Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
  • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
  • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
  • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
  • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
  • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
  • C11C3/06—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils with glycerol

Definitions

• the present invention relates to additive compositions which, when added to various refined petroleum cuts improve their lubricating power.
• These cups constitute what is usually referred to as “middle distillates”. They can be used as fuel bases for engines jet, gas turbines, or diesel engines of all kinds. They characterized by the fact that they consist mainly of hydrocarbons and that their distillation range at atmospheric pressure is between about 130 ° C and about 400 ° C.
• middle distillates thus designates, in addition to distillation cuts direct, possible mixtures of such cuts with cuts resulting from thermal, catalytic or steam cracking, including hydrogenating cracking.
• compositions proposed within the framework of the present invention are intended to combat the insufficiency of the wear protection of fuels which have just been described previously. These compositions make it possible in particular to confer gas oils, which originally lacked antiwear properties natural, sufficient anti-wear power to ensure, in service, functioning without incident on the injection organs.
• the invention therefore provides an additive composition which can be used to increase the lubricating power of middle petroleum distillates, characterized in that it comprises at least one partial ester formed between at least one polyol and at least one monocarboxylic acid from 4 to 24 carbon atoms, said carboxylic acid possibly being linear or branched, saturated, monounsaturated or polyunsaturated, possibly hydroxylated or isomerized (as is the case for isostearic acids).
• the polyols considered in the definition of partial esters used as additives in the context of the invention are mainly propanediol-1,2 (or mono-propylene glycol), propanediol-1,3, butanediol-1,3, butanediol-1,4, neopentyl-glycol, glycerin (or glycerol), diglycerol, polyglycerols, trimethylol-propane and pentaerythritol.
• the main monocarboxylic acids considered are acids linear or weakly branched aliphatics, generally referred to as "fatty acids", which can be chosen for example from butyric, caproic, caprylic acids, capric, lauric, myristic, palmitic, palmitoleic, stearic, oleic, linoleic, linolenic, ricinoleic, arachidic, gadoleic, behenic, erucic and lignoceric, as well as mixtures of isostearic acid isomers.
• fatty acids linear or weakly branched aliphatics
• compositions of the invention are more particularly considered partial esters formed between glycerol and the fatty acids defined above and, among these, diglycerides-1,2 and / or 1,3, alone or in mixtures with mono-glycerides-1 and / or 2, as well as, and preferably, monoglycerides-1 and / or 2 do not containing only traces of 1,2 and / or 1,3 diglycerides.
• Monoglycerides can be obtained very selectively by the enzymatic; in this case, the formation of monoglyceride-1 or of monoglyceride-2, as described for example in the communication by M. Leclerc: “Novo Nordisk Bioindustrie S.A.”, at the Chevreul Days in Toulouse-1990.
• the enzymatic formation of monoglycerides, in this case monoglycerides-1 is also described by B. Steffen et al. in: "Fat Sci. Technology” 97th year n ° 4 (1995) pp 132-136.
• the monoglycerides can also be obtained from glycidol and fatty acids, for example according to European patent EP-B-0 545 477, or, in a more general, using thermal or basic catalysis.
• the main impurities encountered in such a preparation method of monoglycerides are traces of free glycerin, diglycerides, triglycerides and free fatty acids.
• partial esters of glycerol i.e. monoglycerides, diglycerides and mixtures of mono and diglycerides, but we can also consider partial esters of other polyols, or partial esters of glycerol and at least one other polyol in blends.
• the monoglycerides and diglycerides considered in the additive compositions of the invention can be derived from the partial esterification of glycerol with free fatty acids (saturated, monounsaturated or polyunsaturated fatty acids, preferably containing from 8 to 24 carbon atoms and originating for example from the hydrolysis of natural oils, vegetable or animal), used pure or in mixtures; they can also be derived from the transesterification of C 1 to C 4 alcohol esters of these same fatty acids, with glycerol (glycerolysis); they can finally result directly from the transesterification by glycerol of the natural oils themselves, containing these fatty acids linked to glycerol in the form of triglycerides.
• free fatty acids saturated, monounsaturated or polyunsaturated fatty acids, preferably containing from 8 to 24 carbon atoms and originating for example from the hydrolysis of natural oils, vegetable or animal
• free fatty acids saturated, monounsaturated or polyunsatur
• the preferred method of preparation is from oils themselves, which are transesterified by reaction with glycerin additional.
• esters of other polyols it will be preferable to start from an acid fatty or a mixture of fatty acids, unless it is desired to form mixtures of esters partial glycerol and at least one other polyol, in which case the method of obtaining preferred will also be the transesterification of a natural oil, using this polyol alone or a mixture in appropriate proportions of this polyol with glycerin.
• Natural oils and fats that can be used as a base synthesis in the methods of preparation of partial esters by transesterification are very varied. Mention may be made, for example, of oils from copra, babassu, palm kernel, tucum, murumuru and palm, lard, tallow, melted butter, shea, olive, peanut, kapok, bitter date, papaya, coloquinte, croton, nutmeg, purge, hemp, beech, hibiscus, pulghere, camelina, safflower, niger, sunflower, oleic sunflower, rubber, coconut, purga, nut, corn, soy, cotton, sorghum, seed grapes, flax, tobacco, common pine, afzellia, cabbage turnip, mustard, brown mustard, Chinese wood, henceoulier, aleurite, amoora, fir, cramble, perilla, erucic rapeseed, new rapeseed, oleic
• the conditions for preparing the partial polyol esters according to the invention are classic conditions.
• the polyol (s) are used in excess relative to the stoichiometry of the partial esters that one wishes to prepare. So, to prepare mono or diglycerides, 3 to 9 moles of glycerol per mole of acid can be used free fat or per mole of fatty acid contained in the starting triglyceride and one operates for example at temperatures from 180 to 250 ° C.
• the oil cuts to which to be added the compositions of the invention are generally middle distillates of petroleum, such as, for example, those which serve as a basis for diesel fuels (diesel) or for fuels for land, sea or aviation turbines. They are characterized by the fact that they consist mainly of hydrocarbons and that their distillation range at atmospheric pressure is between about 130 ° C and about 400 ° C.
• the incorporation rate of the partial polyol esters to be introduced into the middle distillates according to the invention is generally between 50 and 2000 and preferably between 75 and 200 ppm.
• the monoglycerides and diglycerides were synthesized in laboratory according to known protocols using sodium hydroxide as catalyst, from rapeseed oil (Products A and C) and oleic sunflower oil (Products B and D) and glycerin (Products A, B and C) or a mixture of glycerin and 1,3-propanediol (Product D).
• the diglyceride derived from rapeseed oil (product C) has an approximate content of 62% diglycerides (1.2 + 1.3), 37% in monoglycerides (1 + 2) and approximately 1% in weight Fatty acids.
• the products manufactured as described above are subjected to purification by washing with water in the presence of n-heptane, then evaporation of the n-heptane, in order to completely eliminate the catalyst and the excess polyol.
• the antiwear properties of the compounds A, B, C and D of the invention were measured by means of the device known by the acronym HFRR (High Frequency Reciprocating Rig).
• the anti-wear power of diesel oils is estimated through measuring the wear of a 6 mm diameter ball made of hardened, rubbing 100Cr6 steel reciprocating on a polished 100Cr6 steel top.
• the set of two test tubes test tank is bathed in diesel fuel to be tested.
• a heating system keeps the rooms at 60 ° C, this temperature being very representative of the actual operating conditions of a diesel injection pump on vehicle.
• a mass of 200 g presses the ball against the plane during the movement.
• the diesel fuel used to carry out the HFRR tests has the composition indicated in Table 2 below.
• Measured properties Methods Values initial point of distillation NF M 07-002 213 ° C point at 50% NF M 07-002 270 ° C distillation end point NF M 07-002 312 ° C Density at 20 ° C NF T 60-172 803 kg / m 3 kinematic viscosity at 20 ° C NF T 60-100 4.31 mm 2 / s sulfur content ASTM D 3120 ⁇ 1 mg / l water content NF T 60-154 17 mg / l pour point NF T 60-105 - 42 ° C cloud point NF T 60-105 - 27 ° C
• the test is also carried out with pure diesel fuel without additives.
• Performance review shows that a concentration of around 125 parts per million is enough to give a diesel completely devoid of wear protection natural, sufficient anti-wear power to ensure operation, operation injection device incidents.
• the test is also carried out with pure diesel fuel without additives.
• the test is also carried out with pure diesel fuel without additives.
• the test is also carried out with pure diesel fuel without additives.

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Cited By (12)

Citations (12)

• 1996
  • 1996-08-27 FR FR9610543A patent/FR2752850A1/fr not_active Withdrawn
• 1997
  • 1997-08-25 EP EP97401983A patent/EP0826765A1/de not_active Withdrawn

Patent Citations (12)

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