EP0007257A1 - Process for the preparation of detergent-dispersant agents of high alkali content for lubricating oils and product obtained - Google Patents

Abstract

A process is provided for preparing detergent-dispersant compositions of a TBN of at least about 200, containing at least about 2 percent magnesium, by: (1) sulfurization by sulfur of an alkylphenol in the presence of a magnesium and/or calcium alkylbenzene-sulfonate of a TBN less than or equal to about 150, an alkaline-earth component selected from among lime, mixtures of magnesium oxide and lime, or a magnesium oxide and alkali hydroxide, and an alkylene glycol; (2) optionally precarbonation of the resultant mixture by means of CO2; (3) super-alkalinization and carbonation of the resultant mixture by means of magnesium oxide and possibly lime, CO2 and alkylene glycol; and (4) removal of the excess alkylene glycol. The detergent-dispersant compositions obtained are useful in the improvement of the detergent-dispersant properties of lubricating oils.

Description

The present invention relates to new detergent-dispersants of high alkalinity for lubricating oils.

It is known from English Patent No. 1,015,759 to prepare detergents-dispersants of high alkalinity based on alkylphenates and alkylbenzenesulfonates of alkaline earth metals, by sulfurization of a mixture containing an alkylphenol , an alkaline earth metal alkylbenzenesulfonate, a C8-C18 monoalcohol, an alkaline earth base and glycol, precarbonation of the sulfurized mixture, alkalization of the precarbonated mixture with an alkaline earth base, carbonation then elimination of the glycol and recovery of the detergent -dispersing.

Such a process has the drawback of requiring the use of a C ₈ -C ₁₈ monoalcohol which must then be recycled in practically anhydrous form.

Furthermore, if such a process is satisfactory for the preparation of detergent-dispersants containing a high proportion of alkylphenates, it cannot however be used for the preparation of detergent-dispersants containing a high proportion of alkylbenzenesulfonates. In addition, this process is suitable for the preparation of mixtures of calcium, barium or strontium alkylphenates and alkylbenzenesulfonates; it cannot be used for the preparation of detergent-dispersants containing magnesium.

The Applicant has found a process which does not have the disadvantages of the previous process and which makes it possible to prepare detergent-dispersants based on alkylbenzenesulfonates and metal alkylphenates of TBN (Total Basic Number - Standard ASTM D 2896) greater than 200 containing at least 2% magnesium and possibly at least 0.5% calcium.

• - en ce que l'on fait réagir, à une température comprise entre 100 et 190°C, du soufre sur un alkylphénol portant un ou plusieurs substituants alkyls en C₆-C₆₀ en présence d'une huile de dilution, d'un alkylbenzènesulfonate de magnésium et /ou de calcium de masse moléculaire supérieure à 300 et de T.B.N. inférieur ou égal à 150, d'un constituant, alcalino-terreux choisi parmi-l'hydroxyde dé calcium, les mélanges oxyde de magnésium-hydroxyde de calcium et les mélanges oxyde de magnésium-hydroxydé de métal alcalin et d'un alkylèneglycol,
• - en ce qu'on suralcalinise et carbonate le milieu sulfurisé obtenu à l'aide d'oxyde de magnésium ou d'un mélange oxyde de magnésium-hydroxyde de calcium et de gaz carbonique en présence d'un alkylèneglycol à une température comprise entre 100 et 250°C ;
• - en ce qu'à un stade quelconque de l'étape de suralcalinisation-carbonatation,le milieu réactionnel est traité par 0 à 10%, de préférence par 0 à 5% en poids d'eau par rapport au poids dudit milieu à une température de 100 à 150°C ;
• - en ce qu'on élimine l'alkylèneglycol en excès et en ce qu'on récupère le détergent-dispersant de haute alcalinité ainsi obtenu.

The process for the preparation of detergent-dispersants from alkylphenol, alkylbenzene sulfonates of alkaline earth metals, alkylene glycol, sulfur and carbon dioxide, which is the subject of the invention, is characterized:

• - in that sulfur is reacted, at a temperature between 100 and 190 ° C, on an alkylphenol carrying one or more C ₆ -C ₆₀ alkyl substituents in the presence of a dilution oil, a magnesium and / or calcium alkylbenzenesulfonate with a molecular mass greater than 300 and a TBN less than or equal to 150, an alkaline-earth constituent chosen from calcium hydroxide, magnesium oxide-hydroxide mixtures calcium and magnesium oxide-hydroxide mixtures of alkali metal and an alkylene glycol,
• - in that one over-alkalinizes and carbonates the sulfurized medium obtained using magnesium oxide or a mixture of magnesium oxide-calcium hydroxide and carbon dioxide in the presence of an alkylene glycol at a temperature between 100 and 250 ° C;
• - in that at any stage of the over-alkalinization-carbonation stage, the reaction medium is treated with 0 to 10%, preferably with 0 to 5% by weight of water relative to the weight of said medium at a temperature from 100 to 150 ° C;
• - in that the excess alkylene glycol is removed and in that the high alkalinity detergent-dispersant thus obtained is recovered.

The term “magnesium or calcium alkybenzenesulfonate” denotes any solution containing from 40 to 95% by weight, preferably from 55 to 85% by weight of a magnesium or calcium alkylbenzenesulfonate in a dilution oil which may or may not be be the same as that used to carry out the process which is the subject of the invention. Among the magnesium and / or calcium alkylbenzenesulfonates which can be used, there may be mentioned the magnesium and / or calcium salts of sulfonic acids obtained by sulfonation of alkylbenzenes derived from olefins or from polymers of C olefins ₁₅ -C ₃₀ .

Among the alkylphenols which can be used to carry out the process which is the subject of the invention, mention may preferably be made of those carrying one or more C9-C15 alkyl substituents, and very particularly nonyl, decyl, dodecyl or tetradecylphenols.

Although any type of magnesium oxide can be used, it is preferred, however, to use "active" magnesium oxide. The term "active" magnesium oxide denotes magnesium oxide MgO with a specific surface greater than or equal to 80 m2 / g, for example between 100 and 170 m2 / g. By way of example, mention may be made of "Maglite DE" with a specific surface area close to 140 m2 / g and marketed by Merck, as well as "Ferumag" with a specific surface area close to 160 m2 / g and marketed by RHONE-POULENC INDUSTRIES.

As an example of alkali metal hydroxides, mention may be made of sodium hydroxide, lithium hydroxide, potassium hydroxide, etc.

Among the dilution oils which can be used, it is possible to cite preferably paraffinic oils such as 100 Neutral oil. naphthenic or mixed oils may also be suitable. The amount of dilution oil that can be used is such that the amount of oil contained in the final product (including that from the starting alkylbenzenesulfonate) represents from 20 to 60% by weight of said product and preferably from 25 to 55% of said product.

Among the alkylene glycols which can be used, mention may very particularly be made of glycol; these can optionally be present in mixture with up to 200% by weight of a monoalcohol such as ethylhexanol, tridecyl alcohol, C ₈ -C ₁₄ oxo alcohols and in general alcohols having a boiling point higher than 120 ° C and preferably higher than 150 ° C.

• - l'étape de sulfurisation en présence d'un alkylbenzène sulfonate de magnésium et/ou de calcium, de TBN inférieur ou égal à 50 à une température comprise entre 120 et 190°C, à une pression inférieure ou égale à la pression atmosphérique ; cette étape peut éventuellement être suivie d'une étape supplémentaire réalisée à une température supérieure comprise entre 130 et 185°C, à une pression inférieure ou égale à la pression atmosphérique, afin de terminer l'étape de sulfurisation,
• - l'étape de suralcalinisation-carbonatation au moins en une fois à une température comprise entre 100 et 185°C,
• - le traitement à l'eau à une température comprise entre 100 et 145°C,

Preferably, we will realize:

• - The sulfurization step in the presence of a magnesium and / or calcium alkylbenzene sulfonate, of TBN less than or equal to 50 at a temperature between 120 and 190 ° C, at a pressure less than or equal to atmospheric pressure; this step may possibly be followed by an additional step carried out at a higher temperature of between 130 and 185 ° C., at a pressure less than or equal to atmospheric pressure, in order to complete the sulfurization step,
• - the step of over-alkalinization-carbonation at least once at a temperature between 100 and 185 ° C,
• - treatment with water at a temperature between 100 and 145 ° C,

• - pour l'étape de sulfurisation
  • .de 10 à 70 parties, de préférence de 15 à 60 parties d'alkylphénol pour 100 parties de mélange alkylphénol-alkylbenzénesulfonate de magnésium et/ou de calcium.
  • . de 30 à 90 parties, de préférence de 40 à 85 parties d'elkylbenzènesulfonate de magnésium et/ou de calcium pour 100 parties de mélange alkylphénul-alkylbenzènesulfonate
  • . de 1,5 à 12 parties de préférence de 2,5 à 11 parties de soufre pour 100 parties de mélange alkylphénol-alkylbenzènesulfonate,
  • . de 2 à 30 parties, de préférence de 4 à 20 parties de constituant alcalino-terreux pour 100 parties de mélange alkylphénol-alkylbenzènesulfonate,
  • . jusqu'à 20 parties, de préférence de 1 à 15 parties d'hydroxyde de calcium pour 100 parties. de mélange alkylphénol-alkylbenzènesulfonate
  • . jusqu'à 20 parties, de préférence de 2 à 15 parties d'oxyde de magnésium pour 100 parties de mélange alkylphénol-alkylbenzènesulfonate,
  • . jusqu'à 8 parties, de préférence de 0,05 à 3 parties d'hydroxyde de métal alcalin pour 100 parties de mélange alkylphénol-albenzene sulfonate,
  • . de 5 à 50 parties de préférence de 8 à 30 parties d'alkylène glycol pour 100 parties de mélange alkylphénol-alkylbenzènesulfonate.
• - pour l'étape de suralcalinisation-carbonatation
  • . de 2 à 15 parties, de préférence de 3 à 15 parties d'oxyde de magnésium pour 100 parties de milieu sulfurisé
  • . jusqu'à 15 parties, de préférence jusqu'à 10 parties d'hydroxyde de calcium pour 100 parties de milieu sulfurisé
  • de 4 à 100 parties, de préférence de 7 à 70 parties d'alkylène glycol pour 100 parties du milieu sulfurisé.

The amounts of reagents that can be used to carry out the process of the invention are as follows:

• - for the sulfurization stage
  • from 10 to 70 parts, preferably from 15 to 60 parts of alkylphenol per 100 parts of alkylphenol-alkylbenzenesulfonate mixture of magnesium and / or calcium.
  • . from 30 to 90 parts, preferably from 40 to 85 parts of magnesium and / or calcium elkylbenzenesulfonate per 100 parts of alkylphenul-alkylbenzenesulfonate mixture
  • . 1.5 to 12 parts preferably 2.5 to 11 parts of sulfur per 100 parts of alkylphenol-alkylbenzenesulfonate mixture,
  • . from 2 to 30 parts, preferably from 4 to 20 parts of alkaline-earth constituent per 100 parts of alkylphenol-alkylbenzenesulfonate mixture,
  • . up to 20 parts, preferably 1 to 15 parts of calcium hydroxide per 100 parts. of alkylphenol-alkylbenzenesulfonate mixture
  • . up to 20 parts, preferably from 2 to 15 parts of magnesium oxide per 100 parts of alkylphenol-alkylbenzenesulfonate mixture,
  • . up to 8 parts, preferably from 0.05 to 3 parts of alkali metal hydroxide per 100 parts of alkylphenol-albenzene sulfonate mixture,
  • . from 5 to 50 parts, preferably from 8 to 30 parts of alkylene glycol per 100 parts of alkylphenol-alkylbenzenesulfonate mixture.
• - for the over-alkalization-carbonation stage
  • . from 2 to 15 parts, preferably from 3 to 15 parts of magnesium oxide per 100 parts of sulfurized medium
  • . up to 15 parts, preferably up to 10 parts of calcium hydroxide per 100 parts of sulfurized medium
  • from 4 to 100 parts, preferably from 7 to 70 parts of alkylene glycol per 100 parts of the sulfurized medium.

The amount of CO ₂ can vary between the amount which can be completely absorbed and an excess of 40% by weight of this amount; preferably the amount of CO _{2 will} correspond substantially to that which can be completely absorbed.

The over-alkalization-carbonation stage is preferably carried out in one or two stages.

A variant of the process which is the subject of the invention consists in preparing "in situ" before the sulfurization-neutralization step, the magnesium and / or calcium alkylbenzenesulfonate by the action of MgO or lime on an acid. sulfonic alkylbenzene as defined above in the presence of oil and optionally of alkylene glycol, at a temperature between 40 and 150 ° C, the amount of MgO or lime and oil to be used. 'magnesium and / or calcium alkylbenzenesulfonate obtained present a TBN less than or equal to 150, preferably less than or equal to 50

Another variant of the process which is the subject of the invention consists in carrying out a precarbonation operation after the sulfurization step and before the over-alkalinization-carbonation step. This operation can be carried out at a temperature between 100 and 250 ° C and preferably between 100 and 185 ° C, using carbon dioxide. The amount of CO _{2 that} can be used corresponds, to within 30%, by weight, to that which can be completely absorbed by the sulfurized medium; preferably this amount of C0 _{2 will} correspond substantially to that which can be completely absorbed.

At any stage of this operation, a treatment with water may be carried out in addition to or in place of that provided for in the step of over-alkalinization-carbonation; this treatment can be carried out under the same conditions as those indicated above.

The present invention also relates to detergents-dispersants of high alkalinity obtained by the process described above.

These have the advantage of very good compatibility with viscous oils as well as a very low rate of sediment. They can be added to lubricating oils in amounts depending on the TBN of said detergent-dispersants and depending on the future use of said oils; thus for a petrol engine oil, the amount of TBN detergent-dispersant between 200 and 300 for example to be added is generally between 1 and 3.5%; for a diesel engine oil it is generally between 1.8 and 5%; for a marine engine oil, this can be up to 25%.

The lubricating oils which can thus be improved can be chosen from a wide variety of lubricating oils, such as lubricating oils of naphthenic base, of paraffinic base and of mixed base, of other hydrocarbon lubricants, for example lubricating oils derived from products. coal, and synthetic oils, for example, alkylene polymers, polymers of the alkylene oxide type and derivatives thereof, including polymers of the alkylene oxide type prepared by polymerizing alkylene oxide to presence of water or alcohols, for example ethyl alcohol, esters of dicarboxylic acids, liquid esters of phosphorus, alkylbenzenes and dialkylbenzenes, polyphenyls, alkylbiphenylethers, polymers of silicon.

Additional additives may also be present in said lubricating oils in addition to the detergent-dispersants obtained according to the process of the invention; include, for example, anti-oxidant, anti-corrosion additives, ashless dispersant additives, etc.

The following examples are given for information only and cannot be considered as limiting the scope and spirit of the invention,

Examples 1 to 11

The general mode of preparation (five phases) of the overbased detergent-dispersants given in Examples 1 to 11 is given below, and the quantities of reagents necessary for their preparation are given in Tables 1 to III.

- 1st phase (sulfurization)

• - du dodécylphénol (DDP)
• - de l'huile 100 N
• - une solution à environ 60 % dans de l'huile de dilution 100 N d'un alkylbenzènesulfonate de magnésium (sulfonate Mg en abréviation) de masse moléculaire 470 environ (masse du sel de sodium), solution contenant 1,8 % de magnésium et présentant un TBN de 25 environ,
• - un antimousse commercialisé par RHONE-POULENC sous la dénomination SI 200.

The following are introduced into a 4-liter tetracol reactor equipped with a stirring system and a heating device:

• - dodecylphenol (DDP)
• - 100 N oil
• a solution of approximately 60% in 100 N dilution oil of a magnesium alkylbenzenesulfonate (sulfonate Mg for short) with a molecular mass of approximately 470 (mass of the sodium salt), solution containing 1.8% of magnesium and with a TBN of around 25,
• - an antifoam sold by RHONE-POULENC under the name SI 200.

Then introduced with stirring the alkaline earth constituent selected from lime, mixtures "Maglite DE" -lime or "Maglite DE" -solder and sulfur.

The medium is brought to 145 ° C. under 260 mm of mercury, then glycol is added over 1 hour; it is heated to 165 ° C. and this temperature is maintained for an hour under 260 mm of mercury. ,. 2nd phase (precarbonation)

After breaking the vacuum and heating to 170 ° C, a precarbonation operation is carried out at 170 ° C using carbon dioxide until the absorption of C0 _{2 is complete} (this phase lasts approximately 1 h).

Cool to 110 ° C and add water. 3rd phase (over-alkalinization-carbonation)

A mixture of "Maglite DE" and glycol is introduced at 110 ° C. Carbonate for 4 hours at 110 ° C.

4th phase (over-alkalinization-carbonation)

Water is added. The operation described in the 3rd phase is carried out a second time for 3 hours.

5th phase (separation)

The superalkalinized and carbonated medium is brought to a temperature of 184 ° C under 30 mm of mercury; glycol distills; it is filtered to remove the sediments and a solution in 100 N oil of overbased detergent-dispersant is recovered, the characteristics of which are given in Tables I 'to III'.

Example 12

The operation described in Example 3 is carried out by carrying out the precarbonation step at 140 ° C. at atmospheric pressure.

The characteristics of the product obtained are similar to those of that obtained in Example 3.

Example 13

The operation described in Example 3 is carried out from an 80% solution in 100 N oil of a magnesium alkylbenzene sulfonate of molecular weight approximately 470, solution containing 2.25% of magnesium and having a TBN of 32.

The quantities of reagents used appear in Table IV, the characteristics of the product obtained appear in Table IV '.

Example 14

The operation described in Example 3 is carried out, carried out from a 60% solution in 100 N oil of a magnesium alkylbenzene sulfonate, with a molecular mass of approximately 470, solution containing 2.2% magnesium and having a TBN of 45.

The quantities of reagents used appear in Table IV, the characteristics of the product obtained appear in Table IV '.

Example 15

The operation described in Example 3 is carried out from a 60% solution in 100 N oil of a calcium alkylbenzene sulfonate of molecular weight approximately 470, solution containing 2.7% of calcium and having a TBN of 25, and without adding water during the precarbonation and carbonation operations.

The quantities of reagents used are shown in Table IV; the characteristics of the product obtained are shown in Table IV '.

Example 16

The operation described in Example 3 is carried out without adding water during the precarbonation and carbonation operations.

The product obtained has characteristics equivalent to those of Example 3.

Examples 17 to 24

The operations described in Examples 1 to 11 are carried out under the same conditions, by eliminating the precarbonation step and with the quantities of reagents listed in Table V and V ', VI and VI'.

The characteristics of the products obtained are shown in Tables V 'and VI'.

Examples 25 and 26

The operation described in Example 17 is carried out using a 60% solution in 100 N oil of a calcium alkylbenzenesulfonate of molecular weight approximately 470, solution containing 2.7%. calcium and having a TBN of 25 and performing a carbonation step.

The quantities of reagents as well as the characteristics of the products obtained are shown in Tables VII and VII '.

Examples 27 and 28 Preparation of sulfonate "in situ"

• - une solution à environ 70 % dans de l'huile de dilution d'un acide henzènesulfonique de masse moléculaire 470 environ (masse du sel de sodium)
• - de l'huile 100 N

The following are introduced into the 4-liter tetracol reactor:

• - a solution of approximately 70% in dilution oil of a henzenesulfonic acid of molecular mass approximately 470 (mass of the sodium salt)
• - 100 N oil

Lime or an equilibrium lime-Maglite DE mixture is introduced with stirring; heated at 120 ° C for 1 hour at atmospheric pressure

1st phase (sulfnrisation)

• - du dodécylphénol
• - de la chaux
• - de l'anti-mousse SI 200

The mixture obtained is added

• - dodecylphenol
• - lime
• - SI 200 defoamer

The mixture is heated to 145 ° C. under 260 mm of mercury, glycol is added over 1 hour, then it is brought to 165 ° C. for 1 hour under 200 mm of mercury.

2nd and 3rd phases (over-alkalization-carbonation)

After having cooled the medium to 110 ° C., a mixture of Maglite DE and glycol is added. Carbonate for 1 hour at 110 ° C; water is added and carbonated a second time for 3 hours at 110 ° C.

4th phase

The superalkalinized and carbonated medium is brought to a temperature of 184 ° C under 30 mm of mercury; the glycol distills, and it is filtered to remove the sediments and recover a solution of detergent-dispersants in the oil 100 N.

The quantities of reagents used and the characteristics of the products obtained are shown in Tables VIII and VIII '.

Example 29

The operation described in Example 17 is carried out using the same quantities of reagents, but by carrying out the sulfurization operation first at 165 ° C. for 1 hour under 260 mm of mercury and then for 2 hours at 185 ° C. under 700 mm of mercury.

The product obtained has characteristics equivalent to those of Example 17.

Sediment rate

• - vitesse de rotation de la centrifugeuse 6000 t/mn
• - force centrifuge relative 10.000
• - le produit à analyser est dilué au quart dans de l'essence E (25 cm3 de produit à analyser + 75 cm3 d'essence E)
• - durée de la centrifugation : 10 minutes.

The% of sediments appearing in the tables below were measured according to standard ASTM D 2273-67, with the following modifications, however:

• - speed of rotation of the centrifuge 6000 rpm
• - relative centrifugal force 10,000
• - the product to be analyzed is diluted to a quarter in gasoline E (25 cm3 of product to be analyzed + 75 cm3 of gasoline E)
• - duration of centrifugation: 10 minutes.

Accounting

The compatibility tests appearing in the tables below were carried out by adding 10% by weight of product to be tested to a mineral oil SAE 30, storage of the solution obtained for 1 month at 20 ° C and study of the appearance of the solution as a function of time.

Comparison with commercial products test with the additive alone

The product of Example 7 is added to an SAE 50 oil with a paraffinic tendency so as to obtain a solution containing 125 millimoles of calcium + magnesium. The solution is stored for 15 days at 20 ° C; we see that the solution remains clear.

• - d'alkylbenzènesulfonate de magnésium de TBN 400
• - d'alkylbenzènesulfonate de calcinm de TBN 25
• - d'alkylphénate de calcium de TBN 150

en quantité telle que la solution obtenue contienne 125 millimoles de calcium + magnésium.The same test is carried out with a mixture:

• - magnesium alkylbenzene sulfonate from TBN 400
• - TBN 25 calcinm alkylbenzenesulfonate
• - calcium alkylphenate of TBN 150

in an amount such that the solution obtained contains 125 millimoles of calcium + magnesium.

After 15 days of storage at 20 ° C, the solution is cloudy and flocculent.

- test with the additive in formulation

• - 2 % d'un dispersant à base de polyisobutén^yl succinimide
• - 1,6 millimole d'un dithiophosphate de zinc
• - et 2,3 % de produit de l'exemple 7

A mixture (A) of additives is prepared containing:

• - 2% of a dispersant based on polyisobuten ^and succinimide
• - 1.6 millimole of a zinc dithiophosphate
• - and 2.3% of product from Example 7

This mixture is brought for 25 days to 80 ° C. and is then added to an SAE 30 oil so as to have a concentration of 6.6% by weight of mixture (A).

The solution is stored for 5 days at 80 ° C.

• - 2 % du dispersant à base de polyisobutényl-succinimide
• - 1,6 millimole du dithiophosphate de zinc
• - et 2,3 % d'un mélange constitué :

• d'alkylbenzènesulfonate de magnésium de TBN 400
  • . d'alkylbenzènesulfonate de calcium de TBN 25
  • . d'alkylphénate de calcium de TBN 150 présentant un nombre de millimoles de calcium + magnésium équivalent à celui du produit de l'exemple 7.

The same test is carried out with a mixture (B) consisting of

• - 2% of the dispersant based on polyisobutenyl succinimide
• - 1.6 millimole of zinc dithiophosphate
• - and 2.3% of a mixture consisting of:

• 400 magnesium alkylbenzene sulfonate
  • . of TBN 25 calcium alkylbenzenesulfonate
  • . of calcium alkylphenate of TBN 150 having a number of millimoles of calcium + magnesium equivalent to that of the product of Example 7.

It is found that the solution containing the mixture (A) is lighter and brighter than that containing the mixture (B).

Claims (22)

1) Process for the preparation of detergent-dispersants from alkylphenol, alkylbenzenesulfonates of alkaline earth metals, alkylene glycol, sulfur and carbon dioxide, characterized: - in that is reacted at a temperature between 100 and 190 ° C, of sulfur on an alkylphenol carrying one or more _noun i _{tuants alk} y _{ls C6} - _C60 in the presence of a dilution oil, '' a magnesium and / or calcium alkylbenzenesulfonate with a molecular mass greater than 300 and a TBN less than or equal to 150, of an alkaline earth constituent chosen from calcium hydroxide, magnesium oxide-calcium hydroxide mixtures and mixtures of magnesium oxide-alkali metal hydroxide and an alkylene glycol - in that we alkalinize and carbonate the sulphurized medium obtained using magnesium oxide or a mixture of magnesium oxide-calcium hydroxide and carbon dioxide in the presence of an alkylene glycol at a temperature between 100 and 250 ° C; - in that, at any stage of the over-alkalinization-carbonation stage, the reaction medium is treated with 0 to 10 × by weight of water, relative to the weight of said medium at a temperature between 100 and 150 ° C. . - in that the excess alkylene glycol is removed and in this. that the high alkalinity detergent-dispersant thus obtained is recovered. 2) Process according to claim 1 characterized in that the alkylphenol used contains at least one C ₉ -C ₁₅ alkyl substituent. 3) Method according to claim 2 characterized in that the alkylphenol is chosen from nonyl, decyl, dodecyl or tetradecylphenols. 4) Method according to claim 1 characterized in that the alkylene glycol is glycol. 5) Process according to claims 1 or 4 characterized in that the alkylene glycol is present in mixture with up to 200% of its weight of a monoalcohol with a boiling point above 120 ° C. 6) Method according to claim 5 characterized in that said monoaleool has a boiling point greater than 150 ° C. 7) Method according to claim 1) characterized in that = - the sulfurization step is carried out in the presence of an alkylbenzene sulfonate of magnesium and / or calcium, of TBN less than or equal to 50 at a temperature between 120 and 190 ° C, at a pressure less than or equal to atmospheric pressure and in that said step may optionally be followed by an additional step carried out at a higher temperature between 130 and 185 ° C, at a pressure less than or equal to the atmospheric pressure. 8) Process according to claim 1 or claim 2 characterized in that the alkali metal hydroxide is chosen from sodium hydroxide, lithium hydroxide, potassium hydroxide. 9) Method according to any one of the preceding claims, characterized in that to carry out the sulfurization step, use is made of: - from 10 to 70 parts, of alkylphenol per 100 parts of the alkylphenol-alkylbenzene sulfonate mixture of magnesium and / or calcium, - from 30 to 90 parts, of magnesium and / or calcium alkylbenzenesulfonate per 100 parts of magnesium and / or calcium alkylphenol-alkylbenzenesulfonate mixture - from 1.5 to 12 parts of sulfur per 100 parts of alkylphenol-alkylbenzenesulfonate mixture of magnesium and / or calcium, - from 2 to 30 parts of alkaline-earth component per 100 parts of alkylphenol-alkylbenzene sulfonate mixture of magnesium and / or calcium - up to 20 parts of calcium hydroxide per 100 parts of alkylphenol-alkylbenzenesulfonate mixture of magnesium and / or calcium - up to 20 parts of magnesium oxide per 100 patties of alkylphenol-alkylkenzenesulfonate mixture of magnesium and / or calcium - up to 8 parts of alkali metal hydroxide per 100 parts of alkylphenol-alkylbenzenesulfonate mixture of magnesium and / or calcium - from 5 to 50 parts of alkylene glycol per 100 parts of alkylphenol-alkylbenzene sulfonate mixture of magnesium and / or calcium. 10) Method according to claim 9 characterized in that the sulfurization step is carried out in the presence of: - from 15 to 60 parts of alkylphenol per 100 parts of alkylphenol-alkylbenzenesulfonate mixture of magnesium and / or calcium; - from 40 to 85 parts of magnesium and / or calcium alkylbenzenesulfonate per 100 parts of magnesium and / or calcium alkylphenol-alkylbenzene sulfonate mixture; - from 2.5 to 11 parts of sulfur per 100 parts of alkylphenol-alkylbenzenesulfonate mixture of magnesium and / or calcium; - from 4 to 20 parts of alkaline earth component per 100 parts of magnesium and / or calcium alkylphenol-alkylbenzenesulfonate mixture, - from 1 to 15 parts of calcium hydroxide per 100 parts of alkylphenol-alkylbenzene sulfonate mixture of magnesium and / or calcium; - from 2 to 15 parts of magnesium oxide per 100 parts of an alkylphenol alkylbenzene sulfonate mixture of magnesium and / or calcium; - from 0.05 to 3 parts of alkali metal hydroxide per 100 parts of alkyl _F hénol-alkylbenzene sulfonate mixture of magnesium and / or calcium; - from 8 to 30 parts of alkylene glycol per 100 parts of alkylphenol-alkylbenzenesulfonate mixture of magnesium and / or calcium. 11) Method according to claim 1 characterized in that the step of over-alkalinization-carbonation is carried out at least once at a temperature between 100 and 185 ° C, and using: - from 2 to 15 parts of magnesium oxide per 100 parts of sulfurized mixture; - up to 15 parts of calcium hydroxide per 100 parts of sulfurized mixture; - from 4 to 100 parts of alkylene glycol per 100 parts of sulfurized mixture, the quantity of CO ₂ can vary between the quantity which can be completely absorbed and an excess of 40% by weight of this quantity. 12) Method according to claim 11 characterized in that - the step of over-alkalinization-carbonation is carried out by implementing: - from 3 to 15 parts of active magnesium oxide per 100 parts of sulfurized mixture - up to 10 parts of calcium hydroxide per 100 parts of sulfurized mixture - from 7 to 70 parts of alkylene glycol per 100 parts of sulfurized mixture, the amount of CO ₂ corresponding substantially to that which can be completely absorbed. 13) Method according to claim 11 or claim 12 characterized in that the step of over-alkalinization-carbonation is carried out in one or two stages. 14) Method according to any one of claims 1, 11 and 12 characterized in that the water treatment is carried out at a temperature between 100 and 145 ° C, using 0 to 5 parts by weight d water per 100 parts by weight of reaction medium. 15) Method according to any one of the preceding claims, characterized in that a precarbonation step is carried out after the sulfurization step and before the step of over-alkalinization-carbonation. 16) Method according to claim 15 characterized in that the precarbonation step is carried out at a temperature between 100 and 250 ° C using an amount of C0 ₂ corresponding to more or less 30%, by weight , to that which can be completely absorbed by the sulfurized mixture. 17) Method according to claim 16 characterized in that the precarbonation step is carried out at a temperature between 100 and 185 ° C and in that the amount of C0 ₂ corresponds substantially to that which can be completely absorbed. 18) Process according to any one of claims 15 to 17 characterized in that the reaction medium is subjected to a treatment with 0 to 10% by weight of water at any stage of the precarbonation step at a temperature between 100 and 150 ° C in addition or in place of the water treatment provided for in the over-alkalinization-carbonation stage. 19) Method according to the preceding claim characterized in that the reaction medium is subjected to a treatment with 0 to 5% by weight of water at a temperature between 100 and 145 ° C. 20) Process according to any one of the preceding claims, characterized in that the magnesium and / or calcium alkylbenzenesulfonate used is prepared "in situ" before the sulfurization step. 21) Products obtained by the process forming the subject of any one of claims 1 to 20. 22) Application of the products obtained by the process described in any one of claims 1 to 20 as detergent-dispersant additives for lubricating oils.