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
  • 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
  • C10M121/00—Lubricating compositions characterised by the thickener being a compound of unknown or incompletely defined constitution
  • C10M121/04—Reaction 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
  • 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
  • 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
  • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen 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
  • 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
  • C10M2203/106—Naphthenic fractions
  • C10M2203/1065—Naphthenic 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
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
  • C10M2207/122—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms monocarboxylic
  • C10M2207/1225—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms monocarboxylic used as thickening agent
• • 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
  • C10M2207/128—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 containing hydroxy groups; Ethers thereof
  • C10M2207/1285—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 containing hydroxy groups; Ethers thereof used as thickening agents
• • 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
  • C10M2219/0466—Overbased sulfonic acid salts used as thickening agents
• • 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
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/08—Resistance to extreme temperature
• • 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
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
• • 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
  • C10N2030/18—Anti-foaming property
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/68—Shear 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 present invention is applicable to the field of greases, and more particularly to the field of greases thickened with a complex calcium sulphonate soap.
• the invention relates to a process for the preparation in one phase of a complex calcium sulfonate fat. More particularly, the invention relates to a process for preparing a complex calcium sulfonate grease in one phase, in the absence of boric acid and comprising the implementation of at least one step under pressure.
• the process according to the invention makes it possible to reduce the manufacturing time of a complex calcium sulphonate grease, while maintaining or even improving the manufacturing yield.
• the grease obtained by the process of the invention exhibits in particular good mechanical properties as well as improved thermal resistance and extreme pressure properties.
• lubricating greases are used, which are solid or semi-fluid substances resulting from the dispersion of a thickener in a liquid lubricant, optionally incorporating additives which give them particular properties.
• Thickeners can be organic or inorganic compounds.
• organic thickeners used in the manufacture of fats mention may in particular be made of metal salts of fatty acids and polycarbamides (polyureas).
• lubricating greases are prepared with thickeners such as metal salts of fatty acids.
• the fatty acid is dissolved in the base oil at a relatively high temperature, and then a suitable metal hydroxide is added. After having evaporated by cooking the water which forms during the reaction, it is cooled for a defined period of time, to form the soap network.
• Hydroxides of lithium, sodium, calcium, barium, titanium or aluminum, or certain aluminum trimers are suitable, for example, as metal compounds for the production of grease.
• Long-chain fatty acids of the order of C14 to C28, mainly C18, generally come from vegetable oils (castor oil for example), or animal oils (for example tallow). They can be hydrogenated or hydroxylated.
• the best known derivative is 12 hydroxystearic acid from ricinoleic acid.
• short-chain acids typically comprising between 6 and 12 carbon atoms, such as, for example, azelaic acid or benzoic acid.
• thickeners in particular inorganic such as, for example, bentonite, silica gel, can be used.
• Fats thickened with polyureas do not have sufficient mechanical stability, in particular because of their thixotropic nature, which leads them to break down under mechanical stresses.
• Inorganic thickeners also have problems of mechanical strength and water resistance.
• the thickened greases based on a complex calcium sulphonate soap have been known and used for many years, because they have many properties such as extreme pressure and anti-wear, mechanical resistance, resistance. corrosion, water resistance and thermal stability, especially at high temperatures.
• This type of fat is obtained from the transformation of an overbased calcium sulphonate in the presence in particular of at least one base oil, of at least two distinct acids, one of which is a fatty acid and of at least one minus one base (cf Gareth Fish ET Al, "Calcium Sulfonate Grease Formulation", 2012 ).
• single-phase preparation process means more particularly a process for preparing a complex calcium sulphonate grease comprising a single continuous rise in temperature and a single drop in temperature.
• the document US 5338467 describes a process for the preparation of a complex calcium sulphonate grease, the calcium carbonate particles being in the form of calcite, said process being able to be carried out in a single phase and being able to include pressurizing the constituent mixture of the fat.
• the process examples cited in this document all describe the presence of boric acid. It is the same for the document US 2013/220704 .
• the document US 4560489 describes a process for preparing a complex calcium sulphonate fat which can be implemented in one phase and which can include pressurizing the mixture constituting the fat. Furthermore, this document describes that this process can be implemented in the absence of boric acid. However, this pressurization is carried out by introducing CO 2 into the reactor comprising the mixture.
• the examples described in this document show the importance of the presence of boric acid on the thermal stability properties of the fat obtained at the end of the process.
• the thermal stability of the fat obtained at the end of the process is very low, whereas this stability improves with the increase in the boric acid content.
• the document CN 102703185 describes a process for preparing a complex one-phase calcium sulfonate grease and mixing different components in a pressure reactor.
• the process described in this document includes the presence of boric acid.
• the pressurization of the mixture in the reactor is obtained by adding CO 2 .
• the document US 4824584 describes a process for preparing a complex calcium sulphonate fat which can be implemented in one phase and which can include pressurizing the mixture constituting the fat, without adding boric acid or fatty acid.
• the pressurization is carried out by introducing CO 2 into the reactor comprising the mixture.
• boric acid is a product classified as CMR (carcinogenic, mutagenic and reprotoxic) and therefore represents a potential danger for human health.
• An objective of the present invention is to provide a process which overcomes all or part of the aforementioned drawbacks.
• Another objective of the invention is to provide a method which is simple and which can be easily implemented.
• Another objective of the invention is to provide a complex calcium sulphonate grease whose thermal stability is improved.
• the Applicant has found that it is possible to prepare a complex calcium sulfonate fat by a one-phase process including a step of pressurizing the mixture constituting the fat and without adding boric acid or co. -solvent.
• the present invention makes it possible to implement a process for preparing a complex calcium sulphonate grease making it possible to maintain, or even improve, the yield, while reducing the preparation time.
• the method according to the invention makes it possible to reduce or even eliminate the risks to human health.
• the method according to the invention makes it possible to reduce or even eliminate the risks of the foaming phenomenon.
• the complex calcium sulphonate grease obtained at the end of the process according to the invention has equivalent properties, in particular of mechanical stability and anti-wear, compared to existing complex calcium sulphonate greases.
• the complex calcium sulphonate grease obtained at the end of the process according to the invention exhibits improved properties, in particular of thermal resistance and extreme pressure, compared to existing complex calcium sulphonate greases.
• steps a.i) to a.iii) can be implemented in a different order.
• step a) can first be added the sulfonic acid comprising at least 12 carbon atoms at a temperature of at least 50 ° C and then to the mixture thus obtained can be added the carboxylic acid. comprising at least 12 carbon atoms, and optionally at least one —OH group.
• the method according to the invention makes it possible to limit the risks of loss of product during its use and therefore to optimize its yield.
• the base oil of step a1) according to the present invention can be chosen from oils of mineral, synthetic or natural origin as well as mixtures thereof.
• the mineral or synthetic oils generally used for the preparation of grease belong to one of groups I to V according to the classes defined in the API classification (or their equivalents according to the ATIEL classification) as summarized in Table I below.
• API classification is defined in American Petroleum Institute 1509 "Engine oil Licensing and Certification System” 17th edition, September 2012 .
• the ATIEL classification is defined in " The ATIEL Code of Practice", issue 18, November 2012 .
• Table I Saturated content Sulfur content Viscosity index Group I Mineral oils ⁇ 90% > 0.03% 80 ⁇ VI ⁇ 120 Group II Hydrocracked oils ⁇ 90% ⁇ 0.03% 80 ⁇ VI ⁇ 120 Group III Hydrocracked or hydroisomerized oils ⁇ 90% ⁇ 0.03% ⁇ 120
• PAO Poly alpha olefins
• Mineral base oils include all types of bases obtained by atmospheric and vacuum distillation of crude oil, followed by refining operations such as solvent extraction, deasphalting, solvent dewaxing, hydrotreatment, hydrocracking and hydroisomerization, hydrofinishing.
• the synthetic base oils can be chosen from esters, silicones, glycols, polybutene, polyalphaolefins (PAO), alkylbenzene or alkylnaphthalene.
• the base oils can also be oils of natural origin, for example esters of alcohols and carboxylic acids, which can be obtained from natural resources such as sunflower oil, rapeseed oil, palm oil, soy....
• the base oil from step a.i) is chosen from group I base oils.
• the base oil from step a1) is chosen from group I base oils of Bright Stocks (BSS) type (distillation residue, kinematic viscosity at 100 ° C close to 30 mm 2 / s measured according to standard D-445, typically from 28 to 32 mm 2 / s, and density at 15 ° C ranging from 895 to 915 kg / m 3 ), the base oils of group I of type 330 NS (distillate, density at 15 ° C ranging from 880 to 900 kg / m 3 , kinematic viscosity at 100 ° C close to 12 mm 2 / s measured according to standard D-445), naphthenic group I base oils (viscosity of 100 cSt at 40 ° C measured according to standard D-445) or their mixtures.
• BSS Bright Stocks
• the base oil of step a1) is a mixture of at least one base oil of group I type BSS, of a base oil of group I of type 330 NS and of a naphthenic group I base oil.
• step a.i) of the process according to the invention at least one overbased calcium sulphonate is mixed with the base oil present in the reactor.
• This compound is known to those skilled in the art as a detergent and consists of a calcium salt of a sulfonate.
• the excess metal providing the overbased character to the detergent is in the form of metal salts insoluble in oil, for example carbonate, hydroxide, oxalate, acetate, glutamate, preferably carbonate.
• the metals of these insoluble salts may be the same as those of the detergents soluble in the base oil or else they may be different. They are preferably chosen from calcium, magnesium, sodium or barium.
• the overbased detergents are thus in the form of micelles composed of insoluble metal salts maintained in suspension in the base oil by the detergents in the form of soluble metal salts in the oil.
• the overbased calcium sulfonate is a calcium sulfonate overbased with calcium carbonate.
• BN Base Number
• overbased calcium sulfonates is high, preferably greater than 150 mg KOH / g of detergent.
• BN is measured according to ASTM D-2896.
• the overbased calcium sulfonate of step a1) has a BN of at least 300 mg KOH / g of detergent, preferably ranging from 300 to 500 mg KOH / g of detergent, advantageously from 350 to 450 mg KOH / g of detergent.
• the content by weight of calcium sulfonate ranges from 35 to 55%, preferably from 40 to 50% relative to the total weight of the starting reagents.
• the content by weight of base oil ranges from 45 to 65%, preferably from 50 to 60% relative to the total weight of the starting reagents.
• the mixture of step a.i) can be heated to a temperature of at least 60 ° C, preferably at least 70 ° C, advantageously from 70 to 80 ° C.
• step a.ii) of the process according to the invention is added at least one carboxylic acid comprising at least 12 carbon atoms, and optionally at least one —OH group, at a temperature of at least 20 ° C.
• the carboxylic acid of step a.ii) is chosen from carboxylic acids or hydroxycarboxylic acids comprising from 12 to 24 carbon atoms, preferably from 16 to 20 carbon atoms. .
• the carboxylic acid of step a.ii) is chosen from hydroxycarboxylic acids comprising from 12 to 24 carbon atoms, preferably from 16 to 20 carbon atoms.
• the carboxylic acid of step a.ii) is 12-hydroxystearic acid.
• the content by weight of carboxylic acid ranges from 1 to 4%, preferably from 1.5 to 3% relative to the total weight of the starting reactants.
• step a.ii) further comprises the addition of an anti-foam additive.
• anti-foam additives used in greases are well known to those skilled in the art and can in particular be chosen from silicone compounds.
• the content by weight of anti-foaming additive ranges from 0.01 to 1% relative to the total weight of the starting reagents.
• step a.ii) is carried out at a temperature ranging from 20 to 60 ° C, preferably from 40 to 60 ° C.
• step a.iii) of the process according to the invention is added at least one sulfonic acid comprising at least 12 carbon atoms at a temperature of at least 50 ° C.
• oil-soluble sulfonic acids which can be used in the process according to the invention are well known for preparing thixotropic compositions thickened with a complex calcium sulfonate and in which the calcium carbonate is in the form of calcite crystals.
• R 1 represents a linear or branched, saturated alkyl group comprising at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, more preferably from 10 to 15 carbon atoms, advantageously 12 carbon atoms.
• A represents a benzene group.
• x is equal to 1.
• M represents a hydrogen atom and y is equal to 1.
• the sulfonic acid of step a.iii) is dodecylbenzene sulfonic acid.
• the content by weight of sulfonic acid ranges from 0.5 to 4%, preferably from 1 to 3% relative to the total weight of the starting reagents.
• step a.iii) is carried out at a temperature ranging from 50 to 60 ° C, preferably from 50 to 55 ° C.
• step a.iv) of the process according to the invention is added water.
• the content by weight of water ranges from 1 to 10%, preferably from 3 to 8% relative to the total weight of the starting reactants.
• step a.iv) is carried out at a temperature ranging from 50 to 60 ° C.
• step a.v) of the process according to the invention is added at least one carboxylic acid comprising at least 2 carbon atoms at a temperature of at least 50 ° C.
• the carboxylic acid of step a.v) can be chosen from carboxylic acids comprising from 2 to 6 carbon atoms, preferably from 2 to 4 carbon atoms.
• the carboxylic acid of step av) is acetic acid.
• the content by weight of carboxylic acid ranges from 0.1 to 1%, preferably from 0.4 to 0.8% relative to the total weight of the starting reactants.
• step a.v) is carried out at a temperature of at least 60 ° C, preferably ranging from 60 to 65 ° C.
• the carboxylic acid comprising from 2 to 6 carbon atoms, preferably from 2 to 4 carbon atoms, is added slowly to the mixture present in the reactor.
• slow addition is meant the fact of not adding the entire quantity of carboxylic acid to the mixture present in the reactor all at once and / or over a very short period of time.
• the applicant has observed that the fact of slowly adding the carboxylic acid comprising at least 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, to the mixture present in the reactor makes it possible to reduce or even eliminate the phenomenon of foaming of the mixture present in the reactor.
• step a.vii) of the process according to the invention the temperature is raised to a temperature of at least 80 ° C.
• step a.vii) is carried out at a temperature of at least 85 ° C, preferably 85 to 95 ° C.
• the temperature is maintained at 90 ° C. for a period of at least 15 min, preferably ranging from 15 min to 1 h.
• step a.ix of the process according to the invention, lime is added at a temperature of at least 90 ° C.
• lime according to the invention is meant more particularly calcium hydroxide.
• the lime can be in solid form, such as a powder, or in liquid form, such as an aqueous solution of lime.
• the lime is in the form of a powder.
• the content by weight of added lime ranges from 0.1 to 4%, preferably from 0.5 to 2.5% relative to the total weight of the starting reactants.
• step a.ix is carried out at a temperature ranging from 90 to 95 ° C.
• step a.ix can also further comprise the addition of at least one base oil.
• the base oil added in step a.ix) is identical to the base oil in step a.i)
• the content by weight of base oil added ranges from 1 to 20%, preferably from 5 to 15% relative to the total weight of the starting reagents.
• step c) of the process according to the invention the temperature is raised in the reactor to a temperature of at least 130 ° C. and under a pressure of at least 400 kPa.
• the temperature of step c) ranges from 130 to 160 ° C, preferably from 130 to 150 ° C, advantageously from 140 ° C.
• the temperature rise in step c) is carried out according to a temperature gradient ranging from 1 to 3 ° C./min.
• the pressure of step c) ranges from 400 to 700 kPa, preferably from 500 to 650 kPa.
• the pressure in the reactor in step c) is maintained at a pressure ranging from 500 to 650 kPa, preferably around 600 kPa, at a temperature ranging from 130 to 150 ° C, preferably around 140 ° C, for a period of at least 15 min, preferably ranging from 15 to 80 min, advantageously from 15 to 60 min.
• step c) of the process according to the invention under such conditions allows optimum transformation into calcite.
• optical conversion is understood to mean that all of the amorphous calcium carbonate has been transformed into calcite and that therefore no calcium carbonate remains in amorphous form at the end of the process.
• the monitoring of the transformation of amorphous calcium carbonate into calcite can be done by a measurement method by infrared spectrometry.
• step c) of the process according to the invention in the absence of co-solvents emitting VOCs makes it possible to obtain a process for preparing a complex calcium sulfonate grease having very little or no no danger to human health, and more particularly to the health of people dedicated to its implementation.
• step d) of the process according to the invention decompression and elimination of the water contained in the reactor is carried out.
• Decompression can be implemented by various means well known to those skilled in the art.
• the decompression is implemented by opening the reactor.
• the decompression time is at least 1 h, preferably ranging from 1 h to 3 h.
• the decompression is carried out at a temperature of at least 130 ° C, preferably ranging from 130 to 150 ° C, advantageously around 140 ° C.
• the decompression is carried out for a period of at least 1 h and at a temperature of at least 130 ° C, preferably ranging from 130 to 150 ° C, advantageously around 140 ° C.
• a vacuum draw can be applied to the mixture present in the reactor after decompression.
• step d the decompression is followed by the application of a vacuum draw of the mixture present in the reactor.
• the vacuum drawing can be carried out by various means, for example using a vacuum pump or a deaerator.
• the drawing under vacuum is carried out using at least one deaerator.
• the method according to the invention may further comprise a step di) carried out after step d) and before step e) and comprising the additional addition of at least one base oil.
• the base oil added in step d.i) is identical to the base oil in step a.i).
• the content by weight of base oil ranges from 1 to 20%, preferably from 5 to 15% relative to the total weight of the starting reagents.
• step e) of the process according to the invention cooling of the reactor is carried out.
• the cooling of the reactor can be implemented by various means, for example by keeping the reactor at ambient temperature, by the installation of a cooling device by circulating water around the reactor, by the installation of a cooling device around the reactor ...
• the cooling is carried out by maintaining the mixture present in the reactor at ambient temperature.
• the cooling of step e) is carried out by lowering the temperature to a temperature less than or equal to 90 ° C, preferably from 70 to 90 ° C. .
• the cooling of step e) is implemented with a drop ranging from 1 to 3 ° C / min, preferably around 2 ° C / min.
• the method according to the invention may further comprise a step f) carried out after step e) and comprising the addition of at least one additional additive, optionally followed by a step of grinding the product obtained.
• the additive can be chosen from additives well known to those skilled in the art, such as antioxidant additives, for example antioxidants of the phenolic or amine type, anti-rust additives, such as for example acid dodecylsuccinic, calcium phenates, calcium salicylates, oxidized waxes or amine phosphates, anti-corrosion additives such as tolyltriazoles or derivatives of dimercaptothiadiazole, anti-foam additives or their mixtures.
• antioxidant additives for example antioxidants of the phenolic or amine type
• anti-rust additives such as for example acid dodecylsuccinic, calcium phenates, calcium salicylates, oxidized waxes or amine phosphates
• anti-corrosion additives such as tolyltriazoles or derivatives of dimercaptothiadiazole, anti-foam additives or their mixtures.
• the additive is chosen from anti-oxidants, anti-corrosion agents or their mixtures.
• the content by weight of additive ranges from 0.1 to 10%, preferably from 0.1 to 5% relative to the total weight of the starting reactants.
• the additive of step f) is added at a temperature of at most 90 ° C, preferably ranging from 60 to 90 ° C, advantageously from 70 to 90 ° C.
• the greases obtained by the process according to the invention have a consistency of between 220 and 430 tenths of a millimeter according to the ASTM D217 standard, to cover grades 00, 0, 1, 2 and 3.
• the greases obtained by the process according to the invention have a consistency of between 265 and 295 tenths of a millimeter according to the ASTM D217 standard, to cover grade 2.
• the greases obtained by the process according to the invention have very good thermal resistance.
• the greases obtained by the process according to the invention exhibit a bleeding of less than 0.8% (percentage by mass of oil loss) measured according to standard ASTM D6184 (50 h, 100 ° C) and a bleeding of less than 0.5% (percentage by mass of oil loss) measured according to standard NF T60-191 (168 h, 40 ° C).
• the fats obtained by the process according to the invention are more stable when hot, and more particularly above 140 ° C.
• the greases obtained by the process according to the invention have good extreme pressure performance.
• the greases obtained by the process according to the invention have a welding load measured according to the ASTM D2596 standard greater than 350 kg, preferably greater than or equal to 400 kg.
• the grease compositions obtained by the process according to the invention have a welding load measured according to DIN 51350/4 greater than 350 daN, preferably greater than or equal to 360 daN, more preferably greater than or equal to 370 daN, even more preferably greater than or equal to 380 daN (daN: decanewton).
• the greases obtained by the process according to the invention have a ball wear, obtained by the FAG FE 8 test according to the DIN 51819 standard, of less than 2.
• the greases obtained by the process according to the invention are also very slightly corrosive, in particular towards metals and metal alloys, and more particularly towards copper.
• a method of lubricating a mechanical part comprises at least bringing the mechanical part into contact with a grease as defined above. All the characteristics and preferences presented for the grease also apply to the method of lubricating a mechanical part according to the invention.
• the reactor (1) has a capacity ranging from 2 to 10 tonnes, preferably from 3 to 6 tonnes.
• the stirring device (2) present in the reactor (1) can be chosen from any type of stirring device known to those skilled in the art and used in the preparation of a fat.
• pressurizing any means making it possible to introduce and maintain a particular pressure inside the reactor.
• the pressurizing means (3) can be a pressure cooker.
• heating means is meant any means making it possible to introduce a temperature rise and to maintain a particular temperature inside the reactor.
• the heating means (4) can be a boiler heating a heat transfer fluid.
• the receiving tank (5) has a capacity ranging from 2 to 10 tonnes, preferably from 3 to 6 tonnes.
• the receiving tank (5) can further comprise at least one cooling means (7).
• the cooling means can be chosen from the cooling means used in step e) and described above.
• the transfer means (6) make it possible to convey the complex calcium sulphonate grease from the reactor (1) to the receiving vessel (5).
• the transfer means (6) can in particular be chosen from circulation pumps or pipes.
• the transfer means comprises a circulation pump (8) capable of pumping the complex calcium sulphonate grease outside the reactor (1) so that it is transferred into the receiving tank. (5).
• the production unit further comprises an additive tank (9)
• additive tank any tank comprising at least one additive intended to be added to the mixture present in the reactor (1).
• Example 1 (according to the invention): method A for preparing a fat
• Example 2 (comparative): method B for preparing a fat
• a fat was prepared according to method A in which a boric acid derivative (calcium metaborate) was added to the mixture present in the reactor: the calcium metaborate was added in a content of 2.9% by weight per relative to the total weight of the starting reagents, with the additive package comprising an amino antioxidant and at a temperature of about 80 ° C.
• a boric acid derivative calcium metaborate
• Calcium metaborate behaves in the same way as boric acid, except that calcium metaborate is not a CMR classified product.
• Example 3 (comparative): method C for preparing a fat
• a fat was prepared according to a method C, comparative, in two phases in the presence of boric acid comprising the following steps:
• Example 4 Method D for preparing a fat
• a fat was prepared according to Method A, except that the step of adding water at 57 ° C and the step of adding acetic acid between 60 and 65 ° C were reversed.
• Example 5 (according to the invention): process E for preparing a fat
• the product obtained by process E according to the invention is in the form of a smooth and shiny fat.
• Example 6 (comparative): method F for preparing a fat
• method F does not include a pressurizing step corresponding to step c) according to the invention.
• the product obtained by process F is in the form of a liquid fat.
• Test 1 evaluation of the preparation time associated with processes A, B and C.
• process A makes it possible to obtain the same grade of grease as that obtained by a 2-phase process (process C) or by a one-phase process but comprising a boric acid derivative (method B).
• Test 3 evaluation of the mechanical stability properties of greases obtained by methods A, B and C.
• the penetrability is measured according to the ISO 2137 standard after 100,000 strokes and is expressed in 1/10 mm.
• the “Shell Roller” test is carried out according to the ASTM D1831 standard after 100 h at 80 ° C. and the results are expressed in 1/10 mm; this test mainly consists of rolling the grease using rollers and makes it possible to evaluate the stability of a grease when it is rolled.
• Test 4 evaluation of the thermal resistance properties of greases obtained by processes A, B and C.
• the dropping point is measured according to the NF T60-627 standard and is expressed in degrees Celcius.
• the bleeding after 50 h at 100 ° C. is evaluated according to standard ASTM D6184 and is expressed as a percentage corresponding to a percentage by weight of oil loss.
• the bleeding after 168 h at 40 ° C. is evaluated according to standard NF T60-191 and is expressed as a percentage corresponding to a percentage by mass of oil loss.
• Penetrant testing makes it possible more particularly to evaluate the thermal stability of a grease; the lower the percentage obtained, the better the thermal resistance; the penetrant assessment clearly reflects the quality of a thickener in retaining the oil present in a grease.
• Table VI Grease obtained by implementing method A (method according to the invention) Grease obtained by implementing method B (comparative method) Grease obtained by implementing method C (comparative method) Dropping point (° C) > 300 > 300 > 300 Penetrant penetration 50h / 100 ° C 0.70 0.85 2.70 168h / 40 ° C penetrant penetration 0.47 0.77 0.74
• Test 5 evaluation of the shear resistance properties of greases obtained by processes A and C
• the viscosity is measured according to the DIN 51810-2 standard and is expressed in Pa.s.
• the results of Table VII show a significant difference in hot behavior between a grease obtained by a process according to the invention (process A) and a grease obtained by a two-phase process (process C). Indeed, the greases obtained by a process according to the invention show a slight decrease in viscosity when the temperature increases, while the greases obtained by a two-phase process show a significant drop in viscosity, more particularly from 99 ° C. vs.
• the greases obtained by a process according to the invention exhibit better thermal resistance when hot, and more particularly above 140 ° C.
• Test 6 evaluation of the extreme pressure properties of greases obtained by processes A, B and C.
• the 4-ball EP test is carried out according to standard DIN 51350/4 and is expressed in daN.
• Test 7 evaluation of the anti-corrosion properties of greases obtained by processes A, B and C.
• Emcor test is evaluated according to ISO 11007.
• Test 8 evaluation of the anti-wear properties of greases obtained by processes A, B and C
• Test 9 evaluation of the foaming associated with the process according to the invention
• Foaming can have harmful consequences for the process, which can in particular be manifested by a risk of the mixture present in the reactor overflowing and therefore a loss of product at the end of the process, but also by a longer preparation time.
• Foaming can also have harmful consequences on the fat obtained at the end of the process, which can in particular be manifested by a deterioration of the physicochemical properties of the fat.
• Test 11 evaluation of the thermal resistance properties of greases obtained by processes E and F.
• the dropping point is measured according to the NF T60-627 standard and is expressed in degrees Celcius.
• Table XII Grease obtained by implementing process E (process according to the invention) Grease obtained by implementing method F (comparative method) Dropping point (° C) > 300 Not measurable (liquid product)
• step c) according to the invention with the objective of obtaining complex calcium sulphonate greases having a structure as well as satisfactory physicochemical, mechanical and thermal resistance properties.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Lubricants (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (2)

Publications (2)

Family

ID=50069139

Family Applications (1)

Country Status (12)

Families Citing this family (10)

Family Cites Families (11)

• 2013
  • 2013-11-13 FR FR1361087A patent/FR3013056B1/fr active Active
• 2014
  • 2014-11-12 CN CN201480068423.5A patent/CN105874045B/zh active Active
  • 2014-11-12 ES ES14798820T patent/ES2897503T3/es active Active
  • 2014-11-12 US US15/035,895 patent/US10590362B2/en active Active
  • 2014-11-12 RU RU2016122685A patent/RU2678565C1/ru active
  • 2014-11-12 AU AU2014350173A patent/AU2014350173B2/en active Active
  • 2014-11-12 CA CA2930270A patent/CA2930270C/fr active Active
  • 2014-11-12 MX MX2016006231A patent/MX2016006231A/es unknown
  • 2014-11-12 WO PCT/EP2014/074410 patent/WO2015071331A1/fr active Application Filing
  • 2014-11-12 BR BR112016010835-3A patent/BR112016010835B1/pt active IP Right Grant
  • 2014-11-12 EP EP14798820.8A patent/EP3068853B1/fr active Active
  • 2014-11-12 KR KR1020167015431A patent/KR102263290B1/ko active Active

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events