KR20170052703A - Lubricating composition - Google Patents

Abstract

The present invention provides a lubricating composition comprising a base oil and a detergent; Wherein the detergent comprises 30 mol% or more (based on the total amount of detergent) of a sulfonate detergent having a B1SI (base) of 0.1 to 80 mg KOH / g; Wherein the detergent comprises 30 to 70 mole% (based on the total amount of detergent) of phenate detergent; Wherein the lubricating composition comprises at least 4 wt% detergent based on the total weight of the composition; Wherein the lubricating composition has a TBN (transfer rate) of at least 10 mg KOH / g (according to ASTM D 2896).

Description

[0001] LUBRICATING COMPOSITION [0002]

The present invention relates to a lubricating composition, in particular a lubricating composition for use in an internal combustion engine operated under continuous high load conditions such as marine diesel engines and power applications. More particularly, the present invention relates to marine lubricants.

Marine lubricants are known in the art. For example, EP 1 086 195 discloses a marine cylinder oil composition comprising a lubricating base oil and an overbased detergent component, said composition having a TBN of 50-90 and said detergent component having a viscosity of at least 180 cSt Viscosity and an overbased calcium sulfonate having a TBN of about 400 or greater.

Lubricating compositions used in internal combustion engines suffer from high levels of stress. The lubricating composition provides good lubrication properties under various conditions, amongst which it helps to keep the engine clean, provides thermally and oxidatively stable, provides good wear, corrosion protection, and transports heat from the engine It is important.

Due to the fact that marine engines are typically operated continuously at remote locations often for long periods of time under near-charge conditions, the lubricating compositions used in marine diesel engines are subject to particularly high levels of stress. In addition, since there is little or no chance of changing the lubricating composition in a marine engine, the lubricating composition must have a long life.

The term "marine" will be recognized in the art as not being limited to engines used in marine vessels. That is, the term also includes engines used in power generation applications. These high-grade, fuel-efficient, low-speed and medium-speed marine and stationary diesel engines operate at high pressure, high temperature and long-stroke.

It is an object of the present invention to improve the precipitation forming properties of lubricating compositions, particularly those used in internal combustion engines such as marine diesel engines.

It is a further object of the present invention to provide alternative lubricating compositions for use in internal combustion engines.

It is to be understood that one or more of the above or other objects,

Base oil; And

- detergent;

≪ RTI ID = 0.0 > and / or < / RTI >

Wherein the detergent comprises 30 mol% or more (based on the total amount of detergent) of a sulfonate detergent having a BN (base) of 0.1 to 80 mg KOH / g;

Wherein the detergent comprises 30 to 70 mol% of phenate detergent (based on the total amount of detergent);

Wherein the lubricating composition comprises at least 4 wt% detergent relative to the total weight of the composition;

Wherein the lubricating composition is at least 10 mg KOH / g of TBN (according to ASTM D 2896).

It has now surprisingly been found in accordance with the present invention that the lubricating composition according to the present invention exhibits improved precipitate formation control properties when measured according to DIN 51392 and Komatsu high temperature tube test.

There is no particular limitation on the base oil used in the lubricating composition according to the present invention, and various conventional mineral oils and synthetic oils as well as naturally occurring esters such as vegetable oils can be conveniently used.

The base oils used in the present invention may conveniently comprise a mixture of one or more mineral oils and / or one or more synthetic oils; Thus, according to the present invention, the term "base oil" may mean a mixture containing more than one base oil. Mineral oils include solvent-treated or acid-treated mineral oil-based lubricants and liquid petroleum of the paraffin, naphthene, or mixed paraffin / naphthene type that can be further refined by hydrofinishing and / or dewaxing do.

Base oils suitable for use in the lubricating oil composition of the present invention are group I-III mineral oil base oils, Group IV poly-alpha olefins (PAO), Group I-III Fischer-Tropsch base oils and mixtures thereof .

In the present invention, the terms "Group I", "Group II", "Group III" and "Group IV" refer to a lubricant base oil according to the definition of Category I-IV of the American Petroleum Institute (API). These API categories are defined in [API Publication 1509, 15th edition, Appendix E, April 2002].

Base oils derived from Fischer-Tropsch are known in the art. The term "Fischer-Tropsch derived" means that the base oil is the synthetic product of the Fischer-Tropsch process or is derived therefrom. The base oil derived from the Fischer-Tropsch can also be referred to as a gas-to-liquid (GTL) base oil. Suitable base oils from Fisher-Troughshoe which may conveniently be used as base oils in the lubricating compositions of the present invention are described, for example, in EP 0 776 959, EP 0 668 342, WO 97/21788, WO 00/15736, WO 00/14188, WO WO 00/14187, WO 00/14183, WO 00/14179, WO 00/08115, WO 99/41332, EP 1 029 029, WO 01/18156 and WO 01/57166.

Synthetic oils include hydrocarbon oils such as olefin oligomers (e.g., polyalphaolefin base oils; PAO), dibasic acid esters, polyol esters, polyalkylene glycols (PAG), alkylnaphthalenes and waxes waxy isomerates. Synthetic hydrocarbon base oils sold under the name "Shell XHVI" (trademark) by the Shell group can be conveniently used.

Poly-alpha olefin base oils (PAO) and their preparation are known in the art. Preferred poly-alpha olefin base oils that may be used in the lubricating compositions of the present invention may be derived from linear C ₂ to C ₃₂ , preferably C ₆ to C ₁₆ alpha olefins. Particularly preferred feedstocks for the poly-alpha olefins are 1-octene, 1-decene, 1-dodecene and 1-tetradecene.

The total amount of base oil included in the lubricating composition of the present invention is preferably in an amount in the range of 60 to 99 wt%, more preferably in an amount in the range of 65 to 98 wt%, and most preferably, Is present in an amount ranging from 70 to 95 wt%.

According to a preferred embodiment of the present invention, the base oil contains 50 wt% or more, preferably 60 wt% or more, more preferably 70 wt% or more of Group-III base oil based on the total amount of the base oil.

No particular limitation is imposed on the detergent used in the lubricating composition according to the present invention (however, the requirements of claim 1 are fulfilled), and various conventional detergents can be conveniently used. The term "detergent" may refer to a single detergent or may refer to a mixture containing two or more different detergents. Examples of detergents that can be used are the neutral and over-based sulfonates of metals, especially alkaline or alkaline earth metals such as sodium, potassium, lithium, especially calcium and magnesium, phenates, , Thiophosphonates, salicylates and naphthenates and other useful carboxylates. A preferred metal detergent is a neutral and overbased detergent having a Total Base Number (TBN) (according to ASTM D2896) of 450 mg KOH / g or less. The detergent may be used in a combination of overbased or neutral or both.

As mentioned above, among the compositions according to the present invention, the detergent contains 30 mol% or more (based on the total amount of the detergent) of a sulfonate detergent having a BN (base) of 0.1 to 80 mg KOH / g. This type of sulfonate detergent having a relatively low BN is well known in the art; As an example, WO 96/26919 discloses low BN calcium sulfonates and their preparation.

According to a preferred embodiment of the invention, the detergent comprises at least 35 mol%, preferably at least 40 mol%, more preferably at least 45 mol%, even more preferably at least 50 mol%, most preferably at least 35 mol% of the sulfonate detergent Is at least 55 mol%. Also preferred is a sulfonate detergent wherein the BN is 50 mg KOH / g or less, more preferably 40 mg KOH / g or less.

As mentioned above, among the compositions according to the present invention, the detergent contains 30 to 70 mol% of phenate detergent (based on the total amount of detergent). Preferably, the detergent comprises at least 35 mole percent of phenate detergent, preferably at least 65 mole percent, more preferably at most 60 mole percent, and even more preferably at least 55 mole percent of the phenate detergent, , Even more preferably less than 50 mole percent, and most preferably less than 45 mole percent phenate detergent. It is also preferred that the phenate detergent is an over-base wherein the BN is at least 190 mg KOH / g, preferably at least 200 mg KOH / g, more preferably at least 220 mg KOH / g and most preferably at least 240 mg KOH / It is preferable that it is a de-detergent. Such detergents are well known in the art.

The total amount of detergent in the composition of the present invention is typically 35.0 wt% or less based on the total weight of the lubricating composition. The compositions of the present invention comprise at least 4 wt%, preferably at least 8 wt%, more preferably at least 12 wt% detergents, based on the total weight of the composition.

The lubricating composition according to the present invention can be used as an antioxidant, an anti-wear agent, a dispersing agent, a detergent, an extreme pressure additive, a friction modifier, a viscosity modifier, a pour point depressant, a metal deactivator, a corrosion inhibitor, And one or more other additives such as additional diluent base oils and the like. Preferably, in addition to the detergent, at least a dispersing agent is present in the composition according to the invention; More preferably at least a dispersant and an antiwear agent are present.

The above-mentioned additives are typically present in an amount ranging from 0.01 to 35.0 wt% based on the total weight of the lubricating composition, preferably in an amount ranging from 5.0 to 30.0 wt% based on the total weight of the lubricating composition. More preferably, the lubricating composition according to the present invention contains less than 5.0 wt% of any other additives in addition to one or more detergents. Preferably, the composition does not contain at least one detergent, at least one dispersant, and at least one other additive other than a wear-resistant agent.

Those skilled in the art are well aware of these additives and other additives and are not discussed in further detail herein. Specific examples of such additives are described, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 3rd edition, Vol. 14, pp. 477-526.

Preferably, the composition has a TBN value (in particular according to ASTM D 2896) of not more than 75 mg KOH / g, preferably not more than 70 mg KOH / g, more preferably not more than 65 mg KOH / g, Even more preferably not more than 60 mg KOH / g. The composition has a TBN value (according to ASTM D 2896) of at least 10 mg KOH / g.

Further, the composition preferably has a kinematic viscosity (according to ASTM D 445) at 100 캜 of more than 5.6 mm 2 / s and less than 21.9 mm 2 / s, preferably more than 12.5 mm 2 / s, more preferably more than 16.3 mm 2 / s desirable.

The lubricating composition of the present invention can conveniently be prepared by mixing the base oil (s) with one or more additives.

In another aspect, the present invention provides the use of a lubricating composition according to the invention for improving the control of precipitate formation, in particular according to DIN 51392.

The lubricating composition according to the present invention is generally useful in lubrication equipment, particularly as an engine oil for internal combustion engines. These engine oils include passenger car engines, diesel engines, marine diesel engines, gas engines, 2- and 4-cycle engines, especially marine diesel engines.

The present invention will now be described with reference to the following examples, which are not intended to limit the scope of the invention in any way.

Example

Lubricant composition

A variety of lubricating compositions used as marine cylinder oils in marine diesel engines were formulated.

Table 1 shows the composition and characteristics of the formulations tested; The amount of ingredient is presented in wt% based on the total weight of the fully formulated formulation.

All tested marine diesel engine oil formulations are referred to as the SAE J300 Specification [Revised January 2009; SAE represents the Society of Automotive Engineers]. All tested formulations had a kinematic viscosity (according to ASTM D 445) of greater than 16.3 m < 2 > / s at 100 DEG C and less than 21.9 m < 2 > / s.

All tested marine cylinder oil types contained a combination of base oil, detergent combination and dispersant.

"Base oil 1" was a base oil of Group I base and Bright Stock (commercially available from Shell Chemicals Ltd. (London, UK) under the trade name "Catenex ").

"Base oil 2" was a base oil formulation containing a thickener and 75 wt% Group II base oil; This formulation is commercially available from Chevron Products Company (San Ramon, CA, USA) under the trade designation "Chevron 600 R ".

"Cleaner 1" was an overbased sulfonate detergent with a TBN (according to ASTM D 2896) of 417 mg KOH / g and a soap content of 236 mM Ca ²⁺ (available from Chevron Oronite (Windsor, UK) under the trade designation OLOA 249SX ").

"Detergent 2" was an overbased sulfonate detergent having a TBN of 375 mg KOH / g and a soap content of 317 mM Ca ²⁺ (from JinZhou KangTai Lubricant Additives Co. Ltd. (Liaoning, China) under the trade designation "T106" On the market).

"Cleaner 3" was an overbased phenate detergent with a TBN of 246 mg KOH / g and a soap content of 397 mM Ca ²⁺ (commercially available under the trade designation "Lubrizol 6499" from Lubrizol (Wickliffe, Ohio, USA)).

"Cleaner 4" was an overbased phenate detergent with a TBN of 250 mg KOH / g and a soap content of 282 mM Ca ²⁺ (commercially available from Chevron Oronite under the trade designation "OLOA 219C").

"Detergent 5" was a low BN sulfonate detergent having a TBN of 16 mg KOH / g and a soap content of 410 mM Ca ²⁺ (available under the trade designation "OLOA 246S" from Chevron Oronite).

"Cleaner 6" was a low BN sulfonate detergent with a TBN of 34 mg KOH / g and a soap content of 395 mM Ca ²⁺ (commercially available under the trade designation "LOBASE C-4503" from Chemtura Corporation (Middlebury, USA)).

"Detergent 7" was an overbased sulfonate detergent having a TBN of 9 mg KOH / g and a soap content of 441 mM Ca ²⁺ (commercially available from Chemtura Corporation under the trade designation "LOBASE C-4506").

"Dispersant" was high MW polyisobutene succinimide (commercially available from Afton Chemical Corporation (Richmond, VA, USA) under the trade designation "HiTEC").

The composition of Example 1-10 and Comparative Example 1-2 was obtained by mixing base oil, detergent and dispersant using a conventional lubricant compounding procedure.

The results are shown in Table 1 using the following method:

¹ TBN values were measured according to ASTM D 2896;

² The detergent content (or "soap content") of the individual detergents can be determined by the method of VA Zakupra and SV Timoshenko (All-Union Scientific-Research and Design Institute of the Petroleum Refining and Petrochemical Industry (VNIIPKneftekhim) detergent additives on silica gel ", Khimiya i Tekhnologiya Toplivi Masel, No. 2, pp. 48-52, February, 1980] (according to ASTM D 664) of the soap fraction of detergents after the isolation procedure. Measured values for soap content are expressed as equivalents of Ca ²⁺ millimoles per kg of detergent additive (see soap content as measured for detergents 1-7 above). The detergent (molar) content of each detergent type (eg, low BN sulfonate) is obtained by adding the individual detergent additive contributions (in wt%) in the total formulation that is doubled by the individual detergent content.

^{3 The} ratio of cleaner is calculated (divided by the total amount of each detergent component) and expressed in mole%. In an embodiment, add up to 100% phenate and sulfonate ratios; A low BN sulphonate ratio (i.e. a sulphonate with a BN of 0.1 to 80 mg KOH / g, preferably 0.1 to 50 mg KOH / g) is a subset of the sulfonate ratio.

^{4 The} normalized sediment is based on the total sediment value as measured after testing according to DIN 51392. (Rather than the total sediment), and Comparative Example 3 was referred to as a reference to better reflect the relative values.

Table 1

Table 1 (Continued)

Wolf strip test

To demonstrate the precipitate formation control characteristics of the present invention, measurements were performed using the Wolfstrip test procedure according to DIN 51392 (test duration: 12 hours; plate temperature at 280 占 폚). In the test, the following test conditions were used: a 150 ml oil flow was used in a closed loop; The oil to be tested was pumped in thin film form at 280 ° C for 12 hours at a flow rate of 50 (± 5) ml / h on a removable test strip (the strip was inclined at an angle of 8 ° to the horizontal).

The measured normalized precipitate is shown in Table 1 above, which represents the relative amount compared to the Example having the highest total amount of precipitate (i.e., Comparative Example 3).

Komatsu High Temperature Tube Test

As an alternative test to demonstrate the precipitate formation control characteristics of the present invention, the Swiss Testing procedure No. < RTI ID = 0.0 > STS Nr. Using the Komatsu high temperature tube test procedure according to the visual grading as described in < RTI ID = 0.0 > [452], < / RTI > The Komatsu hot tube test evaluates the high temperature stability of the lubricant. The oil droplets are pushed up by the air in the heated narrow glass capillary tube and the thin film oxidation stability of the lubricant is measured by the degree of formation of the lacquer on the glass tube and graded the generated color of the tube to a scale of 0-10. A grade of 0 indicates formation of heavy sediment and a grade of 10 means a clean glass tube at the end of the test. The method is also described in SAE paper 840262. The level of lacquer formation in the tubes reflects the high temperature stability of the oil and its tendency during use to form precipitates in the high temperature region of the engine. The measured grades (at 290 and 320 ° C) are shown in Table 2 below.

Table 2

Argument

As can be seen from Table 1, the control properties of the precipitate formation on the composition according to the present invention were remarkably improved as compared with Comparative Example 1-2.

As compared to the precipitate formation control properties of Examples 1 to 10, among others, it has been found according to the present invention that at least 40 mole percent of the detergent is a low BN sulfonate detergent (i.e., BN is 0.1 to 80, 50 mg OH / g), while at the same time more than 35 mol% of the total amount of detergent is a phenate detergent (Examples 1-7). In addition, Examples 5 and 6 are particularly preferred because they exhibit smaller amounts of precipitate. It is also preferred that the base oil comprises at least 50 wt% of the Group II base oil.

The preferred precipitate formation control properties according to the present invention were confirmed in the Komatsu hot tube test (see Table 2). Examples 2, 3, 5, and 6 have exceptionally good grades (9.5 out of 10) at 290 ° C and still acceptable values at 320 ° C (5.0 for Examples 2 and 3) to good values 8.5 for 6), whereas Comparative Example 1 did not pass the test at 320 < 0 > C ("clogging").

Claims (1)

A composition as described herein.