EP2931851A1 - Procédé de production d'un détergent métallique surbasique - Google Patents

Procédé de production d'un détergent métallique surbasique

Info

Publication number
EP2931851A1
EP2931851A1 EP13808399.3A EP13808399A EP2931851A1 EP 2931851 A1 EP2931851 A1 EP 2931851A1 EP 13808399 A EP13808399 A EP 13808399A EP 2931851 A1 EP2931851 A1 EP 2931851A1
Authority
EP
European Patent Office
Prior art keywords
metal
overbased
acid
detergent
carboxylic acid
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.)
Withdrawn
Application number
EP13808399.3A
Other languages
German (de)
English (en)
Inventor
Stephen J. Cook
Christopher L. Friend
Gary M. Walker
Brent R. Dohner
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.)
Lubrizol Corp
Original Assignee
Lubrizol Corp
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 Lubrizol Corp filed Critical Lubrizol Corp
Publication of EP2931851A1 publication Critical patent/EP2931851A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
    • C10M135/10—Sulfonic acids or derivatives thereof
    • 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
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/069—Linear chain compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/52—Base number [TBN]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • the present invention relates to a process for producing an overbased metal detergent.
  • the present invention relates to a process for preparing an overbased metal sulfonate having a high total base number (TBN).
  • the present invention further relates to a process for producing a high TBN metal sulfonate detergent for use in lubricants.
  • Lubricants that include detergents are useful in lubrication applications and particularly in engine oils.
  • Engine oils are used in many engines including 2-stroke or 4-stroke engines.
  • Overbased compounds can be used as detergents, particularly in lubricants and can be utilized to neutralise such acids.
  • Overbased detergents are generally oil-soluble particles comprising a metal salt core and a surfactant outer-shell.
  • WO/PCT application 2005/042677A1 discloses a process for preparing an overbased detergent.
  • the process comprises a nine step process including the steps of; (1) providing a metal salt selected from the group consisting of a hydrocarbyl-substituted organic acid, a hydrocarbyl-substituted phenyl, a phenate, a hydrocarbyl-substituted carboxylate and mixtures thereof; (2) further providing methanol and a mixture of alcohols containing two to about seven carbon atoms, wherein the mole ratio of methanol to the mixture of alcohols is about 2.2 or less, to form a mixture; (3) further providing a basic metal compound; (4) reacting the mixture of steps (3) with carbon dioxide to form a carbonated overbased metal sulfonate; (5) performing steps (3) and (4) at least three additional times upon the product of step (4); (6) thereafter removing at least a portion of the water
  • the oil medium is present in an amount such that the weight ratio of acid corresponding to the metal salt of (1) to the oil medium is 0.3 to 1.4; and wherein step (6) is required when the hydrocarbyl substituted organic acid is a hydrocarbyl substituted sulfonic acid.
  • United States patent 6,444,625 discloses a high viscosity overbased sulfonate detergent and also marine cylinder oils containing high viscosity overbased sulfonate detergents. It is disclosed that the overbased calcium sulfonate detergent comprises a TBN of 400 or more and having a viscosity of at least 180mm per second at 100°C.
  • a process for preparing high viscosity overbased calcium sulfonate is also disclosed in US 6,444,625 comprising the steps of; (1) providing a sulfonic acid to the reactor; (2) adding a lime reactant to the reactor for neutralisation and over-basing; (3) adding a aliphatic Ci to C 4 alcohol and a hydrocarbon solvent, to form a process mixture in the reactor, carbonating the process mixture by injecting carbon dioxide into the reactor, adding an oil to the process mixture to form a product mixture, clarifying the product mixture by removing any solids, removing water and any remaining hydrocarbons from the product mixture after clarification, and isolating an overbased calcium sulfonate having a high TBN of at least 400, wherein, during carbonation the exotherm of the reaction is maintained at a temperature between 27°C and 57°C.
  • United States patent 5,384,053 discloses a process for the production of a lubricating oil additive.
  • This document discloses a process carried out with a starting overbased compound and reacting the overbased compound at elevated temperatures in the presence of a glycol.
  • the process disclosed in this document utilizes a carboxylic acid during post-treatment of the highly overbased products.
  • the process does not disclose a process of producing a highly overbased compound from a non-overbased starting compound.
  • the use of glycol in the process necessitates the need for the process to be carried out at elevated temperatures as the step of alcohol stripping of the glycol must be done at high temperatures to be effective.
  • a problem with the above processes is that there is a low uptake of metal salt to form the resultant overbased sulfonate detergent product which results in a slow filtration rate of the product due to a build-up of solid which blocks the filtration pathway.
  • the disclosed technology provides a lubricant composition which exhibits improved frictional performance (i.e. lower friction), improved anti-wear
  • step (4) reacting the mixture of step (4) with carbon dioxide to form a carbonated overbased metal sulfonate
  • steps (1) through (5) are performed sequentially, i.e., (1) followed by (or mixed or reacted with) (2) followed by (or mixed or reacted with) (3) followed by (or mixed or reacted with) (4), and thereafter reacted as in step (5).
  • steps (1) through (4) may be performed in other orders or simultaneously.
  • the process defined by the invention is not an emulsion.
  • the product of the process in one embodiment is not an emulsion.
  • emulsion it is meant to be a colloidal suspension of one immiscible liquid in another e.g., a water-in-oil, or oil-in-water emulsion.
  • the process may comprise an additional step (6) where steps (3), (4) and (5) are performed at least two additional times.
  • the product of either step (5) or step (6) may be heated to at least 150°C in an additional step (7).
  • the product of step (7) may be cooled in a further step (8).
  • the carboxylic acid may consist of 6 to 24 carbon atoms.
  • the carboxylic acid may be saturated and/or unsaturated.
  • the carboxylic acid may be provided at 1 to 20 wt %.
  • the carboxylic acid may be provided at 2 to 20 wt %.
  • the carboxylic acid may be added at 4 to 8 wt % and may be about 7 wt %.
  • the carboxylic acid may be stearic acid.
  • the at least one mono-alcohol may comprise 2 to 10 carbon atoms. Alternatively, at least one mono-alcohol may comprise 2 to 7, 2 to 6, 2 to 5 or 3 to 5 carbon atoms. The at least one mono-alcohol may comprise branched or linear alkyl chains or mixtures thereof.
  • the at least one mono-alcohol may be one or a combination of the following: ethanol, propan-l-ol, propan-2-ol, isopropanol, butan-l-ol, butan-2-ol, isobutanol, pentan-1- ol, pentan-2-ol, penta-3-ol, isopentanol, hexan-l-ol, hexan-3-ol, heptan-l-ol, heptan-2-ol, heptan-3-ol, heptan-4-ol or mixtures thereof.
  • the at least one mono-alcohol may contain at least one butanol and at least one amyl alcohol
  • Methanol may be provided at step (2).
  • the mole ratio of methanol to at least one mono-alcohol may be below 2.2: 1.
  • the mole ratio of methanol to the at least one mono-alcohol may be 1.70: 1, 0.9: 1 to 1.60: 1, 1 : 1 to 1.50: 1, 1 : 1 to 1 : 1.45 or 1.1 : 1 to 1.40: 1.
  • the basic metal compound may be an alkali metal or alkaline earth metal oxide, hydroxide, mixtures thereof, or reactive equivalents.
  • the basic metal compound is calcium oxide, calcium hydroxide, or mixtures thereof.
  • the basic metal compound may be sodium hydroxide.
  • the basic metal compound may be magnesium oxide and/or magnesium hydroxide.
  • Any residual solids and any residual water and alcohols may be substantially or completely removed from the product.
  • step (3) Between 10 and 20 wt % of the total amount of the basic metal compound may be added at each occurrence of step (3).
  • An oil medium may be present.
  • the oil medium may be substantially free of hydrocarbon solvent other than oil of lubricating viscosity.
  • Suitable oils may have a kinematic viscosity at 100°C of 3 cSt (or mm 2 /s) to 20 cSt (or mm 2 /s).
  • the organic acid of step (1) may be a hydrocarbyl-substituted sulfonic acid and may be represented by the formula:
  • each R 1 is independently a hydrocarbyl group having between 6 and 40 carbon atoms;
  • A is a cyclic or acyclic hydrocarbon group; and
  • k is 1 - 5.
  • the total base number (TBN) of the overbased metal salt of the hydrocarbyl- substituted sulfonic acid may be at least 400.
  • the total base number of the metal salt of the hydrocarbyl-substituted sulfonic acid may be between 450 to 550, or 450 to 500.
  • the metal ratio of the metal salt of the hydrocarbyl-substituted sulfonic acid may be at least 20.
  • a method for lubricating an internal combustion engine comprising supplying thereto a lubricant composition comprising the detergent prepared by the process of:
  • a metal salt selected from a group consisting of a hydrocarbyl- substituted organic acid or a mixture of hydrocarbyl-substituted organic acids
  • step (4) reacting the mixture of step (4) with carbon dioxide to form a carbonated overbased metal sulfonate; wherein the resultant overbased metal detergent has a metal equivalent to sulfonic acid substrate ratio of 5: 1 to 27: 1, and preferably 7: 1 to 20: 1 (or 5 to 27, or 7 to 20).
  • the present invention provides a process for preparing an overbased metal detergent in an oil medium.
  • TBN Total Base Number
  • the overbased metal salt of a hydrocarbyl-substituted organic acid is generally formed by causing a reaction between an overbased neutral salt with a metal basic compound forming an overbased metal salt having a high Total Base Number.
  • the process of the present invention is to provide an overbased metal detergent, i.e. one that does not form part of a two phase system of matter or colloid.
  • the process of the present invention may be carried out in the presence of hydrocarbon solvent in addition to the oil of lubricating viscosity.
  • the process may be free of hydrocarbon solvent other that the oil of lubricating viscosity.
  • hydrocarbon solvents can include aliphatic hydrocarbons or aromatic hydrocarbons.
  • suitable aliphatic hydrocarbons include iso-butyl, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane and mixtures thereof.
  • aromatic hydrocarbons include xylene, toluene and mixtures thereof.
  • the metal basic compound is used to supply excess basicity to the overbased material.
  • the metal basic compound can be a hydroxide or oxide of the metal.
  • the metal can be monovalent, divalent, or trivalent.
  • the metal ion M can be an alkali metal, preferably lithium, sodium, or potassium. When potassium is used, it can be used in combination with other metals.
  • the metal ion M can be an alkaline earth metal, preferably magnesium, calcium, barium or mixtures thereof and most preferably calcium which can be used alone or in combination with other metals.
  • trivalent the metal ion M can be aluminium, which can be used alone or in combination with other metals.
  • metal basic compounds 3 with hydroxide functionality include lithium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide and aluminium hydroxide.
  • Suitable elements of metal basic compounds with oxide functionality include lithium oxide, magnesium oxide, calcium oxide and barium oxide.
  • the oxides and/or hydroxides can be used alone or in combination.
  • the oxides or hydroxides can be hydrated or dehydrated, although hydrated is preferred.
  • the metal basic compound is calcium hydroxide, which can be used alone or as mixtures thereof with other metal basic compounds. Calcium hydroxide is often referred to as lime.
  • the metal basic compound 3 is calcium oxide which can be used alone or as mixtures thereof with other metal basic compounds.
  • the overbased metal salt can be formed from the hydrocarbyl-substituted organic sulfonic acid and have metal ratios not exceeding 40: 1 (or 40). Often, salts having weight ratios of 2: 1 to 35 : 1 are used.
  • the metal salt may be selected from the group consisting of a hydrocarbyl- substituted organic sulfonic acid.
  • the metal salt selected from the group consisting of a hydrocarbyl-substituted organic acid, a hydrocarbyl-substituted phenol and mixtures thereof includes a metal salt of the hydrocarbyl-substituted sulfonic acid including those represented by the formula:
  • each R 1 is independently a hydrocarbyl group.
  • the hydrocarbyl group consists of ethylene, propylene, butylene or natural derived groups having 6 to 40, preferably 8 to 35 or 9 to 30 and most preferably 15 to 36 carbon atoms; A can be cyclic or acyclic moieties or mixtures thereof.
  • the hydrocarbyl group is preferably selected from the group consisting of an alkyl, cycloalkyl, aryl, acyl and mixtures thereof. Most preferably the hydrocarbyl group is an alkyl group, k is preferably 1 and R 1 is a branched alkyl group with 6 to 40 carbon atoms.
  • M is a valence of a calcium ion, sodium ion, magnesium ion, or mixtures thereof.
  • Valence is the number of "bonds" an atom or ion may be capable of forming, with one or more other atoms or ions.
  • a calcium or magnesium ion may typically have a valence of two, meaning the number of (R ! ) k - A - S0 3 anions associated with the "M" may be two.
  • One of the valences of Ca or Mg may be associated with an (R !
  • the second valence may be associated with a second (R ⁇ k -A-SCb anion or it may be associated with another anion such as OH or CO 3 .
  • the valence of sodium is one, meaning one (R ! ) k - A - SO 3 anion may be associated with a sodium ion.
  • the metal salt of the hydrocarbyl-substituted sulfonic acid has a hydrocarbyl- substituted sulfonic group that includes natural, synthetic or mixtures thereof.
  • Suitable examples of the hydrocarbyl-substitutes sulfonic acid include polypropene benzenesulfonic acid; and monoalkyl and dialkyl benzenesulfonic acids wherein the alkyl groups contain at least 10 carbons for example, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30 carbons and mixtures thereof.
  • alkyl group examples include branched and/or linear decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl, nonadecyl, eicosyl, un-eicosyl, do-eicosyl, tri-eicosyl. tetra-eicosyl, penta- eicosyl, hexa-eicosyl or mixtures thereof.
  • hydrocarbyl-substituted sulfonic acid examples include polypropene benzenesulfonic acid and C16-C24 alkyl benzenesulfonic acid or mixtures thereof.
  • Other preferred examples include toluene derived sulfonic acids.
  • A is cyclic suitable groups include phenyl or fused bicyclic such as naphthalene, indenyl, indanyl, bicyclopentadienyl and mixtures thereof. Although A includes a fused bicyclic ring, phenyl rings are preferred.
  • A is a chain, the chain can be linear, branched and mixtures thereof, although linear is preferred.
  • Suitable groups include derivatives of carboxylic acids containing 7 to 30, preferably 7 to 20, more preferably 8 to 20 and most preferably 8 to 15 carbon atoms. Further the chain can be saturated or unsaturated, although saturated is preferred.
  • the overbased detergent often has a low in-process viscosity and a low final viscosity.
  • low used in "low in-process viscosity” and a “low final viscosity” defines a viscosity that is lower than would be expected from a conventional overbased metal detergent.
  • the final product often has a final viscosity of less than 300 mm 2 s - " 1 , preferably
  • overbased metal salt of hydrocarbyl-substituted sulfonic acid is a detergent and especially an overbased metal sulfonate with a TBN (Total Base Number) of at least 400, more preferably at least 425, and more preferably at least 450, even more preferably at least 490.
  • the overbased sulfonate detergent could have a TBN of about 500.
  • a metal salt of a phenate such as sulfur-containing phenate, an alkylene (preferably methylene) coupled phenate or mixtures thereof may be employed.
  • a metal salt of a phenate such as sulfur-containing phenate, an alkylene (preferably methylene) coupled phenate or mixtures thereof.
  • alkylene preferably methylene
  • the carboxylic acid may comprise an acid containing 6 to 30 carbon atoms or any combination or mixture of acids therein.
  • the carboxylic acid contains 6 to 24 carbon atoms, 12 to 20 carbon atoms, or 16 to 18 carbon atoms.
  • the carboxylic acid may be linear, branched, or mixtures thereof.
  • the carboxylic acid can be saturated and/or unsaturated. Acids which have a diacid functionality or hydroxyl-substituted acids are not suitable. Tartaric acid and citric acid are also not suitable.
  • the carboxylic acid is stearic acid.
  • Examples of a suitable carboxylic acids include 2-methyl-2-heptanoic acid, 5- methyl-hexanoic acid, 3-methyl-2-heptanoic acid, 2,4,4-trimethyl-2-pentanoic acid, 4,4- dimethyl-2-pentanoic acid, 3-ethyl-2-hexanoic acid, 2-heptanoic acid, 2,3-dimethyl-2- pentanoic acid, 3,5-dimethyl-2-hexanoic acid, 2-methyl-2-pentanoic acid, 3,4,4-trimethyl-2- pentanoic acid, 3-propyl-2-hexanoic acid, 4-methyl-2-pentanoic acid, 2,4-dimethyl-2- pentanoic acid, 3-ethyl-2-pentanoic acid, 3,4-dimethyl-2-pentanoic acid, 4-methyl-2-hexanoic acid, 2,4-dimethyl-2-hexanoic acid, 3-butyl-2-heptanoic
  • the carboxylic acid(s) chosen from the group above is preferably added to the process at 1 to 20%, 2 to 20%, preferably 4 to 7%, or most preferably 7% of reactants.
  • stearic acid is added incrementally in the process.
  • the use of a carboxylic acid and in particular stearic acid in the process reaction, through incremental additional is advantageous. Without being bound by theory it is believed that the acid locates to a micelle of the carbonate core. This leads to a co-solublization of the acid with the metal carbonate significantly lowering the viscosity of the reaction mixture, therefore increasing the rate and efficiency of filtration.
  • the in-process addition of a carboxylic acid further reduces the amount of water needed to reduce the viscosity during the reaction.
  • the alcohols may include methanol and at least one mono-alcohol containing 2 to 10, containing 2 to 7, preferably 2 to 6, more preferably 2 to 5 and most preferably 3 to 5 carbon atoms.
  • the mono-alcohols containing 2 to 10 carbon atoms can include branched or linear alkyl chains or mixtures thereof, although branched is preferred.
  • the mono-alcohols can contain ethanol, propan-l-ol, isopropanol, butan-l-ol, butan-2-ol, isobutanol, pentan-l-ol, pentan-2-ol, penta-3-ol, isopentanol, hexan-l-ol, hexan-3- ol, heptan-l-ol, heptan-2-ol, heptan-3-ol, isooctyl, 2-ethylhexanol, nonanol, decanol, heptan- 4-ol or mixtures thereof.
  • the mixture of alcohols contains at least one butanol and at least one amyl alcohol.
  • the mixture of alcohols is commercially available as isoamyl alcohol from Union Carbide or other suppliers.
  • mono-alcohols are used. Diols are not generally utilized. Mono-alcohols are advantageous over diols during the final stripping of this alcohol; this can be carried out at much lower temperatures, i.e. less than 160°C.
  • the invention further includes an oil medium (considered to be distinct and not part of the hydrocarbon solvent described above), especially an oil of lubricating viscosity.
  • the oil includes natural and synthetic oils, oil derived from hydrocracking, hydrogenation, hydro finishing, unrefined, refined and re -refined oils or mixtures thereof.
  • Unrefined oils are those obtained directly from a natural or synthetic source generally without (or with little) further purification treatment.
  • Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties.
  • Purification techniques include solvent extraction, secondary distillation, acid or base extraction, filtration, percolation and the like.
  • Re -refined oils are also known as reclaimed or reprocessed oils, and are obtained by processes similar to those used to obtain refined oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.
  • Natural oils useful in making the inventive lubricants include animal oils, vegetable oils (e.g. castor oil, lard, oil), mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types and oils derived from coal or shale or mixtures thereof.
  • animal oils e.g. castor oil, lard, oil
  • mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types and oils derived from coal or shale or mixtures thereof.
  • Synthetic lubricating oils are useful and include hydrocarbon oils such as polymerised and interpolymerised olefins (e.g. polybutylenes, polypropylenes, propyleneisobutylene copolymers); poly(l-hexenes), poly(l-octenes), poly(l-decenes), and mixtures thereof; alkyl-benzenes (e.g. dodecylbenzenes, tetradecylbenzenes, di-(2- ethylhexyl)-benzenes); polyphenyls (e.g.
  • Other synthetic lubricating oils include liquid esters of phosphorous-containing acids (e.g. tricresyl phosphate, trioctyl phosphate, and the diethyl ester of decane phosphonic acid), and polymeric tetrahydrofurans. Synthetic oils may be produced by Fischer-Tropsch reactions and often may be hydroisomerised Fischer-Tropsch hydrocarbons or waxes
  • Oils of lubricating viscosity can also be defined as specified in the American
  • the five base oil groups are as follows: Group I (sulfur content >0.03 wt %, and/or ⁇ 90 wt % saturates, viscosity index 80-120); Group II (sulfur content ⁇ 0.03 wt %, and > 90 wt % saturates, viscosity index 80- 120); Group III (sulfur content ⁇ 0.03 wt %, and > 90 wt % saturates, viscosity index > 120); Group IV (all polyalphaolefins (PAOs)); and Group V (all others not included in Groups I, II, III, or IV).
  • the oil of lubricating viscosity comprises an API Group I, II, III, IV, V oil and mixtures thereof.
  • the oil of lubricating viscosity is an API Group I, II, III oil or mixtures thereof.
  • the detergent can be incorporated into a lubricating oil composition that optionally includes at least one other performance additive selected from the group consisting of metal deactivators, detergents other than those prepared by the process of the invention, dispersants, antioxidants, antiwear agents, corrosion inhibitors, anti-scuffmg agents, extreme pressure agents, foam inhibitors, demulsifiers, friction modifiers, viscosity modifiers, pour point depressants and mixtures thereof. Often fully-formulated lubricating oil will contain one or more of these additives.
  • Dispersants are well known in the field of lubricants and include primarily what is known as ashless-type dispersants and polymeric dispersants. Ashless type dispersants are characterized by a polar group attached to a relatively high molecular weight hydrocarbon chain. Typical ashless dispersants include nitrogen-containing dispersants such as N-substituted long chain alkenyl succinimides, also known as succinimide dispersants. Succinimide dispersants are more fully described in U.S. Patents 4,234,435 and 3,172,892.
  • ashless dispersant is high molecular weight esters, prepared by reaction of a hydrocarbyl acylating agent and a polyhydric aliphatic alcohol such as glycerol, pentaerythritol, or sorbitol. Such materials are described in more detail in U.S. Patent 3,381 ,022.
  • Another class of ashless dispersant is Mannich bases. These are materials which are formed by the condensation of a higher molecular weight, alkyl substituted phenol, an alkylene polyamine, and an aldehyde such as formaldehyde and are described in more detail in U.S. Patent 3,634,515.
  • dispersants include polymeric dispersant additives, which are generally hydrocarbon- based polymers which contain polar functionality to impart dispersancy characteristics to the polymer.
  • Dispersants can also be post-treated by reaction with any of a variety of agents. Among these are urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, and phosphorus compounds. References detailing such treatment are listed in U.S. Patent 4,654,403.
  • the amount of dispersant in the present composition can typically be 1 to 10 wt %, or 1.5 to 9.0 percent, or 2.0 to 8.0 percent, all expressed on an oil-free basis.
  • Antioxidants encompass phenolic antioxidants, which may comprise a butyl substituted phenol containing 2 or 3 t-butyl groups. The para position may also be occupied by a hydrocarbyl group or a group bridging two aromatic rings. The latter antioxidants are described in greater detail in U.S. Patent 6,559,105. Antioxidants also include aromatic amines, such as nonylated diphenylamine. Other antioxidants include sulfurized olefins, titanium compounds, and molybdenum compounds. U.S. Pat. No. 4,285,822, for instance, discloses lubricating oil compositions containing a molybdenum and sulfur containing composition.
  • antioxidants will, of course, depend on the specific antioxidant and its individual effectiveness, but illustrative total amounts can be 0.01 to 5, or 0.15 to 4.5, or 0.2 to 4 percent by weight. Additionally, more than one antioxidant may be present, and certain combinations of these can be synergistic in their combined overall effect.
  • Viscosity improvers may be included in the compositions of this invention.
  • Viscosity improvers are usually polymers, including polyisobutenes, poly(meth)acrylates (PMA) and poly(meth)acrylic acid esters, hydrogenated diene polymers, polyalkylstyrenes, esterified styrene-maleic anhydride copolymers, hydrogenated alkenylarene-conjugated diene copolymers and polyolefins.
  • PMA's are prepared from mixtures of methacrylate monomers having different alkyl groups. The alkyl groups may be either straight chain or branched chain groups containing from 1 to 18 carbon atoms. Most PMA's are viscosity modifiers as well as pour point depressants.
  • anti-wear agents include phosphorus-containing antiwear/extreme pressure agents such as metal thiophosphates, phosphoric acid esters and salts thereof, phosphorus-containing carboxylic acids, esters, ethers, and amides; and phosphites.
  • a phosphorus antiwear agent may be present in an amount to deliver 0.01 to 0.2 or 0.015 to 0.15 or 0.02 to 0.1 or 0.025 to 0.08 percent by weight phosphorus.
  • the antiwear agent is a zinc dialkyldithiophosphate (ZDP).
  • ZDP zinc dialkyldithiophosphate
  • suitable amounts may include 0.09 to 0.82 percent by weight.
  • Non-phosphorus-containing anti-wear agents include borate esters (including borated epoxides), dithiocarbamate compounds, molybdenum-containing compounds, and sulfurized olefins.
  • the overbased material is the product formed following the process of the present invention.
  • Detergents in general are typically overbased materials, otherwise referred to as overbased or super-based salts, which are generally homogenous Newtonian systems having, by a metal content, in excess of that which would be present for neutralisation according to the stoichiometry of the metal and the detergent anion.
  • the amount of excess metal is commonly expressed in terms of metal ratio, that is, the ratio of the total equivalent of the metal to the equivalent of the acidic organic compound.
  • Overbased materials are prepared by reacting an acid material (such as carbon dioxide) with an acidic or organic compound, an inert reaction medium (e.g. mineral oil), a stoichiometric excess of a metal base, and a promoter such as a phenyl or alcohol.
  • the acidic organic metal will normally have a sufficient number of carbon atoms, to provide oil solubility.
  • the metal salt selected from the group consisting of a hydrocarbyl-substituted organic acid; a hydrocarbyl-substituted phenol and mixtures thereof of the present invention are useful as detergents in lubricants for internal combustion engines, for example diesel fuelled engines, gasoline fuelled engines, natural gas fuelled engines or mixed gasoline/alcohol fuelled engines.
  • a method for lubricating an internal combustion engine comprising supplying thereto a lubricant comprising the composition as described herein is also provided.
  • the invention is suitable for 2-stroke or 4-stroke engines, in particular marine diesel engines, especially 2-stroke marine diesel engines.
  • the overbased metal detergent can be used as part of a lubricating composition.
  • the lubricating composition may be useful in an internal combustion engine, a driveline device, a hydraulic system, a grease, a turbine, or a refrigerant.
  • the composition further comprises a thickener.
  • the thickener may include simple metal soap thickeners, soap complexes, non-soap thickeners, metal salts of such acid-functionalized oils, polyurea and diurea thickeners, calcium sulfonate thickeners or mixtures thereof. Thickeners for grease are well known in the art.
  • the overbased metal detergent of the present invention can be used in the preparation of a calcium sulfonate grease.
  • the process may provide a method of lubricating an internal combustion engine.
  • the engine components may have a surface of steel or aluminium.
  • An aluminium surface may be derived from an aluminium alloy that may be a eutectic or a hyper-eutectic aluminium alloy (such as those derived from aluminium silicates, aluminium oxides, or other ceramic materials).
  • the aluminium surface may be present on a cylinder bore, cylinder block, or piston ring having an aluminium alloy, or aluminium composite.
  • the internal combustion engine may or may not have an Exhaust Gas
  • the internal combustion engine may be fitted with an emission control system or a turbocharger.
  • emission control system examples include diesel particulate filters (DPF), or systems employing selective catalytic reduction (SCR).
  • the internal combustion engine may be a diesel fuelled engine
  • the internal combustion engine may be a diesel fuelled engine and in another mode a gasoline fuelled engine.
  • the internal combustion engine may be a heavy duty diesel engine.
  • the internal combustion engine may be a 2-stroke or 4-stroke engine.
  • Suitable internal combustion engines include marine diesel engines, aviation piston engines, low-load diesel engines, and automobile and truck engines.
  • the marine diesel engine may be lubricated with a marine diesel cylinder lubricant (typically in a 2-stroke engine), a system oil (typically in a 2-stroke engine), or a crankcase lubricant (typically in a 4-stroke engine).
  • the lubricant composition for an internal combustion engine may be suitable for any engine lubricant irrespective of the sulfur, phosphorus or sulfated ash (ASTM D-874) content.
  • the sulfur content of the engine oil lubricant may be 1 % or less, or 0.8 % or less, or 0.5 % or less, or 0.3 % or less. In one mode the sulfur content may be in the range of 0.001 % to 0.5 %, or 0.01 % to 0.3 %.
  • the phosphorus content may be 0.2 % or less, or 0.12 % or less, or 0.1 % or less, or 0.085 % or less, or 0.08 % or less, or even 0.06 % or less, 0.055 % or less, or 0.05 % or less.
  • the phosphorus content may be 0.04 % to 0.12 %.
  • the phosphorus content may be 100 ppm to 1000 ppm, or 200 ppm to 600 ppm.
  • the total sulfated ash content may be 0.3 % to 1.2 %, or 0.5 % to 1.1 % of the lubricating composition. In one mode the sulfated ash content may be 0.5 % to 1.1 % of the lubricating composition.
  • the lubricating composition may be an engine oil, wherein the lubricating composition may be characterised as having at least one of (i) a sulfur content of 0.5 % or less, (ii) a phosphorus content of 0.12 % or less, and (iii) a sulfated ash content of 0.5 % to 1.1 % of the lubricating composition.
  • the lubricating composition may have a composition as described in the following table:
  • the final calcium hydroxide (93 g) was then added and stirred for 20 minutes. An additional amount of C0 2 gas, about 52 g, is added over 1 hour. Thereafter, the reaction mixture is heated to 150°C to remove volatile solvents and provide a crude mixture with a solids level of 24%. The mixture is filtered through Diatomaceous earth filter aid at a rate of 79 g/hr to give the desired product, having an analysis of calcium 19.2%, TBN (total base number, as mg KOH/g) 507, sulfated ash 63.8%, and KV100 (kinematic viscosity at 100 °C) of 181 mm 2 /s (cSt).
  • Example 3 500 TBN overbased calcium detergent with stearic acid (10%).
  • a third portion of calcium hydroxide (93 g) and stearic acid (25.7 g) is added and stirred for 20 minutes. An additional aliquot of C0 2 gas, about 50 g, is added over 1 hour.
  • a fourth portion of calcium hydroxide (93 g) and stearic acid (25.7 g) is added and stirred for 20 minutes. A further quantity of C0 2 gas, about 50 g, is added over 1 hour.
  • the fifth portion of calcium hydroxide (93.5 g) and stearic acid (25.7 g) was added and the mixture was stirred for 20 minutes. Carbon dioxide gas, about 50 g, is blown through the mixture over 1 hour.
  • the final calcium hydroxide (93 g) and stearic acid (25.7 g) was then added and stirred for 20 minutes. An additional amount of C0 2 gas, about 52 g, is added over 1 hour. Thereafter, the reaction mixture is heated to 150°C to remove volatile solvents and provide a crude mixture with a solids level of 10.4%. The mixture is filtered through Diatomaceous earth filter aid at a rate of 28 g/hr to give the desired product, having an analysis of calcium 18.5%, TBN (total base number, as mg KOH/g) 514, sulfated ash 62.7%, and KV100 (kinematic viscosity at 100 °C) of 946 mm 2 /s (cSt).
  • a third portion of calcium hydroxide (93 g) and stearic acid (18.2 g) is added and stirred for 20 minutes. An additional aliquot of C0 2 gas, about 50 g, is added over 1 hour.
  • a fourth portion of calcium hydroxide (93 g) and stearic acid (18.2 g) is added and stirred for 20 minutes. A further quantity of C0 2 gas, about 50 g, is added over 1 hour.
  • the fifth portion of calcium hydroxide (93.5 g) and stearic acid (18.2 g) was added and the mixture was stirred for 20 minutes. Carbon dioxide gas, about 50 g, is blown through the mixture over 1 hour.
  • the final calcium hydroxide (93 g) and stearic acid (18.2 g) was then added and stirred for 20 minutes. An additional amount of C0 2 gas, about 52 g, is added over 1 hour. Thereafter, the reaction mixture is heated to 150°C to remove volatile solvents and provide a crude mixture with a solids level of 9.2%. The mixture is filtered through Diatomaceous earth filter aid at a rate of 136 g/hr to give the desired product, having an analysis of calcium 19.1%, TBN (total base number, as mg KOH/g) 483, sulfated ash 58.4%, and KV100 (kinematic viscosity at 100 °C) of 21 1 mm 2 /s (cSt).
  • Example 5 400 TBN overbased calcium detergent with stearic acid (7%).
  • a third portion of calcium hydroxide (67 g) and stearic acid (16.7 g) is added and stirred for 20 minutes. An additional aliquot of C0 2 gas, about 38 g, is added over 1 hour.
  • a fourth portion of calcium hydroxide (67 g) and stearic acid (16.7 g) is added and stirred for 20 minutes. A further quantity of C0 2 gas, about 38 g, is added over 1 hour.
  • the fifth portion of calcium hydroxide (67 g) and stearic acid (16.7 g) was added and the mixture was stirred for 20 minutes. Carbon dioxide gas, about 38 g, is blown through the mixture over 1 hour.
  • the final calcium hydroxide (67 g) and stearic acid (16.7 g) was then added and stirred for 20 minutes. An additional amount of C0 2 gas, about 38g, is added over 1 hour. Thereafter, the reaction mixture is heated to 150°C to remove volatile solvents and provide a crude mixture with a solids level of 7.2%. The mixture is filtered through Diatomaceous earth filter aid to give the desired product, having an analysis of calcium 16.9%, TBN (total base number, as mg KOH/g) 401 , sulfated ash 51.5%, and KV100 (kinematic viscosity at 100 °C) of 81 mm 2 /s (cSt).
  • the mixture is filtered through Diatomaceous earth filter aid to give the desired product, having an analysis of calcium 15.5%, TBN (total base number, as mg KOH/g) 400, sulfated ash 52%, and KVlOO (kinematic viscosity at 100 °C) of 110 mm2/s (cSt).
  • the overbased calcium sulfonate detergents are evaluated based on several factors including filterability, bulk kinematic viscosity, TBN to ash ratio, and solids formation. Solids formation is determined by centrifugation. Prior to filtration a sample of the crude mixture is dissolved in hexane (25:75 by volume) and placed into a centrifuge tube. The sample is then centrifuged at 1600 rpm for 20 minutes. The solids settle to the bottom of the tube and are recorded as ml of solids. This value is multiplied by 4 which gives a percentage solids in the bulk detergent.
  • Comparative Example 2 (COMP EX 2) is conventional calcium overbased to 500 TBN without addition of a fatty acid; however an intermediate strip step is employed to maintain viscosity control. While the target TBN is achieved, there is a high level of solids, indicative of a lack of product stability.
  • Example 3 stearic acid was utilized at 10% of the reaction mixture; the acid was added incrementally.
  • Example 5 is an attempt to produce a lower TBN (-400 comparable to commercial overbased calcium sulfonate (COMP EX 6) with improved process conditions as well as improved product performance.
  • a series of OW-20 engine lubricants in Group III base oil of lubricating viscosity are prepared containing the additives described above as well as conventional additives including polymeric viscosity modifier, ashless succinimide dispersant, additional overbased detergents, antioxidants (combination of phenolic ester and diarylamine), zinc dialkyldithiophosphate (ZDDP), as well as other performance additives as follows (Table 3).
  • the phosphorus, sulfur and ash contents of each of the examples are also presented in the table in part to show that each example has a similar amount of these materials and so provide a proper comparison between the comparative and invention examples.
  • 2 - AO includes a mixture of hindered phenol and diarylamine
  • Additional detergent includes small amounts of overbased sodium sulfonate and low overbased calcium sulfonate to balance soap and sulfated ash
  • Ashless friction modifiers include fatty acid amides and polyacid imides
  • the additional additives used in the examples include dispersants, a viscosity modifier, and an antifoam agent, and include some amount of diluent oil.
  • the same additive package is used in each of the examples Testing
  • the Friction Torque Test provides a measure of friction torque of an engine assembly, which is driven by an electric motor.
  • the FTT procedure involves both a preparation phase and a measurement phase.
  • the preparation phase consists of: (a) multiple flushing cycles at high temperature and low engine revolutions with high detergent flushing oil and test sample to minimize potential additive carry over effect from the preceding test, (b) initial friction stabilization (transient) step at high oil temperature and fix (lower) engine rpm to facilitate metal surfaces and additive chemistry actions as well as intermediate heating / cooling cycles at low to medium engine speeds to achieve engine oil temperatures specified in test conditions.
  • the measurement phase comprises both steady and sweep mode friction torque measurements for varying engine speed / oil temperature combinations defined by test conditions that are set based on actual vehicle operating conditions referring to industrial or OEM specific fuel economy testing drive cycles.
  • the lubricant formulations are tested in a motor-driven engine assembly friction tester at variable speed conditions at 88°C. This test measures the frictional torque of the engine lubricated with the test formulation. The results are typically presented as a percent frictional torque reduction versus a standard baseline as a function of speed varying from e.g., 500 RPM (revolutions per minute) to 2500 RPM.
  • hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
  • hydrocarbyl groups include: hydrocarbon substituents, including aliphatic, alicyclic, and aromatic substituents; substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent; and hetero substituents, that is, substituents which similarly have a predominantly hydrocarbon character but contain other than carbon in a ring or chain.

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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

La présente invention concerne un détergent à base de sulfonate métallique surbasique à TBN élevé, le détergent étant préparé par la réaction d'un acide sulfonique organique substitué avec un hydrocarbyle, ou d'un sel métallique de cet acide, avec un composé basique de métal alcalin ou de métal alcalino-terreux en présence d'un mono-alcool et d'un acide carboxylique, et la réaction de ce mélange avec du dioxyde de carbone pour former un sulfonate métallique surbasique carboné. Le détergent métallique surbasique résultant présente un rapport équivalent métallique sur substrat d'acide sulfonique de 5/1 à 27/1. Le produit ainsi préparé est amélioré en termes de propriétés viscosimétriques, de capacité de filtration et de rapport TBN/cendre. Les compositions lubrifiantes contenant ledit détergent surbasique permettent de réduire les frottements et l'usure. L'invention concerne en outre des procédés de lubrification d'un moteur à combustion interne avec un lubrifiant contenant un détergent surbasique préparé comme décrit plus haut.
EP13808399.3A 2012-12-17 2013-12-03 Procédé de production d'un détergent métallique surbasique Withdrawn EP2931851A1 (fr)

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CN106800961B (zh) * 2015-11-25 2020-02-28 中国石油化工股份有限公司 磺酸盐清净剂过碳酸化的处理方法和高碱值磺酸盐清净剂的制备方法
CN106800960B (zh) * 2015-11-25 2020-02-28 中国石油化工股份有限公司 环烷酸盐清净剂过碳酸化的处理方法和高碱值环烷酸盐清净剂的制备方法
PL3421576T3 (pl) * 2017-06-30 2020-08-24 Infineum International Limited Sposób przeciwdziałania zanieczyszczeniu podczas rafinacji

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US4597880A (en) * 1983-09-09 1986-07-01 Witco Corporation One-step process for preparation of overbased calcium sulfonate greases and thickened compositions
TW278098B (fr) * 1992-09-18 1996-06-11 Cosmo Sogo Kenkyusho Kk
GB9411093D0 (en) * 1994-06-03 1994-07-27 Bp Chemicals Additives Detergent additives for lubricating oils, their preparation and use
GB9611317D0 (en) * 1996-05-31 1996-08-07 Exxon Chemical Patents Inc Overbased metal-containing detergents
GB9611316D0 (en) * 1996-05-31 1996-08-07 Exxon Chemical Patents Inc Overbased metal-containing detergents
US6015778A (en) * 1998-03-27 2000-01-18 The Lubrizol Corporation Process for making overbased calcium sulfonate detergents using calcium oxide and a less than stoichiometric amount of water
EP1694802A1 (fr) * 2003-10-30 2006-08-30 The Lubrizol Corporation Procede de preparation d'un detergent hyperbasique
ES2544239T3 (es) * 2005-12-15 2015-08-28 Infineum International Limited Uso de un inhibidor de corrosión de una composición de aceite lubricante
CN101886013B (zh) * 2009-05-14 2013-01-30 中国石油化工股份有限公司 一种混合基质型金属清净剂的制备方法
CN103370402B (zh) * 2010-12-21 2016-04-06 路博润公司 含清净剂的润滑组合物

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