DD299535A5 - TRIEBWERKSSCHMIEROELE - Google Patents

Abstract

The invention relates to an engine lubricating oil for long-term use in crosshead diesel engines, mainly in shipping. The OEl has very good oxidation stability, good anticorrosive behavior and detergent action as well as good water compatibility. According to the invention, these properties are achieved by mixing selected mineral oil components with a detergent inhibitor composition of special weak and highly basic alkaline earth sulfonates and / or phenolates, zinc dialkyl dithiophosphate and special fatty acid amide. Crosshead diesel engines; Schiffsmotorenoele; Oxidationsstabilitaet; Anti corrosion behavior; Detergency; Wasservertraeglichkeit; Additive composition of weakly and highly basic alkaline earth sulfonates}

Description

Field of application of the invention

The invention relates to an engine lubricating oil with very good antioxidant, anti-corrosion, Detergent- and Separierverhalten for long-term use in crosshead diesel engines, mainly in shipping.

Characteristic of the known state of the art

It is known to use low alloyed lubricating oils as circulating oils for engine lubrication of crosshead diesel engines, r * .n. in the range of crankcase, main and Pleullager, crosshead and partly used as a cooling medium for the pistons, while in the cylinder-piston area of these engines usually highly alkaline marine cylinder oils are used (mineral oil technology

26 [1901] 9, pp. 1-20; Lord, Q. M., Lecture 2. Int. Seminar on Performance Requirements, Testing and Development of Lubricants, Fuels and Chemicals, Cairo, 2-6.4.1979).

The engine lubricating oils mentioned must have a good oxidation stability and water compatibility and a good corrosion protection and Separierverhalten and absorb the unavoidable leaks used cylinder oils without loss of function. According to the known art of the art, such engine lubricating oils are prepared on the basis of solvent raffinates with the addition of oxidation inhibitors and rust inhibitors and optionally small amounts of detergents and have alkali metal contents of 0 to 2 mg KOH / g. In the named active substance groups a multiplicity of connection types are in principle well-known (β.Ullmann's Enzyklopädie of the technical chemistry, 4th edition, Bd. 20, publishing house chemistry, Weinheim) and a scarcely overlookable number of individual connections and / or manufacturing procedures in the patent literature in detail described. Thus, there are a variety of preparations and application instructions for alkaline earth sulfonates and Erdalkaliphenolate, without reference to the application mentioned special reference is made. As corrosion inhibitors u. a. Fatty acid amides known in principle (eg in hydraulic oils, S. DD-PS 149536). The same applies to the use of alkoxylates as emulsifiers and corrosion inhibitors (see, inter alia, Chlmija i technol topliv I Masel [1981] 12, pp. 30-38). Crucial to the performance of the engine lubricating oils, however, is the selection of formulation components having such an interaction which ensures that desired properties such as oxidation stability and anti-corrosion behavior are enhanced by synergisms and undesirable side effects, e.g. the tendency to form emulsions difficult to separate with water entering the crankcase via the drive shaft in the simultaneous presence of cylinder scraper oil is largely minimized by antagonisms.

Also recently used as marine circulation oils are so-called multi-purpose oils with higher alkalinity (6 to 10 mgKOH / g), which are also used for the lubrication of diesel fuel powered piston engine plungers.

Disadvantage of the former types of engine lubricating oils is that despite the use of oxidation and corrosion inhibitors partially still insufficient protection against storage corrosion, z. ti. in the Petter W1 test, available (see Table 1), and the detergent-dispersant behavior is often insufficient.

On the other hand, the multi-purpose oils requiring expensive and special additive components are not required in the majority of applications to meet the application requirements.

Object of the invention

OBJECT OF THE INVENTION It is to develop engine lubricating oils with formulations that are advantageous in terms of material economics, which have very good oxidation stability, excellent corrosion protection behavior, and good compatibility with water and cylinder oil leakage while ensuring separability, thereby permitting continuous use in the circulation system of modern, highly stressed crosshead diesel engines.

Explanation of the essence of the invention The invention is based on the object, a lubricating oil for the special conditions of the engine of To develop crosshead diesel engines so that when using substantially existing and / or economically favorable

manufacturable components as well as the maximum use of their synergy effects an unexpected, distinct

Improvement of the oxidative stability, the corrosion protection effect and the water compatibility is achieved. Such engine oils are obtained according to the invention by using a naphthenic, paraffin-containing

and / or mixed base origin base oil having a viscosity at 50 ° C from 40 to 150mmVs1 to 5Ma .-% of a combination of at least two different, matched weak, medium and / or

Highly basic technical ErdtikalisulfonatenAphenolaten, '

0.2 to 1 wt .-%, based on the pure active ingredient, of at least one multifunctional Inhioitors type

zinc dialkyldithiophosphate

and as a special rust inhibitor 0.05 to 0.5% by mass of fatty acid amio ', prepared by condensation of fatty acids of

Chain length range C ₁₈ to C ₂₂ with amines, preferably diethanolamine and / or ethoxylated alkylphenol (alkyl radical C ₇ -C) ₂ ) having an average degree of statistical ethoxylation between 3.5 and 6.5

be added so that a ratio of equivalents of sulfonate to phenolate of 1: 8 to 1: 2ö and a mass ratio of weak to moderate and / or high basic detergents of 1: 1.8 to 1: 5.6, a mass ratio of

alkaline earth sulfonylphenolate to a specific rust inhibitor of from 1: 0.25 to 1: 1.5, and an equivalent ratio of zinc dialkyldithiophosphate to phenolic groups of from 1: 3 to 1: 7.5.

An economical particularly advantageous variant of the composition according to the invention of such an engine oil

and their materially simple solution to be realized results if, within the mentioned detergent inhibitor

Combination as weakly basic detergent a phenolate-containing alkaline earth metal produced in a continuous process Sulfonate with a basicity of 10 to 60 mgKOH / g and equivalents of Sufonate groups from 200 to 400 meq / kg and

phenolic groups of 200 to 500 meq / kg is used, with a particularly good oxidation stability of

Engine lubrication oils is achieved when the manufacturing technology of this product is controlled so that the

at least 30% of sulphonated phenolic groups and 5 to 50% of free alky! phenol or alkylphenol sulphide.

Favorable results in terms of aging stability and motor behavior are also achieved through the use of a

sulfurized medium and / or highly basic calcium phenolates, which has an equivalent phenolic content

Groups of 1100 to 1900mval / kg and, if necessary, a maximum of 200mval / kg sulfonate groups in the form of a Has Erdalkalisulfonates. Beneficial for effectiveness and synergistic interaction with the rest Formulation ingredients turn out to be phenolates, for their preparation, the reaction in common presentation of alkylphenol

Alkaline earth sulfonate, high molecular weight alcohol mixture, diluent oil and sulfur In only one reaction vessel and continuously and the carbonization in the presence of a promoter combination, consisting of 2 to 8 wt .-% of Erdalkalisulfonates, 4 to 15Ma .-% of an aliphatic saturated high molecular weight alcohol mixture, 4 bis 10Ma .-% of a polyhydric alcohol and O ₁ OOS to 0.1 Ma .-% of a dimethylpolysiloxane, based on the total mixture, takes place. The particular advantages of the engine oils according to the invention are that the oxidation stability is significantly improved in unanticipated catfish especially in the high temperature range. The improvement relates equally to the characteristics of the aged oil and the evaluation of the sheets used for the tests with regard to the deposits resulting from the aging (Table 1). An additional confirmation of the results of the composition according to the invention is found in the surprisingly good engine test results shown in Table 3. The superiority of the engine oil formulation according to the invention compared to products of the prior art is based on different criteria for a maximum effectiveness of synergy effects between the individual. Components returned, which, as Tab. 2 shows, surprisingly also has a positive effect on the corrosion protection behavior. Thus, the protective effect of the engine oil according to the invention in relation to water and acid action in some cases significantly exceeds that of the tested brand products. Of particular importance for the separability of the engine lubricating oils required in terms of application technology is that the products according to the invention contain, despite the strong surface-active substances which are used individually, in some cases as emulsifiers, with water which is usually penetrated by the ship, do not form stable emulsions, but release them in a controlled manner.

Example 1 - ,

In 97.8% of a marine base oil having a viscosity of 90 mm Ve at 6O ⁰ C, consisting of a dewaxing, phenol refined and bleached vacuum distillate fraction and dewaxed heavy oil raffinate, are passed through a multicomponent mixing plant or in a mixing vessel

1.28Ma .-% of a highly basic Calclumphenolates with a baseline of 209 mgKOH / g, equivalents of sulfonate of

21 meq / kg and equivalents of phenolic groups of 1320 meq / kg, 0.32 meq of a weakly basic, phenolate-containing calcium sulfonate having a basicity of 24 mgKOH / g,

Equivalent proportions of sulfonate groups of 290 meq / kg and equivalents of phenol groups of 330 meq / kg, 0.8 wt .-% of a zinc dialkyldithlophosphate with a zinc content of about 4.0Ma .-% (0.35Ma .-% based on the pure

Active ingredient), 0.2% by mass of an inhibitor of the fatty acid diethanolamide type, produced by condensation of fatty acids of the fatty acid diethanolamide type

Chain length range C ₁₈ to C ₂₂ with diethanolamine

introduced and homogenized at a temperature of about 70 ° C Intensive. The engine oil obtained in this way with an equivalence ratio of sulfonate groups to phenolic groups of 1:16 and an alkalinity of 2.8 mg / kg / g is distinguished by a high aging stability (Table 1) and a resulting improved sedimentation behavior during engine operation (Table 3) , The corrosion protection effect, which is likewise improved over the known state of the art, is documented in Tfib.

Example 2

97.8% of a Marine base oil having a viscosity of 52 MMCs at 5O ⁰ C, consisting of a through Hydroraffinatlongewonnenen, phenol refined and dewaxing a vacuum distillate fraction and dewaxed Schwerölraffinat be

1.16Ma .-% of a highly basic Calclumphenolates, whose basicity? 45mgKOH / g, equivalents of sulfonate groups

25mval / kg and equivalents of phenolic groups 1470mval / kg, 0.3m% of a weakly basic phenolated calcium sulphonate having a basicity of 31mgKOH / g,

Equivalence rates of sulfonate groups of 310 meq / kg and equivalents of phenolic groups of

340mval / kg,

0.45Ma .-% of a zinc salt of technical Dithlophosphorsäuren with a zinc content of about 8.5Ma .-% (80% active ingredient), 0.2 wt .-% of an inhibitor of the type ethoxylated alkylphenol having a mean degree of ethoxylation of 5 and a length of the alkyl chain of C ₉ to C ₂ (emulsifier MF)

Intensively mixed over test sections or in a mixing container at approx. 70 ° C. A product is obtained with a TBN of about 3 mgKOH / g and an equivalence ratio of sulfonate groups to phenolic groups of about 1:18. The engine lubricating oil produced in this way has improved deposit and corrosion protection properties compared to the prior art (Tables 2 and 3).

Example 3

54Ma. Parts of a highly basic phenolate prepared by mixing in a stirred tank a mixture of 24.8Ma% nonylphenol, 28.0Ma% dewaxed hydroraffinate distillate as a diluent oil, 5.1 mass% calcium alkyl benzene sulphonate having a TBN of 158mgKOH / g, occurs 4.0mA .-% sulfur \ n flake form and 11,2Ma .-% of 2-ethylhexanol, added to the reaction mixture while heating to 13O ⁰ C and 14,4Ma .-% of technical calcium hydroxide and 0.066 wt .-% dimethylpolysiloxane is then added with vigorous stirring 7.0Ma .-% monoethylene glycol, stripped with nitrogen, further heated to 17O ⁰ C in 60 minutes, the reaction water and the hydrogen sulfide immediately removed, stripped for a further 180 minutes, then 180 minutes with 5.5Ma .-% CO ₂ gassed, again stripped with nitrogen, and the promoters of monoethylene glycol and 2-ethylhexanol was distilled off and the resulting product is mechanically cleaned, and

16Ma. Tells of a Weakly Basic Sulfonate Prepared With 73.8Ma.% Of a technical grade alkylbenzenesulfonic acid prepared by Friedel-Crafts alkylation added with a spindle oil in a ratio of 1: 3 to 5.8Ma.% Of a sulfurized Nonylphanols (sulfur content 3.5Ma .-%), 16.1 wt .-% methanol, 0.8Ma .-% aqueous ammonia solution (25%) and 2.5Ma .-% hydrated lime mixed, mixed with 250 ppm silicone oil and under Stirring at temperatures of 41-6O ⁰ C for 25 minutes so fumigated with carbon dioxide, that the molar ratio of calcium carbonate to calcium hydroxide 3.5: 1 and that between phenolate and free phenol is 1.2: 1, and the reaction product then in 40 minutes 128 ⁰ C and heated for a further two hours at 160 ⁰ C and purified by centrifugation.

25Ma.-Parts of a technical Zinkdialkyldithiophosphates (active ingredient content about 45%, Zn content about 4.2Ma .-%) and eMa.-parts of the technical ethoxylated Alkylphenole used in Example 2 emulsifier MF

is prepared, an additive package for engine lubricating oils by intensive mixing at temperatures of 50 to 6O ⁰ C, having the equivalent proportions of sulfonic groups of about 56mval / kg, of phenolic groups of about 960 meq / kg and a AlkalltfSt of 130mgKOH / g. By adding 2.3Ma .-% of this additive package to 97.7 Ma .-% of the base oil used in Example 1 or 2 is an engine lubricating oil with a TBN of about 3mgKOH / g and with excellent aging stability, very good corrosion protection behavior, good resistance produced against water and good separation behavior, which is clearly superior to products of the prior art. Using 3.9% by weight of this additive package in one of the above base oil types, a multi-purpose lubricating oil is obtained which can be successfully used both as engine lubricating oil for crosshead diesel engines and as plunger lubricating oil for diesel fuel driven auxiliary machinery, emergency generators and similarly loaded engines.

BelsploM

The engine lubricating oil according to Example 1 is modified by adding, as a special rust inhibitor, additionally 0.1% by weight of the

ethoxylienen alkylphenols from Example 2 are used.

As a result, the already good deposition and aging behavior of the product is further improved, the excellent Water compatibility and the very good corrosion protection process are not adversely affected. TABLE 1 High-temperature oxidation behavior (test duration 12 h, test temperature: 250 ° C., catalyst: F-naphthenate Increase in viscosity at 50 ° C% rel. 59.4

Increase in resin content% from3. 8.06 Evaluation of the test sheets

(Best grade = 10) point 7

112,15 20,11

49.03 3.73

7.5

1 note additive A in lubricating oil raffinate

2 branded product 1

3 branded product 2

4 Inventive Trlebwerksöl Example 1

Table 2: Corrosion protection behavior

film strength traces of traces of traces of none none • corrosion corrosion corrosion Corrosion, corrosion Bromide test RSI RO R3 RO RO (Best value RO) Glockentost 2 3 1 10 10 (100% rust reached after days)

1 brand additive B in lubricating oil raffinate

2 branded product 1

3 branded product 2

4 Inventive Engine Oil Example 1 6 Inventive Entrained Oil Example 2

Table 3: Deposition behavior and bearing corrosion Test engine Pettar W1 (test time: 36 hours, point rating 10 -

clean)

Ring grooves, paint Pts. 4.2 5.5 4.8 5.5 9.9 Piston bottom, inside Pts. 8.6 9.4 6.7 8.2 9.3 Bearing weight loss mg 64 27 1831 63 20

1 brand additive A in Schmleröl raffinate

2 branded product 1

3 branded product 2

4 Triebworksöl according to the invention Example 1

5 Engine Oil According to the Invention Example 2

Claims (5)

1. Engine Oil for crosshead diesel engines, consisting naphthenic from one of Schmierölraffinaten paraffin, or mixed-basic origin produced base oil having a Vickosität of 40 to 150mm ² / s at 5O ⁰ C and an active substance combination for improving the detergent-dispersant behavior, the thermo-oxidative stability and corrosion protection behavior, characterized in that the active ingredient combination 1 to 5 Ma .-% of a combination of at least two different, matched weak, medium and / or highly basic Erdalkalisulfonatenphenolaten, 0.2 to 1 wt .-%, based on the pure active ingredient, of at least one multifunctional inhibitor of the type Zincdiaikyldithiophosphat and as a specific corrosion inhibitor from 0.05 to 0.5% by mass of a fatty acid amide prepared by condensation of fatty acids of the chain length range C ₁₈ to C ₂₂ with amines, preferably diethanolamine and / or ethoxylated alkylphenols of an alkyl chain length range C ₁₂ having an average degree of statistical ethoxylation of 3 , 5 to 6.5, be added so that an equivalence ratio of sulfonate groups to phenolic groups of 1: 8 to 1:25, a mass ratio of weakly basic to medium and / or highly basic detergents of 1: 1.8 to 1: 5.6 and an equivalence ratio of zinc diallyl dithiophosphate groups to phenolic groups of 1: 3 to 1: 7.5 and a mass ratio of weakly alkaline earth alkaline sulfonatesAphenolate to the specific corrosion inhibitor of 1: 0.25 to 1: 1 , 5 are set. 2. engine lubricating oil according to claim 1, characterized in that as a weakly basic detergent prepared in a continuous process phenolate-containing alkaline earth sulfonate having a basicity of 10 to 60mgKOH / g and equivalents sulfonate groups from 200 to 400mval / kg and phenolic groups from 200 to 500mval / kg is used, the latter to min. 30% sulfurized and 5 to 50% free alkylphenol or alkylphenol sulphide. 3. engine lubricating oil according to claim 1 and 2, characterized in that a calcium sulphonate is used as weakly basic phenolate-containing alkaline earth sulfonate, in its preparation a promoter combination of a technical Alkylphenolsulfid, an aliphatic alcohol and an alkanolamine used and the carbonization at temperatures of 35 to 8O ⁰ C is performed so far that the molar ratio of calcium carbonate to calcium hydroxide at least 3: 1 and at the same time the molar ratio of phenolate to free phenol is at least 1: 1. 4. engine lubricating oil according to claim 1,2 or 3, characterized in that in the active ingredient composition in addition to at least one alkaline earth sulfonate at least one medium and / or highly basic sulfurized calcium phenolate is used with an equivalence of phenolic groups from 1100 to 1900mval / kg, the maximum to to 200mg / kg _t . Sulfonate groups in the form of Erdalkalisulfonrtes contains. 5. engine lubricating oil according to claim 4, characterized in that as sulfurized calcium phenolate, a product is used in the preparation of the reaction in the co-presentation of alkylphenol, alkaline earth sulfonate, high molecular weight alcohol mixture, diluent oil and sulfur in nureinem reaction vessel and is continuously performed and the carbonation in the presence a promoter combination consisting of 2 to 8 wt% of an alkaline earth sulfonate, 4 to 15 wt% of an aliphatic saturated high molecular weight alcohol mixture, 4 to 10 wt% of a polyhydric alcohol and 0.005 to 0.7 wt% of a dimethylpolysiloxane to the overall mix.