EP2733191B1 - Phenatreinigungsmittelherstellung - Google Patents

Phenatreinigungsmittelherstellung Download PDF

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Publication number
EP2733191B1
EP2733191B1 EP13185404.4A EP13185404A EP2733191B1 EP 2733191 B1 EP2733191 B1 EP 2733191B1 EP 13185404 A EP13185404 A EP 13185404A EP 2733191 B1 EP2733191 B1 EP 2733191B1
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EP
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Prior art keywords
calcium
calcium salt
alcohol
detergent
sulphur
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Not-in-force
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EP13185404.4A
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English (en)
French (fr)
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EP2733191A1 (de
Inventor
Oliver Delamore
Dirk Schwaebisch
Adam Marsh
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Infineum International Ltd
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Infineum International Ltd
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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
    • 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
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • 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
    • 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
    • C10M2207/02—Hydroxy compounds
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/022—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy 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
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
    • 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
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more 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
    • 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
    • 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
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • 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

  • This invention relates to making a sulphurised calcium alkyl phenate detergent and to use of the detergent in internal combustion engine lubrication.
  • Sulphurised calcium alkyl phenate detergents are well known additive components for internal combustion engine crankcase lubricating oil compositions.
  • alkylphenol sources nonylphenol, tetrapropenylphenol
  • reproductive toxins there is a desire to identify other phenol sources.
  • US-A-5,910,468 ('468) describes the preparation of sulphurised calcium alkyl phenate from, as the phenol source, distilled or hydrogenated-distilled cashew nut shell liquid (CNSL).
  • Distilled CNSL is a mixture of biodegradable meta-hydrocarbyl substituted phenols, where the hydrocarbyl group is linear and unsaturated, including cardanol.
  • Catalytic hydrogenation of distilled CNSL gives rise to a mixture of meta-hydrocarbyl substituted phenols predominantly rich in 3-pentadecylphenol.
  • a problem with the process described in '468 is to improve the oxidative stability of the sulphurised calcium alkyl phenate detergents thereby produced.
  • the invention provides, in a first aspect, a method of making a sulphurised calcium phenate detergent comprising the stages:
  • the invention provides, in a second aspect, a sulphurised calcium phenate detergent obtainable by the method of the first aspect of the invention.
  • the sulphurised calcium phenate detergent has a kinematic viscosity at 100°C of greater than 750 and less than 1200 cSt, preferably greater than 800 to less than 1150 cSt, as measured by ASTM D445.
  • the invention provides, in a third aspect, a lubricating oil composition comprising, in a major amount, an oil of lubricating viscosity and, in a minor amount, a detergent of the second aspect of the invention.
  • the invention provides, in a fourth aspect, a lubricating oil composition comprising, in a major amount, an oil of lubricating viscosity and, in a minor amount, a detergent of the second aspect of the invention.
  • the invention provides, in a fifth aspect, a method of operating an internal combustion engine comprising fuelling the engine and lubricating the engine with the lubricating oil composition of the fourth aspect of the invention.
  • the calcium salt is preferably calcium oxide or calcium hydroxide.
  • the di- or poly-hydric alcohol which is also known as the promoter, has the function of phase transferring the calcium from the solid phase into the liquid organic phase and is preferably a 1, 2-vicinal diol, for example ethylene glycol.
  • the total amount of calcium salt and of alcohol used must be such as to provide a sulphurised calcium phenate of desired TBN.
  • the first amounts (i.e. in stage (i)) of each of the calcium salt and of the promoter, relative to their respective total amounts are less than 50, such as less than 30, such as 20 or less, expressed as molar percentages.
  • the first amounts of each of the calcium salt and of the alcohol, expressed as molar percentages of their total amounts are not less than 10.
  • a characteristic structural feature of the alkyl phenol materials used in the invention is meta hydrocarbyl-substitution of the aromatic ring where the substituent is attached to the ring at its first (C1) carbon atom.
  • This structural feature is not available by chemical alkyl phenol synthesis such as the Friedel-Crafts reaction of phenol with olefins. The latter typically gives mixtures of ortho and para alkyl phenols (but only around 1% of meta alkyl phenols), and where attachment of the alkyl group to the aromatic ring is at the second (C2) or higher carbon atom.
  • Cardanol the product obtained by distilling technical CNSL, typically contains 3-pentadecylphenol (3%); 3-(8-pentadecenyl) phenol (34-36 %); 3-(8, 11-pentadecadienyl) phenol (21-22%); and 3-(8, 11, 14-pentadecatrienyl) phenol (40-41%), plus a small amount of 5-(pentadecyl) resorcinol (c. 10%), also referred to as cardol.
  • Technical CNSL contains mainly cardanol plus some polymerized material. Cardanol may therefore be expressed as containing significant amounts of meta-linear hydrocarbyl substituted phenol, where the hydrocarbyl group has the formula C 15 H 25-31 and is attached to the aromatic ring at its first carbon atom (C1).
  • both cardanol and technical CNSL contain significant quantities of material having long linear unsaturated side chains and only small quantities of material with long linear saturated side chains.
  • the present invention employs material where a major proportion, preferably all of the phenol, contains material with long linear saturated side chains.
  • Such latter material is obtainable by hydrogenating cardanol; a preferred example is 3-(pentadecyl) phenol, where the pentadecyl group is linear and is attached to the aromatic ring at its first carbon atom. It may constitute 50 or more, 60 or more, 70 or more, 80 or more, or 90 or more, mass % of the additive of the invention. It may contain small quantities of 3-(pentadecyl) resorcinol.
  • the invention does not include technical CNSL.
  • the method may be carried out in the presence of a carboxylic acid or anhydride (which is also known as a co-surfactant) such as a long chain carboxylic acid (e.g. stearic acid or lauric acid, oleic acid or alkylsalicylic acid) or the related esters; a long chain carboxylic amide (e.g. tallow amine); a long chain ethoxylated amine; a phenol or alkyl phenol or methylene bridged alkyl phenol; a hydrocarbyl substituted anhydride or succinic anhydride (e.g. polyisobutene succinic anhydride); or a long chain alkylaryl sulphonic acid.
  • a carboxylic acid or anhydride which is also known as a co-surfactant
  • a carboxylic acid or anhydride which is also known as a co-surfactant
  • a carboxylic acid or anhydride which is also known as a
  • the carboxylic acid or anhydride (co-surfactant) may be present in the range of 1-20, such as 4-12, such as 4-10, such as 4-8, preferably 6-8, mass % based on the total mass of alkyl phenol.
  • the carboxylic acid or anhydride (co-surfactant) is provided in step (ii) to avoid the possibility of its adverse interaction with elemental sulphur in step (i).
  • Process solvents are added to the reaction mixture in order to decrease viscosity of the reaction mixture during synthesis. As is known by those skilled in the art, lowering the viscosity allows improved dispersion of carbon dioxide in the reaction mixture therefore promoting efficient carbonation. These solvents are typically high boiling (>140°C) and unreactive under the conditions used. Examples include isodecanol, cyclohexanol and 2-ethylhexanol.
  • Carbonation is preferably effected at temperatures of greater than 100°C. Carbonation preferably takes place at temperatures from 120 to 210°C, more preferably from 140 to 190°C, most preferably from 150 to 180°C and even most preferably from 160 to 175°C.
  • An oil of lubricating viscosity provides a major proportion of the composition and may be any oil suitable for lubricating an internal combustion engine.
  • viscosity may range in viscosity from light distillate mineral oils to heavy lubricating oils. Generally, the viscosity of the oil ranges from 2 to 40 mm 2 /sec, as measured at 100°C.
  • Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil); liquid petroleum oils and hydrorefined, solvent-treated or acid-treated mineral oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale also serve as useful base oils.
  • Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1-hexenes), poly(1-octenes), poly(1-decenes)); alkybenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulphides and derivative, analogues and homologues thereof.
  • Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc. constitute another class of known synthetic lubricating oils. These are exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, and the alkyl and aryl ethers of polyoxyalkylene polymers (e.g., methyl-polyiso-propylene glycol ether having a molecular weight of 1000 or diphenyl ether of poly-ethylene glycol having a molecular weight of 1000 to 1500); and mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3-C8 fatty acid esters and C13 oxo acid diester of tetraethylene glycol.
  • polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide
  • alkyl and aryl ethers of polyoxyalkylene polymers e.g
  • Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol).
  • dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linole
  • esters includes dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles oftetraethylene glycol and two moles of 2-ethylhexanoic acid.
  • Esters useful as synthetic oils also include those made from C5 to C12 monocarboxylic acids and polyols and polyol esters such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
  • Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxysilicone oils and silicate oils comprise another useful class of synthetic lubricants; such oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexyl)silicate, tetra-(p-tert-butyl-phenyl) silicate, hexa-(4-methyl-2-ethylhexyl)disiloxane, poly(methyl)siloxanes and poly(methylphenyl)siloxanes.
  • oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexy
  • Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.
  • Unrefined, refined and re-refined oils can be used in lubricants of the present invention.
  • Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment.
  • a shale oil obtained directly from retorting operations petroleum oil obtained directly from distillation; or ester oil obtained directly from esterification and used without further treatment, are unrefined oils.
  • Refined oils are similar to unrefined oils except that the oil is further treated in one or more purification steps to improve one or more properties.
  • Many such purification techniques such as distillation, solvent extraction, acid or base extraction, filtration and percolation, are known to those skilled in the art.
  • Re-refined oils are obtained by processes similar to those used to provide refined oils but begin with oil that has already been used in service. Such re-refined oils are also known as reclaimed or reprocessed oils and are often subjected to additional processing using techniques for removing spent additives and oil breakdown products.
  • an oil of lubricating viscosity that may be used in a lubricating oil composition of the present invention, there may be mentioned an oil containing 50 mass % or more of a basestock containing greater than or equal to 90 % saturates and less than or equal to 0.03% sulphur or a mixture thereof. Preferably, it contains 60, such as 70, 80 or 90, mass % or more of said basestock or a mixture thereof.
  • the oil of lubricating viscosity may consist or substantially consist of said basestock or a mixture thereof.
  • Oil of lubricating viscosity may provide 50 mass% or more of the composition. Preferably, it provides 60, such as 70, 80 or 90, mass % or more of the composition.
  • the lubricating oil composition may, for example, be a marine diesel cylinder lubricant ("MDCL”) or a trunk piston engine oil (“TPEO").
  • MDCL marine diesel cylinder lubricant
  • TPEO trunk piston engine oil
  • the phenates of the invention may be used in lubricants for a range of internal combustion engines (spark-ignited or compression-ignited) such as motor vehicle engines and marine engines. Of the latter, there may be mentioned two-stroke marine diesel cross-head engines and marine trunk piston engines.
  • Hydrogenated distilled CNSL (ex Sigma Aldrich, Cardolite Corporation or synthesized from cardanol sourced from various providers) is sulphurised using elemental sulphur (added in one or two steps) in the presence of calcium oxide, solvent and ethylene glycol.
  • ethylene glycol, calcium oxide (such as to provide the required TBN), a co-surfactant and CO 2 are added to the reaction mixture of step (i).
  • the synthesis is completed by vacuum distillation, filtration or centrifugation, and, if necessary, dilution in oil.
  • the product was filtered, and diluted to the required TBN with base oil if necessary.
  • a set of calcium phenate detergents was prepared employing various charges of ethylene glycol promoter and of Ca in each of steps (i) and (ii).
  • test method is performed as follows; ramp at 40°C/min from 50°C to 210°C under an atmosphere of air (689kPa (100psi) and zero flow) then hold at that temperature for up to 2 hours. Open Seiko Aluminium pans are used.
  • Example % EG and Ca step (i)) % EG and Ca (step (ii)) Kinematic Viscosity (cSt) at 100 °C pDSC (mins) 1 30 70 919 93.7 2 50 50 1084 82.8 A (comparative) 70 30 707 74.5 B (comparative) 100 0 346 75.3 •
  • the percentages are molar percentages; equal molar proportions of EG and Ca were present.
  • Examples 1 and 2 are examples of the invention, and Examples A and B are reference examples that are for comparative purposes only.

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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)

Claims (16)

  1. Verfahren zur Herstellung von geschwefeltem Calciumphenat-Detergens, bei dem
    (i) ein oder mehrere Alkylphenol-Materialien, die hydrierte destillierte Cashewnußschalenflüssigkeit mit ersten festgelegten Mengen an Calciumsalz und zwei- oder mehrwertigem Alkohol aufweist, mit Schwefel in der Gegenwart von Lösungsmittel umgesetzt wird und
    (ii) das Produkt aus Schritt (i) mit zweiten festgelegten Mengen des Calciumsalzes und des zwei- oder mehrwertigen Alkoholes umgesetzt wird und das Produkt carbonisiert wird,
    wobei die Gesamtmenge an Calciumsalz und Alkohol so ist, dass ein geschwefeltes Calciumphenat mit gewünschter TBN bereitgestellt wird, und wobei die erste Menge des Calciumsalzes und des Alkoholes in Schritt (i) jeweils bezogen auf ihre Gesamtmenge in dem Verfahren weniger als 50 beträgt, ausgedrückt als Molprozentsatz, und
    wobei der Molprozentsatz der ersten Menge des Calciumsalzes und des Alkoholes jeweils nicht weniger als 5 beträgt, ausgedrückt als Molprozentsatz ihrer Gesamtmengen.
  2. Verfahren nach Anspruch 1, bei dem Schritt (ii) in der Abwesenheit von Schwefel durchgeführt wird.
  3. Verfahren nach einem der vorhergehenden Ansprüche, bei dem das Calciumsalz Calciumoxid oder Calciumhydroxid ist.
  4. Verfahren nach einem der vorhergehenden Ansprüche, bei dem das Alkylphenol-Material 3-Pentadecylphenol umfasst.
  5. Verfahren nach einem der vorhergehenden Ansprüche, welches Verfahren in der Gegenwart von Carbonsäure oder -anhydrid durchgeführt wird.
  6. Verfahren nach Anspruch 5, bei dem die Carbonsäure oder das Carbonsäureanhydrid Stearinsäure oder Polyisobutenbernsteinsäureanhydrid ist.
  7. Verfahren nach einem der vorhergehenden Ansprüche, bei dem der Schwefel elementarer Schwefel ist.
  8. Verfahren nach einem der vorhergehenden Ansprüche, bei dem der zwei- oder mehrwertige Alkohol 1,2-vicinales Diol ist.
  9. Geschwefeltes Calciumphenat-Detergens, das durch das Verfahren gemäß eines der Ansprüche 1 bis 8 erhältlich ist, wobei das geschwefelte Calciumphenat-Detergens eine kinematische Viskosität bei 100 °C von mehr als 750 und weniger als 1200 cSt aufweist, gemessen gemäß ASTM D445.
  10. Verwendung des Detergens gemäß Anspruch 9 in Schiffskurbelwannen-Schmiermittel.
  11. Verwendung nach Anspruch 10 in Schiffskurbelwannen-Schmiermittel, um die oxidative Stabilität des Schmiermittels, gemessen unter Verwendung Dynamischer Differenzkalorimetrie (pDSC) (Europäische Methode Nr. CECL-85-T-99), im Vergleich zu der eines Schmiermittels zu verbessern, das ein Detergens enthält, das in einem einstufigen Calciumsalz-Zugabeverfahren hergestellt worden ist.
  12. Schmierölzusammensetzung, die in einer größeren Menge Öl mit Schmierviskosität und in einer kleineren Menge Detergens gemäß Anspruch 9 umfasst.
  13. Schmierölzusammensetzung nach Anspruch 12, bei der das Öl mit Schmierviskosität 50 Massen-% oder mehr Basismaterial enthält, das mehr als oder gleich 90% gesättigte Materialien und weniger als oder gleich 0,03% Schwefel oder eine Mischung davon enthält.
  14. Schmierölzusammensetzung nach Anspruch 12 oder 13 in der Form von Schiffsdieselzylinder-Schmiermittel.
  15. Schmierölzusammensetzung nach Anspruch 12 oder 13 in der Form von Schiffsdieseltauchkolbenmotor-Schmiermittel.
  16. Verfahren zum Betreiben von einem Dieselverbrennungsmotor, bei dem der Motor angetrieben wird und der Motor mit Schmierölzusammensetzung gemäß eines der Ansprüche 12 bis 15 geschmiert wird.
EP13185404.4A 2012-11-14 2013-09-20 Phenatreinigungsmittelherstellung Not-in-force EP2733191B1 (de)

Priority Applications (1)

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EP13185404.4A EP2733191B1 (de) 2012-11-14 2013-09-20 Phenatreinigungsmittelherstellung

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP12192645 2012-11-14
EP13185404.4A EP2733191B1 (de) 2012-11-14 2013-09-20 Phenatreinigungsmittelherstellung

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EP2733191A1 EP2733191A1 (de) 2014-05-21
EP2733191B1 true EP2733191B1 (de) 2016-04-27

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EP13185404.4A Not-in-force EP2733191B1 (de) 2012-11-14 2013-09-20 Phenatreinigungsmittelherstellung

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US (1) US20140130758A1 (de)
EP (1) EP2733191B1 (de)
JP (1) JP2014098150A (de)
CN (1) CN103805313A (de)
CA (1) CA2833492A1 (de)
SG (1) SG2013084157A (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2674474B1 (de) * 2012-06-13 2015-09-09 Infineum International Limited Prozess zur Herstellung eines Phenat-Detergents
CN104529844B (zh) * 2014-12-03 2016-06-22 锦州康泰润滑油添加剂股份有限公司 一种高碱值硫化烷基酚钙的制备方法
EP3199612A1 (de) * 2016-01-26 2017-08-02 Infineum International Limited Metallreinigungsmittel
EP4077604B1 (de) 2019-12-20 2024-09-04 The Lubrizol Corporation Schmiermittelzusammensetzung, die ein detergens aus cashewnussschalenflüssigkeit enthält
CN121379528A (zh) * 2025-12-25 2026-01-23 山东龙程矿业科技股份有限公司 一种抑尘剂及其制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3379663D1 (en) * 1982-05-14 1989-05-24 Exxon Research Engineering Co Lubricating oil additives
JPH04183792A (ja) * 1990-11-19 1992-06-30 Idemitsu Kosan Co Ltd 過塩基性硫化アルカリ土類金属フェネート及びその用途
US5910468A (en) 1998-04-06 1999-06-08 Indian Oil Corporation Ltd. Process for the preparation of calcium phenate detergents from cashew nut shell liquid
US6339052B1 (en) * 2000-06-30 2002-01-15 Indian Oil Corporation Limited Lubricant compositions for internal combustion engines
EP1903093B1 (de) * 2006-09-19 2017-12-20 Infineum International Limited Schmierölzusammensetzung
EP2447346B1 (de) * 2010-10-28 2014-03-05 Infineum International Limited Schmierung für einen Schiffsmotor

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Publication number Publication date
US20140130758A1 (en) 2014-05-15
CN103805313A (zh) 2014-05-21
SG2013084157A (en) 2014-06-27
JP2014098150A (ja) 2014-05-29
CA2833492A1 (en) 2014-05-14
EP2733191A1 (de) 2014-05-21

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