DE1444923C - Process for the preparation of dispersions of alkaline earth metal compounds - Google Patents

Description

The invention relates to a process for the production of lubricating oils, in particular those which contain barium and calcium compounds. In particular, the procedure is aimed at a method after the oil-soluble barium and calcium compounds in on the basis of hydrocarbons built-up lubricating oils can be introduced, the barium and calcium compounds are kept in a stable, transparent dispersion in the lubricating oil.

The invention further relates to the dispersion of barium and calcium compounds in lubricating oils, giving the oil a high alkali reserve and making the oil more effective against silting should be protected, which is caused by such acids, which are found in prime movers, in which the oils in the crankshaft housing are used to form.

It is an object of the invention to provide a lubricating oil which contains a high reserve of alkali, mainly in the form of stable dispersions of the barium and calcium compounds, in particular of barium and calcium carbonate. Another object of the invention is to provide an additive for lubricating oils which contains a high percentage of barium or calcium in the form of basic compounds together with barium or calcium salts of sulfonates and phosphonates. The latter can be obtained by treating organic substances with phosphorus sulfides, in particular P ₂ S ₅ .

In the production of lubricating oil additives through the action of phosphorus sulfides, for example Phosphorus trisulfide and phosphorus pentasulfide, the usual procedure is to use the phosphonated Products neutralized with different bases, e.g. potassium, calcium or barium hydroxide, whereby oil-soluble compounds are obtained which, as additives to lubricating oils, cause oxidation and sludge formation prevent. These products are very well known detergents and have been widely used Scope in oils for crankshaft housings used for lubrication of internal combustion engines, where they prevent sludge settling and reduce oxidation of the oil, especially where the oil with hot surfaces, for example pistons and cylinder walls, comes into contact. It seemed advisable to keep the alkali reserve of these additives by adding additional calcium or barium hydroxide or carbonate in various ways Way to increase. However, the amount of barium or calcium hydroxide that can be added was limited so far.

The production of oil dispersions of the alkaline earth metal compounds by the action of an alkaline earth metal oxide and methanol on an oil in the presence of an emulsifier has hitherto been difficult because of the formation of gels which are difficult to destroy. This is particularly true for the method of British Patent 780,820. The viscous reaction product can only be heated with difficulty because it burns or burns in the area of the heating surface (cf. in particular page 7, line 99 et seq. Of the patent). In spite of large amounts of filtering hill, it cannot be filtered either. After all, it does not appear possible to carry out this process on an industrial scale. In addition, relatively large amounts of water are added to the reaction mixture, which amount to at least 2 ¹ It ⁰ Io of the weight of the surface-active substances (cf. page 3, line 44 of the patent).

According to the method of French patent specification 1136 852 as alkaline earth metal compounds Hydroxides used, which leads to difficulties in the filtration of the end product, since the used Calcium hydroxide in the oil dispersion in

ίο there is a particle size that the filter pores clogged. In the French patent specification 1157 249, hydroxides of alkaline earth metals were also used used. The French patent 1149 566 is preferably on the use of salts of the Alkylsalicylic acid directed. French patent specification 1153 139 relates to the use of sulfur dioxide with a calcium hydroxide. According to French patents 1148986 and 1152926 are used for the production of oil dispersions of the CaI

ao cium carbonate initially dispersed alkali metal carbonates, and then the oil is treated with a calcium chloride solution.

It has also already been proposed that dispersions of magnesium carbonate in lubricating oils to manufacture. Also the subject of an earlier patent is a method in which one from an alcohol and a basic alkali or alkaline earth compound obtained by introducing carbon dioxide Salt dispersed in a lubricating oil by means of a dispersant and then the dispersion obtained heated to about 150 to 160 ° C to remove solvent and water.

In contrast, the present invention relates to a process for the preparation of dispersions of.

Alkaline earth metal compounds in oils, which is characterized in that calcium or barium oxide with carbon dioxide, oxalic anhydride, P ₂ O ₅ or SO ₂ in the presence of an emulsion of an oil, in particular a mineral lubricating oil, methanol, a hydrocarbon as solvent and an oil-soluble carboxylic acid with more as 12 carbon atoms or an alkali salt or alkaline earth salt thereof is reacted as an emulsifier, that the methanol is separated and oil and solvent are treated with water or steam to prevent gel formation, whereupon the oil dispersion of the metal compounds are separated from the reaction mixture.
The method according to the invention allows the amount of basic calcium or barium compounds in oil to be increased significantly, as can be demonstrated by the standard titration method with acid. In carrying out the present process, an olefin polymer is preferably used as

SS used starting material, which is generally a Has viscosity in the range of about 500 to 3000 SSU at 98.89 ° C, which is a molecular weight between 700 and 1500. These polymers can have a proportionate fractions narrow molecular weight distribution, but also polymer mixtures with a wide spread of molecular weights represent. When using high molecular weight products it has been found that the finished product improves the viscosity index of the lubricating oil to which it has been added. As for making Olefins suitable for these polymers are, for example, propylene, butylene, amylene and u. like. called. These monomers can be used in a very simple manner

3 4

by means of catalysts such as BF ₃ , AlCl ₃ and the like in itself facilitated by the fact that the oil can be polymerized at a higher temperature in a known manner. is brought; furthermore, at this point, other substances than oil can also be used by adding a suitable light lubricating material for the present process, for example a refined 100 neutral, e.g. B. unsaturated hydrocarbon oil, be diluted. Substances refined by distillation, which in the cracking of paraffin wax to lubricating oils, which have viscosities between about 60 and falling, or generally unsaturated hydrocarbons 200 SSU at 37.78 ° C, are suitable substances with a suitable molecular weight and mixing additives, provided that the volatiles have more than 20 carbon atoms. ^: speed is not too low to influence the flammability properties of the finished product, the olefin used as starting material. The polymer is a phosphorus sulfide, preferably amount of diluent oil can appropriately P ₂ S ₅ , in an amount of 5 to 20%, generally at about Vz to 2 parts by weight to a part of about 10 to 15%, in the form of a powder or Granular starting material used olefin polymer lielats added. The reaction mixture is then heated in gen. For most purposes, a dilution in the absence of air is sufficient to oxidize with an equal weight of the additive oil. Prevent it. A gas shell made of carbon is sufficient for this - petrol can also be added to the visdioxide. In order to reduce the viscosity of the phosphorus sulfide during heating and to keep the washing out in suspension in the oil, intensive lightening is carried out.

stirs; the temperature is maintained at about 150 to about The washed, diluted phosphonated 205 "° C for several hours. In general such product can now neutralization step of Vergemeinen is to be supplied to a reaction time of 5 hours at driving. In the preparation of 15O ⁰ C. Sufficient. In the reaction, the sulfur-barium compound is set free by the addition of a hydrogen. Hot aqueous solution of barium hydroxide in After the reaction mass has cooled down enough, it is appropriate, but not, in excess compared to the amount that is with the A 10 to 50% excess appears to reduce the useful viscosity of the intermediate product. Too moderate. The oil is mixed with the barium hydroxide solution for this purpose Volume petroleum-intensively cooked through and the temperature to about ether with a boiling point between 93,33 and 160 ⁰ C increased to the neutralization are added completely 148.9 ° C. After the mass perform a 30. But it can also have been left standing for a shorter period of time, e.g. B. a few hours temperature indicated for a longer period of time up to a day, the unreacted will be turned around. The neutralization can also be accelerated by phosphorus sulfide at the bottom of the reaction vessel, the addition of an alcohol, for example butyl, and the oil alcohol obtained as an intermediate product, which can then be decanted into another vessel 35. The neutralized product is either scoured by washing from the above in which it is exposed to the action of steam. The phosphorus compounds formed as an intermediate product with water and alcohol or by filtration beSulfur compounds, which are released when exposed. During the filtration it is advisable to use a filter of the sulphide on which the hydrocarbons have formed. In this stage 40 the neutralized oil is then dried intensively, and hydrogen sulfide is released, which, if necessary, has to be drawn to a temperature by heating. During the hydrolysis, from 162.78 to 176.67 ° C, or by the removal of phosphoric acid, which is why a drying gas that is more resistant to acids is exposed to the effect of gasoline vapor or another of the hydrolysis. At the Herhige apparatus must be used. For this purpose, the calcium compound is pulverized in a steel tank with a glass covering. Lime is used in the oil instead of the barium hydroxide solution. In the first stage of the process, it can be added. The amount of lime (calcium hydroxide) should be used against an aluminum apparatus. These are sufficient to make up all of the existing in the oil ^! must be neutralized against the effects of sulfur and amount of thioic acid. In general, acidic acids which are formed in the reaction with P ₂ S, it seems expedient to use such an excess of and the aluminum in the absence of water lime that a product with an alkali does not attack, resistant. <value of about 20 to 40 is obtained.

The hydrolysis may conveniently phosphonated oil generally an alkali number of a period of from 1 to 5 hours carried 55 at a In this process step, the neutralized temperature of about 150 to 177 ° C or 205 ⁰ C for about 20 to 30 in the titration with Methyl orange as leads. During hydrolysis, the indicator turns on. It seems expedient to bring the alkalinity of the first stage gasoline * from the reac- tion to a higher value in order to distill off and collect the material. Neutralize acids that occur when using the After hydrolysis, the product is preferably lubricating oil. Attempts have been made to extract this with water in order to remove the water-soluble acids 60 using an excess of barium or, for this purpose, in particular, phosphorus and thio-calcium hydroxide. These attempts include phosphoric acid. For this purpose it is preferred, however, in general, because the barium is preferably a mixture of water and a sodium or calcium compound to form colloidal third alcohol such as isopropyl, butyl, pentyl alcohol, dispersions, which in lubricating oils are not preferably secondary butyl alcohol , in 65 can be resolved. Doing this does not form a ratio of about 1: 1 to 3: 1 when used. transparent solutions. Such colloidal dispersants - The alcohol acts here as an emulsion breaker. In general, sions cannot be carried out by a If the oil is very viscous, the extraction will there- fore be clarified by filtration, as it is either too coarse

5 6

or too fine to be a satisfactory filter, which is heated and removed by removing the solvent.

to bring the result. The colloidal barium solvents, water, etc. in a manner known per se

and calcium compounds also tend to be that can be concentrated. As a result, e.g. B.

Surface of the filter with an impermeable after dehydration between 163 and 177 ° C,

To provide coating, even then; if considerable 5 get a clear liquid oil that in general

Lots of filter aids are used. is red or yellow in color. This can be done without

It has now been found that further barium and calcium can be filtered with a small amount of filter aid umcarbonate can be introduced into the oil in order to achieve a final clarification, When they pull as oxides in the presence of methanol, the end product can have an alkali value of 60 to are set. In the case of barium, the preferred 10 80 mg KOH per gram equivalent or one more wisely used a complex shown below as a higher value. In general, barium methylate was solid referred to as. This complex set that the alkali value achieved approximately three can in a simple manner by converting barium it is times as large as the alkali value of the neutral one oxide and methanol can be obtained. This reaction phosphonated barium product which runs as an output is used very quickly with the development of a considerable amount of material for this process stage, borrowed heat. If this reaction occurs in tech- In the manufacture of the barium methylate can be gronischen If the standard is to be carried out, it is necessary to use granulated barium oxide in order to avoid a loss of methanol due to demolition with methanol over a period of a few hours to avoid. At room temperature, both of which are brought into contact for days. While for example 26.67 ° C, the concentration corresponds to this time the methanol pulp reacts with the coarse of barium in this complex an alkali value granulate, whereby this by swelling into a white of approximately 160. At higher temperatures, gelatinous mass passes over, which further constricts even higher concentrations can be obtained. methanol is easily soluble. It can be traded Cooling the warm solution separates the usual methanol for the production of the barium ' Crystals of the solid complex compound. 35 methylates are used, with a small one

In the case of calcium, calcium oxide and the amount of water will have no harmful effect. It is Methanol is added to the phosphonated oil and, however, it is expedient to use water in an amount above Carbon dioxide introduced into the mixture. To rule out an approximately 5%. Takes while standing To obtain oil with the desired alkali value, the barium methylate solution is a yellow color, inses only required the required amount of the 30 special when the methanol is contaminated. Calculate the barium methylate solution and add it to the There are indications that the barium methylate oil to add. The oil is coordinated with a suitable ethylate in Diluted solvent based on hydrocarbons, which the barium oxide and methanol in certain. B. are bound to one another with a gasoline with a boiling point of other proportions, approximately 121 ° C or an aromatic carbon 35 in addition to the above-described hydrogen phosphide such as benzene, toluene or xylene. Sulfo-hydrocarbons can cause various on-stirring and heating the mixture, the medium can carry out anionic emulsifiers ethanol distilled off with part of the gasoline, again the method of the invention for production which are recovered and fed back into the process of colloidal oil dispersions of calcium and barium. 40 connections can be used. Of particular concern

According to this, the oil has the effect of a meaning here are the oil-soluble sulfonates, like them

Barium binding agent known as mahogany sulfonate, and the oil-dissolving

Makes barium insoluble in water, creating a steel-borne phosphonate. The sulfonates are readily

biles waterproof product is obtained. This is done according to procedures that are well known per se

obtained in the simplest way by treatment with carbon 45, z. B. by sulfonation of lubricating oil fraction

Dioxide gas achieved in an amount necessary for the conversions with SO ₃ or oleum, from which the sulfone

All of the barium in the added barium acids, into the corresponding calcium compounds

methylate to barium carbonate is sufficient. In which to be transferred, either directly or via the

State or in which bond the barium after sodium sulfonate, as e.g. in the USA.-Pa-

the carbonization is present, can not be described with so tent 2,689,221. The

Security can be said. However, sulfonates of metals other than calcium are believed to be used

men, that a complex carbonate-phosphonate will occur, in particular. of metals of I. and

located. The product is a clear oil that belongs to Group II of the Periodic Table / of aluminum

its heating to remove the barium and iron. .

thick and sometimes to a semi-solid mass. 55 Sulphonic acids can also be easily replaced by sulphonic acids.

stares that resembles Staufferfett. Depending on the conditions of alkylated aromatics, such as alkylated benzene

In some circumstances, a friable and naphthalene will be obtained, which is about 15 to

Received sponge. This mass appears to contain an emul- 40 hydrocarbon atoms. To this

sion to be of the oil-in-water type, in which the purpose can be the sulfonic acids immediately such as

Barium phosphonate carbonate complex the outer 6 ° they arise during sulfonation, or in the form of them

Phase forms. It is very difficult to find this product calcium, barium, sodium, ammonium or other

to be heated without using coagulation and decomposing salts. If salts other than

Settlement occurs on the heated surfaces when the calcium or barium in this process

the temperatures are high. It has been found that stage can be used, it is found that a

the intermediate can be converted 65 considerable amount of the cation by calcium or

apparently by reversing the emulsion, namely barium is replaced.

by mixing and heating with a little more anionic emulsifiers for the invented

Amount of water, according to which the product is a liquid oil.

Insic acid, linoleic acid, naphthenic acids, and the methanol obtained in the process can be oxidized again in the process acids formed by paraffin wax. be returned after most of the These can be obtained in the simplest way in the form of their ba water by the one used in the process riura or calcium salts or soaps are used, calcium oxide has been removed.

the. Alkylbenzenesulfonic acids and alkyl amber 5 In some cases it is advantageous to have a small

acids with from 15 carbon atoms upwards amount of water must be added during the reaction,

also suitable. provided that it is gradually in the presence of one

In the case of calcium compounds, the excess of CO ₂ or another acid oxide does not dissolve in methanol as in the case of barium. is fed. It was found that the addition, however, it appears as if calcium oxide had a grain size of about 5 to. 20% water, preferably about 10%, forms plex with the emulsifier, which reacts _{with the acid as related to the carbonic acid (CO 2) used in the reaction.} In the reaction it becomes calcium oxide; sometimes the degree of absorption developed considerable warmth. The temperature of the dispersed calcium carbonate in the oil increases, doors rise by 27 ° C. Intensive stirring.When water is added to the reaction, it is advisable to ensure intimate contact between the 15, by means of a methanol solution, particles of calcium oxide and methanol, in order to obtain an even distribution in the emulsifier, hydrocarbon solvent and CO ₂ reaction mixture, because any local or other acids. After the end of the re-concentration of water in the reaction mixture to action, which can generally lead to the formation of calcium chydrate within 30 minutes, not only up to 2 hours, depending on the effectiveness of the calm in relation to the production of the desired If the blockage occurs, the reaction products are heated if the calcium compound is ineffective, but rather to distill off the methanol and the hydrocarbon solution, which also interferes with the clarification of the product through filtration. It is expedient to fertilize the dispersions of calcium and barium verbinthanol from the reaction mixture by introducing it into oil to remove particles less than 1 micron in diameter from vapors of the boiling solvent, and preferably less, preferably just mentioned - Contained than 0.1 micron in diameter, so that the th hydrocarbon solvents. The usual methanol prerequisites for clarification are present, fraction is condensed and the particle sizes between about 1 and ren are used again in the process. After removing the methanol, it is 10 microns in diameter, e.g. B. 1 to 5 microns. By generally expedient to introduce water to 30 meters, the dispersion is cloudy, although such hydration of the calcium and barium compounds dispersions in the usual filtering methods used in petroleum and prevention of solid or semi-industrial filtering go through solid gels, which often arise, although under certain conditions can. For example, a dispersion with conditions that omit the hydration stage, particles 1 to 3 microns in diameter can be filtered with a bed of diatomaceous earth, depending on the nature of the oil, the concentration of the dispersion and the emulsion used Filtrate is milky or opalescent, gators. Water can either be in liquid form or it is impossible to add such an oil because of its extreme steam, preferably as a liquid-like nature of the dispersion. It has been found that the degree of being an extremely fine filter aid on diatomaceous earth contact with water can be clarified by adding a higher Al-40 basis.

alcohol can be increased, e.g. by butyl- Does the process lead to the dispersing of CaI-

or amyl alcohol. An excellent contact cium and barium compounds in the oil to one

The agent for the hydration stage is aqueous secondary formation of particles or agglomerations of

där butyl alcohol with a water content "of about particles with a diameter between" ί and

28%. 45 50 microns, it will be practically impossible to get the oil

After hydration, the heating will continue to filter as the particles settle on the surface to deposit the remaining hydrocarbon solvent on the filter. With this deposition, the water and possibly also the butyl alcohol form a gradual layer of fine parkohol. If steam is used for the hydrates with diameters down to 1 micron and ion, the hydrocarbon solution can be drawn between coarser particles, which in the solvent with the steam completely carry the fine particles from the oil surface layer are, at the same time the temperature, which is brought to a substantially complete at about 150 175 ⁰ C noticeable. The oil can close off the surface against the passage of liquid which is then fed to the final filtration. In this respect, there is an essential feature that is preferably carried out with one of the known filters of this process in the production of colloidal aids, for example silica gel, aluminum oxide and dispersions of calcium and barium compound diatomaceous earth. fertilize that is relatively free of particles or

It is important that the water removed from the reaction is agglomerates that are coarser than about 5 microns

is concluded to be a hydration of calciumoxy-. In general, according to the present

to prevent it. It is also sufficient if handeis- 60 process dispersions with a colloidal par-

Common methanol is used, which has an overall size of less than 0.1 microns in diameter

mean less than 0.5% and no more than 1% prepares.

Contains water. Is the water content of the methanol The examples below are intended to illustrate the procedure

larger, so the excess water can be explained in more detail,

fan manner by distillation or treatment of the 65 η · · 1 1

Methanol with calcium oxide and subsequent Ab- B e 1 s ρ 1 e I 1

separation of the resulting calcium hydrate to 210 parts by weight of polybutylene with a

to be removed. The molecular weight of 1200 recovered in the process became 60 parts of P., S ₃

9 10

added. The mixture was _{quickly stirred in a CO 2} atmosphere of a neutral oil with a viscosity of sphere and diluted approximately 100 SSU at 37.78 ° C. within 10 minutes. Which raised the temperature to 193 ° C. Thereafter, 45 parts of a mixture was Bariummethylatdie temperature was slowly, over one hour, added to solution, the alkali brought a value from 164 to-204 ⁰ C. The reaction developed 5 pointed. Furthermore, 20 parts of barium sulfonate were mixed with hydrogen sulfide, which was absorbed in alkali. an alkali value of 68 and 100 parts gasoline (250). This was added to remove _{excess P 2} O _5. Kohlendioxyd'wurde filtered to the complete product and hydrolyzed with steam at a temperature carbonization with heating in the mixture between about 93 and 154 ° C, with initiated. At 71 ° C., foam formation occurred as a result of further H ₂ S developed. After hydrolysis of the evaporation of methanol, and after digestion of about 2 hours, the reaction in the evaporation of the solvent began to be essentially complete. zend to form clear gel. By adding 25 parts

The product was washed with 150 parts of water and len water, the gel was rapidly decomposed with an equal amount of aqueous secondary formation of a liquid oil which was washed with dehydra-butyl alcohol at 163 ° C. After standing for 15 was tized. The clear oil was filtered quickly, for one hour the water layer, approximately leaving a clear red oily product with a 190 part, was discarded. An examination of the water-alkali value of 60 and an ash value of 17.57% coating indicated considerable amounts in phosphoric acid was obtained. . ■
after. A second wash with 100 parts of water - If, according to the present process, secondary butyl alcohol and 200 parts of a sulfonate combined with a phosphonate resulted in an emulsion, which is turned on standing, the basic is expediently in an oven overnight at about 65, 5 ° C broke. Barium sulfonate after the carbonization stage to-An addition of gasoline favored the breaking of the set, otherwise as a result of the effect of the carbon emulsion by reducing the oil viscosity. acid an acid sulfonate can be formed with

The oil layer was neutralized with barium hydroxide, the result of which was a decomposition of the sulfonate

lized, with 40 parts dissolved in hot water when heated and dehydrated due to the thermal

Barium oxide were used to avoid a clear mixing instability of free sulfonic acid

Solution of barium hydroxide in water. ' can. However, the addition before carbonization

The mixture was dehydrated and carried out with stirring when the free sulfonic acids are neutral

brought to a temperature of 126.5 ° C. This can be done, for example by adding

after was cooled and added with water and as much barium hydroxide before heating.
Butyl alcohol gewas (; hen that an emulsification

did not occur. , j.J. Example 3

To reduce the viscosity, 100 parts of a phosphonated oil was added by the action of a neutral oil. After filtration was 35 of P ₂ S ₅ to polybutylene with a molecular

the yield 300 parts. The product had a weight of 700 and subsequent hydrolysis and

Alkali value of 2.2 against phenolphthalein and 19 neutralization with Ba (OH) ₂ . In the

against methyl orange. It became a clear red oil mixing with 100 parts of neutral oil

obtained with an ash value (sulfated) of 8.07%. 5.4% ash and an alkali value of 20 were found.

100 parts by weight of this oil was mixed with benzene 40. 200 parts of this oil became 10 parts by weight

diluted and with 17 parts of a barium methylate (5%) of a barium mahogany sulfonate from 68 A.V.,

treated solution, which has an alkali value of 130 200 parts gasoline (boiling point 250 ° C) and 25 parts

exhibited. On stirring, the mixture gave a cloudy secondary butyl alcohol. After cooking

Emulsion into which carbon dioxide was introduced, the solution with 50 parts of barium methylate solution

while increasing the temperature to 82 ° C. 45 (160 AV) the solution became clear. CO ₂ was

On the heated surfaces of the reaction vessel during cooling at a temperature between

a solid, spongy phase separated out. A see 65.5 and 43 ° C initiated. During 20 minutes

Addition of further solvents such as toluene and the solution gelled; then there was 20 parts of water

Xylene, however, increased the degree of dispersion without adding it. The gel broke quickly. The oil was at

to cause liquefaction. At this stage 50 163 ⁰ C was dehydrated and filtered quickly. It resulted

a clear gelatinous mass. There were 50 parts a clear oil with 10.8% ash and 54 A.V.

Water added to the mass, after which the product It was in petroleum spirit (boiling point 200) and in

quickly lost its viscous solid consistency and made 90 parts of neutral oil completely soluble

passed into a thin oil, which at about 150 ° C was a clear, cloud-free solution,

dehydrated and in a sufficient degree 55.

was filtered. The clear red oil had an alkali Be 1 s ρ 1 e I 4

value of 1.5 against phenolphthalein and 80 against As a starting material for the inventive

Methyl orange. Ash (sulfated) 19.75%. Process stage are preferably oil-soluble

... petroleum sulfonates of barium are used, where

B e ι s ρ 1 e j _{6o yon rßenc] c} j d _{ncm he} known Mahaßonisulfonate

Polybutylene having a molecular weight of about the alkali or alkaline earth metals, for example the

760 was _{phosphonated with PJS 5} as above barium sulfonates. Calcium, sodium,

specified. The product was started with steam hydro-potassium, lithium, magnesium, etc.

lysed and neutralized with barium hydroxide. That will. So z. B. a calcium sulfonate of a

by titration determined alkali value of the obtained 65 preferably used oil-soluble petroleum sulfone

oil was 0.5 against phenolphthalein and 39.0 acid treated with barium methylate as follows:

against methyl orange. The sulfated ash amounted to 200 g of a calcium sulfonate lubricating oil solution,

16.18%. 140 parts of this oil were made with 70 parts containing about 30% sulfonate with a molecular weight

11 12

from et -ι 500 contains, 50 ecm petroleum-methanol was distilled off. Appropriately, gasoline with a boiling point of 93 ° C is added. a gasoline dilution of about 1: 1 or 2: 1 is used. The solution was applied with stirring 100 ecm of a (gasoline-oil ratio) to add the Dürch solution of barium methylate, which promotes the mixing and action of the barium. Dissolving barium oxide in methanol (alkali value 5 thereafter, carbon dioxide was absorbed in the oil 160) was obtained. CO ₂ was in the warm with good stirring. The clear solution was passed into the cloudy mixture. Converted on the surface, namely in the warmth with water, a methanol layer formed as a result of the effects. If the solution is allowed to cool, this effect of the CO ₂ separates the complex. In a small amount turns out to be a solid gel, which is difficult to handle. A gummy emulsion formed around the circumference. The solution was then used to remove from the sides of the container. 25 ecm of water were added to gasoline and water, heated to 171 ° C., set and then heated to boiling. to drive out all the water. The hot oil The gummy material dispersed rapidly at about 2% of its weight by filter reversal of the emulsion phases. The oil was mixed and filtered with the aid. The clear, slightly red dehydrated at a temperature of 163 ° C and 15 product had an alkali value of about 68.
quickly filtered. The oil had an alkaline value of 90. . ... against methyl orange and 5 against phenolphthalein. Examples.
Ash value (sulfated) 21.1%. The original A polybutylene having a molecular weight of calcium sulfonate had a Aschwert of 8% and 700 was mixed with 19 percent by weight of P ₂ S ₅ at 238 ⁰ C an alkali value of 18 20 during 20 minutes with a protective sheath of

When the experiment is repeated, the gas is converted to evaporation gas to exclude air.

Omission of the CO ₂ stabilization step possessed the The product was made with an equal amount of gasoline

Product has an alkali value of only 21 (phenol-diluted, filtered and then hydrolyzed with steam.

phthalein) and 26 (methyl orange). The gasoline was removed, and the hot oil that

. . 25 with 50 percent by weight of neutral 150-01

Example 5 _{adds worc} } _en i _{st> wurc} each with filter clay (10%)

7.5 kg of polybutylene, which decolorizes a mixture of the same 149 ° C. The yellow oil was neutralized with one part by weight of a butylene polymer with a barium hydroxide solution in each case, dehydrated with a molecular weight of 750, 1200 and 1700 and filtered. Alkali value: 2.8 (phenolphthalein) and, represented, was in an aluminum container with 1 kg 30 41 (methyl orange). Ash: 12.28%. Phosphorus: a P ₂ S ₅ granulate stirred while heating to 1.54%. Sulfur: 1.33%.
21O ⁰ C and a protective cover of CO ,. After .
the mass for 2.5 hours at this temperature ger B e 1 s ρ ι e 1 7
was kept, it was cooled to 107 ° C, and 7.5 kg of a polybutylene oil with a molecular weight of 7.66 1 gasoline (boiling point 121 ° C) were added under 35 weight of about 800 to 1000, by catalyzing stirring. After standing over the table polymerization of liquid butylene obtained for 24 hours, essentially all of it had become, was _{treated in an aluminum vessel with unreacted P 2} S, as a solid cake on _{top of 1500 g of P 2} S ₅ and 150 g of sulfur. Deposed by the floor. The oil was in a glass-enameled application of a protective gas envelope made of CO ₂ , the steel vessel was decanted and excluded at 177 ° C during a 40 air. The mixture was rapidly steam hydrolyzed for 2 hours, stirring while heating to 204-232 ° C, the gasoline was stripped. After 2 hours, the reaction mixture was cooled and thinned with the recovered gasoline. 6 kg of neutral oil with a viscosity of 90 SSU; 4 kg of neutral oil was diluted at 38 ° C to reduce. The mixture was added to standing viscosity. The oil solution was then left 45, then _{decanted of unreacted P 2} S ₅ with a solution of 3.781 aqueous secondary and extracted with steam for 2 hours at 182 bis butyl alcohol (67%) and 3.781 water. 199 ° C hydrolyzed. It was then with .7.5 kg. After settling, the bottom layer was separated from water and 3 kg of aqueous secondary butyl, and it was again with a solution of alcohol to extract the phosphoric acids, which is 3.781 water and 1.891 aqueous secondary 50 at the Had formed hydrolysis, mixed. The butyl alcohol extracted in order to remove the water layer formed during the extraction was made up of phosphoric acid, which, if it remained in the oil, was thrown. To 423 g of the moist oil, which contains alcohol and later insoluble barium phosphate in colloidal water, 40 g of lime was formed for neutralization purposes, which was added because of the intense peptic acids present. The oil was then dehydrated non-stabilizing effect of the phosphonate from the 55 by heating to 204 ⁰ C and oil can be removed. '". Quickly filtered while hot. It had an alkali value

The extracted oil was neutralized by adding 4. To 283 g of the clear brownish-red obtained

Mixing with a hot aqueous solution of oil, 8 g of calcium oxide were added, the through

Ba (OH) ₂ , which is brought about by the slow addition of 600 g of hydrated lime in a muffle furnace

BaO to hot water was obtained. The oil 60 about 817.5 ° C was obtained. There were 250 ecm

was then freed from the solvents and methanol and 50 ecm gasoline (boiling point 121 ° C)

heated to 149 ° C. with thorough stirring. When added to the oil, then carbon dioxide into the emul-

Allowing to stand, excess barium ion was introduced with rapid stirring. After a

hydroxyd as red sludge. The oil was carbonized for 2 hours

Gasoline (250 ° C) diluted and put 65 thick cream-like mass in a bowl to remove and

all suspended components filtered. The one to drive off the methanol and solvent

Petrol-oil solution was then heated with stirring. The product was more like a thick mush

3.5 kg of a barium methylate solution were added. That as an oil. It was filled with 200 ecm gasoline

13 14

medium mixed. Then 100 ecm of aqueous liquid CaO was filtered. The emulsion settled

Quickly filter the butyl alcohol to hydrate the calcium compounds. The filtrate separated into two

fertilize in the mixture and conversion of the phases, namely in an oil phase below one

Oil-in-water type emulsion is added. Methanol phase. The methanol became from the filtrate

After the mixture obtained has been dehydrated, 5 is distilled off. A clear orange remained

at 165.5 ° C an oil was obtained which quickly turned yellowish oil that was completely dehydrated and

filtered through a bed of diatomaceous earth. remained liquid in the cold. Alkali value 60. The filter

The product was clear and a red-brown oil cake reacted violently with water, which showed

with an alkali value of 57 showed that the cake was mainly composed of a

. ίο there was unreacted excess CaO. in the

Example 8 aqueous extract of the cake, calcium

A lubricating oil with a viscosity of 400 SSU hydroxyd can be detected. This example shows

at 37.8 ° C, which contains about 40% calcium sulfate, that an excess of calcium oxide in the reaction

was applied by sulfonation with oleum, neutralization can be applied to that of the emulsion

with sodium hydroxide, concentration of the sodium 15 by filtration before further treatment of the

sulfonate can be separated with butyl alcohol and exchange of the oil. If necessary, that can

Sodium against calcium with calcium chloride is obtained from the ¹ emulsion separating methanol

th, after which at 149 ⁰ C in the presence of lime process are fed without distillation,

was dehydrated and filtered. The product had r · · l 11

an alkali value of about 18 mg KOH per gram ao. Example 11

and an ash value (sulphated) of 7.6%. To 300 g To 220 g of a calcium sulfonate oil solution that

of this oil, 20 g of calcium oxide in suspension were identical to that of Example 8

added in 200 ecm of methanol. 100 ecm gasoline 40 g calcium oxide suspended in 250 ecm methanol,

(Boiling point 121 ° C) was added to reduce the and 30 ecm gasoline. It was 10 minutes

Viscosity added. The mixture was mixed rapidly for »5 at 54.5 ° C. CO ₂ was during a

stirred while a _{stream of CO 2 was} initiated at a temperature of 10 minutes. Then were

temperature of about 49 ° C for IV2 hours in 4 ecm of water that was dissolved in 25 ecm of methanol,

was directed. The methanol was then added from the, with the water dropwise during

Mixture distilled at 82 ° C. 50 ecm aqueous was added for 8 minutes while maintaining

secondary butyl alcohol were then added to the mixture at 3 ° of the CO ^ feed. The mixture thickened

added to hydrate the calcium compounds. a consistency corresponding to a coat of paint. It

Was dehydrated by heating at 171 ° C. It was necessary from time to time more naphtha

was filtered quickly. The red oil obtained had to be added in order to facilitate the mixing process.

and completely liquid at room temperature. It had a gene. A total of 100 ecm gasoline was used.

Alkali value of 65 and an ash value (sulfated) 35 after carbonization for another 20 minutes

of 13.36%. had to add another 60 ecm of gasoline to reduce it

'the viscosity and after another hour

Example 9 Carbonization time a further 40 ecm of gasoline was added. The same starting material was added as in the attachment. After a carbonization time of game 8, but without using the petrol diluent for 1 hour 35 minutes, the yellow emulsion was detected. 215 g of the calcium sulfonate oil solution were ^quickly filtered. The filtrate was heated to 149 ° C. for 20 g of calcium oxide (freshly burned hydrated lime), expelling the solvent. After that was suspended in 200 ecm of methanol, added. 50 ecm of aqueous butyl alcohol were used to cool the mixture. The mixture was added rapidly with a straight through, and the filtrate was agitated by heating on a motor-driven stirrer and dehydrated to 45 171 ° C. The clear, light oil was heated almost to the boiling point of methanol. again using about. 2 weight CO., Was introduced over one hour. Then percent filter earth filtered to clarify. The filters were fed with 100 ecm of gasoline (boiling point 121 ° C), and the rate of addition was very rapid at the beginning, and the methanol was distilled off at 93 ° C. However, as the filtration progressed, the gel structure became 50 ecm 50 samer, probably because partially aqueous secondary butyl alcohol was added to the filter bed. Which was closed off by coarser particles. The mixture was then dehydrated at 165.5 ° C. Product was a clear oil, filtered at room temperature and at a moderate speed. The liquid, with an alkali value of 2 against phenol product, was a clear red, phthalein at room temperature, which was an indication of insufficient carbonization. Alkali value 90. Ash-55 indicated. The alkali value against methyl orange is 15.8%. was 220. Ash value (sulfated) 29.51%.

Example 10 Example 12

To 250 g of a calcium sulfonate oil solution, 40 g were added to 230 g of calcium mahogany sulfonate, similar to Example 8, a suspension of 40 g of ⁶ ° product used in Example 8

freshly burned calcium hydrate, suspended in calcium oxide, suspended in 250 ecm of methanol,

300 ecm of methanol was added. Set with rapid stirring. The mixture turned into a smooth cream

A thick, creamy emulsion formed. This touched. CO ₂ was passed in for 5 minutes,

was heated at 54.5 ° C for 10 minutes. CO ₂ Then 5 ecm of water were added dropwise to 25 ecm

IV * hours was initiated. 200 ecm of gasoline was added to 65% methanol. As a result of the heat of reaction

added to promote the mixing process. The temperature rose from about 26.5 to 37.8 ^0C. obtained emulsion was through a bed of diatoms- After a total carbonization time of 40 Mi-

soil on a suction filter to remove excess grooves, 200 ecm of gasoline were used to dilute the

Mixture added. The emulsion was quickly filtered with suction. The filtrate was at 176.5 ° C to remove the solvent and quickly filtered again with filter earth. The product obtained was very fluid and pale. It was neutral towards phenolphthalein and had an alkali value of 97 against methyl orange.

Example 13.

Sodium sulfonate byproduct obtained from washing acid treated lubricating oil with caustic soda after treatment with fuming sulfuric acid contained about 1% water and 0.33% sodium sulfate. The active sulfonate content was I ¹ J ⁰ Io assuming a molecular weight of 450 for the sulfonate. The product was basic to phenolphthalein. Alkali value 3.5. The alkali value, determined with methyl organs, was 58.5. 200 g of the solid brown mass was melted and dissolved in 100 cc of gasoline (boiling point of 121 ⁰ C). dissolved. Then 300 ecm of methanol were added, followed by 40 g of calcium oxide. CO ₂ was bubbled into the warm mixture with rapid stirring. A thick, dark brown, creamy paste was formed within 30 minutes, which could be liquefied by adding 100 ecm more gasoline. A further 10 g of calcium oxide were then added and the carbonation continued. After 50 minutes, a further 100 ecm of gasoline was added, and after 1 hour and then after IV2 hours, the same amount of gasoline was added in each case. The carbonization was ended after 2 hours. The emulsion was quickly filtered. When the filtrate was heated to distill off the methanol, coagulation occurred on the heated surface of the vessel. Then 100 ecm of aqueous butyl alcohol were added, which led to the separation of a voluminous pulp, which quickly liquefied to an oil. Dehydration of some of the oil at 149 ° C gave a dark brown semi-solid product. The viscosity of the remaining oil was reduced by adding half the volume of neutral oil. It was then filtered. The product was a clear oil, was liquid at room temperature and gave a clear solution in a light lubricating oil. Alkali value 260. Ash value 31.93%! A calcium determination showed that 86.5% of the ash corresponded to calcium sulfate. The rest mainly consisted of sodium sulfate, which had not been converted.

Example 14

A lubricating oil fraction obtained by distillation from Arabic crude oil was mixed with oleum, containing 25% SO, sulfonated. The sulfonic acid obtained was neutralized with sodium hydroxide, resulting in a solution of sodium sulfonate in non-sulfonated! oil led. The solution obtained was washed out with water and butyl alcohol to remove sodium sulfonate and other impurities cleaned. It was then treated with a calcium chloride solution converted into the calcium salt. It was at a temperature of about 149 ° C in the presence of a a small amount of lime dehydrated. The oil obtained was filtered. A clear red calcium sulfonate solution resulted with an ash value (sulfated) of 8%. 200 g of this were with 100 ecm gasoline (Boiling point about 121 ° C) and 300 ecm of methanol, in which 20 g of calcium oxide were suspended, added. The mixture was heated and stirred rapidly at 60 ° C, during which time a stream of carbon dioxide was introduced was introduced. Additional gasoline was added at intervals to prevent excessive thickening added to the mixture. A total of 300 ecm of petrol was used. . . ·.

After one hour, 4 ecm of water in 25 ecm of methanol were added dropwise. The carbonization continued for 30 minutes after which time all of the water had been added. The resulting emulsion was filtered off with suction. The filtrate was on a hot plate freed from the solvents. It had to be stirred in order to form a gel on the hot To prevent surface. After the methanol phase had evaporated at 65.5 ° C., 50 ecm secondary butyl alcohol added. The clear oleo solution was heated to 126.6 ° C. The oil was very viscous. After cooling to 99 ° C., an aqueous solution of butyl alcohol was added to the oil. After 45 ecm of the aqueous butyl alcohol, the contained about 30% water, to which oil had been added, it suddenly became mushy and liquefied then draw conclusions about the transformation of the emulsion under the action of water let. The oil was then dehydrated at 171 ° C and rapidly passed through a bed of dialome earth filtered. The clear product was liquid in the cold. Alkali value against phenolphthalein 0.2, against methyl orange 220. Aschwert (sulfated) 28.83. When adding the product to an engine oil in one Amount of 1.4% and when tested in a two-stroke engine, an improved cleanliness of the Valve passages and reduced deposit on the spark plugs noted. .

Example 15 ; .

100 g of neutral oil with a viscosity of 90 were added to 100 g of oleic acid (commercially available red oil). 40 g of calcium oxide, suspended in 200 ecm of methanol and 150 ecm of gasoline, were added to this mixture, while a CO ₂ -SIrOm was passed in for one hour at a temperature of about 54.5 ° C. The resulting white emulsion was left unreacted for removal. Calcium oxide filtered. A portion of the slimy filtrate was heated in vacuo to remove the methanol and gasoline. The product was a viscous honey-colored oil. Alkali value 286.

The remainder of the filtrate was heated with a small amount of water and then at 165.5 "C dehydrated. The hot oil was filtered, leaving a product that is very liquid at normal temperature was obtained. Alkali value 272. Ash value (sulfated) 32.5%. The amount of ash is more than two and a half times the amount obtained from calcium oleate in 50% oil solution is obtained. This shows that a predominant part of calcium is present in the product in an invisible colloidal distribution.

Example 16

2.5 kg of pale oil (viscosity 100) were added to 5 kg of the sodium sulfonate described in Example 13 added. The mixture was heated in an aluminum jar until a uniform solution was formed. 7.56 liters of gasoline were added. After that

109621/63

17 18

5.84 1 of methanol, calcium oxide in 1125 g of the oil at 160 ⁰ C was higher Filtrationsaufgeschlämmt were added, keeping the tem- speed observed. The result was a temperature slightly from 54.5 to 57.2 ° C when mixing yield of 13.32 l of clear oil. Alkali value 60. Ash rise. Care was taken to get the value 8.73%. Phosphorus 1.3%. Sulfur 1.64%.
Methanol slurry through a fast run 5 ■
the mixer all lumps of calcium oxide Example 18
were cut up. A _{stream of C0 2 was} introduced into the reaction mixture while stirring to 200 g of a lubricating oil solution of calcium , 4% and an alkali value approximating the Me- io present in the mixture of 19.1, 100 ecm of gasoline and ethanol or its boiling point were equivalent. To remove 120 ecm of methanol, which contained 28 g (V2 mol) of calcium oxide conduction of the heat of reaction, the reaction was added. These constituents were thoroughly cooled with water from the outside of the vessel. After one hour at 37.8 ° C. in a high-speed turbo mixer, the temperature was 58.9 ° C. and mixed with one another. The mixture was left for v / i hours at 43.3 ° C. The excess of methane, 30 g of oxalic anhydride (V2), dissolved dropwise, was driven off by heating to 98.9 ° C. in 100 ecm of methanol added. After 15 minutes, 250 ecm of water were gradually added - the temperature rose to 51.5 ° C and after 25 minutes, care was taken that the temperature rose to 57 ° C. There was still no foaming over 35 Mi. It was then stirred for a few minutes, and the creamy yellow emulsion was mixed with 300 ecm of aqueous butyl alcohol. A further 100 ecm of gasoline were added to the ao. After this mixture was dehydrated at 165.5 ° C and the emulsion was quickly filtered on a suction filter then quickly filtered with suction using a small amount of not around 1% filter earth as filter aid. The alkali value of the calcium oxide set remained. The filtrate became clear oil. Aschwert (sulfated 30.93%). The heated to 93.3 ° C to remove the methanol. The ash was 84% calcium sulfate. A clear oil remained. There were 15 ecm _R. · Ι 17 water was added and the mixture was boiled. Example 1 / ^ _1n ^ _Q hydration to complete one set

To 7.5 kg of polybutylene with a molecular then 10 ecm of aqueous butyl alcohol. The

weight of about 750 1500 g of P ₂ S _{5 were} added. clear oil was then dehydrated at 165.5 ° C and

A protective covering 30 was rapidly filtered over the reaction mixture while it was still hot. Solidified on cooling

built up with CO ₂ to avoid air oxidation the product. It reacted to phenolphthalein

avoid. The mixture became acidic while 4 ^l h hours. Alkali value against methyl orange 3.0. Ash sword

heated, the temperature gradually increasing from 149 (sulfated) 22.5%.

was increased to 226.5 ⁰ C. After that, 7 kg were _.

neutral oil (viscosity 90) added and the solution 35 B e 1 s ρ 1 e 1 19

left to stand overnight. 280 g unreacted to 200 g of a calcium sulfonate oil solution,

P ₂ S ₅ were obtained by filtering the residue as roughly that used in Example 18,

the won. The oil was enamelled with 100 ecm of gasoline and 30 g of calcium oxide,

Transferring the vessel and adding 200 ecm of water, suspended in 100 ecm of methanol, added. Here-

after which steam was turned on for 2 hours at 126.5 ° C., a solution of 23 g of P ₂ O _{5 was added dropwise}

was directed. When cooling to 104.5 ° C, the addition of methanol gradually added

3.78 1 of water were added and this was obtained intensively with the borrowed to a mixture of P ₂ O ₅ in gasoline

oil mixed, which was followed by an addition of 1.5 1, 100 ecm of methanol being used

Butyl alcohol connected. The mix was came over. During the addition of P ₂ O ₅ , the

Left to stand overnight, and a lower layer of water, 45 reaction mixture quickly at a temperature of

approximately 3.78 l, which contained phosphoric acid, was stirred at 59.5 ° C. and an additional 100 ecm

deducted. The oil layer was added to 143.5 ° C gasoline to maintain the consistency of the emulsion,

heats to remove the water and alcohol. which thickened during the addition of acid,

The acid value was 30, which was the main thing to do. After all the acid has been added,

Phosphonic acids and thiophosphonic acids back -5 ° was stirred for 1 hour. To further

was to feed. Decreasing the consistency became even more important

800 g calcium oxide, which is added by roasting lime gasoline. Then it was on a suction filter

hydrate obtained at 926.6 ° C were filtered in. A small amount of the emulsion that is on

5.76 l of methanol had been slurried and the slurry had dried the walls of the mixer

added to the oil together with 3.78 liters of gasoline. 55 Consistency of a waxy varnish. The filtrate

A _{stream of CO 2} was added with rapid stirring to remove the methanol on one

directed. The. Mixture was heated for 4 hours on a hot plate, with a certain difficulty

49 ° C carbonized, meanwhile 80 ecm of water in the temperature range between 71 and

Methanol were added. The methanol was 93.3 ° C because of the thickening and gelation

was released from the mixture by heating to 93.5 ° C. Water and aqueous butyl alcohol were added

fcrnt, with continued introduction of CO ₂ . To remove it was added to the mixture, but it was always

tion of the gasoline and the hydration of the pro-still difficult to the exclusion of gelation

steam was then introduced. Heat by hand until a higher-boiling aromatic solution

A low rate of filtration rate (xylene) was added to a sample. One

dility found, indicating insufficient hydrolysis 65 small amount of lime was also added to

closed. The oil was then brought to 104.5 ° C to bring about a basic reaction. The product

cooled down. It was water and aqueous butyl was a viscous oil. It was with 30 g of new

alcohol added. After repeated dehydration tralem oil diluted, dehydrated at 237.8 ° C and

filtered. The product red oil had an alkali value of 90 (corrected to 104 for dilution) and an ash value (sulfated) of 17.72%, which indicates an undetectable colloidal content Calcium phosphate of about 10% can be inferred.

Example 20

24.45 g calcite crystals were burned in a muffle furnace at 871 ° C., then crushed in a mortar to a coarse powder. A small amount of starch was mixed with the powdered calcite and the mixture was baked for 1 hour. . This was repeated after another addition of starch. The starch is supposed to provide the carbon for the combustion to form carbon monoxide, which is supposed to promote _{the splitting off of CO 2 from the calcite.} 12.4 g of white calcium oxide were obtained, somewhat less than would be expected according to theory (13.7), which is due to a small loss ao during crushing and burning. 150 ecm of methanol was added to the calcium oxide thus obtained, and the slurry was added to 150 g of a calcium sulfonate-in-oil solution (8% ash). 100 cc of gasoline (boiling point 121.1 ° C) was added and a _{stream of CO 2} was introduced into the rapidly stirred mixture. The temperature remained at approximately 30.5 ° C. Then 2 ecm of water dissolved in 30 ecm of methanol were slowly added to the mixture. The temperature rose to 48.9 ° C over 10 minutes and to 54.5 ° C over 40 minutes.

The resulting emulsion was filtered on a suction filter and the filtrate is 93.5 ⁰ C heated to the methanol without gelation to remove. 20 ecm of water were then added and the mixture was boiled. This was followed by the addition of 15 ecm of aqueous butyl alcohol. The oil remained clear. It was dehydrated at 165.5 ° C and quickly filtered with filter earth. Alkali value 76. Ash value (sulphated) 14.66%, which means an increase of 6.66% compared to the sulphonate solution used.

B e i s ρ i e 1 21

A solution of calcium mahogany sulfonate in lubricating oil containing about 40% sulfonate and a Ash content of about 8% was mixed with 100 ecm of gasoline (boiling point 121 ° C.) in 160 g of sulfonate oil diluted. 20 g of calcium oxide, suspended in 150 ecm of methanol, were added to this solution. The mixture was stirred vigorously while a stream of sulfur dioxide was passed in for so long until 20 g were added. This took 20 minutes and the temperature rose to about 57.2 ° C. then 200 ecm more gasoline were added and stirring was carried out for a total of 40 minutes continued. It was left to stand overnight with the mixture separating into two layers, namely a layer of oil below and a clear layer of methanol above. The emulsion was quickly filtered on a suction filter without separating the layers. The methanol was driven off at 82.2 ° C, whereupon the Ul assumed the structure of a gel which solidified on cooling.

Butyl alcohol and benzene were added to the gel, which resulted in a clear solution on heating formed. Lime was added to the solution to ensure complete neutrality. The excess lime was filtered off and the clear filtrate was freed from the solvents without further gel formation and filtered again at a temperature of 171 ° C. This resulted in a shiny, clear red oil, from which a sticky semi-solid mass formed on cooling to room temperature. The oil analysis gave the following results: ash value 7.45%; Titration with phenolphthalein 2.5 acid; against methyl orange 78 base under SOg evolution. When an oil sample was heated with water, an emulsion formed which on drying gave an opalescent oil which was examined under the microscope. There were Calcium sulfite particles were found to be approximately 1 to 3 microns uniform in size. The particles showed a feathery structure at 40X magnification.

The drawing represents the course of the process with specific reference to calcium compounds However, barium compounds can also be produced in the same apparatus if exchanged of barium oxide against calcium oxide.

The emulsifier is from 10 through a flow meter 11 and from there through the line 12 and the pump 13 are supplied to the contact vessel 14. The emulsifier is generally an oil solution of a soap or an oil-soluble organic Acid of sufficiently high molecular weight that surface activity is achieved. Sulfonic acids, Phosphoric acids and fatty acids (carboxylic acids) with more than 12 carbon atoms and im generally 20 to 60 carbon atoms are most suitable for carrying out the process. If these acids and their salts are present as liquids at normal temperature, they can be in can be easily applied in an oil solution, the oil being of animal, vegetable, mineral origin or can be derived from the synthesis (ester). They can also be dissolved in olefin polymers being. The amount of emulsifier in the oil is generally between about 10 and 60%.

If necessary, an additional amount of the same or a different oil can be fed via line 15 be introduced into the emulsifier. A light lubricating oil of the one type suffices for many purposes neutral oil with a viscosity of 60 to 500 SSU at 37.78 ° C. In general it is advisable to also to introduce a hydrocarbon diluent through line 16, generally Petroleum benzine or a solvent from the group of aromatic hydrocarbons, for example Benzene, toluene or xylene. A petroleum spirit with a boiling point between about 121 and 149 ° C is generally preferred, although low-boiling gasolines are also used if appropriate arrangements are made for their recovery.

The emulsifier stream in line 12 becomes a dispersion or slurry coming from 17 of calcium oxide added, which is distributed in 18 in anhydrous methanol, which comes from line 19 will. The dispersion is controlled by means of the flow meter 20 so that the correct one CaO to emulsifier ratio is maintained. Enough CaO is used for the desired ash and alkali value and the desired other properties can be achieved in the product. Commercially available methanol with less than 1% water, preferably less than 0.5% water

suitable. It is advisable that the CaO is so finely divided that the particles pass through a sieve with a mesh size of 0.158 mm. Fine dispersions are desirable for rapid reaction in the subsequent stages of the process. Calcium oxide obtained by calcining calcium carbonate, limestone, marble, calcite and other types of calcium carbonate can be used. It was found, however, that an oxide obtained by dehydrating calcium hydroxide at temperatures between 538 and 1093 ^° C. is more reactive than an oxide made from carbonate. The mixture of emulsifier, oil, calcium oxide and methanol which is fed to the contact vessel 14 generally has the following composition: about 5 to 20 parts by weight of emulsifier, 2 to 40 parts by weight of oil, 2 to 20 parts by weight of methanol and 1 to 4 parts by weight of calcium oxide. There may also be 5 to 50 parts of hydrocarbon diluent present, although this can also be introduced at a later stage of the process to monitor the consistency of the reaction mixture.

Little or no reaction takes place between the constituents of the reaction mixture until they enter contact vessel 40 where they come together with an acid anhydride, in this case the carbonic anhydride or carbon dioxide supplied via line 21. The reaction is exothermic, the temperature from room temperature, about 26.5 to 38 ° C., in line 12 being able to rise to 54.5 to 65.5 ° C. in contact vessel 14: the reaction rate is and can be favored by higher temperatures can be controlled by the rate of supply of CO ₂ and by the amount of cooling created by the cooling jacket 22 around the contact vessel. The contact vessel 14 can be a conventional nozzle mixer or a mechanical mixer of the known turbo-mixer type. If necessary, thorough mixing can be brought about by rapid return of the gases within a stirrer having a conical bottom, in which the gases are drawn off from the top by a suitable compressor and forcibly introduced into the liquid at the bottom of the apparatus in a manner known per se. In order to increase the rate of absorption for the CO., It is advisable to use an overpressure "in the contact vessel of about 1 to 20 atmospheres, even if normal pressure is sufficient. Coming from the contact vessel 14, the reaction mixture passes through the separating apparatus 23, for example, CO ₂ , H ₂ S and air, if present, can be withdrawn via air 24 which leads to a suitable absorber, not shown, to recover methanol and other valuable solvent vapors.

The liquid phase is fed from the separating apparatus 23 via the line 25 and pump 26 to a two-stage contact vessel 27 which is also provided with a cooling jacket 28. There, carbonization is carried out further by introducing carbon dioxide via line 29. The carbon dioxide can be obtained by calcining calcium carbonate or by extracting flue gas with suitable absorbents such as ethanolamine according to the known Girdler process. For this purpose, CO _{2 is} also available on the market as liquid CO ₂ or solid CO ₂ (dry ice).

In order to promote the process sequence, it is expedient to maintain a higher pressure in the contact vessel 27 than in the contact vessel 14 and to maintain temperatures of the order of 51.5 to 121.degree. In general, sufficient about 65.5 ⁰ C. Sufficient cooling is the temperature below the boiling point of methanol at the in the

ίο contact vessel available corresponding pressures held.

From the contact vessel 27, the fully carbonized reaction mixture passes into the separator 29, where unreacted carbon dioxide and other gases are returned via line 21 through the cooler 30 to the contact vessel 14 of the first stage in order to largely quantitatively _{increase the absorption of its CO 2 content} design.
In the contact vessels 14 and 27, the con-

in the presence of the emulsion consisting of oil and methanol as the carbonization progresses, and it is sometimes useful to add more Introduce amounts of a hydrocarbon diluent, which can be done in a simple manner via the Valves provided lines 31 and 32 can be done. The liquid phase at the bottom of separation vessel 29 generally contains emulsified methanol and oil along with colloidally divided calcium salts and 1 to 3 volumes of diluent. Depending on the process conditions, the reactivity of the calcium oxide used and other factors there may also be an excess of calcium oxide from the reaction product must be separated. This can generally be achieved in an extremely simple manner by that the reaction mixture via lines 33 and 34 and the pump 35 a filter 36 and a Separation apparatus 37 is supplied, in which a methanol phase is formed at the top, which is via the line 38 to the dispersing vessel 18 or, if desired, to the contact vessel via the line 39 will. The oil and diluent are then returned via line 40 to the line 33 to be used in the process, the valve 41 being closed when in this way is worked.

In some cases it has been found that the

. Sorption rate of the calcium compounds in oil by introducing a small amount of water in

so the contact vessels 27 or 14 can be increased. Lines 42 and 43 are provided for this purpose. Here, the amount of water can be about 5 to 20% of the weight of the calcium oxide used, generally about 10%. When water " is supplied, it is important that it be done evenly in order to achieve a local concentration Avoid water exposure, resulting in hydration of calcium oxide and disruptive calcium hydroxide would lead. Therefore, the water is best added in the form of a methanol solution, a water concentration of about 5 to 20% is suitable. Under these conditions and with rapid stirring in the contact vessels 27 and 14, the result from the formation of calcium hydroxide resulting difficulties are essentially eliminated.

From 29 the emulsion arrives, either directly or after the filtration described above,

into the vent 44 where the methanol is driven off. The. Methanol vapor comes through that Line 45 to discharge 46. There the methanol is separated from the entrained hydrocarbons. The methanol vapor comes to the condenser 48 and collecting vessel 49 via line 47. The reflux to fractionation vessel 46 is brought about via line 50 and pump 51. That in 49 The methanol collected is fed back into the system by the pump 49 a and via the line 490. The heat for the fractionation vessel 46 can be supplied by means of the steam coil 52.

The heat for operating the vent 44 can be supplied by a steam jacket or a submerged coil. Preferably, _S i is obtained needed for expelling heat from hot methanol hydrocarbon vapors. For this purpose, the hydrocarbons are fed from 46 via line 53 and pump 54 to heater 55, where they are heated and, for the most part, evaporated before they enter the bottom of the vent 44. Additional hydrocarbons can be added via line 56.

The volatilized oil passes from the bottom of vessel 44 at a temperature from about 82 to 99 ° C via line 57 to still 58 where the remaining hydrocarbon diluent is distilled off, preferably with the aid of steam introduced through line 59. It has been found beneficial to supply an excess of water in addition to the steam via line 60, so that there is sufficient water is available for the hydration of the calcium compounds in the oil. Otherwise, the This step of the process will form a solid gel when the hydrocarbon diluent is removed will.

The hydrocarbon vapors come from 58 to cooler 62 and receiver 63, where the Separate hydrocarbons in an upper layer. You are on line 64 through the Drying chamber 65 and the line 66 returned, namely where the course of the process begins. Silica gel, calcium oxide, or other known desiccants can be used in dryer 65 will. The addition of water to the oil in still 58 also makes chemically bound methanol free, which is collected with the condensed water in 63. This is done via a line 27 withdrawn from a still not shown for the purpose of recovering methanol.

From the bladder 58, the flow of oil with the dispersed Calcium compounds fed via line 68 to the dehydration heater 69 by the Steam line 70 leading to cooler 71. The condensate is via the line 72 a not shown Separator supplied to remove the hydrocarbons and alcohols that the oil, such as still described, can be added. A temperature between 149 and 204 ° C is generally sufficient to remove all water. The introduction of a higher alcohol over the Line 73 which is oil soluble, e.g. B. butyl alcohol, amyl alcohol and cyclohexanol, is sometimes beneficial to break any emulsion of water and oil that may form, what promotes dehydration and complete hydration of the dispersed calcium compounds guaranteed. Secondary butyl alcohol saturated with water is preferably used for this purpose.

From the vessel 69 for the dehydration, the hot oil is drawn off via the line 74 and by means of the pump 75 the filter 76 to remove any harmful solids and the like., Which after the filtration may have accumulated in 36 fed. A simple filter press is sufficient for this. The clear oil is led away via line 77. When the filter 36 is flowed through, can some calcium hydroxide or carbonate in the oil be suspended, the unreacted calcium oxide in the oil after leaving the contact vessel 27 originates from.

In some cases, especially when small volumes are introduced into the process, this can Oil are withdrawn from the separator 29 intermittently, it being useful to remove the oil from the Line 33 has two or more heaters or a tank having a conical bottom connected in parallel that are equipped with heating jackets or heating coils and provided with pipelines, to be used alternately. The end process up to the final filtration is partial or total listed in a single vessel.

While the invention has been described using certain specific examples, it is intended to do so not be unnecessarily restricted. So under the inventive idea also the implementation of the entire process fall into a single reaction vessel in which the dispersion of the Calcium compounds due to the action of calcium oxide and an acid or an acid anhydride with almost complete exclusion of water, but in the presence of an emulsion of an oil of Methanol and emulsifiers based on organic acids is obtained. Even if preferably Oil products are made that contain a transparent dispersion of calcium compounds, preferably contain water-insoluble calcium salts, the process according to the invention can also be used for the preparation opalescent oils in which the dispersed particles of calcium compounds at the bottom The limit of the visible range in relation to the particle size can be used.

Instead of carbon dioxide as a stabilizer for the barium or calcium, a large number of other stabilizing agents, for example oxalic acid, sulfur dioxide or another acid are used, which form a water-resistant complex with the phosphonated with the barium and calcium forms oil or sulfonate. However, it is essential to mix with the stabilizer in the Way to make that the formation of colloidal particles, which is not subsequently through filtration can be removed. So particles from 0.1 to 1 micron get through the phosphonate or sulfonate peptized and not removed by filtration. The filtered oil is cloudy and of very little Commercial value. Bring particles with a size less than the wavelength of visible light satisfactory results. The stabilizer for the barium, for example oxalic acid, can be in a Solution of an alcohol, for example methanol, methyl isobutyl carbinol, hydroxyethyl ether or the like. can be added.

The oil products according to the invention, the calcium

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or contain barium compounds, generally show a basic reaction to strong ones Mineral acids. In general, they can be titrated with a base against a standard hydrochloric acid. the Method for determining the acid number or base number, to which reference is always made in the description is carried out as follows:

To an oil sample of 10 g, which is located in a 500 ecm Ehrlenmeyer flask, 100 ecm CCl ₄ , 50 ecm of a 15% NaCl solution and 50 ecm of methanol are added. The mixture is brought to a boil and titrated in the presence of phenolphthalein or methyl orange using a standard KOH solution of an HCl solution with a normality of 0.178. The number of cubic centimeters of standard solution required to reach the end point corresponds directly to the milligrams of KOH per gram of oil tested.

There are many possible uses of the products according to the invention for the person skilled in the art. The main importance lies in the field of lubricating oils for internal combustion engines, the Lubricating greases, oily anti-rust agents for machines, anti-corrosion oils for sea vessels and the machines that are exposed to the seawater. The use also falls under the invention of calcium products with vegetable and animal oils in food and cosmetics. the The amount that is added to these oils depends on the intended use. With lubricating oils shows generally the addition of about 1 to 5% of the additive concentrate having a base number of 50 to an effect.

Claims (3)

Patent claims: 1. A process for the preparation of dispersions of alkaline earth metal compounds in oils, characterized in that calcium or barium oxide with carbon dioxide, oxalic anhydride, P ₂ O ₅ or SO ₂ in the presence of an emulsion of an oil, in particular a mineral lubricating oil, methanol, a hydrocarbon as a solvent and an oil-soluble carboxylic acid having more than 12 carbon atoms or an alkali salt or alkaline earth salt thereof is reacted as an emulsifier, that the methanol is separated and the oil and solvent are treated with water or steam to prevent gel formation, whereupon the oil dispersion of the metal compounds is separated from the reaction mixture . 2. The method according to claim 1, characterized in that barium oxide in the form of his Complex compound with methanol is used. 3. The method according to claim 1, characterized in that as an emulsifier a phosphorus or sulfur-containing oil-soluble organic acid having more than 12 carbon atoms or a Alkali or alkaline earth metal salt thereof is used. 1 sheet of drawings