DE1644950A1 - Acid protective lubricating oil composition for ship engines or the like. - Google Patents

Description

G. Lieu! Υ »

Patent attorney 1 C / / η C η

8 Munich 13, Birnauer Str. 6 ^'b M ^y ^ U

Telephone 345974 and 375537

Case 199 Oomrn. 706 031

SNAM PROGETTI S »p.A., Milan / Italy

-

"Acid protection oil composition for marine

motors or the like "

It is known that the lubrication in the open circuit of cylinders of slow-running 2 T (two-stroke) marine engines has been based on "Antiaeid oils" (acid protection oils) for about 10 years -α ± ®Λ $ ü & B they contain a very large amount of additives »which often make up more than 25 Qewiöhts-J6 '.

The 0-F% inä _ff from which these oils are used w @ ^ © n _£ . hingt with Ai represents "t decreased by used zugefUhrten Treibstoff3I® @. To the

9838/1720

.- ■ fc -

Lowering the running costs of these engines becomes theirs Heavy fuel supplied which has a high sulfur content of up to 4% by weight or more. It's clear, that under these conditions the acidic combustion products " mainly sulfuric acid, need to be neutralized so that they do not have time to corrode the metal of the cylinder housing with which they come into contact.

Even if the neutralization function is obviously the main function of these oils, so these oils must be in addition to this Of course, it also functions as a lubricant and detergent at the same time, since the sludge that collects in the engines is and the products of thermal decomposition of the fuel as well as the lubricant itself must not accumulate and solidify in places where it is necessary that a free movement of mechanical parts is maintained.

Oeslehtisputitet, the piston ring grooves are critical spots. On these. It is possible that when the residues and tar products are present, the piston ring jams completely or partially; eo since it has lost its sealing function $ ehti what follows that it is through m * 6h * M * o? »· Itenepruchuss» gen stirket »is left. Se is fcektfftfifc, Ml viii · «*

00 9838/1720

protective oils as a result of the high additive content required usually the disadvantage is that they lead to the formation of large amounts of residues, which come from the additives themselves, have as a consequence. The amount and physical state of these Residues can affect the proper functioning of the engines, since the openings as well as the flushing and outlet valves are not clogged with a hard material if possible which is difficult to remove.

The hardness and the tendency to agglomeration of the oil residues can go along with the physical properties of Fuels wear marks and scoring on the piston skirt, on the piston ring and on the cylinder housing.

From the above it is evident / that a Anti-acid oil the result of a suitable combination of one certain number of components should be «each of these: Components must fulfill a certain function that does not may be influenced by the functions of the other additives, but rather should be increased by them *

With regard to the detergent function, the additives of. Acid protection oils for Sohlff motors are very similar to the additives » which in oils for engines with a smaller cylinder space be used. On the other hand, there is a difference in the

0 09 8 3B / 172 0.

with regard to the neutralization function on the calcium »or Magnesium salts of organic acids or weak inorganic acids Acids.

In the field of the production of complex and coordinated additives for acid protection oils, processes are known so far in which the oils are natural or basic calcium sulfonates of synthetic origin (alkarylsulfonates), which contain calcium as a fine dispersion of calcium carbonate.

The dispersion obtained is such that the pro. The duct appears to be completely dissolved in the oil and is evident is soluble in most known organic solvents, with the exception of acetone. The method of manufacture these dispersions are known. Either sulfonates with a defined molecular weight or calcium derivatives are used used by phenols and sulfophenol complexes, which are themselves anti-corrosion agents. Will these connections converted into salts in suitable catfish, then put they are also detergents and emollients.

It is known that some manufacturers of these additives are aware of this are interested in treating them in such a way that their residues, which arise during thermal decomposition, become crumbly are and consequently in a simple manner with the help of the air currents, which for charging or for working with air over-

00 98 38/172 0

shot and used for flushing large marine engines « can be removed *

One of the most common methods used in the lubricant field Used for this purpose is to use additives to mix two different bases. Usually is Magnesium the element, its organic derivatives (in general of the organometallic type), which are soluble in oil, are added to the calcium derivatives on such catfish, that the hard residues, which are usually produced during the thermal degradation of the calcium salts, become more crumbly and less through the simultaneous formation of residues, which arise from organomagnesium compounds, agglomerated will.

However, for economic reasons, the use of organomagnesium derivatives normally to one Minimum reduced.

According to the invention, an acid protectant composition is used Provided for the lubrication in the open circuit of the cylinders of slowly running 2 T-Sehiff engines, in which the lubricating, neutralizing and detergent properties are coordinated in such a way that the residues the agglomerates can be sufficiently removed and are crumbly. The aim mentioned above is to be achieved without using magnesiutnorg & nieche derivatives will.

00983871720

It has been found that the above object is achieved with the compositions according to the invention, those from a calcium derivative of a sulfonic acid or from alkylaryl calcium sulfonates, from an organic acid, which has optionally been converted into a salt with an alkaline earth metal where the organic acid has a saturated or unsaturated carbon chain with 10 to JO carbon atoms, a calcium derivative thereof or from phenols or sulfophenols which are free or in the salt form can, and in addition to the anti-corrosion effect also one Can perform a neutralization function depending on the cases that arise, as well as a coupling dispersant, that results from the condensation products of ethylene oxide and Composed of nonylphenol, the ratio of the two condensed compounds fluctuating between 4: 1 and 12: 1, consists. The whole composition is homogenized and dispersed in mineral oil *

The composition of the present invention is composed as follows specified together. The quantity ranges of their components have such limits as necessary of products with a total basicity number, which after the The area of application in which the lubricants are used is variable, is sufficiently broad:

009838/1720

CaO * 0.7 to 2 wt .- ^

Oleic acid 2 to 15 wt.

neutral or overbased calculus -

sulfonate 5 to 13 wt -.%

Ethylene oxide 1 to 5 wt. ~ #

Glycerol 0.1 to 3 ~% by weight.

% - Lanolin 0.1 to j3 wt.

Sulfophenates and complex phenates or

their calcium derivatives 0.05 to 25 wt -.%

Mineral oil. Remainder i

The presence of the specified amount of oleic acid justifies it can be achieved both by their caleium derivatives Improvements that improve the lubricating properties of the oil and the low cost of oleic acid self.

Ophenolen the high content of suif and complex phenols are present "the free or in the form of their alkali metal salts, λ based on the fact * that some of these products have the same time in the form of alkaline earth metal salts, the effect of neutralizing agents to the effect of an antioxidant and corrosion inhibitor, such as emerges from a series of tests which is carried out with an apparatus of the Mc Kee type. The apparatus consists essentially of a heated metal plate on which the oil is reeyolized by oxidation until it becomes acidified, so that it is possible

00983.8 / J720

is, from the oil condition after the test as well as from the quantity and the type of residue that is deposited on the plate itself and from observations made on marine engines under normal conditions Operating conditions were employed to determine a good behavior of the compositions according to the invention. In particular, it was found as a result of the Mc Kee test that the for the preparation of calcium derivatives more suitable molecular weight of the alkylarylsulfonates, which in an effective manner a very able to stabilize high overbasing, is approximately 500. For the production of these alkylary! Sulfonic acids usual sulphonation methods used.

In addition to the overbased sulfonates, it is possible to use the oil Add phenols or sulfophenols, which are in free form or in the form of calcium derivatives.

If the phenols or sulfophenols are free, then they only own an antioxidant and anticorrosion function, whereas them has a neutralization function when used with an alkaline earth metal have been converted into a salt. The most common sulfophenols used and most effective are given below. They are distinguished by the fact that they are aromatic in the molecule 2 Have nuclei that are linked to one another by one or two sulfur atoms.

009838/1 720

While the sulfur has the anti-corrosion properties of these jj Products, the length of the side chains affects the solubility of the product itself.

According to the invention, either the simplest phenols come from Formula R-CgH ^ or the phenols in question, which have different substituents on the nucleus »Furthermore, such phenols which have two or more cores »where the In addition to sulfur, substituent chains also come from bridges Ammonium *, phosphorus and chlorine derivatives or the like ν er, can be bound. In addition to the compounds of the above The general formula used are suIf © phenols those compounds where the structure and nature of the Bridge formationj via which the two rings are connected, varies, introducing new elements or groups of elements. There is also the possibility that the bond between the two nuclei is reinforced, as is the case with the following Connections the case 1st;

009838/1720

OH NH ^ OH OH ^ S OH

being different substituents either in the nucleus or sit in the side chains or in the bridges themselves,

It should be noted that the examples mentioned above are not intended to represent a restriction, but are only intended to indicate the various products that arise from Derive phenols which have only one aromatic nucleus or 2 or more nuclei *

The manufacturing method given below is explained the invention "without restricting it:

2 to 15 parts by weight of a commercially available oleic acid with a mineral oil (essentially based on naphtha) with an average viscosity index and an Engler viscosity mixed at 50 ° C from 7 to 8, whereupon 0.7 to 2 parts by weight of CaO to achieve a homogeneous mixture, 0.1 to 2 parts by weight of glycerol, 0.1 to 3 parts by weight of lanolin and excess water are added with stirring.

The mixture warms up in the moment in a more spontaneous way Way, when the reaction between the calcium oxide and the olein begins.

Ό09838 / 1720

After the occurrence of a hard and viscous mass, it becomes 0.05 up to 25 parts of a sulfophenate or complex phenate with slow heating to remove water and terminate added to the solubilization reaction.

After most of the water has evaporated, the Mass starts to become transparent, will be 5 to 125 parts Calcium sulfonate and 1 to 5 parts of nonylphenol and Äthylenoxyd ^ -Konäensationsprodukte added.

In this way a brownish, viscous mass is obtained. When heated, a viscous liquid is produced. The heating while the temperature is slowly increased to 130 ⁰ C is continued. After the water has completely evaporated, the rest of the mineral oil is added in order to set the required basicity number.

The oil obtained by the process described above is after cooling to the room temperature, as it is assumed in the countries with a cold or temperate climate, or to a temperature of at least 20 to 25 ⁰ C in the countries with a warm climate, ready to use.

00 9833/1720

Claims (5)

Pat e η t a η s ρ r borrowed 1. Acid protective lubricating oil composition, featured by a basic compound, soft by reacting an oxide with an alkaline earth metal. " an organic soluble in oil Acid, a neutral or overbased sulfonate of an alkaline earth metal, a complex phenate and / or sulfophenate has been made, this compound in the mineral oil is solubilized and stabilized in the presence of glycerin and lanolin. 2. Acid protection lubricating oil composition, characterized in that the oil-soluble acid, preferably oleic acid, in an amount of 2 to 15 wt. % » The alkaline earth oxide, preferably calcium oxide, in an amount of 01.7 to 2 wt .- ^ , the neutral or overbased sulfonate of an alkaline earth metal, preferably neutral or overbased calcium sulfonate, in an amount of 5 to 1jJ wt .- ^, the glycerin in an amount of 0.1 to 2 wt .- % and the lanolin in an amount of 0 , 1 to 3 wt .- ^ is used, while the antioxidant of the sulfophenate type and a complex calcium phehat in an amount of 0.05 to 25 wt .- % and the surface-active agent, preferably based on condensation products of ethylene oxide and nonylphenol , can be used in an amount of 1 to 5 wt. 00 9838/172 0 16U950 3 * Process for the preparation of an acid protection lubricant composition, characterized in that 2 to 15 parts by weight of a commercially available oleic acid are mixed with a mineral oil with a viscosity index and an Engler viscosity at 50 ° C. of 7 to 8 "the mixture to achieve a homogeneous mixture, add 0.7 to 1 part by weight of glycerin, 0.1 to; $ parts by weight of lanolin and water while stirring, to obtain a hard and viscous mass 0.0 5 to 25 Parts by weight of sulfophenols or phenols in free form or in the form of alkaline earth salts, preferably calcium salts, I are added, 5 to 13 parts by weight of calcium sulfonate and 1 to 5 parts of nonylphenol-ethylene oxide condensation product are added, the mass after the water has evaporated, after it begins to become transparent, ^{it is heated to 130 0} C and after the evaporation of the water mineral oil is added until the required basic number is reached, 4. Acid protective lubricating oil composition according to the claims 1 and 2, characterized in that the antioxidant | is a calcium sulfophenate ». 5. Acid protection oil composition according to the claims 1 and 2, characterized in that the antioxidant is a complex calcium phenate. 0 0 9838/1720 644950 β. 'Acid protective lubricating oil composition according to the claims 1 and 2, characterized in that the antioxidant a mixture of complex calcium phenate and calcium sulfophenate is. . 009838/1720