EP0006796B1 - Procédé de préparation de détergents-dispersants métalliques suralcalinisés pour huiles lubrifiantes et produits obtenus - Google Patents

Procédé de préparation de détergents-dispersants métalliques suralcalinisés pour huiles lubrifiantes et produits obtenus 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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EP
European Patent Office
Prior art keywords
calcium
parts
weight
alkylphenate
sulphurised
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
EP79400391A
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German (de)
English (en)
French (fr)
Other versions
EP0006796A1 (fr
Inventor
Bernard Demoures
Jean-Louis Le Coent
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Orogil SA
Original Assignee
Orogil SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Orogil SA filed Critical Orogil SA
Priority to AT79400391T priority Critical patent/ATE356T1/de
Publication of EP0006796A1 publication Critical patent/EP0006796A1/fr
Application granted granted Critical
Publication of EP0006796B1 publication Critical patent/EP0006796B1/fr
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12Reaction products
    • C10M159/20Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/24Reaction 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
EP79400391A 1978-06-26 1979-06-14 Procédé de préparation de détergents-dispersants métalliques suralcalinisés pour huiles lubrifiantes et produits obtenus Expired EP0006796B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT79400391T ATE356T1 (de) 1978-06-26 1979-06-14 Verfahren zur herstellung von metall enthaltenden ueberalkalisierten reinigungsmittelloesungen fuer schmieroel und daraus hergestelltes produkt.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7818947A FR2429833A1 (fr) 1978-06-26 1978-06-26 Procede de preparation de detergents-dispersants metalliques suralcalinises pour huiles lubrifiantes
FR7818947 1978-06-26

Publications (2)

Publication Number Publication Date
EP0006796A1 EP0006796A1 (fr) 1980-01-09
EP0006796B1 true EP0006796B1 (fr) 1981-11-04

Family

ID=9209960

Family Applications (1)

Application Number Title Priority Date Filing Date
EP79400391A Expired EP0006796B1 (fr) 1978-06-26 1979-06-14 Procédé de préparation de détergents-dispersants métalliques suralcalinisés pour huiles lubrifiantes et produits obtenus

Country Status (11)

Country Link
US (1) US4412927A (enrdf_load_stackoverflow)
EP (1) EP0006796B1 (enrdf_load_stackoverflow)
JP (1) JPS6056200B2 (enrdf_load_stackoverflow)
AT (1) ATE356T1 (enrdf_load_stackoverflow)
BR (1) BR7903980A (enrdf_load_stackoverflow)
CA (1) CA1124227A (enrdf_load_stackoverflow)
DE (1) DE2961227D1 (enrdf_load_stackoverflow)
ES (1) ES481865A1 (enrdf_load_stackoverflow)
FR (1) FR2429833A1 (enrdf_load_stackoverflow)
MX (1) MX5734E (enrdf_load_stackoverflow)
ZA (1) ZA793197B (enrdf_load_stackoverflow)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2529225B1 (fr) * 1982-06-24 1986-04-25 Orogil Nouvel additif detergent-dispersant metallique de haute alcalinite pour huiles lubrifiantes
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 (zh) * 2021-02-02 2024-02-06 安徽澳润新材料有限公司 一种高碱值磺酸镁清净剂及其制备方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2680096A (en) * 1951-02-12 1954-06-01 California Research Corp Process for preparing sulfurized polyvalent metal phenates
FR1080531A (fr) * 1952-02-01 1954-12-09 Standard Oil Dev Co Préparation de produits composés contenant des sulfonates métalliques et des selsmétalliques de sulfures aromatiques
US3036971A (en) * 1958-12-24 1962-05-29 Socony Mobil Oil Co Inc Lubricating oils containing carbonated basic sulfurized calcium phenates
US3178368A (en) * 1962-05-15 1965-04-13 California Research Corp Process for basic sulfurized metal phenates
USB194963I5 (enrdf_load_stackoverflow) * 1962-05-15
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 (enrdf_load_stackoverflow) * 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 (fr) * 1978-02-08 1979-09-07 Orogil Procede de preparation de detergents-dispersants de haute alcalinite pour huiles lubrifiantes

Also Published As

Publication number Publication date
ZA793197B (en) 1980-06-25
MX5734E (es) 1984-01-25
FR2429833B1 (enrdf_load_stackoverflow) 1982-04-02
FR2429833A1 (fr) 1980-01-25
BR7903980A (pt) 1980-03-25
ATE356T1 (de) 1981-11-15
CA1124227A (fr) 1982-05-25
EP0006796A1 (fr) 1980-01-09
US4412927A (en) 1983-11-01
DE2961227D1 (en) 1982-01-14
ES481865A1 (es) 1980-02-16
JPS5540766A (en) 1980-03-22
JPS6056200B2 (ja) 1985-12-09

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