EP2201089B1 - Cerhaltige additive für schmierstoffzusammensetzungen und herstellungsverfahren dafür - Google Patents

Cerhaltige additive für schmierstoffzusammensetzungen und herstellungsverfahren dafür Download PDF

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Publication number
EP2201089B1
EP2201089B1 EP08802834.5A EP08802834A EP2201089B1 EP 2201089 B1 EP2201089 B1 EP 2201089B1 EP 08802834 A EP08802834 A EP 08802834A EP 2201089 B1 EP2201089 B1 EP 2201089B1
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Prior art keywords
component
cerium
oil
alkaline earth
earth metal
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French (fr)
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EP2201089A2 (de
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Marcello Notari
Luigi D'elia
Orazio Pianta
Massimo Manni
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Eni SpA
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Eni SpA
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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
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04—Hydroxy compounds
    • C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
    • C10M129/40—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms monocarboxylic
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
    • C10M129/42—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms polycarboxylic
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
    • C10M129/54—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/20—Thiols; Sulfides; Polysulfides
    • C10M135/28—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring
    • C10M135/30—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups; Derivatives thereof
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/042—Mixtures of base-materials and additives the additives being compounds of unknown or incompletely defined constitution only
    • 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
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • 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
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • 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
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • 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
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral 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—Overbased sulfonic 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
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/088—Neutral 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
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089—Overbased salts
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
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    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/06—Groups 3 or 13
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    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • the present invention relates to oil dispersible overbased organic salts containing Cerium and an alkaline earth metal, their synthesis method and use in lubricating oils as detergent additives, anti-friction additives, additives for extreme-pressure tribological couplings and also as additives for improving the quality of diesel engine emissions.
  • Cerium-based compounds are well-known in the state of the art, as combustion-enhancing additives for fuels, for reducing the emissions of pollutants, such as particulate, unburned hydrocarbons, carbon monoxide and nitrogen oxides.
  • pollutants such as particulate, unburned hydrocarbons, carbon monoxide and nitrogen oxides.
  • USA patent 4,474,580 for example, the use of a blend of Cerium enolate and Iron enolate is described, and in the USA patent applications 2005/0160663 and 2007/015656 the use is described of compounds containing Cerium, Iron or Platinum as fuel additives.
  • DPF Diesel Particulate Filter
  • overbased products described in the European patent which are dispersed in oil or solvent, are metal phenates, sulphurized metal phenates, metal salicylates, alkyl-aryl metal sulphonates and metal carboxylates, of which carboxylates are preferred.
  • the overbased additive can be previously mixed with the fuel or mixed with the fuel on the vehicle. In that patent the synthesis of those products is not described.
  • Patent application JP 2004/182829 describes the use of an additive for lubricating oils containing boron and a dispersion of metal oxides, among which Cerium oxide, for improving the antifriction properties of the oil and reducing the content of toxic substances in the exhaust gases.
  • Patent application US 2004/194454 describes a lubricating oil with antiwear properties, containing organometallic compounds of Cerium, which when fed to the fuel of a diesel engine equipped with a particulate filter (DPF), facilitates the regeneration of the filter promoting the catalytic oxidation of the particulate.
  • DPF particulate filter
  • German patent DE 3926817 describes the use of lubricating oils containing cerium or cerium alloys for reducing the pollutants contained in exhaust gases.
  • the present invention therefore relates to oil dispersible overbased salts of organic acids containing Cerium and an alkaline earth metal, their synthesis method and use in lubricating oils as detergent additives, antiwear additives, antifriction additives, additives for extreme-pressure tribological couplings and also as additives for improving the quality of the emissions of diesel engines.
  • the use of these additives in lubricating oils for diesel engines allows the compounds containing Cerium to be conveyed onto the particulate trap for the treatment of exhaust gases improving its efficiency.
  • the present invention relates to overbased salts of organic acids, containing Cerium and an alkaline earth metal, dispersible in mineral oil.
  • a synthesis process of the above overbased salts which consists in:
  • the overbased salts of organic acids, containing Cerium and alkaline earth metal, object of the present invention have a Cerium content corresponding to a ratio between the equivalents of Cerium and those of organic acid ranging from 0.1 to 1.2, preferably from 0.4 to 1 and a content of alkaline earth metal corresponding to a ratio between the equivalents of alkaline earth metal and the equivalents of organic acid ranging from 1 to 40, preferably from 5 to 30.
  • Preferred alkaline earth metals are Magnesium and Calcium.
  • the preferred alkaline earth metal is Calcium.
  • the objective of the synthesis methods is not only to prepare salts containing Cerium, but also to obtain a stable colloidal dispersion of these salts in a lubricating base.
  • the achievement of this objective is not easy; if the synthesis is not effected with all the necessary expedients, the additive can be difficult to filter or the coagulation of the colloid may occur with the formation of gel.
  • the synthesis of the Cerium compounds of organic acids comprises the reaction in the presence of the following components:
  • Component A) can be:
  • Examples of sulphonic acids which can be used are di-alkyl benzene sulphonic acids and mono-alkyl benzene sulphonic acids.
  • Examples of di-alkyl benzene sulphonic acids are: dinonyl benzene sulphonic acid, didecyl benzene sulphonic acid, diundecyl benzene sulphonic acid, didodecyl benzene sulphonic acid, dialkyl benzene sulphonic acids which contain alkyl substituents deriving from polypropylene, polyisobutene and poly-1-butene, or mixtures of the above acids.
  • Examples of mono-alkyl benzene sulphonic acids which can be used are those containing alkyl substituents deriving from polypropylene, polyisobutene or mixtures of the above acids.
  • the preferred sulphonic acids have an acid content ranging from 60 to 99% by weight, preferably from 70 to 90% by weight and have an inorganic acidity, expressed as sulphuric acid, preferably lower than 5% by weight.
  • saturated carboxylic acids having formula (II) are capric acid, lauric acid, myristic acid, stearic acid, isostearic acid, arachidic acid, behenic acid and lignoceric acid.
  • unsaturated carboxylic acids having formula (II) are lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, gadoleic acid, erucic acid, linoleic acid and linolenic acid.
  • Mixtures of acids can be used, such as mixtures of synthetic and natural acids, containing both saturated and unsaturated acids.
  • alkyl-substituted salicylic acids are those containing alkyl substituents deriving from polypropylene, polyisobutene and poly-1-butene.
  • A-4) a phenol or sulphurized phenol, optionally substituted with linear or branched alkyl groups, in a number ranging from 1 to 3, preferably from 1 to 2, containing from 6 to 40 carbon atoms.
  • phenols or alkyl-substituted sulphurized phenols are those containing alkyl substituents deriving from polypropylene, polyisobutene and poly-1-butene.
  • Component (A) can also be a mixture of organic acids (A-1), (A-2), (A-3) and (A-4).
  • Component (A) is preferably a sulphonic acid.
  • Component (B) is a basic compound of Cerium in oxidation state (IV), such as Cerium hydroxide (IV), Cerium oxide (IV) or a mixture thereof; or a basic compound of Cerium in oxidation state (III), such as Cerium carbonate (III).
  • the quantity of basic Cerium compound used corresponds to a ratio between the equivalents of the basic Cerium compound and the organic acid equivalents ranging from 0.2 to 2, preferably from 0.5 to 1.5.
  • Component (C) is a solvent or mixture of solvents selected from:
  • the solvent when used, is added in a quantity corresponding to a weight percentage, calculated with respect to the organic acid, ranging from 10 to 800, preferably from 50 to 400.
  • Component (D) is a promoter of the neutralization reaction selected from:
  • the preferred promoters are water and methanol.
  • the promoter is added in a quantity corresponding to a weight percentage, calculated with respect to the basic cerium compound, ranging from 5 to 800, preferably from 10 to 500.
  • component (E) which is a lubricating base oil, as solvent, into the product.
  • the lubricating base oil can be of an animal, vegetable, mineral origin, or it can be a synthetic oil.
  • Mineral and synthetic lubricating base oils are preferred. Suitable mineral lubricating base oils are those deriving from petroleum, such as for example, naphthene-based oils, paraffin-based oils or a mixture of these.
  • Suitable synthetic lubricating base oils are esters, such as dioctyl adipate, dioctyl sebacate, tri-decyl adipate, or polymeric hydrocarbons, such as for example, poly-alpha-olefins or liquid polyisobutenes.
  • Particularly preferred lubricating base oils are mineral-based oils.
  • the lubricating base oil when used, is added at the beginning of the reaction together with the other reagents, or during the reaction, or at the end of the reaction, in a quantity corresponding to a weight percentage, calculated with respect to the organic acid (A), ranging from 30 to 800, preferably from 50 to 300.
  • Other components can be optionally added to control the variation in the viscosity and improve the filterability of the product, such as for example, short-chain carboxylic acids and inorganic halides.
  • the synthesis of the compound of organic acids containing Cerium can be carried out by adding components (A), (B), (D), optionally (C), and (E) to the reaction in any order.
  • the synthesis is preferably effected by mixing all the components (A), (B), (D), optionally (C), and (E) at the beginning, or it can be carried out by initially adding component (B) to a mixture consisting of component (D) and optionally component (C) and subsequently adding component (A).
  • component (E), when used, is added at the beginning together with components (D) and (C), or subsequently to component (A), or a fraction of (E) is added at the beginning together with components (D) and (C) and the remaining fraction of (E) is subsequently added to component (A).
  • the temperature at which the reaction is carried out ranges from 15 to 200°C, preferably from 30 to 150°C.
  • the selection of the optimum temperature depends on the kind of solvent used.
  • the product is recovered by separating, through distillation, the promoter (D), including the reaction water, and the solvent (C), if present. If the synthesis has been effected by adding the lubricating base oil (E), the product at the end is obtained as an oil solution.
  • the distillation of the solvents is carried out by increasing the temperature to a maximum value of 200°C, preferably up to 160°C and maintaining the product at this temperature for the time necessary for obtaining the complete removal of the solvents.
  • the distillation of the solvents can be effected at atmospheric pressure, or under vacuum, or partly at atmospheric pressure and partly under vacuum.
  • the product is filtered using a filtration aid, or, alternatively, it can be centrifuged.
  • the synthesis method of the overbased salts of organic acids, containing Cerium and an alkaline earth metal differs depending on whether the compound to be made overbased is i) a compound of organic acids containing Cerium, or ii) a mixture of an organic compound containing Cerium with an organic acid, or iii) an organic acid.
  • the synthesis method comprises the reaction between the following components:
  • the compound of organic acids containing Cerium which is part of component (A1) is that characterized by a Cerium content corresponding to a ratio between the equivalents of Cerium and those of organic acid, from which it derives, ranging from 0.1 to 1.2, preferably from 0.4 to 1. Increasing of Cerium content lead to a more difficult formation of a stable colloidal dispersion of the overbased salt containing Cerium and an alkaline earth metal.
  • the organic acid optionally contained in the component (A1) is equal to component (A), already described.
  • the mixture consisting of the compound of organic acids containing Cerium and an organic acid can contain a weight percentage of the compound containing Cerium varying from 10 to 99, preferably from 40 to 90.
  • Component (B1) is a basic component of an alkaline earth metal, preferably a basic compound of Calcium, Magnesium, Barium, more preferably a basic compound of Calcium.
  • the basic compound is preferably an oxide or hydroxide.
  • bases are Calcium oxide (CaO) or Calcium hydroxide (Ca(OH) 2 ).
  • Component B(1) can be completely added at the beginning of the reaction, or it can be partly added at the beginning and partly in different intermediate points of the reaction.
  • the quantity of basic compound of alkaline earth metal used corresponds to a ratio between the equivalents of the basic compound of alkaline earth metal and those of component (A1), ranging from 1 to 40, preferably from 5 to 30.
  • Component (C1) is the solvent, the same as component (C), already described above.
  • the solvent is used in a quantity corresponding to a weight percentage, calculated with respect to the component (A1), ranging from 10 to 500, preferably from 50 to 300.
  • Component (D1) is the promoter, the same as component (D), already described above.
  • the promoter is added in a quantity corresponding to a weight percentage, calculated with respect to the basic compound of alkaline earth metal, ranging from 2 to 500, preferably from 5 to 300.
  • Component (F1) is carbon dioxide, used for carbonating the excess of component (B1) contained in the product and subsequently added to each addition of component (B1).
  • the carbon dioxide can be added as a gas or as a solid, preferably as a gas.
  • the quantity of carbon dioxide used corresponds to a ratio between the equivalents of carbon dioxide and those of alkaline earth metal base, ranging from 0.6 to 1.1, preferably from 0.7 to 0.9.
  • the carbon dioxide is preferably added in defect with respect to the base to be carbonated (oxide or hydroxide) in order to stabilize the colloidal dispersion of the product, facilitating its subsequent filtration.
  • component (E1) in the product, as solvent, which is a lubricating base oil, the same as component (E), described above.
  • the lubricating base oil when used, is added at the beginning of the synthesis together with the other reagents, or during the synthesis, or at the end of the synthesis, in a quantity corresponding to a weight percentage, calculated with respect to component (A1) ranging from 30 to 800, preferably from 50 to 300.
  • Other components can be optionally added to promote the carbonation, control the variation in the viscosity and improve the filterability, such as for example short-chain carboxylic acids and inorganic halides.
  • the synthesis, object of the present invention, of overbased salts of organic acids, containing Cerium and an alkaline earth metal, carried out by over-basifying a compound of organic acids containing Cerium, or a mixture of said compound with an organic acid, can be effected by adding components (A1), (B1), (C1), (D1), optionally (E1) to the reaction in any order.
  • Component (F1) must be added subsequently to component (B1).
  • the synthesis can be conveniently carried out by initially adding component (B1) to a mixture consisting of component (C1) and a part of component (E1) and subsequently adding component (A1). After adding component (D1) the carbonation is carried out with carbon dioxide (component F1), after which a second part of component (E1) is added and after maturation the remaining quantity of (E1) is added.
  • the synthesis can also be carried out by initially adding component (B1) to a mixture consisting of component (C1), component (D1) and a part of component (E1) and subsequently adding component (A1). Carbonation is then carried out with carbon dioxide (component F1), after which a second part of component (E1) is added and after maturation the remaining quantity of (E1) is added.
  • the temperature at which the first part of the synthesis is carried out which consists of the neutralization and overbasifying reactions, ranges from 15°C to 200°C, preferably from 30°C to 150°C. The selection of the optimum temperature depends on the nature of the solvent used.
  • the carbonation reaction is carried out at a temperature ranging from 10°C to 150°C, preferably from 15°C to 100°C.
  • the addition of the carbon dioxide as gas is performed over a period of time ranging from 10 minutes to 6 hours, preferably from 1 to 4 hours.
  • the carbonation is followed by maturation, which is carried out at a temperature ranging from 30°C to 150°C, for a time ranging from 10 minutes to 4 hours, preferably from 20 minutes to 3 hours.
  • the product is recovered by separating through distillation, the promoter (D1), including the reaction water, and the solvent (C1). If the synthesis has been carried out by adding lubricating base oil (E1), the end-product is obtained as an oil-solution.
  • the distillation of the solvents is effected by increasing the temperature to a maximum value of 200°C, preferably up to 160°C and maintaining the product at this temperature for the time necessary for obtaining the complete removal of the solvents.
  • the distillation of the solvents can be effected at atmospheric pressure, or under vacuum, or partly at atmospheric pressure and partly under vacuum.
  • the product is filtered using a filtration coadjuvant, or, alternatively it can be centrifuged.
  • the synthesis method comprises reaction between the following components:
  • Component (A2) is an organic acid, the same as component (A), previously described.
  • Component (B2) is a basic compound of Cerium the same as component (B), previously described.
  • the quantity of basic compound of Cerium used corresponds to a ratio between the equivalents of the basic compound of Cerium and those of organic acid ranging from 0.2 to 2, preferably from 0.5 to 1.5.
  • Component (C2) is a basic compound of an alkaline earth metal, the same as component (B1), previously described.
  • the quantity of basic compound of alkaline earth metal used corresponds to a ratio between the equivalents of the basic compound of alkaline earth metal and those of component (A2), ranging from 1 to 40, preferably from 5 to 30.
  • Component (D2) is the solvent, the same as component (C), previously described.
  • the solvent is used in a quantity corresponding to a weight percentage, calculated with respect to component (A2), ranging from 10 to 500, preferably from 50 to 300.
  • Component (E2) is the promoter of the neutralization and carbonation reactions, the same as component (D), previously described.
  • the promoter is added in a quantity corresponding to a weight percentage, calculated with respect to the sum of the basic compounds (B2) and (C2), ranging from 2 to 500, preferably from 5 to 300.
  • Component (G2) is carbon dioxide, which is used as component (F1), previously described.
  • the quantity of carbon dioxide used corresponds to a ratio between the equivalents of carbon dioxide and those of the base in excess with respect to the organic acid, ranging from 0.6 to 1.1, preferably from 0.7 to 0.9.
  • the carbon dioxide is preferably added in defect with respect to the base to be carbonated (oxide or hydroxide) in order to stabilize the colloidal dispersion of the product, facilitating its subsequent filtration.
  • component (F2) which is a lubricating oil
  • component (E) is a lubricating oil
  • the lubricating base oil when used, is added at the beginning of the synthesis together with the other reagents, or during the synthesis, or at the end of the synthesis, in a quantity corresponding to a weight percentage, calculated with respect to component (A2) ranging from 30 to 800, preferably from 50 to 300.
  • Other components can be optionally added to promote the carbonation, control the variation in the viscosity and improve the filterability, such as for example short-chain carboxylic acids and inorganic halides.
  • the synthesis, object of the present invention, of overbased salts of organic acids, containing Cerium and an alkaline earth metal, carried out in a single step by treating an organic acid with basic compounds of Cerium and basic compounds of alkaline earth metal can be effected by adding components (A2), (B2), (C2), (D2), (E2), optionally (F2), to the reaction in any order.
  • Component (G2) must be added subsequently to components (B2) and (C2).
  • the synthesis can be conveniently carried out, for example, by initially adding component (B2) to a mixture consisting of component (D2) and a part of component (F2) and subsequently adding component (A2). Component (C2) is then added followed by component (E2) and the carbonation is subsequently carried out with carbon dioxide (component G2), after which a second part of component (F2) is added and after maturation the remaining quantity of (F2) is added.
  • the synthesis can also be carried out by initially adding component (B2) to a mixture consisting of component (D2), component (E2) and a part of component (F2) and subsequently adding component (A2). Component (C2) is then added and carbonation is subsequently effected with carbon dioxide (component G2), after which a second part of component (F2) is added and, after maturation, the remaining quantity of (F2) is added.
  • the product is recovered by separating through distillation, the promoter (E2), including the reaction water, and the solvent (D2). If the synthesis has been carried out by adding lubricating base oil (F2), the end-product is obtained as an oil-solution.
  • the distillation of the solvents is effected as already described in cases i) and ii) of the synthesis of overbased salts of Cerium and alkaline earth metal.
  • the product is filtered using a filtration aid, or, alternatively, it can be centrifuged.
  • the oil-dispersions of organic acids compounds containing Cerium and overbased salts of organic acids containing Cerium and alkaline earth metals can be used in lubricating compositions as additives with detergent properties, capable of limiting the formation of deposits.
  • the overbased salts of organic acids containing Cerium and alkaline earth metals, containing a large basicity reserve are also capable of neutralizing the acid products formed in the lubricating oil of an internal combustion engine preventing corrosion phenomena.
  • the compounds, object of the present invention can also be used in lubricating compositions as additives capable of improving the antifriction and antiwear properties and as additives for extreme-pressure tribological couplings.
  • the above compounds can also be used in lubricating compositions for improving the quality of internal combustion engine emissions.
  • the use of these additives in lubricating oils for diesel engines allows the compounds containing Cerium to be conveyed onto the particulate trap for the treatment of exhausted gases improving its efficacy.
  • a further object of the present invention therefore relates to lubricating compositions containing one or more lubricating base oils of a synthetic, mineral, vegetable or animal origin and the compounds, object of the present invention.
  • the compounds of organic acids containing Cerium, and the overbased salts of organic acids containing Cerium and an alkaline earth metal can be used in lubricating compositions in a combination, at a concentration expressed as weight percentage with respect to the lubricating oil, ranging from 0.2 to 10, preferably from 0.5 to 7.
  • lubricating compositions used for example as oils for motor vehicles, can also contain, in addition to the above additives, other detergent, antifriction, antiwear additives and supplementary additives for extreme-pressure tribological couplings, antioxidants, dispersants, additives for improving the viscosity index, additives for lowering the slip point and others.
  • the parameter TBN total base number
  • the synthesis reactions of the additives containing Cerium are carried out in a Mettler RC-1 calorimeter consisting of a 5-necked jacketed glass reactor, having a volume of 2 litres, thermostat-regulated by circulation in the jacket of a fluid coming from a thermocryostat and equipped with: a mechanical blade stirrer; a Claisen condenser cooled with tap water, connected to a vacuum line and equipped with a flask for collecting the distillate; a bottom outlet with a teflon tap through which carbon dioxide is bubbled into the reaction mass; a thermocouple for measuring the temperature.
  • the system is controlled by a computer, which allows the desired heating and cooling programs to be set.
  • the feeding of the carbon dioxide is effected by a cylinder, positioned on a balance, which is connected to the bottom of the reactor by means of
  • the stirring is initiated and it is observed that after the addition of methanol neutralization heat develops which increases the internal temperature to about 38-40°C.
  • the internal temperature is increased to 60°C maintaining it at this value for 2 hours.
  • the distillation is continued, reducing the pressure to 100 mbar, for an overall time of 60 minutes, in order to remove the residual volatile substances.
  • the quantity of distillate collected is equal to 101.7 g.
  • the product has a content of sediments, measured in heptane according to the method ASTM D96, equal to 1.8% by volume.
  • the product is treated with a quantity of filtration earth equal to 3% by weight and is filtered on a jacketed steel filter having a volume of 1 litre, with a filtering surface consisting of an 80 mesh steel net.
  • a cake of filtering earth is prepared on the filter before the filtration.
  • the filtration is effected at a temperature of 160°C and with a pressure of 5 atmospheres of nitrogen.
  • the product After filtration, the product has the following characteristics:
  • Cerium (IV) sulphate a small quantity of Cerium (IV) sulphate, deriving from the neutralization of the sulphuric acid present as impurity in the sulphonic acid, is also formed. Assuming that the cerium (IV) sulphate remains dispersed in the product, the following parameters are calculated:
  • the distillation is continued, reducing the pressure to 100 mbar, for an overall time of 60 minutes, in order to remove the residual volatile substances.
  • the quantity of distillate collected is equal to 641.9 g.
  • the product has a content of sediments, measured in heptane according to the method ASTM D96, equal to 2% by volume.
  • the product is treated with a quantity of filtration earth equal to 3% by weight and is filtered on a jacketed steel filter, as described in example 1.
  • the filtration is effected at a temperature of 160°C and with a pressure of 5 atmospheres of nitrogen.
  • the product After filtration, the product has the following characteristics:
  • Cerium (IV) sulphate a small quantity of Cerium (IV) sulphate deriving from the neutralization of the sulphuric acid present as impurity in the sulphonic acid, is also formed. Assuming that the cerium (IV) sulphate remains dispersed in the product, the following parameters are calculated:
  • the reactor is prepared for the carbonation phase, in which carbon dioxide is introduced into the reaction mixture, through the valve situated at the bottom of the reactor, at a flow-rate of 15 Nl/hour, in order to dose 113.5 g of carbon dioxide in 165 minutes.
  • the reaction mixture is heated from 28°C to 50°C in 30 minutes to allow the maturation of the colloidal dispersion.
  • the temperature is maintained at 50°C for 20 minutes and 145.8 g of lubricating oil SN150 are then added.
  • the temperature is brought from 50°C to 65°C in 40 minutes and the post-maturation sediments are determined with the method ASTM D96, proving to be 1.6% by volume.
  • the volatile substances are removed by distillation using the following heating program:
  • the distillation is continued, reducing the pressure to 100 mbar, for an overall time of 60 minutes, in order to remove the residual volatile substances.
  • the quantity of distillate collected is equal to 997.3 g.
  • the product has a content of sediments, measured in heptane according to the method ASTM D96, equal to 1% by volume.
  • the product is treated with a quantity of filtration earth equal to 3% by weight and is filtered on a steel filter, as described in example 1.
  • the filtration is effected at a temperature of 160°C and with a pressure of 5 atmospheres of nitrogen.
  • the product After filtration, the product has the following characteristics:
  • 396 g of methanol and 20.8 g of water are added, maintaining the temperature at 40°C for 10 minutes.
  • the reactor is prepared for the carbonation phase, in which carbon dioxide is introduced into the reaction mixture, through the valve situated at the bottom of the reactor, at a flow-rate of 15 Nl/hour, in order to dose 113.5 g of carbon dioxide in 165 minutes.
  • the reaction mixture is heated from 28°C to 50°C in 30 minutes to allow the maturation of the colloidal dispersion.
  • the temperature is maintained at 50°C for 20 minutes and 148.6 g of lubricating oil SN150 are then added.
  • the temperature is brought from 50°C to 65°C in 40 minutes and the post-maturation sediments are determined with the method ASTM D96, proving to be 1.6% by volume.
  • the quantity of distillate collected is equal to 996 g.
  • the product has a content of sediments, measured in heptane according to the method ASTM D96, equal to 1.8% by volume.
  • the product is treated with a quantity of filtration earth equal to 3% by weight and is filtered on a steel filter, as described in example 1.
  • the filtration is effected at a temperature of 160°C and with a pressure of 5 atmospheres of nitrogen.
  • the product After filtration, the product has the following characteristics:
  • the engine test illustrated hereunder, is suitable for evaluating the impact of the lubricant on the particulate after-treatment systems of diesel internal combustion engines. This evaluation is effected through the collection and analysis of the ash accumulated on the filter. The test is suitably accelerated with the forced increase in the oil consumption, obtained with a method described in patent US 5,913,253 .
  • This method envisages the injection of oil into the suction collector to simulate an increase in the drawing from the suction valves, from the seals on the shaft of the turbocompressor and through the ventilation circuit of the engine base. This method allows the following experimentation objectives to be reached:
  • the oil tank is connected to a load cell for measuring the quantity of oil consumed.
  • the heater has the function of increasing the temperature of the oil to lower the viscosity and guarantee a sufficiently pulverized spray.
  • the injector is of the single-hole type normally used in Diesel engines for fuel injection.
  • the test bench was equipped with a continuous detection system of the quantity of oil injected.
  • the detection of the quantity of oil consumed by the engine was obtained by weighing the oil discharged from the engine every 120 hours.
  • the high load functioning period was specifically established for ensuring a sufficient regeneration of the filtering element by reaction between the oxygen present and the particulate.
  • test cycle is shown in Table 1, which indicates functioning times, regime conditions, motor load and temperature of the exhaust gases (which, as can be seen, represent the main parameter capable of governing the regeneration), for a test period of 2 hours, to be suitably repeated to cover an accumulation of 120 hours, which proved optimum for the rapid screening of different oils in limited time periods
  • Table 1 Phase Time Engine charge Engine regime Discharge temperature Low load accumulation 45 min 20% 3.000 rpm 300°C regeneration 15 min 80% 4.000 rpm 550°C Medium load accumulation 45 min 40% 2.000 rpm 350°C regeneration 15 min 80% 4.000 rpm 550°C
  • a reference gas oil was used, as fuel, for the experimentation, characterized by a very low sulphur content (S ⁇ 10 ppm) and without additivation.
  • Oil 1 Oil 2 Phosphorous (ppm) 1070 1040 Zinc (ppm) 1180 1120 Calcium (ppm) 2560 2540 Magnesium (ppm) 270 250 Cerium (ppm) 550 0 Sulphur (ppm) 8000 8000 Sulfated ashes (wt %) 1.20 1.26
  • the deposit accumulated on the particulate filters was removed from the filters and subsequently characterized.
  • the identification of the elements and compounds present in the deposit was effected by scanning electron microscope analysis (SEM) equipped with EDX (Energy Dispersive X-Ray) module. Table 3 shows the list of elements identified and the relative percentage determined.
  • the Cerium is carried by the lubricating oil onto the DPF filter, where it is available for catalyzing the combustion of the particulate, allowing the regeneration of the filter.
  • the Sulphur has been omitted as this element is characteristic of both the lubricant and the fuel and also because it has been ascertained that most of the sulphur is not collected on the filter, but passes through it in gaseous form.
  • Oil 1 The lubricant called Oil 1 was evaluated on this engine in the test described of 120 hours under mixed functioning conditions (30 hours at high power + 90 hours at intermediate power) without revealing significant engine performances variations.
  • the oil consumption which is considered a health index of the engine, as it tends to rise in the presence of wear or the formation of deposits which hinder the correct movement of the elastic strips, did not show any significant variations with respect to the comparative test effected on Oil 2, containing classical Calcium-based detergents, and with respect to the average consumption of the engine calculated on the values acquired during 6 different tests (Table 5)
  • Example 3 The antifriction and antiwear properties of the overbased sulphonates containing Cerium and Calcium were evaluated according to the method DIN 51384, using the SRV test equipment.
  • the additive tested is that of Example 3 having the following main characteristics:
  • the test was carried out on 5% by weight solutions of the additives in mineral lubricating oil SN 150.
  • the operating conditions used are the following:
  • the test was carried out on solutions at 5% by weight of additives in mineral lubricating oil SN 150.
  • the operating conditions used are the following:

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Claims (26)

  1. Additiv für Schmieröle, umfassend ein metallisches überbasisches Salz einer organischen Säure oder einer Mischung von organischen Säuren, enthaltend Cer und ein Erdalkalimetall mit einem Cer-Gehalt, entsprechend einem Verhältnis zwischen den Äquivalenten des Cers und denen der organischen Säure, in einem Bereich von 0,1 bis 1,2 und einem Gehalt an Erdalkalimetall, entsprechend einem Verhältnis zwischen den Äquivalenten des Erdalkalimetalls und denen der organischen Säure, in einem Bereich von 1 bis 40.
  2. Additiv für Schmieröle gemäß Anspruch 1, umfassend eine stabile, homogene und transparente Öl-Dispersion, im Wesentlichen bestehend aus:
    i. 5-99,9 Gew.-% eines Öls; und
    ii. 0,1-95 Gew.-% des metallischen überbasischen Salzes.
  3. Additiv für Schmieröle gemäß Anspruch 1 oder 2, worin die organische Säure ausgewählt ist aus mindestens einem aus:
    einer Sulfonsäure mit der Formel

            (R1)n-A-SO3H     (I),

    worin R1 eine lineare oder verzweigte Alkylgruppe ist, enthaltend 6 bis 40 Kohlenstoffatome, oder R1 ist ein Alkylsubstituent, abgeleitet von einem Polymer eines C2-C6-Olefins; A ist ein C6-C20-aromatischer Kohlenwasserstoff, ein aliphatischer Kohlenwasserstoff mit 5 bis 20 Kohlenstoffatomen; n ist Null oder eine Ganzzahl in einem Bereich von 1 bis 5;
    einer Carbonsäure mit der Formel:
    Figure imgb0003
    worin R2 eine lineare oder verzweigte Alkyl- oder Alkenylgruppe ist, enthaltend von 6 bis 40 Kohlenstoffatome; R3 ist eine Wasserstoffatom, eine Alkylgruppe, enthaltend von 1 bis 4 Kohlenstoffatome, oder der Rest -CH2COOH;
    einer Salizylsäure, gegebenenfalls substituiert mit linearen oder verzweigten Alkylgruppen, in einer Zahl in einem Bereich von 1 bis 3, enthaltend von 6 bis 40 Kohlenstoffatome;
    einem Phenol oder sulfurisiertem Phenol, gegebenenfalls substituiert mit linearen oder verzweigten Alkylgruppen, in einer Zahl in einem Bereich von 1 bis 3, enthaltend von 6 bis 40 Kohlenstoffatomen.
  4. Additiv für Schmieröle gemäß Anspruch 1, 2 oder 3, worin die Verhältnisse zwischen den Äquivalenten des Cers und denen der organischen Säure in einem Bereich von 0,4 bis 1 sind, wobei die Verhältnisse zwischen den Äquivalenten des Erdalkalimetalls und den Äquivalenten der organischen Säure in einem Bereich von 5 bis 30 liegen.
  5. Additiv für Schmieröle gemäß irgendeinem der vorhergehenden Ansprüche, worin das Cer in dem überbasischen Salz im Oxidationszustand (III) oder (IV) ist.
  6. Additiv für Schmieröle gemäß irgendeinem der vorhergehenden Ansprüche, worin das Erdalkalimetall Calcium, Magnesium oder Barium ist.
  7. Additiv für Schmieröle gemäß irgendeinem der Ansprüche 2 bis 6, worin das Öl des Bestandteils (i) ein Schmieröl ist, ausgewählt aus denjenigen von tierischem, pflanzlichem, mineralischem oder synthetischem Ursprung.
  8. Verfahren zur Synthese von Additiven für Schmieröle nach irgendeinem der vorhergehenden Ansprüche 1 bis 7, umfassend die Reaktion zwischen den folgenden Bestandteilen:
    A1. einer Verbindung einer organischen Säure, enthaltend Cer oder einer Mischung der vorgenannten Verbindungen mit einer organischen Säure;
    B1. einer basischen Verbindung eines Erdalkalimetalls;
    C1. einem Lösemittel oder einer Mischung aus Lösemitteln;
    D1. einem Promoter oder einer Mischung aus Reaktionspromotern;
    E1. gegebenenfalls einem Öl;
    F1. Kohlenstoffdioxid;
    worin die Zugabe der Bestandteile (A1), (B1), (C1), (D1), gegebenenfalls (E1) in einer beliebigen Reihenfolge durchgeführt wird, wobei die Zugabe des Bestandteils (F1) im Anschluss stattfindet, folgend dem Bestandteil (B1).
  9. Verfahren nach Anspruch 8, worin die Synthese umfasst:
    - anfängliche Zugabe von Bestandteil (B1) zu einer Mischung, bestehend aus Bestandteil (C1) und einem Teil des Bestandteils (E1), im Anschluss Zugabe von Bestandteil (A1);
    - Zugabe von Bestandteil (D1);
    - Karbonisierung der erhaltenen Mischung mit Bestandteil (F1);
    - Zugabe, zum Ende der Karbonisierung, von einem zweiten Aliquot des Bestandteils (E1); und
    - Zugabe, nach Reifung, der verbleibenden Quantität von (E1).
  10. Verfahren nach Anspruch 8, worin die Synthese umfasst:
    - anfängliche Zugabe von Bestandteil (B1) zu einer Mischung, bestehend aus Bestandteil (C1), Bestandteil (D1) und einem Aliquot des Bestandteils (E1);
    - anschließende Zugabe von Bestandteil (A1);
    - Karbonisierung der erhaltenen Mischung mit Bestandteil (F1);
    - Zugabe eines zweiten Teils des Bestandteils (E1);
    - Zugabe, nach Reifung, der verbleibenden Quantität von (E1).
  11. Verfahren nach irgendeinem der Ansprüche 8 bis 10, worin das Additiv durch Abtrennung gewonnen wird, mittels Destillation, des Reaktionsprodukts aus dem Reaktionspromoter und aus dem Lösemittel, und durch anschließende Trennung mittels Filtration oder Zentrifugierung von den unlöslichen Nebenprodukten.
  12. Verfahren zur Synthese von Additiven für Schmieröle gemäß irgendeinem der vorhergehenden Ansprüche 1 bis 7, umfassend die Reaktion zwischen den folgenden Bestandteilen:
    A2. einer organischen Säure oder einer Mischung von organischen Säuren;
    B2. einer basischen Verbindung des Cers;
    C2. einer basischen Verbindung eines Erdalkalimetalls;
    D2. einem Lösemittel oder einer Mischung von Lösemitteln;
    E2. einem Promoter oder einer Mischung von Reaktionspromotern;
    F2. gegebenenfalls einem Öl;
    G2. Kohlenstoffdioxid,
    worin die Zugabe der Bestandteile (A2), (B2), (C2), (D2), (E2), gegebenenfalls (F2) in einer beliebigen Reihenfolge durchgeführt wird, wohingegen die Zugabe des Bestandteils (G2) im Anschluss stattfindet, folgend Bestandteil (C2).
  13. Verfahren nach Anspruch 12, worin die Synthese umfasst:
    - anfängliche Zugabe von Bestandteil (B2) zu einer Mischung, bestehend aus Bestandteil (D2) und einem Aliquot des Bestandteils (F2), anschließend Zugabe von Bestandteil (A2);
    - Zugabe von Bestandteil (C2) und Bestandteil (E2);
    - Karbonisierung der erhaltenen Mischung mit Bestandteil (G2);
    - Zugabe, zum Ende der Karbonisierung, von einem zweiten Aliquot des Bestandteils (F2); und
    - Zugabe, nach Reifung, der verbleibenden Quantität von (F2).
  14. Verfahren nach Anspruch 12, worin die Synthese umfasst:
    - anfängliche Zugabe von Bestandteil (B2) zu einer Mischung, bestehend aus Bestandteil (D2), Bestandteil (E2) und einem Teil von Bestandteil (F2);
    - anschließende Zugabe von Bestandteil (A2);
    - Zugabe von Bestandteil (C2);
    - Karbonisierung der erhaltenen Mischung mit Bestandteil (G2);
    - Zugabe eines zweiten Teils des Bestandteils (F2);
    - Zugabe, nach Reifung, der verbleibenden Quantität von (F2).
  15. Verfahren nach irgendeinem der Ansprüche 12 bis 14, worin das Additiv durch Trennung gewonnen wird, mittels Destillation des Reaktionsprodukts aus dem Reaktionspromoter und aus dem Lösemittel, und durch anschließende Abtrennung mittels Filtration oder Zentrifugierung, von den unlöslichen Nebenprodukten.
  16. Verfahren nach Anspruch 8 bis 11, worin die Mischung; bestehend aus der Verbindung von organischen Säuren, enthaltend Cer, und einer organischen Säure; einen Gewichtsprozentsatz der Verbindung, enthaltend Cer, in einem Bereich von 10 bis 99 enthält.
  17. Verfahren nach irgendeinem der Ansprüche 8 bis 16, worin die basische Verbindung des Erdalkalimetalls ausgewählt ist aus einem Oxid oder Hydroxid des Erdalkalimetalls.
  18. Verfahren nach irgendeinem der Ansprüche 8 bis 17, worin das Lösemittel in einer Menge in einem Bereich von 10 bis 500 Gew.-%, berechnet mit Bezug auf Bestandteil (A1) oder (A2), verwendet wird, und ausgewählt ist aus aromatischen oder aliphatischen Kohlenwasserstoffen.
  19. Verfahren nach irgendeinem der Ansprüche 8 bis 18, worin der Reaktionspromoter in einer Menge eingesetzt wird, in einem Bereich von 2 bis 500 Gew.-%, berechnet mit Bezug auf Bestandteil B1 oder der Summe der Bestandteile B2 und C2, und ist ausgewählt aus einem Alkohol, Wasser, einem Glycol, einem Keton, einem Ester einer Carbonsäure.
  20. Verfahren nach irgendeinem der Ansprüche 8 bis 19, worin die Karbonisierungsphase der basischen Verbindung des Erdalkalimetalls bewirkt wird mit Kohlenstoffdioxid in einer solchen Menge, dass ein Verhältnis zwischen den Äquivalenten des Kohlenstoffdioxids und denjenigen der Base des Erdalkalimetalls in Überschuss mit Bezug auf die organische Säure in einem Bereich von 0,6 bis 1,1 ist.
  21. Verfahren nach irgendeinem der Ansprüche 8 bis 20, worin das Schmieröl bei der Verwendung in einer Menge von 30 bis 800 Gew.-%, berechnet mit Bezug auf die Bestandteile (A1) oder (A2), zugegeben wird.
  22. Verfahren nach irgendeinem der Ansprüche 8 bis 21, worin die Reaktion zwischen den Bestandteilen (A1) - (E1) oder zwischen den Bestandteilen (A2) - (F2) bei einer Temperatur in einem Bereich von 15 bis 200 °C stattfindet.
  23. Verfahren nach irgendeinem der Ansprüche 8 bis 22, worin die Karbonisierungsphase bei einer Temperatur in einem Bereich von 10 bis 150 °C stattfindet.
  24. Verfahren nach irgendeinem der Ansprüche 8 bis 23, worin die Trennungsphase des Reaktionsprodukts durch Destillation von dem Reaktionspromoter und dem Lösemittel dadurch bewirkt wird, dass die Temperatur am Ende der Karbonisierung auf einen Maximalwert von 200 °C angehoben wird.
  25. Schmierzusammensetzungen, umfassend ein Basis-Öl bestehend aus einem Schmieröl von tierischem, pflanzlichem, mineralischem oder synthetischem Ursprung und einem Additiv, umfassend ein überbasisches Salz, enthaltend Cer, und ein Erdalkalimetall gemäß irgendeinem der vorhergehenden Ansprüche 1 bis 7, verwendet in einem Bereich von 0,2 bis 10 Gew.-%, berechnet mit Bezug auf das Schmieröl.
  26. Verfahren zur Reduzierung von Emissionen von verschmutzenden Substanzen, die in Abgasen einer internen Verbrennungsmaschine vorliegen und/oder zur Beförderung von Cer-Verbindungen auf den Teilchenfilter in einer internen Verbrennungsmaschine, welches die Verwendung der Schmierzusammensetzung gemäß Anspruch 25 umfasst.
EP08802834.5A 2007-10-09 2008-10-07 Cerhaltige additive für schmierstoffzusammensetzungen und herstellungsverfahren dafür Not-in-force EP2201089B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT001953A ITMI20071953A1 (it) 2007-10-09 2007-10-09 Additivi contenenti cerio per composizioni lubrificanti e metodo per la loro preparazione
PCT/EP2008/008509 WO2009046976A2 (en) 2007-10-09 2008-10-07 Additives containing cerium for lubricating compositions and method for the preparation thereof

Publications (2)

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EP2201089A2 EP2201089A2 (de) 2010-06-30
EP2201089B1 true EP2201089B1 (de) 2018-02-14

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EP (1) EP2201089B1 (de)
ES (1) ES2668642T3 (de)
IT (1) ITMI20071953A1 (de)
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1392158B1 (it) * 2008-11-24 2012-02-22 Eni Spa Procedimento per la preparazione di additivi per lubrificanti, contenenti cerio
CN102287917B (zh) * 2011-06-01 2013-06-19 刘革 甲醇制氢氧化供热系统
CN117887501A (zh) * 2023-12-27 2024-04-16 华北水利水电大学 油溶性硫化铈纳米微粒、合成方法及其作为润滑油添加剂的应用
CN118146851B (zh) * 2023-12-27 2025-11-18 太原理工大学 一种稀土基润滑脂及其制备方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4804489A (en) * 1987-10-29 1989-02-14 The Lubrizol Corporation Low molecular weight viscosity modifying compositions
DE3926817A1 (de) * 1989-08-14 1991-02-21 Miltiathis Markou Schmiermittel fuer eine brennkraftmaschine
FR2751662B1 (fr) * 1996-07-29 1998-10-23 Total Raffinage Distribution Composition organometalliques mixtes, comprenant au moins trois metaux, et leurs applications comme additifs pour combustibles ou carburants
IT1318868B1 (it) * 2000-08-03 2003-09-10 Cesare Pedrazzini Additivo per ridurre il particolato nelle emissioni derivanti dallacombustione di gasolio ed olio combustibile e composizione carburante
EP1344812A1 (de) * 2002-03-13 2003-09-17 Infineum International Limited Überbasisches Metallsalz enthaltende Dieselkraftstoffzusatzzusammensetzungen zur Partikelfalleverbesserung
US6892531B2 (en) * 2003-04-02 2005-05-17 Julius J. Rim System for and methods of operating diesel engines to reduce harmful exhaust emissions and to improve engine lubrication
PT1512736T (pt) * 2003-09-05 2018-05-29 Infineum Int Ltd Composições estabilizadas de aditivos para gasóleo

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WO2009046976A2 (en) 2009-04-16
EP2201089A2 (de) 2010-06-30
ITMI20071953A1 (it) 2009-04-10
ES2668642T3 (es) 2018-05-21
WO2009046976A3 (en) 2009-07-16

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