CN106811266A - Lubricating composition - Google Patents

Abstract

The present invention provides a lubricating composition, the lubricating composition at least comprises a base oil and a detergent; wherein the detergent comprises at least 30 mol% BN (base number) of 0.1-80 mg KOH/g based on the total amount of detergent A sulfonate detergent; wherein the detergent comprises 30-70 mol % of a phenate detergent based on the total amount of detergent; wherein the lubricating composition comprises at least 4 wt % of a detergent based on the total weight of the lubricating composition; wherein The lubricating composition has a TBN (Total Base Number) of at least 10 mg KOH/g (according to ASTM D 2896).

Description

lubricating composition

This application is a divisional application, the filing date of the parent application is October 26, 2010, the application number is 201080048323.8, and the invention name is "lubricating composition".

technical field

The present invention relates to a lubricating composition, in particular to a lubricating composition for use in internal combustion engines operating under sustained high load conditions, such as in marine diesel engines and in power generation applications. More particularly, the present invention relates to a marine lubricant.

technical background

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 contained in 100 An overbased calcium sulfonate having a viscosity of at least 180 cSt and a TBN of about 400 or greater at °C.

Lubricating compositions applied in internal combustion engines are subject to high stress. It is important that the lubricating composition provide good lubricating properties under a variety of conditions to help keep the engine clean, thermally and oxidatively stable, provide good wear, corrosion protection and remove heat from the engine.

Lubricating compositions employed in marine diesel engines are subject to particularly high stresses due to the long-term continuous operation of marine engines, often at near full load, often in remote locations. Additionally, since there is often little or no opportunity to replace lubricating compositions in marine engines, it is desirable for lubricating compositions to have a long life.

It will be understood in the art that the term "marine" is not limited to those engines used in waterborne vessels. That is, the term also includes engines used for power generation purposes. These advanced, fuel efficient, slow and medium speed marine and stationary diesel engines operate at high pressure, high temperature and long stroke.

Contents of the invention

It is an object of the present invention to improve the deposit-forming properties of lubricating compositions used in particular in internal combustion engines such as marine diesel engines.

Another object of the present invention is to provide an alternative lubricating composition for use in internal combustion engines.

The present invention can achieve one or more of the above-mentioned or other objects by providing a lubricating composition, the lubricating composition at least comprising a base oil and a detergent; wherein the detergent comprises at least 30 mol% BN ( Alkali number) is a sulfonate detergent of 0.1-80mg KOH/g; wherein said detergent contains 30-70mol% of phenate detergent based on the total amount of detergent; wherein said lubricating composition is based on the total amount of lubricating composition comprising at least 4% by weight of detergent; and wherein said lubricating composition has a TBN (Total Base Number) of at least 10 mg KOH/g (according to ASTM D 2896).

According to the invention it has now been found surprisingly that the lubricating compositions according to the invention exhibit improved deposit formation control properties as determined in accordance with DIN 51392 and the Komatsu Hot Tube Test (Komatsu Heat Tube Test).

The base oil used in the lubricating composition of the present invention is not particularly limited, and various conventional mineral oils, synthetic oils and naturally derived esters such as vegetable oils can be conveniently used.

The base oil used in the present invention may conveniently comprise a mixture of one or more mineral oils and/or one or more synthetic oils; thus, in accordance with the present invention, the term "base oil" may refer to mixture. Mineral oils include liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic/naphthenic type, which may be further refined by hydrofinishing processes and/or dewaxing.

Suitable base oils for use in the lubricating compositions of the present invention are Group I-III mineral base oils, Group IV polyalphaolefins (PAO), Group I-III Fischer-Tropsch derived base oils, and mixtures thereof.

In the present invention, "Group I", "Group II", "Group III" and "Group IV" base oils refer to lubricating base oils as defined by American Petroleum Institute (API) Groups I-IV . These API classifications are defined in API Publication 1509, 15th Edition, Appendix E, April 2002.

Fischer-Tropsch derived base oils are known in the prior art. The term "Fischer-Tropsch derived" means that the base oil is or is derived from a synthetic product of the Fischer-Tropsch process. Fischer-Tropsch derived base oils may also be referred to as GTL (gas-to-liquid) base oils. Suitable Fischer-Tropsch derived base oils which may conveniently be used as base oils for the lubricating compositions of the invention are found, for example, in EP 0 776 959, EP 0 668 342, WO 97/21788, WO 00/15736, WO 00/14188, 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 (including polyalpha-based oils; PAOs), dibasic acid esters, polyol esters, polyalkylene glycols (PAGs), alkylnaphthalenes, and dewaxed waxy heterogeneous oils. Construct. A synthetic hydrocarbon base oil sold under the name "Shell XHVI" (trade mark) by the Shell Group may conveniently be used.

Polyalphaolefin base oils (PAOs) and their preparation are well known in the art. Preferred polyalphaolefin base oils for use in the lubricating compositions of the present invention may be derived from linear C2 _{- C32} , preferably _C6 - _C16 alpha-olefins. Particularly preferred starting materials for polyalphaolefins are 1-octene, 1-decene, 1-dodecene and 1-tetradecene.

The total amount of base oil incorporated in the lubricating composition of the present invention is preferably 60-99 wt%, more preferably 65-98 wt%, and most preferably 70-95 wt%, based on the total weight of the lubricating composition.

According to a preferred embodiment of the present invention, said base oil comprises at least 50 wt% of Group II base oil, preferably at least 60 wt%, more preferably at least 70 wt%, based on the total amount of base oil.

There is no particular limitation on the detergent used in the lubricating composition of the present invention (as long as the requirements of claim 1 are met), and various conventional detergents can be conveniently used. The term "detergent" may refer to a single detergent or a mixture comprising two or more different detergents. Examples of detergents that may be used include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates and naphthenates and other oil-soluble metal carboxylates salts of metals, especially alkali metals or alkaline earth metals, such as sodium, potassium, lithium and especially calcium and magnesium. Preferred metallic detergents are neutral and overbased detergents with a TBN (Total Base Number according to ASTM D 2896) of at most 450 mg KOH/g. Combinations of detergents, which may be overbased detergents or neutral detergents or both, may be used.

As mentioned above, in the composition of the present invention, the detergent comprises at least 30 mol % of a sulfonate detergent with a BN (base number) of 0.1-80 mg KOH/g based on the total amount of detergent. Such relatively low BN sulfonate detergents are well known in the art. For example, WO 96/26919 discloses low BN calcium sulfonates and their preparation.

According to a preferred embodiment of the present invention, the detergent comprises at least 35 mol% of sulphonate detergent, preferably at least 40 mol%, more preferably at least 45 mol%, even more preferably at least 50 mol%, most preferably at least 55 mol%. It is also preferred that the sulphonate detergent has a BN of at most 50 mg KOH/g, more preferably at most 40 mg KOH/g.

As mentioned above, in the composition of the present invention, the detergent comprises 30-70mol% of phenate detergent based on the total amount of detergent. The detergent preferably comprises at least 35 mol% of phenate detergent; the detergent preferably comprises at most 65 mol% of phenate detergent, more preferably at most 60 mol%, even more preferably at most 55 mol%, still more preferably at most 50 mol%, most preferably up to 45 mol% phenate detergent. It is also preferred that the phenate detergent is an overbased detergent with a BN of at least 190 mg KOH/g, preferably at least 200, more preferably at least 220, most preferably at least 240 mg KOH/g. Such detergents are well known in the art.

The total amount of detergent in the compositions of the invention is generally up to 35.0 wt%, based on the total weight of the lubricating composition. The composition of the invention comprises at least 4 wt%, preferably at least 8 wt%, more preferably at least 12 wt% detergent, based on the total weight of the composition.

The lubricating composition of the present invention may also contain one or more other additives, such as antioxidants, anti-wear agents, dispersants, other detergents, extreme pressure additives, other friction modifiers, viscosity modifiers, pour point depressants, Metal deactivator, preservative, demulsifier, defoamer, seal compatibilizer and additive diluent base oil, etc. Preferably, in addition to the detergent, at least a dispersant is present in the composition of the invention; more preferably, at least a dispersant and an antiwear agent are present.

Based on the total weight of the lubricating composition, the above-mentioned additives are generally present in an amount of 0.01-35.0 wt%, preferably 0.5-30.0 wt%. More preferably, the lubricating composition of the present invention comprises less than 5.0% by weight of any other additive other than one or more detergents. Preferably, the composition is free of other additives than one or more detergents, one or more dispersants and one or more antiwear agents.

Since the above and other additives are familiar to those skilled in the art, they will not be discussed in detail here. Specific examples of these additives are described, for example, in Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, Vol. 14, pp. 477-526.

Preferably, the composition has a Total Base Number (TBN) value of preferably at most 75 mg KOH/g, preferably at most 70 mg KOH/g, more preferably at most 65 mg KOH/g, even more preferably at most 60 mg KOH/g (specifically Measured according to ASTM D 2896). The composition has a total base number (TBN) value (according to ASTM D 2896) of at least 10 mg KOH/g.

In addition, it is preferred that the kinematic viscosity (according to ASTM D 445) of the composition at 100°C is greater than 5.6 mm ² /s and less than 21.9 mm ² /s, preferably greater than 12.5 mm ² /s, more preferably greater than 16.3 mm ² /s.

The lubricating compositions of the present invention may conveniently be prepared by admixing one or more additives with a base oil.

In a further aspect, the present invention provides the use of a lubricating composition according to the invention to improve deposit formation control properties, in particular measured according to DIN 51392.

The lubricating composition of the present invention is generally used for lubricating equipment, but is particularly useful as an engine oil for internal combustion engines. These engine oils include passenger car engines, diesel engines, marine diesel engines, gas engines, two-cycle and four-cycle engines, etc., and especially marine diesel engines.

The invention is described below with reference to the following examples, which do not limit the scope of the invention in any way.

Example

lubricating oil composition

Various lubricating compositions formulated for use as marine cylinder oils in marine diesel engines.

Table 1 lists the composition and properties of the formulations tested; component contents are expressed in wt% based on the total weight of the fully formulated formulation.

All tested marine diesel engine oil formulations were formulated to SAE 50 formulations which meet the so-called SAE J300 specification (revised January 2009, SAE stands for Society of Automotive Engineers). All formulations tested had kinematic viscosities (according to ASTM D 445) at 100°C of greater than 16.3 mm ² /s and less than 21.9 mm ² /s.

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

"Base Oil 1" is a blend of a Group I base oil and bright stock commercially available under the tradename "Catenex" from Shell Chemicals Ltd. (London, UK).

"Base Oil 2" is a base oil blend comprising a thickener and 75% by weight Group II base oil; such a blend is sold, for example, by Chevron Products Company (San Ramon, CA, USA) under the trade designation "Chevron 600R" commercially available.

"Detergent 1" is an overbased sulfonate detergent with a TBN of 417 mg KOH/g (as per ASTM D 2896) and a soap content of 236 mM Ca ²⁺ , manufactured by Chevron Oronite (Windsor, UK) under the tradename "OLOA 249SX" is commercially available.

"Detergent 2" is an overbased sulfonate detergent with a TBN of 375 mg KOH/g and a soap content of 317 mM Ca ²⁺ , sold by JinZhou KangTai Lubricant Additives Co. Ltd. (Liaoning, China) under the trade name "T106 "Commercially available.

"Detergent 3" is an overbased phenate detergent with a TBN of 246 mg KOH/g and a soap content of 397 mM Ca2 ⁺ commercially available from Lubrizol (Wickliffe, Ohio, USA) under the trade designation "Lubrizol 6499".

"Detergent 4" is an overbased phenate detergent with a TBN of 250 mg KOH/g and a soap content of 282 mM Ca2 ⁺ commercially available from Chevron Oronite under the trade designation "OLOA 219C".

"Detergent 5" is a low BN sulfonate detergent with a TBN of 16 mg KOH/g and a soap content of 410 mM Ca2 ⁺ commercially available from Chevron Oronite under the trade designation "OLOA 246S".

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

"Detergent 7" is an overbased sulfonate detergent with a TBN of 9 mg KOH/g and a soap content of 441 mM Ca2 ⁺ , commercially available under the trade designation "LOBASEC-4506" from Chemtura Corporation.

The "dispersant" was a high MW polyisobutylene succinimide commercially available under the trade designation "HiTEC" from Afton Chemical Corporation (Richmond, VA, USA).

The compositions of Examples 1-10 and Comparative Examples 1-2 were obtained by mixing base oil with detergent and dispersant using conventional lubricant mixing procedures.

Apply the following methods as indicated in Table 1:

¹ TBN value is determined according to ASTM D 2896;

² The detergent content (or "soap content") of each detergent is described in the article "Separation of lubeoil detergent additives After the separation procedure described in Khimiya i Tekhnologiya Topliv iMasel, No.2, pp.48-52, February, 1980, TAN measurement (according to ASTM D 664) of the soap fraction of the detergent is determined. The soap content values determined are expressed in equivalent millimoles of Ca2 ⁺ per kg of detergent additive (see soap content determined above for detergents 1-7). The detergent (molar) content of each detergent type (eg, low BN sulfonate) is obtained by summing the contribution (wt %) of each detergent additive in the overall formulation multiplied by the respective detergent content.

³ The proportion of detergent is determined by calculation (dividing each detergent component by the total) and expressed in mol%. In an embodiment, the sum of the phenate ratio and the sulfonate ratio is 100%; the ratio of low BN sulfonate (ie BN is 0.1-80 mg KOH/g, preferably 0.1-50 mg KOH/g sulfonate) ratio as a fraction of the sulfonate ratio.

4Nominal deposits are based ^on total deposit values after testing according to DIN 51392. When compared to Comparative Example 3, it has been shown that nominal deposits (rather than total deposits) better reflect relative values.

Wolf Strip test

In order to verify the deposit formation control performance of the present invention, measurements were carried out according to DIN 51392 using the WolfStrip test procedure (test duration 12 hours, pan temperature 280° C.). During the test, the following test conditions were applied: an oil flow rate of 150ml was applied in a closed loop; the oil was pumped in the form of a thin film at a flow rate of 50(±5)ml/h at 280°C on the movable test belt during the test 12 hours, with the inclination of the strips being 8° relative to the horizontal.

The measured nominal deposits are listed in Table 1 above, and the results represent relative amounts compared to the example with the highest total deposit (ie Comparative Example 3).

Komatsu heat pipe test

In an alternative test to verify the deposit formation control performance of the present invention, measurements were made using the Komatsu heat pipe test procedure following the visual rating explained in Swiss Testing procedure No. STS Nr. 452. The Komatsu heat pipe test evaluates the high temperature stability of lubricants. The air inside a heated thin glass capillary tube pushes oil droplets upward, and the film oxidation stability of the lubricant is measured by the degree of varnish formation on the glass tube, and the final color of the tube is rated on a scale of 0-10. A rating of 0 indicates heavy deposit formation, while a rating of 10 indicates a clean glass tube at the end of the test. This method is also described in SAE paper 840262. The level of varnish formation in the tubes reflects the high temperature stability of the oil and its propensity to form deposits in high temperature areas of the engine during use. The measured ratings (at 290 and 320°C) are given in Table 2 below.

Table 2

Example 2 Example 3 Example 5 Example 6 Comparative example 1 290°C 9.5 9.5 9.5 9.5 8.5 320°C 5.0 5.0 8.5 8.5 jam

discuss

It can be seen from Table 1 that the deposit formation control performance of the composition of the present invention is significantly improved when compared with Comparative Examples 1-2.

From the comparison of the deposit formation control performance of Examples 1-10, it can be seen that according to the present invention, it is preferred that at least 40 mol% of the detergent is a low BN sulfonate detergent (i.e. a BN number of 0.1-80, preferably less than 50 mg KOH/g) and at the same time greater than 35 mol % of the total detergent is an embodiment of the phenate detergent (Examples 1-7). In addition, Examples 5 and 6 are particularly preferred because they have a smaller amount of deposits. Additionally, it is preferred that the base oil comprises at least 50% by weight of a Group II base oil.

The desirable deposit formation control properties of the present invention were confirmed in the Komatsu heat pipe test (see Table 2). Examples 2, 3, 5, and 6 received excellent ratings (9.5 out of 10 overall rating) at 290°C and were still acceptable (5.0 for Examples 2 and 3) to good (practice Examples 5 and 6 have values of 8.5), while Comparative Example 1 fails the test (blockage) at 320°C.

Claims (18)

1. a kind of lubricating composition, the lubricating composition is marine diesel engine oil, and it is included：

Base oil；With

Detersive；

Wherein described base oil class ii base oil comprising at least 50wt% in terms of base oil total amount；

Wherein described detersive is counted comprising at least sulfonate of the 30mol% alkali number BN as 0.1-80mg KOH/g with detersive total amount Detersive；

Wherein described detersive phenate detergents comprising 30-70mol% in terms of detersive total amount, and the phenate detergents are Alkali number BN is the overbased detergent of at least 190mg KOH/g；

Wherein described lubricating composition includes at least detersive of 8wt% with lubricating composition gross weight meter；With

It is at least 10mgKOH/g that the total alkali number TBN of wherein described lubricating composition presses ASTM D 2896.

2. the lubricating composition of claim 1, wherein the detersive includes at least sulfonate detergent of 35mol%.

3. the lubricating composition of claim 2, wherein the detersive includes at least sulfonate detergent of 40mol%.

4. the lubricating composition of claim 3, wherein the detersive includes at least sulfonate detergent of 45mol%.

5. the lubricating composition of claim 4, wherein the detersive includes at least sulfonate detergent of 50mol%.

6. the lubricating composition of any one of claim 1-5, wherein the sulfonate detergent has at most 50mg KOH/g's Alkali number BN.

7. the lubricating composition of any one of claim 1-5, wherein the detersive is peace and quiet comprising at least phenates of 35mol% Agent.

8. the lubricating composition of any one of claim 1-5, wherein the phenate detergents are at least 200mg for alkali number BN The overbased detergent of KOH/g.

9. the lubricating composition of claim 8, wherein it is that at least 220mg KOH/g cross alkali that the phenate detergents are alkali number BN Property detersive.

10. the lubricating composition of claim 9, wherein the phenate detergents are the mistake that alkali number BN is at least 240mg KOH/g Alkaline detersive.

The lubricating composition of 11. claim any one of 1-5, wherein the composition is included at least with the gross weight meter of composition The detersive of 12wt%.

The lubricating composition of 12. claim any one of 1-5, wherein the total alkali number TBN of the composition is at most 75mg KOH/g。

The lubricating composition of 13. claims 12, wherein the total alkali number TBN of the composition is at most 70mg KOH/g.

The lubricating composition of 14. claims 13, wherein the total alkali number TBN of the composition is at most 60mg KOH/g.

The lubricating composition of 15. claim any one of 1-5, wherein the base oil includes at least 60wt%'s in terms of base oil total amount Class ii base oil.

The lubricating composition of 16. claim any one of 1-5, wherein the base oil includes at least 70wt%'s in terms of base oil total amount Class ii base oil.

The lubricating composition of 17. claim any one of 1-16 improves the purposes that deposit forms control performance.

The lubricating composition of 18. claim any one of 1-16 as the engine oil in marine diesel purposes.