EP3902896B1 - Mineralölfreies schmiermittel und verfahren zur herstellung eines mineralölfreien schmiermittels - Google Patents

Mineralölfreies schmiermittel und verfahren zur herstellung eines mineralölfreien schmiermittels Download PDF

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EP3902896B1
EP3902896B1 EP19829548.7A EP19829548A EP3902896B1 EP 3902896 B1 EP3902896 B1 EP 3902896B1 EP 19829548 A EP19829548 A EP 19829548A EP 3902896 B1 EP3902896 B1 EP 3902896B1
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Prior art keywords
mixture
koh
range
temperature
ester
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German (de)
English (en)
French (fr)
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EP3902896C0 (de
EP3902896A1 (de
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Frank Bongardt
Markus John
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Kajo GmbH
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Kajo GmbH
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Priority to HRP20250487TT priority Critical patent/HRP20250487T1/hr
Priority to EP25156216.1A priority patent/EP4545623A3/de
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/24—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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/34—Esters of monocarboxylic acids
    • 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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/36—Esters of polycarboxylic acids
    • 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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/38—Esters of polyhydroxy 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
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/10—Metal oxides, hydroxides, carbonates or bicarbonates
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
    • 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
    • C10M2207/28—Esters
    • C10M2207/2805—Esters 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
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • C10M2207/2815—Esters of (cyclo)aliphatic monocarboxylic acids 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
    • C10M2207/28—Esters
    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
    • C10M2207/2825—Esters of (cyclo)aliphatic oolycarboxylic acids 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
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds 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
    • C10M2207/28—Esters
    • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
    • C10M2207/301—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids 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
    • C10M2207/40—Fatty vegetable or animal oils
    • C10M2207/401—Fatty vegetable or animal oils 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
    • 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
    • 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
    • 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
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • 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
    • C10N2030/40—Low content or no content compositions
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/64—Environmental friendly compositions
    • 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
    • C10N2030/66—Hydrolytic stability
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Form in which the lubricant is applied to the material being lubricated semi-solid; greasy
    • 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 invention relates to a process for producing a lubricant, in which an overbased calcium sulfonate is first produced or prepared, then converted from the vaterite form to the calcite form, and finally a calcium sulfonate grease is produced by heating the mixture.
  • the invention further relates to a lubricant produced by this process.
  • Lubricants are used to reduce friction and wear, to dampen vibrations, for sealing, and as corrosion protection for tools, machines, engines, as well as motor vehicles, aircraft, ships, and their parts.
  • Lubricating greases typically consist of a lubricating oil, a thickener, and auxiliary substances and additives. Lubricating greases generally contain approximately 80% lubricating oil, 5-10% thickener, and 10-15% additives. Examples of lubricating oils include mineral oils, natural or synthetic ester oils, polyalphaolefins, or silicone oils.
  • Synthetic ester oils include, for example, monocarboxylic acid esters, dicarboxylic acid esters, polyol esters, and complex esters.
  • various soaps or inorganic substances e.g. bentonite
  • calcium sulfonates are often used as thickeners, which, in addition to their thickening effect in the grease, also have a corrosion-inhibiting effect due to their basic properties.
  • Calcium sulfonate greases currently available on the market are based exclusively on mineral oils or synthetic base oils such as polyalphaolefins (PAO). Mineral oils and PAOs account for up to 80% of the grease.
  • the core components For the production of calcium sulfonate grease so-called overbased calcium sulfonates are used. These are produced by reacting alkylbenzenesulfonic acids with calcium hydroxide and calcium oxide by introducing carbon dioxide into a mineral carrier oil.
  • Overbased calcium sulfonates generally contain more than 50% mineral oil. With these components, it is not possible to produce rapidly biodegradable calcium sulfonate greases.
  • solubilizers such as water, organic solvents, and acids must also be added, which then have to be removed after production. Filtration is often also necessary to remove non-dispersed solid particles.
  • Biodegradability refers to the decomposition of a lubricant into inorganic substances such as water, salts, carbon dioxide, and biomass with the help of microorganisms. According to the current state of the art, the complete biodegradability of lubricants is determined exclusively by the OECD 301 test methods, which are based on the production of CO2 . Biodegradability is determined at the end of a "10-day test window" and after 28 days of testing. If the lubricant has achieved the required degree of degradation of at least 60% both at the end of the 10-day window and after 28 days of incubation, it is classified as “readily biodegradable” and can be awarded, for example, the EU Ecolabel (EEL).
  • EEL EU Ecolabel
  • the WO 2004/106474 A1 describes lubricants with enhanced biodegradability based on a biodegradable oil, such as a polyol ester (C5-C8) or a polyalkylene glycol, a calcium sulfonate-based thickener, and a naturally occurring phospholipid.
  • a biodegradable oil such as a polyol ester (C5-C8) or a polyalkylene glycol, a calcium sulfonate-based thickener, and a naturally occurring phospholipid.
  • the thickener used is a mixture of overbased magnesium and calcium sulfonates based on mineral oil. Due to the significant mineral oil content, complete biodegradability according to OECD-301 is not possible at the WO 2004/106474 A1 described lubricants cannot be achieved.
  • the DE 22 25 714 A1 discloses a process for producing overbased lubricant additives by preparing a reaction mixture of an oil-soluble detergent or dispersant, a basic magnesium compound, an organic compound containing hydroxyl groups, a promoter, and optionally water in an inert solvent. This reaction mixture is reacted with an acidic gas and heated to remove volatile components.
  • At least one salt of an aliphatic monoamine, diamine, or polyamine, each having a maximum of 10 carbon atoms, or of an aromatic amine with an inorganic acid, an aliphatic monocarboxylic acid having 1 to 20 carbon atoms (including the carbon atom in the carboxyl group), an aliphatic di- or polycarboxylic acid having 2 to 10 carbon atoms, or an aromatic carboxylic acid is used as the promoter.
  • the object of the invention is to provide a process for producing a lubricant that does not require the use or addition of mineral oil, and to create a lubricant that is completely biodegradable.
  • the process according to the invention is characterized in particular by the fact that both the calcium sulfonate and the grease containing it are produced exclusively on an ester basis, so that the end product contains no mineral oil and is therefore easily and completely biodegradable.
  • the lubricant according to the invention achieves the required degree of degradation of at least 60% at the end of the so-called 10-day window and after 28 days, thus meeting the requirements of the OECD 301 test method.
  • replacing mineral oil with organic or synthetic esters eliminates the need for solubilizers, eliminating the need for laborious removal at the end of the production process.
  • the process according to the invention also ensures that the overbased calcium sulfonates are completely dispersed in the reaction mixture, thus eliminating the need for filtration at the end of the process.
  • the conditions for producing the lubricant are selected such that the ester composition is not decomposed under these conditions.
  • the unit [mg KOH/g] refers to the basicity of potassium hydroxide (KOH).
  • the basicity of the mixture is limited in step a) to a maximum TBN of 550 mg KOH/g and in step b) to a maximum TBN of 450 mg KOH/g.
  • Controlling and adjusting or limiting the basicity of the mixture advantageously leads to Esters in the mixture do not saponify, especially under the influence of the high temperatures in steps b) and c).
  • the moderate addition of water also contributes to this.
  • Adjusting the mixture to a water content in the range of 2 wt.% to 20 wt.% in step b) significantly reduces the possibility of ester hydrolysis.
  • Selecting the lowest possible temperatures, particularly in steps a) and b), also advantageously ensures that the esters remain stable in the mixture. In this way, a mineral oil-free, biodegradable calcium sulfonate grease can be produced in a particularly advantageous manner.
  • the at least one alkyl group of the mono-, di-, or tri-alkylbenzenesulfonic acid can be linear, branched, and/or cyclic alkyl groups.
  • at least one alkyl group of the mono-, di-, or tri-alkylbenzenesulfonic acid is a (C10-C18) alkyl group.
  • the mixture in step a) is adjusted to a base number (TBN) in the range of 150 to 550 mg KOH/g, preferably 210 to 450 mg KOH/g or 320 to 420 mg KOH/g, in particular 211 to 399 mg KOH/g.
  • TBN base number
  • the base number of the mixture in step a) can also be adjusted to a TBN in the range of 200 to 500 mg KOH/g or 300 to 500 mg KOH/g or 400 to 500 mg KOH/g or 150 to 450 mg KOH/g or 250 to 450 mg KOH/g or 350 to 450 mg KOH/g or 200 to 400 mg KOH/g or 300 to 400 mg KOH/g.
  • the mixture in step b) is adjusted to a base number (TBN) in the range of 50 to 450 mg KOH/g, preferably 70 to 350 mg KOH/g or 100 to 250 mg KOH/g, in particular 80 to 220 mg KOH/g.
  • TBN base number
  • the base number the mixture in step b) can also be adjusted to a TBN in the range of 100 to 450 mg KOH/g or 200 to 450 mg KOH/g or 300 to 450 mg KOH/g or 350 to 450 mg KOH/g or 50 to 300 mg KOH/g or 100 to 300 mg KOH/g or 200 to 300 mg KOH/g or 150 to 250 mg KOH/g.
  • the mixture in step a) is heated to a temperature in the range from 35°C to 85°C or 45°C to 60°C, in particular 40°C to 82°C.
  • the mixture in step a) can also be heated to a temperature in the range from 45°C to 85°C or 55°C to 85°C or 65°C to 85°C or 75°C to 85°C or 40°C to 70°C or 50°C to 70°C or 60°C to 70°C or 50°C to 80°C or 55°C to 75°C.
  • the mixture in step b) is heated to a temperature in the range of 87°C to 102°C or 85°C to 100°C, in particular 88°C to 99°C.
  • the mixture in step b) can also be heated to a temperature in the range of 90°C to 102°C or 95°C to 102°C or 87°C to 100°C or 90°C to 100°C.
  • the mixture in step c) is heated to a temperature in the range from 100°C to 180°C or 110°C to 170°C, in particular 125°C to 160°C.
  • the mixture in step c) can also be heated to a temperature in the range of 120°C to 180°C or 130°C to 180°C or 140°C to 180°C or 150°C to 180°C or 160°C to 180°C or 150°C to 170°C or 100°C to 160°C or 110°C to 160°C or 120°C to 160°C or 130°C to 160°C or 140°C to 160°C or 170°C to 180°C.
  • the water content of the mixture in step b) is adjusted to a proportion in the range of 5 wt.% to 18 wt.%, in particular 7 wt.% to 15 wt.%.
  • the water content of the mixture in step b) can also be adjusted to a proportion in the range of 5 to 15 wt.%, or 10 to 15 wt.%, or 7 to 18 wt.%, or 10 to 18 wt.%, or 9 to 13 wt.%.
  • step b) To adjust the basicity of the reaction mixture in step b) to a desired TBN, calcium hydroxide and/or at least one mono-, di-, or tri-alkylbenzenesulfonic acid, wherein at least one alkyl group is a (C3-C30) alkyl group, and/or at least one ester composition, wherein the ester composition comprises at least one ester, can be added to the mixture. Furthermore, the addition of one or more of the above-mentioned substances can positively influence the conversion from the vaterite form to the calcite form with regard to the completeness of the conversion.
  • auxiliaries and/or additives can be added to the reaction mixture.
  • acetic acid can be added, preferably in step b), to optionally adjust the desired basicity and to increase the dropping point through the resulting calcium acetate.
  • 12-hydroxystearic acid can be added, preferably after conversion to the calcite form, to optimize the lubricant with regard to its hydrophobic properties, i.e. to increase its resistance to water.
  • phenolic antioxidants e.g. Irganox® L 107, BASF
  • aminic antioxidants e.g.
  • Irganox® L 57, BASF dimercaptothiadiazole derivatives
  • ADDITIN® RC 8213 (Lanxess) dimercaptothiadiazole derivatives
  • all common additives that improve the consistency and properties of the lubricant according to the invention can be added.
  • the invention further relates to a lubricant produced by the inventive process described above.
  • the inventive lubricant contains no mineral oil and is therefore readily biodegradable according to the requirements of the OECD 301 test method. Furthermore, unlike mineral oil-containing greases, it remains fluid even at very low temperatures (-10°C to -20°C) and also has a higher pressure absorption capacity.
  • At least one alkyl group of the mono-, di- or tri-alkylbenzenesulfonate can be linear, branched, and/or cyclic alkyl groups.
  • at least one alkyl group of the mono-, di-, or tri-alkylbenzenesulfonate is a (C10-C18) alkyl group.
  • the ester composition can, for example, comprise a synthetic ester and/or a native (organic) ester.
  • suitable esters include mono- and dicarboxylic acid esters, polyol esters, and complex esters, as well as native ester oils such as rapeseed oil.
  • the ester composition can consist of a single ester or a mixture of two or more different esters.
  • the ester composition should preferably have a viscosity in the range of 2 mm 2 /s to 1,200 mm 2 /s, preferably 10 mm 2 /s to 500 mm 2 /s.
  • the lubricant according to the invention may additionally comprise at least one additive.
  • additives that may be present are phenolic antioxidants (e.g., Irganox® L 107, BASF), amine antioxidants (e.g., Irganox® L 57, BASF), and/or dimercaptothiadiazole derivatives ( ADDITIN® RC 8213 (Lanxess)).
  • the mixture now has a TBN of 399 mg KOH/g.
  • 300 g of complex ester (fatty acids, C18-unsaturated, dimerized, polymer with 2-ethylhexanol and neopentyl glycol), 220 g of C10-14-alkyl benzoic acid, 21 g of acetic acid, 72 g of Ca(OH) 2 , and 180 g of water are then added to the mixture.
  • the mixture is heated to 92 °C.
  • the calcium carbonate has been converted from the vaterite to the calcite form, the mixture is dehydrated at 110 °C.
  • the TBN is now 220 mg KOH/g.
  • the mixture is then heated to 160 °C and held at this temperature for one hour. After cooling, the grease has a consistency (according to ASTM D217) of 292 mm/10 after 60 double strokes. Further technical data can be found in Table 2.
  • the mixture is heated to 92 °C. After the calcium carbonate has been converted from the vaterite to the calcite form, the mixture is dehydrated at 110 °C. The TBN is now 180 mg KOH/g. The mixture is then heated to 150 °C and held at this temperature for half an hour. After cooling, the grease has a consistency (according to ASTM D217) of 299 mm/10 after 60 double strokes. Further technical data can be found in Table 2.
  • rapeseed oil V40: 35 mm2/s
  • 288 g of C10-14-alkyl benzoic acid 24 g of acetic acid, 70 g of Ca(OH) 2 , and 49 g of water are then added to the mixture.
  • the mixture is heated to 88 °C.
  • 167 g of 12-hydroxystearic acid is added and the mixture is dehydrated at 110 °C.
  • the TBN is now 80 mg KOH/g.
  • the mixture is then heated to 125 °C and held at this temperature for 15 minutes. After cooling, the grease has a consistency (according to ASTM D217) of 299 mm/10 after 60 double strokes.

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Lubricants (AREA)
EP19829548.7A 2018-12-24 2019-12-19 Mineralölfreies schmiermittel und verfahren zur herstellung eines mineralölfreien schmiermittels Active EP3902896B1 (de)

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HRP20250487TT HRP20250487T1 (hr) 2018-12-24 2019-12-19 Mazivo bez mineralnog ulja i postupak za proizvodnju maziva bez mineralnog ulja
EP25156216.1A EP4545623A3 (de) 2018-12-24 2019-12-19 Mineralölfreies schmiermittel

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DE102018133586.5A DE102018133586B4 (de) 2018-12-24 2018-12-24 Mineralölfreies Schmierfett und Verfahren zur Herstellung eines mineralölfreien Schmierfetts
PCT/EP2019/086264 WO2020136075A1 (de) 2018-12-24 2019-12-19 Mineralölfreies schmiermittel und verfahren zur herstellung eines mineralölfreien schmiermittels

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GB1399092A (en) * 1971-05-27 1975-06-25 Cooper & Co Ltd Edwin Lubricant additives
GB1547376A (en) * 1975-03-17 1979-06-13 Snam Progetti Ubricants and process for producing lubricating greases
US4981602A (en) * 1988-06-13 1991-01-01 The Lubrizol Corporation Lubricating oil compositions and concentrates
USH1536H (en) * 1995-04-11 1996-06-04 The Lubrizol Corporation Overbased materials in ester media
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
JP2002265969A (ja) * 2001-03-07 2002-09-18 Nippon Koyu:Kk グリース組成物
US7517837B2 (en) 2003-05-22 2009-04-14 Anderol, Inc. Biodegradable lubricants
PE20141377A1 (es) * 2011-10-31 2014-10-10 Nch Corp Composiciones de grasa de sulfonato de calcio a base de carbonato de calcio y metodo de manufactura
JP6051097B2 (ja) * 2013-04-26 2016-12-27 出光興産株式会社 グリースの製造方法
CN104293449B (zh) * 2013-07-17 2016-08-10 中国石油化工股份有限公司 一种复合环烷酸钙基润滑脂及其制备方法
CN105037222A (zh) * 2015-06-25 2015-11-11 锦州惠发天合化学有限公司 高碱值结晶型磺酸钙的制备方法
CN105503670A (zh) * 2016-01-12 2016-04-20 安徽金桐精细化学有限公司 一种高碱值的合成烷基苯磺酸钙纳米清净剂及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
M G JENNINGS ET AL: "Technical Bulletin – TBN In Diesel Engine Oils", 1 January 2012 (2012-01-01), XP055441436, Retrieved from the Internet <URL:http://www.championbrands.com/Tech%20Bulletin%20TBN-Chevron.pdf> [retrieved on 20180116] *

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SG11202106821YA (en) 2021-07-29
CN113366096A (zh) 2021-09-07
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KR20240169721A (ko) 2024-12-03
EP3902896C0 (de) 2025-03-26
JP2022515776A (ja) 2022-02-22
ZA202105074B (en) 2022-08-31
EP4545623A3 (de) 2025-06-25
BR112021012304A2 (pt) 2021-09-08
CA3123499A1 (en) 2020-07-02
KR20210107054A (ko) 2021-08-31
US11920103B2 (en) 2024-03-05
WO2020136075A1 (de) 2020-07-02
DE102018133586B4 (de) 2022-03-03
EP3902896A1 (de) 2021-11-03
ES3026661T3 (en) 2025-06-11
HRP20250487T1 (hr) 2025-06-20
PL3902896T3 (pl) 2025-06-23
KR102778769B1 (ko) 2025-03-10
AU2019412475A1 (en) 2021-07-08
US20220056365A1 (en) 2022-02-24
JP2024127889A (ja) 2024-09-20
CN113366096B (zh) 2023-03-17
AU2019412475B2 (en) 2025-08-14

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