EP0003694B1 - Method for preparing highly based detergents-dispersants for lubricating oils, and product thus obtained - Google Patents

Method for preparing highly based detergents-dispersants for lubricating oils, and product thus obtained Download PDF

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Publication number
EP0003694B1
EP0003694B1 EP79400045A EP79400045A EP0003694B1 EP 0003694 B1 EP0003694 B1 EP 0003694B1 EP 79400045 A EP79400045 A EP 79400045A EP 79400045 A EP79400045 A EP 79400045A EP 0003694 B1 EP0003694 B1 EP 0003694B1
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Prior art keywords
weight
parts
alkylphenol
alkylbenzenesulphonate
mixture
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German (de)
French (fr)
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EP0003694A1 (en
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Jean-Louis Le Coent
Bernard Demoures
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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 new detergent-dispersants of high alkalinity for lubricating oils.
  • the Applicant has found a process which does not have these drawbacks and which makes it possible to prepare detergent-dispersants based on alkylbenzene sulfonates and metal alkylphenates from T.B.N. (Total Basic Number - Norm A.S.T.M. D 2896) greater than 250.
  • Alkylbenzene sulfonate denotes any solution containing from 40 to 90% by weight, preferably 55 to 80% by weight of an alkylbenzene sulfonate 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.
  • the over-alkalization-carbonation stage is preferably carried out in two stages.
  • 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 C 9 -C 15 alkyl substituents, and any particularly nonyl, decyl, dodecyl or tetradecylphenols.
  • alkylbenzene sulfonates which can be used, mention may be made of the salts of sulfonic acids obtained by sulfonation of alkylbenzenes derived from olefins or from polymers of C 15 -C 30 olefins, and from alkaline earth metals such as calcium , barium, magnesium, etc ...
  • alkaline earth bases which can be used, there may be mentioned the oxides or hydroxides of calcium, barium, magnesium; the alkaline earth metal from which the alkaline earth base is derived may or may not be the same as that from which the alkaline earth alkylbenzene sulfonate derived is used.
  • 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 alkylbenzene sulfonate) represents from 20 to 60% by weight of said product, from preferably from 25 to 55% and very particularly from 30 to 40% by weight of said product.
  • alkylene glycols which can be used, mention may very particularly be made of glycol.
  • One of the characteristics of said process is that the addition of alkylene glycol both at the sulfurization stage and at the over-alkalinization-carbonation stage is essential.
  • Another characteristic of said process is that the weight of alkylphenol used relative to the weight of solution of the detergent-dispersant obtained is between about 8 and 18%.
  • the process which is the subject of the present invention is very particularly advantageous for preparing detergent-dispersants containing a high percentage of calcium (at least 10%).
  • the present invention also relates to detergents-dispersants of high alkalinity obtained by the process described above.
  • These 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 300 for example to be added is generally between 1 and 2.5%; for a diesel engine oil, it is generally between 1.8 and 4%; for 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, paraffinic and mixed base lubricating oils, other hydrocarbon lubricants, for example lubricating oils derived from products.
  • coal, and synthetic oils for example alkylene polymers, alkylene oxide type polymers and their derivatives, including alkylene oxide polymers prepared by polymerizing alkylene oxide to presence of water or alcohols, for example ethyl alcohol, esters of dicarboxylic acids, liquid esters of liquid acids of phosphorus acids, alkylbenzenes and dialkyl benzenes, polyphenyls, alkyl biphenyl ethers , polymers of silicon.
  • lubricating oils such as naphthenic, paraffinic and mixed base lubricating oils, other hydrocarbon lubricants, for example lubricating oils derived from products.
  • coal, and synthetic oils for example alkylene polymers, alkylene oxide type poly
  • Additional additives may also be present in 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 precarbonated mixture is put under a pressure of 260 mm of mercury; a mixture of lime and glycol is introduced.
  • the medium is dehydrated for 10 minutes at 145 ° C under 260 mm of mercury, then carbonated at 145 ° C using carbon dioxide for 25 minutes under 260 mm of mercury and then 35 minutes at atmospheric pressure.
  • the operation of the 3rd stage is performed a second time.
  • the superalkalinized and carbonated medium is brought to a temperature of 184 ° C under 300 mm of mercury; glycol distills; it is filtered to remove the sediments and a solution in 100 N oil of overbased detergent-dispersant, the characteristics of which are shown in Table 1, is recovered.
  • Examples 1 to 3 are carried out under the same conditions from a 60% solution in 100 N oil of a calcium alkylbenzene sulfonate, with a molecular mass of approximately 470, solution containing 3.4% of calcium and having a TBN of approximately 45.
  • Examples 1 to 3 are carried out under the same conditions from a 60% solution in 100 N oil of a calcium alkylbenzene sulfonate with a molecular weight of approximately 470, solution containing 1.8% calcium and having a TBN no.
  • Examples 1 to 3 are carried out under the same conditions from an 80% solution in 100 N oil of a calcium alkylbenzene sulfonate, with a molecular mass of approximately 470, solution containing 3.37 % calcium and having a TBN of 33.
  • Example 1 The operation described in Example 1 is carried out by replacing the solution of calcium sulfonate with a solution of approximately 60% in 100 N oil of a magnesium alkylbenzene sulfonate (sulfonate Mg for short) of molecular weight of Approximately 470, solution containing 1.5% magnesium and having a TBN about 20, in order to obtain a detergent-dispersant containing calcium and magnesium.
  • sulfonate Mg for short magnesium alkylbenzene sulfonate
  • Example 4 The operation described in Example 4 is carried out by carrying out the sulfurization step at 165 ° C. at atmospheric pressure for 1 hour; the subsequent stage of dehydration is then superfluous.

Description

La présente invention a pour objet de nouveaux détergents-dispersants de haute alcalinité pour huiles lubrifiantes.The present invention relates to new detergent-dispersants of high alkalinity for lubricating oils.

Il est connu, d'après le brevet anglais n° 1.015.769 de préparer des détergents-dispersants de haute alcalinité par :

  • - sulfurisation d'un mélange contenant un alkylphénol, un alkylbenzène sulfonate métallique, selon un rapport molaire sulfonate/alkylphénol compris entre 0,01 et 1, de préférence entre 0,01 et 0,05, un monoalcool en C8-C18, un oxyde ou hydroxyde de métal alcalino-terreux et du glycol ;
  • - précarbonatation du mélange sulfurisé ;
  • - addition d'oxyde ou d'hydroxyde de métal alcalino-terreux ;
  • - carbonatation du mélange obtenu ;
  • - puis élimination du glycol et récupération du détergent-dispersant obtenu.
It is known from English Patent No. 1,015,769 to prepare high alkalinity detergent-dispersants by:
  • sulfurization of a mixture containing an alkylphenol, a metallic alkylbenzene sulfonate, according to a sulfonate / alkylphenol molar ratio of between 0.01 and 1, preferably between 0.01 and 0.05, a C 8 -C 18 monoalcohol, an alkaline earth metal oxide or hydroxide and glycol;
  • - precarbonation of the sulfurized mixture;
  • - addition of alkaline earth metal oxide or hydroxide;
  • - carbonation of the mixture obtained;
  • - then elimination of the glycol and recovery of the detergent-dispersant obtained.

Il a été constaté que si un tel procédé permettait de préparer d'une manière satisfaisante des détergents-dispersants contenant de forts pourcentages en poids d'alkylphénates de métaux alcalino-terreux, il ne permettait pas de préparer des détergents-dispersants contenant de forts pourcentages en poids d'alkylbenzène sulfonates de métaux alcalino-terreux. En effet, si une quantité importante d'alkylbenzène sulfonate de départ par rapport à celle d'alkylphénol était mise en oeuvre, le mélange à sulfuriser et carbonater présenterait une telle viscosité que toute opération de sulfurisation et de carbonatation serait impossible ; ce problème aurait pu éventuellement être résolu en ajoutant de grandes quantités de monoalcool en C8-C18 ce qui aurait présenté alors de graves inconvénients sur le plan industriel quant au recyclage de ce monoalcool sous forme pratiquement anhydre.It has been found that if such a method makes it possible to prepare detergent-dispersants containing high percentages by weight of alkaline earth metal alkylates in a satisfactory manner, it did not make it possible to prepare detergent-dispersants containing high percentages by weight of alkaline earth metal alkylbenzene sulfonates. In fact, if a large amount of starting alkylbenzene sulfonate relative to that of alkylphenol was used, the mixture to be sulfurized and carbonated would have such a viscosity that any operation of sulfurization and carbonation would be impossible; this problem could possibly have been resolved by adding large amounts of C 8 -C 18 monoalcohol which would then have serious drawbacks on the industrial level as regards the recycling of this monoalcohol in practically anhydrous form.

La demanderesse a trouvé un procédé ne présentant pas ces inconvénients et permettant de préparer des détergents-dispersants à base d'alkylbenzène sulfonates et d'alkylphénates métalliques de T.B.N. (Total Basic Number - Norme A.S.T.M. D 2896) supérieur à 250.The Applicant has found a process which does not have these drawbacks and which makes it possible to prepare detergent-dispersants based on alkylbenzene sulfonates and metal alkylphenates from T.B.N. (Total Basic Number - Norm A.S.T.M. D 2896) greater than 250.

Le procédé de l'invention est un procédé de préparation de détergents-dispersants métalliques, suralcalinisés, par action du soufre à une température comprise entre 100 et 190 °C sur un milieu constitué d'un alkylphénol portant un ou plusieurs substituants alkyles en Cs-Ceo, d'un alkylbenzène sulfonate de métal alcalino-terreux de masse moléculaire supérieure à 300 et de TBN inférieur ou égal à 170, d'une base alcalino-terreuse, d'un alkylèneglycol et d'une huile de dilution, précarbonatation du mélange obtenu par du C02 à une température comprise entre 100 et 250 °C, suralcalinisation par addition de base alcalino-terreuse, carbonatation du mélange précarbonaté obtenu par du C02 à une température comprise entre 100 et 250 °C, élimination de l'alkylèneglycol et récupération du détergent-dispersant suralcalinisé obtenu, ledit procédé étant caractérisé en ce que :

  • au plus 53 % et de préférence de 44 à 53 % de la quantité molaire totale de base alcalino-terreuse mise en oeuvre sont introduits à l'étape de sulfurisation ;
  • au plus 34 % et de préférence de 20 à 34 % de la quantité totale d'alkylèneglycol mise en œuvre sont introduits à l'étape de sulfurisation ;
  • les quantités de réactifs introduites à l'étape de sulfurisation correspondent :
    • - à un rapport molaire alkylbenzène sulfonate/alkylphénol compris entre 0,43 et 5,9, de préférence entre 0,55 et 2,8 et tout particulièrement entre 0,64 et 1,78 ;
    • - à un rapport molaire base alcalino-terreuse/alkylphénol compris entre 1,9 et 4 ;
    • - à un rapport molaire base alcalino-terreuse/alkylèneglycol compris entre 0,73 et 1,69 :
    • - à un rapport molaire soufre/quantité totale de base alcalino-terreuse mise en oeuvre compris entre 0,17 et 0,38 ;
  • les quantités restantes de base alcalino-terreuse et d'alkylèneglycol sont introduites à l'étape de suralcalinisation-carbonatation selon un rapport molaire base alcalino-terreuse/alkylèneglycol compris entre 0,24 et 0,82.
The process of the invention is a process for the preparation of detergents-metallic dispersants, overbased, by the action of sulfur at a temperature between 100 and 190 ° C on a medium consisting of an alkylphenol carrying one or more C s alkyl substituents -C eo , an alkaline earth metal alkylbenzene sulfonate with a molecular mass greater than 300 and a TBN less than or equal to 170, an alkaline earth base, an alkylene glycol and a dilution oil, precarbonation of the mixture obtained with C0 2 at a temperature between 100 and 250 ° C, overbasing by addition of alkaline earth base, carbonation of the precarbonated mixture obtained with C0 2 at a temperature between 100 and 250 ° C, elimination of the alkylene glycol and recovery of the overbased detergent-dispersant obtained, said process being characterized in that:
  • at most 53% and preferably from 44 to 53% of the total molar amount of alkaline earth base used are introduced in the sulfurization step;
  • at most 34% and preferably from 20 to 34% of the total amount of alkylene glycol used are introduced in the sulfurization step;
  • the quantities of reagents introduced in the sulfurization stage correspond:
    • - an alkylbenzene sulfonate / alkylphenol molar ratio of between 0.43 and 5.9, preferably between 0.55 and 2.8 and very particularly between 0.64 and 1.78;
    • - at an alkaline earth / alkylphenol base molar ratio of between 1.9 and 4;
    • - at an alkaline earth / alkylene glycol molar ratio of between 0.73 and 1.69:
    • - a molar sulfur / total amount of alkaline earth base used between 0.17 and 0.38;
  • the remaining amounts of alkaline earth base and alkylene glycol are introduced in the over-alkalinization-carbonation step according to a molar ratio of alkaline earth base / alkylene glycol of between 0.24 and 0.82.

On désigne par « alkylbenzène sulfonate toute solution contenant de 40 à 90 % en poids, de préférence 55 à 80 % 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.“Alkylbenzene sulfonate” denotes any solution containing from 40 to 90% by weight, preferably 55 to 80% by weight of an alkylbenzene sulfonate 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.

D'une manière préférentielle, on réalisera :

  • - l'étape de sulfurisation à partir d'un alkylbenzène sulfonate de T.B.N. inférieur ou égal à 50 à une température comprise entre 120 et 180 °C, à une pression inférieure ou égale à la pression atmosphérique ; cette étape peut éventuellement être suivie d'un stade de déshydratation à une température supérieure comprise entre 130 et 185 °C, de préférence entre 150 et 185 °C, à une pression inférieure ou égale à la pression atmosphérique ;
  • - l'étape de précarbonatation à pression atmosphérique, à une température comprise entre 160 et 185 °C ;
  • - l'étape de suralcalinisation-carbonatation au moins en une fois à une température comprise entre 120 et 180°C, à une pression inférieure ou égale à la pression atmosphérique.
Preferably, we will realize:
  • - The sulfurization step from an alkylbenzene sulfonate of TBN less than or equal to 50 at a temperature between 120 and 180 ° C, at a pressure less than or equal to atmospheric pressure; this step can optionally be followed by a dehydration stage at a higher temperature of between 130 and 185 ° C, preferably between 150 and 185 ° C, at a pressure less than or equal to atmospheric pressure;
  • - The precarbonation step at atmospheric pressure, at a temperature between 160 and 185 ° C;
  • - the over-alkalinization-carbonation step at least once at a temperature between 120 and 180 ° C, at a pressure less than or equal to atmospheric pressure.

L'étape de suralcalinisation-carbonatation est de préférence réalisée en deux stades.The over-alkalization-carbonation stage is preferably carried out in two stages.

Parmi les alkylphénols pouvant être mis en œuvre pour réaliser le procédé, objet de l'invention, on peut citer de préférence ceux portant un ou plusieurs substituants alkyls en C9-C15, et tout particulièrement les nonyl, décyl, dodécyl ou tétradécylphénols.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 C 9 -C 15 alkyl substituents, and any particularly nonyl, decyl, dodecyl or tetradecylphenols.

Parmi les alkylbenzène sulfonates pouvant être mis en oeuvre on peut citer les sels d'acides sulfoniques obtenus par sulfonation d'alkylbenzènes dérivant d'oléfines ou de polymères d'oléfines en C15-C30, et de métaux alcalino-terreux tels que calcium, baryum, magnésium, etc...Among the alkylbenzene sulfonates which can be used, mention may be made of the salts of sulfonic acids obtained by sulfonation of alkylbenzenes derived from olefins or from polymers of C 15 -C 30 olefins, and from alkaline earth metals such as calcium , barium, magnesium, etc ...

Parmi les bases alcalino-terreuses pouvant être mises en oeuvre, on peut citer les oxydes ou hydroxydes de calcium, baryum, magnésium ; le métal alcalino-terreux dont dérive la base alcalino- terreuse peut être ou peut ne pas être le même que celui dont dérive l'alkylbenzène sulfonate alcalino-terreux mis en oeuvre.Among the alkaline earth bases which can be used, there may be mentioned the oxides or hydroxides of calcium, barium, magnesium; the alkaline earth metal from which the alkaline earth base is derived may or may not be the same as that from which the alkaline earth alkylbenzene sulfonate derived is used.

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 également convenir. La quantité d'huile de dilution pouvant être mise en oeuvre est telle que la quantité d'huile contenue dans le produit final (y compris celle provenant de l'alkylbenzène sulfonate de départ) représente de 20 à 60 % en poids dudit produit, de préférence de 25 à 55 % et tout particulièrement de 30 à 40 % en poids dudit produit.Among the dilution oils which can be used, mention may preferably be made of 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 alkylbenzene sulfonate) represents from 20 to 60% by weight of said product, from preferably from 25 to 55% and very particularly from 30 to 40% by weight of said product.

Parmi les alkylèneglycols pouvant être mis en oeuvre, on peut citer tout particulièrement le glycol.Among the alkylene glycols which can be used, mention may very particularly be made of glycol.

Une des caractéristiques dudit procédé est que l'addition d'alkylèneglycol à la fois à l'étape de sulfurisation et à l'étape de suralcalinisation-carbonatation est essentielle.One of the characteristics of said process is that the addition of alkylene glycol both at the sulfurization stage and at the over-alkalinization-carbonation stage is essential.

Une autre caractéristique dudit procédé est que le poids d'alkylphénol mis en oeuvre par rapport au poids de solution du détergent-dispersant obtenu est compris entre environ 8 et 18 %.Another characteristic of said process is that the weight of alkylphenol used relative to the weight of solution of the detergent-dispersant obtained is between about 8 and 18%.

Le procédé faisant l'objet de la présente invention est tout particulièrement intéressant pour préparer des détergents-dispersants contenant un fort pourcentage de calcium (10 % au moins).The process which is the subject of the present invention is very particularly advantageous for preparing detergent-dispersants containing a high percentage of calcium (at least 10%).

Ainsi de tels produits peuvent être préparés à partir de :

  • - dodécylphénol comme alkylphénol
  • - de solutions de 60-80 % dans e l'huile d'un alkylbenzène sulfonate de calcium ou de magnésium de masse moléculaire 470 environ (masse du sel de sodium), comme alkylbenzène sulfonate,
  • - de chaux comme base alcalino-terreuse
  • - de glycol comme alkylèneglycol

avec les quantités suivantes de réactifs :
  • pour l'étape de sulfurisation :
    • - de 5 à 35 parties, de préférence de 10 à 30 parties en poids d'alkylphénol pour 100 parties en poids de mélange alkylphénol-alkylbenzène sulfonate,
    • - de 65 à 95 parties en poids, de préférence de 70 à 90 parties en poids d'alkylbenzène sulfonate pour 100 parties en poids de mélange alkylphénol-alkylbenzène sulfonate,
    • - de 1 à 8 parties, de préférence de 2 à 5 parties en poids de soufre pour 100 parties en poids de mélange alkylphénol-alkylbenzène sulfonate, avec un rapport molaire soufre/quantité totale de chaux mise en oeuvre compris entre 0,17 et 0,38 ;
    • - de 7 à 20 parties, de préférence de 10 à 15 parties en poids de chaux pour 100 parties en poids de mélange alkylphénol-alkylbenzène sulfonate avec un rapport poids de chaux introduit à l'étape de sulfurisation/poids total de chaux mis en oeuvre, inférieur ou égal à 0,53 ;
    • - de 7 à 20 parties, de préférence de 7 à 17 parties en poids de glycol pour 100 parties en poids de mélange alkylphénol-alkylbenzène sulfonate avec un rapport poids de glycol introduit à l'étape de sulfurisation/poids total de glycol mis en oeuvre inférieur ou égal à 0,34.
  • pour l'étape de précarbonatation :
    • , - la quantité de C02 correspond, à plus ou moins 30 %, en poids près, à celle qui peut être complètement absorbée par le mélange sulfurisé ; de préférence cette quantité de C02 correspondra sensiblement à celle pouvant être complètement absorbée ;
  • pour l'étape de suralcalinisation-carbonatation :
    • - addition de 5 à 15 parties, de préférence de 8 à 12 parties en poids de chaux pour 100 parties en poids de mélange précarbonaté,
    • - et de 5 à 50 parties, de préférence de 20 à 40 parties en poids de glycol pour 100 parties en poids de mélange précarbonaté, avec un rapport molaire chaux/glycol compris entre 0,24 et 0,82 ;
    • - la quantité de C02 peut varier entre la quantité pouvant être complètement absorbée et un excès de 40 % en poids de cette quantité ; de préférence, la quantité de C02 correspondra sensiblement à celle pouvant être absorbée.
Thus, such products can be prepared from:
  • - dodecylphenol as alkylphenol
  • solutions of 60-80% in the oil of a calcium or magnesium alkylbenzene sulfonate of molecular weight 470 approximately (mass of the sodium salt), such as alkylbenzene sulfonate,
  • - lime as an alkaline earth base
  • - glycol as alkylene glycol

with the following amounts of reagents:
  • for the sulfurization step:
    • - from 5 to 35 parts, preferably from 10 to 30 parts by weight of alkylphenol per 100 parts by weight of alkylphenol-alkylbenzene sulfonate mixture,
    • from 65 to 95 parts by weight, preferably from 70 to 90 parts by weight of alkylbenzene sulfonate per 100 parts by weight of alkylphenol-alkylbenzene sulfonate mixture,
    • - from 1 to 8 parts, preferably from 2 to 5 parts by weight of sulfur per 100 parts by weight of alkylphenol-alkylbenzene sulfonate mixture, with a molar ratio of sulfur to total amount of lime used between 0.17 and 0 , 38;
    • - from 7 to 20 parts, preferably from 10 to 15 parts by weight of lime per 100 parts by weight of alkylphenol-alkylbenzene sulfonate mixture with a weight ratio of lime introduced during the sulfurization stage / total weight of lime used , less than or equal to 0.53;
    • - from 7 to 20 parts, preferably from 7 to 17 parts by weight of glycol per 100 parts by weight of alkylphenol-alkylbenzene sulfonate mixture with a weight ratio of glycol introduced in the sulfurization stage / total weight of glycol used less than or equal to 0.34.
  • for the precarbonation stage:
    • , - the quantity of C0 2 corresponds, to more or less 30%, by weight, to that which can be completely absorbed by the sulfurized mixture; preferably this amount of C0 2 will correspond substantially to that which can be completely absorbed;
  • for the over-alkalinization-carbonation stage:
    • - addition of 5 to 15 parts, preferably 8 to 12 parts by weight of lime per 100 parts by weight of precarbonated mixture,
    • - And from 5 to 50 parts, preferably from 20 to 40 parts by weight of glycol per 100 parts by weight of precarbonated mixture, with a lime / glycol molar ratio of between 0.24 and 0.82;
    • - The amount of C0 2 can vary between the amount that can be completely absorbed and an excess of 40% by weight of this amount; preferably, the amount of C0 2 will correspond substantially to that which can be absorbed.

La présente invention a également pour objet les détergents-dispersants de haute alcalinité obtenus par le procédé décrit ci-dessus. Ceux-ci peuvent être ajoutés à des huiles lubrifiantes selon des quantités fonction du T.B.N. 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 T.B.N. 300 par exemple à ajouter est généralement comprise entre 1 et 2,5%; pour une huile pour moteur diesel, elle est généralement comprise entre 1,8 et 4% ; 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 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 300 for example to be added is generally between 1 and 2.5%; for a diesel engine oil, it is generally between 1.8 and 4%; for 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 paraffinique 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 liquides d'acides du phosphore, des alkylbenzènes et des dialkyl benzènes, des polyphényles, 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, paraffinic and mixed base lubricating oils, other hydrocarbon lubricants, for example lubricating oils derived from products. coal, and synthetic oils, for example alkylene polymers, alkylene oxide type polymers and their derivatives, including alkylene oxide polymers prepared by polymerizing alkylene oxide to presence of water or alcohols, for example ethyl alcohol, esters of dicarboxylic acids, liquid esters of liquid acids of phosphorus acids, alkylbenzenes and dialkyl benzenes, polyphenyls, alkyl biphenyl ethers , polymers of silicon.

Des additifs supplémentaires peuvent également être présents dans lesdites 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 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 (cinq phases) des détergents-dispersants suralcalinisés faisant l'objet des exemples 1 à 3, et dans le Tableau 1, les quantités de réactifs nécessaires à leur préparation.The general mode of preparation (five phases) of the overbased detergent-dispersants described in Examples 1 to 3 is given below, and in Table 1, the quantities of reagents necessary for their preparation.

1ro phase (sulfurisation) :1st phase (sulfurization):

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

  • - du dodécylphénol (DDP),
  • - de l'huile 100 N,
  • - une solution à environ 60 % dans de l'huile de dilution 100 N 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 T.B.N. de 25 environ,
  • - un antimousse 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:
  • - dodecylphenol (DDP),
  • - 100 N oil,
  • - a solution of approximately 60% in 100 N dilution oil of a calcium alkylbenzene sulfonate (sulfonate Ca for short) of molecular weight approximately 470 (mass of the sodium salt), solution containing 2.7% of calcium and having a TBN of around 25,
  • - an antifoam sold by Rhône-Poulenc under the name SI 200.

On introduit alors sous agitation de la chaux et du soufre ; on porte le milieu à 145 °C sous 260 mm de mercure, puis on ajoute du glycol en 1 heure ; on chauffe à 165 °C et on maintient cette température pendant 1 heure sous 260 mm de mercure pour éliminer complètement l'eau de réaction provenant de la neutralisation de la chaux.Then introduced with stirring lime and sulfur; the medium is brought to 145 ° C. under 260 mm of mercury, then glycol is added over 1 hour; the mixture is heated to 165 ° C. and this temperature is maintained for 1 hour under 260 mm of mercury in order to completely eliminate the reaction water originating from the neutralization of the lime.

L'eau éliminée entraîne toujours avec elle un peu de glycol.The eliminated water always carries with it a little glycol.

2e phase (précarbonatation) ; 2nd phase (précarbonatation);

Après avoir cassé le vide et chauffé à 180 °C, on réalise une opération de précarbonatation à 180 °C à l'aide de gaz carbonique à pression atmosphérique jusqu'à la fin de l'absorption de C02 (cette phase dure environ 2 heures). De l'eau s'élimine en entraînant comme ci-dessus une faible quantité de glycol. Le mélange précarbonaté ainsi obtenu est analysé ; le résultat de cette analyse figure au Tableau 1.After breaking the vacuum and heating to 180 ° C, a precarbonation operation is carried out at 180 ° C using carbon dioxide at atmospheric pressure until the absorption of C0 2 is complete (this phase lasts approximately 2 hours). Water is removed by entraining as above a small amount of glycol. The precarbonated mixture thus obtained is analyzed; the result of this analysis is shown in Table 1.

38 phase (suralcalinisation-carbonatation) :3 8 phase (over-alkalization-carbonation):

Le mélange précarbonaté est mis sous une pression de 260 mm de mercure ; on introduit un mélange de chaux et de glycol.The precarbonated mixture is put under a pressure of 260 mm of mercury; a mixture of lime and glycol is introduced.

Le milieu est déshydraté pendant 10 minutes à 145 °C sous 260 mm de mercure, puis carbonaté à 145 °C à l'aide de gaz carbonique pendant 25 minutes sous 260 mm de mercure puis 35 minutes sous pression atmosphérique.The medium is dehydrated for 10 minutes at 145 ° C under 260 mm of mercury, then carbonated at 145 ° C using carbon dioxide for 25 minutes under 260 mm of mercury and then 35 minutes at atmospheric pressure.

4" phase (suralcalinisation-carbonatation) :4 "phase (over-alkalization-carbonation):

L'opération de la 3e phase est réalisée une seconde fois.The operation of the 3rd stage is performed a second time.

5* phase (séparation) :5 * phase (separation):

On porte le milieu suralcalinisé et carbonaté à une température de 184 °C sous 300 mm de mercure ; le glycol distille ; on filtre pour éliminer les sédiments et on récupère une solution dans de l'huile 100 N de détergent-dispersant suralcalinisé dont les caractéristiques figurent au Tableau l'.The superalkalinized and carbonated medium is brought to a temperature of 184 ° C under 300 mm of mercury; glycol distills; it is filtered to remove the sediments and a solution in 100 N oil of overbased detergent-dispersant, the characteristics of which are shown in Table 1, is recovered.

Exemples 4 à 6Examples 4 to 6

Les opérations décrites aux Exemples 1 à 3, sont réalisées dans les mêmes conditions à partir d'une solution à 60 % dans de l'huile 100 N d'un alkylbenzène sulfonate de calcium, de masse moléculaire de 470 environ, solution contenant 3,4 % de calcium et présentant un T.B.N. de 45 environ.The operations described in Examples 1 to 3 are carried out under the same conditions from a 60% solution in 100 N oil of a calcium alkylbenzene sulfonate, with a molecular mass of approximately 470, solution containing 3.4% of calcium and having a TBN of approximately 45.

Les quantités de réactifs mises en œuvre figurent au Tableau II, les caractéristiques du produit obtenu figurent au Tableau II'.The quantities of reagents used are shown in Table II, the characteristics of the product obtained are shown in Table II '.

Exemples 7 à 9Examples 7 to 9

Les opérations décrites aux Exemples 1 à 3 sont réalisées dans les mêmes conditions à partir d'une solution à 60 % dans de l'huile 100 N d'un alkylbenzène sulfonate de calcium de masse moléculaire de 470 environ, solution contenant 1,8 % de calcium et présentant un T.B.N. nul.The operations described in Examples 1 to 3 are carried out under the same conditions from a 60% solution in 100 N oil of a calcium alkylbenzene sulfonate with a molecular weight of approximately 470, solution containing 1.8% calcium and having a TBN no.

Les quantités de réactifs mises en oeuvre figurent au Tableau III ; les caractéristiques du produit obtenu figurent au Tableau III'.The amounts of reagents used are shown in Table III; the characteristics of the product obtained are shown in Table III '.

Exemples 10 à 12Examples 10 to 12

Les opérations décrites aux Exemples 1 à 3 sont réalisées dans les mêmes conditions à partir d'une solution à 80 % dans de l'huile 100 N d'un alkylbenzène sulfonate de calcium, de masse moléculaire de 470 environ, solution contenant 3,37 % de calcium et présentant un T.B.N. de 33.The operations described in Examples 1 to 3 are carried out under the same conditions from an 80% solution in 100 N oil of a calcium alkylbenzene sulfonate, with a molecular mass of approximately 470, solution containing 3.37 % calcium and having a TBN of 33.

Les quantités de réactifs mises en oeuvre figurent au Tableau IV ; les caractéristiques du produit obtenu figurent au Tableau IV'.The quantities of reagents used are shown in Table IV; the characteristics of the product obtained are shown in Table IV '.

Exemple 13Example 13

L'opération décrite à l'Exemple 1 est réalisée en remplaçant la solution de sulfonate de calcium par une solution à environ 60 % dans de l'huile 100 N d'un alkylbenzène sulfonate de magnésium (sulfonate Mg en abréviation) de masse moléculaire de 470 environ, solution contenant 1,5% de magnésium et présentant un T.B.N. de 20 environ, afin d'obtenir un détergent-dispersant contenant du calcium et du magnésium.The operation described in Example 1 is carried out by replacing the solution of calcium sulfonate with a solution of approximately 60% in 100 N oil of a magnesium alkylbenzene sulfonate (sulfonate Mg for short) of molecular weight of Approximately 470, solution containing 1.5% magnesium and having a TBN about 20, in order to obtain a detergent-dispersant containing calcium and magnesium.

Les quantités de réactifs mises en oeuvre figurent au Tableau V ; les caractéristiques du produit figurent au Tableau V'.The amounts of reagents used are shown in Table V; the characteristics of the product are shown in Table V '.

Exemple 14Example 14

On réalise l'opération décrite à l'Exemple 4 en effectuant l'étape de sulfurisation à 165 °C à pression atmosphérique pendant 1 heure ; le stade subséquent de déshydratation est alors superflu.The operation described in Example 4 is carried out by carrying out the sulfurization step at 165 ° C. at atmospheric pressure for 1 hour; the subsequent stage of dehydration is then superfluous.

Les caractéristiques du produit obtenu sont semblables à celles de celui de l'Exemple 4.The characteristics of the product obtained are similar to that of Example 4.

Exemple 15Example 15

L'opération décrite à l'Exemple 1 est réalisée en réduisant :

  • - la quantité de glycol mise en œuvre à l'étape de sulfurisation à 7,5 %,
  • - et celle mise en oeuvre à l'ensemble des étapes de suralcalinisation-carbonatation à 10%,
  • - et en augmentant la quantité de C02 de 20 % en poids à l'étape de suralcalinisation-carbonatation.
The operation described in Example 1 is carried out by reducing:
  • - the amount of glycol used in the 7.5% sulfurization step,
  • - and that used in all of the 10% over-alkalinization-carbonation stages,
  • - And by increasing the amount of C0 2 by 20% by weight in the over-alkalinization-carbonation stage.

Les caractéristiques du produit obtenu figurent aux Tableaux VI et VI'.

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Figure imgb0013
Figure imgb0014
Figure imgb0015
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Figure imgb0017
Figure imgb0018
 The characteristics of the product obtained are shown in Tables VI and VI '.
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Figure imgb0018

Claims (6)

1. Process for the preparation of superalkalised metal detergents-dispersants by reaction of sulphur, at a temperature between 100 and 190 °C, with a medium consisting of an alkylphenol carrying one or more Ce-Ceo alkyl substituents, of an alkaline earth metal alkylbenzenesulphonate having a molecular weight of more than 300 and a T.B.N. which is less than or equal to 170, of an alkaline earth metal base, of an alkylene glycol and of a diluting oil, precarbonation of the resulting mixture with C02 at a temperature between 100 and 250 °C, superalkalisation by adding alkaline earth metal base, carbonation of the resulting precarbonated mixture with C02 at a temperature between 100 and 250 °C, removal of the alkylene glycol and recovery of the resulting superalkalised detergent-dispersant, the said process being characterised in that :
at most 53 % of the total molar amount of alkaline earth metal base used is introduced in the sulphurisation step ;
at most 34 % of the total amount of alkylene glycol used is introduced in the sulphurisation step ;
the amounts of reactants introduced in the sulphurisation step correspond to :
- a molar ratio alkylbenzenesulphonate/alkylphenol of between 0.43 and 5.9 ;
- a molar ratio alkaline earth metal base/alkylphenol of between 1.9 and 4 ;
- a molar ratio alkaline earth metal base/alkylene glycol of between 0.73 and 1.69 ; and
- a molar ratio sulphur/total amount of alkaline earth metal base used of between 0.17 and 0.38 ; and
the remaining amounts of alkaline earth metal base and alkylene glycol are introduced in the superalkalisation-carbonation step in a molar ratio alkaline earth metal base/alkylene glycol of between 0.24 and 0.82.
2. Process according to claim 1, characterised in that :
from 44 to 53% of the total molar amount of alkaline earth metal base is introduced in the sulphurisation step ;
from 20 to 34 % of the total amount of alkylene glycol is introduced in the sulphurisation step ; and
the molar ratio alkylbenzenesulphonate/alkylphenol in the sulphurisation setp is between 0.55 and 2.8.
3. Process according to claim 2, characterised in that the molar ratio alkylbenzenesulphonate/alkylphenol is between 0.64 and 1.78.'
4. Process according to claim 1, characterised in that :
the alkylphenol used is dodecylphenol ;
the alkylbenzenesulphonate used is a 60-80 % strength solution, in oil, of a calcium or magnesium alkylbenzenesulphonate having a molecular weight of about 470 ;
the alkaline earth metal base used is lime ;
the alkylene glycol used is glycol ;
the sulphurisation step is carried out starting with :
- 5 to 35 parts by weight of alkylphenol per 100 parts by weight of alkylphenol/alkylbenzenesulphonate mixture ;
- 95 to 65 parts by weight of alkylbenzenesulphonate per 100 parts by weight of alkylphenol/alkylbenzenesulphonate mixture ;
- 1 to 8 parts by weight of sulphur per 100 parts by weight of alkylphenol/alkylbenzenesulphonate mixture, with a molar ratio sulphur/total amount of lime used of between 0.17 and 0.38 ;
- 7 to 20 parts by weight of lime per 100 parts by weight of alkylphenol/alkylbenzenesulphonate mixture, with a ratio weight of lime introduced in the sulphurisation step/total weight of lime used which is less than or equal to 0.53 ; and
- 7 to 20 parts by weight of glycol per 100 parts by weight of alkylphenol/alkylbenzenesulphonate mixture, with a ratio weight of glycol introduced in the sulphurisation step/total weight of glycol used which is less than or equal to 0.34 ; and
the following are introduced in the superalkalisation-carbonation step :
- from 5 to 15 parts by weight of lime per 100 parts by weight of precarbonated mixture ; and
- from 5 to 50 parts by weight of glycol per 100 parts by weight of precarbonated mixture, with a molar ratio lime/glycol of between 0.24 and 0.82
5. Process according to claim 4, characterised in that :
the sulphurisation step is carried out in the presence of :
- 10 to 30 parts by weight of alkylphenol per 100 parts by weight of alkylphenol/alkylbenzenesulphonate mixture ;
- 90 to 70 parts by weight of alkylbenzenesulphonate per 100 parts by weight of alkylphenol/alkylbenzenesulphonate mixture ;
- 2 to 5 parts by weight of sulphur per 100 parts by weight of alkylphenol/alkylbenzenesulphonate mixture, with a molar ratio sulphur/total amount of lime of between 0.17 and 0.38 ;
- 10 to 15 parts by weight of lime per 100 parts by weight of alkylphenol/alkylbenzenesulphonate mixture, with a ratio weight of lime introduced in the sulphurisation step/total weight of lime used which is less than or equal to 0.53 ; and
- 7 to 17 parts by weight of glycol per 100 parts by weight of alkylphenol/alkylbenzenesulphonate mixture, with a ratio weight of glycol introduced in the sulphurisation step/total weight of glycol used which is less than or equal to 0.34 ; and
the following are added in the superalkalisationcarbonation step :
- from 8 to 12 parts by weight of lime per 100 parts by weight of precarbonated mixture ; and
- from 20 to 40 parts by weight of glycol per 100 parts by weight of precarbonated mixture, with a molar ratio lime/glycol of between 0.24 and 0.82.
6. Application of the products obtained in any one of the preceding claims as detergent-dispersant additives for lubricating oils.
EP79400045A 1978-02-08 1979-01-24 Method for preparing highly based detergents-dispersants for lubricating oils, and product thus obtained Expired EP0003694B1 (en)

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FR2429831A2 (en) * 1978-06-26 1980-01-25 Orogil NOVEL PROCESS FOR THE PREPARATION OF HIGH ALKALINITY DETERGENT DISPERSANTS FOR LUBRICATING OILS
FR2429833A1 (en) * 1978-06-26 1980-01-25 Orogil PROCESS FOR THE PREPARATION OF SURALKALINATED METAL DETERGENTS-DISPERSANTS FOR LUBRICATING OILS
FR2529226B1 (en) * 1982-06-24 1987-01-16 Orogil PROCESS FOR THE PREPARATION OF SULFURIZED ALKYLPHENATES OF ALKALINE EARTH METALS FOR USE AS ADDITIVES FOR LUBRICATING OILS
FR2529225B1 (en) * 1982-06-24 1986-04-25 Orogil NEW HIGH ALKALINITY METAL DETERGENT-DISPERSANT ADDITIVE FOR LUBRICATING OILS
FR2529224B1 (en) * 1982-06-24 1986-02-07 Orogil NEW SURALKALINIZED DETERGENT-DISPERSANT ADDITIVE FOR LUBRICATING OILS
FR2549080B1 (en) * 1983-07-11 1986-04-04 Orogil PROCESS FOR THE PREPARATION OF VERY HIGH ALKALINITY DETERGENT-DISPERSANT ADDITIVES BASED ON CALCIUM AND DETERGENT-DISPERSANT ADDITIVES FOR LUBRICATING OILS THUS OBTAINED
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US4664246A (en) * 1984-03-28 1987-05-12 Phillips Petroleum Company Apparatus for producing and recovering overbased petroleum sulfonate
FR2584414B1 (en) * 1985-07-08 1987-10-30 Orogil NEW SULFONATED AND SULFURIZED DETERGENT-DISPERSANT ADDITIVES FOR LUBRICATING OILS
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US5318710A (en) * 1993-03-12 1994-06-07 Chevron Research And Technology Company Low viscosity Group II metal overbased sulfurized C16 to C22 alkylphenate compositions
US7405185B2 (en) * 2003-09-26 2008-07-29 Chevron Oronite Company Llc Process for making Group II metal overbased sulfurized alkylphenols
US8198225B2 (en) * 2007-11-29 2012-06-12 Chevron Oronite Company Llc Sulfurized metal alkyl phenate compositions having a low alkyl phenol content
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