KR101545756B1 - Lubricant base oils and lubricant compositions and methods for making them - Google Patents

Abstract

A liquid lubricant base oil composition comprising the following components (i) and (ii) may be prepared by blending the components together and the composition may comprise one or more additives in a lubricant composition that can be used in applications such as marine engine lubricants (I) a base stock comprising at least 95% by weight of saturated hydrocarbons, such as a Group II base stock, a Group III base stock, and / or a Fischer-Tropsch synthesized, waxy, paraffinic And (ii) 0.2 to 30% by weight of aromatic extract, which has a content of less than 3% by weight of polycyclic aromatics extractable with dimethylsulfoxide.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a lubricant base oil and a lubricant composition,

The present invention relates to compositions and methods, particularly lubricant base oil and lubricant compositions and methods of making the same.

The lubricant composition generally comprises a base oil and one or more additives. According to API Standard 1509, "ENGINE OIL LICENSING AND CERTIFICATION SYSTEM ", November 2004, Edition 15, Appendix E, the base stock used for the base oil is one of the five groups ≪ / RTI >

[Table I]

group Saturated hydrocarbon content
(weight%) Sulfur content
(weight%) Viscosity index I <90 And / or > 0.03 And &Gt; 80 and &lt; 120 II ≥ 90 And 0.03 And &Gt; 80 and &lt; 120 III ≥ 90 And 0.03 And ≥120 IV Polyalphaolefin V All base stock not belonging to group I, II, III or IV

In the preparation of marine two-stroke and four-stroke engines, particularly lubricant compositions for engines operating with heavy oil, Group I base stocks are generally preferred over Group II base stocks. However, Group II base stocks have become more readily available, as older older manufacturing facilities for Group I base stocks are closed and tend to manufacture Group II base stocks with new manufacturing facilities.

Group II base stocks may have some performance drawbacks when compared to group I base stocks when used in some lubricant compositions, for example, marine lubricants. These disadvantages include poor dispersibility, poor seal swell performance, poor additive solubility, low miscibility with fuel oil in marine engine applications (which may, for example, cause precipitation formation in the cold part of the engine) , And / or, in some embodiments, poor oxidation stability.

Hydrogenated base stocks are used in industrial lubricant applications (Deckman DE et al., Hart's Lubricants World, September 1997, 20-26) and in commercial, personal and marine engine oils (Deckman DE et al., Hart's Lubricants World, 1997 September, 27-28) (Deckman, DE et al., Hart's Lubricants World, July 1997, pp. 46-50).

According to the literature (Deckman DE et al., Hart's Lubricants World, Sep. 1997, 27-28), " Hydrocracking causes viscosity loss of the base stock, so marine oils are generally formulated with hydrocracked base stock only But it requires the use of a considerable amount of bright stock, but brightstock is not preferred due to the presence of oxidatively unstable aromatics . "

The base stock prepared by hydrogenation processing, including Group II and Group III base stock, has a lower aromatic content and a lower sulfur content than the Group I base stock.

The base stock (Group IV), which is a polyalphaolefin, may also have a high level of saturation.

The base stock from Fischer-Tropsch synthetic, waxy, paraffinic hydrocarbon material also has a low aromatic content and thus also exhibits at least some of the poor performance of the Group II and Group III base stocks in comparison to the Group I base stock . WO 00/14187 and WO 2005/066314 relate to a lubricant composition comprising a Fischer Tropsch derived base stock.

There remains a need for a base oil composition that overcomes or at least mitigates this problem.

It has now been found that the use of 0.2 to 30% by weight of aromatic extract in a base oil comprising a base stock comprising at least 95% by weight of saturated hydrocarbons can overcome or at least alleviate this problem.

Thus, according to a first aspect of the present invention there is provided a liquid lubricant base oil composition comprising: (i) a base stock comprising at least 95% by weight of saturated hydrocarbons, and (ii) from 0.2 to 30% By weight of an aromatic extract which comprises 0.2 to 18% by weight or 1 to 30% by weight, more preferably 1.0 to 18% by weight of an aromatic extract, wherein the aromatic extract has a content of less than 3% by weight of polycyclic aromatics extractable with dimethylsulfoxide .

According to a second aspect of the present invention there is provided a process for preparing a liquid lubricant base oil composition as defined herein which process comprises mixing a base stock comprising at least 95% by weight of saturated hydrocarbons with less than 3% by weight of a polycyclic aromatics extractable with dimethyl sulfoxide To a sufficient aromatic extract having a solubility in water of at least 50% by weight, based on the total weight of the composition, to produce a liquid lubricant base oil composition as defined herein.

According to a third aspect of the present invention there is provided a lubricant base oil composition comprising a lubricant base oil composition as defined herein and at least one additive selected from the group consisting of detergents, dispersants, antiwear additives, antioxidants, antifoaming agents, corrosion inhibitors, pour point depressants, friction modifiers, A lubricant, and an improving agent).

The present invention relates to a process for the preparation of a liquid lubricant base oil composition having a content of less than 3% by weight of a polycyclic aromatic which is extractable in dimethylsulfoxide, in a liquid lubricant base oil composition, wherein the base oil comprises a base stock comprising at least 95% by weight of saturated hydrocarbons, The use of 0.2 to 30% by weight of aromatic extracts solves the problem as defined above. This provides a lubricant base oil that overcomes or at least mitigates at least some of the defects that may be associated with the base stock.

The lubricant base oil composition of the present invention comprises 0.2 to 30% by weight of aromatic extract. Preferably, the lubricant base oil composition of the present invention comprises 0.2 to 18% or 1.0 to 30% by weight of aromatic extract. More preferably, the lubricant base oil composition of the present invention comprises from 1.0 to 18% by weight of aromatic extract.

Preferably, the base stock comprises a base stock containing hydrogenated 95% by weight or more of saturated hydrocarbons and / or a base stock derived from a Fischer-Tropsch synthesized, waxy, paraffinic hydrocarbon material. The present invention is based on the disadvantages that may be associated with the base stock, such as poor dispersibility (e.g. poor dispersion of soot and / or precipitate), poor seal swell performance, fuel oil in marine engine applications (Which may, for example, cause precipitation formation in the cold part of the engine), and also, in some embodiments, overcome at least some of the defects selected from the group consisting of poor oxidation stability, or Providing at least a relaxing lubricant base oil.

Thus, according to a further aspect of the present invention there is provided a lubricating oil composition comprising at least one of the disadvantages of a base stock selected from the group consisting of poor dispersibility, poor seal swelling performance, poor additive solubility, and low miscibility with fuel oil in marine engine applications In an amount of less than 3% by weight of a polycyclic aromatics extractable in dimethylsulfoxide, in a liquid lubricant base oil composition, wherein the base oil comprises a base stock comprising not less than 95% by weight of saturated hydrocarbons, From 0.2 to 30% by weight of an aromatic extract.

In particular, the present invention utilizes a hydrogen-treated base stock, which may include, for example, a Group II base stock and / or a Group III base stock, and / or uses a base stock, which may comprise polyalphaolefins / RTI &gt; The present invention provides a method of using a limited amount of aromatic extract to make a base oil using a base stock derived from a Fischer-Tropsch synthesized, waxy, paraffinic hydrocarbon material. This base oil may be applied to applications in which group I base stocks are commonly used, such as marine engine applications, such as 2-stroke marine diesel engine cylinder oil, 2-stroke marine diesel engines and 4-stroke marine diesel engine cranks Can be used in a sealant composition.

The aromatic extract is preferably made by treatment of one or more refining process streams in a solvent extraction process. Suitable solvent extraction processes include contacting one or more refinery process streams with a solvent such as, for example, Pullrural, n-methylpyrrolidone, sulfur dioxide, Duo-Sol ™ or phenol to selectively extract from the refinery stream, aromatic and heterocyclic materials And forming a solution of these materials in a solvent. The solvent is then recovered from the solution for recycle to the extraction process; The obtained product is an aromatic extract.

The preparation of aromatic extracts is well known in the art and is described, for example, in " Lubricant base oil and wax processing " A. Sequeira, pages 81-118, pub. Marcel Dekker Inc. New York, 1994.

Aromatic extracts can be made by treatment of solvent deasphalted vacuum residue (also known as DAO) made with Duo-Sol ™, propane, butane or a mixture thereof as a solvent for de-asphaltation, in an extraction process , &Lt; / RTI &gt; residual aromatic extract.

The aromatic extract may be a distillate aromatic extract (DAE), which is an aromatic extract made by treating the distillate stream from the vacuum distillation process in an extraction process. Preferably, the distillate aromatic extract is a treated distillate aromatic extract which is a distillate aromatic extract applied to one or more additional treatments. Suitably, the at least one additional treatment is selected from the group consisting of hydrogenation, hydrogenation, hydrodesulfurization, clay treatment, acid treatment and further solvent extraction.

The aromatic extract may have an aromatic content of 60 to 85% by weight (which can be measured by ASTM D 2007).

Aromatic extracts may have properties as described in (Concawe Product Dossier 92/101 "Aromatic Extracts").

Aromatic extracts of distillates may have a boiling point in the range of 250 to 680 ° C (may be measured according to ASTM D 2887). Aromatic extracts of distillates may have dynamic viscosities ranging from 5 to 18000 mm ² / s at 40 ° C (may be measured according to ASTM D 445). Aromatic extracts of distillates may have a dynamic viscosity ranging from 3 to 60 mm ² / s at 100 ° C (may be measured according to ASTM D 445). Aromatic extracts of distillates may have an average molecular mass ranging from 300 to 580 (may be measured according to ASTM D 2887). Aromatic extracts of distillates may have carbon numbers ranging from C ₁₅ to C ₅₄ (may be measured according to ASTM D 2887). Aromatic extracts of distillates may have an aromatic content ranging from 65 to 85% by weight (may be measured according to ASTM D 2007).

The residual aromatic extract may have a boiling point above 380 ° C (may be measured according to ASTM D 2887). The residual aromatic extract may have a dynamic viscosity (measured according to ASTM D 445) of greater than 4000 mm ² / s at 40 ° C. The residual aromatic extract may have a dynamic viscosity (measured according to ASTM D 445) in the range of 60 to 330 mm ² / s at 100 ° C. The residual aromatic extract may have an average molecular mass of greater than 400 (may be measured according to ASTM D 2887). The residual aromatic extract may have a carbon number range greater than C ₂₅ (which may be measured according to ASTM D 2887). The residual aromatic extract may have an aromatic content ranging from 60 to 85% by weight (may be measured according to ASTM D 2007).

Aromatic extracts may contain a polycyclic aromatic compound (PAC), some of which are carcinogens. The amount (wt.%) Of the substance that can be extracted with dimethylsulfoxide (DMSO) is used as an indication of the amount of material (including polycyclic aromatics) in the aromatic extract. IP 346 (Institute of Petroleum Test Method 346) is the method used to determine the weight percent of DMSO extract. Aromatic extracts containing more than 3% by weight of extractable polycyclic aromatics by dimethylsulfoxide are classified as carcinogens and, in some jurisdictions, certain symbols and risk phrases should be given to the substance to indicate health, safety and environmental hazards. do. For at least this reason, the aromatic extract has a content of less than 3% by weight of polycyclic aromatics extractable with dimethylsulfoxide (low PCA extract). More preferably, the aromatic extract is a residual aromatic extract or a treated distillate aromatic extract having a content of less than 3% by weight of polycyclic aromatics extractable with dimethylsulfoxide.

Preferably, the aromatic extract does not contain any significant amount of wax because, if present, the wax can settle out in use.

The base stock of the present invention comprising at least 95% by weight of saturated hydrocarbons can include both hydrogen-treated base stocks and base stocks derived from Fischer-Tropsch synthesized, waxy, paraffinic hydrocarbon materials. Suitably, the base stock of the present invention comprising at least 95% by weight of saturated hydrocarbons may comprise a hydrogen-treated base stock or base stock from Fischer-Tropsch synthesized, waxy, paraffinic hydrocarbon material.

The hydrogen-treated base stock is preferably a Group II and / or Group III base stock as defined in API Standard 1509, " ENGINE OIL LICENSING AND CERTIFICATION SYSTEM ", Annex E,

The base stock comprising at least 95% by weight of saturated hydrocarbons is preferably present in API Standard 1509, " ENGINE OIL LICENSING AND CERTIFICATION SYSTEM ", November 2004, Edition 15, Annex E, which contains at least 95% by weight of saturated hydrocarbons And Group II and / or Group III base stock defined accordingly.

Preferably, the Group II base stock or the Group III base stock is preferably subjected to hydrogen treatment of the vacuum distillate or deasphalted vacuum residue, or to hydrogenation isomerization of the bottom stream from the clean fired hydrocracking furnace Lt; RTI ID = 0.0 &gt; hydrogen &lt; / RTI &gt; The preparation of base stocks by hydrogenation is known in the art and is described, for example, in " Lubricant base oil and wax processing " A. Sequeira, pp. 119-15, pub. Marcel Dekker Inc. New York, 1994).

The base stock comprising at least 95% by weight of saturated hydrocarbons may comprise one or more polyalphaolefins.

Fischer-Tropsch Base stocks derived from synthetic, waxy, paraffinic hydrocarbon materials can be made by any suitable process known for the production of a base stock from the Fischer Tropsch process. Processes for the production of base stocks from Fischer-Tropsch synthetic, waxy, paraffinic hydrocarbon materials which can be used are described, for example, in US4943672, EP-A-0668342 and EP-A-0776959, Incorporated herein by reference. Thus, the base stock can be made by the steps of (i) to (iv): (i) Syngas production, (ii) Fischer-Tropsch synthesis of hydrocarbons from synthesis gas, (iii) Hydrocracking of hydrocarbons for production of naphtha and diesel / kerosene fuel process streams with waxy paraffinic residues, and (iv) hydrogenation of waxy residues for the production of base stocks.

The liquid lubricant base oil composition according to the present invention can be made by blending a base stock containing at least 95% by weight of saturated hydrocarbons with a sufficient aromatic extract to produce a lubricant base oil composition. Blending may be performed in a batch or continuous blending process. Batch blending can be performed by introducing the base stock and aromatic extract into the blending kettle with stirring and / or vortexing of the blending components. Continuous blending can be performed using an in-line mixer to blend the base stock and aromatic extracts. Heating may be required during blending to facilitate handling of aromatic extracts.

Preferably, the liquid lubricant base oil composition of the present invention has a viscosity ranging from 7 to 40 cSt at 100 &lt; 0 &gt; C.

The liquid lubricant base oil composition of the present invention is particularly useful for manufacturing a two-stroke marine diesel engine cylinder oil, a two-stroke marine diesel engine oil or a four-stroke marine diesel engine crankcase lubricant composition.

The liquid lubricant composition according to the present invention may further comprise a liquid lubricant base oil composition as defined herein and one or more additives, preferably a detergent, a dispersant, an antiwear additive, an antioxidant, a defoamer, a corrosion inhibitor, a pour point depressant, a friction modifier, And an index improving agent.

The concentration of the additive in the lubricant composition according to the present invention depends on the intended use of the lubricant composition.

The one or more antioxidants may be present in the lubricant composition at a total concentration of 0 to 1% by weight, usually up to 0.5% by weight.

One or more anti-wear additives may be present in the lubricant composition at a total concentration of 0 to 2% by weight, usually up to 1% by weight.

One or more high peroxide cleansing agents may be present in the lubricant composition at a total concentration of 0 to 40% by weight.

One or more low base cleaners may be present in the lubricant composition at a total concentration of 0 to 10% by weight.

One or more neutral detergents may be present in the lubricant composition at a total concentration of 0 to 2% by weight.

The one or more dispersants may be present in the lubricant composition in a total concentration of 0 to 10% by weight.

The at least one defoamer may be present in the lubricant composition at a total concentration of 0 to 0.1 wt%.

One or more corrosion inhibitors may be present in the lubricant composition at a total concentration of 0 to 1% by weight.

One or more pour point depressants may be present in the lubricant composition at a total concentration of 0 to 1% by weight.

The one or more friction modifiers may be present in the lubricant composition at a total concentration of 0 to 5% by weight.

The one or more tackifiers may be present in the lubricant composition in a total concentration of 0 to 15% by weight.

One or more viscosity index improvers may be present in the lubricant composition at a total concentration of 0 to 20 wt%.

The concentration ranges of the additives may be independent of each other. Alternatively, a combination of the above concentration ranges may be used for any particular lubricant composition.

The liquid lubricant composition of the present invention can be used as a two-stroke marine diesel engine cylinder oil, a two-stroke marine diesel engine system oil or a four-stroke marine diesel engine crankcase lubricant composition.

The concentration ranges for the additives for this lubricant composition according to the present invention are provided in Table II below. These concentration ranges may be independent of each other. Alternatively, a combination of such concentration ranges may be used in any particular lubricant composition.

[Table II]

The present invention will now be described with reference only to Examples and Figure 1, which is a graph of the performance of a base oil with varying amounts of aromatic extracts.

In this experiment, the hydrogen-treated base stock was a Group II base stock containing greater than 97 wt.% Of saturated hydrocarbons. The aromatic extract was a low PCA brightstock extract (less than 3% polycyclic aromatic, BrightStur® Pullulan extract) provided by Shell. The properties of these components are provided in Table III below.

[Table III]

The basestock and aromatic extracts did not appear to contain any significant amounts of waxy material. Aromatic extracts (AE) were blended with varying amounts of Group II base stock to produce base oil compositions. The properties of the base oil composition are provided in Table IV below.

[Table IV]

Additional base oils were made using Group II base stocks and aromatic extracts in different amounts. The oxidation characteristics of the base oil were tested according to the Institute of Petroleum Procedure IP48 and the results are shown in Table V below:

[Table V]

Experiment A is not in accordance with the present invention because it does not contain any aromatic extract.

The results of the viscosity ratio and the change in carbon (DELTA carbon) in aromatic extracts of different concentrations in the base oil are also shown in FIG.

The results of Δ carbon and viscosity ratios show that the aromatic extract provides an improvement in Δ carbon when the aromatic extract concentration is less than about 12 wt% and provides an improvement in the viscosity ratio when the aromatic extract concentration is less than 30 wt%.

These results show the beneficial effect of the presence of 0.2 to 30% by weight of aromatic extract in the base oil composition comprising the base stock comprising at least 95% by weight of saturated hydrocarbons.

A base oil comprising different amounts of aromatic extracts and a salicylate-rich additive package were used to prepare lubricant compositions suitable for use in marine four-stroke engines using heavy oils.

The properties of the formulated lubricant compositions are shown in Table VI below.

[Table VI]

The oxidation characteristics of the lubricant composition were measured. The results are shown in Table VII below.

[Table VII]

The results in Table VII show that some improvements were observed in the Panel Coker Test using steel panels performed according to the in-house method when the aromatic extracts were 12 and 24 wt% , Which means that when an aromatic extract is used, the solubility is improved in the lubricant composition.

The wear characteristics of the lubricant compositions were measured using the Cameron Plint test. The results are shown in Table VIII below.

[Table VIII]

The wear characteristics were compared with reference lubricant formulations having good wear performance and poor wear performance. As a result, exceptionally good wear performance was shown in a lubricant composition having a base oil containing 12% by weight of an aromatic extract. However, there was no significant improvement in wear performance when compared to a composition with 100% Group II base oil when the aromatic extract in the base oil had a concentration of greater than 24% by weight. This data means that the optimum concentration of the aromatic extract is present in the wear characteristics.

Claims (20)

A liquid lubricant base oil composition comprising: (i) a base stock comprising at least 95% by weight of saturated hydrocarbons, and (ii) 0.2 to 30% by weight of an aromatic extract, wherein the aromatic extract has an aromatic content of 60 to 85% by weight and a content of less than 3% by weight of polycyclic aromatics extractable with dimethylsulfoxide. The liquid lubricant base oil composition of claim 1, wherein the aromatic extract comprises from 0.2 to 18% by weight. 3. A liquid lubricant base oil composition according to claim 2 comprising from 1 to 18% by weight of said aromatic extract. The liquid lubricant base oil composition according to claim 1, wherein the aromatic extract is contained in an amount of 1 to 30% by weight. The liquid lubricant base oil composition of claim 1, wherein the aromatic extract is a residual aromatic extract. The liquid lubricant base oil composition of claim 1, wherein the aromatic extract is a distillate aromatic extract. 7. The method of claim 6, wherein the aromatic extract is a distillate aromatic extract, which is a further treated distillate aromatic extract selected from the group consisting of hydrogenation, hydrodesulfurization, clay treatment, acid treatment and further solvent extraction. Oil composition. delete The process according to claim 1, wherein the base stock comprising at least 95% by weight of saturated hydrocarbons comprises a base stock from hydrogen-treated base stock and / or Fischer-Tropsch synthesized, waxy, paraffinic hydrocarbon material, Base oil composition. The liquid lubricant base oil composition of claim 9, wherein the hydrogen-treated base stock is a Group II base stock and / or a Group III base stock. The liquid lubricant base oil composition of claim 1, wherein the base stock comprises Group II base stock and / or Group III base stock. The liquid lubricant base oil composition of claim 1, wherein the base stock comprises at least one polyalphaolefin. A process for preparing a liquid lubricant base oil composition according to any one of claims 1 to 7 and 9 to 12, which comprises mixing a base stock comprising at least 95% by weight of saturated hydrocarbons with an aromatic from 60 to 85 A composition according to any one of claims 1 to 7 and 9 to 12, which is blended with an aromatic extract having a content of% by weight and a content of less than 3% by weight of polycyclic aromatics extractable with dimethylsulfoxide, To produce a liquid lubricant base oil composition according to &lt; RTI ID = 0.0 &gt; claim &lt; / RTI &gt; A liquid lubricant composition comprising a liquid lubricant base oil composition according to any one of claims 1 to 7 and 9 to 12 and at least one additive. 15. The composition of claim 14, wherein the at least one additive is selected from the group consisting of a detergent, a dispersant, an antiwear additive, an antioxidant, a defoamer, a corrosion inhibitor, a pour point depressant, a friction modifier, a tackifier and a viscosity index improver. The liquid lubricant composition according to claim 15, wherein the lubricant composition is used as a lubricant composition for a two-stroke marine diesel engine cylinder oil, a two-stroke marine diesel engine oil or a four-stroke marine diesel engine crankcase lubricant composition. Use according to claim 1 for the reduction of at least one of the drawbacks of a base stock selected from the group consisting of poor dispersibility, poor seal swelling performance, poor additive solubility and low miscibility with fuel oil in marine engine applications &Lt; / RTI &gt; The liquid lubricant base oil composition of claim 17, wherein the lubricant base oil composition is a liquid lubricant base oil composition according to any one of claims 1 to 7 and 9 to 12. Use according to claim 1 for the reduction of at least one of the drawbacks of a base stock selected from the group consisting of poor dispersibility, poor seal swelling performance, poor additive solubility and low miscibility with fuel oil in marine engine applications A liquid lubricant base oil composition in a liquid lubricant composition comprising a liquid lubricant base oil composition according to any one of claims 1 to 7 and one or more additives. Use according to claim 1 for the reduction of at least one of the drawbacks of a base stock selected from the group consisting of poor dispersibility, poor seal swelling performance, poor additive solubility and low miscibility with fuel oil in marine engine applications A lubricant base oil composition according to any one of claims 1 to 7 and 9 to 12 and a lubricant base oil composition according to any one of claims 9 to 12, and a detergent, a dispersant, an antiwear additive, an antioxidant, a defoaming agent, , A pressure-sensitive adhesive, and a viscosity index improver. The liquid lubricant base oil composition according to claim 1,

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