EP0219382B1 - Nouveaux additifs détergents-dispersants suralcalinisés stables à l'hydrolyse pour huiles lubrifiantes et leur procécé de préparation - Google Patents

Nouveaux additifs détergents-dispersants suralcalinisés stables à l'hydrolyse pour huiles lubrifiantes et leur procécé de préparation Download PDF

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Publication number
EP0219382B1
EP0219382B1 EP19860401962 EP86401962A EP0219382B1 EP 0219382 B1 EP0219382 B1 EP 0219382B1 EP 19860401962 EP19860401962 EP 19860401962 EP 86401962 A EP86401962 A EP 86401962A EP 0219382 B1 EP0219382 B1 EP 0219382B1
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EP
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Prior art keywords
alkylphenol
temperature
alkaline earth
range
earth base
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP19860401962
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German (de)
English (en)
French (fr)
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EP0219382A1 (fr
Inventor
Savino Leone
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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
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B1/00—Engines characterised by fuel-air mixture compression
    • F02B1/02—Engines characterised by fuel-air mixture compression with positive ignition
    • F02B1/04—Engines characterised by fuel-air mixture compression with positive ignition with fuel-air mixture admission into cylinder

Definitions

  • the subject of the present invention is novel over-alkalinized detergent-dispersant additives stable to hydrolysis for lubricating oils and their preparation process.
  • the object of the present invention is to improve the hydrolysis stability of additives based on superalkalinated sulfurized alkyl phenates, derivatives of alkyl phenols carrying one or more C 8 -C 30 , preferably C, alkyl substituents. 12 -C 30 , to prevent clogging of the filters and to prevent loss of TBN (Total Basic Number - Standard ASTM D 2896) in the presence of sulfuric acid.
  • C 8 -C 30 preferably C, alkyl substituents. 12 -C 30
  • alkaline earth bases which can be used to carry out the various stages of preparation of the additives which are the subject of the invention, there may be mentioned the oxides or hydroxides of calcium, barium or strontium and very particularly those of calcium.
  • водородн ⁇ е ⁇ о ⁇ ани ⁇ ⁇ олов ⁇ ⁇ ент ⁇
  • methanol and glycol are the preferred “vector” alcohols.
  • third solvents which can be used, mention may be made of xylene, toluene, cyclohexane, ethyl-2-hexanol, oxo alcohols, decyl alcohol, tridecyl alcohol, 2-butoxyethanol, 2-butoxypropanol, propylene glycol methyl ether;
  • carrier glycol / 2-ethylhexanol, glycol / cyclohexane, glycol / xylene, methanol / xylene.
  • the 1st stage that is to say that of neutralization of the alkylphenol, is favorably carried out at a pressure close to atmospheric pressure, at a temperature at least equal to that of formation of the water-third-party azeotrope ; when the chosen third solvent is 2-ethyl hexanol, a tem temperature of the order of 160-170 ° C is preferred; when the latter is cyclohexane, a temperature of 70-80 ° C is well suited; generally the neutralization step is carried out at a temperature of the order of 50 to 200 ° C; the operation takes approximately 2 to 5 hours.
  • the quantity of third solvent used in this stage corresponds to that necessary to obtain a fluid medium, that is to say of viscosity less than approximately 30 cSt under the reaction conditions.
  • a particularly favorable variant for carrying out the neutralization step consists in carrying out this operation in the presence of a catalyst;
  • this catalyst can be halide ions, in particular chlorides introduced via ammonium chloride, calcium chloride, zinc chloride, COOH ions originating from carboxylic acids such as formic, acetic, glycolic acid, or NH 2 functions originating from amines such as polyethylene amines, tris (3-oxa-6-amino-6 hexyl) amine; the amounts of catalyst used can range up to 0.1 mole of halide ion, of COOH ion or of NH 2 function per mole of alkylphenol.
  • the second step that of total elimination of the “vector” alcohol and of the water-third-party azeotrope, can be carried out if necessary in the presence of a dilution oil; this step can be omitted if the vector alcohol / alkylphenol ratio is sufficiently low, for example between 0.05 and 0.15.
  • paraffinic oils such as 100 Neutral oil
  • naphthenic or mixed oils may also be suitable.
  • the third stage that of carboxylation, is most particularly carried out under a pressure of the order of 5 to 15 bar; this operation lasts at least 3 hours and generally from 5 to 15 hours. It is noted that the transformation of the phenate into salicylate is not complete; the conditions used make it possible to achieve a transformation rate of the order of 5 to 25%.
  • One way of increasing this conversion rate consists in carrying out several carboxylation steps, each carboxylation step being preceded by a neutralization step carried out under conditions similar to those of the 1 st step described above and a step of distillation similar to that of the 2 nd step developed above. This can result in a conversion rate of phenate to salicylate of up to 45%; it has been found that it is not necessary to exceed this rate to prepare additives having the desired improvements.
  • the 4th stage that of sulfurization-over-alkalization, is preferably carried out at a temperature of the order of 140 to 160 ° C for 3 to 6 hours approximately; like the neutralization step, it can be, if desired, carried out in the presence of a catalyst such as halide ions, COOH or amine functions in an amount which can range up to 0.1 mole of halide ion, COOH or of amine function per mole of starting alkylphenol.
  • a catalyst such as halide ions, COOH or amine functions in an amount which can range up to 0.1 mole of halide ion, COOH or of amine function per mole of starting alkylphenol.
  • total alkaline earth base means the total amount of alkaline earth base (s) used to carry out all of the steps; “alkaline earth base of overbasing” is understood to mean that intervening in the sulfurization-overbasing stage.
  • the sulfurization is preferably carried out in the presence of potassium hydroxide or soda as catalyst; this operation generally lasts from 3 to 6 hours; the quantity of third solvent used corresponds to that necessary to obtain a fluid medium, that is to say of viscosity less than approximately 30 cSt under the reaction conditions.
  • the carbonation proper is favorably carried out at a temperature of 145-180 ° C under a pressure of 930 102 to 1010. 102 Pa approximately.
  • the carbonated product can optionally be hydrolyzed by a water-third solvent mixture at a temperature of the order of 90-110 ° C in order to obtain a fluid medium, that is to say with a viscosity of less than 30 cSt.
  • dilution oil is introduced in an amount such that the amount of oil contained in the final product represents from 25 to 65% by weight of said product and preferably from 30 to 50% by weight of said product.
  • the additives which are the subject of the invention have a high basicity; the TBN of additives based on calcium salts, for example, easily reaches 250 to 300.
  • the amount of additive to be used to improve the detergent-dispersant properties of lubricating oils is a function of the future use of said oils.
  • the amount of additive to be added is generally between 1 and 3% by weight; for a diesel engine oil, it is generally between 1.5 and 5% by weight, for a marine engine oil, it is generally between 10 and 30%.
  • 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, polymers of the alkylene oxide type 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 phosphorus acids, alkylbenzenes and dialkylbenzenes, polyphenyls, alkylbiphenyl ethers, polymers of silicon .
  • Additional additives may also be present in said lubricating oils alongside the detergent-dispersants obtained according to the process of the invention; mention may, for example, be made of antioxidant, anticorrosive additives, ashless dispersant additives.
  • the medium is brought to 80 ° C. and then a mixture of 225 g of glycol and 430 g of 2-ethylhexanol is introduced over 2 hours.
  • the reaction medium is heated at the bottom to 145 ° C; distillation of the water-2-ethyl-hexanol azeotrope starts approximately 30 min after the start of the addition of the glycol-2-ethyl hexanol mixture and continues for approximately 2 hours.
  • the reaction is allowed to proceed for 4 hours to completely dehydrate the medium.
  • distillate D 1 225 g of distillate D 1 are recovered, containing 76% by weight of water.
  • the bottom temperature reaches 195 ° C.
  • the product obtained is cooled to approximately 150 ° C., then 760 g of 100 Neutral oil are added.
  • the amount of 2 CO 2 introduced is 230 g.
  • the mixture is degassed with stirring, the temperature gradually decreasing.
  • the reactor is purged with nitrogen at the end of degassing, then the product is drawn off at around 100 ° C.
  • the loaded device is placed under slight vacuum (960 10 2 Pa) and the heating is increased.
  • the temperature is then left for 1 hour at 155 ° C; it is gradually brought to 165 ° C. while 350 g of 2-ethylhexanol are introduced to thin the mixture.
  • the temperature is maintained for 1 hour at 165 ° C.
  • the contents of the flask are then carbonated by bubbling CO 2 (65 l / hour) for 1 hour at 165 ° C.
  • the mixture is then brought to 195 ° C. under 960.10 2 Pa; part of the 2-ethyl hexanol distills.
  • Example 1 All the operations described in Example 1 are repeated, the only modification consisting in replacing the 390 g of lime with 293 g of CaO, the sulfurization-over-alkalinization operation being carried out with lime.
  • the carboxylation operation is carried out under the same conditions as in Example 1, the only modification consisting in carboxylating for 10 hours instead of 5 hours.
  • the loaded device is placed under slight vacuum (960 ⁇ 10 2 Pa). Heating is increased. At 155 ° C. 200 g of glycol are added over 30 minutes while the temperature continues to rise. The mixture becomes more viscous and after 1 hour at 155 ° C. the temperature is gradually brought to 165 ° C. and 350 g of 2-ethylhexanol are introduced.
  • the mixture is then carbonated at 165 "C for 75 minutes and 68 g of CO 2 are fixed.
  • the reaction medium is heated to 95 ° C. at the bottom until the start of the water / cyclohexane distillation.
  • the carboxylation step is identical to that of Example 1.
  • the sulfurization-over-alkalinization step is identical to that of Example 1, the solvent used being the same, namely 2-ethyl hexanol.
  • the xylene and the glycol are removed by distillation at 195 ° C. under 2666 Pa.
  • the carboxylation step is identical to that of Example 1.
  • the sulfurization-over-alkalinization step is identical to that of Example 1, the solvent used being the same, namely 2-ethyl hexanol.
  • the characteristics of the product obtained are shown in Table IVa.
  • This step is carried out as in Example 1, from 1600 g of solution obtained.
  • the neutralization step is carried out under the conditions of Example 6.
  • the amount of CO 2 introduced is 100 g.
  • the sulfurization-over-alkalization step is identical to that of Example 1.
  • the neutralization step is carried out under the conditions of Example 6.
  • the amount of CO 2 introduced is 140 g.
  • the sulfurization-over-alkalization step is identical to that of Example 1.
  • the neutralization step is carried out under the conditions of Example 8 (use of CaO).
  • the amount of CO 2 introduced is 235 g.
  • the sulfurization-over-alkalization step is identical to that of Example 1.
  • the solvents are then distilled (150 ° C. at the bottom under 107.10 2 Pa).
  • the distillate represents 165 g.
  • the reaction medium is cooled to 150 ° C. and 150 g of xylene are added.
  • the solvents are then distilled (248 g).
  • the reaction medium is cooled and 150 g of xylene are added.
  • This step is carried out under the conditions described in Example 3 from 530 g of solution.
  • the neutralization step is carried out under conditions identical to those of Example 1.
  • the carboxylation step is carried out under conditions identical to those of Example 1.
  • the loaded device is placed under slight vacuum (960 102 Pa) and the heating is increased.
  • the temperature is then left for 1 hour at 155 ° C; it is gradually brought to 165 ° C. while 350 g of 2-ethylhexanol are introduced to thin the mixture.
  • the temperature is maintained for 1 hour at 165 ° C. and the distillate is recovered.
  • the carbonation is carried out under conditions identical to those of Example 1.
  • the neutralization step is carried out under the conditions described in Example 6, the only modification consisting in introducing 56 g of ammonium chloride at the same time as the 390 g of lime.
  • the charged device is placed under a slight vacuum (960'10 2 Pa) and the heating is increased.
  • the temperature is regulated at 155 ° C.
  • the mixture becomes more viscous and after 1 hour at 155 ° C, the temperature is gradually brought to 165 ° C while 350 g additional 2-ethylhexanol are introduced in order to refluidify the mixture.
  • the temperature is maintained for 30 minutes at 165 ° C.
  • the neutralization step is carried out under conditions identical to those of Example 18.
  • the carboxylation step is carried out under conditions identical to those of Example 1.
  • the charged device is placed under slight vacuum (960 ⁇ 10 2 Pa) and the heating is increased. When the temperature reaches 150 ° C., 170 g of ethylene glycol are added over 30 minutes.
  • the mixture becomes more viscous and after 1 hour at 155 ° C, the temperature is gradually brought to 165 ° C while 400 g of 2-ethylhexanol are introduced to refluidify the mixture.
  • the temperature is maintained for 1 hour at 165 ° C. After 2 hours of sulfurization, 195 g of solvent are distilled, including 75 g of water; 28 g of H 2 S are trapped.
  • the neutralization step is carried out under conditions identical to those of Example 1.
  • the carboxylation step is carried out under conditions identical to those of Example 1.
  • the charged device is placed under slight vacuum (960 ⁇ 10 2 Pa) and the heating is increased.
  • the temperature reaches 130 ° C, 200 g of ethylene glycol are added over 20 minutes while the temperature continues to rise.
  • the mixture becomes more viscous and after 1 hour 30 at 155 ° C the temperature is gradually brought to 165 ° C while 350 g of additional 2-ethylhexanol are introduced to refluidify the mixture.
  • the temperature is maintained for 1 hour 30 minutes at 165 ° C. After 3 hours of sulfurization, 215 g of distillate containing 95 g of water are recovered. 55 g of H 2 S are fixed in the traps.
  • the carbonation is carried out under conditions identical to those of Example 1.
  • the neutralization step is identical to that of Example 6.
  • the carboxylation step is identical to that of Example 1.
  • the loaded device is placed under slight vacuum (960. 10 2 Pa) and the heating is increased. When the temperature reaches 150 ° C., 250 g of ethylene glycol are added over 30 minutes.
  • the temperature is regulated at 155 ° C.
  • the mixture becomes more viscous and after 1 hour at 155 ° C the temperature is gradually brought to 165 ° C while 350 g of additional 2-ethylhexanol are introduced to refluidify the mixture.
  • the contents of the flask are then carbonated by bubbling CO 2 (65 l / h), the temperature being maintained at 165 ° C., 92 g of CO2 are fixed with a yield of 68%.
  • the solvents are partially distilled (460 g of distilled 2-ethylhexanol).
  • the flask is cooled to below 100 ° C. and 75 g of water are added with vigorous stirring at the same time as 2-ethyl hexanol.
  • the temperature is gradually raised to 130 ° C., then 118 g of sulfur are poured in 20 minutes.
  • the temperature is then left for 1 hour at 155 ° C; it is gradually brought to 165 ° C. while 350 g of 2-ethylhexanol are introduced to thin the mixture.
  • the temperature is maintained for 1 hour at 165 ° C.
  • the contents of the flask are then carbonated by bubbling CO 2 (65 I / hour) for 1 hour at 165 ° C.
  • the mixture is then brought to 195 ° C under 960 ⁇ 10 2 Pa; part of the 2-ethyl hexanol distills.
  • the distillation is almost complete when the temperature reaches 195-200 ° C under 27-10-40 ⁇ 102 Pa.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP19860401962 1985-09-17 1986-09-08 Nouveaux additifs détergents-dispersants suralcalinisés stables à l'hydrolyse pour huiles lubrifiantes et leur procécé de préparation Expired EP0219382B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8513731 1985-09-17
FR8513731A FR2587353B1 (fr) 1985-09-17 1985-09-17 Nouveaux additifs detergents-dispersants suralcalinises stables a l'hydrolyse pour huiles lubrifiantes et leur procede de preparation

Publications (2)

Publication Number Publication Date
EP0219382A1 EP0219382A1 (fr) 1987-04-22
EP0219382B1 true EP0219382B1 (fr) 1989-03-22

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Application Number Title Priority Date Filing Date
EP19860401962 Expired EP0219382B1 (fr) 1985-09-17 1986-09-08 Nouveaux additifs détergents-dispersants suralcalinisés stables à l'hydrolyse pour huiles lubrifiantes et leur procécé de préparation

Country Status (7)

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EP (1) EP0219382B1 (es)
JP (1) JPH0751712B2 (es)
BR (1) BR8604401A (es)
CA (1) CA1287830C (es)
DE (1) DE3662532D1 (es)
FR (1) FR2587353B1 (es)
MX (1) MX168383B (es)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NZ221128A (en) * 1986-08-08 1989-09-27 Chevron Res Overbased sulphurised alkylphenols as lube oil additives
JPH0676589B2 (ja) * 1987-07-24 1994-09-28 コスモ石油株式会社 ヒドロキシアルキル安息香酸およびアルキルフェノ−ルのアルカリ土類金属塩硫化混合物の製造法
FR2625219B1 (fr) * 1987-12-23 1990-12-21 Orogil Additifs detergents-dispersants a base de sels de metaux alcalino-terreux et alcalins pour huiles lubrifiantes
FR2625220B1 (fr) * 1987-12-23 1990-12-21 Orogil Procede de preparation d'additifs detergents-dispersants suralcalinises pour huiles lubrifiantes
TW278098B (es) * 1992-09-18 1996-06-11 Cosmo Sogo Kenkyusho Kk

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1094609A (en) * 1965-08-23 1967-12-13 Lubrizol Corp Oil soluble basic alkaline earth metal salts of phenol sulfides
NL134001C (es) * 1965-10-29
FR2529226B1 (fr) * 1982-06-24 1987-01-16 Orogil Procede de preparation d'alkylphenates sulfurises de metaux alcalino-terreux utilisables comme additifs pour huiles lubrifiantes

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Publication number Publication date
MX168383B (es) 1993-05-19
CA1287830C (fr) 1991-08-20
EP0219382A1 (fr) 1987-04-22
FR2587353A1 (fr) 1987-03-20
DE3662532D1 (en) 1989-04-27
JPH0751712B2 (ja) 1995-06-05
JPS6272791A (ja) 1987-04-03
BR8604401A (pt) 1987-05-12
FR2587353B1 (fr) 1987-11-20

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