EP0006796B1 - Process for the preparation of overbased metalliferous detergent-dispersant agents for lubricating oils and product obtained - Google Patents

Process for the preparation of overbased metalliferous detergent-dispersant agents for lubricating oils and product obtained Download PDF

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Publication number
EP0006796B1
EP0006796B1 EP79400391A EP79400391A EP0006796B1 EP 0006796 B1 EP0006796 B1 EP 0006796B1 EP 79400391 A EP79400391 A EP 79400391A EP 79400391 A EP79400391 A EP 79400391A EP 0006796 B1 EP0006796 B1 EP 0006796B1
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Prior art keywords
calcium
parts
weight
alkylphenate
sulphurised
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German (de)
French (fr)
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EP0006796A1 (en
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Bernard Demoures
Jean-Louis Le Coent
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Orogil SA
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Orogil SA
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals

Definitions

  • the present invention relates to a process for the preparation of overbased metal detergent-dispersants, in particular for lubricating oils.
  • the Applicant has found a process making it possible to obtain metal detergent-dispersant additives with TBN (Total Basic Number - Standard ASTM D 2896) greater than 200, in a simple and rapid manner, in the presence of alkylene glycol in small quantities and in the absence of excess monoalcohol or sulfur.
  • TBN Total Basic Number - Standard ASTM D 2896
  • the carbonation operation can be carried out in one or more times, by introducing the necessary quantity defined above of alkaline earth compound and alkylene glycol, in one or more times, each introduction of alkaline compound. earthy and alkylene glycol being followed by a carbonation operation.
  • sulfurized alkylphenate denotes any solution containing from 30 to 80% by weight, preferably from 40 to 70% by weight of a sulfurized alkyl phenate in a dilution oil which may or may not be the same as that used to carry out the process which is the subject of the invention.
  • alkylbenzene sulfonate will denote any solution containing from 40 to 95% by weight, preferably from 55 to 85% by weight of an alkylbenzene sulfonate in a dilution oil which may or may not be the same than that used to carry out the process which is the subject of the invention.
  • sulfurized alkylphenates which can be used, mention may be made of those obtained by sulfurization with sulfur of an alkylphenol preferably carrying one or more C 9 -C 5 alkyl substituents (such as nonyl, decyl, dodecyl or tetradecylphenols) in the presence of an alkaline earth base and an alkylene glycol, optionally followed by carbonation with carbon dioxide.
  • an alkylphenol preferably carrying one or more C 9 -C 5 alkyl substituents (such as nonyl, decyl, dodecyl or tetradecylphenols) in the presence of an alkaline earth base and an alkylene glycol, optionally followed by carbonation with carbon dioxide.
  • alkylbenzene sulfonates which can be used, mention may be made of the salts of sulfonic acids (of molecular weight preferably greater than 400) obtained by sulfonation of petroleum or synthetic fractions obtained by sulfonation of alkylbenzenes derived from olefins or polymers of C 15 -C 30 olefins and of alkaline earth metals such as calcium, and / or magnesium.
  • the alkaline-earth compound to be used consists of oxides or hydroxides of calcium, or of magnesium ... taken alone or as a mixture; the metal from which the alkaline earth alkyl benzene sulfonate and the alkaline earth alkyl phenate used may or may not be the same as that or those contained in the alkaline earth compound.
  • the amount of oil that can be used is such that the amount of oil present in the final product (including that from the sulfurized alkylphenate and the starting alkylbenzene sulfonate) is between 20 and 60%, from preferably between 25 and 55% of said product.
  • 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 , the alcohols having a boiling point higher than 120 ° C and preferably higher than 150 ° C.
  • a monoalcohol such as ethylhexanol, tridecyl alcohol, C 8 -C 14 oxo alcohols and in general , the alcohols having a boiling point higher than 120 ° C and preferably higher than 150 ° C.
  • Another variant of the process which is the subject of the invention consists in preparing, in situ prior to the carbonation operation, the alkylbenzene sulfonate of alkaline earth metal by the action of an oxide or a hydroxide of said alkali metal. -terrous on an alkylbenzene sulfonic acid as defined above, in the presence of oil and optionally alkylene glycol, at a temperature between 40 and 110 ° C, the amount of alkali metal oxide or hydroxide- earthy and of oil to be used being such that the alkylbenzene sulfonate obtained has a TBN less than or equal to 150, preferably less than or equal to 50.
  • the process which is the subject of the invention is very particularly advantageous for preparing detergent-dispersants with a TBN greater than or equal to 250 and having a large percentage by weight of calcium (at least 9%).
  • the process which is the subject of the invention is also advantageous for preparing detergent-dispersants with a TBN greater than 200 and containing at least 2% by weight of magnesium and optionally at least 0.5% by weight of calcium.
  • magnesium oxide any type of magnesium oxide can be used, however, "active" magnesium oxide is preferred.
  • active magnesium oxide denotes magnesium oxide Mg 0 with a specific surface greater than or equal to 80 m2 / g, for example between 100 and 170m2 / g.
  • Maglite DE marketed by Merck and with a specific surface area close to 140 m 2 / g, as well as "Ferumag” marketed by Rhône-Poulenc Industries and with a specific surface area close to 160 m2 / g.
  • 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 detergent-dispersant of TBN 200-300, 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 naphthenic base lubricants with paraffinic base and mixed base, other hydrocarbon lubricants, for example lubricant oils derived from coal products, and synthetic oils, for example alkylene polymers, alkylene oxide type polymers and their derivatives, including alkylene oxide polymers prepared by polymerizing alkylene oxide in the presence of water or alcohols, for example ethyl alcohol, esters of dicarboxylic acids, liquid esters of phosphorus acids, alkylbenzenes and dialkyl benzenes, polyphenols, alkyl biphenyl ethers, polymers silicon.
  • lubricating oils such as naphthenic base lubricants with paraffinic base and mixed base, other hydrocarbon lubricants, for example lubricant oils derived from coal products, and synthetic oils, for example alkylene polymers, alkylene oxide type polymers and their derivatives, including al
  • Additional additives may also be present in the said lubricating oils alongside the detergent-dispersants obtained according to the process of the invention; include, for example, anti-oxidant, anti-corrosion additives, ashless dispersant additives, etc.
  • the reaction medium is carbonated at 145 ° C. using CO 2 for 25 minutes under 260 mm Hg then 35 minutes at atmospheric pressure. Water is eliminated by carrying with it a little glycol.
  • the superalkalinized and carbonated medium is brought to a temperature of 184 ° C. under 30 mm Hg for 1 hour.
  • the glycol distills.
  • the medium is filtered to remove the sediments and a solution is recovered in 100 N oil of overbased detergent-dispersant which is degassed and whose characteristics are shown in Table I.
  • Example 1 to 3 The operation described in Examples 1 to 3 is carried out under the same conditions, starting from a 60% solution in 100 N oil of a sulfurized dodecylphenate and calcium carbonate, said solution containing 5.25% of calcium and 2.6% CO 2 and has a TBN of around 148.
  • Example 7 The operation described in Example 7 is carried out, using as a base stock the TBN 200 product prepared in Example 7, said product consisting of a 44/56 mixture of sulfurized and overbased dodecylphenate of calcium / alkylbenzene sulfonate of overbased magnesium.
  • Glycol is also used in admixture with decanol.
  • Example 7 The operation described in Example 7 is carried out by carrying out the carbonation operation at 140 ° C. at atmospheric pressure for approximately 4 hours without adding water.
  • Example 7 The operation described in Example 7 is carried out by carrying out the carbonation operation for 2 hours at 160 ° C, adding water after having cooled the medium to 110 ° C and continuing the carbonation for another 2 hours at 110 ° C.
  • the medium is heated to 50 ° C. and lime and then glycol are introduced over 30 minutes.
  • the medium is heated at 80 ° C. for 30 minutes and a 60% solution in 100 N dilution oil of calcium sulphurized dodecylphenate is introduced, said solution containing 5.5% of calcium being free of C0 2 and with a TBN of around 153.
  • the medium is brought to and maintained at 145 ° C. under 260 mm Hg for 20 minutes to completely eliminate the reaction water.
  • the eliminated water always carries with it a little glycol.
  • the medium is carbonated at 145 ° C. using C0 2 for 25 minutes under 260 mm Hg and then for 35 minutes at atmospheric pressure.
  • glycol is removed (3rd phase) and the detergent-dispersant solution is filtered (4th phase) as previously in Examples 1 to 3.
  • Example 12 The products of Example 12 are added to an SAE 50 oil with a paraffimic 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.
  • the solution is stored for 5 days at 80 ° C.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

A process is provided for preparing detergent-dispersant compositions of high alkalinity by: 1. Carbonation, at a temperature of between about 100 DEG C. and 250 DEG C., with carbon dioxide of a reaction medium comprising a sulfurized alkylphenate of an alkaline-earth metal having a TBN of between about 1 and 170, an alkaline-earth metal alkylbenzene sulfonate having a molecular weight of more than about 300 and a TBN of less than or equal to about 150, an alkaline-earth metal compound, an alkylene glycol, and a dilution oil; 2. Removal of the alkylene glycol; and 3. Separation of the superalkalinized metallic detergent-dispersant thus obtained. The metallic detergent-dispersant compositions obtained are useful in improving the detergent-dispersant power of lubricating oils.

Description

La présente invention a pour objet un procédé de préparation de détergents-dispersants métalliques suralcalinisés notamment pour huiles lubrifiantes.The present invention relates to a process for the preparation of overbased metal detergent-dispersants, in particular for lubricating oils.

Il est connu d'après le brevet anglais n° 1 015 769 de préparer des détergents-dispersants de haute alcalinité à base d'alkylphénates et d'alkylbenzène sulfonates de métaux alcalino-terreux, par sulfurisation d'un mélange contenant un alkylphénol, un alkyl- benzène sulfonate de métal alcalino-terreux, un monoalcool en C8-C18, une base alcalino-terreuse et du glycol, précarbonatation du mélange sulfurisé, alcalinisation du mélange précarbonaté par une base alcalino-terreuse, carbonatation puis élimination du glycol et récupération du détergent-dispersant.It is known from English Patent No. 1,015,769 to prepare detergents-dispersants of high alkalinity based on alkylphenates and alkylbenzene sulfonates of alkaline earth metals, by sulfurization of a mixture containing an alkylphenol, a alkaline earth metal alkylbenzene sulfonate, a C 8 -C 18 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 detergent-dispersant.

Un tel procédé présente l'inconvénient de nécessiter l'emploi d'un monoalcool en C8-C18 qu'il faut ensuite recycler sous forme pratiquement anhydre.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.

De plus, si un tel procédé est satisfaisant pour la préparation de détergents-dispersants contenant une forte proportion d'alkylphénates, il ne peut toutefois pas être utilisé pour la préparation de détergents-dispersants contenant une forte proportion d'alkylbenzènes sulfonates.In addition, if such a method 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 alkylbenzene sulfonates.

Il a également été proposé (brevet US n°4 057 504) de préparer des détergents-dispersants métalliques en faisant réagir un acide sulfonique organique (ou un de ses sels) et une base alcalino-terreuse sur une composition accélératrice constituée de glycol, d'un alkylphénol et de soufre, puis en carbonatant le mélange sulfurisé obtenu. Il a été constaté qu'un tel procédé ne peut être réalisé qu'en présence d'un fort excès de soufre par rapport à la quantité d'alkylphénol, ce afin d'eviter une viscosité trop importante du milieu à carbonater. Le soufre étant particulièrement corrosif, seuls les produits préparés à partir de faibles quantités d'alkylphénol pourront être utilisés industriellement.It has also been proposed (US Patent No. 4,057,504) to prepare metal detergent-dispersants by reacting an organic sulfonic acid (or a salt thereof) and an alkaline earth base on an accelerating composition consisting of glycol, d 'an alkylphenol and sulfur, then carbonating the sulfurized mixture obtained. It has been found that such a process can only be carried out in the presence of a large excess of sulfur relative to the amount of alkylphenol, in order to avoid too high a viscosity of the medium to be carbonated. Since sulfur is particularly corrosive, only products prepared from small amounts of alkylphenol can be used industrially.

La demanderesse a trouvé un procédé permettant d'obtenir des additifs détergents-dispersants métalliques de TBN (Total Basic Number - Norme A.S.T.M. D 2896) supérieur à 200, d'une manière simple et rapide, en présence d'alkylène glycol en faible quantité et en l'absence de monoalcool ou de soufre en excès.The Applicant has found a process making it possible to obtain metal detergent-dispersant additives with TBN (Total Basic Number - Standard ASTM D 2896) greater than 200, in a simple and rapid manner, in the presence of alkylene glycol in small quantities and in the absence of excess monoalcohol or sulfur.

Le procédé faisant l'objet de l'invention est caractérisé en ce que:

  • 1 ) l'on carbonate à l'aide de gaz carbonique, à une température comprise entre 100 et 250°C, un milieu réactionnel comprenant:
    • - un alkylphénate sulfurisé de calcium et/ou de magnésium de TBN compris entre 0 et 170, ledit alkylphénate portant un ou plusieurs substituants alkyles en C6-C60;
    • - un alkylbenzène sulfonate de calcium et/ou de magnésium de masse moléculaire supérieure à 300 et de TBN inférieur ou égal à 150;
    • - un composé alcalino-terreux choisi parmi la chaux l'oxyde ou l'hydroxyde de magnésium ou leurs mélanges;
    • - un alkylène glycol;
    • - une huile de dilution;

    selon les quantités suivantes de réactifs:
    • - de 5 à 60 parties en poids d'alkylphénate sulfurisé pour 100 parties en poids de mélange alkylphénate sulfurisé + alkylbenzène sulfonate,
    • -de 95 à 40 parties en poids d'alkyl- benzène sulfonate pour 100 parties en poids de mélange alkylphénate sulfurisé + alkylbenzène sulfonate;
    • - de 3 à 30 parties en poids de composé alcalino-terreux pour 100 parties en poids de mélange alkylphénate sulfurisé + alkylbenzène sulfonate;
    • - de 4 à 60 parties en poids d'alkylène glycol pour 100 parties en poids de mélange alkylphénate sulfurisé + alkylbenzène sulfonate, le composé alcalino-terreux et l'alkylène glycol étant introduits selon un rapport molaire composé alcalino-terreux/alkylène glycol compris entre 0,4 et 1,8;
    • - une quantité de C02 comprise entre celle pouvant être complètement absorbée par le milieu réactionnel et un excès de 30 % de cette quantité.
  • 2) en ce que l'on élimine l'alkylène glycol,
  • 3) et en ce que l'on sépare le détergent-dispersant métallique suralcalinisé ainsi obtenu.
The process which is the subject of the invention is characterized in that:
  • 1) carbonization is carried out using carbon dioxide, at a temperature between 100 and 250 ° C., a reaction medium comprising:
    • a sulfurized calcium and / or magnesium alkylphenate of TBN of between 0 and 170, said alkylphenate carrying one or more C 6 -C 60 alkyl substituents;
    • - a calcium and / or magnesium alkylbenzene sulfonate with a molecular mass greater than 300 and a TBN less than or equal to 150;
    • - an alkaline earth compound chosen from lime, magnesium oxide or hydroxide or mixtures thereof;
    • - an alkylene glycol;
    • - a dilution oil;

    according to the following amounts of reagents:
    • - from 5 to 60 parts by weight of sulfurized alkylphenate per 100 parts by weight of sulfurized alkylphenate + alkylbenzene sulfonate mixture,
    • from 95 to 40 parts by weight of alkylbenzene sulfonate per 100 parts by weight of mixture of sulfurized alkylphenate + alkylbenzene sulfonate;
    • - from 3 to 30 parts by weight of alkaline-earth compound per 100 parts by weight of sulfurized alkylphenate + alkylbenzene sulfonate mixture;
    • - from 4 to 60 parts by weight of alkylene glycol per 100 parts by weight of sulfurized alkylphenate + alkylbenzene sulfonate mixture, the alkaline earth compound and the alkylene glycol being introduced according to a molar ratio of alkaline earth compound / alkylene glycol of between 0.4 and 1.8;
    • - An amount of C02 between that which can be completely absorbed by the reaction medium and an excess of 30% of this amount.
  • 2) in that the alkylene glycol is eliminated,
  • 3) and in that the overbased metal detergent-dispersant thus obtained is separated.

Selon ledit procédé, l'opération de carbonation peut être réalisée en une ou plusieurs fois, en introduisant la quantité nécessaire ci-dessus définie de composé alcalino-terreux et d'alkylène glycol, en une ou plusieurs fois, chaque introduction de composé alcalino-terreux et d'alkylène glycol étant suivie d'une opération de carbonatation.According to said method, the carbonation operation can be carried out in one or more times, by introducing the necessary quantity defined above of alkaline earth compound and alkylene glycol, in one or more times, each introduction of alkaline compound. earthy and alkylene glycol being followed by a carbonation operation.

Pour une bonne réalisation de l'invention, l'opération de carbonatation peut être réalisée à l'aide d'une quantité de CO2 sensiblement égale à celle pouvant être complètement absorbée, à une température comprise entre 100 et 185°C, en présence d'un milieu réactionnel comprenant de:

  • - 8 à 55 parties en poids d'alkylphénate sulfurisé pour 100 parties en poids de mélange alkylphénate sulfurisé + alkylbenzène sulfonate,
  • -45 à 92 parties en poids d'alkylbenzène sulfonate pour 100 parties en poids de mélange alkylphénate sulfurisé + alkylbenzène sulfonate,
  • -4 à 25 parties en poids de composé alcalino-terreux pour 100 parties en poids de mélange alkylphénate sulfurisé + alkylbenzène sulfonate,
  • - 5 à 40 parties en poids d'alkylène glycol pour 100 parties en poids de mélange alkyl- phénate sulfurisé + alkylbenzène sulfonate.
For a good implementation of the invention, the carbonation operation can be carried out using a quantity of CO 2 substantially equal to that which can be completely absorbed, at a temperature between 100 and 185 ° C., in the presence a reaction medium comprising of:
  • - 8 to 55 parts by weight of sulfurized alkylphenate per 100 parts by weight of sulfurized alkylphenate + alkylbenzene sulfonate mixture,
  • 45 to 92 parts by weight of alkylbenzene sulfonate per 100 parts by weight of mixture of sulfurized alkylphenate + alkylbenzene sulfonate,
  • 4 to 25 parts by weight of alkaline earth compound per 100 parts by weight of sulfurized alkylphenate + alkylbenzene sulfonate mixture,
  • - 5 to 40 parts by weight of alkylene glycol per 100 parts by weight of mixture of sulfurized alkyl phenate + alkylbenzene sulfonate.

On dénomme par "alkylphénate sulfurisé" toute solution contenant de 30 à 80 % en poids, de préférence de 40 à 70 % en poids d'un alkyl- phénate sulfurisé dans une huile de dilution qui peut être ou peut ne pas être la même que celle mise en oeuvre pour réaliser le procédé objet de l'invention.The term "sulfurized alkylphenate" denotes any solution containing from 30 to 80% by weight, preferably from 40 to 70% by weight of a sulfurized alkyl phenate in a dilution oil which may or may not be the same as that used to carry out the process which is the subject of the invention.

De même, on dénommera par "alkylbenzène sulfonate" toute solution contenant de 40 à 95 % en poids, de préférence de 55 à 85 % en poids d'un alkylbenzène sulfonate dans une huile de dilution qui peut être ou peut ne pas être la même que celle mise en oeuvre pour réaliser le procédé objet de l'invention.Likewise, the term “alkylbenzene sulfonate” will denote any solution containing from 40 to 95% by weight, preferably from 55 to 85% by weight of an alkylbenzene sulfonate in a dilution oil which may or may not be the same than that used to carry out the process which is the subject of the invention.

Parmi les alkylphénates sulfurisés pouvant être mis en oeuvre, on peut citer ceux obtenus par sulfurisation au soufre d'un alkylphénol portant de préférence un ou plusieurs substituants alkyles en C9-C'5 (tels que les nonyl, decyl, dodecyl ou tetradecylphénols) en présence d'une base alcalino-terreuse et d'un alkylène glycol, suivie éventuellement d'une carbonatation par du gaz carbonique.Among the sulfurized alkylphenates which can be used, mention may be made of those obtained by sulfurization with sulfur of an alkylphenol preferably carrying one or more C 9 -C 5 alkyl substituents (such as nonyl, decyl, dodecyl or tetradecylphenols) in the presence of an alkaline earth base and an alkylene glycol, optionally followed by carbonation with carbon dioxide.

Parmi les alkylbenzènes sulfonates pouvant être mis en oeuvre, on peut citer les sels d'acides sulfoniques (de poids moléculaire de préférence supérieur à 400) naturels obtenus par sulfonation de coupes pétrolières ou synthétiques obtenus par sulfonation d'alkylbenzènes dérivant d'oléfines ou de polymères d'oléfines en C15-C30 et de métaux alcalino-terreux tels que calcium, et/ou magnésium.Among the alkylbenzene sulfonates which can be used, mention may be made of the salts of sulfonic acids (of molecular weight preferably greater than 400) obtained by sulfonation of petroleum or synthetic fractions obtained by sulfonation of alkylbenzenes derived from olefins or polymers of C 15 -C 30 olefins and of alkaline earth metals such as calcium, and / or magnesium.

Le composé alcalino-terreux à mettre en oeuvre est constitué d'oxydes ou d'hydroxydes de calcium, ou de magnésium ... pris seuls ou en mélange; le métal dont dérivent l'alkyl- benzène sulfonate alcalino-terreux et l'alkyl- phénate alcalino-terreux mis en oeuvre peut être ou peut ne pas être le même que celui ou ceux contenus dans le composé alcalino-terreux.The alkaline-earth compound to be used consists of oxides or hydroxides of calcium, or of magnesium ... taken alone or as a mixture; the metal from which the alkaline earth alkyl benzene sulfonate and the alkaline earth alkyl phenate used may or may not be the same as that or those contained in the alkaline earth compound.

Parmi les huiles de dilution pouvant être mises en oeuvre, on peut citer de préférence les huiles paraffiniques telles que l'huile 100 Neutral...; les huiles naphténiques ou mixtes peuvent étalement convenir.Among the dilution oils which can be used, mention may preferably be made of paraffinic oils such as 100 Neutral oil, etc .; naphthenic or mixed oils may also be suitable.

La quantité d'huile pouvant être mise en oeuvre est telle que la quantité d'huile présente dans le produit final (y compris celle provenant de l'alkylphénate sulfurisé et l'alkylbenzène sulfonate de départ) soit comprise entre 20 et 60 %, de préférence entre 25 et 55 % dudit produit.The amount of oil that can be used is such that the amount of oil present in the final product (including that from the sulfurized alkylphenate and the starting alkylbenzene sulfonate) is between 20 and 60%, from preferably between 25 and 55% of said product.

Parmi les alkylèneglycols pouvant être mis en oeuvre, on peut citer tout particulièrement le glycol; ceux-ci peuvent éventuellement être présents en mélange avec jusqu'à 200 % de leur poids d'un monoalcool tel que l'éthyl- hexanol, l'alcool tridécylique, les alcools oxo en C8-C14 et d'une manière générale, les alcools ayant un point d'ébullition supérieur à 120°C et de préférence supérieur à 150°C.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 , the alcohols having a boiling point higher than 120 ° C and preferably higher than 150 ° C.

Une variante du procédé faisant l'objet de la présente invention, consiste à réaliser l'opération de carbonatation en une seule étape, en présence de 0 à 25 parties, de préférence de 0 à 15 parties pour 100 parties de melange alkyl- phénate sulfurisé + alkylbenzène sulfonate, d'un pied de cuve de TBN supérieur ou égal à 200 et choisi parmi:

  • a) les alkylphénates sulfurisés et suralcalinisés de métaux alcalino-terreux tels que calcium, et/ou magnésium..., dont le ou les substituants alcoyles sont en Cg-C,5 tels que les substituants nonyle, décyle, dodécyle ou tétradécyle.
  • b) les alkylbenzènes sulfonates suralcalinisés de métaux alcalino-terreux tels que calcium, et/ou magnésium, préparés à partir d'acides sulfoniques naturels ou synthétiques obtenus par sulfonation d'alkylbenzènes dérivant d'oléfines ou de polymères d'oléfines en C15-C30, et de masse moléculaire supérieure à 300, de préférence supérieure à 400.
  • c) les mélanges des produits a) et b).
A variant of the process which is the subject of the present invention consists in carrying out the carbonation operation in a single step, in the presence of 0 to 25 parts, preferably from 0 to 15 parts per 100 parts of sulfurized alkylphenate mixture. + alkylbenzene sulfonate, with a base stock of TBN greater than or equal to 200 and chosen from:
  • a) sulphurized and superalkalinated alkylphenates of alkaline earth metals such as calcium, and / or magnesium, etc., in which the alkyl substituent or substituents are Cg-C, 5 such as the nonyl, decyl, dodecyl or tetradecyl substituents.
  • b) the alkalinized alkylbenzene sulfonates of alkaline earth metals such as calcium, and / or magnesium, prepared from natural or synthetic sulfonic acids obtained by sulfonation of alkylbenzenes derived from olefins or from polymers of C 15 olefins - C 30 , and of molecular mass greater than 300, preferably greater than 400.
  • c) mixtures of products a) and b).

Une autre variante du procédé faisant l'objet de l'invention, consiste à préparer in situ préalablement à l'opération de carbonatation, l'alkylbenzène sulfonate de métal alcalino-terreux par action d'un oxyde ou d'un hydroxyde dudit métal alcalino-terreux sur un acide alkylbenzène sulfonique tel que défini ci-dessus, en présence d'huile et d'alkylène glycol éventuellement, à une température comprise entre 40 et 110°C, la quantité d'oxyde ou d'hydroxyde de métal alcalino-terreux et d'huile à mettre en oeuvre étant telle que l'alkyl- benzène sulfonate obtenu présente un TBN inférieur ou égal à 150, de préférence inférieur ou égal à 50.Another variant of the process which is the subject of the invention consists in preparing, in situ prior to the carbonation operation, the alkylbenzene sulfonate of alkaline earth metal by the action of an oxide or a hydroxide of said alkali metal. -terrous on an alkylbenzene sulfonic acid as defined above, in the presence of oil and optionally alkylene glycol, at a temperature between 40 and 110 ° C, the amount of alkali metal oxide or hydroxide- earthy and of oil to be used being such that the alkylbenzene sulfonate obtained has a TBN less than or equal to 150, preferably less than or equal to 50.

Le procédé faisant l'objet de l'invention est tout particulièrement intéressant pour préparer des détergents-dispersants de TBN supérieur ou égal à 250 et présentant un pourcentage en poids important de calcium (au moins 9 %).The process which is the subject of the invention is very particularly advantageous for preparing detergent-dispersants with a TBN greater than or equal to 250 and having a large percentage by weight of calcium (at least 9%).

Ledit procédé pourra être réalisé à partir d'un alkylphénate sulfurisé de calcium, d'un alkyl- benzène sulfonate de calcium et des quantités suivantes de réactifs:

  • - de 5 à 30 parties en poids, de préférence de 6 à 25 parties en poids d'hydroxyde de calcium pour 100 parties en poids de mélange d'alkylphénate sulfurisé de calcium et d'alkyl- benzène sulfonate de calcium;
  • - de 4 à 60 parties, de préférence de 5 à 40 parties d'alkylène glycol pour 100 parties de mélange constitué d'alkylphénate sulfurisé de calcium et d'alkylbenzène sulfonate de calcium;
  • - et de 0 à 25 parties, de préférence de 0 à 15 parties pour 100 parties d'un mélange d'alkylphénate sulfurisé de calcium et d'alkyl- benzène sulfonate de calcium, d'un pied de cuve de TBN supérieur ou égal à 250 et constitué d'un alkylphénate sulfurisé et suralcalinisé de calcium et/ou d'un alkylbenzène sulfonate suralcalinisé de calcium.
Said process can be carried out using a sulfurized calcium alkylphenate, a calcium alkyl benzene sulfonate and the following amounts of reactants:
  • - from 5 to 30 parts by weight, preferably from 6 to 25 parts by weight of calcium hydroxide per 100 parts by weight of mixture of sulfurized calcium alkylphenate and calcium alkylbenzene sulfonate;
  • - from 4 to 60 parts, preferably from 5 to 40 parts of alkylene glycol per 100 parts of mixture consisting of sulfurized calcium alkylphenate and calcium alkylbenzene sulfonate;
  • - and from 0 to 25 parts, preferably from 0 to 15 parts per 100 parts of a mixture of sulfurized calcium alkylphenate and calcium alkyl benzene sulphonate, of a base stock of TBN greater than or equal to 250 and consisting of a sulfurized and overbased calcium alkylphenate and / or a calcium overbased alkylbenzene sulfonate.

Le procédé faisant l'objet de l'invention est également intéressant pour préparer des détergents-dispersants de TBN supérieur à 200 et contenant au moins 2 % en poids de magnésium et éventuellement au moins 0,5 % en poids de calcium.The process which is the subject of the invention is also advantageous for preparing detergent-dispersants with a TBN greater than 200 and containing at least 2% by weight of magnesium and optionally at least 0.5% by weight of calcium.

Ce procédé consiste alors à mettre en oeuvre:

  • - un alkylphénate sulfurisé de magnésium et/ou de calcium comme alkylphénate sulfurisé de métal alcalino-terreux,
  • - un alkylbenzène sulfonate de magnésium et/ou de calcium comme alkylbenzène sulfonate de métal alcalino-terreux,
  • - de l'oxyde de magnésium éventuellement en mélange avec de l'hydroxyde de calcium comme composé alcalino-terreux,
  • - éventuellement un pied de cuve de TBN supérieur ou égal à 200, constitué d'un alkyl- benzène sulfonate suralcalinisé de magnésium et/ou de calcium et/ou d'un alkylphénate sulfurisé et suralcalinisé de magnésium et/ou de calcium, et éventuellement à traiter à un stade quelconque de l'étape ou des étapes de carbonatation le milieu par 0 à 10 % en poids, de préférence par 0 à 5 % en poids d'eau par rapport au poids dudit milieu.
This process then consists in implementing:
  • a sulfurized alkylphenate of magnesium and / or calcium as a sulfurized alkylphenate of alkaline earth metal,
  • - a magnesium and / or calcium alkylbenzene sulfonate as alkaline earth metal alkylbenzene sulfonate,
  • - magnesium oxide optionally mixed with calcium hydroxide as an alkaline-earth compound,
  • - optionally, a base stock of TBN greater than or equal to 200, consisting of an overbased magnesium and / or calcium alkylbenzene sulfonate and / or a sulfurized and overbased magnesium and / or calcium alkylphenate, and optionally to be treated at any stage of the stage or stages of carbonation of the medium with 0 to 10% by weight, preferably with 0 to 5% by weight of water relative to the weight of said medium.

Ledit procédé pourra être réalisé à l'aide des quantités particulières des réactifs suivants:

  • - de 3 à 25 parties, de préférence de 4 à 18 parties en poids d'oxyde de magnésium pour 100 parties de mélange alkylphénate sulfurisé de magnésium et/ou de calcium et alkylbenzène sulfonate de magnésium et/ou de calcium,
  • - de 0 à 10 parties, de préférence de 0 à 5 parties en poids d'hydroxyde de calcium, pour 100 parties de mélange alkylphénate sulfurisé de magnésium et/ou de calcium et alkyl- benzène sulfonate de magnésium et/ou de calcium.
  • - de 4 à 60 parties, de préférence de 8 à 40 parties d'alkylène glycol pour 100 parties de mélange alkylphénate sulfurisé de magnésium et/ou de calcium et d'alkylbenzène sulfonate de magnésium et/ou de calcium,
  • - de 0 à 25 parties, de préférence de 0 à 15 parties de pied de cuve pour 100 parties de mélange alkylphénate sulfurisé de magnésium et/ou de calcium et d'alkylbenzène sulfonate de magnésium et/ou de calcium.
Said process can be carried out using specific quantities of the following reagents:
  • - from 3 to 25 parts, preferably from 4 to 18 parts by weight of magnesium oxide per 100 parts of sulfurized alkylphenate mixture of magnesium and / or calcium and magnesium and / or calcium alkylbenzene sulfonate,
  • - From 0 to 10 parts, preferably from 0 to 5 parts by weight of calcium hydroxide, per 100 parts of sulfurized alkylphenate mixture of magnesium and / or calcium and magnesium and / or calcium alkyl benzene sulfonate.
  • - from 4 to 60 parts, preferably from 8 to 40 parts of alkylene glycol per 100 parts of sulfurized alkylphenate mixture of magnesium and / or calcium and of magnesium and / or calcium alkylbenzene sulfonate,
  • - from 0 to 25 parts, preferably from 0 to 15 parts of base stock per 100 parts of sulfurized alkylphenate mixture of magnesium and / or calcium and of magnesium and / or calcium alkylbenzene sulfonate.

Bien que n'importe quel type d'oxyde de magnésium puisse être utilisé, on préfère toutefois l'oxyde de magnésium "actif".Although any type of magnesium oxide can be used, however, "active" magnesium oxide is preferred.

On désigne par oxyde de magnésium "actif" de l'oxyde de magnésium Mg 0 de surface spécifique supérieure ou égale à 80 m2/g, par exemple comprise entre 100 et 170m2/g. A titre d'exemple, on peut citer la "Maglite DE" commercialisée par Merck et de surface spécifique voisine de 140 m2/g, ainsi que le "Ferumag" commercialisé par Rhône-Poulenc Industries et de surface spécifique voisine de 160 m2/g.The term “active” magnesium oxide denotes magnesium oxide Mg 0 with a specific surface greater than or equal to 80 m2 / g, for example between 100 and 170m2 / g. By way of example, mention may be made of "Maglite DE" marketed by Merck and with a specific surface area close to 140 m 2 / g, as well as "Ferumag" marketed by Rhône-Poulenc Industries and with a specific surface area close to 160 m2 / g.

La présente invention a également pour objet les détergents-dispersants de haute alcalinité obtenus par le procédé décrit ci-dessus. Ceux-ci présentent l'avantage d'une très bonne compatibilité avec les huiles visqueuses ainsi qu'un très faible taux de sédiments. Il peuvent être ajoutés à des huiles lubrifiantes selon des quantités fonction du TBN desdits détergents-dispersants, et fonction de l'utilisation future desdites huiles; ainsi pour une huile pour moteur à essence, la quantité de détergent-dispersant de TBN 200-300 par exemple à ajouter, est généralement comprise entre 1 et 3,5 %; pour une huile pour moteur diesel, elle est généralement comprise entre 1,8 et 5 %; pour une huile pour moteur marin, celle-ci peut aller jusqu'à 25 %.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 detergent-dispersant of TBN 200-300, 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%.

Les huiles lubrifiantes que l'on peut ainsi améliorer peuvent être choisies parmi des huiles lubrifiantes très variées, comme les huiles lubrifiantes de base naphténique de base paraf- finique et de base mixte, d'autres lubrifiants hydrocarbonés, par exemple des huiles lubrifiantes dérivées de produits de la houille, et des huiles synthétiques, par exemple des polymères d'alkylène, des polymères du type oxyde d'alkylène et leurs dérivés, y compris les polymères d'oxyde d'alkylène préparés en polymérisant de l'oxyde d'alkylène en présence d'eau ou d'alcools, par exemple d'alcool éthylique, les esters d'acides dicarboxyliques, des esters liquides d'acides du phosphore, des alkylbenzènes et des dialkyl benzènes, des polyphénvles, des alkyl biphényl éthers, des polymères du silicium.The lubricating oils which can thus be improved can be chosen from a wide variety of lubricating oils, such as naphthenic base lubricants with paraffinic base and mixed base, other hydrocarbon lubricants, for example lubricant oils derived from coal products, and synthetic oils, for example alkylene polymers, alkylene oxide type polymers and their derivatives, including alkylene oxide polymers prepared by polymerizing alkylene oxide in the presence of water or alcohols, for example ethyl alcohol, esters of dicarboxylic acids, liquid esters of phosphorus acids, alkylbenzenes and dialkyl benzenes, polyphenols, alkyl biphenyl ethers, polymers silicon.

Des additifs supplémentaires peuvent également être présents dans les dites huiles lubrifiantes à côté des détergents-dispersants obtenus selon le procédé de l'invention; on peut citer par exemple des additifs anti-oxydants, anti-corrosion, des additifs dispersants sans cendres...Additional additives may also be present in the said lubricating oils alongside the detergent-dispersants obtained according to the process of the invention; include, for example, anti-oxidant, anti-corrosion additives, ashless dispersant additives, etc.

Les exemples suivants sont donnés à titre indicatif et ne peuvent être considérés comme une limite du domaine et de l'esprit de l'invention.The following examples are given for information only and cannot be considered as limiting the scope and spirit of the invention.

Exemples 1 à 3Examples 1 to 3

On donne ci-après le mode général de préparation des détergents-dispersants suralcalinisés faisant l'objet des exemples 1 à 3 et dans le tableau I, les quantités de réactifs nécessaires à leur préparation et leurs caractéristiques.The general mode of preparation of the overbased detergent-dispersants given in Examples 1 to 3 and in Table I is given below, the quantities of reagents necessary for their preparation and their characteristics.

Préparation du mélange à carbonaterPreparation of the carbonating mixture

On introduit dans un réacteur tétracol de 4 litres muni d'un système d'agitation et d'un dispositif de chauffage:

  • - une solution à 60 % dans de l'huile de dilution 100 Neutral d'un alkylphénate sulfurisé de calcium (phénate Ca en abréviation) obtenu par sulfurisation du dodecyl-phénol par du soufre en présence de chaux; ladite solution de phénate contient 5,5 % de calcium, est exempte de CO2 et présente un TBN de 153 environ.
  • - de l'huile 100 Neutral,
  • - une solution à environ 60 % dans de l'huile de dilution d'un alkylbenzène sulfonate de calcium (sulfonate Ca en abréviation) de masse moléculaire 470 environ (masse du sel de sodium), solution contenant 2,7 % de calcium et présentant un TBN de 25 environ,
  • - un anti-mousse commercialisé par Rhône-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:
  • - A 60% solution in 100 Neutral dilution oil of a sulfurized calcium alkylphenate (phenate Ca for short) obtained by sulfurization of dodecyl-phenol with sulfur in the presence of lime; said phenate solution contains 5.5% calcium, is free of CO 2 and has a TBN of approximately 153.
  • - 100 Neutral oil,
  • - a solution of approximately 60% in dilution oil of a calcium alkylbenzene sulfonate (sulfonate Ca for short) molecular mass approximately 470 (mass of the sodium salt), solution containing 2.7% of calcium and having a TBN of approximately 25,
  • - an anti-foam agent marketed by Rhône-Poulenc under the name SI 200.

On introduit alors sous agitation de la chaux et du glycol et on porte et maintient le milieu à 145°C sous 260 mm de mercure pendant 20 minutes pour éiminer complètement l'eau provenant de l'action de la chaux: l'eau éliminée entraine toujours avec elle un peu de glycol.Lime and glycol are then introduced with stirring and the medium is brought to and maintained at 145 ° C. under 260 mm of mercury for 20 minutes to completely eliminate the water coming from the action of lime: the eliminated water causes always with it a little glycol.

1 ère phase (carbonatation)1st phase (carbonation)

Après avoir réajusté la quantité de glycol à sa valeur première, on carbonate le milieu réactionnel à 145°C à l'aide de CO2 pendant 25 minutes sous 260 mm Hg puis 35 minutes à pression atmosphérique. De l'eau s'élimine en entrainant avec elle un peu de glycol.After having readjusted the amount of glycol to its initial value, the reaction medium is carbonated at 145 ° C. using CO 2 for 25 minutes under 260 mm Hg then 35 minutes at atmospheric pressure. Water is eliminated by carrying with it a little glycol.

2ème phase (élimination du glycol)2nd phase (elimination of glycol)

On porte le milieu suralcalinisé et carbonaté à une température de 184°C sous 30 mm Hg pendant 1 heure. Le glycol distille.The superalkalinized and carbonated medium is brought to a temperature of 184 ° C. under 30 mm Hg for 1 hour. The glycol distills.

3ème phase (séparation)3rd phase (separation)

Le milieu est filtré pour éliminer les sédiments et on récupère une solution dans de l'huile 100 N de détergent-disperant suralcalinisé que l'on dégaze et dont les caractéristiques figurent au tableau I.The medium is filtered to remove the sediments and a solution is recovered in 100 N oil of overbased detergent-dispersant which is degassed and whose characteristics are shown in Table I.

Exemples 4 à 6Examples 4 to 6

L'opération décrite aux exemples 1 à 3 est réalisée dans les mêmes conditions, à partir d'une solution à 60 % dans de l'huile 100 N d'un dodecylphénate sulfurisé et carbonaté de calcium, ladite solution contenant 5,25 % de calcium et 2,6 % de CO2 et présente un TBN de 148 environ.The operation described in Examples 1 to 3 is carried out under the same conditions, starting from a 60% solution in 100 N oil of a sulfurized dodecylphenate and calcium carbonate, said solution containing 5.25% of calcium and 2.6% CO 2 and has a TBN of around 148.

Les quantités de réactifs nécessaires et les caractéristiques des produits obtenus figurent au tableau II.The quantities of reagents required and the characteristics of the products obtained are shown in Table II.

Exemple 7Example 7

On donne ci-après le mode général de préparation d'un détergent-dispersant suralcalinisé et dans le tableau III les quantités de réactifs nécessaires à sa préparation et ses caractéristiques.The general mode of preparation of an overbased detergent-dispersant is given below and in Table III the quantities of reagents necessary for its preparation and its characteristics.

On introduit dans un réacteur tétracol de 4 litres muni d'un système d'agitation et d'un dispositif de chauffage:

  • - une solution à 60 % dans de l'huile de dilution 100 Neutral, d'un alkylphénate sulfurisé de calcium (phénate Ca en abréviation) obtenu par sulfurisation du dodécylphénol par du soufre en présence de chaux; ladite solution de phénate contient 5,5 % de calcium, est exempte de C02 et présente un TBN de 153 environ.
  • - une solution à environ 60 % dans der l'huile de dilution d'un alkylbenzène sulfonate 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.
  • ―de l'anti-mousse SI 200.
The following are introduced into a 4-liter tetracol reactor equipped with a stirring system and a heating device:
  • - a 60% solution in 100 Neutral dilution oil, of a sulfurized calcium alkylphenate (Ca phenate for short) obtained by sulfurization of dodecylphenol with sulfur in the presence of lime; said phenate solution contains 5.5% calcium, is free of C0 2 and has a TBN of approximately 153.
  • - a solution of about 60% in der the dilution oil of a magnesium alkylbenzene sulfonate (sulfonate Mg for short) of molecular weight about 470 (mass of the sodium salt), solution containing 1.8% of magnesium and having a TBN of around 25.
  • SI SI 200 defoamer.

On introduit alors sous agitation de la "Maglite DE" et du glycol et on porte le milieu à 110°C.Then introduced with stirring "Maglite DE" and glycol and the medium is brought to 110 ° C.

On carbonate à l'aide C02 pendant 3 heures à 110°C, on ajoute de l'eau et on continue la carbonatation jusqu'à la fin de l'absorption du CO2; l'opération dure 5 heures.Carbonate using C0 2 for 3 hours at 110 ° C, add water and continue carbonation until the absorption of CO 2 is completed ; the operation lasts 5 hours.

Le glycol est éliminé (2ème phase) et la solution de détergent-dispersant est filtrée (3ème phase) comme précédemment aux exemples 1 à 3.The glycol is eliminated (2nd phase) and the detergent-dispersant solution is filtered (3rd phase) as previously in Examples 1 to 3.

Les caractéristiques du produit obtenu figurent au tableau III.The characteristics of the product obtained are shown in Table III.

Exemple 8Example 8

On réalise l'opération décrite à l'exemple 7, en utilisant comme pied de cuve le produit de TBN 200 préparé à l'exemple 7 ledit produit étant constitué d'un mélange 44/56 dodécylphénate sulfurisé et suralcalinisé de calcium/ alkylbenzène sulfonate de magnésium suralcalinisé.The operation described in Example 7 is carried out, using as a base stock the TBN 200 product prepared in Example 7, said product consisting of a 44/56 mixture of sulfurized and overbased dodecylphenate of calcium / alkylbenzene sulfonate of overbased magnesium.

Les quantités de réactifs mises en oeuvre et les caractéristiques des produits obtenus figurent aux tableaux IV et IV'.The quantities of reagents used and the characteristics of the products obtained are shown in Tables IV and IV '.

Exemple 9Example 9

On réalise l'opération décrite à l'exemple 7, en présence d'un pied de cuve de TBN 275 et constitué de:

  • - 50 % en poids de dodécylphénate de calcium sulfurisé de TBN 150;
  • - et 50 % en poids d'alkylbenzène sulfonate de magnésium de TBN 400.
The operation described in Example 7 is carried out, in the presence of a TBN 275 base stock and consisting of:
  • - 50% by weight of sulfurized calcium dodecylphenate of TBN 150;
  • - And 50% by weight of magnesium alkylbenzene sulfonate of TBN 400.

Le glycol est également utilisé en mélange avec du décanol.Glycol is also used in admixture with decanol.

Les quantités de réactifs mises en oeuvre et les caractéristiques du produit obtenu figurent aux tableaux IV et IV'.The quantities of reagents used and the characteristics of the product obtained are shown in Tables IV and IV '.

Exemple 10Example 10

L'opération décrite à l'exemple 7 est réalisée en effectuant l'opération de carbonatation à 140°C à pression atmosphérique pendant environ 4 heures sand addition d'eau.The operation described in Example 7 is carried out by carrying out the carbonation operation at 140 ° C. at atmospheric pressure for approximately 4 hours without adding water.

Les caractéristiques du produit obtenu sont semblables à celles de celui de l'exemple 7.The characteristics of the product obtained are similar to that of Example 7.

Exemple 11Example 11

L'opération décrite à l'exemple 7 est réalisée en effectuant l'opération de carbonatation pendant 2 heures à 160°C, en ajoutant de l'eau après avoir refroidi le milieu à 110°C et en poursuivant la carbonatation pendant encore 2 heures à 110°C.The operation described in Example 7 is carried out by carrying out the carbonation operation for 2 hours at 160 ° C, adding water after having cooled the medium to 110 ° C and continuing the carbonation for another 2 hours at 110 ° C.

Les caractéristiques du produit obtenu sont semblables à celles de celui de l'exemple 7.The characteristics of the product obtained are similar to that of Example 7.

Exemples 12 à 14Examples 12 to 14

On donne ci-après le mode général de préparation des détergents-dispersants suralcalinisés faisant l'objet des exemples 12 à 14 et dans le tableau V les quantités de réactifs nécessaires à leur préparation.The general mode of preparation of the overbased detergent-dispersants given in Examples 12 to 14 is given below and the quantities of reactants in Table V necessary for their preparation.

On introduit dans un réacteur tétracol de 4 litres muni d'un système d'agitation et d'un dispositif de chauffage:

  • - une solution à environ 70 % dans de l'huile de dilution d'un acide alkylbenzène sulfonique de masse moléculaire 470 environ (masse du sel de sodium),
  • - de l'huile 100 N,
  • - de l'anti-mousse SI 200.
The following are introduced into a 4-liter tetracol reactor equipped with a stirring system and a heating device:
  • - a solution of approximately 70% in dilution oil of an alkylbenzene sulfonic acid of molecular mass approximately 470 (mass of the sodium salt),
  • - 100 N oil,
  • - SI 200 anti-foam.

On chauffe le milieu vers 50°C et on introduit de la chaux puis du glycol en 30 minutes.The medium is heated to 50 ° C. and lime and then glycol are introduced over 30 minutes.

Le milieu est chauffé à 80°C pendant 30 minutes et on introduit une solution à 60 % dans de l'huile de dilution 100 N de dodecylphénate sulfurisé de calcium, ladite solution contenant 5,5 % de calcium, étant exempte de C02 et présentant un TBN de 153 environ.The medium is heated at 80 ° C. for 30 minutes and a 60% solution in 100 N dilution oil of calcium sulphurized dodecylphenate is introduced, said solution containing 5.5% of calcium being free of C0 2 and with a TBN of around 153.

On porte et maintient le milieu à 145°C sous 260 mm Hg pendant 20 minutes pour éliminer complètement l'eau de réaction. L'eau éliminée entraine toujours avec elle un peu de glycol.The medium is brought to and maintained at 145 ° C. under 260 mm Hg for 20 minutes to completely eliminate the reaction water. The eliminated water always carries with it a little glycol.

lère phase de carbonatation1st carbonation phase

On carbonate le milieu à 145°C à l'aide de C02 pendant 25 minutes sous 260 mm Hg puis pendant 35 minutes à pression atmosphérique.The medium is carbonated at 145 ° C. using C0 2 for 25 minutes under 260 mm Hg and then for 35 minutes at atmospheric pressure.

2ème phase de carbonatation2nd carbonation phase

On introduit de nouveau sous agitation de la chaux et du glycol; on porte et maintient le milieu à 145°C sous 260 mm Hg pendant 20 minutes pour éliminer l'eau de réaction.Lime and glycol are again introduced with stirring; the medium is brought to and maintained at 145 ° C. under 260 mm Hg for 20 minutes to remove the reaction water.

On carbonate à 145°C à l'aide de C02 pendant 25 minutes sous 260 mm Hg puis 35 minutes à pression atmosphérique. De l'eau s'élimine en entrainant avec elle un peu de glycol.Carbonated at 145 ° C using C0 2 for 25 minutes under 260 mm Hg and then 35 minutes at atmospheric pressure. Water is eliminated by carrying with it a little glycol.

Le glycol est éliminé (3ème phase) et la solution de détergent-dispersant est filtrée (4ème phase) comme précédemment aux exemples 1 à 3.The glycol is removed (3rd phase) and the detergent-dispersant solution is filtered (4th phase) as previously in Examples 1 to 3.

Les quantités de réactifs mises en oeuvre et les caractéristiques des produits obtenus figurent aux tableaux V et V'.The quantities of reagents used and the characteristics of the products obtained are shown in Tables V and V '.

Taux de sédimentsSediment rate

Les % de sédiments figurant dans les tableaux ci-des-sous ont été mesurés selon la norme A.S.T.M. D 2273-67, en apportant toutefois les modifications suivantes:

  • -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. Compatibilité
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. Compatibility

Les tests de compatibilité figurant dans les tableaux ci-dessous ont été réalisés par addition de 10 % en poids de produit à tester à une huile minérale SAE 30, stockage de la solution obtenue pendant 1 mois à 20°C et étude de l'aspect de la solution en fonction du temps.The compatibility tests appearing in the tables below were carried out by adding 10% by weight of product to be tested to a SAE 30 mineral oil, storage of the solution obtained for 1 month at 20 ° C. and study of the appearance. of the solution as a function of time.

Comparaison avec les produits du commerce -Test avec l'additif seulComparison with commercial products - Test with the additive alone

Les produit de l'exemple 12 est ajouté à une huile SAE 50 à tendance paraffimique de façon à obtenir une solution contenant 125 millimoles de calcium + magnésium. La solution est stockée pendant 15 jours à 20°C; on constate que la solution reste limpide.The products of Example 12 are added to an SAE 50 oil with a paraffimic 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.

Le même test est réalisé avec un mélange:

  • -d' alkylbenzène sulfonate de magnésium de TBN 400,
  • -d'alkylbenzène sulfonate de calcium 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 of TBN 400,
  • - TBN 25 calcium alkylbenzene sulfonate,
  • - calcium alkylphenate of TBN 150. in an amount such that the solution obtained contains 125 millimoles of calcium + magnesium.

Après 15 jours de stockage à 20°C, la solution est trouble et floculeuse.After 15 days of storage at 20 ° C, the solution is cloudy and flocculent.

-Test avec l'additif en formulation-Test with the additive in formulation

On prépare un mélange (A) d'additifs contenant:

  • -2 % d'un dispersant à base de polyiso- butenyl succinimide,
  • -1,6 millimole d'un dithiophosphate de zinc,
  • - et 2, 3 % de produit de l'exemple 12. Ce mélange est porté pendant 25 jours à 80°C, puis est ajouté à une huile SAE 30 de manière à avoir une concentration de 6,6 % en poids de mélange (A).
A mixture (A) of additives is prepared containing:
  • -2% of a dispersant based on polyisobutenyl succinimide,
  • -1.6 millimole of a zinc dithiophosphate,
  • - And 2, 3% of product from Example 12. This mixture is brought for 25 days to 80 ° C., then is added to an SAE 30 oil so as to have a concentration of 6.6% by weight of mixture ( AT).

La solution est stockée pendant 5 jours à 80°C.The solution is stored for 5 days at 80 ° C.

Le même test est réalisé avec un mélange (B) constitué de:

  • - 2 % du dispersant à base de polyiso- butenyl succinimide,
  • - 1,6 millimole du dithiophosphate de zinc,
  • - et 2, 3 % d'un mélange constitué:
    • . d'alkylbenzène sulfonate de magnésium de TBN 400
    • . d'alkylbenzène sulfonate 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 12.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:
    • . magnesium alkylbenzene sulfonate from TBN 400
    • . TBN 25 calcium alkylbenzene sulfonate
    • . of calcium alkylphenate of TBN 150

having a number of millimoles of calcium + magnesium equivalent to that of the product of Example 12.

On constate que la solution contenant le mélange (A) est plus claire et plus brillante que celle contenant le mélange (B).

Figure imgb0001
Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007
 It is found that the solution containing the mixture (A) is lighter and brighter than that containing the mixture (B).
Figure imgb0001
Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007

Claims (12)

1. Process for the preparation of superalkalised metal detergents-dispersants, characterised in that:
A) a reaction medium comprising:
a sulphurised alkylphenate of calcium and/or magnesium, with a TBN of between 0 and 170, the said alkylphenate carrying one or more C6-C60 alkyl substituents;
a calcium and/or magnesium alkylbenzenesulphonate with a molecular weight of more than 300 and a TBN which is less than or equal to 150;
an alkaline earth metal compound chosen from amongst lime, magnesium oxide or hydroxide or mixtures thereof;
an alkylene glycol; and
a diluting oil,
is carbonated with carbon dioxide, at a temperature between 100 and 250°C, using the following amounts of reactants:
from 5 to 60 parts by weight of sulphurised alkylphenate per 100 parts by weight of the mixture of sulphurised alkylphenate + alkyl- benzenesuIphonate;
from 40 to 95 parts by weight of alkylbenzenesulphonate per 100 parts by weight of the mixture of sulphurised alkylphenate + alkylbenzenesulphonate;
from 3 to 30 parts by weight of alkaline earth metal compound per 100 parts by weight of the mixture of sulphurised alkylphenate + alkylbenzenesulphonate;
from 4 to 60 parts by weight of alkylene glycol per 100 parts by weight of the mixture of sulphurised alkylphenate + alkylbenzenesulphonate, the alkaline earth metal compound and the alkylene glycol being introduced in a molar ratio alkaline earth metal compound/ alkylene glycol of between 0.4 and 1.8; and
an amount of C02 between that which can be completely absorbed by the reaction medium and an excess of 30% over this amount;
B) the alkylene glycol is removed; and
C) the superalkalised metal detergent-dispersant thus obtained is separated off.
2. Process according to Claim 1, characterised in that the carbonation operation is carried out in one or more stages by introducing the amount defined in Claim 1 of alkaline earth metal compound and of alkylene glycol, in one or more stages, each introduction of alkaline earth metal compound and alkylene glycol being followed by a carbonation operation.
3. Process according to Claim 1 or Claim 2, characterised in that the carbonation operation is carried out at a temperature between 100 and 185°C, in the presence of a reaction medium comprising:
from 8 to 55 parts by weight of sulphurised alkylphenate per 100 parts by weight of the mixture of sulphurised alkylphenate + alkylbenzenesulphonate;
from 45 to 92 parts by weight of alkylbenzenesulphonate per 100 parts by weight of the mixture of sulphurised alkylphenate + alkylbenzenesulphonate;
from 4 to 25 parts by weight of alkaline earth metal compound per 100 parts by weight of the mixture of sulphurised alkylphenate + alkylbenzenesulphonate; and
from 5 to 40 parts by weight of alkylene glycol per 100 parts by weight of the mixture of sulphurised alkylphenate + alkylbenzenesulphonate,
the amount of carbon dioxide required being essentially equal to that which can be completely absorbed.
4. Process according to any one of Claims 1 to 3, characterised in that the alkylene glycol is glycol.
5. Process according to any one of Claims 1 to 4, characterised in that the alkylene glycol is present in a mixture with up to 200% by weight of a monoalcohol having a boiling point above 120°C.
6. Process according to any one of the preceding claims, characterised in that the carbonation operation is carried out in a single step in the presence of 0 to 25 parts, per 100 parts of the mixture of sulphurised alkylphenate + alkylbenzenesulphonate, of a heel with a TBN which is greater than or equal to 200, chosen from amongst:
a) superalkalised and sulphurised alkyl- phenates of calcium and/or magnesium, in which the alkyl substituent or substituents are C9-C 15 ;
b) superalkalised alkylbenzenesulphonates of calcium and/or magnesium, prepared from natural or synthetic sulphonic acids obtained by the sulphurisation of alkylbenzenes derived from olefines or from Cll-C30 olefine polymers having a molecular weight above 300; and
c) mixtures of the products a) and b).
7. Process according to Claim 6, characterised in that the carbonation operation is carried out in the presence of 0 to 15 parts of the said heel per 100 parts of the mixture of sulphurised alkylphenate + alkylbenzenesulphonate.
8. Process according to any one of Claims 1 to 7, characterised in that the carbonation operation is carried out on a mixture of the following reactants in the following amounts:
from 5 to 60 parts by weight of sulphurised calcium alkylphenate per 100 parts by weight of the mixture of sulphurised calcium alkylphenate + calcium alkylbenzenesulphonate;
from 40 to 95 parts by weight of calcium alkylbenzenesulphonate per 100 parts by weight of the mixture of calcium alkylphenate + calcium alkylbenzenesulphonate;
from 5 to 30 parts by weight of calcium hydroxide per 100 parts by weight of the mixture of sulphurised calcium alkylphenate + calcium alkylbenzenesulphonate;
from 4 to 60 parts of alkylene glycol per 100 parts of the mixture of sulphurised calcium alkylphenate + calcium alkylbenzenesulphonate; and
from 0 to 25 parts, per 100 parts of the mixture of sulphurised calcium alkylphenate + calcium alkylbenzenesulphonate, of a heel with a TBN which is greater than or equal to 250, consisting of a sulphurised and superalkalised calcium alkylphenate and/or a superalkalised calcium alkylbenzenesulphonate.
9. Process according to Claim 8, characterised in that the amounts of reactants are as follows:
8 to 55 parts by weight of sulphurised calcium alkylphenate per 100 parts by weight of the mixture of sulphurised calcium alkylphenate + calcium alkylbenzenesulphonate;
45 to 92 parts by weight of calcium alkylbenzenesulphonate per 100 parts by weight of the mixture of sulphurised calcium alkylphenate + calcium alkylbenzenesulphonate;
6 to 25 parts by weight of calcium hydroxide per 100 parts by weight of the mixture of sulphurised calcium alkylphenate + calcium alkylbenzenesulphonate;
5 to 40 parts of alkylene glycol per 100 parts of the mixture of calcium alkylphenate + calcium alkylbenzenesulphonate; and
0 to 15 parts, per 100 parts of the mixture of sulphurised calcium alkylphenate + calcium alkylbenzenesulphonate, of the said heel with a TBN which is greater than or equal to 250.
10. Process according to any one of Claims 1 to 7, characterised in that the carbonation operation is carried out on a mixture of the following reactants in the following amounts:
from 5 to 60 parts by weight of sulphurised alkylphenate of magnesium and/or calcium per 100 parts by weight of the mixture of sulphurised alkylphenate of magnesium and/or calcium + alkylbenzenesulphonate of magnesium and/ or calcium;
from 95 to 40 parts by weight of alkylbenzenesulphonate of magnesium and/or calcium per 100 parts by weight of the mixture of sulphurised alkylphenate of magnesium and/or calcium + alkylbenzenesulphonate of magnesium and/or calcium;
from 3 to 25 parts by weight of magnesium oxide per 100 parts of the mixture of sulphurised alkylphenate of magnesium and/or calcium + alkylbenzenesulphonate of magnesium and/or calcium;
from 0 to 10 parts by weight of calcium hydroxide per 100 parts of the mixture of sulphurised alkylphenate of magnesium and/or calcium + alkylbenzenesulphonate of magnesium and/or calcium;
from 4 to 60 parts of alkylene glycol per 100 parts of the mixture of sulphurised alkylphenate of magnesium and/or calcium + alkylbenzenesulphonate of magnesium and/or calcium; and
from 0 to 25 parts, per 100 parts of the mixture of sulphurised alkylphenate of magnesium and/or calcium + alkylbenzenesulphonate of magnesium and/or calcium, of a heel with a TBN which is greater than or equal to 200, consisting of a superalkalised alkylbenzenesulphonate of magnesium and/or calcium, and/or of a sulphurised and superalkalised alkylphenate of magnesium and/or calcium,
and in that, at any stage of the carbonation step or steps, the medium is treated with 0 to 10% by weight of water, relative to the weight of the said reaction medium.
11. Process according to Claim 10, characterised in that the amounts of the reactants are as follows:
from 8 to 55 parts by weight of sulphurised alkylphenate of magnesium and/or calcium per 100 parts by weight of the mixture of sulphurised alkylphenate of magnesium and/or calcium + alkylbenzenesulphonate of magnesium and/or calcium;
from 45 to 92 parts by weight of alkylbenzenesulphonate of magnesium and/or calcium per 100 parts by weight of the mixture of sulphurised alkylphenate of magnesium and/or calcium + alkylbenzenesulphonate of magnesium and/or calcium;
from 4 to 18 parts by weight of magnesium oxide per 100 parts of the mixture of sulphurised alkylphenate of magnesium and/or calcium + alkylbenzenesulphonate of magnesium and/or calcium;
from 0 to 5 parts by weight of calcium hydroxide per 100 parts of the mixture of sulphurised alkylphenate of magnesium and/or calcium + alkylbenzenesulphonate of magnesium and/or calcium;
from 8 to 40 parts of alkylene glycol per 100 parts of the mixture of sulphurised alkylphenate of magnesium and/or calcium + alkylbenzenesulphonate of magnesium and/or calcium;
from 0 to 15 parts of the said heel with a TBN which is greater than or equal to 200, per 100 parts of the mixture of sulphurised alkylphenate of magnesium and/or calcium + alkylbenzenesulphonate of magnesium and/or calcium; and
from 0 to 5% by weight of water, relative to the weight of the reaction medium.
12. Application of the products obtained in accordance with the process described in any one of Claims 1 to 11 as detergent-dispersant additives for lubricating oils.
EP79400391A 1978-06-26 1979-06-14 Process for the preparation of overbased metalliferous detergent-dispersant agents for lubricating oils and product obtained Expired EP0006796B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT79400391T ATE356T1 (en) 1978-06-26 1979-06-14 PROCESS FOR MANUFACTURE OF METAL CONTAINING OVERBASED CLEANING SOLUTIONS FOR LUBRICATION OIL AND PRODUCT MADE THEREOF.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7818947A FR2429833A1 (en) 1978-06-26 1978-06-26 PROCESS FOR THE PREPARATION OF SURALKALINATED METAL DETERGENTS-DISPERSANTS FOR LUBRICATING OILS
FR7818947 1978-06-26

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EP0006796A1 EP0006796A1 (en) 1980-01-09
EP0006796B1 true EP0006796B1 (en) 1981-11-04

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JP (1) JPS6056200B2 (en)
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CA (1) CA1124227A (en)
DE (1) DE2961227D1 (en)
ES (1) ES481865A1 (en)
FR (1) FR2429833A1 (en)
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FR2529225B1 (en) * 1982-06-24 1986-04-25 Orogil NEW HIGH ALKALINITY METAL DETERGENT-DISPERSANT ADDITIVE FOR LUBRICATING OILS
US4614602A (en) * 1985-05-01 1986-09-30 Amoco Corporation Lubricant overbased detergent-dispersants with improved solubility
US4938880A (en) * 1987-05-26 1990-07-03 Exxon Chemical Patents Inc. Process for preparing stable oleaginous compositions
US4973411A (en) * 1989-09-15 1990-11-27 Texaco Inc. Process for the preparation of sulfurized overbased phenate detergents
CN113186015B (en) * 2021-02-02 2024-02-06 安徽澳润新材料有限公司 High-base-number magnesium sulfonate detergent and preparation method thereof

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US2680096A (en) * 1951-02-12 1954-06-01 California Research Corp Process for preparing sulfurized polyvalent metal phenates
FR1080531A (en) * 1952-02-01 1954-12-09 Standard Oil Dev Co Preparation of compound products containing metal sulphonates and metal salts of aromatic sulphides
US3036971A (en) * 1958-12-24 1962-05-29 Socony Mobil Oil Co Inc Lubricating oils containing carbonated basic sulfurized calcium phenates
USB194963I5 (en) * 1962-05-15
US3178368A (en) * 1962-05-15 1965-04-13 California Research Corp Process for basic sulfurized metal phenates
US3336224A (en) * 1965-04-28 1967-08-15 Chevron Res High alkalinity overbased phenate
US3493516A (en) * 1966-05-04 1970-02-03 Chevron Res Carboxylate modified phenates
GB1429243A (en) * 1973-02-22 1976-03-24 Orobis Ltd Overbased phenates
GB1469289A (en) * 1974-07-05 1977-04-06 Exxon Research Engineering Co Detergent additives
JPS57354B2 (en) * 1974-12-20 1982-01-06
JPS5272707A (en) * 1975-12-15 1977-06-17 Karonaito Kagaku Kk Preparation of additive for perbasic lubricating oil
FR2416942A1 (en) * 1978-02-08 1979-09-07 Orogil PROCESS FOR PREPARING DETERGENT-DISPERSANTS OF HIGH ALKALINITY FOR LUBRICATING OILS

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EP0006796A1 (en) 1980-01-09
FR2429833A1 (en) 1980-01-25
FR2429833B1 (en) 1982-04-02
DE2961227D1 (en) 1982-01-14
JPS5540766A (en) 1980-03-22
BR7903980A (en) 1980-03-25
MX5734E (en) 1984-01-25
ATE356T1 (en) 1981-11-15
ZA793197B (en) 1980-06-25
US4412927A (en) 1983-11-01
CA1124227A (en) 1982-05-25
ES481865A1 (en) 1980-02-16

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