubricants for cylinders in accordance with the present invention are suitable for high-sulfur fuel oil, and for low-sulfur fuel.

Preferably, according to the present invention, the proposed oil to cylinder having defined in accordance with ASTM D 2896, ranging from 40 to 80 milligrams of sodium hydroxide of potassium per gram lubricant, preferably from 65 to 75 or more preferably make up 70 milligrams sodium hydroxide of potassium per gram of lubricant.

In accordance with another embodiment, lubricant according to the present invention, as determined in accordance with ASTM D 2896, 45 to 60 milligrams of sodium hydroxide of potassium per gram lubricant, preferably from 45 to 55 or more preferably equal to 50 milligrams of sodium hydroxide of potassium per gram of lubricant.

In accordance with another embodiment lubricant according to the present invention, as determined in accordance with ASTM D 2896, ranges from 54 to 60 milligrams of sodium hydroxide of potassium per gram lubricant, preferably, it is 57, or preferably also equal to 55 milligrams of sodium hydroxide of potassium per gram of lubricant.

In accordance with another embodiment lubricant according to the present invention, as determined in accordance with ASTM D 2896 is 40 to 50 milligrams of sodium hydroxide of potassium per gram lubricant, preferably 45 milligrams of sodium hydroxide of potassium per gram of lubricant.

According to one embodiment, for reasons connected with cost and availability, (e) bold(e) Amin(s) and their derivatives produced from palm, olive, peanut, conventional or oilseed rape, conventional or oilseeds sunflower, soybeans or cotton-seed oil, beef fat, or of palmitic, stearic, oleic, linoleic or acid.

According to one embodiment, fatty amines selected from amines derived from fatty acids, containing from 16 to 18 carbon atoms.

To avoid the phenomenon of , which is detected high mass content of fatty amines in the lubricating matter, preferably fatty amines, containing 12 to 24 carbon atoms, preferably from 16 to 22 carbon atoms.

According to one embodiment of fatty amines are mono - or polyamines, preferably , and derivatives of fatty amine are derivatives of mono - or polyamine, preferably derived diamine.

In a preferred embodiment they are polyamines General formula R-[NH(CH 2 ) 3 ]n-NH 2 , where n is an integer, the duration between 1 and 3, and R is fatty chain of saturated or unsaturated fatty acids, containing at least 16 carbon atoms, preferably fatty chain of oleic acid, and derivatives of fatty amine derivatives represent the same diamines.

Derivatives of fatty amine according to the present invention are, for example derivatives described above amines. These derivatives, for example chosen from amines have 1 to 5 groups of ethylene oxide, and .

In lubricating substances according to the present invention, and/or neutral detergents preferably chosen from carboxylates, sulphonates, salicylates, , and mixed detergents, representing a combination of at least two of the following types of detergents.

Preferably, they are compounds based on metals, selected from the group consisting of calcium, magnesium, sodium, or barium, preferably calcium or magnesium.

They are thanks insoluble salts of metals selected from the group of carbonates of alkaline and alkaline earth metals, preferably calcium carbonate.

These detergents provide additional , which is not provided fatty amines and their derivatives in oils for cylinders in accordance with the invention.

In accordance with the preferred embodiment of the mass content detergents relative to the total mass of the lubricant is chosen so that provided by carbonates metals contributed at least 5 milligrams of sodium hydroxide of potassium per gram lubricant, preferably at least 10 milligrams of sodium hydroxide of potassium per gram of lubricant to the total value of specified lubricant for cylinders.

In accordance with especially preferred embodiment of the mass content and perhaps neutral detergents relative to the total mass of the lubricant is chosen so that in the lubricating matter for cylinders according to the present invention, the contribution of organic provided soap detergents, is at least 5 milligrams of sodium hydroxide of potassium per gram lubricant substances, preferably at least 10 milligrams of sodium hydroxide of potassium per gram lubricant substances.

Preferably, lubricant according to the present invention, contains 50 to 90 wt.% base oil, from 4 to 30 wt.% at least one of the detergent-based alkaline or alkaline earth metals, metal carbonates, possibly in combination with one or more than one neutral detergent, and from 2 to 40 wt.% one or more fatty amine and/or derivatives of fatty amine, as described above.

Lubricants in accordance with the invention may contain one or more functional additive, selected from the dispersal agent, antiwear additives, supplements, antioxidant and/or anti-corrosion additives.

For example, they may contain from 0.01 wt.% up to 6 wt.% preferably from 0.1 wt.% up to 4 wt.% one or more than one antiwear additives.

They can also contain 0.1 wt.% up to 4 wt.% preferably from 0.4 wt% up to 2 wt.% dispersal agent.

Lubricants for cylinders according to the invention preferably have a kinematic viscosity at 100 C, component from 12.5 to 26.1 cSt (grade SAE 40, 50, 60), preferably component from 16.3 to 21,9 cSt (grade 50).

In accordance with especially preferred embodiment of lubricants for cylinders according to the invention have a kinematic viscosity at 100 C, component from 18 to 21.5 FTAs, preferably from 19 to 21.5 FTAs.

Preferably, lubricants, cylinders according to the invention, contains from 60% to 90% relative to the total mass of lubricating substances, mixtures of one or more of the base oil, relating to the Groups 1-5 according to the nomenclature of the American petroleum Institute (API - American Petroleum Institute), preferably Groups 1 or 2 according to the same item.

This mixture of base oils can contain from 10 to 25 wt.% of the total mass of the lubricant base oil Group I type BSS (distillation residue, which has a kinematic viscosity at 100 degrees approximately 30 mm 2 /s, usually from 28 to 32 mm 2 /s, and with a density at 15 C, component from 895 to 915 kg/m 3 ), and 50-70% of mass of the total mass of the lubricant base oil Group I, belonging to neutral in relation to the solvent (Solvent Neutral type (product distillation, with a density at 15 C, component from 880 to 900 kg/m 3 , with kinematic viscosity at 100 C about 11 mm 2 /s SN 500, or approximately 12 mm 2 /s SN 600).

In accordance with another embodiment in oils for cylinders in accordance with the invention of the underlying(s) oil(as) is partially or completely replaced(s) one or more than one a thickener and/or improving YVES (viscosity index) polymers.

Another task for the invention relates to the application of the lubricant, described above, as the only lubricant for cylinders that can be used with any type of liquid fuel sulfur is less than 4,5%; preferably, the sulfur content in the specified liquid fuel constitutes from 0.5 to 4%of mass.

Preferably, one and the same lubricant for cylinders according to the invention can be used as liquid fuel with a sulphur content of less than 1.5%of mass, and liquid fuel with a sulphur content of more than 3 wt.%, or even more than 3.5%of mass.

In accordance with the preferred embodiment of the same lube for cylinders according to the invention can be used as liquid fuel with a sulphur content of less than 1%mass, and liquid fuel with a sulfur content greater than 3%of mass.

Another task for the invention relates to the application of the lubricant, described above, for the corrosion prevention and/or reduction of deposition of insoluble salts of metals in the two-stroke marine engines during combustion of any type of liquid fuel sulfur is less than 4.5%of mass.

In accordance with another task of the invention refers to the application of one or more call of low-soluble fatty amines and their derivatives, such as fatty amines and their derivatives, described above, to provide an alternative , without education any solid metal deposits in lubricating substances for cylinder two-stroke marine diesel engines with , measured according to ASTM D 2896 greater than or equal to 15, preferably more than 20, preferably more than 30, it is most preferable to more than 40 milligrams of sodium hydroxide of potassium per gram of lubricant.

Another task of the invention refers to a method of manufacture of lubricant described above, where the bold(e) Amin(s) and/or their derivatives add in the form of separate components of the lubricant for cylinders with , as determined in accordance with ASTM D 2896 greater than or equal to 15, preferably more than 20, preferably more than 30, it is most preferable to more than 40 milligrams of sodium hydroxide of potassium per gram of the lubricant, which may include one or more functional additive.

According to one embodiment of the lubricant is prepared by dissolving one or more concentrate supplements for marine lubricants, which include(s) bold(e) Amin(s) and/or their derivatives.

In accordance with another task of the invention refers to concentrate additives for manufacture of lubricant for cylinders with , as determined in accordance with ASTM D 2896 greater than or equal to 15, preferably more than 20, preferably more than 30, it is most preferable to more than 40 milligrams hydroxide per gram of the lubricant of the concentrate has , amounting to 250 to 300, and contains one or more than one bold Amin and/or derivative fatty amine having constituting 150 to 600 mg of potassium hydroxide/g Amin in accordance with ASTM D 2896, where mass content in per cent of these fatty amines and/or derivatives in concentrate is selected so as to obtain the concentrate with the contribution to defined in accordance with ASTM D 2896, ranging from 35 up to 270 milligrams of potassium hydroxide in g concentrate.

Detailed description of the invention

Fatty amines and their derivatives as an alternative to the detergents source :

Fatty amines, used in lubricating substances in accordance with the present invention, are primary, secondary, or tertiary monoamines or polyamines, containing one or more chain, or their derivatives.

These compounds have a private basicity, which enables to apply them as an important source of in lubricating substances, cylinders, as a substitute for detergents, in particular detergents. Own fatty amines and derivatives used in the present invention, measured according to ASTM D 2896, as a rule, is from 150 to 600 milligrams of sodium hydroxide of potassium per gram, preferably from 200 to 500 milligrams of sodium hydroxide of potassium per gram.

They are surfactants type, polar head which consists of a nitrogen atom (and perhaps one or more of the oxygen atom in the case of derivative type and amines), and part consists of aliphatic(their) circuit(s).

Fatty amines mainly derived from carboxylic acids. These acids in the presence of ammonia obtaining NITRILES, which are then subjected to catalytic obtaining primary, secondary or tertiary amines.

Source fatty acids, of fatty amines represent, for example, Caprylic acid, , capric, , , , myristic, , palmitic, margarine, stearic, , arachidonic acid, , , , , , , , , , , or acid or unsaturated fatty acids, such as palm olein, oleic, , , linoleic, a-linolenic, linoleic, di-Homo-with-linolenic, arachidonic, or acid.

Preferred fatty acids obtained by hydrolysis of triglycerides present in vegetable and animal oils, such as copra, palm, olive, peanut, rapeseed, sunflower, soya, cotton or flax oil, beef fat, etc.; natural oils can be genetically modified to increase the content of some fatty acids, for example , rapeseed oil or sunflower oil.

Fatty amines, which are used in lubricating substances in accordance with the invention, preferably derived from natural plant or animal sources. Treatment, which allows to get fatty amines from natural oils, may result in the formation of mixtures of primary, secondary and tertiary monoamines and polyamines.

In lubricants in accordance with the present invention may, for example, be included products containing in different proportions some or all of the connections corresponding to the following formulas:

R-NHCH2-R

R-[NH(CH 2 ) 3 ] 2-NH 2

R-[NH(CH 2 ) 3 ] 2-NH 2

where n is an integer greater than or equal to 1, and R is a fatty chain originating from the fatty(s) acid(lot), present(their) in the original oil. The same fatty monoamines or polyamines can also contain several fatty chains originating from different fatty acids.

These products can also be used in purified form, containing mainly one type of amines, such as mainly .

Thus, it is preferable to use a product consisting of diamines with the formula R-[NH(CH 2 ) 3 ] 2-NH 2 , where R can be represented as a set of fatty acids, originating from a natural source, such as beef fat.

You can also use refined products. For example, it is preferable to use amines derived from oleic acid, in particular with the formula R-[NH(CH 2 ) 3 ] 2-NH 2 , where R is a fatty chain of oleic acid.

So fatty amines in accordance with the present invention preferably include at least one chain consisting of at least 16 carbon atoms, preferably at least 18 carbon atoms.

In order to avoid gelling, which sometimes occurs at high mass content in the lubricating matter of fatty amines, preferred, in particular, are fatty amines, containing 12 to 24 carbon atoms, preferably from 16 to 22 carbon atoms.

amines in accordance with the invention is between 150 and 600, and the minimum number of units provided by these amines, is 10 milligrams of sodium hydroxide of potassium per gram lubricant that allows to use them in the lubricating substance with a minimum content of about 2%of mass. However, this content can a standard way to increase to values of about 20 wt.% for example, providing 40 or more units using amine with 200.

Derivatives of fatty amines:

In lubricating substances according to the present invention, the alternative in relation to detergents may be provided for by derivatives of fatty amines. These derivatives are, for example, ethoxylated amines, obtained by condensation of ethylene oxide with the primary or secondary amines, obtained by the reaction of tertiary fatty amines and hydrogen peroxide, or Quaternary ammonium salts, reproduced by synthesis of tertiary amines.

lubricants according to the present invention,

lubricants according to the present invention, provided neutral or detergents on the basis of alkaline or alkaline-earth metals and one or more bold amine and/or their derivatives.

The value of this , measured according to ASTM D 2896, can be from 5 to 100 mg KOH/g or above. Lubricant with a fixed value selected depending on the conditions of use of this lubricant, in particular in accordance with the content of sulphur in the use of liquid fuel and lubricants for cylinders.

Lubricants in accordance with the present invention are suitable for use as lubricants for cylinders, regardless of the content of sulphur in fuel oils used as fuel in the engine.

Thus, lubricants for cylinder two-stroke marine engines in accordance with the invention have greater than or equal to 15, preferably more than 20, preferably more than 30, more preferably more than 40, preferably constitutes from 40 to 80.

In accordance with the preferred embodiment of the invention oiling the composition has the value , measured according to ASTM D 2896, suitable for use with sour liquid fuel having a sulphur content of 4.5%mass, that is ranges from 65 to 75, or even 70.

In accordance with another embodiment lubricants according to the present invention, 45 to 60, preferably from 45 to 55, or even equal to 50.

According to one embodiment of lubricants according to the present invention is between 55 to 60, or even equal to 57, or even equal to 55.

In lubricating substances according to the present invention, the contribution to the provided fatty amines and derivatives, at least 10 units, preferably at least 20 units, preferably at least 30 units, even more preferably at least 40 units. Contribution to provided by bold Amin in the lubricating matter (in milligrams sodium hydroxide of potassium per gram end of the lubricant, or "units" ), calculated on the basis of his own , in accordance with ASTM D 2896, and its mass content in percentage in the finished lubricant matter:

Amin lubricating =. Amin /100

Amin lubrication. =the contribution of Amin in in the finished lubricant matter

x=% by weight of Amin in the finished lubricant matter

Amin =own Amin himself (ASTM D 28-96).

Thus, in the case of a lubricant with 70 according to the present invention, fatty amines and derivatives provide a minimum of 14% . In the case of a lubricant with 55 according to the present invention, fatty amines and derivatives provide a minimum of 18% . In the case of a lubricant with 40 according to the present invention, fatty amines and derivatives provide at least 25% .

Because these fatty amines and their derivatives have ranging from 100 to 600, preferably from 200 to 400, the mass content in percentage of these compounds in lubricating substances according to the present invention is more than 1.7% (10 units provided by amine with 600), as a rule, more than 2%.

The inclusion of amines with a high content can also lead to problems with toxicity.

To prepare lubricants suitable in case of the high and the low content of sulfur, as a rule, work with about 55 or 57, 70, where at least 10 units provided detergents. Thus, as a maximum, 60 units usually provide the fatty amines, which corresponds to the maximum mass content in percentage of fatty amines about 10, 15, 30, or 40% for amines 600, 400, 200, 150, respectively.

Suddenly the applicant also found that only lubricants, in which the contribution of the make and amines and detergents, demonstrate satisfactory efficiency (i.e. in the order of 100 or more), up to a maximum level secured by metal carbonates detergents.

Not wanting to be subject to any theory, the Complainant believes that these metal carbonates, which form the last reserve of basicity for use as a lubricant for cylinders with high content of sulphur, have slow kinetics of neutralization of sulfuric acid compared with Soaps and amines.

Thus, the contribution of the provided by carbonates metals originating from detergents, is in lubricating substances according to the present invention, as a maximum of 20 units (20 milligrams of potassium hydroxide gram-lubricant). This contribution in , hereinafter designated "carbonate " or "CaCO 3 , " measured in accordance with the method described in Example 1 below.

The composition of conventional oils with greater than or equal to 40, in accordance with the invention, thus, changed by replacing fatty amines on detergents in such a way that they provide at least 10 units lubricant, preferably at least 30 units lubricant, which gives the possibility to prevent corrosion problems when using liquid fuel (about 4, 5 wt.%).

It also appears the possibility of reducing sediment formation of insoluble salts of metals, providing (such as CaCO3 ), in the case of the use of low sulphur liquid fuels (1,5 wt.% and less). This decrease is directly related to the decrease detergents, was possible due to the structure of the composition in accordance with the present invention.

Thus, lubricants according to the present invention, in particular with , ranging from 65 to 75, for example 70, can be used with sour and liquid fuel.

or detergents

The detergents used in lubricating compositions in accordance with the present invention are well known to specialists in the field of technology.

Detergents, usually used in the manufacture of lubricating compositions, are, as a rule, anionic compounds containing a long lipofilnuu hydrocarbon chain and head. Associate cation, as a rule, represents a radical cations of alkali or alkali earth metal.

Detergents preferably chosen from the salts of alkali or alkali earth metal and a carboxylic acid, sulphonates, salicylates, and .

Alkaline and alkaline-earth metals preferably is a calcium, magnesium, sodium or barium.

These salts of metals may contain metal approximately stoichiometric quantity. In this case, detergents are referred to as "" or "neutral", although they still provide some basicity. These "neutral" detergents, as a rule, have , measured according to ASTM D2896, less than 150 mg KOH/g or less than 100, or even less than 80 mg KOH/g

This type of so-called neutral detergents may partially contribute to the lubricants in accordance with the present invention. For example, use neutral detergents, such as carboxylates, sulfonates, salicilata, , of alkali and alkali-earth metals such as calcium, sodium, magnesium, or barium.

When the metal is present in abundance (in an amount greater than the stoichiometric number), this is called a . Their is high, more than 150 mg KOH/g, and typically ranges from 200 to 700 mg KOH/g, typically ranging from 250 to 450 mg KOH/g

The excess of metal, which provides nature of detergent, presented in the form of salts of metals, which are not soluble in fuel, for example carbonate, hydroxide, oxalate, acetate, glutamate, preferably carbonate.

In the same detergent fiber metals of these insoluble salts may be the same or different from the metal of low-soluble detergent. They are preferably chosen from calcium, magnesium, sodium, or barium.

These micelles can contain one or more type of insoluble salts of metals, stable one or more than one type of detergent.

detergents containing one type of soluble salts of metal with detergent and, as a rule, are named according to the nature of the hydrophobic chains specified detergent.

Thus, they considered relevant to , , or type depending on whether this is a detergent, respectively, phenolate, salicylate, sulfonate or .

detergents considered relevant to the mixed type, if micelles contain several types of detergents, the differing nature of their hydrophobic chains.

For use in oiling compositions in accordance with the present invention of oil-soluble metal salts preferably represent , sulfonates, musk and mixed phenolate - detergents and/or salicylates calcium, magnesium, sodium, or barium.

Insoluble salts of metals, providing nature, are carbonates of alkali and alkali earth metal, preferably calcium carbonate.

detergents used in lubricating compositions in accordance with the present invention, preferably represent , sulfonates, musk and mixed phenolate - sulfonate - detergents, calcium carbonate.

provided by detergents. in lubricating substances according to the invention:

In lubricating substances according to the present invention, the part provided insoluble salts of metals and detergents, in particular metal carbonates.

Thus, the mass content detergents relative to the total mass of the lubricant is chosen so that the contribution to the total specified lubricant for cylinder base number, secured by metal carbonates, is, as a maximum, 20 milligrams of sodium hydroxide of potassium per gram of lubricant.

provided by metal carbonates, measure for detergent separately and/or in the finished matter in accordance with the method described in Example 1. As a rule, in detergent fiber provided by metal carbonates, ranges from 50 to 95% of the total detergent separately.

These insoluble salts of metals also have a favorable anti-wear effect if they are supported dispersed in matter in the form of stable micelles, what happens when they are present in abundance on the number of sulfuric acid, which must be neutralized during operation.

Thus, in accordance with the preferred embodiment of the invention insoluble salts of metals with detergents provide at least 5 milligrams of sodium hydroxide of potassium per gram lubricant (or 5 "units ") in lubricating substances according to the present invention, preferably at least 10 units .

In addition to these detergents that are metal-containing soap essentially or or type, also contribute to the lubricants according to the present invention. This contribution in , hereinafter referred to as "organic ", are both neutral and from detergents.

These metal-containing soap from his side have a positive impact on the behavior of lubricants for cylinders in thermal loads. Thus, it is preferable that some part of lubricants according to the present invention, provided the specified Soaps.

In accordance with the preferred embodiment of the lubricating substances for cylinders in accordance with the present invention organic provided Soaps, contributed at least 5 milligrams of sodium hydroxide of potassium per gram lubricant, preferably at least 10 milligrams of sodium hydroxide of potassium per gram of lubricant.

Thus, lubricants according to the present invention, measured according to ASTM D289, includes at least 3 separate components:

- provided fatty amines, defined as a function of amines, measured according to ASTM 2896, and mass content in percentage of fatty amines.

- provided insoluble salts of metals with detergents, called in a broader sense "carbonate " or "CaCO 3 "and the measured using the method described in Example 1 below.

- "Organic" provided Soaps and perhaps a neutral detergent, obtained as a difference between total lubricant and other components that contribute to.

Base oils

In General, base oils, used for the manufacture of lubricants in accordance with the present invention may constitute mineral oil, synthetic, or plant origin and their blends.

Mineral or synthetic oils, mainly used pursuant to this application, refer to one of the classes defined in the classification API, as summarized in the table below.

The content of saturated components

Sulfur content

Viscosity index

Group 1 Mineral oil

>0,03%

80≤YVES<120

Group 2 Subjected to complex oil

& GE; 90%

80≤YVES<120

Group 3 oil

& GE; 90%

PJSC (poly-alpha-olefin)

The other grounds are not included in the main group 1-4

Mineral oils in Group 1 can be obtained by the distillation of the selected naphthenic or paraffin crude oil, then by cleaning these products distillation using techniques such as the extraction solvent, solvent or catalytic , or hydrogenation.

Oil in Groups 2 and 3 have been obtained using heavier cleaning methods, for example by a combination of , hydrocracking, catalytic hydrogenation and dewaxing.

Examples of synthetic bases in Groups 4 and 5 include -olefins, , and benzenes.

These base oils can be used individually or in a mixture. Mineral oil can be combined with synthetic oil.

Cylinder oils for two-stroke marine diesel engines have a stamp on the viscosity of the SAE 40 to SAE-60 (classification SAE - Society of Automotive Engineers), as a rule SAE 50 is equivalent to the kinematic viscosity at 100 C, component from 16.3 to 21.9 mm 2 /c.

Oil grade 40 have a kinematic viscosity at 100 C, component from 12.5 to 16.3 FTAs.

Oil of mark 50 have a kinematic viscosity at 100 C, component from 16.3 to 21,9 FTAs.

Oil grade 60 have a kinematic viscosity at 100 C, component from 21.9 to 26.1 FTAs.

In accordance with industry practice is preferable to receive structures cylinder oils for two-stroke marine diesel engines, having a kinematic viscosity at 100 C, component from 18 to 21.5, preferably from 19 to 21.5 mm 2 /s (cSt).

This viscosity can be obtained with a mixture of additives and base oil, for example, containing the mineral bases of Group 1, such as neutral to the solvent base (for example SN 500 or SN 600), and high-viscosity residual oil. You can use any other combination of a mineral or synthetic the bases, or the grounds of plant origin, possessing in mixtures with viscosity additives, compatible with the class SAE 50.

As a rule, the standard composition of the lubricant for the cylinders for low-speed two-stroke marine diesel engines class SAE 40 - SAE 60, preferably SAE 50 (in accordance with the classification SAE J300) and includes at least 50% of mass lube base oil mineral and/or synthetic origin, suitable for use in ship engines, for example, related to the Group 1 according to the classification of the API that is obtained by the distillation of selected crude oil, then clear these distillation products using techniques such as the extraction solvent, solvent or catalytic , or hydrogenation. Their viscosity index (BPI) is from 80 to 120; the content of sulfur in it is more than 0,03% and the content of saturated components is less than 90%.

As a rule, the standard composition of the lubricant for the cylinders for low-speed two-stroke marine diesel engines includes 18-25% of mass respect to the total mass of the lubricant base oil Group I type BSS (distillation residue, which has a kinematic viscosity at 100 C approximately 30 mm 2 /s, usually from 28 to 32 mm 2 /s, and with a density at 15 C, component from 895 to 915 kg/m 3 ), and 50-60%of mass respect to the total mass of lubricating substances in Group I of base oil type SN 600 (product distillation with a density at 15 C, component from 880 to 900 kg/m 3 , and with a kinematic viscosity at 100 C for approximately 12 mm 2 /s).

supplements:

The Complainant has shown that the introduction of significant quantities of fatty amines (usually approximately 5-15%of mass, or more than 10%mass, or even the order of 20 wt.%) in lubricants according to the present invention has the effect of reducing the viscosity of the lubricant. Thus, it may be necessary in particular in the case of a higher content of amines enter lubricants according to the present invention, and/or improve viscosity index polymers having the effect of increasing the viscosity of the lubricant. This allows lubricants for cylinder having appropriate for their application viscosity grade.

Thus, according to one embodiment of the lubricating substances for cylinders according to the present invention, the basic(s) of oil(a) are fully owned by one or more than one addition, the role of which is to increase the viscosity of the composition in a warm and a cold condition, or the additives improving viscosity index (BPI).

These additives most often represent low-molecular-weight polymers order 2000-50000 Dalton (MM).

These can be chosen from polyisobutylene (about 2000 Dalton), polyacrylate or (about 30,000 daltons), olefin copolymers, olefin and alpha-olefin copolymer of ethylene-propylene , , high molecular weight poly-alpha-olefins (viscosity at 100 C 150) or styrene-olefin copolymers, hydrogenated or .

In lubricating substances for cylinders according to the present invention, the polymers used for partial or full replacement of one or more than one base oil, preferably represent the above-mentioned type thickeners polyisobutylene (for example, presented on the market under the name Indopol H2100).

They preferred to be present in the amount of 5-20% of mass in lubricating substances for cylinders according to the invention, preferably from 8 to 20% in the case of Amina more than 15 wt.%.

Antiwear additives:

Lubricants according to the present invention contain at equivalent fewer detergents compared with those in the standard lubricating substances for cylinders. Thus, lubricant, cylinders 70 usually contains about 25% of mass detergents, whereas in lubricating substances according to the invention with 70 this content can be reduced to approximately 15%, or even be less than 5%.

As mentioned above, these connections can have a positive anti-aging effect. Into force of this lubricants for cylinders according to the invention preferably contain anti-Wear additives.

Antiwear additives protect friction surfaces through the formation of protective film, adsorbed on these surfaces. The most often used zinc or DTPZn. Various phosphorus-, sulphur-, nitrogen, chlorine and boron-containing compounds are also found in this category.

There is a variety of anti-wear additives, but the most frequently used category is a category of supplements containing phosphorus and sulphur, such as metals, in particular zinc, and more specifically zinc or DTPZn. The preferred compounds have the formula (Zn((SP(S)(OR1)(OR 2 )) 2 where R1 and R2 are alkyl groups, preferably containing 1-18 carbon atoms. DTPZn as a rule is present in a quantity of the order of 0.1 to 2%of mass.

and polysulphides, in particular, sulfa olefins, are also commonly used anti-wear additives.

Anti-wear additives and EP additives nitrogen and sulphur type, such as, for example dithiocarbamates metal, in particular molybdenum, also usually present in lubricating compositions. Glycerol esters are also anti-Wear additives. For example, we can mention the mono-, di - and , and .

Anti-wear additives and EP additives are presented in the compositions of lubricants in the amount of 0.01 to 6%, preferably from 0.1 to 4%.

In accordance with the preferred embodiment of lubricants for cylinders according to the present invention, contain at least 0.5 wt.% one or more antiwear additives.

Preferred Antiwear additives are of type DTPZn.

Dispersing agents

Dispersing agents are well known additives used at preparation of lubricating compositions, in particular for use in the marine region. Their main role is to maintain in the suspended condition of particles, initially present or emerging in the lubricating compositions during its use in the engine. They prevent their agglomeration by actions on the steric obstacles. They can also have a synergistic effect in respect of neutralization.

Dispersing agents used as additives in lubricants, as a rule, contain polar group associated with the relatively long hydrocarbon chain, as a rule, contains 50-400 carbon atoms. Polar group usually comprises at least one nitrogen, oxygen or phosphorus.

Connections originating from succinic acid, are dispersing agents, in particular used as additives in lubricants. In particular, the use suktinimida, obtained by condensation of succinic acid anhydrides and amines, esters succinic acid, obtained by condensation of succinic acid anhydrides and alcohols or polyols.

These connections then you can handle the various connections, in particular, sulfur, oxygen, formaldehyde, carbon acids and compounds containing boron and zinc to obtain, for example or blocked zinc .

The Foundation of the Mannich reaction, obtained by polycondensation of phenols, substituted alkyl groups, formaldehyde, and primary or secondary amines are compounds used as dispersing agents in lubricating substances.

According to one embodiment of the present invention is used at least 0,1% of the dispersion agent. Can be used dispersing agent site polyisobutylene , for example or blocked zinc.

Other functional additives

The composition of the lubricant in accordance with the present invention can also contain any functional additives suitable for use, for example typical supplements, compensating effect of detergents detergents, which can be, for example polar polymers such as , , antioxidants and/or corrosion inhibitors, such as metal-organic detergents, or . The latter are known to specialists in the field of technology. These additives are generally contained in quantity from 0,1 up to 5 wt.%.

In accordance with the present invention described compositions of grease refer to connections, taken separately, before mixing, it should be understood that these connections can both save and do not save the same chemical form before and after mixing. Preferably, lubricants according to the present invention, obtained by mixing compounds, taken separately, are not in emulsion form or microemulsions.

Concentration of additives for marine lubricants:

Fatty amines and derivatives contained in lubricating substances according to the present invention, can be particularly included in the lubricant in the form of individual additives. However, fatty amines and derivatives contained in lubricating substances according to the present invention may also be included in concentrate supplements for marine lubricant.

Standard concentrates and additives for marine lubricant for cylinders, as a rule, consist of a mixture of the above components, detergents, dispersing agents, or other functional additives, base oils prior to dilution, in proportions that allow to obtain the diluted in a carrier oil lubricants for cylinder having defined in accordance with ASTM D 2896, greater than or equal to 15, preferably more than 20, preferably more than 30, it is most preferable to more than 40 milligrams of sodium hydroxide of potassium per gram of lubricant. This mixture, as a rule, contains detergent content with respect to the total mass of a concentrate more than 80%, preferably greater than 90%, the content of the dispersion agent is from 2 to 15%, preferably from 5 to 10%, the content of other functional additives makes from 0%to 5%, preferably from 0.1 to 1%. specified concentrates, measured according to ASTM D 2896, typically ranges from 250 to 300 milligrams of potassium hydroxide in g concentrate, typically of the order of 275 milligrams of potassium hydroxide in g concentrate.

In accordance with one of the tasks of the invention refers to concentrate additives for manufacture of lubricant for cylinder having defined in accordance with ASTM, greater than or equal to 15, preferably more than 20, preferably more than 30, more preferably more than 40 milligrams of sodium hydroxide of potassium per gram of the lubricant of the concentrate has , amounting to 250 to 300, and contains one or more bold Amin and/or derivatives of fatty amine with ranging from 150 to 600 mg of sodium hydroxide/g Amin in accordance with ASTM D 2896, where mass content of the percentage specified fatty amines and/or derivatives in concentrate chosen in such a way, to get the concentrate, giving contribution , determined in accordance with ASTM D 2896 of between 35 (14% from 250 to 270 (90% of the 300) milligrams of potassium hydroxide in g concentrate.

In accordance with another embodiment of the mass content in percentage of these fatty amines and/or derivatives in concentrate chosen in such a way, to get the concentrate, giving contribution , determined in accordance with ASTM D 2896 of 60 (25% of 250) and 225 (75% of the 300) milligrams of potassium hydroxide in g concentrate.

In accordance with another embodiment of the mass content in percentage of these fatty amines and/or derivatives in concentrate chosen in such a way, to get the concentrate, giving contribution , determined in accordance with ASTM D 2896 of 135 (55% of 250) to 225 (75% of the 300) milligrams of potassium hydroxide in g concentrate.

Fatty amines in concentrates according to the invention as an alternative to the detergents source are as described above as well as in the examples that follow.

Concentrates in accordance with the invention also contain some amount of base oil, a small but sufficient to facilitate the use of these concentrates additives.

Measurement differences in performance between normal comparative lubricant and lubricant the invention

Certainly, the present invention is not limited to described, and examples presented and incarnations, but can have many variations available to a person skilled in the art.

Examples:

Example 1: this example is for a description of the method for measuring the contribution of insoluble salts of heavy metals, available in , lubricating compositions containing a specified detergents:

The measurement of total basicity (the so-called or base number) of finished lubricants or detergents carry out using the method ASTM D2896. composed of two different forms:

- carbonate provided detergent carbonates metals such as calcium carbonate, hereinafter called the "",

- the so-called organic provided soap detergent, essentially type or the type ether salicylate or sulfonate.

Carbonate , hereinafter referred to as " CaCO3 ", measured in the long oil or individual in accordance with the following procedure. It is based on the principle of attacks carbonate (calcium), sample, sulfuric acid. This carbonate turns into carbon dioxide, according to a response;

Because the volume of the reactor is constant, pressure increases in proportion to the release of CO 2 .

Way: in a reaction vessel with a volume of 100 ml, equipped with a cover, which installed a differential pressure gauge, give the required amount of product, 3 which should be measured, so as not to exceed the limit of measurement differential pressure gauge, which meets the increasing pressure of 600 MB. The number is determined by the schedule in figure 2, specifying for each product weight (from 1 to 10 grams, from right to left in figs) pressure measured on the differential pressure gauge (which corresponds to an increase in pressure due to the release of CO 2 ) depending on the share of in the sample. If the value 3 unknown, then hang a small amount, approximately 4 G. In all cases, the mass of the sample (m).

Reaction vessel may be made of , glass, polycarbonate etc or any other material for heat exchange with the environment, so that the internal temperature of the vessel quickly reach equilibrium with the ambient temperature.

A small quantity of liquid base oil type SN 600 injected into the reaction vessel containing a small magnetic stirrer.

Approximately 2 ml of concentrated sulfuric acid is placed in a reaction vessel, trying not to stir the environment at this stage.

Cover and site gauge screw on the reaction vessel. Thread can be lubricated. Their delay to ensure full closing.

Exercise mixing, which continued for as long as is necessary for stabilization of pressure and to achieve equilibrium temperature of the environment. Sufficient period of 30 minutes. Register to increase the pressure P and the temperature T C C (St).

Site is cleaned with a solvent type.

Calculation method

For pressure calculation using the formula of a perfect gas.

P=Partial pressure of CO2 (PA) (1 PA=10 -2 MB)

V=Volume of the container (m 3 ).

P=8,32 (J).

T=273+σ(C)=(Kelvin).

n=number of mol released WITH 2

Calculation of the number of mol CO 2 .

m* carbonate = mg KOH equivalent.

m = mass of the product in grams

carbonate = expressed in KOH per 1 g equivalent.

released CO 2 , i.e. the number of mol CO 2 released :

The formula for calculating the pressure? depending on carbonate.

The formula for calculation of carbonate on the basis of pressure CO 2

Setting fixed the values that are associated with the test conditions, receive a simplified formula:

PCO 2 =value, read on the differential pressure gauge in mbar=registered R

V = volume of the container in m 3 =0,0001.

R = 8,32 (J).

T = 273+σ(C)=(Kelvin). total=recorded temperature of the environment.

m=mass of the product, introduced into the reaction vessel.

The result is a CaCO3 , expressed in mg KON/g

Example 2: this example is used to describe the test enthalpy, which makes it possible to measure efficiency of lubricants against sulphuric acid.

The presence or availability of main classifications included in the lubricant, in particular in the lubricant, cylinders for two-stroke marine engine relative to the molecules of the acids can be quantitatively determined with the help of dynamic test speed control or the kinetics of neutralization.

Principle:

Acid-base neutralization reactions, as a rule, are exothermic and, therefore, it is possible to measure the output of the heat produced by the reaction of sulphuric acid in lubricating substances, which are tested. This allocation is supervised by an increase in temperature for a long time in reactor type Dewar vessel.

Based on these measurements, you can calculate the index of quantifying the effectiveness of the lubricant according to the present invention, compared with a lubricant used as a comparative, and represents a fixed number of units that must be addressed for a specific added amount of acid. test lubricant preferably is excessive relative to necessary, to neutralise the added amount of acid. To test lubricants with 70 in the following examples add the amount of acid corresponding to the neutralization of 55 units .

Thus, the performance index is calculated relative to the comparative oil, which is assigned a value of 100. It is the ratio of the reaction time for neutralization of comparative (S earlier versions.) and the sample being measured (S Rev ):

Index of neutralizing the effectiveness of=S earlier versions. /S Rev x 100

The value of this time the reaction of neutrality, which are of the order of seconds, define curves to the increase of temperature depending on the time during the neutralization (see the curve in figure 1).

The duration of S is equal to the difference t f-t i honey time at temperature in the end of the reaction and the time when the temperature in the beginning of the reaction.

T i at temperature in the beginning of the reaction corresponds to the first increase in temperature after start mixing.

Time t f at a temperature in the end of the reaction is a time after which the temperature signal remains stable for a period of time equal to or greater than half of the reaction time.

Lubricant is most effective when it provides short neutralization and, consequently, a high index.

Equipment used:

The geometry of the reactor and agitators as well as the conditions of functioning chosen so that they were within the range of chemical, where the diffusion restriction in the oil phase negligibly.

Thus, in your current hardware configuration depth of the liquid layer should be equal to the inner diameter of the reactor, and a spiral mixer should be positioned approximately 1/3 up to the level of liquid.

The equipment consists of adiabatic reactor 300 ml cylindrical type with inner diameter of 52 mm and internal height of 185 mm, with a stirring rod, equipped screw with inclined blades, 22 mm in diameter; blade diameter is from 0.3 to 0.5 relative to the diameter of the Dewar vessel, i.e. from 15.6 to 26 mm

The position of the screw is fixed at a distance of approximately 15 mm from the base of the reactor. Mixing system is driven by a motor with variable speed from 10 to 5000 rpm and a registration system temperature depending on time.

This system is suitable for measuring the response time from about 5 to about 20 seconds and to measure the increase of temperature of several tens of degrees, from a temperature of about 20 C-35 C, preferably approximately 30 degrees C. Position of the system of registration of temperature in the Dewar vessel is fixed.

Mixing system controlled in such a way that the reaction takes place in chemical range: in the configuration of the equipment according to the present invention, the fan speed is controlled at the level of 2000.min, and the position of the system is fixed.

In addition, the range of chemical reactions also depends on the level of oil is placed in the Dewar vessel, which should be equal to the diameter of the flask, and that fits the context of this experiment is that the mass of the test substance approximately 86,

For testing lubricants with 70 placed in the reactor amount of acid corresponding to the neutralization of 55 units .

4,13 g 95% of concentrated sulfuric acid and 85.6 g tested lubricant placed in the reactor in the event of lubricant with 70.

After placing the mixing system inside the reactor so that acid and lubricant mix well and reproduced in the two tests, start mixing for monitoring of the reaction in the chemical range. System for reading of data is a constant.

Implementation of test enthalpy - calibration:

To calculate the indexes of the efficiency of lubricants in accordance with the present invention using the above method, the authors of the invention chosen as a comparative neutralization reaction time measured for cylinder oils for two-stroke marine engine with 70 (measured according to ASTM D 2896), not containing fatty amines, in accordance with the present invention.

This oil is obtained from the mineral Foundation formed by mixing the product distillation, having a density at 15 C, component from 880 to 900 kg/m 3 , with the remainder of distillation, having density, component from 895 to 915 kg/m 3 (high viscosity residual oil) at a ratio of "product of the distillation/balance equal to 3.

To this Foundation type concentrate containing calcium sulfonate with equal to 400 mg KOH/g dispersing agent and phenolate calcium equal to 250 mg KOH/g This oil is prepared in a special way to achieve neutralizing capacity, sufficient for use with liquid fuel with high sulphur content, namely S contents more than 3% or even 3.5%.

Comparative lubricant contains 25,50% by weight of this concentrate. It equal to 70 is provided solely detergents ( and sulfonates), contained in this concentrate.

This comparative lubricant has a viscosity at 100 C, component from 18 to 21.5 mm 3 /C.

Time of reaction of neutralization of this oil (comparative Href) is 10,59 seconds, and index it neutralizing the effectiveness of a fixed value of 100.

Example 3: this example describes by comparing the impact of secured by metal carbonates, on the performance of cylinder oils, namely on their efficiency.

In this example, use multiple cylinder oils A, B, and C with 70 , in which part of is provided, as in the comparative oil, at the expense of concentrate detergents, and the other part is provided by a mixture of fatty polyamines, derived from beef fat, containing mainly palmitic, stearic and butyric acids. This mixture of amines has 460 mg KOH/g It consists of compounds with the formula K[NH-(CH 2 ) 3 ] n NH 2 , where R is a chain fatty palmitic, stearic or oil acids and n is an integer, constituting from 0 to 3.

Comparative oil is oil 70 for two-stroke marine engine named in the preceding example, the Href.

Table 1 below summarizes all of the characteristics of the comparative oil and tested samples, as well as all the values of their performance indices.

mass % songs

Concentrate + sulfonates

Fatty (poly)amines, 460 mg KOH/g, ASTM D2896

Base oils of Group 1

Properties

KB 100 (kinematic viscosity) (cSt), ASTM D445

KB 40 (cSt), ASTM D445

RUR 221.1

Total (mg KOH/g, ASTM D 2896)

From it provided fatty amines (mg KOH/g, ASTM D 2896)

0 (0% )

11,50 (16%)

34,50 (47%)

From it provided by CaCO 3 (mg KOH/g)

51,0 (74% )

42,6 (60%)

34,2 (49%)

25,8 (35%)

Index of neutralizing the effectiveness (IE)

It should be noted that the index of neutralizing the effectiveness of the lubricant is significantly lower than 100, when the contribution of provided by metal carbonates, is more than 20 milligrams of sodium hydroxide of potassium per gram of lubricant.

Example 4: this example in accordance with the invention describes the impact of the contribution made to metal carbonates, on the parameters of cylinder oils, namely efficiency.

Comparative oil is oil 70 for two-stroke marine engine, named in Example 1, the Href.

Oil with G J contain as an alternative source of for detergents compound containing mainly bold diamine obtained from oleic acid, having a formula RNH(CH 2 ) 3 NH 2 , where R is a fatty chain of oleic acid. this connection is 320 mg KOH/g (Dinoram About).

Oil and L contain as an alternative source of for detergents compound containing mainly bold With 16 Amin type dimethyl--Amin. this connection is 200 mg KOH/g (Genamine 16R).

Fatty amines in this example, provide approximately 40 units of the total value of 70, approximately 57%. The remaining provided detergents type neutral phenolate, phenolate and sulfonate.

It should be noted that the index of neutralizing the effectiveness of the lubricant is more than 100 in the case when the contributions to the value metal carbonates, is less than 20 milligrams of sodium hydroxide of potassium per gram of lubricant.

In addition, it should be noted that oil G demonstrates a moderate anti-wear effect (as measured, for example, in a test ASTM D2670, effected in the device with a rod and a V-shaped blocks FALEX) compared with the comparative Href. Thus, the carried out attempts to compensate the decrease in antiwear characteristics by adding antiwear additive type DTPZn to oils H, I, J, K and L.

This decrease operational characteristics is probably due to a reduction of detergents, which in the form of stable micelles have a positive anti-aging effect (on the contrary, if micelles , for example when detergents are in abundance in relation to the amount of acid produced during operation, the formation of solid metal deposits that cause wear).

Characteristics and operating parameters of oils obtained in this manner are summarised in Table 2. Oil, H, I, J and K are the preferred oil in accordance with the invention, possessing performance index, comparable or even greater than the comparative oil and viscosity gives possibility to use as a lubricant for cylinders.

mass % songs

and/or sulfonates

Neutral

Fatty oleic acid, 320 mg KOH/g, ASTM D2896

Genamine 16 R 200 mg KOH/g, ASTM D2896

Base oils of Group 1

Polyisobutylene Indopol H2100

Dispersing agent

Properties

KB 100 (cSt), ASTM D445

KB 40 (cSt), ASTM D445

Total (mg KOH/g, ASTM D 2896.)

From it ,

provided fatty amines (mg KOH/g, ASTM D 2896)

From it provided by SASO 3 (mg KOH/g)

51,0 (74% )

16,9 (24%)

16,9 (24%)

16,9 (23%)

16,0 (23%)

16,9 (24%)

16,9 (24%)

Index of neutralizing the effectiveness of (FROM)

1. Lubricant for cylinder having (total base number), as determined in accordance with ASTM D 2896 greater than or equal to 15 mg hydroxide potassium per gram lubricant containing: a) one or more lube base oil for ship engines, b) at least one detergent based on alkaline or alkaline-earth metals, metal carbonates, possibly in combination with one or more neutral detergent, in one or more bold amine containing 16 to 22 carbon atoms and has , as determined in accordance with ASTM D 2896, constituting from 150 to 600 mg hydroxide potassium per gram, with a mass content in per cent of fatty amines respect to the total mass of the lubricant is chosen so that the contribution of provided by these compounds, in General specified lubricant for cylinder was at least 10 mg hydroxide potassium per gram of lubricant, and the mass content in percentage detergents respect to the total mass of the lubricant is chosen so that the contribution of provided by carbonates metals, in General specified lubricant for cylinder was, as a maximum, 20 mg hydroxide potassium per gram of lubricant.

2. Lubricant for cylinders of claim 1, wherein oil-soluble fatty amines have , as determined in accordance with ASTM D 2896, constituting from 200 to 500 mg hydroxide of potassium per gram.

3. Lubricant for cylinders of claim 1, wherein the mass content in percentage of fatty amines respect to the total mass of the lubricant is chosen so that the contribution of provided by these compounds, in General specified lubricant for cylinder was at least 30 mg hydroxide potassium per gram of lubricant.

4. Lubricant for cylinders of claim 1, wherein the mass content in percentage of fatty amines respect to the total mass of the lubricant is chosen so that provided by these compounds, was at least 15% specified lubricant for cylinders.

5. Lubricant for cylinders of claim 1, wherein the mass content in percentage of fatty amines respect to the total mass of the lubricant is chosen so that provided by these compounds, was at least 30% specified lubricant for cylinders.

6. Lubricant for cylinders of claim 1, wherein the mass content in percentage of fatty amines respect to the total mass of the lubricant is chosen so that provided by these compounds, constituted at least 50% specified lubricant for cylinders.

8. Lubricant for cylinders of claim 1, wherein (s) bold(s) Amin(s) received from palms, olives, peanuts, conventional or oilseed rape, conventional or oilseeds sunflower, soybeans or cotton-seed oil, beef fat, or of palmitic, stearic, oleic, linoleic or acid.

9. Lubricant for cylinders of claim 1, wherein (e) bold(e) Amin(s) are derived from fatty acids, containing from 16 to 18 carbon atoms.

10. Lubricant for cylinders of claim 1, wherein the fatty amines are polyamines, corresponding to General formula R-[NH(CH 2 ) 3 ] n-NH 2 , where n is an integer from 1 to 3, and R is a fatty chain saturated or unsaturated fatty acids, containing at least 16 carbon atoms.

11. Lubricant for cylinder to 10, where R is a fatty chain of oleic acid.

12. Lubricant for cylinders of claim 1, wherein the fatty amines are , corresponding to General formula R-NH-CH(2 ) 3-NH 2 , where R is a fatty chain saturated or unsaturated fatty acids, containing at least 16 carbon atoms.

13. Lubricant for the cylinder 12, in which R is a fatty chain of oleic acid.

14. Lubricant for cylinders of claim 1, wherein and/or neutral detergents selected from carboxylates, sulphonates, salicylates, , , and mixed detergents containing a combination of at least two of these types of detergents.

15. Lubricant for cylinders of claim 1, wherein and/or neutral detergents are compounds based on metals, selected from the group consisting of calcium, magnesium, sodium, or barium.

16. Lubricant for the cylinder item 15, which and/or neutral detergents are compounds based on metals, selected from the group consisting of calcium, magnesium.

17. Lubricant for cylinders of claim 1, wherein detergents insoluble salts of metals, selected from a group of carbonates of alkaline and alkaline earth metals.

18. Lubricant for cylinders of claim 1, wherein the mass content in percentage detergents respect to the total mass of the lubricant is chosen in such a way that the contribution provided by carbonates metals, in General specified lubricant for cylinder was at least 5 mg hydroxide potassium per gram of lubricant.

19. Lubricant for the cylinder see item 18, in which the mass content in percentage detergents respect to the total mass of the lubricant is chosen in such a way that the contribution provided by carbonates metals, in General specified lubricant for cylinder was at least 10 mg hydroxide potassium per gram of lubricant.

20. Lubricant for cylinders of claim 1, wherein the mass content in percentage and perhaps neutral detergents respect to the total mass of the lubricant is chosen in such a way that the contribution of organic provided by detergent Soaps, lubricating substances for cylinders in accordance with this invention was at least 5 mg hydroxide potassium per gram of lubricant.

21. Lubricant for the cylinder 20, in which the mass content in percentage and perhaps neutral detergents respect to the total mass of the lubricant is chosen in such a way that the contribution of organic provided by detergent Soaps, lubricating substances for cylinders in accordance with this invention was at least 10 mg hydroxide potassium per gram of lubricant.

22. Lubricant for cylinders according to claim 1, characterized in that it is the kinematic viscosity, measured according to ASTM D445 at 100 C, is from 12.5 to 26.1 FTAs.

23. Lubricant for the cylinder p.22, notable for its kinematic viscosity, measured according to ASTM D445 at 100 C, is from 16.3 to 21,9 FTAs.

24. Lubricant for cylinders of claim 1, wherein the one or more base oil partially or completely replaced by one or more polymers, which are thickeners and/or improving viscosity index (BPI).

25. The application of a lubricant for cylinder on any one of claims 1 to 24 as the only lubricant for cylinders that can be used with a liquid fuel having a sulfur content less than 1.5%by weight, and with a liquid fuel having a sulfur content greater than 3.5%.

26. The application of a lubricant for cylinder on any one of claims 1 to 24 as the only lubricant for cylinders that can be used with a liquid fuel having a sulfur content less than 1 wt.%, and with a liquid fuel having a sulfur content greater than 3%by weight.

27. Apply the lubricant to any one of claims 1 to 24 to prevent corrosion in the two-stroke marine engines during combustion of any type of liquid fuel sulfur less than 4.5 wt.%.

28. Apply the lubricant to any one of claims 1 to 24 for reducing the formation of insoluble deposits of salts of metals in the two-stroke marine engines during combustion of any type of liquid fuel sulfur less than 4.5 wt.%.

29. Concentrate additives for preparation of the lubricant for cylinders with , as determined in accordance with ASTM D 2896 greater than or equal to 15 mg hydroxide potassium per gram of the lubricant of the concentrate has , amounting to 250 to 300, and contains one or more bold Amin with , ranging from 150 to 600 mg of potassium hydroxide/g Amin in accordance with ASTM D 2896, where mass content in per cent of these fatty amines in concentrate is selected so as to provide input for the specified concentrate, determined in accordance with ASTM D 2896 of between 35 up to 270 mg of potassium hydroxide in g concentrate.